JP7279732B2 - Resin composition, adhesive film, printed wiring board and semiconductor device - Google Patents

Description

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

2. Description of the Related Art As a technique for manufacturing printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition. For example, Patent Literature 1 discloses a technique of forming an insulating layer with a low dielectric loss tangent by curing a resin composition containing an epoxy resin, an active ester compound and a carbodiimide compound.

Due to the recent trend toward lighter, thinner, shorter and smaller printed wiring boards, the number of layers is increasing due to the build-up of printed wiring boards. becomes a problem. As a technique for suppressing such cracks and circuit distortion problems, for example, Patent Document 2 discloses that the coefficient of thermal expansion of the insulating layer formed is suppressed by increasing the content of the inorganic filler in the resin composition. Techniques are disclosed.

JP 2006-335834 A JP 2010-202865 A

The present inventors have found that when manufacturing a printed wiring board, in order to form an insulating layer with a low dielectric loss tangent and a low coefficient of thermal expansion, the resin composition described in Patent Document 1 is blended with a high content of an inorganic filler. Tried. While the resulting resin composition provides an insulating layer exhibiting the desired dielectric loss tangent and coefficient of thermal expansion, it may result in an insulating layer inferior in properties such as elongation at break, surface roughness, and peel strength. The inventors have found.

The present invention provides a resin composition that can provide an insulating layer that is excellent in all of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength when manufacturing a printed wiring board. is the subject.

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

That is, the present invention includes the following contents.
[1] (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin and (E) an inorganic filler, wherein the content of the component (E) is the resin composition A resin composition having a content of 40% by mass or more when the non-volatile component therein is taken as 100% by mass.
[2] The resin composition according to [1], wherein component (D) has a weight average molecular weight of 10,000 to 200,000.
[3] Component (D) is a thermoplastic resin having one or more atoms selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms or a functional group containing a carbon-carbon double bond, [ 1] or the resin composition according to [2].
[4] Component (D) is a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, a thiol group, an enol group, an enamine group, a urea group, a cyanate group, an isocyanate group, a thioisocyanate group, a diimide group, The resin composition according to any one of [1] to [3], which is a thermoplastic resin having one or more functional groups selected from the group consisting of alkenyl groups, allene groups and ketene groups.
[5] Component (D) is one or more thermoplastic resins selected from the group consisting of phenoxy resins, polyvinyl acetal resins, acid anhydride group-containing vinyl resins, polyimide resins, polyamideimide resins, and styrene-based elastomer resins. The resin composition according to any one of [1] to [4].
[6] The resin composition according to any one of [1] to [5], wherein component (C) has a weight average molecular weight of 500 to 5,000.
[7] The resin composition according to any one of [1] to [6], wherein the NCO content of component (C) is 5% by mass or less.
[8] The resin composition according to any one of [1] to [7], wherein the content of component (E) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. .
[9] The resin composition according to any one of [1] to [8], wherein component (E) has an average particle size of 0.01 μm to 3 μm.
[10] The resin composition according to any one of [1] to [9], wherein component (E) is silica.
[11] The resin composition according to any one of [1] to [10], further comprising (F) a curing accelerator.
[12] The resin composition according to [11], wherein component (F) is 4-dimethylaminopyridine or 1-benzyl-2-phenylimidazole.
[13] Any of [1] to [12], wherein the resin composition is cured to form an insulating layer, and the surface of the insulating layer has an arithmetic mean roughness (Ra) of 140 nm or less after roughening treatment. The resin composition according to .
[14] The resin composition according to any one of [1] to [13], wherein a cured product of the resin composition has an elongation at break of 2% or more.
[15] The resin composition according to any one of [1] to [14], wherein a cured product of the resin composition has a glass transition temperature (Tg) of 165°C or higher.
[16] An adhesive film comprising a support and a layer of the resin composition according to any one of [1] to [15] bonded to the support.
[17] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [15].
[18] A semiconductor device including the printed wiring board according to [17].

According to the present invention, there is provided a resin composition that can provide an insulating layer that is excellent in all of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength when manufacturing a printed wiring board. can do.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments.

[Resin composition]
The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin and (E) an inorganic filler, and the content of the component (E) is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass.

When a resin composition containing (A) an epoxy resin, (B) an active ester compound and (C) a carbodiimide compound is blended with a high content of (E) an inorganic filler, the resulting resin composition has a low dielectric The present inventors have found that while providing an insulating layer exhibiting tangent and a low coefficient of thermal expansion, it may result in an insulating layer inferior in properties such as elongation at break, surface roughness, peel strength, and the like. By further containing (D) a thermoplastic resin, the resin composition of the present invention provides an insulating layer that is excellent in elongation at break, surface roughness and peel strength while maintaining low dielectric loss tangent and low coefficient of thermal expansion. This is what makes it possible. In this regard, even if (D) a thermoplastic resin is added to (B) a resin composition that does not contain an active ester compound, the desired elongation at break, surface roughness and peel strength cannot be achieved. Even if (D) a thermoplastic resin is added to (C) a resin composition that does not contain a carbodiimide compound, the desired elongation at break, surface roughness and peel strength cannot be achieved. If (D) a thermoplastic resin is added to (E) a resin composition having a low inorganic filler content, the desired dielectric loss tangent and coefficient of thermal expansion cannot be achieved in the first place. These are clearly grasped from the results of comparative examples shown later. Thus, the effect of the resin composition of the present invention is that, in addition to (A) epoxy resin, (B) active ester compound, (C) carbodiimide compound, (D) thermoplastic resin, and a certain amount or more of ( E) A specific and synergistic effect resulting from the combined use of inorganic fillers.

Each component contained in the resin composition of the present invention is described below.

<(A) Epoxy resin>
The resin composition of the present invention contains an epoxy resin as component (A).

Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, Phenol novolak type epoxy resin, alicyclic epoxy resin having an ester skeleton, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy Resins, cresol novolak type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100 mass %, at least 50 mass % or more of the epoxy resin preferably has two or more epoxy groups in one molecule. Among them, an epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20 ° C. (hereinafter referred to as "liquid epoxy resin"), and three or more epoxy groups in one molecule, It preferably contains an epoxy resin that is solid at a temperature of 20° C. (hereinafter referred to as “solid epoxy resin”). By using both a liquid epoxy resin and a solid epoxy resin as epoxy resins, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolak type epoxy resin, and alicyclic epoxy resin having an ester skeleton. , and epoxy resins having a butadiene structure are preferred, and bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, alicyclic epoxy resins having an ester skeleton, and naphthalene type epoxy resins are more preferred, and bisphenol A type epoxy resins and bisphenol AF type epoxy resins are more preferable, and bisphenol AF type epoxy resins are particularly preferable from the viewpoint of excellent physical property balance of cured products. Specific examples of liquid epoxy resins include "HP4032", "HP4032H", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation, and "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation. ” (bisphenol A type epoxy resin), “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “YL7760” (bisphenol AF type epoxy resin), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "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 Corporation, "Celoxide 2021P" manufactured by Daicel Corporation ” (alicyclic epoxy resin having an ester skeleton) and “PB-3600” (epoxy resin having a butadiene structure). These may be used individually by 1 type, and may be used in combination of 2 or more type.

Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin and tetraphenylethane type epoxy resin are preferred, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin and biphenyl type epoxy resin are more preferred. Specific examples of solid epoxy resins include "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation, " N-695" (cresol novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000 ” (naphthylene ether type epoxy resin), Nippon Kayaku Co., Ltd. “EPPN-502H” (trisphenol type epoxy resin), “NC7000L” (naphthol novolac type epoxy resin), “NC3000H”, “NC3000”, "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin), manufactured by Mitsubishi Chemical Corporation "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin (biphenyl type epoxy resin)), "YX8800" (anthracene type epoxy resin), Osaka Gas Chemical Co., Ltd. " PG-100", "CG-500", "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S ” (tetraphenylethane type epoxy resin) and the like.

When a liquid epoxy resin and a solid epoxy resin are used together as the epoxy resin, the ratio by mass (liquid epoxy resin:solid epoxy resin) is in the range of 1:0.1 to 1:8. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within this range, i) when used in the form of an adhesive film, moderate adhesiveness is provided, and ii) when used in the form of an adhesive film. iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the above effects i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1:0.3 to 1:7 by mass. is more preferred, and a range of 1:0.6 to 1:6 is even more preferred.

The content of the epoxy resin in the resin composition is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 35% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. More preferably 10% to 35% by mass or 10% to 30% by mass.
In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, even more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product is sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing one equivalent of epoxy groups.
The weight average molecular weight of the epoxy resin is preferably 100-5000, more preferably 250-3000, still more preferably 400-1500. Here, the weight average molecular weight of the epoxy resin is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

<(B) Active ester compound>
The resin composition of the present invention contains an active ester compound as component (B).

The active ester compound is a compound having one or more active ester groups in one molecule. By using it, it is possible to provide an insulating layer that is excellent in all properties of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength.

As the active ester compound, a compound having two or more active ester groups in one molecule is preferable. A compound having two or more highly active ester groups in one molecule is preferably used. An active ester compound may be used individually by 1 type, and may be used in combination of 2 or more type.

From the viewpoint of improving heat resistance, an active ester compound 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 is preferred. Among them, an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from a phenol compound, a naphthol compound and a thiol compound is more preferable, and a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group. Obtained by reacting, more preferably an aromatic compound having two or more active ester groups in one molecule, a carboxylic acid compound having at least two or more carboxy groups in one molecule, and a phenolic hydroxyl group An aromatic compound obtained by reacting with an aromatic compound and having two or more active ester groups in one molecule is even more preferable. The active ester compound may be linear or branched. Also, if the carboxylic acid compound having at least two or more carboxyl groups in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring, Heat resistance can be increased.

Examples of carboxylic acid compounds include aliphatic carboxylic acids having 1 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 8) and aromatic compounds having 7 to 20 carbon atoms (preferably 7 to 10). Carboxylic acids are mentioned. Examples of aliphatic carboxylic acids include acetic acid, malonic acid, succinic acid, maleic acid and itaconic acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred, from the viewpoint of heat resistance.

The thiocarboxylic acid compound is not particularly limited, and examples thereof include thioacetic acid and thiobenzoic acid.

Examples of the phenolic compound include phenolic compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and still more preferably 6 to 22). Preferred specific examples include hydroquinone, Resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, tri Hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol and the like. As the phenol compound, a phenol novolak and a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP-A-2013-40270 may also be used.

Examples of naphthol compounds include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20 carbon atoms). ,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. Naphthol novolacs may also be used as naphthol compounds.

Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene-type diphenol, phenol novolak, phosphorus atom-containing oligomers having phenolic hydroxyl groups are preferred, catechol, 1,5 -dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene-type diphenol, phenol novolac, phosphorus having a phenolic hydroxyl group Atom-containing oligomers are more preferred, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-type diphenol, phenol novolak, phenol Further preferred are phosphorus atom-containing oligomers having a hydroxy group, such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, phenol novolak, and phosphorus atoms having a phenolic hydroxyl group. Oligomers containing dicyclo Pentadiene-type diphenols are particularly preferred.

The thiol compound is not particularly limited, and examples thereof include benzenedithiol, triazinedithiol, and the like.

Preferred specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolac, and a benzoylated phenol novolak. Examples include active ester compounds and active ester compounds obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. Active ester compounds and active ester compounds obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferred. In the present invention, the "dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Active ester compounds containing a dicyclopentadiene-type diphenol structure include, more specifically, compounds of the following formula (1).

（式中、Ｒはフェニル基又はナフチル基であり、ｋは０又は１を表し、ｎは繰り返し単位の平均数で０．０５～２．５である。）

(Wherein, R is a phenyl group or a naphthyl group, k represents 0 or 1, and n is the average number of repeating units of 0.05 to 2.5.)

From the viewpoint of reducing dielectric loss tangent and improving heat resistance, R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5.

As the active ester compound, active ester compounds disclosed in JP-A-2004-277460 and JP-A-2013-40270 may be used, and commercially available active ester compounds may also be used. Examples of commercially available active ester compounds include, for example, active ester compounds containing a dicyclopentadiene type diphenol structure such as EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation), active esters containing a naphthalene structure, EXB9416-70BK (manufactured by DIC Corporation) as an ester compound, DC808 (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, and YLH1026 (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac (manufactured by DIC Corporation) and EXB9050L-62M (manufactured by DIC Corporation) as a phosphorus atom-containing active ester compound.

In combination with (C) a carbodiimide compound, (D) a thermoplastic resin, and a certain amount or more of an inorganic filler (E), which will be described later, dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength The content of the active ester compound in the resin composition is preferably 1% by mass or more from the viewpoint of obtaining an insulating layer that is excellent in all properties, particularly from the viewpoint of obtaining an insulating layer that exhibits low surface roughness and high peel strength. , more preferably 3% by mass or more, and even more preferably 5% by mass or more. Although the upper limit of the content of the active ester compound is not particularly limited, it is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

Further, when the number of epoxy groups of (A) epoxy resin is 1, the number of reactive groups of (B) active ester compound is preferably 0.2 to 2, more preferably 0.3, from the viewpoint of obtaining an insulating layer with good mechanical strength. ~1.5 is more preferred, and 0.35 to 1 is even more preferred. Here, the "epoxy group number of the epoxy resin" is the sum of the values obtained by dividing the solid content mass of each epoxy resin present in the resin composition by the epoxy equivalent for all the epoxy resins. In addition, "reactive group" means a functional group capable of reacting with an epoxy group, and "the number of reactive groups of the active ester compound" refers to the solid content mass of the active ester compound present in the resin composition. It is the sum of all the values divided by the reactive group equivalent.

