KR20220014835A - Resin composition - Google Patents

Abstract

The present invention provides a resin composition and the like from which a cured product with low dielectric properties and excellent adhesion between copper foils can be obtained. The present invention comprises the resin composition comprising: (A) a polyether ether ketone compound with a maleimide group, and; (B) a resin containing an aromatic ring and a radically polymerizable unsaturated group.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. Moreover, this invention relates to 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 buildup method which piles up an insulating layer and a conductor layer alternately is known. In the manufacturing method by a build-up system, generally, an insulating layer hardens a resin composition, and is formed. As such a resin composition, the resin composition disclosed by patent document 1 is known, for example.

[Patent Document 1] Japanese Patent Laid-Open No. 2019-66792

The cured product formed by curing the resin composition can be used as an insulating layer of a printed wiring board of a semiconductor device. Accordingly, it is required to lower the dielectric properties (dielectric constant and dielectric loss tangent) of the cured product. Moreover, it is preferable that the insulating layer formed with this hardened|cured material is excellent in adhesiveness between copper foils.

This invention was created in view of said subject, It is a resin composition from which a hardened|cured material with a low dielectric characteristic and excellent in adhesiveness between copper foil can be obtained; a resin sheet comprising a resin composition layer comprising the resin composition; a printed wiring board including an insulating layer formed of a cured product of the resin composition; and a semiconductor device including the printed wiring board. aims to provide

As a result of the present inventors earnestly examining in order to solve the said subject, this inventor uses the resin containing (A) a polyether ether ketone compound which has a maleimide group, and (B) an aromatic ring and a radically polymerizable unsaturated group It discovered that said subject could be solvable by doing, and this invention was completed.

That is, the present invention includes the following.

[1] (A) a polyether ether ketone compound having a maleimide group, and

(B) A resin composition comprising a resin containing an aromatic ring and a radically polymerizable unsaturated group.

[2] The resin composition according to [1], wherein the number average molecular weight of the component (A) is 10000 or less.

[3] The resin composition according to [1] or [2], wherein the component (A) has a maleimide group at the terminal.

[4] The resin composition according to any one of [1] to [3], wherein the content of the component (A) is 5% by mass or more and 60% by mass or less when the resin component in the resin composition is 100% by mass.

[5] of [1] to [4], wherein the component (B) contains any one of a maleimide radical polymerizable compound containing a maleimide group and a vinylphenyl radical polymerizable compound containing a vinylphenyl group The resin composition as described in any one.

[6] The resin composition according to any one of [1] to [5], wherein the content of the component (B) is 20% by mass or more and 60% by mass or less when the resin component in the resin composition is 100% by mass.

[7] The resin composition according to any one of [1] to [6], further comprising (C) an inorganic filler.

[8] The resin composition according to [7], wherein the content of the component (C) is 30% by mass or more and 80% by mass or less when the nonvolatile component in the resin composition is 100% by mass.

[9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer.

[10] The resin composition according to any one of [1] to [9], which is for forming an insulating layer for forming a conductor layer.

[11] 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 [10].

[12] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [10].

[13] A semiconductor device comprising the printed wiring board according to [12].

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the hardened|cured material which has a low dielectric characteristic and is excellent in the adhesiveness between copper foil; a resin sheet comprising a resin composition layer comprising the resin composition; a printed wiring board including an insulating layer formed of a cured product of the resin composition; and a semiconductor device including the printed wiring board. can provide

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below by showing embodiments and examples. However, this invention is not limited to the embodiment and illustration shown below, The range which does not deviate from the range which does not deviate from the range which does not deviate from the claim of this invention and its equivalent can be implemented by changing arbitrarily.

[resin composition]

The resin composition of this invention contains resin containing (A) the polyether ether ketone compound which has a maleimide group, and (B) an aromatic ring and a radically polymerizable unsaturated group. According to such a resin composition, the hardened|cured material excellent in adhesiveness with copper foil with a low dielectric characteristic can be obtained.

The resin composition may further contain arbitrary components, such as (C) inorganic filler, (D) polymerization initiator, (E) thermoplastic resin, (F) elastomer, and (G) other additives as needed.

<(A) polyether ether ketone compound having maleimide group>

The resin composition contains, as component (A), a polyether ether ketone compound having a maleimide group. The maleimide group is represented by the following formula (A-1). By containing component (A) in a resin composition, the hardened|cured material excellent in adhesiveness with copper foil with a low dielectric characteristic can be obtained.

Formula (A-1)

(A) component can use the compound which has a maleimide group and has a polyether ether ketone structure. It is preferable to have 1 or more per (A) component molecule, It is more preferable to have 2 or more, It is preferable to have 10 or less, It is more preferable to have 5 or less, It is more preferable to have 3 or less. It is preferable to have a maleimide group at the terminal of (A) component from a viewpoint of obtaining the hardened|cured material excellent in dielectric properties, and, as for a maleimide group, it is more preferable to have a maleimide group at both terminals.

(A) Component has a polyether ether ketone structure. As the polyether ether ketone structure, it is preferable to have a structure represented by the following general formula (A-2).

Formula (A-2)

In Formula (A-2), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , and Ar ⁵ each independently represent a divalent aromatic hydrocarbon group. n represents the integer of 2-50. * indicates a bond.

An aromatic hydrocarbon group represents the hydrocarbon group containing an aromatic ring. However, the aromatic hydrocarbon group does not need to be constituted of only an aromatic ring, and may contain a chain structure or an alicyclic hydrocarbon group in a part thereof, and the aromatic ring may be any one of monocyclic, polycyclic and heterocyclic rings.

Examples of the divalent aromatic hydrocarbon group include an arylene group, an aralkylene group, and a group having an arylene-alkylene-arylene structure.

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.

The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and still more preferably an aralkylene group having 7 to 15 carbon atoms. Examples of such an aralkylene group include a benzylene group and a group having a biphenylene-methylene structure.

Arylene in the group having an arylene-alkylene-arylene structure is the same as the above-described arylene group. As alkylene, a C1-C10 alkylene group is preferable, a C1-C6 alkylene group is more preferable, A C1-C3 alkylene group is still more preferable. As such alkylene, methylene, ethylene, propylene, etc. are mentioned, for example. Moreover, alkylene may have a substituent. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; A halogenated alkyl group etc. are mentioned, A C1-C3 alkyl group and halogenated alkyl group are preferable, a methyl group and a trifluoromethyl group are more preferable, and a methyl group is still more preferable. Specific examples of the group having such an arylene-alkylene-arylene structure include structures represented by the following formulas (1) to (2). Among them, the group represented by the general formula (1) is preferable.

Formula (1)

Formula (2)

In the formula, "*" represents a bond.

Among these, as Ar ¹ , Ar ² , Ar ⁴ , and Ar ⁵ , an arylene group or a group having an arylene-alkylene-arylene structure is preferable, an arylene group is more preferable, and a phenylene group is still more preferable. Ar ³ is preferably an arylene group or a group having an arylene-alkylene-arylene structure, more preferably a group having an arylene-alkylene-arylene structure, and a phenylene-dimethylmethylene-phenylene structure A group (group represented by the general formula (1)) is more preferable.

n represents the integer of 2-50, Preferably the integer of 3-40 is shown, More preferably, the integer of 4-30 is shown, More preferably, the integer of 5-20 is shown.

Specific examples of the structure represented by the formula (A-2) include, but are not limited to, structures represented by the following formulas (A1) to (A2) (in the formula, * is a bond represents).

Formula (A1)

Formula (A2)

n1 and n2 are the same as n in the formula (A-2).

(A) As a component, it is preferable that it is a compound represented by following formula (A-3).

Formula (A-3)

In the formula, D ¹ and D ² each independently represent a single bond or a divalent linking group. Ar ¹¹ , Ar ¹² , Ar ¹⁴ , and Ar ¹⁵ are each independently the same as Ar ¹ , Ar ² , Ar ⁴ , and Ar ⁵ in Formula (A-2). Ar ¹³ is each independently the same as Ar ³ in formula (A-2). m is the same as n in the formula (A-2).

D ¹ and D ² each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and a group in which a plurality of these are linked. The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group.

As a divalent aliphatic hydrocarbon group, a C1-C18 linear or branched alkylene group, a C2-C18 linear or branched alkenylene group, etc. are mentioned, for example. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. As a C2-C18 linear or branched alkenylene group, a vinylene group, 1-methylvinylene group, propenylene group, 1-butenylene group, 2-butenylene group etc. are mentioned, for example.

Examples of the divalent alicyclic hydrocarbon group include a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, for example, a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, Cycloalkylene groups (including a cycloalkylidene group), such as a 1,2-cyclohexylene group, a 1, 3- cyclohexylene group, a 1, 4- cyclohexylene group, and a cyclohexylidene group, etc. are mentioned.

As a divalent aromatic hydrocarbon group, a C6-C14 arylene group etc. are mentioned, for example, For example, a 1,2-phenylene group, a 1, 4- phenylene group, a 1, 3- phenylene group, 4 ,4'-biphenylene group, 3,3'-biphenylene group, 2,6-naphthylene group, 2,7-naphthylene group, 1,8-naphthylene group, anthracenylene group, etc. are mentioned.

An aromatic heterocycle and a non-aromatic heterocycle are contained in the heterocycle constituting the divalent heterocyclic group. Examples of the heterocycle include 3- to 10-membered rings having a carbon atom and at least one heteroatom in atoms constituting the ring, condensed rings thereof, and the like. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example. A 3-10 membered ring is preferable and, as for a heterocyclic ring, a 4-6 membered ring is more preferable. As a heterocyclic ring which comprises a bivalent heterocyclic group, For example, 3-membered rings, such as an oxirane ring; 4-membered rings, such as an oxetane ring; Furan ring, tetrahydrofuran ring, oxazole ring, isoxazole ring, γ-butyrolactone ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, pyrrole ring, pyrrolidine ring, pyrazole ring, imidazole ring , 5-membered rings such as triazole rings; 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring, 4-oxo-4H-thiopyran ring, isocyanuric ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring , 6-membered rings such as piperazine ring; bridging rings such as 3-oxatricyclo[4.3.1.1 ^4,8 ]undecan-2-one ring and 3-oxatricyclo[4.2.1.0 ^4,8 ]nonan-2-one ring; Benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring, isochroman ring, benzothiophene ring, indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring Condensed rings, such as a purine ring, etc. are mentioned. The divalent heterocyclic group is a group obtained by removing two hydrogen atoms from the structural formula of the heterocyclic ring.

Among them, D ¹ and D ² preferably represent a divalent aromatic hydrocarbon group from the viewpoint of significantly obtaining the effects of the present invention, more preferably an arylene group having 6 to 16 carbon atoms, a 1,2-phenylene group; 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, 3,3'-biphenylene group, 2,6-naphthylene group, 2,7-naphthylene group, 1, It is more preferable to represent an 8-naphthylene group or an anthracenylene group, and it is particularly preferable to represent a 1,2-phenylene group, a 1,4-phenylene group, or a 1,3-phenylene group.

(A) Although the following are mentioned as a specific example of a component, this invention is not limited to this. In the following formula, na and nb each independently represent an integer of 2 to 50.

Formula Ai

Formula Aii

(A) As a component, a commercially available thing may be used and what was synthesize|combined by a well-known method may be used for it. (A) As a synthesis|combining method of a component, it can synthesize|combine using the synthesis method described in Polymer 1989, p.978, for example. (A) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(A) The weight average molecular weight of the component is preferably 1000 or more, more preferably 1200 or more, still more preferably 1400 or more, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to copper foil. Preferably it is 10000 or less, More preferably, it is 7500 or less, More preferably, it is 5000 or less.

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 number average molecular weight of the component is preferably 1000 or more, more preferably 1200 or more, still more preferably 1400 or more, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to copper foil. Preferably it is 10000 or less, More preferably, it is 7500 or less, More preferably, it is 5000 or less.

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

(A) As content of component, when the non-volatile component in a resin composition is 100 mass % from a viewpoint of obtaining the hardened|cured material which has low dielectric characteristic and excellent adhesiveness with copper foil, Preferably it is 5 mass % or more, More preferably Preferably it is 10 mass % or more, More preferably, it is 15 mass % or more, 20 mass % or more, Preferably it is 40 mass % or less, More preferably, it is 35 mass % or less, More preferably, it is 30 mass % or less.

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

(A) As content of component, when the resin component in a resin composition is 100 mass % from a viewpoint of obtaining the hardened|cured material which has low dielectric characteristic and is excellent in adhesiveness with copper foil, Preferably it is 5 mass % or more, More preferably is 10 mass % or more, more preferably 20 mass % or more, 30 mass % or more, 40 mass % or more, preferably 60 mass % or less, more preferably 55 mass % or less, still more preferably 50 mass % or more. is below. A resin component means the component except the (C) inorganic filler among the nonvolatile components in a resin composition.

<(B) Resin containing an aromatic ring and a radically polymerizable unsaturated group>

A resin composition contains resin containing an aromatic ring and a radically polymerizable unsaturated group as (B) component. However, (B) component excludes the thing corresponding to (A) component. (B) By containing resin containing an aromatic ring and a radically polymerizable unsaturated group in a resin composition, the hardened|cured material which has a low dielectric characteristic and is excellent in adhesiveness with copper foil can be obtained.

