CN114058267A

CN114058267A - Resin composition

Info

Publication number: CN114058267A
Application number: CN202110858638.9A
Authority: CN
Inventors: 川合贤司
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2020-07-29
Filing date: 2021-07-28
Publication date: 2022-02-18
Also published as: JP2022025704A; TW202212474A; JP7443975B2; KR20220014835A

Abstract

The invention provides a resin composition which can obtain a cured product with low dielectric property and excellent adhesion with a copper foil. The solution of the present invention is a resin composition comprising: (A) a polyether ether ketone compound having a maleimide group, and (B) a resin containing an aromatic ring and a radical polymerizable unsaturated group.

Description

Resin composition

Technical Field

The present invention relates to a resin composition. The present invention also relates to a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

Background

As a manufacturing technique of a printed wiring board, a manufacturing method based on a stack (build) method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method by the stack system, the insulating layer is generally formed by curing a resin composition. As such a resin composition, for example, a resin composition disclosed in patent document 1 is known.

[ Prior art documents ]

[ patent document ]

Patent document 1: japanese patent laid-open publication No. 2019-66792.

Disclosure of Invention

Problems to be solved by the invention

A cured product formed by curing the resin composition can be used as an insulating layer of a printed wiring board of a semiconductor device. Therefore, it is required to lower the dielectric characteristics (dielectric constant and dielectric loss tangent) of the cured product. Further, it is desired that the insulating layer formed from the cured product has excellent adhesion to the copper foil.

The present invention was made in view of the above problems, and an object of the present invention is to provide: a resin composition which can give a cured product having low dielectric characteristics and excellent adhesion to a copper foil; a resin sheet having a resin composition layer comprising the resin composition; a printed wiring board comprising an insulating layer formed from a cured product of the resin composition; and a semiconductor device including the printed wiring board.

Means for solving the problems

As a result of diligent research directed toward solving the above problems, the present inventors have found that: the above problems can be solved by using (a) a polyether ether ketone compound having a maleimide group and (B) a resin containing an aromatic ring and a radical polymerizable unsaturated group, and the present invention has been completed.

That is, the present invention includes the following;

[1] a resin composition comprising:

(A) polyether ether ketone compound having maleimide group, and

(B) a resin containing an aromatic ring and a radical 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 a 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, assuming that the resin component in the resin composition is 100% by mass;

[5] the resin composition according to any one of [1] to [4], wherein the component (B) contains: any radical polymerizable compound of maleimide radical polymerizable compounds containing maleimide groups and vinyl phenyl radical polymerizable compounds containing vinyl phenyl groups;

[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, assuming that 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 to 80 mass% based on 100 mass% of nonvolatile components in the resin composition;

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

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

[11] a resin sheet, comprising:

a support, and

a resin composition layer comprising the resin composition according to any one of [1] to [10] provided on the support;

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

[13] a semiconductor device comprising the printed wiring board of [12 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: a resin composition which can give a cured product having low dielectric characteristics and excellent adhesion to a copper foil; a resin sheet having a resin composition layer comprising the resin composition; a printed wiring board comprising an insulating layer formed from a cured product of the resin composition; and a semiconductor device including the printed wiring board.

Detailed Description

The present invention will be described below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and can be implemented by arbitrarily changing the embodiments and examples without departing from the scope of the claims and their equivalents.

[ resin composition ]

The resin composition of the present invention comprises: (A) a polyether ether ketone compound having a maleimide group, and (B) a resin containing an aromatic ring and a radical polymerizable unsaturated group. According to the resin composition, a cured product with low dielectric property and excellent adhesion with a copper foil can be obtained.

The resin composition may further contain, if necessary, optional components such as (C) an inorganic filler, (D) a polymerization initiator, (E) a thermoplastic resin, (F) an elastomer, and (G) other additives.

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

The resin composition contains a polyether ether ketone compound having a maleimide group as the component (a). The maleimide group is represented by the following formula (A-1). By containing the component (A) in the resin composition, a cured product having low dielectric characteristics and excellent adhesion to a copper foil can be obtained;

[ chemical formula 1]

(A) As the component (B), a compound having a maleimide group and a polyether ether ketone structure can be used. The maleimide group is preferably at least 1 maleimide group, more preferably at least 2 maleimide groups, still more preferably at most 10 maleimide groups, still more preferably at most 5 maleimide groups, and still more preferably at most 3 maleimide groups per 1 molecule of the component (A). The maleimide group is preferably a maleimide group at the terminal of the component (A), more preferably maleimide groups at both terminals, from the viewpoint of obtaining a cured product excellent in dielectric properties.

(A) The component has a polyetheretherketone structure. The polyether ether ketone structure is preferably a polyether ether ketone structure having a structure represented by the following formula (A-2);

[ chemical formula 2]

In the formula (A-2), Ar¹、Ar²、Ar³、Ar⁴And Ar⁵Each independently represents a divalent aromatic hydrocarbon group. n represents an integer of 2 to 50. It represents a chemical bond.

The aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring. However, the aromatic hydrocarbon group does not necessarily have to be composed of only aromatic rings, and a part thereof may contain a chain structure or an alicyclic hydrocarbon group, and the aromatic rings may be any 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.

The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include phenylene, naphthylene, anthrylene, and biphenylene.

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 benzylidene group and a group having a biphenylene-methylene structure.

The arylene group in the group having an arylene-alkylene-arylene structure is the same as the arylene group described above. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Examples of such alkylene groups include methylene, ethylene, and propylene. Further, the alkylene group optionally has a substituent. Examples of the substituent include: an alkyl group having 1 to 3 carbon atoms; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; and a halogenated alkyl group, preferably an alkyl group having 1 to 3 carbon atoms or a halogenated alkyl group, more preferably a methyl group or a trifluoromethyl group, and still more preferably a methyl group. Specific examples of such a group having an arylene-alkylene-arylene structure include structures represented by the following formulas (1) to (2). Among them, preferred is a group represented by the formula (1);

[ chemical formula 3]

Wherein "" denotes a chemical bond.

Among them, as Ar¹、Ar²、Ar⁴And Ar⁵The arylene group or the group having an arylene-alkylene-arylene structure is preferred, the arylene group is more preferred, and the phenylene group is further preferred. As Ar³The arylene group or the group having an arylene-alkylene-arylene structure is preferred, the group having an arylene-alkylene-arylene structure is more preferred, and the group having a phenylene-dimethylmethylene-phenylene structure (the group represented by the formula (1)) is even more preferred.

n represents an integer of 2 to 50, preferably an integer of 3 to 40, more preferably an integer of 4 to 30, further preferably an integer of 5 to 20.

Specific examples of the structure represented by the formula (A-2) include, for example, the structures represented by the following formulae (A1) to (A2), but are not limited to these structures (wherein, represents a chemical bond);

[ chemical formula 4]

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

As the component (A), a compound represented by the following formula (A-3);

[ chemical formula 5]

In the formula, D¹And D²Each independently represents a single bond or a divalent linking group. Ar (Ar)¹¹、Ar¹²、Ar¹⁴And Ar¹⁵Each independently of Ar in formula (A-2)¹、Ar²、Ar⁴And Ar⁵The same is true. Ar (Ar)¹³Each independently of Ar in formula (A-2)³The same is true. m is the same as n in the formula (A-2).

D¹And D²Each independently represents 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.

Examples of the divalent aliphatic hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, and a linear or branched alkenylene group having 2 to 18 carbon atoms. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene and the like. Examples of the linear or branched alkenylene group having 2 to 18 carbon atoms include an ethenylene group, a 1-methylethenylene group, an propenylene group, a 1-butenylene group, and a 2-butenylene group.

Examples of the divalent alicyclic hydrocarbon group include divalent alicyclic hydrocarbon groups having 3 to 18 carbon atoms, and examples thereof include cycloalkylene groups (including cycloalkylidene groups) such as 1, 2-cyclopentylene group, 1, 3-cyclopentylene group, cyclopentylidene group, 1, 2-cyclohexylene group, 1, 3-cyclohexylene group, 1, 4-cyclohexylene group, and cyclohexylidene group.

Examples of the divalent aromatic hydrocarbon group include arylene groups having 6 to 14 carbon atoms, and examples thereof include 1, 2-phenylene, 1, 4-phenylene, 1, 3-phenylene, 4 '-biphenylene, 3' -biphenylene, 2, 6-naphthylene, 2, 7-naphthylene, 1, 8-naphthylene, and anthracenylene.

The heterocyclic ring constituting the divalent heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of the heterocyclic ring include a 3-to 10-membered ring having a carbon atom and at least 1 kind of hetero atom among atoms constituting the ring, a condensed ring (condensed ring) thereof, and the like. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. The heterocycle is preferably a 3-to 10-membered ring, more preferably a 4-to 6-membered ring. Examples of the heterocyclic ring constituting the divalent heterocyclic group include: 3-membered rings such as oxirane rings; a 4-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, a gamma-butyrolactone ring, a thiophene ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring, or the like; 6-membered rings such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring, 4-oxo-4H-thiopyran ring, isocyanuric acid ring (isocyanuric ring), pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring and piperazine ring; 3-oxatricyclo [4.3.1.1^4,8]Undecane-2-one ring, 3-oxatricyclo [4.2.1.0^4,8]A bridged ring such as a nonane-2-one ring; and fused rings such as a benzofuran ring, an isobenzofuran ring, a 4-oxo-4H-benzopyran ring, a chroman ring, an isochroman ring, a benzothiophene ring, an indole ring, an indoline ring, a quinoline ring, an acridine ring, a naphthyridine ring, a quinazoline ring, and a purine ring. The divalent heterocyclic group is a group obtained by removing 2 hydrogen atoms from the structural formula of the above-mentioned heterocycle.

Wherein as D¹And D²From the viewpoint of remarkably obtaining the effect of the present invention, it is preferably a divalent aromatic hydrocarbon group, more preferably an arylene group having 6 to 16 carbon atoms, further preferably a1, 2-phenylene group, a1, 4-phenylene group, a1, 3-phenylene group, a4, 4 '-biphenylene group, a3, 3' -biphenylene group, a2, 6-naphthylene group, a2, 7-naphthylene group, a1, 8-naphthylene group, or an anthracenylene group, and particularly preferably a1, 2-phenylene group, a1, 4-phenylene group, or a1, 3-phenylene group.

Specific examples of the component (A) include the following, but the present invention is not limited thereto. In the formula, na and nb independently represent an integer of 2 to 50;

[ chemical formula 6]

(A) As the component (C), a commercially available one or one synthesized by a known method may be used. The component (A) can be synthesized, for example, by a synthesis method described in Polymer 1989, p 978. (A) The components can be used alone in 1 kind, also can be combined with more than 2 kinds.

The weight average molecular weight of the component (A) is preferably 1000 or more, more preferably 1200 or more, further preferably 1400 or more, preferably 10000 or less, further preferably 7500 or less, further preferably 5000 or less, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to a copper foil. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

The number average molecular weight of the component (A) is preferably 1000 or more, more preferably 1200 or more, further preferably 1400 or more, preferably 10000 or less, further preferably 7500 or less, further preferably 5000 or less, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to a copper foil. The number average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

The content of the component (a) is preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more and 20 mass% or more, further preferably 40 mass% or less, further preferably 35 mass% or less, further preferably 30 mass% or less, based on 100 mass% of nonvolatile components in the resin composition, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to a copper foil. In the present invention, the content of each component in the resin composition is a value obtained when the nonvolatile component in the resin composition is 100 mass%, unless otherwise specified.

The content of the component (a) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, 30% by mass or more, and 40% by mass or more, further preferably 60% by mass or less, further preferably 55% by mass or less, and further preferably 50% by mass or less, based on 100% by mass of the resin component in the resin composition, from the viewpoint of obtaining a cured product having low dielectric characteristics and excellent adhesion to a copper foil. The resin component is a component obtained by removing (C) the inorganic filler from nonvolatile components in the resin composition.

< (B) a resin containing an aromatic ring and a radical-polymerizable unsaturated group

The resin composition contains, as the component (B): a resin containing an aromatic ring and a radical polymerizable unsaturated group. However, the component (B) excludes substances belonging to the component (A). By containing (B) a resin containing an aromatic ring and a radical polymerizable unsaturated group in the resin composition, a cured product having low dielectric characteristics and excellent adhesion to a copper foil can be obtained.

(B) As the component (b), a resin containing an aromatic ring and a radical polymerizable unsaturated group in the molecule can be used. (B) The aromatic ring contained in the component (A) may be an aromatic carbocyclic ring or an aromatic heterocyclic ring. The aromatic ring may be a monocyclic aromatic ring, a fused aromatic ring in which 2 or more monocyclic aromatic rings are fused, or a fused aromatic ring in which 1 or more monocyclic non-aromatic rings are fused to 1 or more monocyclic aromatic rings. Examples of the aromatic ring include: monocyclic aromatic rings such as benzene rings and pyridine rings; a fused aromatic ring such as an indane ring, a fluorene ring, a naphthalene ring, etc. Among them, the aromatic ring is preferably an aromatic carbocyclic ring. The number of carbon atoms of the aromatic carbocyclic ring is preferably 6 or more and 10 or less.

