KR20210109457A - Resin composition - Google Patents

Abstract

The present invention relates to a resin composition which an inhibit stains generated upon the lamination thereof, a resin sheet including the resin composition, a printed circuit board including a dielectric layer formed by using the resin composition, and a semiconductor device. The resin composition includes: (A) an eposy resin; and (B) an active ester compound having at least one selected from the groups represented by chemical formula (1)- chemical formula (3), wherein * represents a bonding arm, and n represents an integer of 1-5.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. Moreover, it is related with the resin sheet obtained using the said resin composition, a printed wiring board, and a semiconductor device.

As a manufacturing technique of a printed wiring board, the manufacturing method by the build-up system which piles up an insulating layer and a conductor layer alternately is known.

As an insulating material of the printed wiring board used for such an insulating layer, the resin composition is disclosed by patent document 1, for example.

Japanese Patent Laid-Open No. 2018-199797

The insulating layer is generally formed by laminating a resin composition layer on a substrate and thermosetting it. As a result of earnest examination by the present inventors, when an insulating layer was formed by laminating the resin composition layer containing the conventional resin composition, it was discovered that the uniformity of the surface of an insulating layer falls and it becomes easy to produce unevenness (uniformity after lamination). . When such unevenness exists on the surface of an insulating layer, the wiring formability of an insulating layer may deteriorate.

The subject of the present invention is a resin composition capable of suppressing the unevenness generated when the resin composition is laminated; a resin sheet containing the resin composition; A printed wiring board provided with the insulating layer formed using the said resin composition, and a semiconductor device are provided.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, the present inventors discovered that the said subject could be solved by containing the active ester compound which has a specific group, and came to complete this invention.

That is, the present invention includes the following contents.

[1] (A) an epoxy resin, and

(B) an active ester compound having at least one of the groups represented by the following formulas (1) to (3)

A resin composition containing

(In the above formula, * represents a bond. In formula (3), n represents an integer of 1 to 5)

[2] The resin composition according to [1], wherein the component (B) is an active ester compound represented by the following general formula (b-1).

(In general formula (b-1),

Ar ¹¹ each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3),

Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent,

Ar ¹³ each independently represents a divalent group consisting of a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a combination thereof. a represents an integer from 1 to 6, b represents an integer from 0 to 10)

^{[3] The resin composition according to [2], wherein Ar 13} in the general formula (b-1) each independently represents a divalent group obtained by combining an oxygen atom and a divalent aromatic hydrocarbon group which may have a substituent.

[4] The resin composition according to any one of [1] to [3], wherein the component (B) is an active ester compound represented by the following general formula (b-3).

(In general formula (b-3),

Ar ³¹ each independently represents the group represented by the formula (1), the group represented by the formula (2), or the group represented by the formula (3). a2 represents an integer of 1 to 6, c2 represents an integer of 1 to 5, and d each independently represents an integer of 0 to 6)

[5] The resin composition according to any one of [1] to [4], further comprising (C) an inorganic filler.

[6] The resin composition according to any one of [1] to [5], which is for forming an insulating layer.

[7] The resin composition according to any one of [1] to [6], which is for forming an insulating layer for forming a conductor layer.

[8] A resin sheet comprising a support and a resin composition layer provided on the support and comprising the resin composition according to any one of [1] to [7].

[9] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [7].

[10] A semiconductor device comprising the printed wiring board according to [9].

Resin composition which can suppress the unevenness after lamination which arises when a resin composition is laminated by this invention; a resin sheet containing the resin composition; A printed wiring board provided with the insulating layer formed from the hardened|cured material of the said resin composition, and a semiconductor device can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the suitable embodiment. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily changed without departing from the scope of the claims of the present invention and equivalents thereof.

[resin composition]

The resin composition of the present invention contains (A) an epoxy resin and (B) an active ester compound having at least one of groups represented by the following formulas (1) to (3). By containing (B) component in a resin composition, generation|occurrence|production of the stain|uniformity after lamination which may arise when the resin composition layer containing a resin composition is laminated can be suppressed. Moreover, in this invention, it is excellent also normally also in plating peeling strength, copper foil adhesiveness, and copper foil adhesiveness after HAST, and also a dielectric property is low, and hardened|cured material with a low arithmetic mean roughness (Ra) can also be obtained.

(In the above formula, * represents a bond. In formula (3), n represents an integer of 1 to 5)

The resin composition may further contain arbitrary components in combination with (A)-(B) component. As arbitrary components, (C) inorganic filler, (D) hardening|curing agent, (E) hardening accelerator, (F) other additives, etc. are mentioned, for example. Hereinafter, each component included in the resin composition will be described in detail.

<(A) Epoxy resin>

The resin composition contains (A) an epoxy resin as (A) component. (A) As a component, a bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol is, for example, Type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, Glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclo A hexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that the resin composition contains the epoxy resin which has two or more epoxy groups in 1 molecule as (A) component. From the viewpoint of significantly obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the nonvolatile component of component (A) is preferably 50% by mass or more, more preferably is 60% by mass or more, particularly preferably 70% by mass or more.

Epoxy resins include a liquid epoxy resin at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20°C (hereinafter sometimes referred to as “solid epoxy resin”). . The resin composition may contain only a liquid epoxy resin as component (A), may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin, but the desired effect of the present invention is significantly reduced From the viewpoint of obtaining, it is preferable to include only a solid epoxy resin.

As a solid epoxy resin, the solid epoxy resin which has 3 or more epoxy groups in 1 molecule is preferable, and the aromatic solid epoxy resin which has 3 or more epoxy groups in 1 molecule is more preferable.

Examples of the solid-state epoxy resin include a bixylenol-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, and a non A phenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenylethane type epoxy resin are preferable, and a naphthol type epoxy resin is more preferable.

As a specific example of a solid epoxy resin, "HP4032H" by DIC (naphthalene type epoxy resin); "HP-4700", "HP-4710" by DIC company (naphthalene type tetrafunctional epoxy resin); "N-690" by DIC (cresol novolak-type epoxy resin); "N-695" by DIC (cresol novolak-type epoxy resin); "HP-7200", "HP-7200HH", and "HP-7200H" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" by DIC company (naphthylene ether type epoxy resin); "EPPN-502H" by Nippon Kayaku Co., Ltd. (trisphenol type epoxy resin); "NC7000L" by a Nippon Kayaku company (naphthol novolak-type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) by the Nippon Kayaku company; "ESN475V" (naphthol type epoxy resin) by the Nitetsu Chemical & Materials company; "ESN485" (naphthol novolak-type epoxy resin) by a Nitetsu Chemical & Materials company; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) by a Mitsubishi Chemical company; "YX4000HK" by a Mitsubishi Chemical company (bixylenol type epoxy resin); "YX8800" by Mitsubishi Chemical (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" by a Mitsubishi Chemical company (bisphenol AF type|mold epoxy resin); "YL7800" by Mitsubishi Chemical (fluorene type epoxy resin); "jER1010" by Mitsubishi Chemical (solid bisphenol A epoxy resin); "jER1031S" (tetraphenylethane type epoxy resin) by a Mitsubishi Chemical company, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As a liquid epoxy resin, the liquid epoxy resin which has two or more epoxy groups in 1 molecule is preferable.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin , an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure, more preferably a naphthalene type epoxy resin do.

As a specific example of a liquid epoxy resin, "HP4032", "HP4032D", "HP4032SS" by DIC company (naphthalene type epoxy resin); "828US", "jER828EL", "825", "Epicoto 828EL" by Mitsubishi Chemical Corporation (bisphenol A epoxy resin); "jER807", "1750" by a Mitsubishi Chemical company (bisphenol F-type epoxy resin); "jER152" by Mitsubishi Chemical (phenol novolak-type epoxy resin); "630" and "630LSD" by Mitsubishi Chemical (glycidylamine type epoxy resin); "ZX1059" (mixture of a bisphenol A epoxy resin and a bisphenol F epoxy resin) by the Nitetsu Chemical & Materials company; "EX-721" by the Nagase Chemtex company (glycidyl ester type epoxy resin); "Celoxide 2021P" by Daicel (alicyclic epoxy resin which has ester skeleton); "PB-3600" by Daicel (epoxy resin which has a butadiene structure); "ZX1658", "ZX1658GS" (liquid 1, 4- glycidyl cyclohexane type epoxy resin) by the Nitetsu Chemical & Materials company, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(A) When a liquid epoxy resin and a solid epoxy resin are used in combination as a component, their ratio (liquid epoxy resin:solid epoxy resin) is a mass ratio, preferably 1:1 to 1:20 , more preferably 1:1.5 to 1:15, particularly preferably 1:2 to 1:10. When the amount ratio of the liquid epoxy resin and the solid epoxy resin is within this range, the desired effect of the present invention can be significantly obtained. Moreover, when using in the form of a resin sheet normally, moderate adhesiveness is formed. Moreover, when using in the form of a resin sheet normally, sufficient flexibility is acquired and handling property improves. Moreover, usually, the hardened|cured material which has sufficient breaking strength can be obtained.

The epoxy equivalent of component (A) is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., more preferably 80 g/eq. to 2000 g/eq., even more preferably 110 g/eq. to 1000 g/eq. By being set to this range, the crosslinking density of the hardened|cured material of a resin composition layer becomes enough, and the insulating layer with a small surface roughness can be formed. Epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JISK7236.

The weight average molecular weight (Mw) of the component (A) is preferably 100 to 5000, more preferably 200 to 3000, still more preferably 250 to 1500 from the viewpoint of significantly obtaining the desired effect of the present invention.

The weight average molecular weight of resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

(A) The content of the component is preferably 1% by mass or more, more preferably 1% by mass or more, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. It is 5 mass % or more, More preferably, it is 10 mass % or more. The upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less from the viewpoint of significantly obtaining the desired effect of the present invention.

In addition, in this invention, content of each component in a resin composition is a value at the time of making 100 mass % of non-volatile components in a resin composition unless otherwise indicated.

<(B) an active ester compound having at least one of the groups represented by the following formulas (1) to (3)>

The resin composition contains, as component (B), an active ester compound having at least any one of groups represented by the following formulas (1) to (3). (B) By containing a component in a resin composition, it becomes possible to suppress generation|occurrence|production of the unevenness after lamination. In addition, by containing the component (B) in the resin composition, it is usually excellent in plating peel strength, copper foil adhesion, and copper foil adhesion after HAST, and also has low dielectric properties and low arithmetic mean roughness (Ra) It is also possible to obtain a cured product have.