<(C) Carbodiimide compound>
The resin composition of the present invention contains a carbodiimide compound as component (C).

The carbodiimide compound is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule, and the above (B) active ester compound, (D) a thermoplastic resin described later, and a certain amount or more When used in combination with (E) an inorganic filler, it is possible to provide an insulating layer that is excellent in all properties of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength. The carbodiimide compound is preferably a compound having two or more carbodiimide groups in one molecule. A carbodiimide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

In one embodiment, the carbodiimide compound contained in the resin composition of the present invention contains a structural unit represented by the following formula (2).

（式中、Ｘは、アルキレン基、シクロアルキレン基又はアリーレン基を表し、これらは置換基を有していてもよい。ｐは１～５の整数を表す。Ｘが複数存在する場合、それらは同一でも相異なってもよい。＊は結合手を表す。）

(Wherein, X represents an alkylene group, a cycloalkylene group or an arylene group, which may have a substituent .p represents an integer of 1 to 5. When there are multiple Xs, they are They may be the same or different. * represents a bond.)

The number of carbon atoms in the alkylene group represented by X is preferably 1-20, more preferably 1-10, still more preferably 1-6, 1-4, or 1-3. The number of carbon atoms does not include the number of carbon atoms of substituents. Suitable examples of the alkylene group include methylene group, ethylene group, propylene group and butylene group.

The number of carbon atoms in the cycloalkylene group represented by X is preferably 3-20, more preferably 3-12, still more preferably 3-6. The number of carbon atoms does not include the number of carbon atoms of substituents. Preferable examples of the cycloalkylene group include cyclopropylene group, cyclobutylene group, cyclopentylene group and cyclohexylene group.

The arylene group represented by X is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms in the arylene group is preferably 6-24, more preferably 6-18, still more preferably 6-14, still more preferably 6-10. The number of carbon atoms does not include the number of carbon atoms of substituents. Preferable examples of the arylene group include phenylene group, naphthylene group and anthracenylene group.

In combination with (B) an active ester compound, (D) a thermoplastic resin, and a certain amount or more of (E) an inorganic filler, the dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength are improved. From the viewpoint of realizing an excellent insulating layer, X is preferably an alkylene group or a cycloalkylene group, which may have a substituent.

The alkylene group, cycloalkylene group or aryl group represented by X may have a substituent. Examples of the substituents include, but are not limited to, halogen atoms, alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkyloxy groups, aryl groups, aryloxy groups, acyl groups and acyloxy groups. Halogen atoms used as substituents include, for example, fluorine, chlorine, bromine and iodine atoms. Alkyl groups and alkoxy groups used as substituents may be linear or branched, and preferably have 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 10 carbon atoms. 6, 1-4, or 1-3. The number of carbon atoms in the cycloalkyl group or cycloalkyloxy group used as a substituent is preferably 3-20, more preferably 3-12, still more preferably 3-6. The aryl group used as a substituent is a group obtained by removing one hydrogen atom on the aromatic ring from an aromatic hydrocarbon, and preferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 18 carbon atoms. is 6-14, even more preferably 6-10. The number of carbon atoms in the aryloxy group used as a substituent is preferably 6-24, more preferably 6-18, still more preferably 6-14, still more preferably 6-10. The acyl group used as a substituent refers to a group represented by the formula: -C(=O)-R ¹ (wherein R ¹ represents an alkyl group or an aryl group). The alkyl group represented by R ¹ may be linear or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 6 carbon atoms, 1-4, or 1-3. The number of carbon atoms in the aryl group represented by R ¹ is preferably 6-24, more preferably 6-18, still more preferably 6-14, still more preferably 6-10. The acyloxy group used as a substituent refers to a group represented by the formula: --OC(=O)--R ¹ (wherein R ¹ has the same meaning as above). Among them, the substituent is preferably an alkyl group, an alkoxy group, or an acyloxy group, and more preferably an alkyl group.

In formula (2), p represents an integer of 1-5. In combination with (B) an active ester compound, (D) a thermoplastic resin, and a certain amount or more of (E) an inorganic filler, the dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength are improved. From the viewpoint of realizing an excellent insulating layer, p is preferably 1 to 4, more preferably 2 to 4, and still more preferably 2 or 3.

In formula (2), when there are multiple X's, they may be the same or different. In one preferred embodiment, at least one X is an alkylene group or a cycloalkylene group, which may have a substituent.

In a preferred embodiment, the carbodiimide compound is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, when the mass of the entire molecule of the carbodiimide compound is 100% by mass. More preferably, 80 mass % or more or 90 mass % or more of the structural unit represented by formula (2) is contained. The carbodiimide compound may consist essentially of the structural unit represented by formula (2), except for the terminal structure. The terminal structure of the carbodiimide compound is not particularly limited, but examples thereof include alkyl groups, cycloalkyl groups and aryl groups, which may have substituents. The alkyl group, cycloalkyl group, and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group, and aryl group described for the substituents that the group represented by X may have. Further, the substituent that the group used as the terminal structure may have may be the same as the substituent that the group represented by X may have.

From the viewpoint of suppressing the generation of outgassing when curing the resin composition, the weight average molecular weight of the carbodiimide compound is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, and even more preferably 800 or more. Especially preferably, it is 900 or more or 1000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the carbodiimide compound is preferably 5000 or less, more preferably 4500 or less, still more preferably 4000 or less, still more preferably 3500 or less, and particularly preferably 3000 or less. is. The weight average molecular weight of the carbodiimide compound can be measured, for example, by a gel permeation chromatography (GPC) method (converted to polystyrene).

Incidentally, the carbodiimide compound may contain an isocyanate group (-N=C=O) in the molecule due to its manufacturing method. From the viewpoint of obtaining a resin composition exhibiting good storage stability, and furthermore from the viewpoint of realizing an insulating layer exhibiting desired properties, the content of isocyanate groups in the carbodiimide compound (also referred to as "NCO content") is It is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less or 0.5% by mass or less.

A commercial item may be used for the carbodiimide compound. Commercially available carbodiimide compounds include, for example, Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07 and V-09 manufactured by Nisshinbo Chemical Co., Ltd., and Stabaxol (registered trademark) manufactured by Rhein Chemie. P, P400, and Hykasil 510.