The aromatic ring contained in the component (B) may have a substituent bonded thereto. The number of substituents bonded to 1 aromatic ring may be 1, or 2 or more. When the number of the substituents is 2 or more, these 2 or more substituents may be the 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. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.

The number of carbon atoms of the alkyloxy group is preferably 1 to 10. Examples of the alkyloxy group include methoxy, ethoxy, propoxy, and butoxy.

The number of carbon atoms of 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 of the aryl group is preferably 6 to 10. Examples of the aryl group include a phenyl group and a naphthyl group.

The number of carbon atoms of the aryloxy group is preferably 6 to 10. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, and the like.

The number of carbon atoms of the arylthio group is preferably 6 to 10. Examples of the arylthio group include phenylthio group and naphthylthio group.

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom and the like.

Among them, the aromatic ring contained in the component (B) is preferably an unsubstituted or alkyl group bonded thereto.

(B) The number of aromatic rings contained in the component (A) is usually 1 or more, preferably 2 or more. (B) When the component (B) contains 2 or more aromatic rings, these 2 or more aromatic rings may be the same or different.

(B) The radical polymerizable unsaturated group contained in component (a) represents a group containing an unsaturated bond exhibiting radical polymerizability, and the radical polymerizable unsaturated group is a concept including a case where the radical polymerizable unsaturated group is contained in the molecular skeleton of component (B) as a divalent group having an unsaturated bond. Examples of the radical polymerizable unsaturated group include groups containing an ethylenic double bond. The component (B) containing such a radically polymerizable unsaturated group can be radically polymerized by heat or active energy rays to cure the 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 fumaryl group, a maleoyl group, a benzocyclobutene group, and an allyl group. (B) The number of the radical polymerizable unsaturated groups contained in the component (A) is usually not less than 1, preferably not less than 2. (B) When component (b) contains 2 or more radically polymerizable unsaturated groups, these 2 or more radically polymerizable unsaturated groups may be the same or different.

The component (B) may be any resin as long as it contains an aromatic ring and a radical polymerizable unsaturated group. The component (B) is preferably selected from

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

(B2) A resin containing a maleimide group and an aromatic ring, (B3) a resin containing a radical polymerizable unsaturated group and benzocyclobutene,

1 or more of them.

(B) The component (A) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. For example, the component (B1) and the component (B2) may be used in combination.

- (B1) resin containing vinyl group and aromatic ring

(B1) Component (B) is a resin belonging to component (B), and therefore is a resin containing a vinyl group as a radical polymerizable unsaturated group and an aromatic ring. (B1) The component (A) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. (B1) The number of vinyl groups per 1 molecule of the component (A) may be 1, or 2 or more, preferably 2.

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

[ chemical formula 7]

In the formula (B1-1), R^A1、R^A2And R^A3Each independently represents a hydrogen atom or an alkyl group; r^A4Each independently represents an alkyl group; m is_a1Represents 0 or 1; m is_a2Represents an integer of 0 to 4Counting; it represents a chemical bond.

In the formula (B1-1), R^A1、R^A2And R^A3Each independently represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 18, more preferably 1 to 12, further 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 tert-butyl group. Wherein R is^A1Preferably a hydrogen atom or a methyl group, R^A2And R^A3Preferably a hydrogen atom.

In the formula (B1-1), R^A4Each independently represents an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, further 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 tert-butyl group. Wherein R is^A1Methyl is preferred.

In formula (B1-1), m_a1Represents 0 or 1. R^A1When it is a hydrogen atom, m_a1Preferably 0. Furthermore, R^A1When is alkyl, m_a1Preferably 1.

In formula (B1-1), m_a2Represents an integer of 0 to 4. m is_a2Preferably 0 to 2.

The component (B1-1) may contain 1 group represented by the formula (B1-1), preferably 2 or more groups, per 1 molecule.

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

[ chemical formula 8]

In the formula (B1-2), L¹Represents a divalent linking group; r^B11、R^B12、R^B13、R^B21、R^B22And R^B23Each independently represents a hydrogen atom or an alkyl group; r^B14、R^B15、R^B24And R^B25Each independently represents an alkyl group; r^B16And R^B26Each independently represents an alkylene group; m is_b11And m_b21Each independently represents 0 or 1; m is_b12、m_b13、m_b22And m_b23Each independently represents an integer of 0 to 4; m is_b14And m_b24Each independently represents an integer of 0 to 300; m is_b15And m_b25Each independently represents 0 or 1.

In the formula (B1-2), L¹Represents a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, arylene, alkylarylene, heteroarylene, -O-, -NH-, -NR^x-、-CO-、-CS-、-SO-、-SO₂-, -C (═ O) O-, -NHC (═ O) -, -NC (═ O) N-, -NHC (═ O) O-, -C (═ O) -, -S-, and a combination of a plurality of these. R^xRepresents a hydrocarbon group having 1 to 12 carbon atoms. L is¹The number of carbon atoms of (B) is usually 60 or less, preferably 48 or less, more preferably 36 or less, particularly preferably 24 or less.

In the formula (B1-2), R^B11、R^B12、R^B13、R^B21、R^B22And R^B23Each independently represents a hydrogen atom or an alkyl group. R^B11、R^B12、R^B13、R^B21、R^B22And R^B23May be reacted with R in the formula (B1-1)^A1、R^A2And R^A3The same is true. Wherein R is^B11And R^B21Preferably a hydrogen atom or a methyl group, R^B12、R^B13、R^B22And R^B23Preferably a hydrogen atom.

In the formula (B1-2), R^B14、R^B15、R^B24And R^B25Each independently represents an alkyl group. R^B14、R^B15、R^B24And R^B25May be reacted with R in the formula (B1-1)^A4The same is true. Wherein R is^B14、R^B15、R^B24And R^B25Methyl is preferred.

In the formula (B1-2), R^B16And R^B26Each independently represents an alkylene group. Alkylene radicalThe number of carbon atoms of (A) is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 3. The alkylene group is preferably a linear alkylene group, more preferably a methylene group.

In formula (B1-2), m_b11And m_b21Each independently represents 0 or 1.

In formula (B1-2), m_b12、m_b13、m_b22And m_b23Each independently represents an integer of 0 to 4. m is_b12、m_b13、m_b22And m_b23Preferably 1 to 4, more preferably 2 to 3, particularly preferably 2.

In formula (B1-2), m_b14And m_b24Each independently represents an integer of 0 to 300. In detail, m_b14And m_b24Usually 0 or more, preferably 1 or more, usually 300 or less, preferably 100 or less, more preferably 50 or less, further preferably 20 or less, particularly preferably 10 or less.

In formula (B1-2), m_b15And m_b25Each independently represents 0 or 1. m is_b11When is 0, m_b15Preferably 1, m_b11When is 1, m_b15Preferably 0. Furthermore, m_b21When is 0, m_b25Preferably 1, m_b21When is 1, m_b25Preferably 0.

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

[ chemical formula 9]

In the formula (B1-3), L²Represents a divalent linking group; r^C15And R^C25Each independently represents an alkyl group; r^C16And R^C26Each independently represents an alkylene group; m is_c14And m_c24Each independently represents an integer of 0 to 300.

In the formula (B1-3), L²Represents a divalent linking group. L is²Can be reacted with L in the formula (B1-2)¹The same is true. Wherein L is²Preferably, it isA divalent group represented by the following formula (B1-4);

[ chemical formula 10]

In the formula (B1-4), X¹～X⁸Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. It represents a chemical bond.

In the formula (B1-3), R^C15And R^C25Each independently represents an alkyl group. R^C15And R^C25May be reacted with R in the formula (B1-1)^A4The same is true. Wherein R is^C15And R^C25Methyl is preferred.

In the formula (B1-3), R^C16And R^C26Each independently represents an alkylene group. R^C16And R^C26May be reacted with R in the formula (B1-2)^B16And R^B26The same is true. Wherein R is^C16And R^C26And methylene is more preferable.

In formula (B1-3), m_c14And m_c24Each independently represents an integer of 0 to 300. m is_c14And m_c24Can be combined with m in the formula (B2)_b14And m_b24The same is true. In the formula (B1-3), m is preferably excluded_c14And m_c24One of them is 0.

Examples of the compound represented by the formula (B1-3) include compounds represented by the following formula (B1-5). In the formula (B1-5), m_c14And m_c24Represents the same number as in the formula (B1-3). The compound represented by the formula (B1-5) is available as "OPE-2 St" manufactured by Mitsubishi gas chemical company;

[ chemical formula 11]

Other preferable examples of the compound represented by the formula (B1-2) include compounds represented by the following formula (B1-6):

[ chemical formula 12]

In the formula (B1-6), L³Represents a divalent linking group; r^D11And R^D21Each independently represents a hydrogen atom or an alkyl group; r^D14、R^D15、R^D24And R^D25Each independently represents an alkyl group; m is_d14And m_d24Each independently represents an integer of 0 to 300.

In the formula (B1-6), L³Represents a divalent linking group. L is³Can be reacted with L in the formula (B1-2)¹The same is true. Wherein L is³Preferably selected from alkylene, alkenylene, -O-, -NR^x-、-CO-、-CS-、-SO-、-SO₂Any of (A), (B), (C) and (C), preferably an alkylene group, particularly preferably isopropylidene (-C (CH))₃)₂-)。

In the formula (B1-6), R^D11And R^D21Each independently represents a hydrogen atom or an alkyl group. R^D11And R^D21May be reacted with R in the formula (B1-2)^B11And R^B21The same is true. Wherein R is^D11And R^D21Methyl is preferred.

In the formula (B1-6), R^D14、R^D15、R^D24And R^D25Each independently represents an alkyl group. R^D14、R^D15、R^D24And R^D25May be reacted with R in the formula (B1-1)^A4The same is true. Wherein R is^D14、R^D15、R^D24And R^D25Methyl is preferred.

In formula (B1-6), m_d14And m_d24Each independently represents an integer of 0 to 300. m is_d14And m_d24Can be reacted with m in the formula (B1-2)_b14And m_b24The same is true. Furthermore, m_b14And m_b24The total of (2) or more is preferred.

Examples of the compound represented by the formula (B1-6) include compounds represented by the following formula (B1-7). In the formula (B1-7), L³、m_d14And m_d24The same as those of the corresponding symbols in the formula (B1-6). Formula (B)1-7) is available as "NORYL SA 9000" manufactured by SABIC corporation;

[ chemical formula 13]

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

[ chemical formula 14]

In the formula (B1-8), R^E1、R^E2And R^E3Each independently represents a hydrogen atom or an alkyl group; r^E4Each independently represents an alkyl group; r^E5、R^E6And R^E7Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m is_e1Represents 0 or 1; m is_e2Represents an integer of 0 to 4; it represents a chemical bond.

In the formula (B1-8), R^E1、R^E2And R^E3Each independently represents a hydrogen atom or an alkyl group. R^E1、R^E2And R^E3May be reacted with R in the formula (B1-1)^A1、R^A2And R^A3The same is true. Wherein R is^E1、R^E2And R^E3Preferably a hydrogen atom.

In the formula (B1-8), R^E4Each independently represents an alkyl group. R^E4May be reacted with R in the formula (B1-1)^A4The same is true.

In the formula (B1-8), R^E5、R^E6And R^E7Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Wherein R is^E5、R^E6And R^E7Preferably a hydrogen atom.

In formula (B1-8), m_e1Represents 0 or 1, preferably 0.

In formula (B1-8), m_e2Represents an integer of 0 to 4, preferably 0.

The molar content of the structural unit represented by the formula (B1-8) is preferably within a specific range relative to 100 mol% of the total of all the structural units contained in the polymer comprising the structural unit represented by the formula (B1-8). Specifically, the molar content of the structural unit represented by the formula (B1-8) is preferably from 2 to 95 mol%, more preferably from 8 to 81 mol%. Further, the average number of the structural units represented by the formula (B1-8) contained in the molecule of the polymer 1 is preferably 1 to 160, more preferably 3 to 140.

The polymer comprising the structural unit represented by the formula (B1-8) may further comprise an arbitrary structural unit in combination with the structural unit represented by the formula (B1-8). Examples of the optional structural unit include a structural unit represented by the following formula (B1-9):

[ chemical formula 15]

In the formula (B1-9), R^E8、R^E9And R^E10Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ar (Ar)^E1Represents an optionally substituted aryl group. As Ar^E1Examples of the substituent that may be contained include an alkyl group having 1 to 6 carbon atoms. It represents a chemical bond.

Examples of the polymer containing a structural unit represented by the formula (B1-9) include: a copolymer comprising a structural unit represented by the following formula (B1-10), a structural unit represented by the following formula (B1-11), and a structural unit represented by the following formula (B1-12) in combination. In the formulae (B1-10), (B1-11) and (B1-12), the symbols represent a bond. In the copolymer, the molar contents 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) are 8 to 54 mol%, 0 to 92 mol%, and 0 to 89 mol%, respectively. Further, the average numbers 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) contained in the molecule of the copolymer 1 are 1 to 160, 0 to 350, and 0 to 270, respectively. The copolymer is available as "ODV-XET (X03)", "ODV-XET (X04)" and "ODV-XET (X05)" manufactured by Nikko-Tekko chemical Co., Ltd.;

[ chemical formula 16]

(B1) The components may be used alone in 1 kind, or 2 or more kinds may be used in combination at an arbitrary ratio.

