CN115926426A

CN115926426A - Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board

Info

Publication number: CN115926426A
Application number: CN202211642615.5A
Authority: CN
Inventors: 紫垣将彦; 高野健太郎
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2018-05-28
Filing date: 2019-05-27
Publication date: 2023-04-07
Also published as: KR20210016533A; CN115785664A; JP7276333B2; WO2019230661A1; CN112204107B; CN112204107A; TW202003662A; JPWO2019230661A1; CN115850947A; TWI802699B

Abstract

Provided are a resin composition having excellent appearance during processing and a low dielectric constant, and a prepreg, a metal foil-clad laminate, a resin composite sheet and a printed wiring board using the resin composition. The resin composition contains a thermosetting resin (A) and a filler (B), and the filler (B) contains hollow particles (B) having an average particle diameter of 0.01 to 10 [ mu ] m and satisfying the following formula (i). 1. Ltoreq. D.ltoreq.10. Cndot. Formula (i) wherein D represents the number of bubbles contained in the hollow particles (b).

Description

Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board

The present application is a divisional application of applications entitled "resin composition, prepreg, metal foil-clad laminate, resin composite sheet, and printed wiring board" having an application date of 2019, 05 and 27, and an application number of 2019800357185.

Technical Field

The present invention relates to a resin composition, and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board using the resin composition. Particularly to a resin composition for electronic materials.

Background

In recent years, high integration and miniaturization of semiconductors used in communication devices, personal computers, and the like have been advanced, and accordingly, various characteristics required for a laminate for semiconductor packaging (for example, a metal foil-clad laminate or the like) used in a printed wiring board used for them have been increasingly strict. Examples of the main properties required include low water absorption, low dielectric constant, low dielectric loss tangent, and low thermal expansion coefficient.

In order to obtain a printed wiring board having improved these various properties, a resin composition used as a material for the printed wiring board has been studied.

For example, patent document 1 discloses a prepreg containing a modified polyphenylene ether composition and a filler having a dielectric constant of 3.5 or less, wherein the modified polyphenylene ether composition contains a modified polyphenylene ether having an ethylenically unsaturated group at the end (hereinafter, sometimes simply referred to as modified polyphenylene ether) and a crosslinking-type curing agent, and the modified polyphenylene ether is represented by the following formula and has a number average molecular weight of 1000 to 7000.

In the above formula, X represents an aryl group, (Y) _m Denotes a polyphenylene ether moiety, R ¹ 、R ² 、R ³ Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, m represents an integer of 1 to 100, n represents an integer of 1 to 6, and q represents an integer of 1 to 4.

Hollow silica is used as the filler.

Patent document 2 describes a photocurable and thermosetting resin composition for producing a printed wiring board, which is characterized by containing (a) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, (D) a thermosetting component, and (E) a hollow filler. In the examples of patent document 2, a hollow filler having an average particle diameter of 16 μm is used.

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open publication No. 2017-075270

Patent document 2: JP 2017-522580A

Disclosure of Invention

Problems to be solved by the invention

Here, although a filler (filler) can be used as a material of a prepreg using a thermosetting resin, the filler itself generally tends to increase the dielectric constant of the resulting prepreg.

On the other hand, in patent document 1, the hollow silica is a hollow silica containing a plurality of bubbles therein. When such hollow silica is used, the effect of lowering the dielectric constant can be confirmed, but in view of recent high demand, further lowering of the dielectric constant is required. Further, it has been found that depending on the type of hollow silica, the hollow silica may have poor appearance when processed into a resin sheet, a prepreg, or the like.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a resin composition having an excellent appearance during processing and a further reduced dielectric constant, and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board using the resin composition.

Means for solving the problems

Under the above problems, the present inventors have studied and found that: the above problem can be solved by using hollow particles and setting the number of bubbles in the hollow particles to 1 to 10. Specifically, the above object is achieved by the following means < 1 >, preferably < 2 > to < 15 >.

< 1 > a resin composition comprising a thermosetting resin (A) and a filler (B),

the filler (B) contains hollow particles (B) satisfying the following formula (i) and having an average particle diameter of 0.01 to 10 μm,

d is more than or equal to 1 and less than or equal to 10. Formula (i)

In the formula (i), D represents the number of bubbles contained in the hollow particles (b).

< 2 > the resin composition according to < 1 >, wherein the hollow particles (b) have a water absorption of 3.0% or less when treated at 85 ℃ and 85% relative humidity for 48 hours.

< 3 > the resin composition according to < 1 > or < 2 >, wherein the hollow particles (b) are 1 or more selected from the group consisting of silica, alumina, aluminum hydroxide, boehmite, and boron nitride.

< 4 > the resin composition according to any one of < 1 > to < 3 >, wherein the thermosetting resin (A) is at least 1 resin selected from the group consisting of a maleimide compound (C), an epoxy resin (D), a phenol resin (E), a cyanate ester compound (F) and a modified polyphenylene ether (G) having an ethylenically unsaturated group at a terminal (excluding maleimide).

< 5 > the resin composition < 4 > wherein the modified polyphenylene ether (G) is contained in an amount of 1 to 90 parts by mass based on 100 parts by mass of the total amount of the thermosetting resin (A) in the resin composition.

< 6 > the resin composition according to < 4 > or < 5 >, wherein the maleimide compound (C) is contained in an amount of 1 to 90 parts by mass based on 100 parts by mass of the total amount of the thermosetting resin (A) in the resin composition.

< 7 > the resin composition according to any one of < 4 > to < 6 >, wherein the cyanate ester compound (F) is contained in an amount of 1 to 90 parts by mass based on 100 parts by mass of the total of the thermosetting resins (A) in the resin composition.

< 8 > the resin composition according to any one of < 1 > to < 7 >, wherein the filler (B) is contained in an amount of 50 to 1600 parts by mass based on 100 parts by mass of the total amount of the thermosetting resin (A) in the resin composition.

< 9 > a prepreg formed from a substrate and the resin composition as defined in any one of < 1 > -to < 8 >.

< 10 > the prepreg according to < 9 > wherein the thickness of the prepreg is 5 to 200 μm.

< 11 > the prepreg according to < 9 > or < 10 >, wherein the substrate is a glass cloth.

< 12 > a metal-foil-clad laminate comprising: a layer comprising at least 1 prepreg of any one of the formulas (9) to (11), and a metal foil disposed on one or both surfaces of the layer comprising the prepreg.

< 13 > a resin composite sheet comprising a support and a layer formed of the resin composition as defined in any one of < 1 > -to < 8 > and disposed on the surface of the support.

< 14 > the resin composite sheet < 13 >, wherein the resin composite sheet has a thickness of 5 to 200 μm.

< 15 > a printed wiring board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer,

the insulating layer includes at least one of a layer formed from the resin composition described in any one of < 1 > -8 > and a prepreg described in any one of < 9 > -11 >.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a resin composition having an excellent appearance during processing and a further reduced dielectric constant, and a prepreg, a metal foil-clad laminate, a resin composite sheet, and a printed wiring board using the resin composition can be provided.

Drawings

FIG. 1 shows a schematic representation of a hollow particle.

Fig. 2 is a graph obtained by plotting Dk in examples 1 and 2 and comparative examples 1 to 3.

Detailed Description

The present invention will be described in detail below. In the present specification, "to" means to include the numerical values described before and after the "to" as the lower limit value and the upper limit value.

A resin composition according to an embodiment of the present invention (hereinafter, also referred to as "the present embodiment") is characterized by containing a thermosetting resin (a) and a filler (B), and the filler (B) contains hollow particles (B) satisfying the following formula (i) and having an average particle diameter of 0.01 to 10 μm.

D is more than or equal to 1 and less than or equal to 10. Formula (i)

That is, the hollow particles (b) have a hollow inside, and the number of bubbles is 1 to 10.

The hollow particles (b) in the present embodiment include hollow particles called balloon type, for example, as shown in the schematic view of fig. 1 (1). The reason why the dielectric constant can be reduced by using such hollow particles (b) is presumed as follows.