In combination with (B) an active ester compound, (D) a thermoplastic resin, and a certain amount or more of (E) an inorganic filler, dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength From the viewpoint of obtaining an insulating layer that is also excellent in the properties of , the content of the carbodiimide compound in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, 3% by mass or more, 4% by mass or more, or 5% by mass or more. % by mass or more is more preferable. Although the upper limit of the content of the carbodiimide compound is not particularly limited, it is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

<(D) Thermoplastic resin>
The resin composition of the present invention contains a thermoplastic resin as component (D).

Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, vinyl resins containing acid anhydride groups, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, styrene elastomer resins, polyethersulfone resins, polyphenylene ether resins, and polysulfone resin and the like. The thermoplastic resin may be used singly or in combination of two or more. As the thermoplastic resin, one having a glass transition temperature of 80° C. or higher is preferable.

Among them, in combination with (B) an active ester compound, (C) a carbodiimide compound, and a certain amount or more of (E) an inorganic filler, dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength From the viewpoint of obtaining a more excellent insulating layer, the thermoplastic resin is one selected from the group consisting of phenoxy resins, polyvinyl acetal resins, acid anhydride group-containing vinyl resins, polyimide resins, polyamideimide resins, and styrene-based elastomer resins. It is preferable that it is above.

From the viewpoint of obtaining an insulating layer with good mechanical strength, the weight average molecular weight of the thermoplastic resin is preferably 10,000 or more, more preferably 15,000 or more, even more preferably 20,000 or more, and even more preferably 25,000 or more, or 30,000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the thermoplastic resin is preferably 200,000 or less, more preferably 180,000 or less, still more preferably 160,000 or less, and even more preferably 150,000 or less. The weight average molecular weight of the thermoplastic resin can be measured, for example, by gel permeation chromatography (GPC). Specifically, the weight-average molecular weight (in terms of polystyrene) of the thermoplastic resin is measured by LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K- manufactured by Showa Denko Co., Ltd. as a column. 804L/K-804L can be measured at a column temperature of 40° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

In combination with (B) an active ester compound, (C) a carbodiimide compound, and a certain amount or more of (E) an inorganic filler, dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength From the viewpoint of obtaining an insulating layer with excellent properties, particularly from the viewpoint of obtaining an insulating layer with high peel strength, the thermoplastic resin contains one or more atoms selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms, or carbon- It is preferred to have functional groups containing carbon double bonds. Such functional groups include hydroxyl group, carboxyl group, acid anhydride group, epoxy group, amino group, thiol group, enol group, enamine group, urea group, cyanate group, isocyanate group, thioisocyanate group, diimide group and alkenyl group. , an allene group and a ketene group. As the acid anhydride group, a carboxylic acid anhydride group is preferred. Suitable examples of alkenyl groups include vinyl groups, allyl groups and styryl groups. By using a thermoplastic resin having such a functional group, the resulting insulating layer tends to have a high glass transition temperature, and an insulating layer exhibiting good heat resistance can be realized. When the thermoplastic resin contains such a functional group, the functional group equivalent of the thermoplastic resin is preferably 100,000 or less, more preferably 90,000 or less, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, 30,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 6,000 or less, or 5,000 or less. Although the lower limit of the functional group equivalent is not particularly limited, it can be usually 50 or more, 100 or more.

Preferred thermoplastic resins will be described in more detail below, but thermoplastic resins obtained by further adding the above functional groups to the thermoplastic resins shown below according to known procedures can also be suitably used in the present invention. .

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. A phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both phenoxy resins containing bisphenol A skeleton), "YX8100" (phenoxy resin containing bisphenol S skeleton), and "YX6954" ( bisphenolacetophenone skeleton-containing phenoxy resin); Examples include "YL7290" and "YL7482".

Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, 5000-A, 6000-C, and 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Lec BH series and BX series manufactured by Sekisui Chemical Co., Ltd., KS series (for example, KS-1), BL series, BM series and the like.

The acid anhydride group-containing vinyl resin can be obtained, for example, by copolymerizing an acid anhydride group-containing monomer (d1) and another monomer (d2). Examples of the acid anhydride group-containing monomer (d1) include maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride. The other monomer (d2) is not particularly limited as long as it can be copolymerized with the acid anhydride group-containing monomer (d1). may be used. Specific examples of acid anhydride group-containing vinyl resins include "EF-30", "EF-40", "EF-60" and "EF-80" manufactured by CRAY VALLEY HSC.

Specific examples of the polyimide resin include "Ricacoat SN-20" and "Ricacoat PN-20" manufactured by Shin Nippon Rika Co., Ltd., and "Unidic V-8000" manufactured by DIC Corporation. Specific examples of the polyimide resin also include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (JP-A-2006-37083), a polysiloxane skeleton-containing polyimide ( Modified polyimides such as those disclosed in JP-A-2002-12667, JP-A-2000-319386, WO2010/53186, etc.).

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

Styrenic elastomeric resins include, for example, block copolymers containing a block of styrene or an analogue thereof as at least one terminal block and an elastomeric block of a conjugated diene or its hydrogenation product as at least one intermediate block. can be done. In particular, styrene-butadiene diblock copolymers, styrene-butadiene block copolymers, styrene-isoprene diblock copolymers, styrene-isoprene triblock copolymers, hydrogenated styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene block copolymers, Hydrogenated styrene-isoprene diblock copolymers, hydrogenated styrene-isoprene triblock copolymers, hydrogenated styrene-butadiene random copolymers, and the like. Specific examples of styrene-based elastomer resins include Asaprene, Tufprene, and Asaflex available from Asahi Chemical Industry Co., Ltd.; Hybler and Septon available from Kuraray Co., Ltd.;

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

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

In combination with (B) an active ester compound, (C) a carbodiimide compound, and a certain amount or more of (E) an inorganic filler, dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength From the viewpoint of obtaining an insulating layer having excellent properties, the content of the thermoplastic resin in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more. , more preferably 2% by mass or more. Although the upper limit of the content of the thermoplastic resin is not particularly limited, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 15% by mass or less.

<(E) Inorganic filler>
The resin composition of the present invention contains a certain amount or more of an inorganic filler as the component (E).

In combination with (B) an active ester compound, (C) a carbodiimide compound, and (D) a thermoplastic resin, it is excellent in all properties of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength. From the viewpoint of obtaining an insulating layer, particularly from the viewpoint of obtaining an insulating layer with a low dielectric loss tangent and a low coefficient of thermal expansion, the content of the inorganic filler in the resin composition layer is 40% by mass or more, preferably 45% by mass or more, More preferably 50% by mass or more, still more preferably 55% by mass or more or 60% by mass or more. In the present invention in which an inorganic filler is used in combination with (B) an active ester compound, (C) a carbodiimide compound, and (D) a thermoplastic resin, elongation at break, surface roughness and peel strength are reduced. However, the content of inorganic fillers can be further increased. For example, the content of the inorganic filler in the resin composition is 62% by mass or more, 64% by mass or more, 66% by mass or more, 68% by mass or more, 70% by mass or more, 72% by mass or more, or 74% by mass or more. can be increased to

The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less, from the viewpoint of the mechanical strength of the resulting insulating layer. .