(In the above formula, * represents a bond. In formula (3), n represents an integer of 1 to 5)

(B) component can use the compound which has at least any one of groups represented by Formula (1)-(3), and has an active ester site|part which can react with (A) component. (B) As a component, it is preferable to have at least any one of groups represented by Formula (1)-(3) at the terminal. (B) As a component, the group from which both terminals differ may be sufficient, and the same group may be sufficient as both terminals.

The group represented by Formula (1) may be a group derived from cresol shown below. It is preferable that the methyl group in the group represented by Formula (1) is couple|bonded with any one of an ortho position, meta position, and para position with respect to an oxygen atom, and it is more preferable that it couple|bonds at an ortho position.

The group represented by Formula (2) may be a group derived from the phenylphenol shown below. The phenyl group in the group represented by the formula (2) is preferably bonded to any one of the ortho position, meta position, and para position with respect to the oxygen atom of the phenol moiety, more preferably ortho position to the oxygen atom. .

The group represented by Formula (3) may be a group derived from the styrenated phenol shown below. It is preferable that the styrene moiety in the group represented by the formula (3) is bonded to any one of the ortho position, meta position, and para position with respect to the oxygen atom of the phenol moiety, and more preferably ortho position to the oxygen atom of the phenol moiety. do.

In Formula (3), n represents the integer of 1-5, it is preferable to represent the integer of 1-3, It is more preferable to represent the integer of 1-2.

(in the above formula, n1 is the same as n in the formula (3))

It is preferable that (B) component is a compound represented by the following general formula (b-1).

(In the general formula (b-1), Ar ¹¹ each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3), and Ar ¹² is, Each independently represents a divalent aromatic hydrocarbon group which may have a substituent, Ar ¹³ is each independently a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, and sulfur represents a divalent group consisting of an atom or a combination thereof, a represents an integer from 1 to 6, b represents an integer from 0 to 10)

In the general formula (b-1), Ar ¹¹ each independently represents the group represented by the formula (1), the group represented by the formula (2), or the group represented by the formula (3). Groups represented by formulas (1) to (3) are as described above. Among them, the group represented by the formula (1) and the group represented by the formula (2) are preferable.

In the general formula (b-1), Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent. As a divalent aromatic hydrocarbon group, an arylene group, an aralkylene group, etc. are mentioned, An arylene group is preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is still more preferable. As such an arylene group, a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group etc. are mentioned, for example. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferable, an aralkylene group having 7 to 20 carbon atoms is more preferable, and an aralkylene group having 7 to 15 carbon atoms is still more preferable. Among these, a phenylene group is preferable.

In the general formula (b-1), Ar ¹³ is each independently a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a combination thereof. It represents a divalent group which consists of these, and the divalent group which consists of these combinations is preferable. The divalent aromatic hydrocarbon group is the same as the divalent aromatic hydrocarbon group represented by ^{Ar 12 .}

As the divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is more preferable, an alkylene group or a cycloalkylene group is preferable, and a cycloalkylene group is more preferable.

As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is still more preferable. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, and a 1,2-dimethyl group. ethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, etc. are mentioned.

As a cycloalkylene group, a C3-C20 cycloalkylene group is preferable, A 3-15 cycloalkylene group is more preferable, A 5-10 cycloalkylene group is still more preferable. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, and a cycloheptyl group.

The divalent group composed of these combinations is preferably a divalent group in which a divalent aromatic hydrocarbon group which may have a substituent and an oxygen atom are combined, a divalent aromatic hydrocarbon group which may have one or more substituents, and one or more oxygen atoms A divalent group obtained by alternately combining , is more preferred, and more preferred is a divalent group obtained by alternatingly combining a naphthylene group which may have one or more substituents and one or more oxygen atoms. Therefore, the naphthyleneoxy group which may have a substituent is more preferable.

The divalent aromatic hydrocarbon group represented by ^{Ar 12 , the divalent aromatic hydrocarbon group represented by Ar 13} , and the divalent aliphatic hydrocarbon group may have a substituent. The number of substituents may be one, and a plurality may be sufficient as them. As a substituent, a C6-C20 aryl group, a C1-C10 alkyl group, a C1-C10 alkoxy group, a halogen atom etc. are mentioned, for example. A substituent may be included independently, or may be included in combination of 2 or more type.

As a C6-C20 aryl group, a benzyl group, a phenyl group, a naphthyl group, anthracenyl group, a tolyl group, a xylyl group etc. are mentioned, for example, A benzyl group is preferable.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso pentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, A cycloheptyl group, a cyclooctyl group, and a cyclononyl group are mentioned.

Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, and an octyloxy group. time, a nonyloxy group, etc. are mentioned.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. The above-described substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). As a secondary substituent, you may use the thing similar to the above-mentioned substituent, unless otherwise stated.

In general formula (b-1), a represents the integer of 1-6, it is preferable to represent the integer of 1-5, It is more preferable to represent the integer of 1-3. On the other hand, when the compound represented by general formula (b-1) is an oligomer or a polymer, a represents the average value.

In general formula (b-1), b represents the integer of 0-10, it is preferable to represent the integer of 0-5, It is more preferable to represent the integer of 0-3, and 0 is still more preferable. On the other hand, when the compound represented by general formula (b-1) is an oligomer or a polymer, b represents the average value.

(B) It is preferable that a component is a compound represented by general formula (b-2).

(In the general formula (b-2), Ar ²¹ each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3), and Ar ²² is, Each independently represents the divalent aromatic hydrocarbon group which may have a substituent, Ar ²³ each independently represents the divalent aromatic hydrocarbon group which may have a substituent, a1 represents an integer of 1 to 6, and c1 represents 1 to represents an integer of 5)

Ar ²¹ each independently represents the group represented by the formula (1), the group represented by the formula (2), or the group represented by the formula (3). Groups represented by formulas (1) to (3) are as described above. Among them, the group represented by the formula (1) and the group represented by the formula (2) are preferable.

Ar ²² each independently represents a divalent aromatic hydrocarbon group which may have a substituent. Ar ²² is the same as ^{Ar 12} in the general formula (b-1).

Ar ²³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent. Ar ²³ is the same as the divalent aromatic hydrocarbon group which may have a substituent for ^{Ar 13} in the general formula (b-1).

In general formula (b-2), a1 represents the integer of 1-6. a1 is the same as a in general formula (b-1).

In general formula (b-2), c1 represents the integer of 1-5. It is preferable that the integer of 1-4 is represented, and, as for c1, it is more preferable that the integer of 1-3 is represented.

(B) It is preferable that a component is a compound represented by general formula (b-3).

(In the general formula (b-3), Ar ³¹ each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3). a2 is 1 to represents an integer of 6, c2 represents an integer of 1 to 5, and d each independently represents an integer of 0 to 6)

Ar ³¹ each independently represents the group represented by the formula (1), the group represented by the formula (2), or the group represented by the formula (3). Groups represented by formulas (1) to (3) are as described above. Among them, the group represented by the formula (1) and the group represented by the formula (2) are preferable.

In general formula (b-3), a2 represents the integer of 1-6. a2 is the same as a in the general formula (b-1).

In general formula (b-3), c2 represents the integer of 1-5. c2 is the same as c1 in the general formula (b-2).

In general formula (b-3), each d independently represents the integer of 0-6. It is preferable that the integer of 1-5 is represented, and, as for d, it is more preferable that the integer of 1-4 is represented.

The component (B) may use what was synthesize|combined by a well-known method, For example, it can synthesize|combine by the method described in the following example. (B) The synthesis of the component can be performed, for example, by the method described in International Publication No. 2018/235424 or International Publication No. 2018/235425.

(B) As a weight average molecular weight of component, from a viewpoint of obtaining the effect of this invention remarkably, Preferably it is 150 or more, More preferably, it is 200 or more, More preferably, it is 250 or more, Preferably it is 4000 or less, More preferably is 3000 or less, more preferably 2500 or less. (B) The weight average molecular weight of component is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

(B) The active ester equivalent (unsaturated bond equivalent) of the component is preferably 50 g/eq or more, more preferably 100 g/eq. above, more preferably 150 g/eq., preferably 2000 g/eq. Hereinafter, more preferably 1000 g/eq. Hereinafter, more preferably 500 g/eq. is below. The active ester equivalent is the mass of component (B) containing 1 equivalent of an unsaturated bond.

Amount ratio of component (A) and component (B) is 1:0.01 to 1:20 in a ratio of [the total number of epoxy groups of component (A)]: [the total number of active ester groups in component (B)]. preferably, 1:0.1 to 1:10 are more preferable, and 1:0.5 to 1:5 are still more preferable. Here, "the total number of the epoxy groups of (A) component" is the value which summed up all the values obtained by dividing the mass of the nonvolatile component of (A) component present in the resin composition by the epoxy equivalent. In addition, "the total number of active ester groups of component (B)" is the total value of all the values obtained by dividing the mass of the non-volatile components of component (B) in the resin composition by the equivalent of active ester groups. The effect of the present invention can be remarkably obtained by making the ratio of the component (A) and the component (B) within this range.

(B) Content of component, From a viewpoint of suppressing the generation|occurrence|production of the unevenness after lamination, with respect to 100 mass % of non-volatile components in a resin composition, Preferably it is 5 mass % or more, More preferably, it is 10 mass % or more, More preferably Preferably it is 15 mass % or more, Preferably it is 30 mass % or less, Preferably it is 25 mass % or less, More preferably, it is 20 mass % or less.

<(C) Inorganic filler>

The resin composition may contain the inorganic filler as (C)component further as an arbitrary component other than the component mentioned above. (C) By using an inorganic filler, the dielectric characteristic and insulation performance of the hardened|cured material of a resin composition can be improved.

An inorganic compound is used as a material of an inorganic filler. Examples of the inorganic filler material include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, carbonic acid. Calcium, 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, zircon Barium acid, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, etc. are mentioned. Among these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as a silica, spherical silica is preferable. (C) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

(C) As a commercial item of a component, For example, "UFP-30" by a Denka company; "SP60-05", "SP507-05" by the Shin-Nitetsu Sumikin Materials company; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatech Corporation; "Silly writing NSS-3N", "Silly writing NSS-4N", "Silly writing NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Adomatex Corporation, etc. are mentioned.

(C) The specific surface area of the component is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, and particularly preferably 3 m 2 /g or more. Although there is no particular limitation on the upper limit, it is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less. The specific surface area can be obtained by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multi-point method.

(C) The average particle diameter of the component is preferably 0.01 µm or more, more preferably 0.05 µm or more, particularly preferably 0.1 µm or more, and preferably 5 µm from the viewpoint of significantly obtaining the desired effect of the present invention. Hereinafter, more preferably, it is 2 micrometers or less, More preferably, it is 1 micrometer or less.