As component (B), resin which contains an aromatic ring and a radically polymerizable unsaturated group in a molecule|numerator can be used. (B) An aromatic hydrocarbon ring may be sufficient as the aromatic ring contained in component, and an aromatic heterocyclic ring may be sufficient as it. In addition, the aromatic ring may be a monocyclic aromatic ring, or may be a condensed aromatic ring obtained by condensing two or more monocyclic aromatic rings, or may be a condensed aromatic ring obtained by condensing one or more monocyclic aromatic rings to one or more monocyclic aromatic rings. Directional rings are also good. As these aromatic rings, For example, monocyclic aromatic rings, such as a benzene ring and a pyridine ring; Condensed aromatic rings, such as an indan ring, a fluorene ring, and a naphthalene ring; can be heard Especially, as for an aromatic ring, an aromatic carbocyclic ring is preferable. The number of carbon atoms in the aromatic carbocyclic ring is preferably 6 or more and 10 or less.

(B) A substituent may couple|bond with the aromatic ring contained in component. One may be sufficient as the number of the substituent couple|bonded with one aromatic ring, and 2 or more may be sufficient as it. When the number of substituents is two or more, these two or more substituents may be same or different.

Examples of the substituent include an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a halogen atom, a hydroxyl group, and a mercapto group.

The number of carbon atoms in the alkyl group is preferably 1 to 10. As an alkyl group, a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group, etc. are mentioned, for example.

The number of carbon atoms in the alkyloxy group is preferably 1 to 10. As an alkyloxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example.

The number of carbon atoms in the alkylthio group is preferably 1 to 10. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group.

The number of carbon atoms in the aryl group is preferably 6 to 10. As an aryl group, a phenyl group, a naphthyl group, etc. are mentioned, for example.

The number of carbon atoms in the aryloxy group is preferably 6 to 10. As an aryloxy group, a phenyloxy group, a naphthyloxy group, etc. are mentioned, for example.

The number of carbon atoms in the arylthio group is preferably 6 to 10. As an arylthio group, a phenylthio group, a naphthylthio group, etc. are mentioned, for example.

The number of carbon atoms in the cycloalkyl group is preferably 3 to 10. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

As a halogen atom, a fluorine atom, a chlorine atom, an iodine atom, etc. are mentioned, for example.

Especially, as for the aromatic ring which (B) component contains, it is preferable that the substituent is not couple|bonded, or that the alkyl group has couple|bonded.

(B) The number of the aromatic rings contained in component is 1 or more normally, Preferably it is 2 or more. (B) When a component contains two or more aromatic rings, these two or more aromatic rings may be same or different.

The radically polymerizable unsaturated group contained in the component (B) represents a group containing an unsaturated bond exhibiting radical polymerizability, and the radically polymerizable unsaturated group is a divalent group having an unsaturated bond in the molecular skeleton of the component (B). It is also a concept that includes As this radically polymerizable unsaturated group, the group containing an ethylenic double bond is mentioned, for example. (B) component containing such a radically polymerizable unsaturated group can generate|occur|produce radical polymerization with a heat|fever or an active energy ray, and can harden a resin composition.

Examples of the radical polymerizable unsaturated group include a maleimide group, a vinyl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, a maleoyl group, a benzocyclobutene group, and an allyl group. . (B) The number of the radically polymerizable unsaturated groups which a component contains is 1 or more normally, Preferably it is 2 or more. (B) When a component contains two or more radically polymerizable unsaturated groups, these two or more radically polymerizable unsaturated groups may be same or different.

(B) As a component, what is necessary is just resin containing an aromatic ring and a radically polymerizable unsaturated group. (B) As a component,

(B1) a resin containing a vinyl group and an aromatic ring;

(B2) a resin containing a maleimide group and an aromatic ring, and

(B3) a resin containing a radically polymerizable unsaturated group and benzocyclobutene

It is preferable that at least one selected from

(B) A component may be used individually by 1 type, and may be used in combination of 2 or more type. For example, you may use combining (B1) component and (B2) component.

-(B1) Resin containing a vinyl group and an aromatic ring-

Since component (B1) is resin which belongs to component (B), it is resin containing the vinyl group as a radically polymerizable unsaturated group, and an aromatic ring. (B1) A component may be used individually by 1 type, and may be used in combination of 2 or more type. (B1) One may be sufficient as the number of vinyl groups per molecule of component, and two or more may be sufficient, and two are preferable.

(B1) One embodiment of the component includes a group represented by the following general formula (B1-1).

Formula (B1-1)

In formula (B1-1), R ^A1 , R ^A2 and R ^A3 each independently represent a hydrogen atom or an alkyl group; R ^A4 each independently represents an alkyl group; m _a1 represents 0 or 1; m _a2 represents an integer of 0 to 4; * represents a bond.

In formula (B1-1), R ^A1 , R ^A2 and R ^A3 each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 6, particularly preferably 1 to 2. The alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a t-butyl group. Among them, a hydrogen atom or a methyl group is preferable for R ^A1 , and a hydrogen atom is preferable for R ^A2 and R ^A3 .

In general formula (B1-1), R ^A4 each independently represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 2. The alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a t-butyl group. Among them, R ^A1 is preferably a methyl group.

In general formula (B1-1), m _a1 represents 0 or 1. When R ^A1 is a hydrogen atom, m _a1 is preferably 0. Further, when R ^A1 is an alkyl group, _ma 1 is preferably 1.

In general formula (B1-1), m _a2 represents the integer of 0-4. m _a2 is preferably 0 to 2.

(B1-1) The component may contain one group represented by the general formula (B1-1) per molecule, but it is preferable to include two or more.

(B1-1) As a component, the compound containing a vinyl group and polyphenylene ether skeleton is preferable. As a component (B1-1) containing a polyphenylene ether skeleton, the compound represented by the following general formula (B1-2) is mentioned.

Formula (B1-2)

In formula (B1-2), L ¹ represents a divalent linking group; R ^B11 , R ^B12 , R ^B13 , R ^B21 , R ^B22 and R ^B23 each independently represent a hydrogen atom or an alkyl group; R ^B14 , R ^B15 , R ^B24 and R ^B25 each independently represent an alkyl group; R ^B16 and R ^B26 each independently represent an alkylene group; m _b11 and m _b21 each independently represent 0 or 1; m _b12 , m _b13 , m _b22 and m _b23 each independently represent an integer of 0 to 4; m _b14 and m _b24 each independently represent an integer of 0 to 300; m _b15 and m _b25 each independently represent 0 or 1.

In the general formula (B1-2), L ¹ represents a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, an alkylarylene group, a heteroarylene group, -O-, -NH-, -NR ^x -, -CO-, -CS-, -SO -, -SO ₂ -, -C(=O)O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S- and the group which combined these two or more are mentioned. R ^x represents a hydrocarbyl group having 1 to 12 carbon atoms. The carbon atom number of L< ¹ > is 60 or less normally, More preferably, it is 48 or less, More preferably, it is 36 or less, Especially preferably, it is 24 or less.

In formula (B1-2), R ^B11 , R ^B12 , R ^B13 , R ^B21 , R ^B22 and R ^B23 each independently represent a hydrogen atom or an alkyl group. R ^B11 , R ^B12 , R ^B13 , R ^B21 , R ^B22 and R ^B23 may be the same as R ^A1 , R ^A2 and R ^A3 in Formula (B1-1). Among them, a hydrogen atom or a methyl group is preferable for ^RB11 and ^RB21 , and a hydrogen atom is preferable for ^RB12 , R ^B13 , ^RB22 and ^RB23 .

In formula (B1-2), R ^B14 , R ^B15 , R ^B24 and R ^B25 each independently represent an alkyl group. R ^B14 , R ^B15 , R ^B24 and R ^B25 may be the same as R ^A4 in Formula (B1-1). Among them, R ^B14 , R ^B15 , R ^B24 and R ^B25 are preferably a methyl group.

In formula (B1-2), R ^B16 and R ^B26 each independently represent an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3. As an alkylene group, a linear alkylene group is preferable and a methylene group is more preferable.

In the formula (B1-2), m _b11 and m _b21 each independently represent 0 or 1.

In general formula (B1-2), m _b12 , m _b13 , m _b22 and m _b23 each independently represent an integer of 0-4. m _b12 , m _b13 , m _b22 and m _b23 are preferably 1 to 4, more preferably 2 to 3, particularly preferably 2.

In the formula (B1-2), m _b14 and m _b24 each independently represent an integer of 0 to 300. Specifically, m _b14 and m _b24 are usually 0 or more, preferably 1 or more, and usually 300 or less, preferably 100 or less, more preferably 50 or less, still more preferably 20 or less, particularly preferably less than 10.

In the formula (B1-2), m _b15 and m _b25 each independently represent 0 or 1. When m _b11 is 0, m _b15 is preferably 1, and when m _b11 is 1, m _b15 is preferably 0. Further, when m _b21 is 0, m _b25 is preferably 1, and when m _b21 is 1, m _b25 is preferably 0.

Preferred examples of the compound represented by the formula (B1-2) include a compound represented by the following formula (B1-3).

Formula (B1-3)

In formula (B1-3), L ² represents a divalent linking group; R ^C15 and R ^C25 each independently represent an alkyl group; R ^C16 and R ^C26 each independently represent an alkylene group; m _c14 and m _c24 each independently represent an integer of 0 to 300.

In the general formula (B1-3), L ² represents a divalent linking group. L ² may be the same as L ¹ in Formula (B1-2). Among them, L ² is preferably a divalent group represented by the following general formula (B1-4).

Formula (B1-4)

In the formula (B1-4), X ¹ to X ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. * represents a bond.

In formula (B1-3), R ^C15 and R ^C25 each independently represent an alkyl group. R ^C15 and R ^C25 may be the same as R ^A4 in Formula (B1-1). Among them, R ^C15 and R ^C25 are preferably a methyl group.

In formula (B1-3), R ^C16 and R ^C26 each independently represent an alkylene group. R ^C16 and R ^C26 may be the same as R ^B16 and R ^B26 in Formula (B1-2). Among them, R ^C16 and R ^C26 are more preferably a methylene group.

In the formula (B1-3), m _c14 and m _c24 each independently represent an integer of 0 to 300. m _c14 and m _c24 may be the same as m _b14 and m _b24 in Formula (B2). Further, in the general formula (B1-3), preferably, a configuration in which one of m _c14 and m _c24 is 0 is excluded.

Examples of the compound represented by the formula (B1-3) include a compound represented by the following formula (B1-5). In the formula (B1-5), m _c14 and m _c24 represent the same numbers as in the formula (B1-3). The compound represented by the general formula (B1-5) can be obtained as "OPE-2St" manufactured by Mitsubishi Gas Chemical.

Formula (B1-5)

As another preferred example of the compound represented by the formula (B1-2), a compound represented by the following formula (B1-6) is exemplified.

Formula (B1-6)

In general formula (B1-6), L ³ represents a divalent linking group; R ^D11 and R ^D21 each independently represent a hydrogen atom or an alkyl group; R ^D14 , R ^D15 , R ^D24 and R ^D25 each independently represent an alkyl group; m _d14 and m _d24 each independently represent the integer of 0-300.

In the general formula (B1-6), L ³ represents a divalent linking group. L ³ may be the same as L ¹ in Formula (B1-2). Among them, L ³ is preferably any one selected from the group consisting of an alkylene group, an alkenylene group, -O-, -NR ^x -, -CO-, -CS-, -SO-, -SO ₂ - and an alkylene group is preferable, and an isopropylidene group (-C(CH ₃ ) ₂ -) is particularly preferable.

In the formula (B1-6), R ^D11 and R ^D21 each independently represent a hydrogen atom or an alkyl group. R ^D11 and R ^D21 may be the same as R ^B11 and R ^B21 in Formula (B1-2). Among them, R ^D11 and R ^D21 are preferably a methyl group.

In formula (B1-6), R ^D14 , R ^D15 , R ^D24 and R ^D25 each independently represent an alkyl group. R ^D14 , R ^D15 , R ^D24 and R ^D25 may be the same as R ^A4 in formula (B1-1). Among them, R ^D14 , R ^D15 , R ^D24 and R ^D25 are preferably a methyl group.

In the formula (B1-6), m _d14 and m _d24 each independently represent an integer of 0 to 300. m _d14 and m _d24 may be the same as m _b14 and m _b24 in Formula (B1-2). Moreover, it is preferable that the sum total of m _b14 and m _b24 is 2 or more.

Examples of the compound represented by the formula (B1-6) include a compound represented by the following formula (B1-7). In the formula (B1-7), L ³ , m _d14 and m _d24 are the same as in the formula (B1-6). The compound represented by general formula (B1-7) can be obtained as "NORYL SA9000" by SABIC.

Formula (B1-7)

(B1-1) Another embodiment of the component is a polymer including a structural unit represented by the following general formula (B1-8).