The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, with silica being particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available spherical fused silica include “SO-C2” and “SO-C1” manufactured by Admatechs Co., Ltd.

The average particle diameter of the inorganic filler is not particularly limited, but from the viewpoint of obtaining an insulating layer on which fine wiring can be formed, it is preferably 3 μm or less, more preferably 2 μm or less, 1 μm or less, 0.7 μm or less, 0.5 μm or less, 0.4 μm or less, or 0.3 μm or less is more preferable. On the other hand, the average particle size of the inorganic filler is preferably 0.01 μm or more from the viewpoint of obtaining a resin varnish having an appropriate viscosity and good handleability when forming a resin varnish using a resin composition. 0.03 μm or more is more preferable, and 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more is even more preferable. The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction particle size distribution measuring apparatus, and the median diameter can be used as the average particle size for measurement. As the measurement sample, one obtained by ultrasonically dispersing an inorganic filler in water can be preferably used. "LA-500", "LA-750", "LA-950" manufactured by Horiba, Ltd. and the like can be used as the laser diffraction particle size distribution analyzer.

Inorganic fillers include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, and titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents such as. 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. silane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) and the like.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and further preferably 0.5 mg/m ² or less. preferable.

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

<(F) Curing accelerator>
The resin composition of the present invention may further contain a curing accelerator as component (F).

The curing accelerator is not particularly limited, but includes, for example, amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, guanidine-based curing accelerators. Accelerators are preferred. A hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.

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

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

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

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

Among them, in combination with the above components (A) to (E), from the viewpoint of obtaining an insulating layer that is more excellent in dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength, as a curing accelerator, 4-dimethylaminopyridine and 1-benzyl-2-phenylimidazole are particularly preferred.

The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 0.005% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass.

<Other ingredients>
-Curing agent-
The resin composition of the present invention may further contain a curing agent (excluding component (B)). By containing a curing agent, the insulation reliability, peel strength, and mechanical strength of the resulting insulating layer can be enhanced. The curing agent is not particularly limited, and examples thereof include phenol-based curing agents, naphthol-based curing agents, cyanate-ester-based curing agents, and benzoxazine-based curing agents. The curing agent may be used singly or in combination of two or more. Among these, in combination with the above components (A) to (E), from the viewpoint of obtaining an insulating layer that is more excellent in dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength, a phenolic curing agent , naphthol-based curing agents, and cyanate ester-based curing agents are preferred.

As the phenolic curing agent and the naphtholic curing agent, a phenolic curing agent having a novolac structure or a naphtholic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of peel strength, a nitrogen-containing phenolic curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenolic curing agent or a triazine skeleton-containing naphthol curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength to the conductor layer. Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, “MEH-7700”, “MEH-7810” and “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", Nippon Steel & Sumikin Chemical Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD2090" manufactured by DIC Corporation ” and the like.

The cyanate ester curing agent is not particularly limited. bisphenol F type, bisphenol S type, etc.), cyanate ester curing agents, and prepolymers obtained by partially triazinizing these. Specific examples include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylphenyl)methane, Bifunctional cyanate resins such as 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol novolacs and cresol novolaks polyfunctional cyanate resins derived from, etc., and prepolymers obtained by partially triazinizing these cyanate resins. Commercially available cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins) and "BA230" (a part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. is triazined to form a trimer) and the like.

Specific examples of benzoxazine-based curing agents include “HFB2006M” manufactured by Showa High Polymer Co., Ltd., and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

The content of the curing agent in the resin composition is not particularly limited, but from the viewpoint of the mechanical strength of the resulting insulating layer, it is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 6% by mass. .

-Flame retardants-
The resin composition of the present invention may further contain a flame retardant. Examples of flame retardants include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type. Although the content of the flame retardant in the resin composition is not particularly limited, it is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass.

－Organic filler－
The resin composition of the present invention may further contain an organic filler. As the organic filler, any organic filler that can be used in forming an insulating layer of a printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, silicone particles, etc. Rubber particles are preferred.

The rubber particles are not particularly limited as long as they are fine particles of a resin that is insoluble and infusible in an organic solvent by chemically cross-linking a resin exhibiting rubber elasticity. Examples include acrylonitrile-butadiene rubber particles, butadiene rubber particles, Examples include acrylic rubber particles. Specific examples of rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by Aica Kogyo Co., Ltd.) Paraloid EXL2655. , and EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.).

The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the organic filler is measured using a concentrated particle size analyzer ("FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.). It can be measured by preparing a standard and using the median diameter as the average particle diameter. The content of the organic filler in the resin composition is preferably 1% by mass to 10% by mass, more preferably 2% by mass to 5% by mass.

The resin composition of the present invention may further contain other components as necessary. Such other components include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, as well as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, coloring agents and curable resins. and other resin additives.

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 ingredients as necessary and mixing and dispersing using a rotary mixer or the like.

The resin composition of the present invention can provide a cured product (insulating layer) with a low dielectric loss tangent. The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of dielectric loss tangent> below. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonator perturbation method. From the viewpoint of preventing heat generation at high frequencies and reducing signal delay and signal noise, the dielectric loss tangent is preferably 0.010 or less, more preferably 0.009 or less, and 0.008 or less, 0.007 or less, or 0.006 or less. More preferred. The lower limit of the dielectric loss tangent is preferably as low as possible, but it can usually be 0.001 or more.

The resin composition of the present invention can provide a cured product (insulating layer) with a low coefficient of thermal expansion. The coefficient of linear thermal expansion of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of Glass Transition Temperature and Coefficient of Linear Thermal Expansion> below. Specifically, the average linear thermal expansion coefficient in the plane direction at 25 to 150° C. can be measured by thermomechanical analysis using a tensile loading method. The cured product of the resin composition of the present invention is preferably 40 ppm/°C or less, more preferably 35 ppm/°C or less, still more preferably 30 ppm/°C or less, even more preferably 25 ppm/°C or less, and particularly preferably 20 ppm/°C or less. can indicate the linear thermal expansion coefficient of Although the lower limit of the coefficient of linear thermal expansion is not particularly limited, it is usually 1 ppm/°C or more.