(B1) The vinyl equivalent of the component (A) is preferably 250 to 1200g/eq, more preferably 300 to 1100g/eq. The radical polymerizable unsaturated group equivalent means the mass of the radical polymerizable aromatic resin per 1 equivalent of vinyl group. (B1) When the radical polymerizable unsaturated group equivalent of the component (b) is within the above range, the effects of the present invention can be remarkably obtained.

(B1) The weight average molecular weight of the component (A) is preferably 1000 to 40000, more preferably 1500 to 35000. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

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

(B2) Component (B) is a resin belonging to component (B), and therefore is a resin containing a maleimide group as a radical polymerizable unsaturated group and an aromatic ring. However, in the component (B2), the component (A) is not included. (B2) The component (A) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(B2) The number of maleimide groups per 1 molecule of the component (A) may be 1, or 2 or more, preferably 2. For the maleimide group, as described above.

The component (B2) is preferably selected from (B2-1) maleimide compounds comprising an aromatic ring and an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide group,

(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 containing a trimethylindan skeleton

1 or more of them.

Here, the term "directly" means: in the component (B2-1), no other group is present between the nitrogen atom of the maleimide group and the aliphatic group having 5 or more carbon atoms; in the (B2-2) component, no other group is present between the nitrogen atom of the maleimide and the aromatic ring.

{ (B2-1) composition }

The component (B2-1) is a maleimide compound comprising an "aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide" and an "aromatic ring". The component (B2-1) can be obtained, for example, by subjecting a component containing an aliphatic amine compound (e.g., a diamine compound having a dimer acid skeleton) and maleic anhydride, and optionally, a tetracarboxylic dianhydride to an imidization reaction.

Examples of the aliphatic group having 5 or more carbon atoms include an alkyl group, an alkylene group, and an alkenylene group.

The alkyl group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 50 or less carbon atoms, still more preferably 45 or less carbon atoms, and still more preferably 40 or less carbon atoms. The alkyl group may be linear, branched or cyclic, and among them, linear is preferred. Examples of such an alkyl group include pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like. The alkyl group having 5 or more carbon atoms may have a substituent of an alkylene group having 5 or more carbon atoms.

The alkylene group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 50 or less, still more preferably 45 or less, and still more preferably 40 or less. The alkylene group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic alkylene group is a concept including "a case of being composed only of a cyclic alkylene group" and "a case of including both a linear alkylene group and a cyclic alkylene group". Examples of the 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, a hexadecylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

The number of carbon atoms of the alkenylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, further preferably 50 or less, further preferably 45 or less, further preferably 40 or less. The alkenylene group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic alkenylene group is a concept including "a case where the cyclic alkenylene group is composed only of" and "a case where both of the linear alkenylene group and the cyclic alkenylene group are included". Examples of such an alkenylene group include a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, a decenylene group, an undecenylene group, a dodecenylene group, a tridecenylene group, a heptadecenylene group, a thirty-hexaenylene group, a group having an octenylene-cyclohexenylene structure, a group having an octenylene-cyclohexenylene-octenylene structure, and a group having a propenylene-cyclohexenylene-octenylene structure.

As the component (B2-1), preferred are compounds represented by the following formula (B2-1-1):

[ chemical formula 17]

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. Wherein any of the substituents of M and L comprises an aromatic ring.

M represents a divalent aliphatic group having 5 or more carbon atoms and optionally having a substituent. The divalent aliphatic group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 50 or less, still more preferably 45 or less, and still more preferably 40 or less carbon atoms. The aliphatic group may be linear, branched or cyclic, and among them, linear is preferred. Here, the cyclic aliphatic group is a concept including "a case where the cyclic aliphatic group is formed only" and "a case where both of the linear aliphatic group and the cyclic aliphatic group are included". Examples of the divalent aliphatic group include an alkylene group and an alkenylene group. As the alkylene group and alkenylene group, those mentioned above are mentioned.

Examples of the substituent for M include a halogen atom, -OH, -O-C_1-10Alkyl, -N (C)_1-10Alkyl radical)₂、C_1-10Alkyl radical, C_2-30Alkenyl radical, C_2-30Alkynyl, C_6-10Aryl, -NH₂、-CN、-C(O)O-C_1-10Alkyl, -COOH, -C (O) H, -NO₂And the like. Here, the term "C_x-y"(x and y are positive integers, and x < y is satisfied) means that the number of carbon atoms of the organic group described immediately after the term is x to y. For example, "C_1-10The expression "alkyl" denotes an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. The 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 alkylene, alkenylene, alkynylene, arylene, -C (═ O) -O-, -NR⁰-(R⁰Hydrogen atom, alkyl group having 1 to 3 carbon atoms), oxygen atom, sulfur atom, C (═ O) NR⁰A divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, a combination of 2 or more divalent groups of these, and the like. Alkylene groups, alkenylene groups, alkynylene groups, arylene groups, divalent groups derived from phthalimide, divalent groups derived from pyromellitic diimide, and groups in which 2 or more kinds of divalent groups are combined optionally have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide means a divalent group derived from phthalimide, specifically a group represented by the general formula (B2-1-2). The divalent group derived from pyromellitic diimide means a divalent group derived from pyromellitic diimide, specifically a group represented by the general formula (B2-1-3). Wherein ". sup." represents a chemical bond;

[ chemical formula 18]

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. The alkylene group may be linear, branched or cyclic. 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, a tridecylene group, a heptadecylene group, a hexadecylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

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. The alkenylene group may be linear, branched or cyclic. Examples of such alkenylene groups include methylvinylene, cyclohexenylene, pentenylene, hexenylene, heptenylene, octenylene, and the like.

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. The alkynylene group may be linear, branched or cyclic. Examples of such an alkynylene group include methylacetylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, and the like.

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 yet more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

The alkylene group, alkenylene group, alkynylene group, and arylene group as the divalent linking group in L may have a substituent. As the substituent, an alkyl group having 5 or more carbon atoms is preferred, as in the substituent for M in the general formula (B2-1-1).

Examples of the group consisting of a combination of 2 or more divalent groups in L include: a divalent group composed of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group composed of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group composed of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; and so on. Groups composed of a combination of 2 or more divalent groups can form a ring such as a condensed ring by the combination of the groups. The number of repeating units of a group consisting of 2 or more divalent groups may be 1 to 10.

Among these, L in the general formula (B2-1-1) is preferably 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, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a divalent group formed by combining 2 or more of these groups. Among them, as L, it is more preferable that: an alkylene group; a divalent group having a structure of alkylene-a divalent group derived from phthalimide-an oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of alkylene-a divalent group derived from phthalimide-oxygen atom-arylene-alkylene-arylene-oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of an alkylene-divalent group derived from pyromellitic diimide; a divalent group having a structure of alkynylene-a divalent group derived from phthalimide-an oxygen atom-a divalent group derived from phthalimide; a divalent group having the structure alkynylene-a divalent group derived from phthalimide-oxygen atom-arylene-alkynylene-arylene-oxygen atom-a divalent group derived from phthalimide; divalent radicals having the structure of alkynylene-a divalent radical derived from pyromellitic diimide.

The maleimide resin represented by the general formula (B2-1-1) is preferably a maleimide resin represented by the general formula (B2-1-4):

[ chemical formula 19]

In the general formula (B2-1-4), M¹Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and each Z independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, or a divalent group having an aromatic ring which may have a substituent. t represents an integer of 1 to 10. Wherein M is¹Any of the substituents and Z includes an aromatic ring.

M¹Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M¹The same as M in the general formula (B2-1-1).

Each Z independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, or a divalent group having an aromatic ring which may have a substituent. Examples of the divalent aliphatic group in Z include an alkylene group and an alkenylene group. The divalent aliphatic group may be any of a chain, a branched chain and a cyclic group, and among them, a cyclic divalent aliphatic group having 5 or more carbon atoms, which may have a substituent, is preferable.

The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, further preferably 50 or less, further preferably 45 or less, further 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.

The number of carbon atoms of the alkenylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, further preferably 50 or less, further preferably 45 or less, further preferably 40 or less. The alkenylene group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic alkenylene group is a concept including "a case where the cyclic alkenylene group is composed only of the cyclic alkenylene group" and "a case where both the linear alkenylene group and the cyclic alkenylene group are included". Examples of such an alkenylene group include a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, a decenylene group, an undecenylene group, a dodecenylene group, a tridecenylene group, a heptadecenylene group, a thirty-hexaenylene group, a group having an octenylene-cyclohexenylene structure, a group having an octenylene-cyclohexenylene-octenylene structure, and a group having a propenylene-cyclohexenylene-octenylene structure.

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 diimide ring, an aromatic heterocycle, etc., and a benzene ring, a phthalimide ring, and a pyromellitic diimide ring are preferable. That is, as the divalent group having an aromatic ring, a divalent group having a benzene ring which may be substituted, a divalent group having a phthalimide ring which may be substituted, and a divalent group having a pyromellitic diimide ring which may be substituted are preferable. 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 composed of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group composed of an alkylene group and a divalent group derived from pyromellitic diimide; a divalent group derived from pyromellitic diimide; a group composed of a divalent group derived from phthalimide and an alkylene group; and so on. The arylene group is the same as the arylene group in the divalent linking group represented by L in the general formula (B2-1-1).

The alkylene group represented by Z and the divalent group having an aromatic ring may have a substituent. As the substituent, the same as the substituent optionally having M in the general formula (B2-1-1) can be mentioned.

Specific examples of the group represented by Z include the following groups. Wherein ". sup." represents a chemical bond;

[ chemical formula 20]

[ chemical formula 21]

The compound represented by the general formula (B2-1-1) is preferably any of the compounds represented by the general formula (B2-1-5) and the compounds represented by the general formula (B2-1-6);

[ chemical formula 22]

In the general formula (B2-1-5), M²And M³Each independently represents a divalent aliphatic group having 5 or more carbon atoms and optionally having a substituent, R⁴⁰Each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group formed by combining 2 or more of these groups. t1 represents an integer of 1 to 10;

in the general formula (B2-1-6), M⁴、M⁶And M⁷Each independently represents an optionally substituted aliphatic group having 5 or more carbon atoms, M⁵Each independently represents a divalent group having an aromatic ring optionally having a substituent, R⁴¹And R⁴²Each independently represents 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.

M²And M³Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M²And M³As the divalent aliphatic group having 5 or more carbon atoms represented by M in the general formula (B2-1-1), triacontahenylene (ヘキサトリアコンチニレン group) and triacontahylylene are preferable.

R⁴⁰Each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group consisting of 2 or more of themA combination of groups. The arylene group and the alkylene group are the same as those in the divalent linking group represented by L in the general formula (B2-1-1). As R⁴⁰Preferably, the group is a combination of 2 or more divalent groups or an oxygen atom.

As R⁴⁰The group consisting of a combination of 2 or more divalent groups in (2) includes a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of the group consisting of a combination of 2 or more kinds of divalent groups include the following groups. Wherein ". sup." represents a chemical bond;

[ chemical formula 23]

M⁴、M⁶And M⁷Each independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent. M⁴、M⁶And M⁷As the aliphatic group having 5 or more carbon atoms which may have a substituent represented by M in the general formula (B2-1-1), a hexylene group, a heptylene group, an octylene group, a nonylene group and a decylene group are preferable, and an octylene group is more preferable.

M⁵Each independently represents a divalent group having an aromatic ring which may have a substituent. M⁵The divalent group having an aromatic ring optionally having a substituent(s) as represented by Z in the general formula (B2-1-4) is preferably a group composed of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; the group comprising a combination of a divalent group derived from phthalimide and an alkylene group, more preferably a combination of an alkylene group and a divalent group derived from pyromellitic diimide. The arylene group and the alkylene group are the same as those in the divalent linking group represented by L in the general formula (B2-1-1).

As M⁵Specific examples of the group include the following groups. Wherein ". sup." represents a chemical bond;

[ chemical formula 24]

R⁴¹And R⁴²Each independently represents an alkyl group having 5 or more carbon atoms. R⁴¹And R⁴²As the alkyl group having 5 or more carbon atoms, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group are preferable, and a hexyl group and an octyl group are more preferable.

u1 and u2 each independently represent an integer of 1 to 15, preferably an integer of 1 to 10.

Specific examples of the component (B2-1) include the following compounds (B-i) to (B-ii), but are not limited to these specific examples. Wherein v represents an integer of 1 to 10;

[ chemical formula 25]

Specific examples of the component (B2-1) include "BMI 1500" (a compound of formula (B-i)) and "BMI 1700" (a compound of formula (B-ii)) manufactured by DESIGNER MOLECULES.

The weight average molecular weight (Mw) of the component (B2-1) is preferably 150 to 5000, more preferably 300 to 2500.

The maleimide group equivalent of the component (B2-1) is preferably 50g/eq to 2000g/eq, more preferably 100g/eq to 1000g/eq, and still more preferably 150g/eq to 500g/eq, from the viewpoint of remarkably obtaining the desired effect of the present invention. The maleimide group equivalent is the mass of the (B2-1) component containing 1 equivalent of maleimide group.

{ (B2-2) composition }

The component (B2-2) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide. The component (B2-2) can be obtained, for example, by subjecting a component containing an aromatic amine compound (such as an aromatic diamine compound) and maleic anhydride to imidization.