Formula (B1-8)

In the formula (B1-8), R ^E1 , R ^E2 and R ^E3 each independently represent a hydrogen atom or an alkyl group; R ^E4 each independently represents an alkyl group; R ^E5 , R ^E6 and R ^E7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m _e1 represents 0 or 1; m _e2 represents an integer of 0 to 4; * represents a bond.

In the formula (B1-8), R ^E1 , R ^E2 and R ^E3 each independently represent a hydrogen atom or an alkyl group. R ^E1 , R ^E2 and R ^E3 may be the same as R ^A1 , R ^A2 and R ^A3 in Formula (B1-1). Among them, R ^E1 , R ^E2 , and R ^E3 are preferably a hydrogen atom.

In general formula (B1-8), R ^E4 each independently represents an alkyl group. R ^E4 may be the same as R ^A4 in Formula (B1-1).

In the formula (B1-8), R ^E5 , R ^E6 , and R ^E7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, R ^E5 , R ^E6 , and R ^E7 are preferably a hydrogen atom.

In general formula (B1-8), m _e1 represents 0 or 1, Preferably it is 0.

In general formula (B1-8), m _e2 represents the integer of 0-4, Preferably it is 0.

The molar content of the structural unit represented by the formula (B1-8) with respect to 100 mol% in total of the total structural units contained in the polymer including the structural unit represented by the formula (B1-8) is within a specific range. desirable. Specifically, the molar content of the structural unit represented by the formula (B1-8) is preferably 2 mol% to 95 mol%, more preferably 8 mol% to 81 mol%. Moreover, it is preferable that it is 1-160, and, as for the average number of the structural units represented by general formula (B1-8) which one molecule of said polymer contains, it is more preferable that it is 3-140.

The polymer including the structural unit represented by the general formula (B1-8) may further include any structural unit in combination with the structural unit represented by the general formula (B1-8). Examples of the optional structural unit include a structural unit represented by the following formula (B1-9).

Formula (B1-9)

In the formula (B1-9), R ^E8 , R ^E9 and R ^E10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ar ^E1 represents an aryl group which may have a substituent. Examples of the substituent Ar ^E1 may have include an alkyl group having 1 to 6 carbon atoms. * represents a bond.

Examples of the polymer comprising the structural unit represented by the formula (B1-9) include a structural unit represented by the following formula (B1-10), a structural unit represented by the following formula (B1-11), and and a copolymer comprising a combination of structural units represented by the general formula (B1-12). In general formula (B1-10), general formula (B1-11), and general formula (B1-12), * represents a bond. In this copolymer, the molar content of the structural unit represented by the formula (B1-10), the structural unit represented by the formula (B1-11), and the structural unit represented by the formula (B1-12) is, 8 mol% to 54 mol%, 0 mol% to 92 mol%, 0 mol% to 89 mol%. In addition, the average number of structural units represented by formula (B1-10), structural units represented by formula (B1-11), and structural units represented by formula (B1-12) in one molecule of this copolymer is 1 to 160, 0 to 350 and 0 to 270, respectively. This copolymer can be obtained as "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" manufactured by Nittetsu Chemical & Materials.

Formula (B1-10)

Formula (B1-11)

Formula (B1-12)

(B1) A component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

(B1) The vinyl group equivalent of component becomes like this. Preferably it is 250 g/eq. to 1200 g/eq., more preferably 300 g/eq. to 1100 g/eq. A radically polymerizable unsaturated group equivalent shows the mass of radically polymerizable aromatic resin per 1 equivalent of a vinyl group. When the radically polymerizable unsaturated group equivalent of the component (B1) is within the above range, the effects of the present invention can be significantly obtained.

(B1) The weight average molecular weight of a component becomes like this. Preferably it is 1000-40000, More preferably, it is 1500-35000. The weight average molecular weight of resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

-(B2) resin containing maleimide group and aromatic ring-

Since component (B2) is resin which belongs to component (B), it is resin containing a maleimide group as a radically polymerizable unsaturated group, and an aromatic ring. However, as for (B2) component, the thing corresponding to (A) component is excluded. (B2) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(B2) One may be sufficient as the number of maleimide groups per molecule of a component, and two or more may be sufficient, and two are preferable. The maleimide group is as described above.

(B2) As a component,

(B2-1) a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide group and an aromatic ring;

(B2-2) a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group, and

(B2-3) a maleimide compound comprising a trimethylindane skeleton;

It is preferable that at least one selected from

Here, the term "direct" means that in the component (B2-1), there is no other group between the nitrogen atom of the maleimide group and the aliphatic group having 5 or more carbon atoms, and in the component (B2-2), maleimide It means that there is no other group between the nitrogen atom of the imide and the aromatic ring.

{(B2-1) component}

(B2-1) A component is a maleimide compound containing the C5 or more aliphatic group and aromatic ring directly couple|bonded with the nitrogen atom of maleimide. The component (B2-1) can be obtained by, for example, imidizing a component containing an aliphatic amine compound (such as a diamine compound having a dimer acid skeleton), maleic anhydride, and, if necessary, tetracarboxylic dianhydride. have.

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 carbon atoms in the alkyl 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. Any of linear, branched, and cyclic|annular form may be sufficient as this alkyl group, and linear is especially preferable. As such an alkyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group etc. are mentioned, for example. The C5 or more alkyl group may have as a substituent of the C5 or more alkylene group.

The number of carbon atoms in the alkylene 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. Linear, branched or cyclic any may be sufficient as this alkylene group, and linear is especially preferable. Here, the cyclic alkylene group is a concept that includes both a case consisting of a cyclic alkylene group and a case containing both a linear alkylene group and a cyclic alkylene group. Examples of such an alkylene group include a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, and a hexatriacone group. The group which has a tylene group, the group which has an octylene-cyclohexylene structure, the group which has an octylene-cyclohexylene-octylene structure, and a propylene-cyclohexylene-octylene structure, etc. are mentioned.

The number of carbon atoms in the alkenylene 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. Linear, branched, or cyclic any may be sufficient as this alkenylene group, and linear is especially preferable. Here, the cyclic alkenylene group is a concept that includes both a case consisting of only a cyclic alkenylene group and a case containing both a linear alkenylene group and a cyclic alkenylene group. As such an alkenylene group, for example, pentynylene group, hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecinylene group, dodecinylene group, tridecinylene group, hepta Decynylene group, hexatriacontinylene group, octynylene-cyclohexynylene group having a structure, octynylene-cyclohexynylene-octynylene structure having a group, propynylene-cyclohexynylene-octynylene structure having a structure and the like.

(B2-1) As a component, the compound represented by the following general formula (B2-1-1) is preferable.

Formula (B2-1-1)

In the general formula (B2-1-1), 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. However, any one of the substituent and L which M has contains an aromatic ring.

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. Linear, branched, or cyclic any may be sufficient as this aliphatic group, and linear is especially preferable. Here, the cyclic aliphatic group is a concept that includes both a case composed of only a cyclic aliphatic group and a case containing both a linear aliphatic group and a cyclic aliphatic group. As a divalent aliphatic group, an alkylene group, an alkenylene group, etc. are mentioned. The alkylene group and the alkenylene group are as described above.

Examples of the substituent for M include a halogen atom, -OH, -OC _1-10 alkyl group, -N(C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _6-10 aryl group, -NH ₂ , -CN, -C(O)OC _1-10 alkyl group, -COOH, -C(O)H, -NO ₂ , and the like. Here, the term “C _xy ” (x and y are positive integers, satisfying x<y) indicates that the number of carbon atoms in the organic group described immediately after this term is x to y. 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. 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 general formula (B2-1-2). The divalent group derived from pyromellitic acid diimide represents a divalent group derived from pyromellitic acid diimide, and is specifically a group represented by general formula (B2-1-3). In the formula, "*" represents a bond.

General formula (B2-1-2)

General formula (B2-1-3)

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 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 50 carbon atoms, more preferably an alkenylene group having 2 to 45 carbon atoms, particularly preferably an alkenylene group having 2 to 40 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 50 carbon atoms, more preferably an alkynylene group having 2 to 45 carbon atoms, particularly preferably an alkynylene group having 2 to 40 carbon atoms. do. Any of linear, branched, and cyclic|annular form may be sufficient as this alkynylene group. Examples of the alkynylene group include a methylethynylene group, a cyclohexynylene group, a pentynylene group, a hexynylene group, a heptynylene group, and an 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, it is the same as the substituent of M in general formula (B2-1-1), Preferably it is a C5 or more alkyl group.

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; a divalent group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; and the like. 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 repeating unit of 1-10 repeating units 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 (B2-1-1), 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 carbon It is preferable that the number of atoms is a divalent group composed of an alkyl group having 5 or more atoms, 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, as L, an alkylene group; a divalent group having the structure of an alkylene group-phthalimide-derived divalent group-oxygen atom- a phthalimide-derived divalent group; a divalent group having a 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; a divalent group having a structure of alkynylene group-phthalimide-derived divalent group-oxygen atom-phthalimide-derived divalent group; a divalent group having a structure of alkynylene group-phthalimide-derived divalent group-oxygen atom-arylene group-alkynylene group-arylene group-oxygen atom-phthalimide-derived divalent group; A divalent group having a structure of a divalent group derived from alkynylene-pyromellitic diimide is more preferable.

It is preferable that maleimide resin represented by general formula (B2-1-1) is maleimide resin represented by general formula (B2-1-4).

General formula (B2-1-4)

In the general formula (B2-1-4), 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 a divalent aliphatic group having 5 or more carbon atoms which may have a substituent An aliphatic group or a divalent group having an aromatic ring which may have a substituent is shown. t represents the integer of 1-10. However, any one of the substituent and Z which M ¹ has includes an aromatic ring.

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 (B2-1-1).

Z each independently represents a divalent group having an aromatic ring which may have a substituent or a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. As a divalent aliphatic group in Z, an alkylene group, an alkenylene group, etc. are mentioned, for example. The divalent aliphatic group may be any of chain, branched, and cyclic, and among these, a cyclic, that is, a cyclic divalent aliphatic 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.

The number of carbon atoms in the alkenylene 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. Linear, branched, or cyclic any may be sufficient as this alkenylene group, and linear is especially preferable. Here, the cyclic alkenylene group is a concept that includes both a case consisting of only a cyclic alkenylene group and a case containing both a linear alkenylene group and a cyclic alkenylene group. As such an alkenylene group, for example, pentynylene group, hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecinylene group, dodecinylene group, tridecinylene group, hepta Decynylene group, hexatriacontinylene group, octynylene-cyclohexynylene group having a structure, octynylene-cyclohexynylene-octynylene structure having a group, propynylene-cyclohexynylene-octynylene structure having a structure and the like.

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 phthalimide-derived divalent group, 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 diimide; a divalent group derived from pyromellitic acid diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group; and the like. The arylene group is the same as the arylene group in the divalent linking group represented by L in the general formula (E2-1-1).

The divalent group which has an alkylene group and an aromatic ring which Z represents may have a substituent. As a substituent, it is the same as the substituent which M in general formula (B2-1-1) may have.

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

It is preferable that the compound represented by the general formula (B2-1-1) is any one of the compound represented by the general formula (B2-1-5) and the compound represented by the general formula (B2-1-6). .

General formula (B2-1-5)

General formula (B2-1-6)

In the general formula (B2-1-5), M ² and M ³ each independently represent 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, or an alkyl group. It represents a divalent group consisting of a ren group or a combination of two or more of these groups. t1 represents the integer of 1-10.

In the general formula (B2-1-6), M ⁴ , M ⁶ and M ⁷ each independently represents an 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 a , 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 (B2-1-1) is 5 or more, and preferably a hexatriacontinylene group or a hexatriacontylene group.

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 linking group represented by L in the general formula (B2-1-1). As R ⁴⁰ , it is preferable that it is a group consisting of a combination of two or more types of divalent groups or an oxygen atom.

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 an aliphatic group having 5 or more carbon atoms which may have a substituent. M ⁴ , M ⁶ and M ⁷ are the same as an aliphatic group having 5 or more carbon atoms which may have a substituent represented by M in the general formula (B2-1-1), and a hexylene group, a heptylene group, an octylene group, and a nonylene group , a decylene group is 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 (B2-1-4), 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 (B2-1-1).

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.

(B2-1) As a specific example of a component, the compound of the following (B-i) - (B-ii) is mentioned, It is not limited to these specific examples. In the formula, v represents an integer from 1 to 10.

Formula (B-i)

Formula (B-ii)

(B2-1) As a specific example of a component, "BMI1500" (compound of general formula (B-i)), "BMI1700" (compound of general formula (B-ii)) manufactured by Designer Molecules, etc. are mentioned.

(B2-1) The weight average molecular weight (Mw) of a component becomes like this. Preferably it is 150-5000, More preferably, it is 300-2500.

(B2-1) The maleimide group equivalent of the component 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 component (B2-1) containing 1 equivalent of maleimide group.

{(B2-2) component}

(B2-2) A component is a maleimide compound which has an aromatic ring directly couple|bonded with the nitrogen atom of maleimide. (B2-2) A component can be obtained by making imidation-react, for example, an aromatic amine compound (aromatic diamine compound etc.) and the component containing maleic anhydride.