(C) The average particle diameter of component can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle size distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution measuring apparatus, and making the intermediate diameter into an average particle diameter. As the measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial bottle, and what was dispersed for 10 minutes by ultrasonic wave can be used. For the measurement sample, using a laser diffraction particle size distribution measuring device, the used light source wavelength is set to blue and red, and the volume-based particle size distribution of component (C) is measured by a flow cell method, and the obtained particle size distribution is intermediate As the diameter, the average particle diameter can be calculated. As a laser diffraction type particle size distribution measuring apparatus, "LA-960" by Horiba Corporation, etc. are mentioned, for example.

It is preferable that component (C) is processed by the surface treating agent from a viewpoint of improving moisture resistance and dispersibility. As the surface treatment agent, for example, a vinylsilane coupling agent, a (meth)acrylic coupling agent, a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, An alkoxysilane, an organosilazane compound, a titanate type coupling agent, etc. are mentioned. Especially, from a viewpoint of acquiring the effect of this invention remarkably, a vinylsilane-type coupling agent, a (meth)acrylic-type coupling agent, and an aminosilane-type coupling agent are preferable. In addition, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

As a commercial item of a surface treatment agent, For example, Shin-Etsu Chemical Co., Ltd. make "KBM1003" (vinyl triethoxysilane), Shin-Etsu Chemical Co., Ltd. make "KBM503" (3-methacryloxypropyltriethoxysilane), “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “ KBE903” (3-aminopropyltriethoxysilane), “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “SZ-31” (Hexa) manufactured by Shin-Etsu Chemical Co., Ltd. methyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. " KBM-7103" (3,3,3-trifluoropropyl trimethoxysilane) etc. are mentioned.

It is preferable that the grade of the surface treatment by a surface treating agent falls within a predetermined range from a viewpoint of the dispersibility improvement of an inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2 parts by mass to 5 parts by mass, preferably surface-treated at 0.2 parts by mass to 3 parts by mass, and 0.3 parts by mass to 2 parts by mass. It is preferable that it is surface-treated.

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

The amount of carbon per unit surface area of an inorganic filler can be measured, after washing-processing the inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, MEK in a sufficient amount as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, followed by ultrasonic cleaning at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" by Horiba Corporation, etc. can be used.

As content of an inorganic filler, when the nonvolatile component in a resin composition is 100 mass % from a viewpoint of obtaining the effect of this invention remarkably, Preferably it is 50 mass % or more, More preferably, it is 60 mass % or more, More preferably is 70 mass % or more, Preferably it is 90 mass % or less, More preferably, it is 80 mass % or less, More preferably, it is 75 mass % or less.

<(D) curing agent>

The resin composition may contain the hardening|curing agent as (D)component further as arbitrary components other than the component mentioned above. However, those corresponding to (B) component are excluded.

(D) As the curing agent, a compound capable of reacting with the component (A) to cure the resin composition can be used, for example, an active ester curing agent that does not correspond to the component (B), a phenol curing agent, and a benzoxazine-based curing agent. curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, cyanate ester curing agents, maleimide curing agents, polyphenylene ether curing agents (styrene curing agents), and the like. Among them, any one of a phenol-based curing agent, a carbodiimide-based curing agent, a maleimide-based curing agent, and a polyphenylene ether-based curing agent is preferable from the viewpoint of significantly obtaining the effects of the present invention.

Examples of the active ester curing agent include curing agents having one or more active ester groups in one molecule. Among them, as the active ester curing agent, phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. having two or more ester groups with high reaction activity in one molecule compounds are preferred. It is preferable that the said active ester type hardening|curing agent is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferable.

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

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

Preferred specific examples of the active ester curing agent 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 product of phenol novolac, and phenol novolac and active ester compounds containing benzoylate. Especially, the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structure consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents are active ester compounds containing a dicyclopentadiene type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC" -8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", (manufactured by DIC); As an active ester compound containing a naphthalene structure, "HPC-8150-62T", "EXB-8100L-65T", "EXB-8150L-65T", "EXB9416-70BK", "HPC-8900-70BK" (manufactured by DIC Corporation) ); "DC808" (made by Mitsubishi Chemical) as an active ester compound containing the acetylated product of phenol novolac; "YLH1026" (made by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing the benzoyl compound of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester curing agent that is an acetylated product of phenol novolac; Examples of the active ester curing agent that is a benzoyl product of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

As a phenolic hardening|curing agent, the hardening|curing agent which has 1 or more, Preferably it has 2 or more hydroxyl groups couple|bonded with the aromatic ring (a benzene ring, a naphthalene ring, etc.) in 1 molecule is mentioned. Especially, the compound which has the hydroxyl group couple|bonded with the benzene ring is preferable. Moreover, from a viewpoint of heat resistance and water resistance, the phenolic hardening|curing agent which has a novolak structure is preferable. Moreover, from an adhesive viewpoint, a nitrogen-containing phenol-type hardening|curing agent is preferable, and a triazine skeleton containing phenol-type hardening|curing agent is more preferable. In particular, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness.

As a specific example of a phenol type hardening|curing agent and a naphthol type hardening|curing agent, Meiwa Kasei Corporation make "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H"; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Corporation; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V" manufactured by Nittetsu Chemical & Materials Co., Ltd. "SN-375", "SN-395"; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P" manufactured by DIC Corporation, "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165"; "GDP-6115L", "GDP-6115H", "ELPC75", etc. made from Gunei Chemical Co., Ltd. are mentioned.

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by Showa Kobunshi, "Pd", "Fa", "ALP-d" by Shikoku Kasei Co., Ltd., "ODA-BOZ" by JFE Chemicals are mentioned can

Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", "V-07" manufactured by Nisshinbo Chemical; Stabakusol (trademark) P manufactured by Rhein Chemis, etc. are mentioned.

Examples of the acid anhydride curing agent include curing agents having at least one acid anhydride group in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. Anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, anhydride Trimellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1, Polymeric acid anhydrides, such as 3-dione, ethylene glycol bis (anhydro trimellitate), and styrene maleic acid resin which copolymerized styrene and maleic acid, etc. are mentioned. A commercial item may be used for an acid anhydride type hardening|curing agent, For example, "MH-700" by a Nippon Rika company, etc. are mentioned.

Examples of the amine-based curing agent include curing agents having at least one amino group in one molecule, for example, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like. From the viewpoint of exhibiting a desired effect, aromatic amines are preferable. Primary amine or secondary amine is preferable and, as for an amine type hardening|curing agent, primary amine is more preferable. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone , 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl ) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-amino) Phenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4 ,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. are mentioned. Commercially available amine curing agents may be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard AA", "Kayahard AB", "Kayahard AS" manufactured by Nippon Kayaku Co., Ltd. , "Epicure W" manufactured by Mitsubishi Chemical, etc. are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6- Dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4- cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cya bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; A prepolymer etc. in which these cyanate resins were partially triazine-ized are mentioned. As a specific example of a cyanate ester type hardening|curing agent, "PT30" and "PT60" by Ronza Japan (all are phenol novolak-type polyfunctional cyanate ester resin); "ULL-950S" (polyfunctional cyanate ester resin); "BA230" and "BA230S75" (prepolymer in which a part or all of bisphenol A dicyanate was triazine-ized and became a trimer) etc. are mentioned.

A maleimide-type hardening|curing agent is a compound containing the maleimide group represented by following formula (D-1) in a molecule|numerator. A maleimide-type hardening|curing agent may be used individually by 1 type, and may be used in combination of 2 or more types.

The number of maleimide groups per molecule of the maleimide-based curing agent is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more, from the viewpoint of significantly obtaining the desired effect of the present invention. , Preferably it is 10 or less, More preferably, it is 6 or less, Especially preferably, it is 3 or less.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the maleimide-based curing agent preferably has either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably has an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

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

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

In the maleimide-based curing agent, it is preferable that the nitrogen atom of the maleimide group is directly bonded to a monovalent or divalent aromatic hydrocarbon group from the viewpoint of significantly obtaining the desired effect of the present invention. Here, "direct" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

It is preferable that a maleimide-type hardening|curing agent has a structure represented, for example by following formula (D-2).

In the formula (D-2), R ³¹ and R ³⁶ represent a maleimide group, R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and D is each independently It represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

^{R 32} , R ³³ , R ³⁴ and R ³⁵ in formula (D-2) each independently represent a hydrogen atom, an alkyl group, or an aryl group, and a hydrogen atom is preferable.

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

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. A monocyclic ring may be sufficient as an aryl group, and a condensed ring may be sufficient as it. As such an aryl group, a phenyl group, a naphthyl group, anthracenyl group etc. are mentioned, for example.

The alkyl group and the aryl group may have a substituent. Examples of the substituent include a halogen atom, -OH, -OC _1-6 alkyl group, -N(C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6-10 aryl group, -NH ₂ , -CN , -C(O)OC _1-10 alkyl group, -COOH, -C(O)H, -NO ₂ etc. are mentioned. Here, the term "C _pq " (p and q are positive integers and satisfy p < q) indicates that the number of carbon atoms in the organic group described immediately after this term is p to q. For example, the _{expression "C 1-10} alkyl group" represents an alkyl group having 1 to 10 carbon atoms. These substituents may combine with each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring.

D in Formula (D-2) represents a divalent aromatic group. Examples of the divalent aromatic group include a phenylene group, a pthylene group, an anthracenylene group, an aralkyl group, a biphenylene group, and a biphenylaralkyl group, and among these, a biphenylene group and a biphenylaralkyl group are preferable. and a biphenylene group is more preferable. The divalent aromatic group may have a substituent. The substituent is the same as the substituent which the alkyl group represented by ^{R 32} in the formula (D-2) may have.

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

a represents the integer of 1-100, Preferably it is 1-50, More preferably, it is 1-20, More preferably, it is 1-5.

As a maleimide-type hardening|curing agent, resin represented by Formula (D-3) is preferable.

In the formula (D-3), R ³⁷ and R ³⁸ represent a maleimide group. a1 represents the integer of 1-100.

a1 is the same as a in Formula (D-2), and a preferable range is also the same.

A commercial item can be used for such a maleimide-type hardening|curing agent. As a commercial item, "MIR-3000-70MT" by Nippon Kayaku Co., Ltd. etc. is mentioned, for example.

Moreover, as another embodiment of a maleimide-type hardening|curing agent, it is a compound which has at least 1 maleimide group in a molecule|numerator.

In this maleimide-type hardening|curing agent, it is preferable that the C5 or more aliphatic group is directly couple|bonded with the nitrogen atom of the maleimide group. Examples of the aliphatic group having 5 or more carbon atoms include an alkyl group, an alkylene group, and an alkenylene group.