The aromatic ring may be carbocyclic or heterocyclic. Examples of the aromatic ring include: monocyclic aromatic rings such as benzene ring, furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, and pyrazine ring; a fused ring formed by fusing at least 2 monocyclic aromatic rings such as a naphthalene ring, an anthracene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a benzoxazole ring, a benzisoxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, and a phthalazine ring; and a condensed ring in which 1 or more monocyclic non-aromatic rings are condensed onto 1 or more monocyclic aromatic rings, such as an indane ring, a fluorene ring, and a tetralin ring. Among them, the aromatic ring is preferably a monocyclic aromatic ring, and more preferably a benzene ring.

As the component (B2-2), a maleimide compound represented by the following formula (B2-2-1) is preferred,

[ chemical formula 26]

In the formula, R^cEach independently represents a substituent; x^cEach independently represents a single bond, alkylene, alkenylene, -O-, -CO-, -S-, -SO-, -SO₂-, -CONH-, -NHCO-, -COO-, or-OCO- (preferably a single bond or alkylene); z^cEach independently represents a non-aromatic ring optionally having a substituent, or an aromatic ring optionally having a substituent (preferably an aromatic ring optionally having a substituent, particularly preferably a benzene ring optionally having a substituent); s represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, further preferably an integer of 1 to 20); t1 each independently represents an integer of 0 or 1 or more; u independently represents an integer of 0 to 2 (preferably 0).]Particularly preferred are maleimide compounds represented by the formulae (B2-2-2) to (B2-2-5).

[ chemical formula 27]

In the formula, R^c1、R^c2And R^c3Each independently represents an alkyl group; x^c1And X^c2Each independently represents a single bond or an alkylene group; s represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, further preferably an integer of 1 to 20); t' represents an integer of 1 to 5; v1, v2 and v3 each independently represent an integer of 0 to 2 (preferably 0). The s unit, t' unit, u unit, v1 unit, v2 unit, and v3 unit may be the same or different.

In another embodiment, the component (B2-2) is preferably a compound represented by the following formula (B2-2-6):

[ chemical formula 28]

In the formula, R³¹And R³⁶Represents a maleimido group, R³²、R³³、R³⁴And R³⁵Each independently represents a hydrogen atom, an alkyl group, or an aryl group, and each D 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 in the formula (B2-2-6)³²、R³³、R³⁴And R³⁵Each independently represents a hydrogen atom, an alkyl group, or an aryl group, preferably a hydrogen atom.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. 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. The aryl group may be a single ring or a condensed ring. Examples of such aryl groups include phenyl, naphthyl and anthryl.

The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, -OH, -O-C_1-6Alkyl, -N (C)_1-10Alkyl radical)₂、C_1-10Alkyl radical, C_6-10Aryl, -NH₂、-CN、-C(O)O-C_1-10Alkyl, -COOH, -C (O) H, -NO₂And the like. Here, "C" is_p-qThe term "(p and q are positive integers, and p < q.) means that the organic group described immediately after the term has p to q carbon atoms. For example, "C_1-10The expression "alkyl" denotes an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a fused ring.

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

D in the formula (B2-2-6) represents a divalent aromatic group. Examples of the divalent aromatic group include phenylene, naphthylene, anthrylene, aralkyl, biphenylene, and biphenylaralkyl groups, and among them, biphenylene and biphenylaralkyl groups are preferable, and biphenylene is more preferable. The divalent aromatic group optionally has a substituent. As a substituent, with R in the formula (B2-2-6)³²The substituents which the alkyl group optionally has are the same.

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

a represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, further preferably 1 to 5.

As the component (B2-2), a resin represented by the formula (B2-2-7):

[ chemical formula 29]

In the formula, R³⁷And R³⁸Represents a maleimide group. a1 represents an integer of 1 to 100.

a1 is the same as a in the formula (B2-2-6), and preferable ranges are the same.

Examples of commercially available products of the component (B2-2) include: "MIR-3000-70 MT" manufactured by Nippon chemical company; "BMI-50P" manufactured by KI-Chemical company; "BMI-1000", "BMI-1000H", "BMI-1100H", "BMI-4000", "BMI-5100", manufactured by Dahe chemical industry Co., Ltd; "BMI-4, 4' -BPE" manufactured by KI-Chemical company "," BMI-70 ", and" BMI-80 "manufactured by KI-Chemical company, and the like.

The weight average molecular weight (Mw) of the component (B2-2) is preferably 150 to 5000, more preferably 300 to 2500.

The equivalent of the maleimide group-containing functional group of the component (B2-2) is preferably 50 to 2000g/eq, more preferably 100 to 1000g/eq, still more preferably 150 to 500g/eq, particularly preferably 200 to 300g/eq.

{ (B2-3) composition }

The component (B2-3) is a maleimide compound having a trimethylindan skeleton. The trimethylindan skeleton is a skeleton represented by the following formula (B2-3-1).

[ chemical formula 30]

Substituents may be bonded to the benzene ring contained in the trimethylindane skeleton. 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. Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, tert-butyl, and the like;

the number of carbon atoms of the alkyloxy group is preferably 1 to 10. Examples of the alkyloxy group include methoxy, ethoxy, propoxy, butoxy, and the like;

the number of carbon atoms of 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 of the aryl group is preferably 6 to 10. Examples of the aryl group include phenyl, naphthyl, and the like;

the number of carbon atoms of the aryloxy group is preferably 6 to 10. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, and the like;

the number of carbon atoms of the arylthio group is preferably 6 to 10. Examples of the arylthio group include phenylthio group, naphthylthio group and the like;

the number of carbon atoms of the cycloalkyl group is preferably 3 to 10. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, and the like; examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom and the like.

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

The number of substituents bonded to 1 benzene ring included in the trimethylindane skeleton may be 1 or 2 or more. The number of substituents bonded to the benzene ring included in the trimethylindane skeleton is usually 0 or more and 3 or less. When the number of the substituents is 2 or more, those 2 or more substituents may be the same or different. Among them, it is preferable that no substituent is bonded to the benzene ring contained in the trimethylindane skeleton.

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

The component (B2-3) preferably contains an aromatic ring skeleton in addition to the aforementioned trimethylindan skeleton. The number of ring-forming carbon atoms of the aromatic ring skeleton is preferably 6 to 10. Examples of the aromatic ring skeleton include a benzene ring skeleton and a naphthalene ring skeleton. The number of the aromatic ring skeleton contained in the 1 molecule of the component (B2-3) is preferably 1 or more, more preferably 2 or more, further preferably 6 or less, further preferably 4 or less, particularly preferably 3 or less. When the component (B2-3) contains 2 or more aromatic ring skeletons in addition to the trimethylindan skeleton, those aromatic ring skeletons may be the same or different.

The aromatic ring contained in the aromatic ring skeleton may be substituted. Examples of the substituent include: the substituent described above as a substituent that can be bonded to the benzene ring contained in the trimethylindane skeleton, and a nitro group. The number of substituents bonded to 1 aromatic ring may be 1, or 2 or more. The number of substituents bonded to the aromatic ring is usually 0 or more and 4 or less. When the number of the substituents is 2 or more, those 2 or more substituents may be the same or different.

The component (B2-3) preferably contains a divalent aliphatic hydrocarbon group in addition to the above-mentioned trimethylindan skeleton. In particular, when the component (B2-3) contains an aromatic ring skeleton other than the benzene ring contained in the trimethylindane skeleton, it is preferable that the component (B2-3) contains a divalent aliphatic hydrocarbon group. In this case, the divalent aliphatic hydrocarbon group is preferably a group in which a benzene ring included in the trimethylindan skeleton is bonded to an aromatic ring skeleton. In addition, the divalent aliphatic hydrocarbon group preferably connects aromatic ring skeletons to each other.

The divalent aliphatic hydrocarbon group has preferably 1 or more, more preferably 12 or less, still more preferably 8 or less, particularly preferably 5 or less carbon atoms. The divalent aliphatic hydrocarbon group is more preferably an alkylene group which is a saturated aliphatic hydrocarbon group. Examples of the divalent aliphatic hydrocarbon group include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; ethylidene (-CH (CH)₃) -) propylidene (-CH (CH)₂CH₃) -) isopropylidene (-COOR-), C (-CH (CH)₃)₂-) ethylmethylmethylene (-C (CH)₃)(CH₂CH₃) -) diethyl methylene (-C (CH)₂CH₃)₂-) and the like; and the like. When (B2-3) the maleimide compound containing a trimethylindan skeleton contains 2 or more divalent aliphatic hydrocarbon groups in addition to the trimethylindan skeleton, those divalent aliphatic hydrocarbon groups may be the same or different.

The component (B2-3) preferably has a structure represented by the following formula (B2-3-2). The entirety of the component (B2-3) may have a structure represented by the formula (B2-3-2), or a part of the component (B2-3) may have a structure represented by the formula (B2-3-2);

[ chemical formula 31]

(wherein Ar is^a1Represents a divalent aromatic hydrocarbon group optionally having a substituent; r^a1Each independently represents 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; r^a2Each independently represents 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 mercapto group; r^a3Each independently represents a divalent aliphatic hydrocarbon group; n is_a1Represents a positive integer; n is_a2Each independently represents an integer of 0 to 4; n is_a3Each independently represents an integer of 0 to 3. R^a1The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. R^a2The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. n is_a2When 2 to 4, R^a1May be the same or different within the same ring. n is_a3When 2 to 3, R^a2May be the same or different within the same ring).

In the formula (B2-3-2), Ar^a1Represents a divalent aromatic hydrocarbon group optionally having a substituent. The divalent aromatic hydrocarbon group preferably has 6 or more carbon atoms, more preferably 20 or less carbon atoms, and still more preferably 16 or less carbon atoms. Examples of the divalent aromatic hydrocarbon group include phenylene and naphthylene. Examples of the substituent which 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, and the like,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, and a mercapto group. The hydrogen atom of each substituent is in turn optionally replaced by a halogen atom. Specific examples of these substituents include, for example, the same substituents as those that can be bonded to the benzene ring contained in the trimethylindane skeleton. When the divalent aromatic hydrocarbon group has a substituent, the number of the substituent is preferably 1 to 4. When the number of the substituents of the divalent aromatic hydrocarbon group is 2 or more, those 2 or more substituents may be the same or different. Wherein Ar is^a1Divalent aromatic hydrocarbon groups having no substituent are preferred.

In the formula (B2-3-2), R^a1Each independently represents 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. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups are optionally replaced with halogen atoms. Specific examples of these groups include, for example, the same groups as those substituents that can be bonded to the benzene ring included in the trimethylindane skeleton. Wherein R is^a1More 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, particularly preferably an alkyl group having 1 to 4 carbon atoms.

In the formula (B2-3-2), R^a2Each independently represents 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 mercapto group. The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups are optionally replaced with halogen atoms. As specific for these groupsFor example, the same substituents as those that can be bonded to the benzene ring included in the trimethylindane skeleton are exemplified. Wherein R is^a2More 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.

In the formula (B2-3-2), R^a3Each independently represents a divalent aliphatic hydrocarbon group. The preferable range of the divalent aliphatic hydrocarbon group is as shown above.

In the formula (B2-3-2), n_a1Representing a positive integer. n is_a1It is preferably 1 or more, more preferably 10 or less, still more preferably 8 or less.

In the formula (B2-3-2), n_a2Each independently represents an integer of 0 to 4. n is_a2Preferably 2 or 3, more preferably 2. A plurality of n_a2May be different but is preferably the same. When n is_a2When it is 2 or more, plural R^a1May be the same or different within the same ring.

In the formula (B2-3-2), n_a3Each independently represents an integer of 0 to 3. A plurality of n_a3May be different but is preferably the same. n is_a3Preferably 0.

The component (B2-3) particularly preferably has a structure represented by the following formula (B2-3-3). The whole of the component (B2-3) may have a structure represented by the formula (B2-3-3), or a part of the component (B2-3) may have a structure represented by the formula (B2-3-3);

[ chemical formula 32]

(in the formula, R^b1Each independently represents 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; r^b2Independently represent an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, or an alkylthio group having 1 to 10 carbon atomsAn 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 mercapto group; n is_b1Represents a positive integer; n is_b2Each independently represents an integer of 0 to 4; n is_b3Each independently represents an integer of 0 to 3. R^b1The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. R^b2The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. When n is_b2When 2 to 4, R^b1May be the same or different within the same ring. When n is_b3When 2 to 3, R^b2May be the same or different within the same ring).

In the formula (B2-3-3), R^b1、R^b2、n_b1、n_b2And n_b3Are respectively reacted with R in the formula (B2-3-2)^a1、R^a2、n_a1、n_a2And n_a3The same is true.

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

[ chemical formula 33]

In the formula (B2-3-4), R^c1、R^c2、n_c2And n_c3Are respectively reacted with R in the formula (A4)^a1、R^a2、n_a2And n_a3The same is true. Further, in the formula (B2-3-4), n_c1The number of the repeating units is an integer of 1 to 20. Further, in the formula (B2-3-4), it represents a chemical bond. For example, in the formula (B2-3-2), n is n for the component (B2-3)_a23 or less, and 2 or more of R are not bonded to the maleimide group in the ortho-position and para-position of the maleimide group-bonded benzene ring with respect to the maleimide group^a1In the case of (2), 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). This is achieved byIn addition, for the component (B2-3), for example, in the formula (B2-3-3), n_b23 or less, and 2 or more of the ortho-and para-positions of the maleimide group-bonded benzene ring to the maleimide group are not bonded with R^b1In the case of (2), 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).