The aromatic ring may be a carbocyclic ring or a heterocyclic ring. Examples of the aromatic ring include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, pyra monocyclic aromatic rings, such as a true ring; Naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzoimidazole ring, indazole ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring, quinoline ring , a condensed ring in which two or more monocyclic aromatic rings such as an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring and a phthalazine ring are condensed; Condensed rings etc. which 1 or more monocyclic non-aromatic rings condensed to 1 or more monocyclic aromatic rings, such as an indan ring, a fluorene ring, and a tetralin ring, are mentioned. Especially, as an aromatic ring, a monocyclic aromatic ring is preferable and a benzene ring is more preferable.

(B2-2) As a component, the compound represented by the following general formula (B2-2-1) is preferable.

Formula (B2-2-1)

In the formula, each R ^c independently represents a substituent; X ^c is each independently a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO- , or -OCO- (preferably a single bond or an alkylene group); Z ^c is each independently a non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent (preferably an aromatic ring which may have a substituent, particularly preferably a benzene ring which may have a substituent) indicate; s represents an integer of 1 or more (preferably an integer from 1 to 100, more preferably an integer from 1 to 50, still more preferably an integer from 1 to 20); t1 each independently represents 0 or an integer of 1 or more; u each independently represents an integer of 0 to 2 (preferably 0).], particularly preferably, formulas (B2-2-2) to (B2-2-5). ):

Formula (B2-2-2)

Formula (B2-2-3)

Formula (B2-2-4)

Formula (B2-2-5)

In the formula, R ^c1 , R ^c2 and R ^c3 each independently represent an alkyl group; X ^c1 and X ^c2 each independently represent a single bond or an alkylene group; s represents an integer of 1 or more (preferably an integer from 1 to 100, more preferably an integer from 1 to 50, still more preferably an integer from 1 to 20); t' represents an integer of 1 to 5; v1, v2, and v3 each independently represent the integer of 0-2 (preferably 0). In addition, the s unit, the t unit, the t' unit, the u unit, the v1 unit, the v2 unit, and the v3 unit may be the same or different for each unit, respectively.

Moreover, as another embodiment, it is preferable that the component (B2-2) has a structure represented, for example by following general formula (B2-2-6).

Formula (B2-2-6)

In the formula, 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 each independently 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 the formula (B2-2-6) 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. There is no restriction|limiting in particular as a substituent, For example, a halogen atom, -OH, -OC _1-6 alkyl group, -N(C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6-10 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.

The above-mentioned substituent may further have a substituent (Hereinafter, it may be called "secondary substituent."). As a secondary substituent, you may use the thing similar to the above-mentioned substituent unless otherwise stated.

D in the general formula (B2-2-6) represents a divalent aromatic group. As a divalent aromatic group, a phenylene group, a naphthylene group, anthracenylene, an aralkyl group, a biphenylene group, a biphenyl aralkyl group etc. are mentioned, for example, Among these, a biphenylene group and a biphenyl aralkyl group 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 (B2-2-6) 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.

(B2-2) As a component, resin represented by general formula (B2-2-7) is preferable.

Formula (B2-2-7)

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

a1 is the same as a in general formula (B2-2-6), and a preferable range is also the same.

(B2-2) As a commercial item of a component, For example, "MIR-3000-70MT" by a Nippon Kayaku company; "BMI-50P" by Keii Kasei Corporation; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", "BMI-5100" manufactured by Yamato Kaseiko Co., Ltd.; "BMI-4,4'-BPE" by Keii Kasei Corporation, "BMI-70", "BMI-80" by Keii Kasei Corporation, etc. are mentioned.

(B2-2) The weight average molecular weight (Mw) of a component becomes like this. Preferably it is 150-5000, More preferably, it is 300-2500.

(B2-2) The functional group equivalent of the maleimide group of a component becomes like this. Preferably it is 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., particularly preferably 200 g/eq. to 300 g/eq.

{(B2-3) component}

(B2-3) A component is a maleimide compound containing trimethylindane skeleton. The trimethylindane skeleton represents a skeleton shown in the following general formula (B2-3-1).

Formula (B2-3-1)

A substituent may couple|bond with the benzene ring which trimethylindane skeleton contains. Examples of the substituent include an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a halogen atom, a hydroxyl group, and a mercapto group.

The number of carbon atoms in the alkyl group is preferably 1 to 10. As an alkyl group, a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group, etc. are mentioned, for example.

The number of carbon atoms in the alkyloxy group is preferably 1 to 10. As an alkyloxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example.

The number of carbon atoms in the alkylthio group is preferably 1 to 10. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group.

The number of carbon atoms in the aryl group is preferably 6 to 10. As an aryl group, a phenyl group, a naphthyl group, etc. are mentioned, for example.

The number of carbon atoms in the aryloxy group is preferably 6 to 10. As an aryloxy group, a phenyloxy group, a naphthyloxy group, etc. are mentioned, for example.

The number of carbon atoms in the arylthio group is preferably 6 to 10. As an arylthio group, a phenylthio group, a naphthylthio group, etc. are mentioned, for example.

The number of carbon atoms in the cycloalkyl group is preferably 3 to 10. As a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group etc. are mentioned, for example.

As a halogen atom, a fluorine atom, a chlorine atom, an iodine atom, etc. are mentioned, for example.

Among the above substituents, a hydrogen atom of an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, and a cycloalkyl group may be substituted with a halogen atom.

The number of substituents couple|bonded with one benzene ring which trimethylindane skeleton contains may be 1, and 2 or more may be sufficient as it. The number of substituents couple|bonded with the benzene ring which trimethylindane skeleton contains is 0 or more and 3 or less normally. When the number of substituents is two or more, these two or more substituents may be same or different. Especially, it is preferable that the substituent is not couple|bonded with the benzene ring which trimethylindane frame|skeleton contains.

(B2-3) The number of trimethylindane skeletons contained in 1 molecule of a component may be 1, and 2 or more may be sufficient as it. The upper limit may be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

(B2-3) It is preferable that a component further contains aromatic ring skeleton in addition to the trimethylindane skeleton mentioned above. The number of ring-constituting carbons in the aromatic ring skeleton is preferably 6 to 10. As aromatic ring skeleton, a benzene ring skeleton, a naphthalene ring skeleton, etc. are mentioned, for example. (B2-3) The number of the aromatic ring skeletons contained in one molecule of the component is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, particularly preferably usually less than 3. (B2-3) When a component adds and contains 2 or more aromatic ring skeleton to trimethylindane skeleton, these aromatic ring skeleton may be same or different.

A substituent may couple|bond with the aromatic ring contained in said aromatic ring skeleton. As a substituent, the substituent mentioned above as a substituent which can couple|bond with the benzene ring contained in trimethylindane skeleton contains, and a nitro group is mentioned, for example. One may be sufficient as the number of the substituent couple|bonded with one aromatic ring, and 2 or more may be sufficient as it. The number of substituents couple|bonded with an aromatic ring is 0 or more and 4 or less normally. When the number of substituents is two or more, these two or more substituents may be same or different.

(B2-3) It is preferable that a component further contains a divalent aliphatic hydrocarbon group in addition to the trimethylindane skeleton mentioned above. In particular, when component (B2-3) contains aromatic ring skeletons other than the benzene ring which trimethylindane skeleton contains, it is preferable that component (B2-3) contains a divalent aliphatic hydrocarbon group. In this case, it is preferable that the divalent aliphatic hydrocarbon group connects between the benzene ring and aromatic ring skeleton which a trimethylindane skeleton contains. Moreover, it is preferable that the divalent aliphatic hydrocarbon group connects between aromatic ring skeletons.

The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 or more, preferably 12 or less, more preferably 8 or less, particularly preferably 5 or less. As the divalent aliphatic hydrocarbon group, an alkylene group as a saturated aliphatic hydrocarbon group is more preferable. Examples of the divalent aliphatic hydrocarbon group include a straight-chain alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; Ethylene group (-CH(CH ₃ )-), propylidene group (-CH(CH ₂ CH ₃ )-), isopropylidene group (-C(CH ₃ ) ₂ -), ethylmethylmethylene group (-C branched chain alkylene groups such as (CH ₃ )(CH ₂ CH ₃ )-) and diethylmethylene group (—C(CH ₂ CH ₃ ) ₂ -); and the like. (B2-3) When the maleimide compound having a trimethylindane skeleton contains two or more divalent aliphatic hydrocarbon groups in addition to the trimethylindane skeleton, these divalent aliphatic hydrocarbon groups may be the same or different.

(B2-3) It is preferable that a component contains the structure shown by following formula (B2-3-2). (B2-3) The whole component may have a structure represented by general formula (B2-3-2), and the part of (B2-3) component may have a structure shown by general formula (B2-3-2).

Formula (B2-3-2)

(In the formula, Ar ^a1 represents a divalent aromatic hydrocarbon group which may have a substituent; R ^a1 is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, or a carbon atom An alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms , a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R ^a2 is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms of an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, represents a hydroxyl group or a mercapto group; R ^a3 each independently represents a divalent aliphatic hydrocarbon group; n _a1 represents a positive integer; n _a2 each independently represents an integer of 0 to 4; n _a3 each independently represents an integer of 0 to 3. The hydrogen atom of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R ^a1 is a halogen atom The hydrogen atom of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R ^a2 may be substituted with a halogen atom. n _a2 is 2 to 4 In the case of , R ^a1 may be the same or different within the same ring. When n _a3 is 2 to 3, R ^a2 may be the same or different within the same ring.)

In the formula (B2-3-2), Ar ^a1 represents a divalent aromatic hydrocarbon group which may have a substituent. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 or more, preferably 20 or less, and more preferably 16 or less. Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group. Examples of the substituent that the divalent aromatic hydrocarbon group may have include an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and 6 carbon atoms. an aryl group having to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group. have. The hydrogen atom of each substituent may further be substituted by the halogen atom. Moreover, as a specific example of these substituents, the same example as a substituent which can couple|bond with the benzene ring contained in trimethylindane skeleton is mentioned, for example. When the divalent aromatic hydrocarbon group has a substituent, the number of the substituents is preferably 1 to 4. When the number of substituents which the divalent aromatic hydrocarbon group has is two or more, these two or more substituents may be same or different. Among them, Ar ^a1 is preferably a divalent aromatic hydrocarbon group having no substituent.

In the formula (B2-3-2), R ^a1 is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms; An aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, Or a mercapto group is shown. The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same examples of the substituents capable of being bonded to the benzene ring contained in the trimethylindane skeleton. Among them, R ^a1 is more preferably at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. , an alkyl group having 1 to 4 carbon atoms is particularly preferred.

In the formula (B2-3-2), R ^a2 is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, An aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercap indicates soil. The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same examples of the substituents capable of being bonded to the benzene ring contained in the trimethylindane skeleton. Among them, R ^a2 is more preferably at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. do.

In the formula (B2-3-2), R ^a3 each independently represents a divalent aliphatic hydrocarbon group. The preferred range of the divalent aliphatic hydrocarbon group is as described above.

In the general formula (B2-3-2), n _a1 represents a positive integer. n _a1 is preferably 1 or more, preferably 10 or less, more preferably 8 or less.

In general formula (B2-3-2), n _a2 represents the integer of 0-4 each independently. n _a2 becomes like this. Preferably it is 2 or 3, More preferably, it is 2. Although a plurality of n _a2 may be different, it is preferable that they are the same. When n _a2 is 2 or more, a plurality of R ^a1s may be the same or different within the same ring.

In general formula (B2-3-2), n _a3 represents the integer of 0-3 each independently. Although a plurality of n _a3 may be different, it is preferable that they are the same. n _a3 is preferably 0.

(B2-3) It is especially preferable that a component contains the structure shown by following formula (B2-3-3). (B2-3) The whole component may have a structure represented by general formula (B2-3-3), and the part of (B2-3) component may have a structure shown by general formula (B2-3-3).

Formula (B2-3-3)

(In the formula, R ^b1 is, each independently, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, 6 to 10 carbon atoms an aryl group, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R ^b2 is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, carbon represents an aryloxy group having 6 to 10 atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n _b1 is a positive integer , n _b2 each independently represents an integer from 0 to 4 n _b3 each independently represents an integer from 0 to 3. R ^b1 represents an alkyl group, an alkyloxy group, an alkylthio group, or an aryl group , the hydrogen atom of the aryloxy group, the arylthio group, and the cycloalkyl group may be substituted with a halogen atom ^Alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cyclo The hydrogen atom of the alkyl group may be substituted with a halogen atom. When n _b2 is 2 to 4, R ^b1 may be the same or different within the same ring. When n _b3 is 2 to 3, R ^b2 is the same It may be the same or different within the ring.)

In the formula (B2-3-3), R ^b1 , R ^b2 , n _b1 , n _b2 and n _b3 are, respectively, R ^a1 , R ^a2 , n _a1 , n _a2 in the formula (B2-3-2) and n _a3 .

(B2-3) The component may further contain the structure represented by the following general formula (B2-3-4).