That is, the hollow particles (b) of a balloon type or the like contain a gas (e.g., air) inside the particles or form a vacuum space. Therefore, even if a prepreg, a layer formed of the prepreg, a substrate (metal foil (copper foil)/laminate of layers formed of the prepreg/metal foil (copper foil)) is produced, it is likely to exist directly in the form of particles containing gas or vacuum spaces inside. Further, since the dielectric constant of a gas such as air or a vacuum space is low, the dielectric constant of the resin composition can be reduced.

On the other hand, the hollow particles described in patent document 1 are particles called porous particles or porous bodies, and as shown in fig. 1 (2), the particles have a large number of large-sized open pores on the surface, and the amount of hydroxyl groups on the surface is large, and are easily affected by water. Therefore, when the resin composition is used as a prepreg or the like, the dielectric constant and the dielectric loss tangent tend to be high.

In addition, although the hollow particles described in patent document 2 can be expected to have a low dielectric constant, the appearance at the time of molding is inherently poor. In the present invention, this is successfully avoided by adjusting the particle diameter of the hollow particles.

The hollow particles (b) used in the present invention are hollow particles having a hollow inside, but the hollow particles do not exclude a case where the surface of the particles further includes open pores within a range not departing from the gist of the present invention.

The present invention will be described in detail below with reference to embodiments of the present invention (hereinafter, also referred to as "the present embodiment") as an example.

< thermosetting resin (A) >)

The resin composition of the present embodiment contains a thermosetting resin (a).

The thermosetting resin (a) preferably contains 1 or more resins selected from the group consisting of a maleimide compound (C), an epoxy resin (D), a phenolic resin (E), a cyanate ester compound (F), and a modified polyphenylene ether (G) having an ethylenically unsaturated group at the terminal (excluding maleimide), and more preferably contains 1 or more resins selected from the group consisting of a maleimide compound (C), an epoxy resin (D), a cyanate ester compound (F), and a modified polyphenylene ether (G).

The thermosetting resin (a) is preferably a blend of the above 2 or more resins, more preferably contains at least the maleimide compound (C) and the cyanate ester compound (F), further preferably contains at least the maleimide compound (C), the cyanate ester compound (F) and the modified polyphenylene ether (G), and further preferably contains at least the maleimide compound (C), the epoxy resin (D), the cyanate ester compound (F) and the modified polyphenylene ether (G).

The thermosetting resin (a) may contain at least 1 or more selected from the group consisting of an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group other than the compounds (C), (F), and (G), an elastomer, and an active ester compound.

The thermosetting resin in the present embodiment contains a component that is cured by heat and constitutes a resin component, in addition to the polymer component.

The resin component means a component other than the filler and the solvent in the resin composition.

The resin composition in the present embodiment preferably contains 5 to 80% by mass of the thermosetting resin (a) in total, more preferably 5 to 70% by mass, and still more preferably 5 to 60% by mass.

An example of the thermosetting resin (a) in the present embodiment is a form in which the thermosetting resin (a) contained in the composition contains at least a maleimide compound (C). In the present embodiment, the maleimide compound (C) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more of the thermosetting resin (a). As the compound (resin) other than the maleimide compound (C), a resin selected from the thermosetting resins (a) is preferable.

In addition, another example of the thermosetting resin (a) in the present embodiment is a form in which the thermosetting resin (a) contained in the composition contains at least the modified polyphenylene ether (G). In the present embodiment, the modified polyphenylene ether (G) preferably accounts for 50 mass% or more, more preferably 70 mass% or more, and still more preferably 90 mass% or more of the thermosetting resin (a). The resin other than the modified polyphenylene ether (G) is preferably a resin selected from the thermosetting resins (a).

An example of the blend form of the resin composition in the present embodiment (blend form a) is a form in which the total of the maleimide compound (C), the epoxy resin (D), the cyanate ester compound (F) and the modified polyphenylene ether (G) accounts for 80 mass% or more, preferably 90 mass% or more, and more preferably 95 mass% or more of the total amount of the thermosetting resin (a).

Another example of the blend form of the resin composition in the present embodiment (blend form B) is a case where the mass ratio of the maleimide compound (C) to the modified polyphenylene ether (G) (maleimide compound (C): modified polyphenylene ether (G)) is 1:0.1 to 3.0, and may be in a form of 1:0.3 to 2.0, and may be 1:0.6 to 1.8. By setting such a blending ratio, the effects of the present invention can be more effectively exhibited.

In the present embodiment, it is preferable that both of the blend forms a and B described above are satisfied.

[ maleimide compound (C) ]

The maleimide compound (C) is a compound having 1 or more maleimide groups in 1 molecule. Among them, preferred are bismaleimide compounds and polymaleimide compounds having 2 or more maleimide groups in 1 molecule.

As an example of the maleimide compound (C), a maleimide compound represented by formula (1) can be mentioned. When the maleimide compound represented by the formula (1) is used for a material for a printed wiring board (for example, a laminate or a metal foil-clad laminate), excellent heat resistance can be imparted, and the peel strength of a metal foil (copper foil), low water absorption, stain resistance and flame resistance can be improved.

In the formula (1), a plurality of R independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and n represents 1 < n.ltoreq.5.

In the formula (1), a plurality of R's each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc.), or a phenyl group. Among them, from the viewpoint of further improving the flame resistance and the peeling strength of the metal foil (copper foil), a group selected from the group consisting of a hydrogen atom, a methyl group, and a phenyl group is preferable, one of a hydrogen atom and a methyl group is more preferable, and a hydrogen atom is even more preferable.

In the formula (1), n is an average value and represents 1 < n.ltoreq.5. From the viewpoint of more excellent solvent solubility, n is preferably 4 or less, more preferably 3 or less, and further preferably 2 or less.

The maleimide compound represented by the above formula (1) can be produced by a known method, or a commercially available compound can be used. Examples of commercially available products include "MIR-3000" manufactured by Nippon Kabushiki Kaisha.

Examples of maleimide compounds other than those mentioned above include 4,4 '-diphenylmethane bismaleimide, phenylmethaneimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) -phenyl) propane, 3,3' -dimethyl-5,5 '-diethyl-4,4' -diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 4,4 '-diphenylether bismaleimide, 4,4' -diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, polyphenylmethylenemaleimide, prepolymers thereof, and prepolymers thereof.

The lower limit of the content of the maleimide compound (C) is preferably 1 part by mass or more, and more preferably 10 parts by mass or more, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition, when the maleimide compound (C) is contained. When the content of the maleimide compound (C) is 1 part by mass or more, the flame resistance tends to be improved. When the maleimide compound (C) is contained, the upper limit of the content of the maleimide compound (C) is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, even more preferably 75 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and even more preferably 55 parts by mass or less, based on 100 parts by mass of the thermosetting resin (a) in the resin composition. When the content of the maleimide compound (C) is 90 parts by mass or less, the peel strength and low water absorption of the metal foil (copper foil) tend to be improved.

The resin composition in the present embodiment may contain only 1 kind of maleimide compound (C), or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.

< epoxy resin (D) >)

The epoxy resin (D) is not particularly limited as long as it is a compound or resin having 2 or more epoxy groups in 1 molecule.

Examples of the epoxy resin (D) include bisphenol a type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, bisphenol a novolac type epoxy resins, glycidyl ester type epoxy resins, aralkyl novolac type epoxy resins, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, cresol novolac type epoxy resins, polyfunctional phenol type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, naphthalene skeleton-modified novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, alicyclic epoxy resins, polyhydric alcohol type epoxy resins, phosphorus-containing epoxy resins, compounds obtained by epoxidizing double bonds of glycidyl amine, glycidyl ester, butadiene and the like, compounds obtained by reaction of hydroxyl group-containing silicone resins and epichlorohydrin, and the like. Among them, from the viewpoint of further improving flame retardancy and heat resistance, preferred are biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins, and more preferred are biphenyl aralkyl type epoxy resins.