The component (B2-3) may be used alone in 1 kind, or 2 or more kinds may be used in combination in an arbitrary ratio.

The maleimide group equivalent of the component (B2-3) is preferably at least 50g/eq, more preferably at least 100g/eq, particularly preferably at least 200g/eq, still more preferably at most 2000g/eq, still more preferably at most 1000g/eq, particularly preferably at most 800g/eq. The maleimide group equivalent represents the mass of the maleimide compound per 1 equivalent of maleimide group. When the maleimide group equivalent of the component (E2-3) is in the above range, the effect of the present invention can be remarkably obtained.

The method for producing the component (B2-3) is not particularly limited. The component (B2-3) can be produced, for example, by the method described in Japanese patent publication (Kokai) No. 2020 and 500211. According to the production method described in Japanese patent laid-open 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 has a structure represented by the following formula (B2-3-5). Thus, the (B2-3) component may comprise: a maleimide compound having a structure represented by the formula (B2-3-5).

[ chemical formula 34]

(in the formula, R¹Each independently represents 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; r²Each independently represents 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 mercapto group; n is₁Represents an average number of repeating units of 0.95 to 10.0; n is₂Each independently represents an integer of 0 to 4; n is₃Each independently represents an integer of 0 to 3. R¹The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. R²The hydrogen atoms of the alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups of (a) are optionally replaced with halogen atoms. When n is₂When 2 to 4, R¹May be the same or different within the same ring. When n is₃When 2 to 3, R²May be the same or different within the same ring).

In the formula (B2-3-5), R¹、R²、n₂And n₃Are respectively reacted with R in the formula (B2-3-2)^a1、R^a2、n_a2And n_a3The same is true.

In the formula (B2-3-5), n₁Represents the average number of repeating units, and is in the range of 0.95 to 10.0. According to the production method described in Japanese patent laid-open publication No. 2020-500211, a group of maleimide compounds having a structure represented by the formula (B2-3-5) can be obtained. The average number of repeating units n as represented by formula (B2-3-5)₁As can be seen from the graph showing that the content of the maleimide compound having a structure represented by the formula (B2-3-5) obtained in this way was less than 1.00, the maleimide compound having a repeating unit number of 0 of the trimethylindane skeleton was contained. Therefore, the maleimide compound having a repeating unit of 0 trimethyl indane skeleton may be removed from the maleimide compound having a structure represented by the formula (B2-3-5) by purification to obtain the component (B2-3), and only the component (B2-3) thus obtained may be contained in the resin composition. However, the resin composition contains the number of repeating units having a trimethylindan skeletonIn the case of 0 maleimide compound, the effects of the present invention can be obtained. In addition, in the case of omitting purification, the cost can be controlled. Therefore, it is preferable that the resin composition contains "a maleimide compound having a structure represented by the formula (B2-3-5)" instead of the maleimide compound having 0 repeating unit of the trimethylindane skeleton.

In the formula (B2-3-5), the average number of repeating units n₁It is preferably at least 0.95, more preferably at least 0.98, still more preferably at least 1.0, particularly preferably at least 1.1, preferably at most 10.0, more preferably at most 8.0, still more preferably at most 7.0, particularly preferably at most 6.0. Average number of repeating units n₁When the content is within the above range, the effects of the present invention can be remarkably obtained. In particular, the glass transition temperature of the resin composition can be effectively increased.

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

[ chemical formula 35]

The maleimide compound comprising the structure represented by the formula (B2-3-5) may further comprise the structure represented by the aforementioned formula (B2-3-4). For example, in the case of a maleimide compound comprising a structure represented by the formula (B2-3-5), n is in the formula (B2-3-5)₂3 or less, and 2 or more of the ortho-and para-positions of the maleimide group-bonded benzene ring to the maleimide group are not bonded with R¹In the case of (4), the structure represented by the formula (B2-3-4) may be included in combination with the structure represented by the formula (B2-3-5).

The molecular weight distribution Mw/Mn calculated by Gel Permeation Chromatography (GPC) measurement of the maleimide compound having a structure represented by the formula (B2-3-5) is preferably within a specific range. The molecular weight distribution is a value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and is represented by "Mw/Mn". Specifically, the molecular weight distribution Mw/Mn of the maleimide compound having the structure represented by the formula (B2-3-5) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, further preferably 1.2 to 3.6, particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw/Mn of the maleimide compound comprising the structure represented by the formula (B2-3-5) is in the aforementioned range, the effects of the present invention can be remarkably obtained.

In the maleimide compound comprising the structure represented by the formula (B2-3-5), the average number of repeating units n₁The amount of the maleimide compound of 0 is preferably in a specific range. The average number of repeating units n in the GPC measurement of the maleimide compound having a structure represented by the formula (B2-3-5)₁The amount of the maleimide compound of 0 can be expressed in area% based on the result of its GPC measurement. Specifically, in the chromatogram obtained by the aforementioned GPC measurement, the "average repeating unit number n" is used₁The ratio (% by area) of the peak area of the maleimide compound of 0 "to the total area of the peaks of the maleimide compound having the structure represented by the formula (B2-3-5)" may be represented by the average repeating unit number n₁An amount of the maleimide compound of 0. Specifically, the average number of repeating units n is calculated based on 100 area% of the total amount of the maleimide compound having a structure represented by the formula (B2-3-5)₁The amount of the maleimide compound of 0 is preferably 32 area% or less, more preferably 30 area% or less, further preferably 28 area% or less. Average number of repeating units n₁When the amount of the maleimide compound of 0 is in the foregoing range, the effect of the present invention can be remarkably obtained.

The maleimide group equivalent of the maleimide compound having a structure represented by the formula (B2-3-5) is preferably in the same range as that of the above-mentioned component (B2-3). When the maleimide equivalent of the maleimide compound having a structure represented by formula (B2-3-5) is in the above range, the effect of the present invention can be remarkably obtained.

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

(B3) Component (B) is a resin belonging to component (B), and therefore is a resin containing a radical-polymerizable unsaturated group and benzocyclobutene as an aromatic ring. (B3) The component (A) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(B3) The structure of the component (a) is not particularly limited as long as it contains a benzocyclobutene group and a radical polymerizable unsaturated group which can generate an isomer diene by heating. The component (B3) is preferably a component (B3) having 2 or more benzocyclobutene groups in 1 molecule, from the viewpoint of providing a cured product having good adhesion to the copper foil. The component (B3) is preferably a radical polymerizable unsaturated group having a divalent aliphatic group having an unsaturated bond, from the viewpoint of providing a cured product having good adhesion to the copper foil.

In one embodiment, component (B3) comprises a compound represented by the following formula (B3-1):

[ chemical formula 36]

In the formula (B3-1), R¹⁰⁰Represents a divalent aliphatic group having an unsaturated bond, L¹⁰⁰Represents a single bond or a divalent linking group, R^A100Represents an alkyl group, a cyano group or a halogen atom, R^A200Represents 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. R¹、R^A1And R^A2Each independently optionally having a substituent. Multiple existence of R¹May be the same or different, R^A1When plural, they may be the same or different, R^A2When a plurality of them exist, they may be the same or different.

R¹⁰⁰The divalent group represented by (A) preferably has 1 to 3 unsaturated bonds, more preferably 1 or 2, further preferably 1. The unsaturated bond may be a double bond or a triple bond, and is preferably a double bond. R¹⁰⁰The divalent group represented is preferably alkenylene or alkynylene. R¹⁰⁰The number of carbon atoms of the divalent group is preferably 2 to 10, more preferably 2 to 6 or 2 to 4. Having no substituent in the above carbon atomsThe number of carbon atoms.

As L¹⁰⁰The divalent linking group represented is not particularly limited as long as it is a divalent group formed by 1 or more (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeleton atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, and may be, for example, a in the formula (B1-3) described later¹²The divalent group and the siloxane skeleton described above. Wherein L is¹⁰⁰A siloxane skeleton is preferred. Thus, in one embodiment, the (B3) component has a siloxane backbone.

R^A100The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, 1 to 4 or 1 to 3 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of a substituent. As R^A100The halogen atom represented is preferably a chlorine atom or a bromine atom.

R^A200The alkyl group and the alkoxy group are preferably those having 1 to 10 carbon atoms, more preferably 1 to 6, 1 to 4 or 1 to 3 carbon atoms. R^A200The number of carbon atoms in the alkyl moiety in the trialkylsilyl group represented by (a) is preferably 1 to 3, more preferably 1 or 2. The number of carbon atoms does not include the number of carbon atoms of a substituent. Further, as R^A200The halogen atom represented is preferably a chlorine atom or a bromine atom.

The component (B3) is preferably nA3 is 1, more preferably L in the formula (B3-1) from the viewpoint of obtaining a cured product excellent in adhesion to copper foil¹⁰⁰Is a siloxane backbone.

In a preferred embodiment, the component (B3) contains a compound represented by the following formula (B3-2):

[ chemical formula 37]

In the formula (B3-2), R¹⁰⁰、R^A100、R^A200nA1 and nA2 as described in formula (B3-1), R²⁰⁰Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an arylalkyl group, or an aryl group, and nA4 represents an integer of 1 to 10. R²Optionally havingAnd (4) a substituent. Multiple existence of R²⁰⁰May be the same or different.

R²⁰⁰The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, 1 to 4 or 1 to 3 carbon atoms. R²The cycloalkyl group represented by (A) preferably has 3 to 10 carbon atoms, more preferably 4 to 6 carbon atoms. R²⁰⁰The number of carbon atoms of the arylalkyl group is preferably 7 to 20, more preferably 7 to 15 or 7 to 12. The aryl moiety in arylalkyl is preferably phenyl. R²⁰⁰The number of carbon atoms of the aryl group is preferably 6 to 14, more preferably 6 to 10. As the aryl group, a phenyl group is preferred. The number of carbon atoms does not include the number of carbon atoms of a substituent.

nA4 represents an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 or 2, particularly preferably 1.

R¹⁰⁰、R^A100、R^A200nA1 and nA2 are as described in formula (B3-1), wherein R is preferred¹⁰⁰Is an alkenylene group having 2 to 4 carbon atoms, and nA1 and nA2 are 0.

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

[ chemical formula 38]

In the formula (B3-3), R²⁰⁰And nA4 as illustrated in formula (B3-2).

(B3) The component (A) can be produced, for example, according to the procedures described in U.S. Pat. No. 4812588 and U.S. Pat. No. 5138081. Further, as the component (B3), commercially available products can be used, and as the compound represented by the formula (B3-3), for example, there are compounds of the cyclic series "cyclic 3022-35" manufactured by the Dow chemical company having a structure represented by the following formula.

[ chemical formula 39]

As previously mentioned, benzocyclobutene groups produce the isomeric diene, causing a cycloaddition reaction of the Diels-Alder (Diels-Alder) type. Therefore, the component (B3) may contain, in addition to the compounds (monomers) represented by the above formulae (B3-1) to (B3-3), dimers or polymers produced by addition reaction of the compounds.

(B3) The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component (B) are not particularly limited, but Mw or Mn is preferably 2000 or less, more preferably 1800 or less, further preferably 1600 or less, 1500 or less, 1400 or less, 1200 or less or 1000 or less. The lower limit of the molecular weight is not particularly limited, and may be, for example, 250 or more and 300 or more. (A) The Mw and Mn of the component (B) can be measured as values in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

The content of the component (B) is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more, based on 100% by mass of nonvolatile components in the resin composition, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to a copper foil. (B) The upper limit of the content of the component (B) is not particularly limited, but is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.

The content of the component (B) is preferably 20 mass% or more, more preferably 30 mass% or more, further preferably 40 mass% or more, further preferably 60 mass% or less, further preferably 55 mass% or less, further preferably 50 mass% or less, based on 100 mass% of the resin component in the resin composition, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to a copper foil.

(C) inorganic filler

The resin composition may further contain (C) an inorganic filler as an optional component in addition to the above components. By containing (C) an inorganic filler in the resin composition, a cured product having excellent dielectric characteristics can be obtained.

As a 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, calcium 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 zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphotungstate phosphate, and the like. Among them, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as the silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more.

Examples of commercially available products of (C) the inorganic filler include: "UFP-30" manufactured by the electric chemical industry Co., Ltd.; "SP 60-05" and "SP 507-05" manufactured by Nissi iron-alloy materials Corp; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Admatech (Admatech); "UFP-30" manufactured by Denka corporation; "Silfil (シルフィル) NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Deshan (Tokuyama); "SC 2500 SQ", "SO-C4", "SO-C2", "SO-C1", "SC 2050-SXF", manufactured by Yatoma corporation; and the like.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the average particle size of the (C) inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, more preferably 5 μm or less, further preferably 2 μm or less, further preferably 1 μm or less.