Formula (B2-3-4)

In the formula (B2-3-4), R ^c1 , R ^c2 , n _c2 and n _c3 are the same as R ^a1 , R ^a2 , n _a2 and n _a3 in the formula (A4), respectively. In addition, in general formula (E2-3-4), n _c1 is the number of repeating units, and represents the integer of 1-20. In addition, in general formula (E2-3-4), * represents a bond. For example, in the component (B2-3), in the general formula (B2-3-2), n _a2 is 3 or less, and the benzene ring to which the maleimide group is bonded is in the ortho and para positions with respect to the maleimide group, When R ^a1 is not bonded to two or more, the structure represented by the above formula (B2-3-4) may be included in combination with the structure represented by the formula (B2-3-2). For example, in the component (B2-3), in the general formula (B2-3-3), n _b2 is 3 or less, and the benzene ring to which the maleimide group binds is ortho-positioned and para-positioned to the maleimide group. Among them, when R ^b1 is not bonded to at least two of them, the structure represented by the above formula (B2-3-4) may be included in combination with the structure represented by the formula (B2-3-3). have.

(B2-3) A component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

(B2-3) Maleimide group equivalent of a component becomes like this. Preferably it is 50 g/eq. or more, more preferably 100 g/eq. or more, particularly preferably 200 g/eq. or more, preferably 2000 g/eq. Hereinafter, more preferably 1000 g/eq. or less, particularly preferably 800 g/eq. is below. The maleimide group equivalent represents the mass of the maleimide compound per equivalent of the maleimide group. (E2-3) When the maleimide group equivalent of the component is within the above range, the effects of the present invention can be significantly obtained.

(B2-3) There is no restriction|limiting in particular in the manufacturing method of a component. (B2-3) The component can be manufactured, for example by the method described in Invention Association Publication No. 2020-500211. According to the manufacturing method described in this Invention Association Publication No. 2020-500211, a maleimide compound having a distribution in the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method contains the structure represented by the following general formula (B2-3-5). Therefore, (B2-3) component may contain the maleimide compound containing the structure represented by general formula (B2-3-5).

Formula (B2-3-5)

(In the formula, R ¹ is, each independently, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, 6 to 10 carbon atoms an aryl group, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R ² is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, carbon represents an aryloxy group having 6 to 10 atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n ₁ is 0.95 to 10.0 represents the average number of repeating units of; n ₂ each independently represents an integer of 0 to 4; n ₃ represents each independently an integer of 0 to 3. R ¹ represents an alkyl group, an alkyloxy group, an alkyl The hydrogen atom of thio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atom Alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, aryl of R< ² > The hydrogen atom of the thio group and the cycloalkyl group may be substituted with a halogen atom. When n ₂ is 2 to 4, R ¹ may be the same or different in the same ring. When n ₃ is 2 to 3, R ² may be the same or different within the same ring.)

In the formula (B2-3-5), R ¹ , R ² , n ₂ and n ₃ are the same as R ^a1 , R ^a2 , n _a2 and n _a3 in the formula (B2-3-2), respectively .

In the formula (B2-3-5), n ₁ represents the average number of repeating units, and the range is 0.95 to 10.0. According to the manufacturing method described in Publication No. 2020-500211 of the Invention Association Publication No. 2020-500211, group 1 maleimide compounds including the structure represented by Chemical Formula (B2-3-5) can be obtained. Maleimide comprising the structure represented by the general formula (B2-3-5) obtained in this way, as can be seen from the fact that the average number of repeating units n ₁ in the general formula (B2-3-5) can be smaller than 1.00 The compound may include a maleimide compound in which the number of repeating units of the trimethylindane skeleton is 0. Then, from the maleimide compound having the structure represented by the formula (E2-3-5), the maleimide compound having 0 repeating units in the trimethylindane skeleton is removed by purification to obtain the component (B2-3), The resin composition may contain only the obtained (B2-3) component. However, even when the maleimide compound of which the number of repeating units of the trimethylindane skeleton is 0 is contained in the resin composition, the effect of this invention can be acquired. Moreover, when a refinement|purification is abbreviate|omitted, suppression of cost is possible. Then, it is preferable that the resin composition contains the maleimide compound containing the structure represented by general formula (B2-3-5) without removing the maleimide compound whose number of repeating units of a trimethylindane skeleton is 0.

In the formula (B2-3-5), the average number of repeating units n ₁ is preferably 0.95 or more, more preferably 0.98 or more, still more preferably 1.0 or more, particularly preferably 1.1 or more, and preferably It is 10.0 or less, More preferably, it is 8.0 or less, More preferably, it is 7.0 or less, Especially preferably, it is 6.0 or less. When the average number of repeating units n ₁ is within the above range, the effects of the present invention can be significantly obtained. In particular, the glass transition temperature of a resin composition can be raised effectively.

Examples of the structure represented by the general formula (B2-3-5) include the following.

The maleimide compound including the structure represented by the formula (B2-3-5) may further include a structure represented by the formula (B2-3-4). For example, in the maleimide compound having a structure represented by the general formula (B2-3-5), in the general formula (B2-3-5), n ₂ is 3 or less and benzene to which the maleimide group is bonded. When R ¹ is not bonded to at least two of the ortho-position and para-position to the maleimide group of the ring, in combination with the structure represented by the formula (B2-3-5), the formula (E2-3-4) It may include a structure represented by .

It is preferable that molecular weight distribution Mw/Mn computed from gel permeation chromatography (GPC) measurement exists in the specific range of the maleimide compound containing the structure represented by general formula (B2-3-5). Molecular weight distribution is a value calculated|required by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and it is represented by "Mw/Mn." Specifically, the molecular weight distribution Mw/Mn of the maleimide compound containing the structure represented by the general formula (B2-3-5) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, still more preferably 1.2 to 3.6, particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw/Mn of the maleimide compound having the structure represented by the formula (B2-3-5) is within the above range, the effects of the present invention can be significantly obtained.

It is preferable that the quantity of the maleimide compound of which the average number of repeating units n< ₁ > is 0 among the maleimide compounds containing the structure represented by general formula (B2-3-5) exists in a specific range. When the above GPC measurement of a maleimide compound having a structure represented by the formula (B2-3-5) is performed, the amount of the maleimide compound having an average number of repeating units n ₁ of 0 is determined based on the results of the GPC measurement. It can be expressed as area %. Specifically, in the chromatogram obtained by the GPC measurement, the average number of repeating units n ₁ with respect to the total area of the peaks of the maleimide compound containing the structure represented by the formula (B2-3-5) is 0 By the ratio (area %) of the area of the peak of the maleimide compound, the amount of the maleimide compound in which the average number of repeating units n ₁ is 0 can be expressed. Specifically, the amount of the maleimide compound having an average number of repeating units n ₁ of 0 with respect to 100 area % of the total amount of the maleimide compound having the structure represented by the formula (B2-3-5) is preferably 32 areas. % or less, more preferably 30 area% or less, still more preferably 28 area% or less. When the amount of the maleimide compound having an average number of repeating units n ₁ of 0 is within the above range, the effects of the present invention can be significantly obtained.

It is preferable that the maleimide group equivalent of the maleimide compound containing the structure represented by Formula (B2-3-5) exists in the same range as the maleimide group equivalent of the above-mentioned (B2-3) component. When the maleimide group equivalent of the maleimide compound having the structure represented by the formula (B2-3-5) is within the above range, the effects of the present invention can be significantly obtained.

-(B3) a resin containing a radically polymerizable unsaturated group and benzocyclobutene-

Since component (B3) is resin which belongs to component (B), it is resin containing benzocyclobutene as a radically polymerizable unsaturated group and an aromatic ring. (B3) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(B3) The structure is not specifically limited as long as the component contains the benzocyclobutene group and radically polymerizable unsaturated group which can generate|occur|produce an isomer diene by heating. As (B3) component, it is preferable that the viewpoint of forming hardened|cured material with favorable adhesiveness between copper foil that (B3) component has two or more benzocyclobutene groups in 1 molecule. (B3) It is preferable to have a radically polymerizable unsaturated group as a divalent aliphatic group which has an unsaturated bond from a viewpoint of forming the hardened|cured material with favorable adhesiveness between copper foil as for a component.

In one embodiment, component (B3) contains the compound represented by the following general formula (B3-1).

Formula (B3-1)

In the formula (B3-1), R ¹⁰⁰ represents a divalent aliphatic group having an unsaturated bond, L ¹⁰⁰ represents a single bond or a divalent linking group, R ^A100 represents an alkyl group, a cyano group or a halogen atom, R ^A200 represents an alkyl group, a trialkylsilyl group, an alkoxy group or a halogen atom, nA1 represents an integer of 0 to 2, nA2 represents an integer of 0 to 3, and nA3 represents 0 or 1. R ¹ , R ^A1 and R ^A2 may each independently have a substituent. A plurality of R ^1s may be the same or different, and when there are a plurality of R ^A1 s, they may be the same or different, and when there are a plurality of R ^A2 , they may be the same or different.

The divalent group represented by R ¹⁰⁰ has preferably 1 to 3 unsaturated bonds, more preferably 1 or 2, still more preferably 1 unsaturated bond. Although a double bond or a triple bond may be sufficient as an unsaturated bond, it is preferable that it is a double bond. The divalent group represented by R ¹⁰⁰ is preferably an alkenylene group or an alkynylene group. The number of carbon atoms in the divalent group represented by R ¹⁰⁰ is preferably 2 to 10, more preferably 2 to 6 or 2 to 4. The number of carbon atoms of the substituent is not included in the number of carbon atoms.

As the divalent linking group represented by L ¹⁰⁰ , at least one selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) is not particularly limited as long as it is a divalent group composed of skeletal atoms, and for example, a divalent group described as A ¹² in formula (B1-3) described later or a siloxane skeleton may be used. Among them, L ¹⁰⁰ is preferably a siloxane skeleton. Therefore, in one Embodiment, (B3) component has a siloxane skeleton.

The number of carbon atoms in the alkyl group represented by R ^A100 is preferably 1 to 10, more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms of the substituent is not included in the number of carbon atoms. The halogen atom represented by R ^A100 is preferably a chlorine atom or a bromine atom.

The number of carbon atoms in the alkyl group and the alkoxy group represented by R ^A200 is preferably 1 to 10, more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms in the alkyl moiety in the trialkylsilyl group represented by R ^A200 is preferably 1 to 3, more preferably 1 or 2. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Moreover, as a halogen atom represented by R ^A200 , a chlorine atom or a bromine atom is preferable.

(B3) From a viewpoint of obtaining the hardened|cured material excellent in copper foil adhesiveness, as for component (B3), in general formula (B3-1), it is preferable that nA3 is 1, and it is preferable that L ¹⁰⁰ is a siloxane skeleton.

In one suitable embodiment, component (B3) contains the compound represented by following formula (B3-2).

Formula (B3-2)

In Formula (B3-2), R ^{100 ,} R ^A100 , R ^A200 , nA1 and nA2 are as described in Formula (B3-1), and R ²⁰⁰ is a hydrogen atom, an alkyl group, a cycloalkyl group, an arylalkyl group, or an aryl group and nA4 represents the integer of 1-10. R ² may have a substituent. A plurality of R ²⁰⁰ may be the same or different.

The number of carbon atoms in the alkyl group represented by R ²⁰⁰ is preferably 1 to 10, more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms in the cycloalkyl group represented by R ² is preferably 3 to 10, more preferably 4 to 6. The number of carbon atoms in the arylalkyl group represented by R ²⁰⁰ is preferably 7 to 20, more preferably 7 to 15 or 7 to 12. The aryl moiety in the arylalkyl group is preferably a phenyl group. The number of carbon atoms in the aryl group represented by R ²⁰⁰ is preferably 6 to 14, more preferably 6 to 10. As the aryl group, a phenyl group is preferable. The number of carbon atoms of the substituent is not included in the number of carbon atoms.

It is preferable that the integer of 1-10 is represented, the integer of 1-5 is represented, and, as for nA4, the integer of 1 or 2 is represented, and 1 is more preferable.

R ¹⁰⁰ , R ^A100 , R ^A200 , nA1 and nA2 are as described in formula (B3-1), but among them, it is preferable that R ¹⁰⁰ is an alkenylene group having 2 to 4 carbon atoms, and nA1 and nA2 are 0. do.

In one particularly suitable embodiment, the component (B3) contains a compound represented by the following general formula (B3-3).

Formula (B3-3)

In Formula (B3-3), R ²⁰⁰ and nA4 are as described in Formula (B3-2).

(B3) The component can be prepared according to the procedure described in, for example, US Patent 4812588 specification, US Patent 5138081 specification, etc. In addition, as the component (B3), a commercially available product may be used, for example, as a compound represented by the general formula (B3-3), there is a CYCLOTENE series manufactured by Dow Chemical Corporation, and “CYCLOTENE3022-35” is represented by the following formula have a structure

As described above, the benzocyclobutene group produces an isomeric diene and causes a Diels-Alder type cyclization addition reaction. Accordingly, the component (B-3) may contain, in addition to the compounds (monomers) represented by the formulas (B3-1) to (B3-3), etc., a dimer or a polymer produced by an addition reaction of these compounds.