The number of maleimide groups per molecule of the maleimide-based curing agent may be one, but is preferably two or more, preferably 10 or less, more preferably 6 or less, particularly preferably 3 or less. . By using a maleimide-based curing agent having two or more maleimide groups per molecule, the effects of the present invention can be significantly obtained.

It is preferable that a maleimide-type hardening|curing agent is represented by the following general formula (D-4).

In the general formula (D-4), M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. The number of carbon atoms in the divalent aliphatic group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. As a divalent aliphatic group, an alkylene group, an alkenylene group, etc. are mentioned, for example. ^{The substituent for M is the same as the substituent which the alkyl group represented by R 32} in the formula (D-2) may have, and the substituent is preferably an alkyl group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR ⁰ -(R ⁰ is a hydrogen atom, a carbon atom 1 to 3 alkyl group), an oxygen atom, a sulfur atom, C(=O)NR ⁰ -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and two or more kinds of divalent groups The group which consists of a combination of groups, etc. are mentioned. A group consisting of a combination of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and two or more types of divalent groups has the number of carbon atoms You may have 5 or more alkyl groups as a substituent. The divalent group derived from phthalimide represents a divalent group derived from phthalimide, and is specifically a group represented by the general formula (D-5). The divalent group derived from pyromellitic acid diimide represents a divalent group derived from pyromellitic acid diimido, and is specifically a group represented by the general formula (D-6). In the formula, "*" represents a bond.

The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, particularly preferably an alkylene group having 1 to 40 carbon atoms. do. Any of linear, branched, and cyclic|annular form may be sufficient as this alkylene group. Examples of such an alkylene group include a methylethylene group, a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, and a tridecylene group. , a heptadecylene group, a hexatriacontylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, etc. can be heard

The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, particularly preferably an alkenylene group having 2 to 10 carbon atoms. do. The alkenylene group may be linear, branched or cyclic. Examples of the alkenylene group include a methylethylenylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, and an octenylene group.

The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, particularly preferably an alkynylene group having 2 to 10 carbon atoms. do. Any of linear, branched, and cyclic|annular form may be sufficient as this alkynylene group. Examples of such alkynylene group include methylethynylene group, cyclohexynylene group, pentynylene group, hexynylene group, heptynylene group, and octynylene group.

The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 14 carbon atoms. and an arylene group having 6 to 10 carbon atoms is more preferable. As an arylene group, a phenylene group, a naphthylene group, anthracenylene group, etc. are mentioned, for example.

The alkylene group, alkenylene group, alkynylene group, and arylene group which are divalent coupling groups in L may have a substituent. As a substituent, the formula (D-2) R ³² is an alkyl group which may have the same as the substituents, and preferably represents on the number of carbon atoms is an alkyl group of 5 or more.

Examples of the group consisting of a combination of two or more divalent groups in L include a divalent group consisting of a combination of an alkylene group, a divalent group derived from phthalimide and an oxygen atom; a divalent group consisting of a combination of a phthalimide-derived divalent group, an oxygen atom, an arylene group, and an alkylene group; and a divalent group composed of a combination of an alkylene group and a divalent group derived from pyromellitic diimide. The group which consists of a combination of 2 or more types of divalent groups may form rings, such as a condensed ring, by combining each group. Moreover, the number of repeating units of 1-10 may be sufficient as the group which consists of a combination of 2 or more types of divalent groups.

Among them, as L in the general formula (D-4), an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, an alkylene group having 1 to 50 carbon atoms which may have a substituent, and a carbon atom It is preferable that the number is a divalent group consisting of an alkyl group of 5 or more, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or a combination of two or more of these groups. Among them, examples of L include an alkylene group; a divalent group having the structure of an alkylene group-phthalimide-derived divalent group-oxygen atom-phthalimide-derived divalent group; a divalent group having the structure of an alkylene group-phthalimide-derived divalent group-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-phthalimide-derived divalent group; A divalent group having a structure of a divalent group derived from alkylene-pyromellitic diimide is more preferable.

It is preferable that the maleimide-type hardening|curing agent represented by general formula (D-4) is represented by general formula (D-7).

In the general formula (D-7), M ¹ each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and Z each independently represents an alkylene group or substituent having 5 or more carbon atoms which may have a substituent represents a divalent group having an aromatic ring which may have t represents the integer of 1-10.

M ¹ each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M ¹ is the same as M in general formula (D-4), and represents an alkylene group or an alkenylene group.

Z each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent. As the alkylene group for Z, any of chain, branched, and cyclic may be used, and among them, a cyclic, that is, a cyclic alkylene group having 5 or more carbon atoms which may have a substituent is preferable. The number of carbon atoms in the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure. have.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by Z include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, and an aromatic heterocycle, A benzene ring, a phthalimide ring, and a pyromellitic acid diimide ring are preferable. That is, the divalent group having an aromatic ring is a divalent group having a benzene ring which may have a substituent, a divalent group having an optionally substituted phthalimide ring, and a pyromellitic acid diimide ring which may have a substituent. A divalent group having Examples of the divalent group having an aromatic ring include a group composed of a combination of a divalent group derived from phthalimide and an oxygen atom; a group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; a divalent group derived from pyromellitic acid diimide; The group which consists of a combination of the divalent group derived from a phthalimide, and an alkylene group, etc. are mentioned. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (F-4).

The divalent group which has an alkylene group and an aromatic ring which Z represents may have a substituent. The substituent is the same as the substituent which the alkyl group represented by ^{R 32} in the general formula (D-2) may have.

Specific examples of the group represented by Z include the following groups. In the formula, "*" represents a bond.

The maleimide-based curing agent represented by the general formula (D-4) is any one of a maleimide-based curing agent represented by the general formula (D-8) and a maleimide-based curing agent represented by the general formula (D-9) it is preferable

In the general formula (D-8), M ² and M ³ each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and R ⁴⁰ each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group composed of a combination of two or more of these groups. t1 represents the integer of 1-10.

In the general formula (D-9), M ⁴ , M ⁶ and M ⁷ each independently represent a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and M ⁵ is each independently an aromatic ring which may have a substituent represents a divalent group having , and R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

M ² and M ³ each independently represent a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M ² and M ³ are the same as the divalent aliphatic group in which the number of carbon atoms represented by M in the general formula (D-4) is 5 or more, and represents an alkylene group or an alkenylene group, and is a hexatriacontylene group or a hexatriacontylene group. group is preferred.

R ⁴⁰ each independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more kinds of divalent groups thereof. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent coupling group represented by L in the general formula (F-4). R ⁴⁰ is preferably a group or an oxygen atom composed of a combination of two or more divalent groups.

As a group which consists of a combination of 2 or more types of divalent group in R<^40> , the combination of an oxygen atom, an arylene group, and an alkylene group is mentioned. The following groups are mentioned as a specific example of the group which consists of a combination of 2 or more types of divalent groups. In the formula, "*" represents a bond.

M ⁴ , M ⁶ and M ⁷ each independently represent a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M ⁴ , M ⁶ and M ⁷ are the same as the divalent aliphatic group having 5 or more carbon atoms which may have a substituent represented by M in the general formula (D-4), and represent an alkylene group or an alkenylene group, and hexylene A group, a heptylene group, an octylene group, a nonylene group, and a decylene group are preferable, and an octylene group is more preferable.

M ⁵ each independently represents a divalent group having an aromatic ring which may have a substituent. M ⁵ is the same as the divalent group having an aromatic ring which may have a substituent represented by Z in the general formula (D-7), and is a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; A group consisting of a combination of a divalent group derived from phthalimide and an alkylene group is preferable, and a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide is more preferable. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (D-4).

Specific examples of the group represented by M ^{5 include the following groups.} In the formula, "*" represents a bond.

R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. R ⁴¹ and R ⁴² are the same as the above-described alkyl group having 5 or more carbon atoms, preferably a hexyl group, a heptyl group, an octyl group, a nonyl group or a decyl group, and more preferably a hexyl group or an octyl group.

u1 and u2 each independently represent the integer of 1-15, The integer of 1-10 is preferable.

As a specific example of a maleimide-type hardening|curing agent, the compound of the following (D1)-(D3) is mentioned. However, the maleimide-based curing agent is not limited to these specific examples. In the formula, v represents an integer from 1 to 10.

Specific examples of the maleimide-based curing agent include "BMI1500" (compound of formula (D1)) manufactured by DMI, "BMI1700" (compound of formula (D2)), "BMI689" (compound of formula (D3)), etc. can

The maleimide group equivalent of the maleimide-based curing agent is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to 1000 g/eq., more preferably 150 g/eq. to 500 g/eq. Maleimide group equivalent is the mass of the maleimide-type hardening|curing agent containing 1 equivalent of maleimide group.

The polyphenylene ether-based curing agent is a curing agent having a vinylphenyl group. A vinylphenyl group is group which has a structure shown below.

(* indicates a bond)

The polyphenylene ether-based curing agent preferably has two or more vinylphenyl groups per molecule from the viewpoint of obtaining a cured product having a low dielectric loss tangent.

The polyphenylene ether-based curing agent preferably has a cyclic structure from the viewpoint of obtaining a cured product having a low dielectric loss tangent. As a cyclic structure, a bivalent cyclic group is preferable. As the divalent cyclic group, any of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure may be used. Moreover, you may have two or more bivalent cyclic groups.

From the viewpoint of significantly obtaining the desired effect of the present invention, the divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, preferably a 20-membered ring or less, more preferably is a 15-membered ring or less, more preferably a 10-membered ring or less. In addition, as a bivalent cyclic group, a monocyclic structure may be sufficient or a polycyclic structure may be sufficient.

As for the ring in the divalent cyclic group, the skeleton of the ring may be constituted by hetero atoms other than carbon atoms. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, An oxygen atom is preferable. The hetero atom may have one in said ring, and may have two or more.

Specific examples of the divalent cyclic group include the following divalent groups (i) or (ii).

(in divalent groups (i) and (ii), R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁶¹ , and R ⁶² are each independently a halogen atom, an alkyl group having 6 or less carbon atoms; or a phenyl group, and R ⁵³ , R ⁵⁴ , R ⁵⁸ , R ⁵⁹ , and R ⁶⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group)

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. A methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group etc. are mentioned as a C6 or less alkyl group, It is preferable that it is a methyl group. R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁶¹ , and R ⁶² preferably represent a methyl group. R ⁵³ , R ⁵⁴ , R ⁵⁸ , R ⁵⁹ , and R ⁶⁰ are preferably a hydrogen atom or a methyl group.

Moreover, a bivalent cyclic group may combine several divalent cyclic group. As a specific example in the case of combining a bivalent cyclic group, the divalent cyclic group represented by a following formula (D4) is mentioned.