The epoxy resin (D) is preferably contained within a range not to impair the effects of the present invention. From the viewpoint of moldability and adhesion, the lower limit of the content of the epoxy resin (D) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition, when the epoxy compound (D) is contained. When the content of the epoxy resin (D) is 0.1 part by mass or more, the peel strength and toughness of the metal foil (copper foil) tend to be improved. When the epoxy compound (D) is contained, the upper limit of the content of the epoxy resin (D) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and further more preferably 8 parts by mass or less, relative to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition. When the content of the epoxy resin (D) is 50 parts by mass or less, the electrical characteristics tend to be improved.

The resin composition in the present embodiment may contain only 1 kind of epoxy resin (D), or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.

The resin composition in the present embodiment may be configured to contain substantially no epoxy resin (D). The substantial absence means that the content of the epoxy resin (D) is less than 0.1 part by mass relative to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

< phenolic resin (E) >)

The phenolic resin (E) is not particularly limited as long as it is a compound or a resin having 2 or more phenolic hydroxyl groups in 1 molecule.

Examples of the phenol resin (E) include bisphenol a type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol a novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, multifunctional phenol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton-modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic type phenol resin, polyhydric alcohol type phenol resin, phosphorus-containing phenol resin, hydroxyl group-containing silicone resin and the like. Among them, from the viewpoint of further improving the flame resistance, at least 1 kind selected from the group consisting of biphenyl aralkyl type phenol resin, naphthol aralkyl type phenol resin, phosphorus-containing phenol resin and hydroxyl group-containing silicone resin is preferable.

The phenolic resin (E) is preferably contained within a range not to impair the effects of the present invention. When the phenolic resin (E) is contained, the content of the phenolic resin (E) is preferably 0.1 part by mass or more, and preferably 50 parts by mass or less, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

The resin composition in the present embodiment may contain only 1 kind of the phenol resin (E), or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.

The resin composition in the present embodiment may be configured to substantially contain no phenol resin (E). The term "substantially free" means that the content of the phenolic resin (E) is less than 0.1 part by mass relative to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

Cyanate ester Compound (F) >)

The cyanate ester compound (F) is not particularly limited as long as it has a cyanate ester structure.

Examples of the cyanate ester compound (F) include at least 1 selected from the group consisting of naphthol aralkyl type cyanate ester compounds (naphthol aralkyl type cyanate esters), naphthylene ether type cyanate ester compounds, phenol novolac type cyanate ester compounds, biphenyl aralkyl type cyanate ester compounds, bisphenol a type cyanate ester compounds, diallyl bisphenol a type cyanate ester compounds, bisphenol M type cyanate ester compounds, xylene resin type cyanate ester compounds, triphenol methane type cyanate ester compounds, and adamantane skeleton type cyanate ester compounds. Among them, from the viewpoint of further improving the plating adhesion and the low water absorption property, at least 1 selected from the group consisting of naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds and xylene resin type cyanate ester compounds is preferable, and naphthol aralkyl type cyanate ester compounds are more preferable. These cyanate ester compounds (F) can be prepared by a known method, and commercially available products can be used. In the cyanate ester compound having a naphthol aralkyl skeleton, a naphthylene ether skeleton, a xylene skeleton, a triphenylolmethane skeleton or an adamantane skeleton, the number of functional group equivalents is large, and unreacted cyanate groups are reduced, so that the water absorption tends to be further reduced. Further, since the metal plating layer mainly has an aromatic skeleton or an adamantane skeleton, the plating adhesion tends to be further improved.

The cyanate ester compound (F) is preferably contained within a range not to impair the effects of the present invention. When the cyanate ester compound (F) is contained, the lower limit of the content of the cyanate ester compound (F) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition. When the content of the cyanate ester compound (F) is 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more, there is a tendency that heat resistance, combustion resistance, chemical resistance, low dielectric constant, low dielectric loss tangent, and insulation properties are improved. When the cyanate ester compound (F) is contained, the upper limit of the content of the cyanate ester compound (F) is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, further preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and further more preferably 50 parts by mass or less, relative to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

The resin composition in the present embodiment may contain only 1 kind of cyanate ester compound (F), or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably in the above range.

< modified polyphenylene ether (G) >, having ethylenically unsaturated group at end (excluding maleimide)

The modified polyphenylene ether (G) having an ethylenically unsaturated group (excluding maleimide) at the terminal (hereinafter also referred to as modified polyphenylene ether (G)) is, for example, a modified product in which all or part of the polyphenylene ether terminal is end-modified with a substituent having an ethylenic carbon-carbon unsaturated double bond. The "polyphenylene ether" in the present specification means a compound having a phenylene ether skeleton represented by the following formula (X1).

(in the formula (X1), R ²⁴ 、R ²⁵ 、R ²⁶ And R ²⁷ May be the same or different and represents an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom or a hydrogen atom. )

The modified polyphenylene ether (G) may further comprise a repeating unit represented by the formula (X2) and/or a repeating unit represented by the formula (X3).

(in the formula (X2), R ²⁸ 、R ²⁹ 、R ³⁰ 、R ³⁴ 、R ³⁵ The alkyl groups may be the same or different and each represents an alkyl group having 6 or less carbon atoms or a phenyl group. R is ³¹ 、R ³² 、R ³³ The hydrogen atoms, alkyl groups having 6 or less carbon atoms or phenyl groups may be the same or different. )

(in the formula (X3), R ³⁶ 、R ³⁷ 、R ³⁸ 、R ³⁹ 、R ⁴⁰ 、R ⁴¹ 、R ⁴² 、R ⁴³ The alkyl groups may be the same or different and each represents a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. -A-is a linear, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms)

The modified polyphenylene ether (G) may be partially or wholly functionalized with an ethylenically unsaturated group such as a vinylbenzyl group, an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxyl group, a silyl group, or the like. These modified polyphenylene ethers may be used in combination of 1 type or 2 or more types. Examples of the polyphenylene ether having a hydroxyl group at the terminal include SA90 manufactured by SABICINNOVOLVIS Plastics, inc.

The method for producing modified polyphenylene ether (G) is not particularly limited as long as the effect of the present invention can be obtained. For example, a modified polyphenylene ether functionalized with a vinylbenzyl group can be produced by: the bifunctional phenylene ether oligomer and vinylbenzyl chloride were dissolved in a solvent, and a base was added thereto under heating and stirring to react, thereby solidifying the resin. The modified polyphenylene ether functionalized with a carboxyl group can be produced, for example, as follows: polyphenylene ether and unsaturated carboxylic acid or a functional derivative thereof are melt-kneaded in the presence or absence of a radical initiator to react. Or by dissolving a polyphenylene ether and an unsaturated carboxylic acid or a functionalized derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting the resulting solution.

As the ethylenically unsaturated group of the modified polyphenylene ether (G) having an ethylenically unsaturated group (excluding maleimide) at the terminal, there may be mentioned alkenyl groups such as vinyl, allyl, acryloyl, methacryloyl, propenyl, butenyl, hexenyl and octenyl; cycloalkenyl groups such as cyclopentenyl and cyclohexenyl; alkenylaryl groups such as vinylbenzyl and vinylnaphthyl, and vinylbenzyl is preferred. The two ethylenically unsaturated groups at both ends may be the same functional group or different functional groups.

The modified polyphenylene ether (g) may have a structure represented by formula (11).

(in the formula (11), X represents an aromatic group, (Y) m represents a polyphenylene ether moiety, and R ¹ 、R ² 、R ³ Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, m represents an integer of 1 to 100, n represents an integer of 1 to 6, and q represents an integer of 1 to 4. Preferably R ¹ 、R ² 、R ³ Is a hydrogen atom. N is preferably an integer of 1 or more and 4 or less, more preferably n is 1 or 2, and still more preferably n is 1. Further, q is preferably an integer of 1 to 3, more preferably q is 1 or 2, and still more preferably q is 2. )

The modified polyphenylene ether (g) in the present embodiment is preferably represented by formula (2).

Among them, - (O-X-O) -is preferably represented by formula (3) and/or formula (4).