(B3) Although the weight average molecular weight (Mw) and number average molecular weight (Mn) of component are not specifically limited, It is preferable that Mw or Mn is 2000 or less, It is more preferable that it is 1800 or less, 1600 or less, 1500 or less, 1400 or less , more preferably 1200 or less or 1000 or less. The lower limit of the molecular weight is not particularly limited, and can be, for example, 250 or more, 300 or more. (A) Mw and Mn of component can be measured as a polystyrene conversion value by the gel permeation chromatography (GPC) method.

(B) The content of component is preferably 10 mass% or more, more preferably 10 mass% or more, when the nonvolatile component in the resin composition is 100 mass% from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to copper foil. Preferably it is 15 mass % or more, More preferably, it is 20 mass % or more. (B) Although the upper limit of content of component is not specifically limited, Preferably it is 40 mass % or less, More preferably, it is 35 mass % or less, More preferably, it is 30 mass % or less.

(B) As content of component, when a resin component in a resin composition is 100 mass % from a viewpoint of obtaining the hardened|cured material which has low dielectric characteristic and excellent adhesiveness with copper foil, Preferably it is 20 mass % or more, More preferably is 30 mass % or more, more preferably 40 mass % or more, Preferably it is 60 mass % or less, More preferably, it is 55 mass % or less, More preferably, it is 50 mass % or less.

<(C) Inorganic filler>

The resin composition may contain the (C) inorganic filler as arbitrary components other than the component mentioned above. (C) By containing an inorganic filler in a resin composition, it becomes possible to obtain the hardened|cured material excellent in a dielectric characteristic.

As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler 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 an inorganic filler, "UFP-30" by a Denka Chemical Industry Co., Ltd. product, for example; "SP60-05", "SP507-05" by the Shin-Nitetsu Sumikin Materials company; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex Corporation; "UFP-30" by Denka Corporation; "Silly writing NSS-3N", "Silly writing NSS-4N", "Silly writing NSS-5N" by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2050-SXF" manufactured by Adomatex Corporation; and the like.

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

(C) The average particle diameter of an inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle diameter distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle diameter 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, using a light source wavelength as blue and red, measuring the volume-based particle size distribution of the inorganic filler by a flow cell method, and measuring the median diameter from the obtained particle size distribution to calculate the average particle diameter. As a laser diffraction type particle size distribution measuring apparatus, "LA-960" by Horiba Corporation, "SALD-2200" by Shimadzu Corporation, etc. are mentioned, for example.

(C) The specific surface area of the inorganic filler is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, particularly preferably 3 m 2 /g or more from the viewpoint of significantly obtaining the desired effect of the present invention. . Although there is no particular restriction 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 is measured using a BET fully automatic specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec), by adsorbing nitrogen gas to the sample surface, and calculating the specific surface area using the BET multi-point method to measure the specific surface area of the inorganic filler can be obtained by

(C) It is preferable that the inorganic filler is treated with the surface treating agent from a viewpoint of improving moisture resistance and dispersibility. As a surface treatment agent, For example, Fluorine-containing silane coupling agents, such as 3,3,3-trifluoropropyl trimethoxysilane; aminosilane-based coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; Epoxysilane-type coupling agents, such as 3-glycidoxy propyl trimethoxysilane; mercaptosilane-based coupling agents such as 3-mercaptopropyltrimethoxysilane; silane-based coupling agent; alkoxysilanes such as phenyltrimethoxysilane; Organosilazane compounds, such as hexamethyldisilazane, a titanate type coupling agent, etc. are mentioned. In addition, a surface treatment agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

As a commercial item of a surface treatment agent, For example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. make "KBM803" (3-mercaptopropyltrimethoxy) silane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical “SZ-31” (hexamethyldisilazane) manufactured by Koji Corporation, “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM-4803” manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane couple) ring 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 0.2 parts by mass to 5 parts by mass of a surface treatment agent, preferably 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 the sheet form, 1 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable.

(C) 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.

(C) As the content of the inorganic filler, from the viewpoint of significantly obtaining the effect of the present invention, when the nonvolatile component in the resin composition is 100 mass%, preferably 30 mass% or more, more preferably 35 mass% or more, More preferably, it is 40 mass % or more, Preferably it is 80 mass % or less, More preferably, it is 70 mass % or less, More preferably, it is 60 mass % or less, 55 mass % or less.

<(D) polymerization initiator>

The resin composition may contain the (D) polymerization initiator as arbitrary components other than the component mentioned above. (D)component has a function which accelerates|stimulates the bridge|crosslinking of the radically polymerizable unsaturated group in (B) component normally. (D) A component may be used individually by 1 type, and may use 2 or more types together.

(D) Examples of the polymerization initiator include dit-hexyl peroxide, t-butylcumyl peroxide, t-butylperoxyacetate, α,α′-di(t-butylperoxy)diisopropylbenzene; and peroxides such as t-butylperoxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butylperoxybenzoate.

(D) As a commercial item of a polymerization initiator, "Perhexyl D", "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl by Nichiyo Co., Ltd." are, for example, O", "perbutyl ND", "perbutyl Z", "percumyl P", "percumyl D", etc. are mentioned.

(D) The content of the polymerization initiator is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of significantly obtaining the desired effect of the present invention. , More preferably, it is 0.05 mass % or more, Preferably it is 0.3 mass % or less, More preferably, it is 0.2 mass % or less, More preferably, it is 0.1 mass % or less.

(D) The content of the polymerization initiator, from the viewpoint of significantly obtaining the desired effect of the present invention, when the resin component in the resin composition is 100 mass%, preferably 0.1 mass% or more, more preferably 0.5 mass% or more, More preferably, it is 1 mass % or more, Preferably it is 5 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 2 mass % or less.

<(E) Thermoplastic resin>

The resin composition may further contain (E) a thermoplastic resin as an arbitrary component other than the component mentioned above.

(E) As a thermoplastic resin as a component, For example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone. Resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. are mentioned. Among them, a phenoxy resin is preferable from the viewpoint of significantly obtaining the effects of the present invention. In addition, a thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene. and phenoxy resins having at least one skeleton selected from the group consisting of skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. Any one of functional groups, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin.

Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" by a Mitsubishi Chemical company (bisphenol S skeleton containing phenoxy resin); "YX6954" (bisphenolacetophenone skeleton containing phenoxy resin) by a Mitsubishi Chemical company; "FX280" and "FX293" manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation; and the like.

As polyvinyl acetal resin, polyvinyl formal resin and polyvinyl butyral resin are mentioned, for example, Polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Denki Chemical Co., Ltd. ; S-rec BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series manufactured by Sekisui Chemical Co., Ltd.; and the like.

Examples of the polyolefin resin include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; Polyolefin type elastomers, such as a polypropylene and an ethylene-propylene block copolymer, etc. are mentioned.

As a specific example of polyimide resin, "Ricacoat SN20" and "Ricacoat PN20" by a New Nippon Rica company are mentioned.

As a specific example of polyamideimide resin, "Viromax HR11NN" and "Viromax HR16NN" by Toyobo Co., Ltd. are mentioned. Specific examples of the polyamideimide resin include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing polysiloxane skeleton) manufactured by Hitachi Chemical.

As a specific example of polyether sulfone resin, "PES 5003P" by Sumitomo Chemical Co., Ltd. etc. is mentioned.

As a specific example of polysulfone resin, the polysulfone "P1700" by Solvay Advanced Polymers, "P3500", etc. are mentioned.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl tere. A phthalate resin etc. are mentioned.

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

(E) The content of the thermoplastic resin is preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 100% by mass or more of the nonvolatile component in the resin composition from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 3 mass % or more, Preferably it is 10 mass % or less, More preferably, it is 8 mass % or less, More preferably, it is 5 mass % or less.

(E) As the content of the thermoplastic resin, from the viewpoint of significantly obtaining the effect of the present invention, when the resin component in the resin composition is 100 mass %, preferably 1 mass % or more, more preferably 3 mass % or more, further Preferably it is 5 mass % or more, Preferably it is 20 mass % or less, More preferably, it is 15 mass % or less, More preferably, it is 10 mass % or less.

<(F) Elastomer>

The resin composition may further contain the (F) elastomer as an arbitrary component other than the component mentioned above. (F) The elastomer as the component is a resin having flexibility, preferably a resin having rubber elasticity or a resin showing rubber elasticity by polymerization with other components. Examples of the rubber elasticity include resins exhibiting an elastic modulus of 1 GPa or less when a tensile test is performed at a temperature of 25°C and a humidity of 40% RH in accordance with Japanese Industrial Standards (JIS K7161).

In one embodiment, (F) elastomer, in a molecule|numerator, polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure It is preferable that it is a resin which has 1 or more types of structures chosen from a polycarbonate structure and a polystyrene structure. "(meth)acrylate" refers to a methacrylate and an acrylate.

Further, in another embodiment, the (F) elastomer is preferably at least one selected from a resin having a glass transition temperature (Tg) of 25°C or lower and a liquid resin at 25°C or lower. The glass transition temperature of resin whose glass transition temperature (Tg) is 25 degrees C or less becomes like this. Preferably it is 20 degrees C or less, More preferably, it is 15 degrees C or less. Although the lower limit of a glass transition temperature is not specifically limited, Usually, it can be made into -15 degreeC or more. Moreover, as resin which is liquid at 25 degreeC, Preferably it is resin which is liquid at 20 degrees C or less, More preferably, it is resin which is liquid at 15 degrees C or less. A glass transition temperature can be measured by DSC (differential scanning calorimetry).

(F) An elastomer is an amorphous resin component which can melt|dissolve in the organic solvent normally. This (F) elastomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

(F) As an elastomer, resin containing a polybutadiene structure is mentioned, for example. The polybutadiene structure may be contained in the main chain or may be contained in the side chain. In addition, a part or all of polybutadiene structure may be hydrogenated. Resin containing a polybutadiene structure may be called "polybutadiene resin." Specific examples of the polybutadiene resin include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" manufactured by Clay Valle. ” (polybutadiene containing an acid anhydride group), “GQ-1000” (polybutadiene introduced with hydroxyl groups and carboxyl groups) manufactured by Nippon Soda Corporation, “G-1000”, “G-2000”, “G-3000” (both terminals) Hydroxyl group polybutadiene), "GI-1000", "GI-2000", "GI-3000" (polybutadiene hydrogenated with hydroxyl groups at both ends), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase Chemtex , and the like. Moreover, as a specific example of a polybutadiene resin, the linear polyimide which uses as a raw material hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (Unexamined-Japanese-Patent No. 2006-37083, International Publication No. 2008/153208) described polyimide), phenolic hydroxyl group-containing butadiene), and the like. The content rate of the butadiene structure of the said polyimide resin becomes like this. Preferably it is 60 mass % - 95 mass %, More preferably, it is 75 mass % - 85 mass %. For the detail of the said polyimide resin, description of Unexamined-Japanese-Patent No. 2006-37083 and International Publication No. 2008/153208 can be considered into consideration, and this content is integrated in this specification.

(F) As an elastomer, resin containing a poly(meth)acrylate structure is mentioned, for example. Resin containing a poly(meth)acrylate structure may be called "poly(meth)acrylic resin." As a specific example of a poly (meth)acrylic resin, Nagase Chemtex Co., Ltd. Teisan resin, "ME-2000", "W-116.3", "W-197C", "KG-25" manufactured by Negami Kogyo Co., Ltd., "KG-3000" etc. are mentioned.

(F) As an elastomer, resin containing a polycarbonate structure is mentioned, for example. Resin containing a polycarbonate structure may be called "polycarbonate resin." Specific examples of the polycarbonate resin include "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei, "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kuraray. ) and the like. Moreover, the linear polyimide which uses a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials can also be used. The content rate of the carbonate structure of the said polyimide resin becomes like this. Preferably it is 60 mass % - 95 mass %, More preferably, they are 75 mass % - 85 mass %. For the details of the polyimide resin, the description of International Publication No. 2016/129541 can be considered, and the content is incorporated herein by reference.

(F) As an elastomer, resin containing a polysiloxane structure is mentioned, for example. Resin containing a polysiloxane structure may be called "siloxane resin." As a specific example of a siloxane resin, "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., an amine group-terminated polysiloxane and a linear polyimide using a tetrabasic acid anhydride as raw materials (International Publication No. 2010) /053185, Japanese Unexamined Patent Publication No. 2002-12667, and Japanese Unexamined Patent Application, First Publication No. 2000-319386) and the like).

(F) As an elastomer, resin containing a polyalkylene structure or a polyalkyleneoxy structure is mentioned, for example. A resin containing a polyalkylene structure is sometimes referred to as an "alkylene resin". In addition, resin containing a polyalkyleneoxy structure may be called "alkyleneoxy resin." The polyalkyleneoxy structure preferably has a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and polyalkylene having 5 to 6 carbon atoms. The oxy structure is particularly preferred. As a specific example of an alkylene resin and alkyleneoxy resin, "PTXG-1000", "PTXG-1800" by the Asahi Kasei Seni company, etc. are mentioned.