(In formula (D4), R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ are each independently a halogen atom, an alkyl group having 6 or less carbon atoms, or represents a phenyl group, and R ⁷³ , R ⁷⁴ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. d2 represents an integer from 0 to 300. However, the case where either of d1 and d2 is 0 is excluded)

R ⁷¹ , R ⁷² , R ⁸⁵ and R ⁸⁶ are the same as ^{R 51} in formula (i). R ⁷³ , R ⁷⁴ , R ⁸³ and R ⁸⁴ are the same as ^{R 53} in formula (i). R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ , and R ⁸² are the same as ^{R 55} in formula (ii). R ⁷⁸ , R ⁷⁹ , and R ⁸⁰ are the same as ^{R 58} in formula (ii).

d1 and d2 represent the integers of 0-300. However, the case where one of d1 and d2 is 0 is excluded. As d1 and d2, it is preferable to represent the integer of 1-100, It is more preferable to represent the integer of 1-50, It is more preferable to represent the integer of 1-10. d1 and d2 may be the same or different.

The divalent cyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, and an oxo group. group etc. are mentioned, An alkyl group is preferable.

The vinylphenyl group may be directly couple|bonded with the divalent cyclic group, and may couple|bond via the divalent coupling group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O) N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc. are mentioned, The group which combined these two or more may be sufficient. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 5 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Rengi is more preferable. The alkylene group may be linear, branched, or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a xylene group, and a 1,1-dimethylethylene group, and a methylene group, an ethylene group, and a 1,1- A dimethylethylene group is preferable. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is more preferable, and an alkenylene group having 2 to 5 carbon atoms is still more preferable. The arylene group or heteroarylene group is preferably an arylene group or heteroarylene group having 6 to 20 carbon atoms, and more preferably an arylene group or heteroarylene group having 6 to 10 carbon atoms. As a divalent linking group, an alkylene group is preferable, and a methylene group is especially preferable.

The polyphenylene ether-based curing agent is preferably represented by the following general formula (D-10).

(In the general formula (D-10), R ⁹¹ and R ⁹² each independently represent a divalent linking group. Ring B1 represents a divalent cyclic group)

R ⁹¹ and R ⁹² each independently represent a divalent linking group. The divalent linking group is the same as the above divalent linking group.

Ring B1 represents a divalent cyclic group. Ring B1 is the same as the above divalent cyclic group.

Ring B1 may have a substituent. As a substituent, it is the same as the substituent which the said divalent cyclic group may have.

Hereinafter, specific examples of the polyphenylene ether-based curing agent are shown, but the present invention is not limited thereto.

(q1 is the same as d1 in the formula (D4), and q1 is the same as d2 in the formula (D4))

A commercial item may be used for a polyphenylene ether type hardening|curing agent, For example, "OPE-2St" by a Mitsubishi Gas Chemical company, etc. are mentioned. A polyphenylene ether type hardening|curing agent may be used individually by 1 type, and may be used in combination of 2 or more types.

The number average molecular weight of the polyphenylene ether-based curing agent is preferably 3000 or less, more preferably 2500 or less, still more preferably 2000 or less and 1500 or less from the viewpoint of significantly obtaining the desired effect of the present invention. The lower limit is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more and 1000 or more. A number average molecular weight is a polystyrene conversion number average molecular weight measured using gel permeation chromatography (GPC).

(D) The content of the curing agent is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 100% by mass of the nonvolatile component in the resin composition from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 10 mass % or more, Preferably it is 25 mass % or less, More preferably, it is 20 mass % or less, More preferably, it is 15 mass % or less.

When the number of epoxy groups in the component (A) is 1, the number of active groups in the (D) curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably 2 or less, more preferably Preferably it is 1.8 or less, More preferably, it is 1.6 or less, Especially preferably, it is 1.4 or less. Here, "the number of active groups of (D) hardening|curing agent" is the value which summed all the value obtained by dividing the mass of the nonvolatile component of the (D) hardening|curing agent which exists in a resin composition by the active group equivalent. When the number of epoxy groups in the component (A) is 1, the number of active groups in the curing agent (D) is in the above range, so that the desired effect of the present invention can be significantly obtained.

<(E) curing accelerator>

The resin composition may contain the hardening accelerator as component (E) further as arbitrary components other than the above-mentioned component.

(E) As a component, a phosphorus type hardening accelerator, an amine type hardening accelerator, an imidazole type hardening accelerator, a guanidine type hardening accelerator, a metal type hardening accelerator, etc. are mentioned, for example. (E) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphoniumdecanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. are mentioned, Triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimida Zolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-unde Silimidazolyl-(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-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, imidazole compounds and epoxy resins of adducts, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As an imidazole-type hardening accelerator, you may use a commercial item, for example, "P200-H50" by Mitsubishi Chemical, etc. are mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. are mentioned, dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and tin, is mentioned, for example. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate, organocopper complexes such as copper(II)acetylacetonate, and zinc(II)acetylacetonate. organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

(E) the content of the component, from the viewpoint of significantly obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is 100 mass%, preferably 0.01 mass% or more, more preferably 0.02 mass% or more, More preferably, it is 0.03 mass % or more, Preferably it is 1 mass % or less, More preferably, it is 0.5 mass % or less, More preferably, it is 0.1 mass % or less.

<(F) Other additives>

The resin composition may further contain other additives as arbitrary components other than the components mentioned above. As such an additive, resin additives, such as a thermoplastic resin, a flame retardant, a thickener, an antifoamer, a leveling agent, and an adhesion-imparting agent, etc. are mentioned, for example. These additives may be used individually by 1 type, and may be used in combination of 2 or more type. Each content can be set suitably if it is a person skilled in the art.

The preparation method of the resin composition of this invention is not specifically limited, For example, the method of adding a solvent etc. to a compounding component as needed, and mixing and dispersing using a rotary mixer etc. are mentioned.

<Physical properties and uses of the resin composition>

A resin composition contains (A) component and (B) component. Thereby, generation|occurrence|production of the nonuniformity which arises when the resin composition layer containing a resin composition is laminated can be suppressed. Moreover, in this invention, it is excellent also normally also in plating peeling strength, copper foil adhesiveness, and copper foil adhesiveness after HAST, and also a dielectric property is low, and hardened|cured material with a low arithmetic mean roughness (Ra) can also be obtained.

A resin composition shows the characteristic that generation|occurrence|production of a stain can be suppressed, when the resin composition layer containing a resin composition is laminated. Specifically, it is carried out according to the method described in Examples to be described later. At this time, there is usually no unevenness at all, and it is a completely uniform surface. The details of evaluation of the unevenness after lamination can be measured according to the method described in Examples described later.

The roughened surface after roughening the hardened|cured material surface which thermosetted the resin composition at 130 degreeC for 30 minutes and then 170 degreeC for 30 minutes usually shows the characteristic that arithmetic mean roughness (Ra) is low. Therefore, said hardened|cured material forms the insulating layer with low arithmetic mean roughness. As arithmetic mean roughness, Preferably it is 300 nm or less, More preferably, it is 250 nm or less, More preferably, it is 200 nm or less. On the other hand, the lower limit of the arithmetic mean roughness can be 30 nm or more. Evaluation of arithmetic mean roughness Ra can be measured according to the method described in the Example mentioned later.

A cured product obtained by thermosetting a resin composition at 190°C for 90 minutes usually exhibits a characteristic of low dielectric properties (dielectric loss tangent). Accordingly, the cured product forms an insulating layer having a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.004 or less, still more preferably 0.003 or less. The lower limit of the dielectric loss tangent can be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in Examples to be described later.

The cured product obtained by thermosetting the resin composition at 130° C. for 30 minutes, then at 170° C. for 30 minutes, and then at 200° C. for 90 minutes usually has a peel strength between the conductor layer (plated conductor layer) formed by plating. It exhibits excellent characteristics. Therefore, the said hardened|cured material forms the insulating layer excellent in the peeling strength between a plating conductor layer. The peeling strength is preferably 0.3 kgf/cm or more, more preferably 0.35 kgf/cm or more, and still more preferably 0.4 kgf/cm or more. The upper limit of peeling strength can be 10 kgf/cm or less, etc. The measurement of the peeling strength of a plating conductor layer can be measured according to the method as described in the Example mentioned later.

The hardened|cured material which thermosetted the resin composition at 130 degreeC for 30 minutes, then 170 degreeC for 30 minutes, and then 200 degreeC for 90 minutes usually shows the characteristic that it is excellent in the peeling strength between copper foil (copper foil adhesiveness). Therefore, the said hardened|cured material forms the insulating layer excellent in the peeling strength between copper foil. The peeling strength is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm or more, and still more preferably 0.5 kgf/cm or more. The upper limit of peeling strength can be 10 kgf/cm or less, etc. The measurement of copper foil adhesiveness can be measured according to the method as described in the Example mentioned later.

The hardened|cured material which thermosetted the resin composition at 130 degreeC for 30 minutes and then 170 degreeC for 30 minutes is usually the peeling strength between the copper foil after a HAST test (130 degreeC, humidity 85%RH, 100 hours) (after HAST) Copper foil adhesiveness) is excellent. Therefore, the said hardened|cured material forms the insulating layer excellent in the peeling strength after HAST between copper foil. The copper foil adhesiveness after HAST becomes like this. Preferably it is 0.15 kgf/cm or more, More preferably, it is 0.2 kgf/cm or more, More preferably, it is 0.25 kgf/cm or more. The upper limit of copper foil adhesiveness after HAST can be made into 10 kgf/cm or less etc. The measurement of copper foil adhesiveness after HAST can be measured according to the method as described in the Example mentioned later.

When the resin composition of this invention laminates the resin composition layer containing a resin composition, generation|occurrence|production of a stain can be suppressed. Therefore, the resin composition of this invention can be used suitably as a resin composition for an insulation use. Specifically, it can be suitably used as a resin composition (resin composition for forming an insulating layer for forming a conductor layer) for forming the insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer. have.

In the multilayer printed wiring board described later, a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board), and a resin composition for forming an interlayer insulating layer of a printed wiring board (printed wiring board) resin composition for forming an interlayer insulating layer of

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is a resin composition for a redistribution forming layer as an insulating layer for forming a redistribution layer ( It can be used suitably also as the resin composition for redistribution forming layer formation) and the resin composition (resin composition for semiconductor chip sealing) for sealing a semiconductor chip. When the semiconductor chip package is manufactured, a redistribution layer may be additionally formed on the sealing layer.

(1) the step of laminating a temporarily fixed film on the substrate,

(2) the step of temporarily fixing the semiconductor chip on the temporarily fixing film,

(3) forming a sealing layer on the semiconductor chip;

(4) the step of peeling the substrate and the temporarily fixed film from the semiconductor chip,

(5) a step of forming a rewiring forming layer as an insulating layer on the surface where the substrate and the temporarily fixed film of the semiconductor chip are peeled; and

(6) Step of forming a redistribution layer as a conductor layer on the redistribution forming layer

[Resin Sheet]

The resin sheet of this invention contains a support body and the resin composition layer provided on the said support body and formed from the resin composition of this invention.