(in the formula (3), R ⁴ 、R ⁵ 、R ⁶ 、R ¹⁰ 、R ¹¹ The alkyl groups may be the same or different and each represents an alkyl group having 6 or less carbon atoms or a phenyl group. R is ⁷ 、R ⁸ 、R ⁹ The hydrogen atoms, alkyl groups having 6 or less carbon atoms or phenyl groups may be the same or different. )

(in the formula (4), R ¹² 、R ¹³ 、R ¹⁴ 、R ¹⁵ 、R ¹⁶ 、R ¹⁷ 、R ¹⁸ 、R ¹⁹ The alkyl groups may be the same or different and each represents a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. -A-is a linear, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms. )

Further, - (Y-O) -is preferably represented by formula (5).

(in the formula (5), R ²² 、R ²³ The alkyl groups may be the same or different and each have 6 or less carbon atoms or a phenyl group. R is ²⁰ 、R ²¹ May be the same or different and is hydrogen atom, carbonAlkyl or phenyl of 6 or less), 1 structure or 2 or more structures are randomly arranged. )

a. b represents an integer of 0 to 100, and at least one of b is not 0.

Examples of the-A-in the formula (4) include, but are not limited to, 2-valent organic groups such as methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis (1-methylethylidene), 1,3-phenylenebis (1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethyidene.

Among the above-mentioned modified polyphenylene ethers (g), R is preferred ⁴ 、R ⁵ 、R ⁶ 、R ¹⁰ 、R ¹¹ 、R ²⁰ 、R ²¹ Is alkyl of 3 or less carbon atoms and R ⁷ 、R ⁸ 、R ⁹ 、R ¹² 、R ¹³ 、R ¹⁴ 、R ¹⁵ 、R ¹⁶ 、R ¹⁷ 、R ¹⁸ 、R ¹⁹ 、R ²² 、R ²³ Polyphenylene ether having a hydrogen atom or an alkyl group having 3 or less carbon atoms, particularly, more preferably- (O-X-O) -represented by the formula (3) or the formula (4) is the formula (9), the formula (10) and/or the formula (11), the- (Y-O) -represented by the formula (5) is a structure represented by the formula (12) or the formula (13) or a structure represented by the formula (12) and the formula (13) which are randomly arranged.

(in the formula (10), R ⁴⁴ 、R ⁴⁵ 、R ⁴⁶ 、R ⁴⁷ The hydrogen atoms may be the same or different and each represents a hydrogen atom or a methyl group. -B-is a linear, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms. )

As a specific example of-B-, the same one as that of-A-in the formula (4) may be mentioned.

(in the formula (11), -B-is a linear, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms)

The number average molecular weight of the modified polyphenylene ether (G) in terms of polystyrene obtained by GPC is preferably 500 or more and 3000 or less. When the number average molecular weight is 500 or more, the resin composition of the present embodiment tends to be more inhibited from being sticky when formed into a coating film. When the number average molecular weight is 3000 or less, the solubility in a solvent tends to be further improved.

The modified polyphenylene ether (G) preferably has a weight average molecular weight in terms of polystyrene obtained by GPC method of 800 or more and 10000 or less, more preferably 800 or more and 5000 or less. When the lower limit value is not less than the above-mentioned lower limit value, the dielectric constant and the dielectric loss tangent tend to be lower, and when the upper limit value is not more than the above-mentioned upper limit value, the solubility in a solvent, the low viscosity, and the moldability tend to be further improved.

The equivalent weight of the carbon-carbon unsaturated double bond at the terminal of the modified polyphenylene ether (G) is preferably 400 to 5000G, more preferably 400 to 2500G, per 1 carbon-carbon unsaturated double bond. When the lower limit value is not less than the above-mentioned lower limit value, the dielectric constant and the dielectric loss tangent tend to be lower. When the content is not more than the upper limit, solubility in a solvent, low viscosity, and moldability tend to be further improved.

The method for producing a modified polyphenylene ether represented by the formula (2) in the present embodiment is not particularly limited, and for example, it can be produced by a step of subjecting a bifunctional phenol compound and a 1-functional phenol compound to oxidative coupling to obtain a bifunctional phenylene ether oligomer (oxidative coupling step) and a step of subjecting the terminal phenolic hydroxyl group of the obtained bifunctional phenylene ether oligomer to vinylbenzyl etherification (vinylbenzyl etherification step). Further, as the modified polyphenylene ether, for example, mitsubishi gas chemical corporation (OPE-2 St1200, etc.) can be used.

In the oxidative coupling step, for example, a bifunctional phenol compound, a 1-functional phenol compound and a catalyst are dissolved in a solvent, and oxygen is blown into the solution under heating and stirring to obtain a bifunctional phenylene ether oligomer. The bifunctional phenol compound is not particularly limited, and examples thereof include at least 1 selected from the group consisting of 2,2',3,3',5,5' -hexamethyl- (1,1 ' -biphenol) -4,4' -diol, 4,4' -methylenebis (2,6-dimethylphenol), 4,4' -dihydroxyphenylmethane and 4,4' -dihydroxy-2,2 ' -diphenylpropane. The 1-functional phenol compound is not particularly limited, and examples thereof include 2,6-dimethylphenol and/or 2,3,6-trimethylphenol. The catalyst is not particularly limited, and examples thereof include copper salts (e.g., cuCl, cuBr, cuI, cuCl) ₂ 、CuBr ₂ Etc.), amines (e.g., di-N-butylamine, N-butyldimethylamine, N '-di-t-butylethylenediamine, pyridine, N' -tetramethylethylenediamine, piperidine, imidazole, etc.), etc. The solvent is not particularly limited, and examples thereof include at least 1 selected from the group consisting of toluene, methanol, methyl ethyl ketone, and xylene.

In the vinylbenzyl etherification step, for example, the resin can be produced by dissolving the bifunctional phenylene ether oligomer obtained in the oxidative coupling step and vinylbenzyl chloride in a solvent, adding a base to the solution under heating and stirring to cause reaction, and then solidifying the resin. The vinylbenzyl chloride is not particularly limited, and examples thereof include at least 1 selected from the group consisting of o-vinylbenzyl chloride, m-vinylbenzyl chloride and p-vinylbenzyl chloride. The base is not particularly limited, and examples thereof include at least 1 selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide. In the vinylbenzyl etherification step, an acid may be used to neutralize the base remaining after the reaction. The acid is not particularly limited, and examples thereof include at least 1 selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and nitric acid. The solvent is not particularly limited, and examples thereof include at least 1 selected from the group consisting of toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, dichloromethane, and chloroform. Examples of the method for solidifying the resin include a method of evaporating the solvent to dry it, a method of mixing the reaction solution with a poor solvent and reprecipitating the mixture, and the like.

When the modified polyphenylene ether (G) is contained, the lower limit of the content of the modified polyphenylene ether (G) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 15 parts by mass or more, further more preferably 20 parts by mass or more, and still further more preferably 25 parts by mass or more, relative to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition. When the modified polyphenylene ether (G) is contained, the upper limit of the content of the modified polyphenylene ether (G) is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, further preferably 70 parts by mass or less, and further preferably 60 parts by mass or less, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition. When the content of the modified polyphenylene ether (G) is in the above range, the low dielectric loss tangent and the reactivity tend to be further improved.

The resin composition in the present embodiment may contain only 1 type of modified polyphenylene ether (G), or may contain 2 or more types. When 2 or more species are contained, the total amount is preferably within the above range.

[ oxetane resin ]

The oxetane resin is not particularly limited as long as it is a compound having 2 or more oxetanyl groups.

Examples of the oxetane resin include oxetane, alkyl oxetane (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (product of Toyo Seisakusho Co., ltd.), and OXT-121 (product of Toyo Sesukusho Sesugaku Co., ltd.).

The oxetane resin is preferably contained within a range in which the effect of the present invention is not impaired. The lower limit of the content of the oxetane resin is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition, when the oxetane resin is contained. When the content of the oxetane resin is 0.1 part by mass or more, the peel strength and toughness of the metal foil (copper foil) tend to be improved. When an oxetane resin is contained, the upper limit of the content of the oxetane resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and further more preferably 8 parts by mass or less, relative to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition. When the content of the oxetane resin is 50 parts by mass or less, the electrical characteristics tend to be improved.

The resin composition in the present embodiment may contain only 1 kind of oxetane resin, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.