(F) As an elastomer, resin containing a polyisoprene structure is mentioned, for example. A resin containing a polyisoprene structure is sometimes referred to as an "isoprene resin". As a specific example of an isoprene resin, "KL-610", "KL613" by Kuraray Corporation, etc. are mentioned.

(F) As an elastomer, resin containing a polyisobutylene structure is mentioned, for example. Resin containing a polyisobutylene structure may be called "isobutylene resin." Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation. can

(F) As an elastomer, resin containing a polystyrene structure is mentioned, for example. Resin containing a polystyrene structure may be called "styrene resin." Examples of the styrene resin include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene -propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, A hydrogenated styrene-butadiene block copolymer, a hydrogenated styrene- isoprene block copolymer, a hydrogenated styrene-butadiene random copolymer, etc. are mentioned. As a specific example of a styrene resin, Hydrogenated styrene thermoplastic elastomer "H1041", "Taftec H1043", "Taftec P2000", "Taftec MP10" (made by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomers "EpoFriend AT501" and "CT310" (manufactured by Daicel Corporation); Modified styrene-based elastomer having a hydroxyl group “Septon HG252” (manufactured by Kuraray Corporation); a modified styrenic elastomer having a carboxyl group “Taftec N503M”, a modified styrene-based elastomer having an amino group “Taphtec N501”, a modified styrenic elastomer having an acid anhydride group “Taphtec M1913” (manufactured by Asahi Kasei Chemicals); Unmodified styrene-based elastomer "Septon S8104" (made by Kurare Corporation; styrene-ethylene/butylene-styrene block copolymer "FG1924" (made by Kraton)) is mentioned.

(F) The number average molecular weight (Mn) of the elastomer is preferably 1,000 or more, more preferably 1500 or more, still more preferably 3000 or more, particularly preferably 5000 or more, preferably 1,000,000 or less, more preferably is less than or equal to 900,000. The number average molecular weight (Mn) can be measured in terms of polystyrene using GPC (gel permeation chromatography).

(F) The content of the elastomer is preferably 1% by mass or more, more preferably 2% 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 3 mass % or more, Preferably it is 10 mass % or less, More preferably, it is 8 mass % or less, More preferably, it is 5 mass % or less.

(F) As content of elastomer, when the resin component in a resin composition is 100 mass % from a viewpoint of obtaining the effect of this invention remarkably, Preferably it is 1 mass % or more, More preferably, it is 3 mass % or more, More preferably Preferably it is 5 mass % or more, Preferably it is 20 mass % or less, More preferably, it is 15 mass % or less, More preferably, it is 10 mass % or less.

<(G) Other additives>

The resin composition may further contain other additives as arbitrary components other than the component mentioned above. Examples of such additives include thermosetting resins such as epoxy resins, curing agents, curing accelerators, organic fillers, thickeners, defoamers, leveling agents, adhesion imparting agents, and flame retardants. These may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

A resin composition can be manufactured by mixing the above-mentioned component in arbitrary order, for example. Further, in the process of mixing each component, heating and/or cooling may be performed by appropriately adjusting the temperature. In addition, during or after mixing of each component, stirring may be performed using a stirring apparatus, such as a mixer, to disperse|distribute each component uniformly. Moreover, you may perform a defoaming process to a resin composition as needed.

<Physical properties and uses of the resin composition>

Since the resin composition contains the component (A) and the component (B) in combination, a cured product having low dielectric properties and excellent adhesion to copper foil can be obtained.

A cured product obtained by thermosetting the resin composition at 190°C for 90 minutes has a low dielectric constant Dk. Accordingly, when an insulating layer is formed from this cured product, an insulating layer having a low dielectric constant can be obtained. For example, the dielectric constant Dk of the hardened|cured material obtained by hardening|curing a resin composition under the conditions described in the Example mentioned later becomes like this. Preferably it is 3.0 or less, More preferably, it is 2.9 or less, More preferably, it is 2.8 or less. The lower limit of the dielectric constant Dk of the cured product is not particularly limited, but may be 0.1 or more. The dielectric constant of hardened|cured material can be measured by the method demonstrated in an Example.

A cured product obtained by thermosetting the resin composition at 190°C for 90 minutes has a low dielectric loss tangent. Accordingly, when an insulating layer is formed from this cured product, an insulating layer having a low dielectric loss tangent can be obtained. For example, the dielectric loss tangent Df of the cured product obtained by curing the resin composition under the conditions described in Examples to be described later is preferably 0.010 or less, more preferably 0.005 or less, and still more preferably 0.004 or less. The lower limit of the dielectric constant Df of the cured product is not particularly limited, but may be 0.001 or more. The dielectric loss tangent of hardened|cured material can be measured by the method demonstrated in an Example.

The hardened|cured material obtained by thermosetting a resin composition at 190 degreeC for 90 minute(s) can make high the adhesiveness between copper foil (copper foil adhesiveness). For example, when the insulating layer and the copper foil are formed by the method described in Examples to be described later, the adhesion between the insulating layer and the copper foil is preferably 0.2 kgf/cm or more, more preferably 0.3 kgf/cm or more. , particularly preferably 0.4 kgf/cm or more. Although the upper limit of adhesiveness is not specifically limited, For example, it may be 10.0 kgf/cm or less. The adhesiveness between an insulating layer and copper foil can be measured by the method demonstrated in an Example.

The resin composition which concerns on one Embodiment of this invention is suitable as a resin composition for insulation use, Especially, it is especially suitable as a resin composition for insulation layer formation. Therefore, for example, a resin composition is suitable as a resin composition for forming the insulating layer of a printed wiring board (resin composition for insulating layer formation of a printed wiring board). In addition, the resin composition is suitable 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. do. The resin composition is also widely used in applications in which the resin composition can be used, such as a resin sheet, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, a component embedding resin, etc. can

In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to the present embodiment is used to form a redistribution forming layer as an insulating layer for forming a redistribution layer. It is suitable also as a resin composition (resin composition for rewiring forming layer formation) for this purpose, and a resin composition (resin composition for semiconductor chip sealing) for sealing a semiconductor chip. When the semiconductor chip package is manufactured, on the sealing layer, a redistribution layer may be further formed.

(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 redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporarily fixed film are peeled, and

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

The resin composition mentioned above can be used also when a printed wiring board is a circuit board with a built-in component.

[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 plastic material, metal foil, and a release paper are mentioned, for example, The film which consists of a plastic 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”). .) polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES) ), polyether ketone, polyimide, and the like. 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 as the copper foil. 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-" 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. 7", "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. On the other hand, 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 the other layer 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 (namely, 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.

The 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 to a support using a die coater, etc., and further drying to form a resin composition layer. .

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; Amide solvents, such as dimethylformamide, dimethylacetamide (DMac), and N-methylpyrrolidone, etc. are mentioned. 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 also varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30 mass % to 60 mass % of an organic solvent, by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes, the resin composition layer can form.

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 which concerns on one Embodiment of this invention contains the insulating layer formed with the hardened|cured material obtained by hardening|curing the above-mentioned resin composition.

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) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate

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

The "inner-layer substrate" used in the 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. In addition, 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 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 further be formed is also contained in "inner-layer board|substrate". When a printed wiring board is a circuit board with a built-in component, you may use the inner-layer board which incorporated the component.

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-compressing the resin sheet to the inner layer substrate from the support side. As a member (hereinafter also referred to as a "thermal compression member") for heat-bonding the resin sheet to the inner layer substrate, a heated metal plate (such as a SUS head plate) or a metal roll (such as a SUS roll) is exemplified. On the other hand, it is preferable not to press the thermocompression-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 compression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination may be 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, a smoothing treatment of the laminated resin sheet may be performed 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 conditions similar to the thermocompression-bonding conditions of the said lamination|stacking. A smoothing process can be performed with a commercially available laminator. In addition, the lamination|stacking and smoothing process may be performed continuously using the above-mentioned commercially available vacuum laminator.

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

In the step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. Curing conditions of a resin composition layer are not specifically limited, You may use the conditions employ|adopted when forming the insulating layer of a printed wiring board. Although you may harden a resin composition layer by irradiation of active energy rays, such as an ultraviolet-ray, it is made to thermoset by heating normally.

For example, the thermosetting conditions of the resin composition layer also vary depending on the type of the resin composition, but in one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, More preferably, it is 170 degreeC - 210 degreeC. 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. to 120 ° C., preferably 60 ° C. to 115 ° C., more preferably 70 ° C. to 110 ° C., for 5 minutes or more, Preferably, you may preheat for 5 minutes - 150 minutes, More preferably, it is 15 minutes - 120 minutes, More preferably, it is 15 minutes - 100 minutes.

The method of manufacturing a printed wiring board may further include (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. When the support is removed after the step (II), the support is removed between the steps (II) and (III), between the steps (III) and (IV), or between the steps (IV) and (V). may be carried out in In addition, if necessary, the formation of the insulating layer and the conductor layer in the steps (I) to (V) may be repeated to form a multilayer wiring board.

Step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Depending on the composition of the resin composition used for formation of an insulating layer, you may implement a process (III) using a drill, a laser, plasma, etc., for example. 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. For example, the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralizing liquid can be performed in this order, and an insulating layer can be roughened.

As a swelling liquid used for a roughening process, an alkali solution, surfactant solution, etc. are mentioned, for example, Preferably it is an alkali solution. As an alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As a commercially available swelling liquid, "Swelling Deep Security P", "Swelling Deep Security SBU" by Atotech Japan, etc. are mentioned, for example. The swelling treatment by the swelling liquid is not particularly limited, and for example, it can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 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.

As an oxidizing agent used for a roughening process, the alkaline permanganic acid solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned, for example. 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-manganic acid solutions, such as "Concentrate Compact CP" and "Dosing Solution Securigans P" by Atotech Japan, are mentioned, for example.

As a neutralizing 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 5 minutes 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, arithmetic mean roughness Ra of the insulating layer surface after a roughening process becomes like this. Preferably it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more. Moreover, the root mean square roughness (Rq) of the surface of the insulating layer after roughening becomes like this. Preferably it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 300 nm or less. It does not specifically limit about a lower limit, For example, it can be set as 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) 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 one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer, and as the alloy layer, for example, an alloy of two or more metals selected from the group described above (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium) a layer formed of an alloy). 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 multi-layer 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.

The conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a method such as a semi-additive method or a full additive method. It is preferable to form by the semi-additive method from a viewpoint of the simplicity of manufacture. Hereinafter, an example in which the conductor layer is formed by a semi-additive method is shown.

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 part of the plating seed layer corresponding to the 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]

A semiconductor device according to an embodiment of the present invention includes the printed wiring board described above. This semiconductor device can be manufactured using the printed wiring board mentioned above.

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

[Example]

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" indicating quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the operation described below was performed in an environment of normal temperature and normal pressure, unless otherwise specified.

<Preparation of maleimide resin A>

A MEK solution (70% by mass of nonvolatile components) of maleimide resin A synthesized by the method described in Synthesis Example 1 of Invention Association Publication No. 2020-500211 was prepared. This maleimide resin A has a structure represented by a following formula.

When the FD-MS spectrum of maleimide resin A is measured, the peaks of M+=560, 718, and 876 are confirmed. These peaks correspond to the case where n ₁ is 0, 1, and 2, respectively. Further, when the maleimide resin A is analyzed by GPC and the value of the number of repeating units n ₁ of the indane skeleton moiety is calculated based on the number average molecular weight, n ₁ =1.47 and molecular weight distribution (Mw/Mn) = 1.81. In addition, in 100 area% of the total amount _of maleimide compound A1, the content rate of the maleimide resin of which the average number of repeating units n1 is ₀ is 26.5 area%.

The FD-MS spectrum of said maleimide resin A shows what was measured by the following measuring apparatus and measurement conditions.

(FD-MS spectrum measurement device and measurement conditions)

Measuring device: JMS-T100GC AccuTOF

Measuring conditions

Measuring range: m/z=4.00 to 2000.00

Rate of change: 51.2mA/min

Final current value: 45mA

Cathode voltage: -10kV

Logging Interval: 0.07sec

GPC of said maleimide resin A shows what was measured by the following measuring apparatus and measurement conditions.

Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation

Column: Guard column "HXL-L" by Tosoh Corporation, "TSK-GEL G2000HXL" by Tosoh Corporation, "TSK-GEL G2000HXL" by Tosoh Corporation, "TSK-GEL G3000HXL" by Tosoh Corporation, and "TSK-GEL G3000HXL" by Tosoh Corporation -GEL G4000HXL”

Detector: RI (Differential Refractometer)

Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation

Measurement conditions: Column temperature 40°C

Developing solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: Monodisperse polystyrene of known molecular weight is used in accordance with the measurement manual of "GPC Workstation EcoSEC-WorkStation".

Sample: What filtered the 1.0 mass % tetrahydrofuran solution in conversion of the nonvolatile component of a maleimide compound with a microfilter (50 microliters).