The thickness of the resin composition layer is preferably 50 µm or less, more preferably 40 µm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film; More preferably, it is 30 micrometers or less. Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, it can be 5 micrometers or more, etc.

As a support body, the film which consists of a plastics material, metal foil, and a release paper are mentioned, for example, The film which consists of a plastics material, and metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). ) such as polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), Polyether ketone, polyimide, etc. are mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good.

A support body may give a mat treatment, a corona treatment, and an antistatic treatment to the surface to join with the resin composition layer.

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface to join with the resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin, for example. A commercial item may be used for the support body with a release layer, for example, "SK-1", "AL-5", "AL-7" by Lintec which is a PET film which has a release layer which has an alkyd resin type mold release agent as a main component. ', "Lumira T60" by Tore Corporation, "Purex" by Teijin Corporation, "Uni-pil" by Unichika Corporation, etc. are mentioned.

Although it does not specifically limit as thickness of a support body, The range of 5 micrometers - 75 micrometers is preferable, and the range of 10 micrometers - 60 micrometers is more preferable. Moreover, when using a support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is the said range.

In one embodiment, the resin sheet may further contain other layers as needed. As such another layer, the protective film according to the support body etc. which were provided in the surface which is not joined to the support body of a resin composition layer (that is, the surface on the opposite side to a support body), etc. are mentioned, for example. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin composition layer, and a flaw can be suppressed.

A resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish on a support using a die coater, etc., and further drying to form a resin composition layer. have.

As an organic solvent, 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; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and 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.

You may perform drying by well-known methods, such as a heating and hot-air spraying. Although drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably it is made to dry so that it may become 5 mass % or less. Although it changes with the boiling point of the organic solvent in a resin varnish, for example, when using the resin varnish containing 30 mass % - 60 mass % of an organic solvent, by drying at 50 degreeC - 150 degreeC for 3 minutes - 10 minutes, the resin composition layer can be formed.

A resin sheet can be wound up and stored in roll shape. When a resin sheet has a protective film, it becomes usable by peeling off a protective film.

[Printed wiring board]

The printed wiring board of this invention contains the insulating layer formed with the hardened|cured material of the resin composition of this invention.

A printed wiring board can be manufactured by the method including the process of following (I) and (II) using the above-mentioned resin sheet, for example.

(I) Step of laminating the resin composition layer of the resin sheet on the inner-layer substrate so as to be bonded to the inner-layer substrate

(II) Step of thermosetting the resin composition layer to form an insulating layer

The "inner-layer substrate" used in step (I) is a member used as a substrate for a printed wiring board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene. An ether substrate etc. are mentioned. Moreover, the said board|substrate may have a conductor layer on the one side or both surfaces, and this conductor layer may be pattern-processed. An inner-layer substrate in which a conductor layer (circuit) is formed on one or both surfaces of the substrate is sometimes referred to as an "inner-layer circuit board". Moreover, when manufacturing a printed wiring board, the intermediate product in which an insulating layer and/or a conductor layer should be further formed is also included in the "inner-layer board|substrate" referred to in this invention. When the printed wiring board is a circuit board with a built-in component, an inner-layer board having a built-in component can be used.

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. As a member (hereinafter also referred to as a "thermocompression bonding member") which heat-compresses a resin sheet to an inner-layer board|substrate, a heated metal plate (SUS mirror plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. On the other hand, it is preferable not to press the thermocompression-compression-bonding member directly to the resin sheet, but to press through an elastic material, such as a heat-resistant rubber, so that the resin sheet may fully follow the surface unevenness|corrugation of an inner-layer board|substrate.

You may perform lamination|stacking of an inner-layer board|substrate and a resin sheet by the vacuum lamination method. In the vacuum lamination method, the thermocompression pressure 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 It is the range of 1.47 MPa, Preferably the thermocompression-bonding time is the range of 20 second - 400 second, More preferably, it is the range of 30 second - 300 second. Lamination is preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressure laminator by the Meiki Sesakusho company, the vacuum applicator by the Nikko Materials company, a batch type vacuum pressure laminator etc. are mentioned, for example.

After lamination, the laminated resin sheet may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing the thermocompression-bonding member from the support side. The press conditions of the smoothing process can be made into the same conditions as the thermocompression-bonding conditions of the said lamination|stacking. A smoothing process can be performed with a commercially available laminator. In addition, you may perform lamination|stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

In the process (II), the resin composition layer is thermosetted to form an insulating layer. The thermosetting conditions of a resin composition layer are not specifically limited, When forming the insulating layer of a printed wiring board, you may use the conditions normally employ|adopted.

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

Before thermosetting a resin composition layer, you may preheat a resin composition layer at temperature lower than hardening temperature. For example, prior to thermosetting the resin composition layer, at a temperature of 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 115 ° C or less, more preferably 70 ° C or more and 110 ° C or less), the resin composition layer is You may preheat for 5 minutes or more (preferably for 5 minutes - 150 minutes, More preferably, it is 15 minutes - 120 minutes, More preferably, it is 15 minutes - 100 minutes).

When manufacturing a printed wiring board, you may further perform the process of (III) the process of drilling in an insulating layer, the process of (IV) roughening an insulating layer, and the process of (V) forming a conductor layer. You may implement these process (III) - process (V) according to various methods well-known to those skilled in the art used for manufacture of a printed wiring board. On the other hand, when the support is removed after the step (II), the removal of the support is carried out between the steps (II) and (III), between the steps (III) and (IV), or between the steps (IV) and the step (V). ) may be performed between If necessary, the formation of the insulating layer and the conductor layer in the steps (II) to (V) may be repeated to form a multilayer wiring board.

Step (III) is a step of drilling 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, a laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer and the like. You may determine the dimension and shape of a hole suitably according to the design of a printed wiring board.

Process (IV) is a process of roughening an insulating layer. Usually, in this process (IV), the removal of smear is also performed. The procedure and conditions of a roughening process are not specifically limited, When forming the insulating layer of a printed wiring board, the well-known procedure and conditions normally used are employable. For example, the insulating layer can be roughened by performing the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralizing liquid in this order. Although it does not specifically limit as swelling liquid used for a roughening process, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. As a commercially available swelling liquid, "Swelling Deep Securiganth P", "Swelling Deep Securiganth SBU", "Swelling Deep Securigant P" manufactured by Atotech Japan, etc. are mentioned, for example. have. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer in a 30 degreeC-90 degreeC swelling liquid for 1 minute - 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganic acid solution which melt|dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Moreover, as for the density|concentration of the permanganate in an alkaline permanganic acid solution, 5 mass % - 10 mass % are preferable. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as "concentrate compact CP" and "dosing solution securigans P" by Atotech Japan, are mentioned, for example. Moreover, as a neutralization liquid used for a roughening process, an acidic aqueous solution is preferable, and as a commercial item, "reduction solution securigant P" by Atotech Japan company is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30°C to 80°C for 1 minute to 30 minutes. The method of immersing the target object roughened by the oxidizing agent from points, such as workability|operativity, in the neutralization liquid of 40 degreeC - 70 degreeC for 5 minutes - 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness Ra of the insulating layer surface after roughening is preferably 300 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less. Although it does not specifically limit about a minimum, Preferably it is 30 nm or more, More preferably, it is 40 nm or more, More preferably, it is 50 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter.

A process (V) is a process of forming a conductor layer, and forms a conductor layer on an insulating layer. The conductor material used for a conductor layer is not specifically limited. In a suitable embodiment, the conductor layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer is, for example, an alloy of two or more metals selected from the group described above (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy) a layer formed of Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy , a copper/titanium alloy alloy layer is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel/chromium alloy is more preferable, and a single metal layer of copper This is more preferable.

The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types 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 a nickel-chromium alloy.

Although the thickness of a conductor layer depends on the design of a desired printed wiring board, it is 3 micrometers - 35 micrometers generally, Preferably it is 5 micrometers - 30 micrometers.

In one embodiment, the conductor layer may be formed by plating. For example, by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method, a conductor layer having a desired wiring pattern can be formed, and from the viewpoint of simplicity of manufacture, a semi-additive method It is preferable to form by the additive method. Hereinafter, the example in which a conductor layer is formed by the semiadditive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern for exposing a portion of the plating seed layer corresponding to a desired wiring pattern is formed. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[Semiconductor device]

The semiconductor device of this invention contains the printed wiring board of this invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of the semiconductor device include various semiconductor devices provided in electric products (eg, computers, mobile phones, digital cameras and televisions) and vehicles (eg, motorcycles, automobiles, trams, ships, and aircraft). have.

The semiconductor device of this invention can be manufactured by mounting a component (semiconductor chip) in the conduction|electrical_connection location of a printed wiring board. The "conduction point" is "a location through which an electric signal is transmitted in a printed wiring board", and the location may be a surface, a buried location, or any place. In addition, a semiconductor chip will not be specifically limited if it is an electric circuit element which uses a semiconductor as a material.

The semiconductor chip mounting method at the time of manufacturing a semiconductor device is not specifically limited as long as the semiconductor chip functions effectively, Specifically, a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer (BBUL) The mounting method by , the mounting method by the anisotropic conductive film (ACF), the mounting method by the non-conductive film (NCF), etc. are mentioned. Here, "a mounting method using a bumpless build-up layer (BBUL)" is "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board, and the semiconductor chip and wiring on the printed wiring board are connected".

[Example]

Hereinafter, the present invention will be described in more detail using Examples, but the present invention is not limited to these Examples. In addition, in the following description, unless otherwise indicated, "part" and "%" mean "part by mass" and "% by mass", respectively.

<Synthesis Example 1: Synthesis of active ester compound (B-1)>

2,7-dihydroxynaphthalene 320 g (2.0 mol), benzyl alcohol 184 g (1.7 mol), and para-toluenesulfonic acid monohydrate 5.0 g were poured into a flask equipped with a thermometer, dropping funnel, cooling tube, separator tube, and stirrer. Then, at room temperature, the mixture was stirred while blowing nitrogen. Then, it heated up to 150 degreeC, and stirred for 4 hours, distilling the produced|generated water out of the system. After completion of the reaction, 900 g of methyl isobutyl ketone and 5.4 g of a 20% aqueous sodium hydroxide solution were added to neutralize, and the aqueous layer was removed by liquid separation, washed with water 3 times with 280 g of water, and the methyl isobutyl ketone was removed under reduced pressure. 460 g of a benzyl-modified naphthalene compound (A-1) was obtained. The obtained benzyl-modified naphthalene compound (A-1) was a black solid and had a hydroxyl equivalent of 180 grams/equivalent.