The resin composition in the present embodiment may be configured to contain substantially no oxetane resin. The substantial absence means that the content of the oxetane resin is less than 0.1 part by mass relative to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

Benzo oxazine compound

The benzoxazine compound is not particularly limited as long as it has 2 or more dihydrobenzoxazine rings in 1 molecule.

Examples of the benzoxazine compound include bisphenol a type benzoxazine BA-BXZ (product of seiko chemical corporation), bisphenol F type benzoxazine BF-BXZ (product of seiko chemical corporation), bisphenol S type benzoxazine BS-BXZ (product of seiko chemical corporation), and the like.

It is preferable to contain the benzoxazine compound in a range not to impair the effects of the present invention. When the benzoxazine compound is contained, the content of the benzoxazine compound is preferably 0.1 part by mass or more, and preferably 50 parts by mass or less, based on 100 parts by mass of the total sum of the thermosetting resins (a) in the resin composition.

The resin composition in the present embodiment may contain only 1 kind of benzoxazine compound, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.

The resin composition in the present embodiment may be a composition that does not substantially contain a benzoxazine compound. The substantial absence means that the content of the benzoxazine compound is less than 0.1 part by mass with respect to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

< Compound having polymerizable unsaturated group >)

The compound having a polymerizable unsaturated group other than the maleimide compound (C), the epoxy resin (D), the phenol resin (E), the cyanate ester compound (F), and the modified polyphenylene ether (G) is not particularly limited as long as it is a compound having 2 or more polymerizable unsaturated groups other than the above-mentioned components (C) to (G).

Examples of the compound having a polymerizable unsaturated group include vinyl compounds (e.g., ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl, etc.), acrylates (e.g., methyl (meth) acrylate, etc.), (meth) acrylates of monohydric or polyhydric alcohols (e.g., 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.), epoxy (meth) acrylates (e.g., bisphenol a type epoxy (meth) acrylate, bisphenol F epoxy (meth) acrylate, etc.), benzocyclopentene resins, bis (maleimide compounds, etc.

It is preferable to contain a compound having a polymerizable unsaturated group within a range not impairing the effects of the present invention. When the compound having a polymerizable unsaturated group is contained, the content is preferably 0.1 part by mass or more, and preferably 50 parts by mass or less, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

The resin composition in the present embodiment may contain only 1 kind of compound having a polymerizable unsaturated group, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.

The resin composition in the present embodiment may be configured to contain substantially no compound having a polymerizable unsaturated group. Substantially free means that the content of the compound having a polymerizable unsaturated group is less than 0.1 part by mass with respect to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

Elastomer

The elastomer in the present embodiment is not particularly limited, and a known elastomer can be widely used.

Examples of the elastomer include at least 1 selected from the group consisting of polyisoprene, polybutadiene, styrene-butadiene, butyl rubber, ethylene-propylene rubber, styrene-butadiene-ethylene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butylene-styrene, styrene-propylene-styrene, styrene-ethylene-propylene-styrene, fluororubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof. Among them, from the viewpoint of excellent electrical characteristics, at least 1 selected from the group consisting of styrene-butadiene, styrene-butadiene-ethylene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butylene-styrene, styrene-propylene-styrene, styrene-ethylene-propylene-styrene, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof is preferable, and from the viewpoint of further excellent compatibility with the modified polyphenylene ether (G), at least 1 selected from the group consisting of styrene-butadiene rubber, and isoprene rubber is more preferable.

The SP value of the elastomer in the present embodiment is preferably 9 (cal/cm) from the viewpoint of excellent electrical characteristics ³ ) ^1/2 The following. SP value is called dissolution parameter and is measured by 1cm ³ Square root of the heat of vaporization (cal/cm) required for the vaporization of a liquid ³ ) ^1/2 And (4) calculating. Generally, the smaller the value, the lower the polarity, and the closer the value, the higher the affinity between the 2 components, and the SP value of the elastomer is 9 (cal/cm) ³ ) ^1/2 In the following, the electrical characteristics of the resin composition more suitable for a printed wiring board for high-frequency use can be obtained.

The weight average molecular weight of the elastomer in this embodiment in terms of polystyrene obtained by GPC is 80000 or more and is solid at 25 ℃, and therefore, when the elastomer is used for a material for a printed wiring board (for example, a laminated board or a metal foil-clad laminated board), crack resistance is further improved, and therefore, the elastomer is preferable. On the other hand, if the weight average molecular weight in terms of polystyrene obtained by GPC method is 40000 or less and is liquid at 25 ℃, warpage when a substance applied to a film is bonded to a substrate is reduced, and therefore, the polystyrene-coated film is particularly suitable as a build-up material for a printed wiring board.

The elastomer is preferably contained within a range not to impair the effects of the present invention. The lower limit of the content of the elastomer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition, when the elastomer is contained. When the content of the elastomer is 5 parts by mass or more, the electrical characteristics tend to be further improved. When the elastomer is contained, the upper limit of the content of the elastomer is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, further preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and further more preferably 50 parts by mass or less, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition. When the content of the elastomer is 20 parts by mass or less, the flame resistance tends to be improved.

The resin composition in the present embodiment may contain only 1 kind of elastomer, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably in the above range.

The resin composition in the present embodiment may be configured to contain substantially no elastomer. The substantial absence means that the content of the elastomer is less than 1 part by mass per 100 parts by mass of the total amount of the thermosetting resin (a) in the resin composition.

Active ester compound

The active ester compound is not particularly limited, and examples thereof include compounds having 2 or more active ester groups in 1 molecule.

The active ester compound may be a linear, branched or cyclic compound. Among them, from the viewpoint of further improving the heat resistance, preferred is an active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound, more preferred is an active ester compound obtained by reacting a carboxylic acid compound with 1 or more compounds selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound, still more preferred is an aromatic compound having 2 or more active ester groups in 1 molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group, and particularly preferred is an aromatic compound having 2 or more active ester groups in 1 molecule obtained by reacting a compound having at least 2 or more carboxylic acids in 1 molecule with an aromatic compound having a phenolic hydroxyl group. The carboxylic acid compound includes 1 or more selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid, and among them, from the viewpoint of further improving the heat resistance, 1 or more selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid is preferable, and 1 or more selected from the group consisting of isophthalic acid and terephthalic acid is more preferable. Examples of the thiocarboxylic acid compound include 1 or more selected from the group consisting of thioacetic acid and thiobenzoic acid. The phenol compound or naphthol compound may include 1 or more selected from the group consisting of hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, biscyclopentadienyl diphenol, and phenol novolak, and from the viewpoint of further improving heat resistance and solvent solubility, preferably bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, alpha-naphthol, beta-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, biscyclopentadienylbenzophenone, phenol novolac, more preferably 1 or more selected from the group consisting of catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, biscyclopentadienylphenol, and phenol novolac, further preferably 1,5-dihydroxynaphthalene, 3282 z3282-dihydroxynaphthalene, 2,6, dihydroxybenzophenone, trihydroxy-benzenediol, trihydroxy-benzophenone, trihydroxy-phenol novolac, and further preferably 1 or more selected from the group consisting of catechol, dihydroxybenzophenone, trihydroxy-phenol novolac, and phenol novolac, and particularly preferably 1 or more selected from the group consisting of dihydroxy benzophenone, trihydroxy benzophenone, tetrahydroxy benzophenone, dicyclopentadienyl diphenol, and phenol novolac (preferably 1 or more selected from the group consisting of dicyclopentadienyl diphenol and phenol novolac, and more preferably dicyclopentadienyl diphenol). As the thiol compound, 1 or more selected from the group consisting of benzenedithiol and triazine dithiol may be cited. The active ester compound is preferably a compound having at least 2 or more carboxylic acids in 1 molecule and containing an aliphatic chain from the viewpoint of further improving the compatibility with the epoxy resin (D), and is preferably a compound having an aromatic ring from the viewpoint of further improving the heat resistance. As a more specific active ester compound, an active ester compound described in Japanese patent application laid-open No. 2004-277460 can be mentioned.