(C) The average particle diameter of the inorganic filler can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is measured as an average particle size. As a sample for measurement, a sample obtained by weighing 100mg of the inorganic filler and 10g of methyl ethyl ketone in a vial and dispersing them by ultrasonic waves for 10 minutes can be used. For the measurement sample, the volume-based particle size distribution of the inorganic filler was measured by a flow cell method using a laser diffraction type particle size distribution measuring apparatus using blue and red light sources at a wavelength, and the average particle size was calculated from the obtained particle size distribution as a median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Ltd., and "SALD-2200" manufactured by Shimadzu, Ltd.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the specific surface area of the (C) inorganic filler is preferably 1m²More than g, preferably 2m²More than g, particularly preferably 3m²More than g. The upper limit is not particularly limited, but is preferably 60m²Less than 50 m/g²Less than or equal to 40 m/g²The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area can be obtained by: the specific surface area of the inorganic filler was measured by adsorbing nitrogen gas onto the surface of the sample using a BET full-automatic specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountech corporation) and calculating the specific surface area by a BET multipoint method.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler (C) is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents such as 3,3, 3-trifluoropropyltrimethoxysilane; aminosilicone-based coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; an epoxy silane coupling agent such as 3-glycidoxypropyltrimethoxysilane; mercaptosilane coupling agents such as 3-mercaptopropyltrimethoxysilane; a silane-based coupling agent; alkoxysilanes such as phenyltrimethoxysilane; an organic silazane compound such as hexamethyldisilazane; titanate-based coupling agents, and the like. The surface treatment agent may be used alone or in combination of two or more.

Examples of commercially available surface treatment agents include: "KBM 403" (3-glycidoxypropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBM 803" (3-mercaptopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBE 903" (3-aminopropyltriethoxysilane) manufactured by shin-Etsu chemical industries, "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "SZ-31" (hexamethyldisilazane) manufactured by shin-Etsu chemical industries, "KBM 103" (phenyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by shin-Etsu chemical industries, and "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane) manufactured by shin-Etsu chemical industries.

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

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. 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 0.02mg/m²Above, preferably 0.1mg/m²The above, more preferably 0.2mg/m²The above. 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 form of a sheet, it is preferably 1mg/m²The concentration is preferably 0.8mg/m or less²The concentration is preferably 0.5mg/m or less²The following.

(C) The amount of carbon per unit surface area of the inorganic filler material can be measured after subjecting the surface-treated inorganic filler material to a cleaning treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, a sufficient amount of MEK was added as a solvent to the inorganic filler material surface-treated by the surface treatment agent, and ultrasonic cleaning was performed at 25 ℃ for 5 minutes. After removing the supernatant liquid and drying the solid components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd., can be used.

The content of the inorganic filler (C) is preferably 30 mass% or more, more preferably 35 mass% or more, further preferably 40 mass% or more, further preferably 80 mass% or less, further preferably 70 mass% or less, further preferably 60 mass% or less and 55 mass% or less, based on 100 mass% of nonvolatile components in the resin composition, from the viewpoint of remarkably obtaining the effects of the present invention.

< (D) polymerization initiator

The resin composition may further contain (D) a polymerization initiator as an optional component in addition to the above components. (D) Component (B) generally has a function of promoting crosslinking of the radical polymerizable unsaturated group in component (B). (D) The component (A) may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Examples of the polymerization initiator (D) include peroxides such as di-t-hexyl peroxide, t-butylcumyl peroxide, t-butyl peroxyacetate, α' -di (t-butylperoxy) diisopropylbenzene, t-butyl peroxylaurate, t-butyl peroxy2-ethylhexanoate, t-butyl peroxyneodecanoate, and t-butyl peroxybenzoate.

Examples of commercially available products of the polymerization initiator (D) include: "PERHEXYL D", "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", "PERBUTYL O", "PERBUTYLND", "PERBUTYLZ", "PERCUYLP", "PERCUUMYLD", and the like, manufactured by RIGAL OIL CORPORATION.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the (D) polymerization initiator is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, further preferably 0.05 mass% or more, further preferably 0.3 mass% or less, further preferably 0.2 mass% or less, further preferably 0.1 mass% or less, with respect to 100 mass% of nonvolatile components in the resin composition.

The content of the polymerization initiator (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 5% by mass or less, further preferably 3% by mass or less, further preferably 2% by mass or less, based on 100% by mass of the resin component in the resin composition, from the viewpoint of remarkably obtaining the effect desired in the present invention.

< (E) thermoplastic resin

The resin composition may further contain (E) a thermoplastic resin as an optional component in addition to the above components.

Examples of the thermoplastic resin of component (E) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. Among these, phenoxy resins are preferred from the viewpoint of remarkably obtaining the effect of the present invention. In addition, the thermoplastic resin may be used alone, or two or more kinds may be used in combination.

Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of skeletons selected from a bisphenol a skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenol (novolac) skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The phenoxy resin may have a phenolic hydroxyl group or an epoxy group at its terminal.

Specific examples of the phenoxy resin include: "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton) manufactured by Mitsubishi chemical company; "YX 8100" (phenoxy resin having bisphenol S skeleton) manufactured by Mitsubishi chemical corporation; "YX 6954" (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Mitsubishi chemical company; "FX 280" and "FX 293" manufactured by Nissin iron-on-Steel chemical Co., Ltd; "YL 7500BH 30", "YX 6954BH 30", "YX 7553BH 30", "YL 7769BH 30", "YL 6794", "YL 7213", "YL 7290", "YL 7482" and "YL 7891BH 30", manufactured by mitsubishi chemical corporation; and the like.

Examples of the polyvinyl acetal resin include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of the polyvinyl acetal resin include "electrochemical Butyral (Denka butyl) 4000-2", "electrochemical Butyral 5000-A", "electrochemical Butyral 6000-C", "electrochemical Butyral 6000-EP" manufactured by the electric chemical industry Co., Ltd; S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Water accumulation chemical industry; and the like.

Examples of the polyolefin resin include ethylene 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 elastomers such as polypropylene and ethylene-propylene block copolymers.

Specific examples of the polyimide resin include "RIKACOAT SN 20" and "RIKACOAT PN 20" manufactured by shin-shin chemical company.

Specific examples of the polyamide-imide resin include "VYLOMAX HR11 NN" and "VYLOMAX HR16 NN" manufactured by tokyo corporation. Specific examples of the polyamideimide resin include modified polyamideimides such as "KS 9100" and "KS 9300" (polyamideimide having a polysiloxane skeleton) manufactured by hitachi chemical company.

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by sumitomo chemical corporation.

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

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, and the like.

From the viewpoint of remarkably obtaining the effect of the present invention, the weight average molecular weight (Mw) of the (E) thermoplastic resin is preferably 8000 or more, more preferably 10000 or more, particularly preferably 20000 or more, preferably 70000 or less, more preferably 60000 or less, particularly preferably 50000 or less.

The content of the thermoplastic resin (E) is preferably 1 mass% or more, more preferably 2 mass% or more, further preferably 3 mass% or more, preferably 10 mass% or less, further preferably 8 mass% or less, further preferably 5 mass% or less, based on 100 mass% of nonvolatile components in the resin composition, from the viewpoint of remarkably obtaining the effects of the present invention.

The content of the thermoplastic resin (E) is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, preferably 20 mass% or less, further preferably 15 mass% or less, further preferably 10 mass% or less, based on 100 mass% of the resin component in the resin composition, from the viewpoint of remarkably obtaining the effect of the present invention.

Elastomer (F)

The resin composition may further contain (F) an elastomer as an optional component in addition to the above components. The elastomer as the component (F) is a resin having flexibility, and is preferably a resin exhibiting rubber elasticity by polymerizing with a resin having rubber elasticity or other components. Examples of the rubber elasticity include the following resins: for example, a resin exhibiting an elastic modulus of 1GPa or less when subjected to a tensile test at a temperature of 25 ℃ and a humidity of 40% RH in accordance with Japanese Industrial standards (JIS K7161).

In one embodiment, (F) the elastomer is preferably a resin having 1 or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, and a polystyrene structure in a molecule. "(meth) acrylate" means methacrylate and acrylate.

In another embodiment, the elastomer (F) is preferably 1 or more selected from the group consisting of a resin having a glass transition temperature (Tg) of 25 ℃ or lower and a resin that is liquid at 25 ℃ or lower. The glass transition temperature (Tg) of the resin is preferably not more than 20 ℃ and more preferably not more than 15 ℃. The lower limit of the glass transition temperature is not particularly limited, and may be usually-15 ℃ or higher. The resin that is liquid at 25 ℃ is preferably a resin that is liquid at 20 ℃ or lower, more preferably a resin that is liquid at 15 ℃ or lower. The glass transition temperature can be measured by DSC (differential scanning calorimetry).

(F) Elastomers are generally amorphous resin compositions that are soluble in organic solvents. The elastomer (F) may be used alone in 1 kind, or may be used in combination of 2 or more kinds at an arbitrary ratio.

Examples of the elastomer (F) include resins having a polybutadiene structure. The polybutadiene structure may be contained in the main chain or may be contained in the side chain. In addition, the polybutadiene structure may be partially or fully hydrogenated. A resin having a polybutadiene structure is sometimes referred to as "polybutadiene resin". Specific examples of the polybutadiene resin include "Ricon 130MA 8", "Ricon 130MA 13", "Ricon 130MA 20", "Ricon 131MA 5", "Ricon 131MA 10", "Ricon 131MA 17", "Ricon 131MA 20", "Ricon 184MA 6" (polybutadiene containing an acid anhydride group), "GQ-1000" (polybutadiene containing a hydroxyl group and a carboxyl group) manufactured by Nippon Cauda, and "G-1000", "G-2000", "G-3000" (both-terminal hydroxyl polybutadiene), and "GI-1000", "GI-2000", "GI-3000" (both-terminal hydroxyl hydrogenated polybutadiene), and "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX. Specific examples of the polybutadiene resin include linear polyimides prepared from hydroxyl-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in jp 2006-37083 a and international publication No. 2008/153208), and phenolic hydroxyl group-containing butadienes. The content of the butadiene structure in the polyimide resin is preferably 60 to 95% by mass, more preferably 75 to 85% by mass. The details of the polyimide resin can be found in Japanese patent laid-open No. 2006-37083 and International publication No. 2008/153208, which are incorporated herein by reference.

Examples of the elastomer (F) include resins having a poly (meth) acrylate structure. A resin containing a poly (meth) acrylate structure is sometimes referred to as a "poly (meth) acrylic resin". Specific examples of the poly (meth) acrylic resin include TEISANRESIN manufactured by Nagase ChemteX, ME-2000, W-116.3, W-197C, KG-25, KG-3000 manufactured by Kokusan Kogyo Co.

Examples of the elastomer (F) include resins having a polycarbonate structure. A resin containing a polycarbonate structure is sometimes referred to as a "polycarbonate resin". Specific examples of the polycarbonate resin include "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090" and "C-3090" (polycarbonate diols) manufactured by Colorado. Further, linear polyimide using a hydroxyl-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride as raw materials can also be used. The content of the carbonate structure in the polyimide resin is preferably 60 to 95% by mass, more preferably 75 to 85% by mass. The details of the polyimide resin can be found in international publication No. 2016/129541, and the contents thereof are incorporated in the present specification.

Examples of the elastomer (F) include resins having a polysiloxane structure. Resins containing polysiloxane structures are sometimes referred to as "silicone resins". Specific examples of the silicone resin include "SMP-2006", "SMP-2003 PGMEA", "SMP-5005 PGMEA", and linear polyimides produced from an amino-terminated polysiloxane and a tetrabasic acid anhydride (International publication No. 2010/053185, Japanese patent application laid-open Nos. 2002-12667 and 2000-319386).

Examples of the elastomer (F) include resins having a polyalkylene structure or a polyalkyleneoxy structure. Resins containing polyalkylene structures are sometimes referred to as "alkylene resins". Further, a resin containing a polyalkyleneoxy structure is sometimes referred to as "alkyleneoxy resin". The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, particularly preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of the alkylene resin and the alkyleneoxy resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi chemical fiber company.

Examples of the elastomer (F) include resins having a polyisoprene structure. A resin having a polyisoprene structure is sometimes referred to as an "isoprene resin". Specific examples of the isoprene resin include "KL-610" and "KL 613" manufactured by Coli.

Examples of the elastomer (F) include resins having a polyisobutylene structure. A resin having a polyisobutylene structure is sometimes referred to as an "isobutylene resin". Specific examples of the isobutylene resin include "SIBTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by KANEKA, Inc.

Examples of the elastomer (F) include resins having a polystyrene structure. A resin having a polystyrene structure is sometimes referred to as "styrene resin". Examples of the styrene resin include a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), a styrene-ethylene-butylene-styrene block copolymer (SEBS), a styrene-ethylene-propylene-styrene block copolymer (SEPS), a styrene-ethylene-propylene-styrene block copolymer (SEEPS), a styrene-butadiene-butylene-styrene block copolymer (SBBS), a styrene-butadiene diblock copolymer, a hydrogenated styrene-butadiene block copolymer, a hydrogenated styrene-isoprene block copolymer, and a hydrogenated styrene-butadiene random copolymer. Specific examples of the styrene resin include: hydrogenated styrene-based thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP 10" (manufactured by Asahi Kasei corporation); epoxidized styrene-butadiene thermoplastic elastomers "Epofriend AT 501" and "CT 310" (manufactured by celluloid corporation); a modified styrene elastomer "SEPTON HG 252" (manufactured by clony corporation) having a hydroxyl group; a modified styrene-based elastomer "Tuftec N503M" having a carboxyl group, a modified styrene-based elastomer "Tuftec N501" having an amino group, and a modified styrene-based elastomer "Tuftec M1913" having an acid anhydride group (manufactured by asahi chemicals); an unmodified styrene-based elastomer "SEPTON S8104" (manufactured by korea corporation); styrene-ethylene/butylene-styrene block copolymer "FG 1924" (manufactured by Kraton corporation).