The resin composition of the present invention can provide a cured product (insulating layer) exhibiting good elongation at break. The elongation at break of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of elongation at break> below. Specifically, it can be measured by a tensile test method in accordance with Japanese Industrial Standards (JIS K7127). The cured product of the resin composition of the present invention is preferably 2% or more, more preferably 2.1% or more, still more preferably 2.2% or more, still more preferably 2.3% or more, 2.4% or more , or an elongation at break of 2.5% or more. The upper limit of the elongation at break is preferably 30% or less, more preferably 20% or less, still more preferably 10% or less.

The resin composition of the present invention can provide a cured product (insulating layer) with low surface roughness. The arithmetic mean roughness (Ra) of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of arithmetic mean roughness (Ra)> below. It is desired that the surface of the insulating layer after the roughening treatment has small surface irregularities in order to reduce the loss of electrical signals. Specifically, the resin composition is cured to form an insulating layer, and the arithmetic mean roughness (Ra) of the insulating layer surface after the surface of the insulating layer is roughened is preferably 140 nm or less, more preferably 130 nm. The following is more preferable, 120 nm or less is more preferable, 110 nm or less is even more preferable, and 100 nm or less is particularly preferable. From the viewpoint of obtaining sufficient peel strength, the lower limit of the arithmetic mean roughness (Ra) is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 15 nm or more.

The resin composition of the present invention can provide a cured product (insulating layer) with high peel strength. The peel strength of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of Peel Strength of Plated Conductor Layer> below. Specifically, when the resin composition is cured to form an insulating layer, and the surface of the insulating layer after roughening is plated to form a conductor layer, peeling between the obtained conductor layer and the insulating layer The strength is preferably 0.50 kgf/cm or more, more preferably 0.55 kgf/cm or more, and even more preferably 0.60 kgf/cm or more. Although the upper limit of the peel strength is not particularly limited, it can usually be 1.2 kgf/cm or less.

The resin composition of the present invention can also provide a cured product (insulating layer) with a high glass transition temperature (Tg). The glass transition temperature (Tg) of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of elongation at break> below. The cured product of the resin composition of the present invention can exhibit a glass transition temperature (Tg) of preferably 165° C. or higher, more preferably 170° C. or higher, 175° C. or higher, or 180° C. or higher. Although the upper limit of the glass transition temperature (Tg) is not particularly limited, it is usually 250°C or less.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and can It can be more preferably used as a resin composition for forming a resin composition for forming an interlayer insulation layer of a printed wiring board (a resin composition for an interlayer insulation layer of a printed wiring board), and for forming an interlayer insulation layer on which a conductor layer is formed by plating It can be more suitably used as a resin composition (a resin composition for an interlayer insulating layer of a printed wiring board in which a conductor layer is formed by plating). The resin composition of the present invention also includes adhesive films, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, component-embedding resins, and the like. Can be used for a wide range of applications.

[Adhesive film]
Although the resin composition of the present invention can be used in the form of a varnish, industrially it is generally preferred to use it in the form of an adhesive film.

The adhesive film comprises a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, even more preferably 60 μm or less, and even more preferably 50 μm or less or 40 μm or less, from the viewpoint of thinning the printed wiring board. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it is usually 5 μm or more or 10 μm or more.

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

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

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

The support may be subjected to matte treatment or corona treatment on the surface thereof to be bonded to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface of the side bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include alkyd resin release agents such as “SK-1”, “AL-5” and “AL-7” manufactured by Lintec Corporation.

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

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

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

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

In the adhesive film, a protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust from adhering to the surface of the resin composition layer and scratches on the surface of the resin composition layer. The adhesive film can be wound into a roll and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

The adhesive film of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for an insulating layer of a printed wiring board). The resin composition for forming the interlayer insulation layer on which the conductor layer is formed by plating (for the interlayer insulation layer of the printed wiring board that forms the conductor layer by plating). for insulating layers).

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention.

In one embodiment, the printed wiring board of the present invention can be produced by a method including the following steps (I) and (II) using the adhesive film described above.
(I) Step of laminating an adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) Step of thermosetting the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) mainly means a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or a substrate having A circuit board on which a patterned conductor layer (circuit) is formed. The term "inner layer substrate" as used in the present invention also includes an inner layer circuit board that is an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board.

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

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

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., and the like.

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

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

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

The thermosetting conditions for the resin composition layer are not particularly limited, and conditions that are commonly used for forming insulating layers of printed wiring boards may be used.

For example, the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., but the curing temperature is in the range of 120° C. to 240° C. (preferably in the range of 150° C. to 210° C., more preferably in the range of 170° C. to 190° C. range), and the curing time can be in the range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).

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

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer on the surface of the insulating layer may be further carried out. good. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V).

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

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order. The swelling liquid is not particularly limited, but may be an alkaline solution, a surfactant solution, or the like, preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securigans P and Swelling Dip Securigans SBU manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. Examples of the oxidizing agent include, but are not limited to, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 80° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan Co., Ltd. Moreover, as a neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial product, for example, Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd. can be mentioned. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidant solution in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes.

Step (V) is a step of forming a conductor layer on the surface of the insulating layer.

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

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

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

The conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. An example of forming a conductor layer by a semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, unnecessary plating seed layers are removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

As described above, by producing a printed wiring board using the resin composition of the present invention, the dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength are all excellent. can be advantageously manufactured.

[Semiconductor device]
A semiconductor device can be manufactured using the printed wiring board of the present invention. Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

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

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

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. In addition, "part" means a mass part.

[Measurement method/evaluation method]
First, various measurement methods and evaluation methods will be explained.

<Preparation of sample for peel strength and arithmetic mean roughness (Ra value) measurement>
(1) Surface treatment of inner layer circuit board Glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic Corporation "R1515A") on which inner layer circuits are formed. The copper surface was roughened by etching 1 μm on both sides with “CZ8101” manufactured by MEC Co., Ltd.

(2) Lamination of adhesive films The adhesive films prepared in Examples and Comparative Examples are laminated using a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), and the resin composition layer is an inner layer circuit. Both sides of the inner layer circuit board were laminated so as to be bonded to the board. The lamination process was performed by pressure bonding for 30 seconds at 100° C. and a pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds.

(3) Curing of Resin Composition After lamination of the adhesive film, the resin composition layer was thermally cured at 100° C. for 30 minutes and then at 180° C. for 30 minutes to form an insulating layer. After that, the support was peeled off to expose the insulating layer.