The active ester compound may be commercially available or may be prepared by a known method. Commercially available products include compounds having a biscyclopentadienyl diphenol structure (for example, EXB9451, EXB9460S, HPC-8000-65T (all products of DIC Co., ltd.), and the like), acetylated products of phenol novolacs (for example, DC808 (product of Mitsubishi chemical Co., ltd.), and benzoylated products of phenol novolacs (for example, YLH1026, YLH1030, YLH1048 (all products of Mitsubishi chemical Co., ltd.)). EXB9460S is preferable from the viewpoint of further improving the storage stability of the varnish and reducing the thermal expansion coefficient of the cured product.

The active ester compound can be produced by a known method, for example, by a condensation reaction of a carboxylic acid compound and a hydroxyl compound. Specific examples thereof include a method in which (a) a carboxylic acid compound or a halide thereof, (b) a hydroxyl compound, and (c) an aromatic monohydroxy compound are reacted at a ratio of 0.05 to 0.75 mol of the phenolic hydroxyl group of (b) and 0.25 to 0.95 mol of (c) to 1 mol of the carboxyl group or the acid halide group of (a).

It is preferable to contain the active ester compound within a range not to impair the effects of the present invention. When the active ester compound is contained, the content of the active ester compound is preferably 1 part by mass or more, and preferably 90 parts by mass or less, based on 100 parts by mass of the total sum of the thermosetting resins (a) in the resin composition.

The resin composition in the present embodiment may contain only 1 active ester compound, or may contain 2 or more species. When 2 or more species are contained, the total amount is preferably within the above range.

The resin composition in the present embodiment may be configured to contain substantially no active ester compound. The substantial absence means that the content of the active ester compound is less than 1 part by mass relative to 100 parts by mass of the total amount of the thermosetting resin (a) in the resin composition.

Specific examples of the blending form of the resin composition according to the present embodiment include combinations of naphthol aralkyl type cyanate ester, maleimide compound represented by formula (1), biphenyl aralkyl type epoxy resin, and modified polyphenylene ether (g). The blending ratio of their combination was the same as in the above-mentioned blend forms A and B.

The resin composition in the present embodiment is preferably composed of the thermosetting resin (A) having an acid value of less than 40 mgKOH/g. That is, it is preferable that the thermosetting resin (A) having an acid value of 40mgKOH/g or more is not substantially contained. The substantial absence means that the content of the thermosetting resin (A) having an acid value of 40mgKOH/g or more is less than 1 part by mass per 100 parts by mass of the total amount of the thermosetting resins (A) in the resin composition. By substantially not containing the thermosetting resin (A) having an acid value of 40mgKOH/g or more, the effect of moldability can be more effectively exhibited.

< filling Material (B) >)

The resin composition of the present embodiment contains a filler (B), preferably an inorganic filler.

The resin composition of the present embodiment contains, as the filler (B), hollow particles (B) satisfying the formula (i) and having an average particle diameter of the hollow particles of 0.01 to 10 μm.

D is more than or equal to 1 and less than or equal to 10. Formula (i)

Here, the bubble means a closed space contained inside the particle. In such particles, the ratio of the gas (for example, air) to be contained or the ratio of the space to be formed in a substantially vacuum state increases, and the dielectric constant of the resin composition can be reduced. The dielectric constant has been reduced mainly by adjusting the resin. It is surprising that the dielectric constant can be lowered by the hollow particles (b).

The number of bubbles in the hollow particles (b) in the present embodiment is 1 to 10, and the lower limit of the number of bubbles is preferably 1 or more. The upper limit value is preferably 8 or less, more preferably 6 or less, and further preferably 4 or less.

The number of bubbles is determined by: the cured product of the resin composition was polished to obtain a cross section, and the number of bubbles was counted by observing an SEM (Scanning Electron Microscope) image of the cross section to calculate an average value.

The average particle diameter of the hollow particles (b) in the present embodiment is 0.01 to 10 μm. By using hollow particles having a small particle diameter, the appearance and insulation properties when a resin sheet or a metal-clad laminate (copper-clad laminate) is produced can be improved.

The lower limit of the average particle diameter of the hollow particles (b) is preferably 0.1 μm or more, more preferably 0.3 μm or more, and may be 0.4 μm or more. The upper limit value is preferably 8 μm or less, more preferably 6 μm or less, and still more preferably 4 μm or less.

In the present invention, the average particle diameter is the value of the median particle diameter (D50). In the present invention, the median particle diameter is measured with a laser diffraction/scattering particle size distribution measuring apparatus (wet type). As the laser diffraction/scattering particle size distribution measuring apparatus, for example, LMS-30 manufactured by SEISHIN ENTERPRISE co.

The water absorption of the hollow particles (b) when treated at 85 ℃ and 85% relative humidity for 48 hours is preferably 3.0% or less, more preferably 2% or less, and still more preferably 1% or less. The lower limit of the water absorption is preferably 0%, but is actually 0.01% or more.

The water absorption can be measured as follows: the weight change before and after treatment was calculated from the change in weight after treatment in an atmosphere of 85 ℃ and 85% relative humidity in the dry state for 48 hours.

The hollow particles (b) are preferably an inorganic filler, more preferably 1 or more selected from the group consisting of silica, alumina, aluminum hydroxide, boehmite, and boron nitride, and even more preferably silica.

The bubble content of the hollow particles (b) is preferably 10% or more, and more preferably 15% or more. The upper limit of the bubble content is not particularly limited, and is, for example, 60% or less, preferably 40% or less, and may be 30% or less. Here, the bubble content means [ (density of bubble-free particles-density of hollow particles (b)/density of bubble-free particles ] × 100. Bubble-free particles refer to the density of the particles assuming no bubbles in the hollow particles.

The density (specific gravity) of the hollow particles (b) is preferably 2.1g/cm ³ Hereinafter, more preferably 2.0g/cm ³ Hereinafter, more preferably 1.9g/cm ³ The following. The lower limit of the density is not particularly limited, but is actually 1.0g/cm ³ The above.

As an example of the hollow particles (b) in the present embodiment, ESPHERIQUE N15 (JGC Catalysts and Chemicals ltd. Products) can be exemplified.

On the other hand, examples of the hollow particles (b) in the present embodiment do not include porous silica such as P15C, L C, N C manufactured by JGC Catalysts and Chemicals ltd.

The total content of the hollow particles (b) in the resin composition is preferably 20 to 1600 parts by mass, more preferably 50 to 1600 parts by mass, even more preferably 75 to 1200 parts by mass, even more preferably 75 to 1000 parts by mass, even more preferably 75 to 750 parts by mass, even more preferably 75 to 500 parts by mass, and particularly preferably 75 to 300 parts by mass, based on 100 parts by mass of the total sum of the thermosetting resins (a) in the resin composition.

The content of the hollow particles (b) in the resin composition is preferably 43 to 96 vol%, more preferably 53 to 95 vol%, further preferably 53 to 94 vol%, further preferably 53 to 92 vol%, further preferably 53 to 88 vol%, and further preferably 53 to 82 vol% of the total of the thermosetting resin (a) and the hollow particles (b) in the resin composition.

The hollow particles (b) may be used alone in 1 kind, or in combination of 2 or more kinds. When 2 or more species are used, the total amount is in the above range.

The resin composition of the present embodiment may or may not contain a filler (also referred to as another filler) other than the hollow particles (b). The other filler material may be an organic filler material or an inorganic filler material, preferably an inorganic filler material. Examples of the other filler include silica (e.g., fused silica, natural silica, synthetic silica, amorphous silica, aerosil, white carbon, etc.), metal oxide (e.g., titanium white, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, etc.), metal nitride (e.g., boron nitride, aggregated boron nitride, aluminum nitride, etc.), metal sulfate (e.g., barium sulfate, etc.), metal hydrate (e.g., aluminum hydroxide heat-treated product (obtained by heat-treating aluminum hydroxide to reduce partial crystal water), boehmite, magnesium hydroxide, etc.), molybdenum compound (e.g., molybdenum oxide, zinc molybdate, etc.), zinc (e.g., zinc borate, zinc stannate, etc.), clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, a-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G-20, glass short fibers (e.g., glass including hollow E-glass, T-glass, D-glass, S-glass, Q-glass, etc.), glass fine glass, etc., glass fine glass, glass particles, and the like.