203.0 g of isophthalic acid chloride (number of moles of acid chloride groups: 2.0 moles) and 1400 g of toluene were charged to a flask equipped with a thermometer, dropping funnel, cooling tube, flow dividing tube, and stirrer, and the system was dissolved under reduced pressure by nitrogen substitution. Then, 72.4 g (0.67 mol) of orthocresol and 240 g (number of moles of phenolic hydroxyl groups: 1.33 mol) of the benzyl-modified naphthalene compound (A-1) were injected, and the inside of the system was purged with nitrogen under reduced pressure to dissolve. Then, 0.70 g of tetrabutylammonium bromide was dissolved and the inside of a system was controlled to 60 degrees C or less, performing nitrogen gas purging, and 400 g of 20% sodium hydroxide aqueous solution was dripped over 3 hours. Then, stirring was continued for 1.0 hour under these conditions. After completion of the reaction, the liquid was separated and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactant was dissolved, stirred and mixed for 15 minutes, and the mixture was left to separate and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, water|moisture content was removed by decanter dehydration, and the active ester compound (B-1) in the state of the toluene solution of 65 mass % of non-volatile matters was obtained. The active ester equivalent of the obtained active ester compound (B-1) was 238 g/eq.

<Synthesis Example 2: Synthesis of active ester compound (B-2)>

203.0 g of isophthalic acid chloride (number of moles of acid chloride groups: 2.0 moles) and 1400 g of toluene were charged to a flask equipped with a thermometer, dropping funnel, cooling tube, flow dividing tube, and stirrer, and the system was dissolved under reduced pressure by nitrogen substitution. Next, 113.9 g (0.67 mol) of orthophenylphenol and 240 g (number of moles of phenolic hydroxyl group: 1.33 mol) of the benzyl-modified naphthalene compound (A-1) were charged, and the inside of the system was purged with nitrogen under reduced pressure to dissolve. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and the inside of a system was controlled to 60 degrees C or less, performing nitrogen gas purging, and 400 g of 20% sodium hydroxide aqueous solution was dripped over 3 hours. Then, stirring was continued for 1.0 hour under these conditions. After completion of the reaction, the liquid was separated and the aqueous layer was removed. In addition, water was added to the toluene layer in which the reactant was dissolved, stirred and mixed for 15 minutes, and the mixture was left to separate and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, water|moisture content was removed by decanter dehydration, and the active ester compound (B-2) in the state of the toluene solution of 65 mass % of non-volatile matters was obtained. The active ester equivalent of the obtained active ester compound (B-2) was 206 g/eq.

<Synthesis Example 3: Synthesis of active ester compound (B-3)>

203.0 g of isophthalic acid chloride (number of moles of acid chloride groups: 2.0 moles) and 1400 g of toluene were charged to a flask equipped with a thermometer, dropping funnel, cooling tube, flow dividing tube, and stirrer, and the system was dissolved under reduced pressure by nitrogen substitution. Then, 132.7 g (0.67 mol) of styrenated phenol phenol and 240 g (number of moles of phenolic hydroxyl group: 1.33 mol) of the benzyl-modified naphthalene compound (A-1) were charged, and the inside of the system was purged with nitrogen under reduced pressure to dissolve. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and the inside of a system was controlled to 60 degrees C or less, performing nitrogen gas purging, and 400 g of 20% sodium hydroxide aqueous solution was dripped over 3 hours. Then, stirring was continued for 1.0 hour under these conditions. After completion of the reaction, the aqueous layer was removed by static separation. In addition, water was added to the toluene layer in which the reactant was dissolved, stirred and mixed for 15 minutes, and the mixture was left to separate and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, water|moisture content was removed by decanter dehydration, and the active ester compound (B-3) in the state of the toluene solution of 65 mass % of non-volatile matter was obtained. The active ester equivalent of the obtained active ester compound (B-3) was 259 g/eq.

The active ester compound (B-1) to the active ester compound (B-3) were identified as follows. As a result of identification, in the active ester compound (B-1), Ar ^{31 in the} general formula (b-3) has a group represented by the formula (1), and the active ester compound (B-2) in the general formula (b-) ^{Ar 31} of 3) has a group represented by formula (2), and in the active ester compound (B-3), Ar ³¹ of general formula (b-3) is a group represented by formula (3) (n=1 to 5) was found to have

<Example 1: Preparation of resin composition 1>

(A) 3 parts of epoxy resin "ESN475V" (manufactured by Nittetsu Chemical & Materials Co., Ltd., epoxy equivalent: about 330 g/eq.) as component (A) and epoxy resin "HP-4032-SS" as component (A) (manufactured by DIC Corporation) , epoxy equivalent: about 144 g/eq.) 7 parts were dissolved in 10 parts of methyl ethyl ketone (MEK) to obtain an epoxy resin solution A.

In the epoxy resin solution A, 25 parts of active ester compound (B-1) as component (B), and amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) as component (C). Silica (average particle diameter 0.77 µm, manufactured by Adomatex Corporation "SO-C2") (hereinafter also referred to as "inorganic filler A") 65 parts, (E) imidazole compound "1B2PZ" as component "1B2PZ" (manufactured by Shikoku Kasei Corporation) 0.2 part was added, it disperse|distributed uniformly with a high-speed rotation mixer, and the resin varnish A was prepared.

The average particle diameter of the inorganic filler A was 0.5 micrometer, and the specific surface area was 5.9 m<2>/g.

<Example 2: Preparation of resin composition 2>

In Example 1, 25 parts of the active ester compound (B-1) was replaced with 25 parts of the active ester compound (B-2).

Except for the above, a resin composition 2 was prepared in the same manner as in Example 1.

<Example 3: Preparation of resin composition 3>

In Example 1, 25 parts of the active ester compound (B-1) was replaced with 25 parts of the active ester compound (B-3).

Except for the above, a resin composition 3 was prepared in the same manner as in Example 1.

<Example 4: Preparation of resin composition 4>

In Example 1,

changing the amount of the active ester compound (B-1) from 25 parts to 22 parts,

The amount of the imidazole compound (1B2PZ manufactured by Shikoku Kasei Kogyo Co., Ltd.) was changed from 0.2 part to 0.02 part,

2 parts of triazine-containing cresol novolac resin (“LA-3018-50P” manufactured by DIC, methoxypropanol solution having a solid content of 50% by mass), carbodiimide-based resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent) About 216, toluene solution of 50 mass % of solid content) 1 part was used.

Except for the above, a resin composition 4 was prepared in the same manner as in Example 1.

<Example 5: Preparation of resin composition 5>

In Example 2,

changing the amount of the active ester compound (B-2) from 25 parts to 22 parts,

The amount of the imidazole compound (1B2PZ manufactured by Shikoku Kasei Kogyo Co., Ltd.) was changed from 0.2 part to 0.02 part,

2 parts of triazine-containing cresol novolac resin (“LA-3018-50P” manufactured by DIC, methoxypropanol solution having a solid content of 50% by mass), carbodiimide-based resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent) About 216, toluene solution of 50 mass % of solid content) 1 part was used.

Except for the above, a resin composition 5 was prepared in the same manner as in Example 2.

<Example 6: Preparation of resin composition 6>

In Example 3,

changing the amount of the active ester compound (B-3) from 25 parts to 22 parts,

The amount of the imidazole compound (1B2PZ manufactured by Shikoku Kasei Kogyo Co., Ltd.) was changed from 0.2 part to 0.02 part,

2 parts of triazine-containing cresol novolac resin (“LA-3018-50P” manufactured by DIC, methoxypropanol solution having a solid content of 50% by mass), carbodiimide-based resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent) About 216, toluene solution of 50 mass % of solid content) 1 part was used.

Except for the above, a resin composition 6 was prepared in the same manner as in Example 3.

<Example 7: Preparation of resin composition 7>

In Example 1,

changing the amount of the active ester compound (B-1) from 25 parts to 22 parts,

The amount of the imidazole compound (1B2PZ manufactured by Shikoku Kasei Kogyo Co., Ltd.) was changed from 0.2 part to 0.02 part,

2 parts of triazine-containing cresol novolac resin ("LA-3018-50P" manufactured by DIC, methoxypropanol solution having a solid content of 50% by mass) is used,

2 parts of vinylbenzyl resin ("OPE-2St" by Mitsubishi Gas Chemicals, toluene solution of 65 mass % of solid content) was used.

Except for the above, a resin composition 7 was prepared in the same manner as in Example 1.

<Example 8: Preparation of resin composition 8>

In Example 7,

2 parts of vinyl benzyl resin ("OPE-2St" manufactured by Mitsubishi Gas Chemical Company, toluene solution having a solid content of 65% by mass), maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Corporation, toluene/MEK having a solid content of 70% by mass) solution) was replaced with 2 parts.

Except for the above, a resin composition 8 was prepared in the same manner as in Example 7.

<Example 9: Preparation of resin composition 9>

In Example 7,

2 parts of vinylbenzyl resin ("OPE-2St" by Mitsubishi Gas Chemical Company, toluene solution with a solid content of 65 mass %) was replaced with 1 part of maleimide resin ("BMI-689" by DMI).

Except for the above, a resin composition 9 was prepared in the same manner as in Example 7.

<Example 10: Preparation of resin composition 10>

In Example 7,

2 parts of vinyl benzyl resin ("OPE-2St" by Mitsubishi Gas Chemical Company, toluene solution of 65 mass % of solid content) was replaced with 1 part of maleimide-type resin ("BMI-1500" by DMI).

Except for the above, a resin composition 10 was prepared in the same manner as in Example 7.

<Comparative Example 1: Preparation of resin composition 11>

In Example 1, 25 parts of the active ester compound (B-1) was replaced with 25 parts of another curing agent (active ester curing agent, manufactured by DIC, "HPC8150-62T", 62% solid content toluene solution).

Except for the above, a resin composition 11 was prepared in the same manner as in Example 1.

<Comparative Example 2: Preparation of resin composition 12>

In Example 1, 25 parts of the active ester compound (B-1) was replaced with 23 parts of another curing agent (active ester curing agent, manufactured by DIC, "HPC8000-65T", 65% solid content toluene solution).

Except for the above, a resin composition 12 was prepared in the same manner as in Example 1.

<Comparative Example 3: Preparation of resin composition 13>

In Example 4, 22 parts of active ester compound (B-1) was replaced with 22 parts of other hardening|curing agents (active ester type hardening|curing agent, the DIC company make, "HPC8150-62T", toluene solution of 62% of solid content).