(4) Roughening treatment The inner layer circuit board with the exposed insulating layer is soaked in a swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., an aqueous sodium hydroxide solution containing diethylene glycol monobutyl ether) at 60 ° C. for 10 minutes. immersed, and then immersed in an oxidizing agent ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., an aqueous solution with a potassium permanganate concentration of about 6% by mass and a sodium hydroxide concentration of about 4% by mass) at 80 ° C. for 20 minutes. Finally, it was immersed in a neutralizing solution (“Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd., hydroxylamine sulfate aqueous solution) at 40° C. for 5 minutes. After that, it was dried at 80° C. for 30 minutes. The obtained substrate is called "evaluation substrate a".

(5) Formation of Conductor Layer A conductor layer was formed on the roughened surface of the insulating layer according to the semi-additive method.
That is, the roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Then, after annealing by heating at 150° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm, and annealing treatment was performed at 200° C. for 60 minutes. The obtained substrate is called "evaluation substrate b".

<Measurement of arithmetic mean roughness (Ra)>
For the evaluation substrate a, a non-contact surface roughness meter (“WYKO NT3300” manufactured by Bcoinstruments) was used in VSI contact mode, with a 50x lens and a measurement range of 121 μm × 92 μm. The Ra value was obtained from the numerical value obtained. . It was measured by determining the average value of 10 randomly selected points.

<Measurement of peel strength of plated conductor layer>
The peel strength of the insulating layer and the conductor layer was measured for the evaluation substrate b in accordance with Japanese Industrial Standards (JIS C6481). Specifically, the conductor layer of the evaluation substrate b was cut into a portion having a width of 10 mm and a length of 100 mm. The load (kgf/cm) was measured when 35 mm was peeled off to obtain the peel strength. A tensile tester (“AC-50C-SL” manufactured by TSE Co., Ltd.) was used for the measurement.

<Measurement of elongation at break>
The adhesive films prepared in Examples and Comparative Examples were heated at 200° C. for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The resulting cured product is referred to as “evaluation cured product c”. The cured product c for evaluation was subjected to a tensile test in accordance with Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.) to measure the elongation at break.

<Measurement of glass transition temperature and linear thermal expansion coefficient>
The cured product c for evaluation was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed using a thermomechanical analyzer ("Thermo Plus TMA8310" manufactured by Rigaku Co., Ltd.) by a tensile load method. Analysis was carried out. Specifically, after mounting the test piece on the thermomechanical analyzer, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. Then, in the second measurement, the glass transition temperature (Tg; °C) and the average coefficient of linear thermal expansion (CTE; ppm/°C) in the range from 25°C to 150°C were calculated.

<Measurement of dielectric loss tangent>
The cured product c for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm. The dielectric loss tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Two test pieces were measured, and the average value was calculated.

<Example 1>
Bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "828US", epoxy equivalent about 180) 10 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent about 269) 25 parts, bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) 25 parts, and phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass ) was heated and dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 15 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC Corporation, a 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%), Active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, non-volatile component 65% by mass toluene solution) 20 parts, carbodiimide compound (Nisshinbo Chemical Co., Ltd. "V-03", NCO content 0% by mass, non-volatile component 50% by mass toluene solution) 20 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 10% by mass MEK solution) 3 parts, aminosilane coupling agent ( 275 parts of spherical silica surface-treated with Shin-Etsu Chemical Co., Ltd. ("KBM573") (average particle size: 0.5 μm, Admatechs Co., Ltd.: "SO-C2") is mixed and uniformly mixed with a high-speed rotating mixer. Dispersed to prepare a resin varnish.

A PET film with an alkyd resin release layer (“AL5” manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. A resin varnish is evenly applied to the release layer of the support so that the thickness of the resin composition layer after drying is 30 μm, and dried at 80° C. to 120° C. (average 100° C.) for 4 minutes. , to prepare an adhesive film.

<Example 2>
A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that the amount of the carbodiimide compound ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution with a nonvolatile content of 50% by mass) was changed to 80 parts. bottom.

<Example 3>
100 parts of spherical silica (average particle diameter 0.5 μm, Admatechs “SO-C2”) surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. “KBM573”) A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that the

<Example 4>
275 parts of spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was added to an aminosilane-based Except for changing to 275 parts of spherical silica (average particle size 0.3 μm, “SO-C1” manufactured by Admatechs Co., Ltd.) surface-treated with a coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) , a resin varnish and an adhesive film were prepared in the same manner as in Example 1.

<Example 5>
20 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, an active group equivalent of about 223, a toluene solution of 65% by mass of non-volatile components) was added to an active ester compound ("EXB9050L-62M" manufactured by DIC Corporation). A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that 21 parts of MEK solution having an active group equivalent of about 334 and a non-volatile component of 62% by mass) was used.

<Example 6>
3 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 10% by mass), a curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole, solid A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that 6 parts of a 10% by weight MEK solution was used.

<Example 7>
20 parts of a carbodiimide compound ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution of 50% by mass of non-volatile components) was added to a carbodiimide compound ("V-07" manufactured by Nisshinbo Chemical Co., Ltd., NCO content of 0.5 mass A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that the content was changed to 20 parts of a toluene solution containing 50% by mass of non-volatile components.

<Example 8>
20 parts of phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was added to polyvinyl butyral resin (glass transition temperature 105 ° C., manufactured by Sekisui Chemical Co., Ltd. “ A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that KS-1", a 1:1 solution of ethanol and toluene containing 15% by mass of non-volatile components) was changed to 40 parts.

<Example 9>
20 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was added to an acid anhydride group-containing vinyl resin (manufactured by CRAY VALLEY HSC "EF-30 , a cyclohexanone solution having a solid content of 50%) was changed to 12 parts, in the same manner as in Example 1 to prepare a resin varnish and an adhesive film.

<Example 10>
20 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), polyimide resin (manufactured by Shin Nippon Rika Co., Ltd. "SN-20", solid content A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that 30 parts of a 20% N-methyl-2-pyrrolidone (NMP) solution was used.

<Example 11>
20 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), polyimide resin ("Unidic V-8000" manufactured by DIC Corporation, non-volatile components A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that the amount was changed to 15 parts of a 40% by mass ethyl diglycol acetate solution.

<Example 12>
10 parts of a bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180) was changed to 10 parts of an alicyclic epoxy resin having an ester skeleton ("Celoxide 2021P" manufactured by Daicel Corporation). A resin varnish and an adhesive film were produced in the same manner as in Example 2 except for the above.

<Example 13>
The amount of triazine skeleton-containing phenol-based curing agent (“LA-3018-50P” manufactured by DIC Corporation, a hydroxyl equivalent of about 151, a 2-methoxypropanol solution with a solid content of 50%) was changed to 5 parts, and a benzoxazine-based A resin varnish and an adhesive film were prepared in the same manner as in Example 2, except that 10 parts of a curing agent (“Pd” manufactured by Shikoku Kasei Kogyo Co., Ltd., cyclohexanone solution with a solid content of 50%) was added.