When the resin composition in the present embodiment contains the hollow particles (B) and the other filler, the lower limit of the total content of the filler (B) (the total content of the hollow particles (B) and the other filler) is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 75 parts by mass or more, relative to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition. The upper limit of the total content of the filler (B) is preferably 1600 parts by mass or less, more preferably 1200 parts by mass or less, still more preferably 1000 parts by mass or less, yet more preferably 750 parts by mass or less, yet more preferably 500 parts by mass or less, yet more preferably 300 parts by mass or less, and may be 250 parts by mass or less, and particularly may be 200 parts by mass or less, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

When the filler is contained in the resin composition, the content of the filler other than the hollow particles (b) is preferably 20 to 300 parts by mass, and more preferably 75 to 300 parts by mass, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

When the filler is contained in the resin composition, the content of the filler other than the hollow particles (B) is preferably 5 to 90% by mass, more preferably 5 to 70% by mass, even more preferably 5 to 50% by mass, and even more preferably 5 to 30% by mass of the filler (B).

On the other hand, the resin composition of the present embodiment may be substantially free of the other filler. The substantial absence of the other filler means that the content of the other filler is less than 5% by mass, preferably 1% by mass or less, of the content of the filler (B).

< dispersant >

The resin composition of the present embodiment preferably uses a dispersant (e.g., a wetting dispersant) together.

As the wetting dispersant, for example, a wetting dispersant used for coating materials is generally preferable, and a copolymer-based wetting dispersant is more preferable. Specific examples of the wetting dispersant include Disperbyk-110, disperbyk-2009, 111, 161, 180, BYK-W996, BYK-W9010, BYK-W903, BYK-W940, and the like, which are available from Ltd. The wetting dispersant may be used singly or in combination of 2 or more.

The lower limit of the content of the dispersant is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 1 part by mass or more, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition. The upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

The dispersant may be used alone in 1 kind or in combination of 2 or more kinds. When 2 or more species are used, the total amount is in the above range.

< curing Accelerator >

The resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include imidazoles such as triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl diperoxyphthalate, etc.; azo compounds such as azobisnitrile; tertiary amines such as N, N-dimethylbenzylamine, N-dimethylaniline, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-N-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, catechol, and the like; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, manganese octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate, and the like; the organic metal salts are dissolved in a hydroxyl group-containing compound such as phenol or bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; and organotin compounds such as dioctyltin oxide, other alkyltin, and alkyltin oxide.

Preferred curing accelerators are imidazoles and organometallic salts, more preferably both are used in combination.

The lower limit of the content of the curing accelerator is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and still more preferably 0.1 parts by mass or more, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition. The upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less, based on 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

The curing accelerator may be used alone in 1 kind or in combination of 2 or more kinds. When 2 or more species are used, the total amount is in the above range.

Organic solvent

The resin composition of the present embodiment may contain an organic solvent. In this case, the resin composition of the present embodiment is in a form (solution or varnish) in which at least a part, preferably all, of the various resin components described above are dissolved or compatible in an organic solvent. The organic solvent is not particularly limited as long as it is a polar organic solvent or a nonpolar organic solvent capable of dissolving or compatibilizing at least a part, preferably all, of the various resin components, and examples of the polar organic solvent include ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (e.g., propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (e.g., dimethoxyacetamide, dimethylformamide, etc.), and examples of the nonpolar organic solvent include aromatic hydrocarbons (e.g., toluene, xylene, etc.).

The organic solvent may be used alone in 1 kind or in combination of 2 or more kinds. When 2 or more species are used, the total amount is in the above range.

< other ingredients >

In addition to the above components, the resin composition of the present embodiment may contain various polymer compounds such as thermoplastic resins and oligomers thereof, and various additives. Examples of the additives include flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow control agents, lubricants, defoamers, dispersants, leveling agents, gloss agents, and polymerization inhibitors. These additives may be used alone in 1 kind or in combination of 2 or more kinds.

The resin composition of the present embodiment may be configured to contain substantially no photopolymerization initiator. The substantial absence means that the content of the photopolymerization initiator is less than 0.01 part by mass, preferably 0 part by mass of the resin composition. By not substantially containing a photopolymerization initiator, the effect of the storage stability of the product against light can be more effectively exhibited.

< Property of resin composition >

The resin composition of the present embodiment has a water absorption of preferably 1.20% or less, more preferably 0.55% or less, and even more preferably 0.50% or less, after treating the metal foil-clad laminate for 3 hours at 121 ℃ under 2 atmospheres in a pressure cooker tester in accordance with JIS C6481. The lower limit is preferably 0%, but is actually 0.10% or more. More specifically, the water absorption was measured by the method described in the examples below.

The resin composition of the present embodiment preferably has a Dk (2 GHz) of 3.50 or less, more preferably less than 3.40. The lower limit value is, for example, substantially 3.33 or more.

The Dk (10 GHz) of the resin composition of the present embodiment is preferably 3.30 or less, more preferably 3.23 or less, still more preferably less than 3.20, and even more preferably 3.18 or less. The lower limit value may be, for example, 2.50 or more, further 3.00 or more, and particularly 3.09 or more. More specifically, dk was measured according to the method described in the examples below.

The Tg determined from the loss modulus (E') of the resin composition of the present embodiment may be about 100 to 500 ℃ and may be about 287 to 300 ℃.

The Tg of the resin composition of the present embodiment, which is determined from the loss tangent (tan δ), is preferably 305 to 320 ℃.

The Tg determined from the loss modulus (E') and the loss tangent (tan. Delta.) was measured as described in examples below.

< use >)

The resin composition of the present embodiment can be suitably used as an insulating layer of a printed wiring board or a material for encapsulating a semiconductor. The resin composition of the present embodiment can be suitably used as a material constituting a prepreg, a metal foil-clad laminate using the prepreg, a resin composite sheet, and a printed wiring board.

The resin composition of the present embodiment can be used as a material for a layered molded article (including a film-like article, a sheet-like article, and the like) such as an insulating layer of a printed wiring board, a prepreg, a resin composite sheet, and the like, but when the layered molded article is produced, the lower limit of the thickness thereof is preferably 5 μm or more, and more preferably 10 μm or more. The upper limit of the thickness is preferably 200 μm or less, and more preferably 180 μm or less. When the thickness is in the above range and the hollow particles (b) are particles having an average particle diameter of 0.01 to 10 μm, a better appearance can be obtained when the particles are formed into a layer. Further, a material having more excellent insulating properties when formed into a layer can be obtained. The thickness of the layered material is, for example, a thickness including a substrate when the resin composition of the present embodiment is impregnated into a substrate such as a glass cloth.

The material formed from the resin composition of the present embodiment can be used for the purpose of forming a pattern by exposure and development, and can also be used for the purpose of not performing exposure and development. Particularly suitable for the application without exposure and development.

Prepreg

The prepreg of the present embodiment is formed of a prepreg base material and the resin composition of the present embodiment. The prepreg of the present embodiment can be obtained, for example, by applying the resin composition of the present embodiment to a substrate (for example, impregnation or coating), and then semi-curing the resin composition by heating (for example, a method of drying at 120 to 220 ℃ for 2 to 15 minutes). In this case, the amount of the resin composition (including the cured product of the resin composition) adhering to the substrate, that is, the amount of the resin composition (including the filler) relative to the total amount of the prepreg after semi-curing, is preferably in the range of 20 to 99% by mass.