(F) The number average molecular weight (Mn) of the elastomer is preferably 1000 or more, more preferably 1500 or more, further preferably 3000 or more, particularly preferably 5000 or more, preferably 1000000 or less, more preferably 900000 or less. The number average molecular weight (Mn) can be measured in terms of polystyrene using GPC (gel permeation chromatography).

The content of the elastomer (F) is preferably 1 mass% or more, more preferably 2 mass% or more, further preferably 3 mass% or more, preferably 10 mass% or less, further preferably 8 mass% or less, further preferably 5 mass% or less, based on 100 mass% of nonvolatile components in the resin composition, from the viewpoint of remarkably obtaining the effects of the present invention.

The content of the elastomer (F) is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, preferably 20 mass% or less, further preferably 15 mass% or less, further preferably 10 mass% or less, based on 100 mass% of the resin component in the resin composition, from the viewpoint of remarkably obtaining the effect of the present invention.

< (G) other additives

In addition to the above-mentioned components, other additives may be further contained as optional components in the resin composition. Examples of such additives include thermosetting resins such as epoxy resins, curing agents, curing accelerators, organic fillers, thickeners, defoaming agents, leveling agents, adhesion imparting agents, and flame retardants. These additives may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.

The resin composition can be produced by, for example, mixing the above components in an arbitrary order. In addition, heating and/or cooling can be performed by appropriately adjusting the temperature during the process of mixing the components. During or after the mixing of the respective components, the components may be uniformly dispersed by stirring with a stirring device such as a mixer. Further, the resin composition may be subjected to a defoaming treatment as necessary.

< Properties and uses of resin composition >

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

A cured product obtained by thermally curing the resin composition at 190 ℃ for 90 minutes has a low dielectric constant Dk. Therefore, when an insulating layer is formed from the cured product, an insulating layer having a low dielectric constant can be obtained. For example, the dielectric constant Dk of a cured product obtained by curing the resin composition under the conditions described in the examples described later is preferably 3.0 or less, more preferably 2.9 or less, and still more preferably 2.8 or less. The lower limit of the dielectric constant Dk of the cured product is not particularly limited, and may be 0.1 or more. The dielectric constant of the cured product can be measured by the method described in examples.

A cured product obtained by thermally curing the resin composition at 190 ℃ for 90 minutes has a low dielectric loss tangent. Therefore, when an insulating layer is formed from the cured product, an insulating layer having a low dielectric loss tangent can be obtained. For example, the dielectric loss tangent Df of a cured product obtained by curing the resin composition under the conditions described in examples 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 loss tangent Df of the cured product is not particularly limited, and may be 0.001 or more. The dielectric loss tangent of the cured product can be measured by the method described in examples.

The cured product obtained by heat-curing the resin composition at 190 ℃ for 90 minutes can improve the adhesion to a copper foil (copper foil adhesion). For example, when the insulating layer and the copper foil are formed by the method described in the examples described later, the adhesion between the insulating layer and the copper foil is preferably 0.2kgf/cm or more, more preferably 0.3kgf/cm or more, and particularly preferably 0.4kgf/cm or more. The upper limit of the adhesiveness is not particularly limited, and may be, for example, 10.0kgf/cm or less. The adhesion between the insulating layer and the copper foil can be measured by the method described in the examples.

The resin composition according to one embodiment of the present invention is suitable as a resin composition for insulation applications, and particularly suitable as a resin composition for forming an insulation layer. Therefore, for example, the resin composition is suitable as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). Further, the resin composition is suitable as a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer (a resin composition for forming an insulating layer for forming a conductor layer). The resin composition can be used in a wide range of applications where the resin composition can be used, such as a resin sheet, a sheet-like laminate material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, and a component embedding resin.

For example, when the semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present embodiment is also suitable as: a resin composition for forming a rewiring layer as an insulating layer (a resin composition for forming a rewiring layer), the insulating layer being an insulating layer for forming a rewiring layer; and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When the semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer;

(1) a step of laminating a temporary fixing film on the base material,

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

(3) a step of forming a sealing layer on the semiconductor chip,

(4) a step of peeling the base material and the temporary fixing film from the semiconductor chip,

(5) a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled, and

(6) and forming a rewiring layer as a conductor layer on the rewiring-forming layer.

The resin composition can be used even when the printed wiring board is a component built-in circuit board.

[ resin sheet ]

The resin sheet of the present invention comprises a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

From the viewpoint of making the printed wiring board thin and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 5 μm or more.

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

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

When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferred. As the copper foil, a foil formed of a single metal of copper may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.

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

Further, as the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having a release layer, commercially available products can be used, and examples thereof include "SK-1", "AL-5" and "AL-7" manufactured by Linekaceae, which are PET films having a release layer containing an alkyd resin-based release agent as a main component, "Lumiror T60" manufactured by Toray, manufactured by Ditika, and "Unipel" manufactured by Unitika.

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

In one embodiment, the resin sheet may further include other layers as necessary. Examples of the other layer include a protective film provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support) and selected for the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust or the like to the surface of the resin composition layer or generation of damage on the surface of the resin composition layer.

The resin sheet can be produced, for example, by: a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and the resin varnish is applied to a support using a die coater or the like, and then dried to form a resin composition layer.

Examples of the organic solvent include: ketones such as acetone, Methyl Ethyl Ketone (MEK) and cyclohexanone; acetates 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. The organic solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The drying can be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, and drying is performed so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. The drying conditions vary depending on the boiling point of the organic solvent in the resin varnish, and for example, when a resin varnish containing 30 to 60 mass% of the organic solvent is used, the resin composition layer can be formed by drying at50 to 150 ℃ for 3 to 10 minutes.

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

[ printed Wiring Board ]

A printed wiring board according to an embodiment of the present invention includes an insulating layer formed of a cured product obtained by curing the resin composition.

The printed wiring board can be produced, for example, by a method including the steps (I) and (II) below using the above-described resin sheet;

(I) a step of laminating the resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate, and (II) a step of curing the resin composition layer to form an insulating layer.

The "inner layer substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductive layer on one or both surfaces thereof, and the conductive layer may be subjected to patterning. An inner layer substrate having a conductor layer formed on one surface or both surfaces of a substrate may be referred to as an "inner layer circuit substrate". In addition, an intermediate manufactured article in which an insulating layer and/or a conductor layer is to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate". When the printed wiring board is a component-embedded circuit board, an inner layer substrate in which components are embedded may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressure-bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressure bonding the resin sheet to the inner layer substrate (hereinafter, also referred to as "heat-pressure bonding member") include a heated metal plate (SUS end plate or the like) and a metal roll (SUS roll). It is preferable that the thermocompression bonding member is not directly pressed against the resin sheet, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The lamination of the inner substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heating and press-bonding temperature is preferably in the range of 60 to 160 ℃, more preferably 80 to 140 ℃, the heating and press-bonding pressure is preferably in the range of 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the heating and press-bonding time is preferably in the range of 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably performed under reduced pressure of 26.7hPa or less.

The lamination can be carried out by means of a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Nikko corporation, a vacuum applicator (vacuum applicator) manufactured by Nikko-Materials, and a batch vacuum pressure laminator.

After the lamination, the heat and pressure bonding member is pressed under atmospheric pressure, for example, from the support side, whereby the smoothing treatment of the laminated resin sheets can be performed. The pressing conditions for the smoothing treatment may be set to the same conditions as the above-described conditions for the heat and pressure bonding of the laminate. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing processes can be continuously performed using a commercially available vacuum laminator as described above.

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

In the step (II), the resin composition layer is cured to form an insulating layer formed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions employed in forming the insulating layer of the printed wiring board can be used. The resin composition layer can be cured by irradiation with active energy rays such as ultraviolet rays, but is usually thermally cured by heating.

For example, the heat curing conditions of the resin composition layer vary depending on the kind of the resin composition, and in one embodiment, the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and further preferably 170 to 210 ℃. The curing time may be preferably from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, and still more preferably from 15 minutes to 100 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, before the resin composition layer is thermally cured, the resin composition layer is preheated at a temperature of 50 to 120 ℃, preferably 60 to 115 ℃, more preferably 70 to 110 ℃ for 5 minutes or more, preferably 5 to 150 minutes, more preferably 15 to 120 minutes, further preferably 15 to 100 minutes.

The method for manufacturing a printed wiring board may further include (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. When the support is removed after the step (II), the removal of the support may be performed between the steps (II) and (III), between the steps (III) and (IV), or between the steps (IV) and (V). If necessary, the insulating layer and the conductor layer may be formed by repeating the steps (I) to (V) to form a multilayer wiring board.

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

The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), stain is also removed. The step and conditions of the roughening treatment are not particularly limited. For example, the roughening treatment may be performed on the insulating layer by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid.

Examples of the swelling solution used for the roughening treatment include an alkali solution and a surfactant solution, and an alkali solution is preferred. The alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available Swelling liquids include "spinning Dip securigant P" and "spinning Dip securigant SBU" manufactured by amatt JAPAN (ato ech JAPAN). The swelling treatment with the swelling solution is not particularly limited, and may be performed, for example, by immersing the insulating layer in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing 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 to 80 ℃ for 5 to 15 minutes.

As the oxidizing agent used in the roughening treatment, for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide is exemplified. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution securigant P" manufactured by amett japan.

The neutralizing Solution used for the roughening treatment is preferably an acidic aqueous Solution, and examples of commercially available products include "Reduction Solution securigant P" manufactured by amatt japan. The treatment with the neutralizing solution may be performed by immersing the treated surface on which the roughening treatment with the oxidizing agent is performed in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of handling and the like, it is preferable to immerse the object subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.

In one embodiment, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 500nm or less, more preferably 400nm or less, and further preferably 300nm or less. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like. The root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500nm or less, more preferably 400nm or less, and further preferably 300nm or less. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains 1 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. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed of an alloy of 2 or more metals selected from the above-described group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoint of versatility of forming a conductor layer, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferable, 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 is even more preferable.

The conductor layer may have a single-layer structure, or may have a multilayer structure in which 2 or more layers of single metal layers or alloy layers made of different metals or alloys are stacked. 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.

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

The conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a method such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, the metal oxide film is preferably formed by a semi-additive method. An example of forming a conductor layer by a semi-additive method is shown below.

A plating seed layer is formed on a surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer in accordance with a desired wiring pattern. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[ semiconductor device ]

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

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

Examples

The present invention will be specifically explained below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "part" and "%" representing amounts are "part by mass" and "% by mass", respectively, unless otherwise specified. The following operations are performed under an ambient temperature and pressure atmosphere unless otherwise stated.

< preparation of Maleimide resin A >

An MEK solution (nonvolatile content: 70 mass%) of maleimide resin A synthesized by the method described in Synthesis example 1 of Japanese patent application laid-open Specification No. 2020-500211 was prepared. The maleimide resin A has a structure represented by the following formula.

[ chemical formula 40]

When the FD-MS spectrum of maleimide resin a was determined, peaks of M + ═ 560, 718, and 876 were observed. These peaks correspond to n, respectively₁In the case of 0, 1 and 2. Further, when the maleimide resin A was analyzed by GPC, the number n of repeating units of the indane skeleton portion was determined based on the number average molecular weight₁When the value of (1) is n₁Molecular weight distribution (Mw/Mn) 1.81. Further, in the maleimide compound A₁Average number of repeating units n in 100 area% of the total amount of (A)₁The content ratio of the maleimide resin of 0 was 26.5 area%.

The FD-MS spectrum of the maleimide resin a represents the measurement result under the following measurement apparatus and measurement conditions;

(FD-MS Spectrum measuring apparatus and measuring conditions)

A measuring device: JMS-T100GCAccuTOF

Measurement conditions

Measurement range: m/z is 4.00-2000.00

Rate of change: 51.2mA/min

Final current value: 45mA

Cathode voltage: -10kV

Recording interval: 0.07 sec.

The GPC of the maleimide resin a described above represents the result of measurement using the following measurement apparatus and measurement conditions: a measuring device: HLC-8320GPC, manufactured by Tosoh Corporation "

Column: "HXL-L" manufactured by Tosoh corporation, TSK-GEL G2000HXL manufactured by Tosoh corporation, "TSK-GEL G2000 HXL" manufactured by Tosoh corporation, "TSK-GEL G3000 HXL" manufactured by Tosoh corporation, and "TSK-GEL G4000 HXL" manufactured by Tosoh corporation "

A detector: RI (differential refractometer)

Data processing: "GPC WorkStation EcoSEC-WorkStation" manufactured by Tosoh corporation "

The measurement conditions were as follows: column temperature 40 deg.C

Tetrahydrofuran as developing solvent

Flow rate 1.0 ml/min standard: according to the aforementioned handbook of measurement of "EcoSeC-WorkStation at GPC WorkStation", monodisperse polystyrene having a known molecular weight is used;

sample preparation: a tetrahydrofuran solution containing 1.0 mass% of the maleimide compound in terms of nonvolatile matter was filtered through a microfilter (50. mu.l).