<Example 14>
20 parts of a phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass) was mixed with the siloxane skeleton-containing polyimide resin of Synthesis Example 1 (solid content of 55% by mass)10. A resin varnish and an adhesive film were produced in the same manner as in Example 2, except that the content was changed to 9 parts.

[Synthesis Example 1]
20 parts of 3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride (BTDA) was placed in a 500 mL separable flask equipped with a water content receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer. 70.9 parts of γ-butyrolactone, 7 parts of toluene, 61.5 parts of diaminosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd. "X-22-9409", amine equivalent weight 665), 2,6-bis(1-hydroxy-1 7.4 parts of -trifluoromethyl-2,2,2-trifluoroethyl)-1,5-naphthalenediamine (HFA-NAP) was added, and the reaction was carried out by stirring at 45°C for 2 hours under a nitrogen stream. rice field. Then, the temperature of this reaction solution was raised, and condensed water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160°C. When it was confirmed that a predetermined amount of water was accumulated in the water content receiver and that water was no longer seen to flow out, the temperature was further raised and the mixture was stirred at 200°C for 1 hour. After that, the mixture was cooled to finish, and a varnish containing 55% by mass of a siloxane skeleton-containing polyimide resin having a hexafluoroisopropanol group (HFA group) was produced. In this case, the content of the siloxane structure in the resin is 70.9 mass % and the HFA group equivalent is 2881 g/mol.

<Example 15>
10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180) was changed to 10 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 235). A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that

<Comparative Example 1>
A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of a carbodiimide compound ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution containing 50% by mass of non-volatile components) was not used.

<Comparative Example 2>
Resin in the same manner as in Example 1 except that 20 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, an active group equivalent of about 223, a toluene solution of 65% by mass of non-volatile components) was not used. A varnish and an adhesive film were produced.

<Comparative Example 3>
A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of a phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass) was not used. was made.

<Comparative Example 4>
The compounding amount of spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) was 40. A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that the parts were changed to .

Table 1 shows the results.

Claims (23)

A resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin and (E) silica, wherein the non-volatile component in the resin composition is 100 mass %, the content of component (E) is 40% by mass or more and 85 % by mass or less, the content of component (A) is 5 % by mass or more and 40% by mass or less, and the content of component (C) is 1% by mass or more and 30% by mass or less, the content of component (D) is 1% by mass or more, and component (D) is one selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms or more atoms or a thermoplastic resin having a functional group containing a carbon-carbon double bond ,
A resin composition, wherein a cured product of the resin composition has a dielectric loss tangent of 0.010 or less at a frequency of 5.8 GHz and a temperature of 23°C . Component (D) is one or more thermoplastic resins selected from the group consisting of phenoxy resins, polyvinyl acetal resins, acid anhydride group-containing vinyl resins, polyimide resins, polyamideimide resins and styrene elastomer resins. Item 1. The resin composition according to item 1. A resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin and (E) silica, wherein the non-volatile component in the resin composition is 100 mass %, the content of component (E) is 40% by mass or more and 85 % by mass or less, the content of component (A) is 5 % by mass or more and 40% by mass or less, and component (D) is phenoxy One or more thermoplastic resins selected from the group consisting of resins, polyvinyl acetal resins, vinyl resins containing acid anhydride groups, polyimide resins, and polyamideimide resins ,
A resin composition, wherein a cured product of the resin composition has a dielectric loss tangent of 0.010 or less at a frequency of 5.8 GHz and a temperature of 23°C . 4. The resin composition according to claim 3, wherein the content of component (C) is 1% 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 any one of claims 1 to 4, further comprising one or more curing agents selected from phenolic curing agents, naphthol curing agents, cyanate ester curing agents and benzoxazine curing agents. . The resin composition according to any one of claims 1 to 5, wherein component (C) has a weight average molecular weight of 500 to 5,000. Component (D) is a thermoplastic resin having at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms or a functional group containing a carbon-carbon double bond. 7. The resin composition according to any one of 6. (D) component is a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, a thiol group, an enol group, an enamine group, a urea group, a cyanate group, an isocyanate group, a thioisocyanate group, a diimide group, an alkenyl group, 8. The thermoplastic resin according to any one of claims 1 to 7, which is a thermoplastic resin having one or more functional groups selected from the group consisting of allene groups and ketene groups (but different from component (A)). of the resin composition. The resin composition according to any one of claims 1 to 8, wherein component (D) has a weight average molecular weight of 10,000 to 200,000. The resin composition according to any one of claims 1 to 9, wherein the content of component (D) is 1 % by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. thing. (A) The epoxy resin contains a liquid epoxy resin and a solid epoxy resin, and the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is 1:0.3. The resin composition according to any one of claims 1 to 10, which is in the range of ~1:7. The resin composition according to any one of claims 1 to 11, wherein the content of component (A) is 5 % by mass or more and 35% by mass or less when the non-volatile component in the resin composition is 100% by mass. thing. The resin composition according to any one of claims 1 to 12, wherein the content of component (E) is 50% by mass or more and 85 % by mass or less when the non-volatile component in the resin composition is 100% by mass. thing. The resin composition according to any one of claims 1 to 13, wherein the content of component (E) is 62% by mass or more and 85 % by mass or less when the non-volatile component in the resin composition is 100% by mass. thing. The resin composition according to any one of claims 1 to 14, wherein component (E) has an average particle size of 0.01 µm to 3 µm. The resin composition according to any one of claims 1 to 15, further comprising (F) a curing accelerator. 17. The resin composition according to claim 16, wherein component (F) is 4-dimethylaminopyridine or 1-benzyl-2-phenylimidazole. The resin composition is cured to form an insulating layer, and the surface of the insulating layer has an arithmetic mean roughness (Ra) of 5 nm or more and 140 nm or less after roughening treatment, and the roughening treatment is performed on the surface of the insulating layer. in a swelling liquid at 30° C. to 90° C. for 1 to 20 minutes, in an oxidizing agent solution at 60° C. to 80° C. for 10 to 30 minutes, in a neutralizing liquid at 30° C. to 80° C. for 5 to 30 minutes. The resin composition according to any one of claims 1 to 17, which is performed by immersing in order. Claim 1, wherein the cured product of the resin composition has an elongation at break of 2% or more and 10% or less as measured by a tensile test method according to Japanese Industrial Standards (JIS K7127). 19. The resin composition according to any one of 18. The resin composition according to any one of claims 1 to 19, wherein a cured product of the resin composition has a glass transition temperature (Tg) of 165°C or higher and 250°C or lower. An adhesive film comprising a support and a layer of the resin composition according to any one of claims 1 to 20 bonded to the support. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 20. A semiconductor device comprising the printed wiring board according to claim 22 .