Except for the above, a resin composition 13 was prepared in the same manner as in Example 4.

<Comparative Example 4: Preparation of resin composition 14>

In Example 3, 22 parts of the active ester compound (B-2) were replaced with 21 parts of other curing agents (active ester curing agent, manufactured by DIC, "HPC8000-65T", 65% solid content toluene solution).

Except for the above, a resin composition 14 was prepared in the same manner as in Example 3.

<Evaluation of unevenness after lamination, arithmetic mean roughness, measurement of peeling strength of plated conductor layer>

(1) Preparation of resin sheet A having a thickness of the resin composition layer of 40 µm

As a support body, the polyethylene terephthalate film ("AL5" by Lintec company, 38 micrometers in thickness) provided with the mold release layer was prepared. On the release layer of this support body, the resin composition obtained by the Example and the comparative example was apply|coated uniformly so that the thickness of the resin composition layer after drying might be set to 40 micrometers. Then, the resin composition was dried at 80 degreeC - 100 degreeC (average of 90 degreeC) for 4 minutes, and the resin sheet A containing a support body and a resin composition layer was obtained.

(2) Preparation of the inner layer substrate

Both sides of the glass cloth base epoxy resin double-sided copper clad laminate (copper foil thickness 18 µm, substrate thickness 0.4 mm, Panasonic Corporation "R1515A") on which the inner-layer circuit was formed were coated with a micro-etchant ("CZ8101" manufactured by Mack Corporation) to 1 µm It etched and roughened the copper surface.

(3) Lamination of resin sheet A

Using a batch-type vacuum pressurizing laminator (manufactured by Nikko Materials, a two-stage build-up laminator "CVP700"), it laminated on both surfaces of the inner-layer substrate so that the resin composition layer was in contact with the inner-layer substrate. After lamination was pressure-reduced for 30 second and air pressure was adjusted to 13 hPa or less, it was performed by crimping|bonding at 120 degreeC and pressure 0.74 MPa for 30 second. Then, it hot-pressed for 60 second at 100 degreeC and the pressure of 0.5 MPa.

(4) thermosetting of the resin composition layer

Thereafter, the inner layer substrate on which the resin sheet A was laminated was put into an oven at 130° C. and heated for 30 minutes, then transferred to an oven at 170° C. and heated for 30 minutes, and the resin composition layer was thermosetted to form an insulating layer. . Then, the support body was peeled, and the cured substrate A which has an insulating layer, an inner-layer board|substrate, and an insulating layer in this order was obtained.

(5) Evaluation of stains after lamination

About both surfaces of the cured substrate A, observation of the surface uniformity of the part (surface on the opposite side to the laminated board) on which the resin sheet A was laminated was visually observed and evaluated as follows.

(circle): A nonuniformity is not observed at all, and it is a completely uniform surface.

x: A non-uniform part is observed in the part on which the resin sheet was laminated.

(6) Harmonization processing

The desmear process as a roughening process was performed to the hardened board|substrate A. As a desmear process, the following wet desmear process was implemented.

(Wet desmear treatment)

The cured substrate A was immersed in a swelling solution (“Swelling Deep Securigant P” manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60° C. for 5 minutes, followed by an oxidizing agent solution (Atotech Japan) It was immersed at 80 degreeC for 20 minute(s) in the "Concentrate Compact CP" manufactured by Tec Japan, an aqueous solution having a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%). Next, after immersing in the neutralizing liquid ("Reduction Solution Securigant P" manufactured by Atotech Japan, sulfuric acid aqueous solution) at 40 degreeC for 5 minutes, it dried at 80 degreeC for 15 minutes.

(7) Measurement of the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment

The arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment was calculated using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Bluka Corporation) in VSI mode and a 50x lens to a value obtained with a measurement range of 121 µm × 92 µm. saved by It measured by calculating|requiring the average value of 10 points|pieces, respectively.

(8) 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 substrate after roughening _{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 heating at 150 degreeC for 30 minutes and performing annealing process, the etching resist was formed, and it pattern-formed by etching. Then, copper sulfate electroplating was performed, the 25-micrometer-thick conductor layer was formed, and the annealing process was performed at 190 degreeC for 60 minutes. The obtained board|substrate is called "evaluation board|substrate B".

(9) Measurement of Peeling Strength of Plated Conductor Layer

The measurement of the peeling strength of an insulating layer and a conductor layer was performed based on Japanese Industrial Standards (JIS C6481). Specifically, in the conductor layer of the evaluation substrate B, a cutout of a portion having a width of 10 mm and a length of 100 mm is made, and this end is peeled off and picked up with a household tool, and 35 mm is peeled off in the vertical direction at a rate of 50 mm/min at room temperature. The load (kgf/cm) was measured to determine the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

<Evaluation of genetic characteristics>

The dielectric properties were evaluated by measuring the value of the dielectric loss tangent (Df). Specifically, the cured product B for evaluation was prepared as follows, and the dielectric loss tangent (Df) was measured.

The resin sheet A obtained by the Example and the comparative example was hardened|cured in 190 degreeC oven for 90 minutes. The hardened|cured material of the resin composition layer was obtained by peeling a support body from the resin sheet A taken out from oven. The hardened|cured material was cut out to 80 mm in length and 2 mm in width, and it was set as the hardened|cured material B for evaluation.

For each cured product B for evaluation, the value of the dielectric loss tangent (Df value) 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. ) was measured. It measured with two test pieces, and the average was computed.

<Measurement of copper foil adhesion (peel strength)>

(1) Preparation of substrate for adhesion evaluation

As the inner-layer substrate, a glass cloth-based epoxy resin double-sided copper clad laminate having a copper foil on the surface (copper foil thickness 18 µm, substrate thickness 0.8 mm, "R1515A" manufactured by Panasonic Corporation) was prepared. All the copper foils on the surface of the inner layer substrate were removed by etching. Then, drying was performed at 190 degreeC for 30 minutes.

The resin sheet A obtained in the above-mentioned Examples and Comparative Examples was subjected to a batch-type vacuum pressurization laminator (manufactured by Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700") so that the resin composition layer was bonded to the inner-layer substrate, Laminated on both sides of the inner layer substrate. This lamination was performed by pressure-reducing for 30 second and making atmospheric|air pressure 13 hPa or less, and then crimping|bonding for 30 second at the temperature of 100 degreeC, and the pressure of 0.74 MPa.

Next, the laminated resin sheet A was hot-pressed under atmospheric pressure, 100 degreeC, and the pressure of 0.5 MPa for 60 second, and it smoothed. Then, the support body was peeled, and "intermediate|middle multilayer body I" which contains a resin composition layer, an inner-layer board|substrate, and a resin composition layer in this order was obtained.

On the other hand, a copper foil having a glossy surface (thickness of 35 µm, "3EC-III" manufactured by Mitsui Kinzoku Co., Ltd.) was prepared. The gloss surface of this copper foil was etched by the copper etching amount of 1 micrometer using the micro-etching agent ("CZ8101" by Mack Corporation), and roughening process was performed. The copper foil obtained in this way is called "roughened copper foil."

This roughened copper foil was laminated on both surfaces of the intermediate|middle multilayer body I so that the surface which gave the roughening process of the said roughened copper foil might bond to the resin composition layer of the intermediate|middle multilayer body I. This lamination was performed under the same conditions as lamination|stacking of the resin sheet to the inner-layer board|substrate mentioned above. Thereby, "intermediate|middle multilayer body II" containing roughened copper foil, a resin composition layer, an inner-layer board|substrate, a resin composition layer, and roughened copper foil in this order was obtained.

This intermediate multilayer body II was put into an oven at 100° C. and heated for 30 minutes, then transferred to an oven at 170° C. and heated for 30 minutes. Next, the intermediate multilayer body II was taken out from the oven under room temperature atmosphere, and then further put into an oven at 200° C. and further heated for 90 minutes. Thereby, the resin composition layer is thermosetted, and the roughened copper foil, the insulating layer as the hardened|cured material of the resin composition layer, the inner layer substrate, the insulating layer as the hardened|cured material of the resin composition layer, and the "evaluation board|substrate containing the roughened copper foil in this order" C" was obtained. In this evaluation board|substrate C, roughened copper foil corresponds to a conductor layer.

(2) Measurement of copper foil adhesion (peel strength)

The peeling strength between roughened copper foil and an insulating layer was measured using said evaluation board|substrate C. The measurement of this peeling strength was performed based on JISC6481. The peeling strength was specifically, measured by the following operation.

In the roughened copper foil of the evaluation board|substrate C, the cutout surrounding the rectangular part of width 10mm and length 100mm was put. One end of this rectangular portion was peeled off and picked up with a household tool (manufactured by TSE Co., Ltd., Autocom-type testing machine "AC-50C-SL"). A range of 35 mm in length of the rectangular portion was removed in the vertical direction, and the load (kgf/cm) at the time of peeling was measured as the peeling strength. The said peeling was performed at room temperature at the speed|rate of 50 mm/min. Moreover, copper foil adhesiveness (peel strength) was measured again after a HAST test (130 degreeC, humidity 85%RH, 100 hours).

In Examples 1 to 10, it was confirmed that even in the case where component (C) to component (E) was not contained, the same result as in the above example was obtained, although there was a difference in the degree.

Claims (10)

(A) an epoxy resin, and
(B) an active ester compound having at least one of the groups represented by the following formulas (1) to (3)
A resin composition containing

(In the above formula, * represents a bond. In formula (3), n represents an integer of 1 to 5) The resin composition according to claim 1, wherein the component (B) is an active ester compound represented by the following general formula (b-1).

(In general formula (b-1),
Ar ¹¹ each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3),
Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent,
Ar ¹³ each independently represents a divalent group consisting of a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a combination thereof. a represents an integer from 1 to 6, b represents an integer from 0 to 10) ^{The resin composition according to claim 2, wherein Ar 13} in the general formula (b-1) each independently represents a divalent group obtained by combining a divalent aromatic hydrocarbon group which may have a substituent and an oxygen atom. The resin composition according to claim 1, wherein the component (B) is an active ester compound represented by the following general formula (b-3).

(In general formula (b-3),
Ar ³¹ each independently represents the group represented by the formula (1), the group represented by the formula (2), or the group represented by the formula (3). a2 represents an integer of 1 to 6, c2 represents an integer of 1 to 5, and d each independently represents an integer of 0 to 6) The resin composition according to claim 1, further comprising (C) an inorganic filler. The resin composition according to claim 1, which is for forming an insulating layer. The resin composition according to claim 1, which is for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 7 provided on the support. The printed wiring board containing the insulating layer formed with the hardened|cured material of the resin composition in any one of Claims 1-7. A semiconductor device comprising the printed wiring board according to claim 9 .