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the maleimide resin A, and the average number of repeating units "n ₁ " contributing to the indane skeleton in the maleimide resin are determined by the above GPC measurement. What was computed from the obtained GPC chart is shown. In addition, the average number _of repeating units "n1" shows what was computed based on the number average molecular weight (Mn). Specifically, with respect to the compound in which n ₁ is 0 to 4, the theoretical molecular weight and the actual molecular weight in GPC are plotted on the scatter plot, and an approximate straight line is drawn. And the number average molecular weight (Mn) is calculated|required from the point shown by the measured value Mn(1) on this straight line, and average repeating unit _number "n1" is computed further. In addition, based on the result of GPC measurement, the content rate (area %) of the maleimide resin of which the average number of repeating units n ₁ is 0 in 100 area% of the total amount of maleimide resin A is computed. For details, reference may be made to Invention Association Publication No. 2020-500211.

<Synthesis of PEEK (polyether ether ketone) compound A>

In a 500 mL flask (3 necks) equipped with a stirring device, an argon inlet tube, and a Dean Stark device, 31.443 g of 4,4'-difluorobenzophenone, 13.223 g of resorcinol, 29.894 g of anhydrous potassium carbonate, N-methyl 180 mL of pyrrolidone and 90 mL of toluene were added, heated while stirring in an argon atmosphere, and toluene was refluxed at 130 to 140°C for 4 hours. Then, it further heated and toluene was distilled off at 170-180 degreeC. Furthermore, after continuing stirring at 170-180 degreeC for 10 hours, it returned to room temperature, and obtained the product 1.

To the flask containing the product 1, 5.233 g of 4-aminophenol, 6.628 g of anhydrous potassium carbonate, 18 mL of N-methylpyrrolidone, and 90 mL of toluene were added, and heated while stirring under an argon atmosphere, and heated at 130 to 140°C for 3 Time toluene was refluxed. Then, it heated and distilled off toluene at 170-180 degreeC, and stirring was continued for 4 hours, maintaining the said temperature. Then, it cooled to room temperature, and powdery solid was obtained by adding and filtering the reaction liquid to 5000 mL of methanol. This powdery solid was repeatedly washed with methanol and water, and then dried at 100°C for 8 hours to obtain 37.461 g of a powdery solid (Diamine-A).

0.878 g of Diamine-A, 4.943 g of maleic anhydride, and 240 mL of N-methylpyrrolidone were placed in a 500 mL flask (3 neck) equipped with a stirrer and an argon inlet tube, and the mixture was stirred at room temperature under an argon atmosphere for 18 hours. . Then, 8.576 g of acetic anhydride and 0.689 g of sodium acetate were added, and it stirred at 60 degreeC for 6 hours. After returning the reaction liquid to room temperature, powdery solid was obtained by adding the reaction liquid to 5000 mL of methanol. After washing this powdery solid repeatedly with methanol and water, it dried at 100 degreeC for 8 hours, and 28.434g of PEEK compounds A represented by the following formula were obtained. The number average molecular weight calculated by GPC measurement of PEEK compound A was 2230.

[Example 1]

15 parts of PEEK compound A, an aromatic ring and a resin containing a radically polymerizable unsaturated group ("OPE-2St" manufactured by Mitsubishi Gas Chemical, a toluene solution having a number average molecular weight of 2200, a nonvolatile matter of 65% by mass) 25 parts, a polymerization initiator (Nichi) 0.5 parts of peroxide manufactured by a similar manufacture "Perbutyl (registered trademark) C"), spherical silica surface-treated with an inorganic filler (amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO" manufactured by Adomatex Corporation) -C2", average particle diameter 0.5 μm, specific surface area 5.8 m 2 /g) 30 parts, and an ester type phenoxy resin (“YL7891BH30” manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass) ) 10 parts were mixed, and it disperse|distributed uniformly using the high-speed rotation mixer, and obtained the resin varnish.

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, said resin varnish was apply|coated uniformly so that the thickness of the resin composition layer after drying might be set to 40 micrometers. Then, the resin varnish was dried at 80 degreeC - 100 degreeC (average 90 degreeC) for 4 minutes, and the resin sheet containing a support body and a resin composition layer was obtained.

[Example 2]

In Example 1, 25 parts of resin containing an aromatic ring and a radically polymerizable unsaturated group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a number average molecular weight of 1200, and a toluene solution having a nonvolatile content of 65% by mass) 25 parts of an aromatic ring and radical It was replaced with 25 parts of resin containing a polymerizable unsaturated group ("ODV-XET(X04)" (weight average molecular weight 3110, vinyl group equivalent 380 g/eq., 65 mass % solution) by a Nittetsu Chemical & Materials company.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Example 3]

In Example 1, 25 parts of resin containing an aromatic ring and a radically polymerizable unsaturated group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a number average molecular weight of 1200, and a toluene solution having a nonvolatile content of 65% by mass) 25 parts of an aromatic ring and radical It replaced with 16 parts of resin ("SA9000-111" by SABIC, number average molecular weight 1850-1950) containing a polymerizable unsaturated group.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Example 4]

In Example 1, the amount of the resin containing an aromatic ring and a radically polymerizable unsaturated group ("OPE-2St" manufactured by Mitsubishi Gas Chemicals, a toluene solution having a number average molecular weight of 1200 and a nonvolatile content of 65% by mass) is 25 parts to 20 turn into wealth,

In addition, a resin containing an aromatic ring and a radically polymerizable unsaturated group (biphenyl aralkyl maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.), maleimide group equivalent: 275 g/eq., non-volatile content of 70% MEK/toluene mixed solution) 5 parts were used.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Example 5]

In Example 1, the amount of the resin containing an aromatic ring and a radically polymerizable unsaturated group ("OPE-2St" manufactured by Mitsubishi Gas Chemicals, a toluene solution having a number average molecular weight of 1200, and a nonvolatile content of 65% by mass) is 25 parts to 12 turn into wealth,

Furthermore, 6 parts of resin ("BMI-1500" by Designer Molecules, maleimide group equivalent 750 g/eq.) containing an aromatic ring and a radically polymerizable unsaturated group was used.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Example 6]

In Example 1, 25 parts of resin containing an aromatic ring and a radically polymerizable unsaturated group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a number average molecular weight of 1200, and a toluene solution having a nonvolatile content of 65% by mass) 25 parts of an aromatic ring and radical It replaced with 46 parts of resin (The Dow Chemical Company "CYCLOTENE3022-35", the mesitylene solution of 35 mass % of non-volatile components) containing a polymerizable unsaturated group.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Example 7]

In Example 1, 25 parts of resin containing an aromatic ring and a radically polymerizable unsaturated group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1200, toluene solution having a nonvolatile content of 65% by mass) 25 parts, maleimide resin A changed to part 23.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Example 8]

In Example 1, 10 parts of an ester-type phenoxy resin ("YL7891BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK having a solid content of 30% by mass and cyclohexanone) 10 parts of an elastomer (manufactured by Kraton, styrene-ethylene/butylene) -Styrene block copolymer "FG1924") was replaced with 3 parts.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Comparative Example 1]

In Example 1,

Without using 15 parts of PEEK compound A,

The amount of the resin containing an aromatic ring and a radically polymerizable unsaturated group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a number average molecular weight of 1200, a toluene solution having a nonvolatile content of 65% by mass) is changed from 25 parts to 48 parts,

Spherical silica surface-treated with inorganic filler (amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Adomatex, average particle diameter 0.5 μm, specific surface area 5.8 m 2 /g) The amount of was changed from 30 parts to 35 parts.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Comparative Example 2]

In Example 2,

Without using 15 parts of PEEK compound A,

The amount of the resin containing an aromatic ring and a radically polymerizable unsaturated group ("ODV-XET (X04)" manufactured by Nittetsu Chemical & Materials Co., Ltd. (weight average molecular weight 3110, vinyl equivalent weight 380 g/eq., 65 mass % solution) is 25 change from part to part 48,

Spherical silica surface-treated with inorganic filler (amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Adomatex, average particle diameter 0.5 μm, specific surface area 5.8 m 2 /g) The amount of was changed from 30 parts to 35 parts.

Except for the above, it carried out similarly to Example 2, and obtained the resin varnish and the resin sheet.

[Comparative Example 3]

In Example 3,

Without using 15 parts of PEEK compound A,

Change the amount of the resin containing an aromatic ring and a radically polymerizable unsaturated group ("SA9000-111" manufactured by SABIC, number average molecular weight 1850-1950) from 16 parts to 31 parts,

Spherical silica surface-treated with inorganic filler (amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Adomatex, average particle diameter 0.5 μm, specific surface area 5.8 m 2 /g) The amount of was changed from 30 parts to 35 parts.

Except for the above, it carried out similarly to Example 3, and obtained the resin varnish and the resin sheet.

[Comparative Example 4]

In Example 1,

Without using 15 parts of PEEK compound A,

25 parts of a resin containing an aromatic ring and a radically polymerizable unsaturated group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Company, a toluene solution having a number average molecular weight of 1200, and a nonvolatile content of 65% by mass) containing an aromatic ring and a radically polymerizable unsaturated group Replace with 45 parts of resin (biphenyl aralkyl maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., MEK/toluene mixed solution with 70% nonvolatile matter)),

Spherical silica surface-treated with inorganic filler (amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Adomatex, average particle diameter 0.5 μm, specific surface area 5.8 m 2 /g) The amount of was changed from 30 parts to 35 parts.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Measurement of dielectric properties (permittivity and dielectric loss tangent)]

The resin sheet produced by the Example and the comparative example was heated at 190 degreeC for 90 minute(s), and the resin composition layer was thermosetted. Then, the support body was peeled, and the hardened|cured material of the resin composition was obtained. This cured product was cut into a test piece having a width of 2 mm and a length of 80 mm. About the said test piece, the dielectric constant Dk and dielectric loss tangent Df were measured at the measurement frequency of 5.8 GHz, and the measurement temperature of 23 degreeC by the cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies. Measurement was performed on three test pieces, and the average value is shown in the table below.

[Measurement of copper foil adhesion]

(1) Substrate treatment of copper foil

The polished surface of "3EC-III" (electric field copper foil, 35 µm) manufactured by Mitsui Kinzoku Kozan was etched to 1 µm with a micro-etching agent ("CZ8101" manufactured by Mack Corporation) to roughen the copper surface, followed by a rust prevention treatment (CL8300) ) was carried out. Moreover, it heat-processed in 130 degreeC oven for 30 minutes. This copper foil is called CZ copper foil.

(2) Preparation of the inner layer substrate

Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 µm, substrate thickness 0.4 mm, Panasonic Corporation "R1515A") on which an inner-layer circuit is formed are etched to 1 µm with a micro-etching agent ("CZ8101" manufactured by Mack Corporation) A roughening treatment of the copper surface was performed.

(3) Lamination of copper foil and formation of insulating layer

Using a batch vacuum pressurized laminator (manufactured by Nikko Materials, a two-stage build-up laminator, "CVP700"), the resin composition layer of the resin sheet was laminated on both surfaces of the inner layer substrate so that it 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 performed by pressure-bonding at 120 degreeC and pressure 0.74 MPa for 30 second. Then, hot pressing was performed at 100 DEG C and a pressure of 0.5 MPa for 60 seconds. On the resin composition layer, the treated surface of CZ copper foil was laminated under the conditions similar to the above. And the evaluation board|substrate was produced by hardening|curing a resin composition layer on 190 degreeC and hardening conditions for 90 minutes, and forming an insulating layer.

(4) Measurement of copper foil adhesion before reliability test

The produced evaluation board was cut into 150 x 30 mm pieces. In the copper foil part of the small piece, using a cutter, an incision of 10 mm in width and 100 mm in length is made, one end of the copper foil is peeled off and picked up with a clipper, and 35 mm is peeled off in the vertical direction at a speed of 50 mm/min at room temperature. The load (kgf/cm) was measured, and the peel strength was calculated|required. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement. The measurement was performed based on Japanese Industrial Standards (JIS C6481), and the following references|standards evaluated the copper foil adhesiveness before a reliability test.

* In a table|surface, content of (A) component shows content of (A) component at the time of making the resin component in a resin composition 100 mass %. (C) Content of component shows content of (C)component at the time of setting it as 100 mass % of non-volatile components in a resin composition.

Claims (13)

(A) a polyether ether ketone compound having a maleimide group, and
(B) A resin composition comprising a resin containing an aromatic ring and a radically polymerizable unsaturated group. The resin composition of Claim 1 whose number average molecular weight of (A) component is 10000 or less. The resin composition of Claim 1 in which (A) component has a maleimide group at the terminal. The resin composition of Claim 1 whose content of (A) component is 5 mass % or more and 60 mass % or less, when the resin component in a resin composition is 100 mass %. The resin composition according to claim 1, wherein the component (B) contains any one of a maleimide radical polymerizable compound containing a maleimide group and a vinylphenyl radical polymerizable compound containing a vinylphenyl group. The resin composition of Claim 1 whose content of (B) component is 20 mass % or more and 60 mass % or less, when the resin component in a resin composition is 100 mass %. The resin composition according to claim 1, further comprising (C) an inorganic filler. The resin composition of Claim 7 whose content of (C)component is 30 mass % or more and 80 mass % or less, when content of the non-volatile component in a resin composition is 100 mass %. 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 10 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 1-10. A semiconductor device comprising the printed wiring board according to claim 12 .