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" that contribute to the indane skeleton of the maleimide resin₁"represents a value calculated from a GPC chart obtained by the aforementioned GPC measurement. Further, the average number of repeating units "n₁"represents a value calculated based on the number average molecular weight (Mn). In particular, for n₁The theoretical molecular weight and the molecular weight actually measured in GPC are plotted on a scattergram for compounds of 0 to 4, and an approximate straight line is drawn. Then, the number average molecular weight (Mn) is determined from the point represented by the actually measured value Mn (1) on the straight line, and the average number of repeating units "n" is calculated₁". Further, based on the results of GPC measurement, the average number of repeating units n in 100 area% of the total amount of the maleimide resin A was calculated₁The content ratio (area%) of the maleimide resin was 0. For details, reference may be made to japanese invention association public technical bulletin technical number 2020-.

< Synthesis of PEEK (polyether Ether Ketone) Compound A >

A500 mL flask (three-necked flask) equipped with a stirrer, an argon introduction tube, and a Dean-Stark apparatus was charged with 31.443g of 4, 4' -difluorobenzophenone, 13.223g of resorcinol, 29.894g of anhydrous potassium carbonate, 180mL of N-methylpyrrolidone, and 90mL of toluene, heated under stirring under an argon atmosphere, and refluxed with toluene at 130 to 140 ℃ for 4 hours. Then, the mixture is further heated, and toluene is distilled off at 170 to 180 ℃. And further stirring for 10 hours at 170-180 ℃, and then returning to room temperature to obtain a product 1.

5.233g of 4-aminophenol, 6.628g of anhydrous potassium carbonate, 18mL of N-methylpyrrolidone, and 90mL of toluene were added to a flask containing product 1, and the mixture was heated again under stirring under an argon atmosphere, and toluene was refluxed at 130 to 140 ℃ for 3 hours. Then, the mixture was heated to distill off toluene at 170 to 180 ℃, and further, the stirring was continued for 4 hours while maintaining the temperature. Then, the reaction mixture was cooled to room temperature, and added to 5000mL of methanol, followed by filtration to obtain a powdery solid. The powdery solid was repeatedly washed with methanol and water, and then dried at 100 ℃ for 8 hours to obtain 37.461g of powdery solid (Diamine-A).

A500 mL flask (three-necked flask) equipped with a stirrer and an argon introduction tube was charged with 0.878g of diamine-A, 4.943g of maleic anhydride, and 240mL of N-methylpyrrolidone, and stirred at room temperature for 18 hours under an argon atmosphere. Then, 8.576g of acetic anhydride and 0.689g of sodium acetate were added thereto, and the mixture was stirred at 60 ℃ for 6 hours. After the reaction solution was returned to room temperature, the reaction solution was added to 5000mL of methanol, whereby a powdery solid was obtained. This powdery solid was repeatedly washed with methanol and water, and then dried at 100 ℃ for 8 hours to obtain 28.434g of a PEEK compound represented by the following formula. The number average molecular weight of the PEEK compound a calculated by GPC measurement was 2230;

[ chemical formula 41]

[ example 1]

A PEEK compound A15 parts, a resin containing an aromatic ring and a radical polymerizable unsaturated group ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation, number average molecular weight 2200, toluene solution containing 65 mass% of nonvolatile matter), 25 parts of a polymerization initiator ("PERBUTYL (registered trademark) C" manufactured by Nichigan corporation), 0.5 part of a polymerization initiator ("PERBUTYL C") and an inorganic filler ("SO-C2" manufactured by Yado Mar corporation, average particle diameter 0.5 μm and specific surface area 5.8 m)²30 parts by weight of a phenolic resin and an ester-type phenoxy resin"YL 7891BH 30" by water chestnut chemical corporation, solid content 30 mass% of 1: 1 solution) and dispersed uniformly by a high-speed rotary mixer to obtain a resin varnish.

As a support, a polyethylene terephthalate film (AL 5, manufactured by Linekekaceae) having a release layer was prepared (thickness: 38 μm). The resin varnish was uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer became 40 μm. Then, the resin varnish was dried at 80 to 100 ℃ (average 90 ℃) for 4 minutes to obtain a resin sheet including a support and a resin composition layer.

[ example 2]

In example 1, 25 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("OPE-2 St" manufactured by mitsubishi gas chemical corporation, number average molecular weight 1200, toluene solution having a nonvolatile content of 65 mass%) was changed to 25 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("ODV-XET (X04)" manufactured by ri fe chemical corporation (weight average molecular weight 3110, vinyl equivalent 380g/eq., 65 mass%) in an amount of 25 parts;

in the same manner as in example 1 except for the above matters, a resin varnish and a resin sheet were obtained.

[ example 3]

In example 1, 25 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation, number average molecular weight 1200, toluene solution containing 65 mass% of nonvolatile matter) was changed to 16 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("SA 9000-111", manufactured by SABIC corporation, number average molecular weight 1850-;

[ example 4]

In example 1, the amount of the resin containing an aromatic ring and a radical polymerizable unsaturated group ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation, number average molecular weight 1200, toluene solution containing 65 mass% of nonvolatile matter) was changed from 25 parts to 20 parts,

further, 5 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group (biphenylaralkyl type maleimide compound ("MIR-3000-70 MT", Maleimide equivalent: 275g/eq., 70% nonvolatile MEK/toluene mixed solution, manufactured by Nippon chemical Co., Ltd.);

[ example 5]

In example 1, the amount of the resin containing an aromatic ring and a radical polymerizable unsaturated group ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation, number average molecular weight 1200, and toluene solution having a nonvolatile content of 65 mass%) was changed from 25 parts to 12 parts,

further, 6 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("BMI-1500", Maleimide equivalent 750g/eq., manufactured by design polymers Co.) was used;

[ example 6]

In example 1, 25 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("OPE-2 St" manufactured by mitsubishi gas chemical corporation, number average molecular weight 1200, toluene solution having a nonvolatile content of 65 mass%) was changed to 46 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("CYCLOTENE 3022-35" manufactured by dow chemical corporation, mesitylene solution having a nonvolatile content of 35 mass%);

[ example 7]

In example 1, 25 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("OPE-2 St" manufactured by mitsubishi gas chemical corporation, number average molecular weight 1200, toluene solution containing 65 mass% of nonvolatile matter) was changed to 23 parts of maleimide resin a;

[ example 8]

In example 1, 10 parts of an ester-type phenoxy resin (YL 7891BH30, manufactured by mitsubishi chemical corporation, 1: 1 solution of MEK and cyclohexanone having a solid content of 30 mass%) was changed to 3 parts of an elastomer (styrene-ethylene/butylene-styrene block copolymer "FG 1924", manufactured by Kraton corporation);

Comparative example 1

In the case of the example 1, the following,

15 parts of PEEK compound A was not used, and the amount of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation, number average molecular weight 1200, toluene solution having a nonvolatile content of 65 mass%) was changed from 25 parts to 48 parts,

spherical silica (SO-C2, product of Yadmama, average particle diameter 0.5 μm, specific surface area 5.8 m) surface-treated with an inorganic filler (KBM 573, product of shin-Etsu chemical Co., Ltd.)²The amount of/g) was changed from 30 parts to 35 parts;

Comparative example 2

In the case of the embodiment 2, the following,

the PEEK compound a15 parts were not used,

the amount of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("ODV-XET (X04)" manufactured by Nippon iron chemical Co., Ltd. (weight-average molecular weight 3110, vinyl equivalent 380g/eq., 65 mass% solution) was changed from 25 parts to 48 parts,

spherical silica (SO-C2, product of Yadu Ma Co., Ltd., "average particle diameter 0.5 μm, specific surface area 5.8 m) surface-treated with an inorganic filler (KBM 573, product of shin-Etsu chemical Co., Ltd.)²The amount of/g) was changed from 30 parts to 35 parts;

in the same manner as in example 2 except for the above matters, a resin varnish and a resin sheet were obtained.

Comparative example 3

In the case of the embodiment 3, the following,

the PEEK compound a15 parts were not used,

the amount of the resin containing an aromatic ring and a radical polymerizable unsaturated group (SA 9000-111, manufactured by SABIC Co., Ltd.; number average molecular weight 1850-,

in the same manner as in example 3 except for the above matters, a resin varnish and a resin sheet were obtained.

Comparative example 4

In the case of the example 1, the following,

15 parts of a PEEK compound was not used, and 25 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation, number average molecular weight 1200, toluene solution having a nonvolatile content of 65% by mass) was changed to 45 parts of a resin containing an aromatic ring and a radical polymerizable unsaturated group (biphenyl aralkyl type maleimide compound ("MIR-3000-70 MT" manufactured by Nippon chemical corporation, maleimide equivalent: 275g/eq., MEK/toluene mixed solution having a nonvolatile content of 70%)),

[ measurement of dielectric characteristics (dielectric constant and dielectric loss tangent) ]

The resin sheets prepared in examples and comparative examples were heated at 190 ℃ for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off to obtain a cured product of the resin composition. The cured product was cut into test pieces having a width of 2mm and a length of 80 mm. For the test piece, the dielectric constant Dk and the dielectric loss tangent Df were measured by a resonance cavity perturbation method at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃ using "HP 8362B" manufactured by Agilent technologies. The measurement was performed for 3 test pieces, and the average value thereof is shown in the following table.

[ measurement of copper foil adhesion ]

(1) Base treatment of copper foil

A glossy surface of "3 EC-III" (electrolytic copper foil, 35 μm) manufactured by Mitsui Metal mining Co., Ltd was etched by 1 μm with a microetching agent ("CZ 8101" manufactured by Meige (MEC) Co., Ltd.), roughened copper surface was treated, and then rust-proofing treatment was performed (CL 8300). Further, the heat treatment was carried out in an oven at 130 ℃ for 30 minutes. This copper foil is referred to as a CZ copper foil.

(2) Preparation of inner layer substrate

The both surfaces of the glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.4mm thick, "R1515A" manufactured by panasonic corporation) on which the inner layer circuit was formed were etched by a microetching agent ("CZ 8101" manufactured by meige corporation) for 1 μm to roughen the copper surface.

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

A batch type vacuum press Laminator (2-Stage build up Laminator) "CVP 700", manufactured by Nikko-Materials, was used to laminate both surfaces of the inner substrate so that the resin composition layer of the resin sheet was in contact with the inner substrate. The lamination was carried out by: the pressure was reduced for 30 seconds to adjust the pressure to 13hPa or less, and then the pressure was bonded at 120 ℃ for 30 seconds at a pressure of 0.74 MPa. Next, hot pressing was performed at 100 ℃ for 60 seconds under a pressure of 0.5 MPa. On the resin composition layer, the treated surface of the CZ copper foil was laminated under the same conditions as described above. Then, the resin composition layer was cured under the curing conditions of 190 ℃ for 90 minutes to form an insulating layer, thereby producing an evaluation substrate.

(4) Measurement of copper foil adhesion before reliability test

The resulting evaluation substrate was cut into 150X 30mm pieces. The copper foil portion of the small piece was cut at a portion having a width of 10mm and a length of 100mm by a cutter, one end of the copper foil was peeled off, the copper foil was sandwiched by a jig, and a load (kgf/cm) at which the copper foil portion was peeled off at a speed of 50 mm/min at a vertical direction of 35mm at room temperature was measured to determine a peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement. The copper foil adhesion before the reliability test was evaluated according to the following criteria, which were measured according to japanese industrial standards (JIS C6481).

[ Table 1]

(Table 1)

In the table, the content of the component (A) represents the content of the component (A) when the resin component in the resin composition is 100 mass%. (C) The content of component (C) represents the content of component (C) assuming that the nonvolatile content in the resin composition is 100 mass%.

Claims

1. A resin composition comprising:

(A) polyether ether ketone compound having maleimide group, and

(B) a resin containing an aromatic ring and a radical polymerizable unsaturated group.

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

3. The resin composition according to claim 1, wherein component (A) has a maleimide group at a terminal.

4. The resin composition according to claim 1, wherein the content of the component (A) is 5% by mass or more and 60% by mass or less, assuming that the resin component in the resin composition is 100% by mass.

5. The resin composition according to claim 1, wherein the component (B) contains: a maleimide-based radical polymerizable compound containing a maleimide group and a vinylphenyl-based radical polymerizable compound containing a vinylphenyl group.

6. The resin composition according to claim 1, wherein the content of the component (B) is 20% by mass or more and 60% by mass or less, assuming that the resin component in the resin composition is 100% by mass.

7. The resin composition according to claim 1, further comprising (C) an inorganic filler.

8. The resin composition according to claim 7, wherein the content of the component (C) is 30 to 80% by mass, based on 100% by mass of nonvolatile components in the resin composition.

9. The resin composition according to claim 1, which is used for forming an insulating layer.

10. The resin composition according to claim 1, which is used for forming an insulating layer, the insulating layer being an insulating layer for forming a conductor layer.

11. 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.

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

13. A semiconductor device comprising the printed wiring board of claim 12.