The substrate is not particularly limited as long as it is a substrate used for various printed wiring board materials. Examples of the material of the substrate include glass fibers (e.g., E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, and spherical glass), inorganic fibers other than glass (e.g., quartz), and organic fibers (e.g., polyimide, polyamide, polyester, and liquid crystal polyester). The form of the substrate is not particularly limited, and examples thereof include substrates made of layered fibers such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. In particular, a base material made of long fibers such as glass cloth is preferable. Here, the long fiber is, for example, a fiber having a number average fiber length of 6mm or more. These substrates may be used alone in 1 or 2 or more. Among these substrates, woven fabrics subjected to a super-open treatment and a mesh-blocking treatment are preferable from the viewpoint of dimensional stability, glass woven fabrics subjected to a surface treatment with a silane coupling agent such as an epoxy silane treatment and an aminosilane treatment are preferable from the viewpoint of moisture absorption and heat resistance, and low dielectric glass cloths composed of glass fibers exhibiting low dielectric constant properties and low dielectric loss tangent such as L-glass, NE-glass, and Q-glass are preferable from the viewpoint of electrical characteristics. The thickness of the substrate is not particularly limited, and may be, for example, about 0.01 to 0.19 mm.

Metal foil clad laminated plate

The metal foil-clad laminate of the present embodiment includes: a layer formed of at least 1 sheet of the prepreg of the present embodiment, and a metal foil disposed on one or both surfaces of the layer formed of the prepreg. The metal foil-clad laminate of the present embodiment can be produced, for example, by the following method: at least 1 prepreg of the present embodiment is arranged (preferably, 2 or more sheets are stacked) and a metal foil is arranged on one surface or both surfaces thereof to perform lamination molding. More specifically, the prepreg can be produced by laminating and molding a metal foil such as copper or aluminum on one or both surfaces of the prepreg. The number of the prepregs is preferably 1 to 10, more preferably 2 to 10, and still more preferably 2 to 7. The metal foil is not particularly limited as long as it is a metal foil used for a material for a printed wiring board, and examples thereof include a copper foil such as a rolled copper foil and an electrolytic copper foil. The thickness of the metal foil (copper foil) is not particularly limited, and may be about 2 to 70 μm. Examples of the molding method include a method generally used for molding a laminate for a printed wiring board and a laminate, and more specifically, a method using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, or the like, at a temperature of about 180 to 350 ℃, a heating time of about 100 to 300 minutes, and a surface pressure of 20 to 100kg/cm ² A method of performing lamination molding under right and left conditions. Further, a multilayer board can also be produced by combining the prepreg of the present embodiment with a separately produced inner layer wiring (also referred to as an inner layer circuit board) and laminating and molding the same. As a method for producing a laminate, for example, 1 sheet of the prepreg of the present embodiment is laminated with 35 μm metal foil (copper foil) on both surfaces thereof, and the laminate is formed by the above-described forming method, then an inner layer circuit is formed, the circuit is blackened to form an inner layer circuit board, and then the inner layer circuit board and the prepreg of the present embodiment are alternately arranged 1 by 1The metal foil (copper foil) is further disposed on the outermost layer, and the laminate is laminated and molded under the aforementioned conditions, preferably under vacuum, thereby producing a laminate. The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board.

Printed circuit board

The printed wiring board of the present embodiment is a printed wiring board including an insulating layer and a conductor layer disposed on the surface of the insulating layer, and the insulating layer includes at least one of a layer formed from the resin composition of the present embodiment and a layer formed from the prepreg of the present embodiment. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method thereof is not particularly limited. An example of a method for manufacturing a printed wiring board is shown below. First, a metal foil-clad laminate such as the copper-clad laminate is prepared. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, and an inner layer substrate is manufactured. The surface of the inner layer circuit of the inner layer substrate is subjected to surface treatment for improving the adhesive strength as required, and then a required number of prepregs are stacked on the surface of the inner layer circuit, and further a metal foil for an outer layer circuit is stacked on the outer side of the prepregs, and the prepregs are integrally molded by heating and pressing. In this manner, a multilayer laminated board in which an insulating layer composed of a base material and a cured product of a thermosetting resin composition is formed between an inner layer circuit and an outer layer circuit metal foil is manufactured. Next, the multilayer laminated board is subjected to drilling for via holes and via holes, and then a plating film for electrically connecting the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the hole, and further, the metal foil for the outer layer circuit is subjected to etching treatment to form the outer layer circuit, thereby manufacturing a printed wiring board.

The printed wiring board obtained in the above manufacturing example had the following structure: the resin composition of the present embodiment is a resin composition for a semiconductor device, which contains an insulating layer and a conductor layer formed on the surface of the insulating layer. That is, the prepreg of the present embodiment (for example, a prepreg formed of a base material and the resin composition of the present embodiment impregnated or applied thereto) and the layer of the metal foil-clad laminate of the present embodiment formed of the resin composition are the insulating layer of the present embodiment.

Resin composite sheet

The resin composite sheet of the present embodiment includes a support and a layer formed of the resin composition of the present embodiment disposed on the surface of the support. The resin composite sheet can be used as a film for lamination or a dry film solder resist. The method for producing the resin composite sheet is not particularly limited, and examples thereof include a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied (coated) to a support and dried to obtain a resin composite sheet.

Examples of the support used herein include, but are not particularly limited to, polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, release films obtained by coating the surfaces of these films with a release agent, organic film substrates such as polyimide films, conductor foils such as copper foils and aluminum foils, and plate-like supports such as glass plates, SUS plates, and FRPs.

Examples of the coating method (coating method) include a method of coating a support with a solution obtained by dissolving the resin composition of the present embodiment in a solvent using a bar coater, a die coater, a doctor blade, a baker, or the like. After drying, the support may be peeled from the resin composite sheet obtained by laminating the support and the resin composition, or the support may be etched to form a single-layer sheet (resin sheet). The resin composition of the present embodiment is dissolved in a solvent to form a solution, and the solution is supplied into a mold having a sheet-shaped cavity and dried to form a sheet-shaped resin composition.

In the production of the single-layer sheet or the resin composite sheet according to the present embodiment, the drying conditions for removing the solvent are not particularly limited, but the solvent is likely to remain in the resin composition at a low temperature, and the resin composition is cured at a high temperature, and therefore, the drying is preferably performed at a temperature of 20 to 200 ℃ for 1 to 90 minutes. In the single layer sheet or the resin composite sheet, the resin composition may be used in an uncured state in which only the solvent is dried, or may be used in a semi-cured (B-stage) state as necessary. The thickness of the resin layer of the single-layer or resin composite sheet of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment and the coating thickness, and is not particularly limited, but is preferably 0.1 to 500 μm since a solvent tends to remain when drying when the coating thickness is generally increased.

Examples

The present invention will be described in more detail with reference to examples. Materials, amounts, ratios, processing contents, processing order, and the like shown in the following examples may be appropriately changed without departing from the gist of the present embodiment. Therefore, the scope of the present embodiment is not limited to the specific examples shown below.

Synthesis example 1 Synthesis of modified polyphenylene ether

Synthesis of bifunctional phenylene Ether oligomer

CuBr was charged into a 12L longitudinal reactor equipped with a stirrer, a thermometer, an air inlet tube and a baffle ₂ 9.36g (42.1 mmol), 1.81g (10.5 mmol) of N, N ' -di-t-butylethylenediamine, 67.77g (671.0 mmol) of N-butyldimethylamine, 2,600g of toluene, and a mixed gas obtained by mixing nitrogen and air to adjust the oxygen concentration to 8 vol% were stirred at a reaction temperature of 40 ℃ and a mixed solution of 2,2',3,3',5,5' -hexamethyl- (1,1 ' -biphenol) -4,4' -diol 129.32g (0.48 mol), 2,6-dimethylphenol 878.4g (7.2 mol), 1.22g (7.2 mmol) of N, N ' -di-t-butylethylenediamine, 26.35g (3432 zxft) of N-butyldimethylamine was added dropwise over 230 minutes while stirring at a flow rate of 5.2L/min. After the completion of the dropwise addition, 1,500g of water in which 48.06g (126.4 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N aqueous hydrochloric acid solution and then with pure water. The resulting solution was concentrated to 50% by mass with an evaporator to obtain 1981g of a toluene solution of a bifunctional phenylene ether oligomer (resin "A"). The number average molecular weight of the resin "A" in terms of polystyrene obtained by GPC was 1975, and that of the resin "A" obtained by GPC wasThe weight average molecular weight in terms of polystyrene was 3514 and the hydroxyl group equivalent was 990.

Synthesis of modified polyphenylene ether

833.4g of a toluene solution of resin "A", 76.7g of vinylbenzyl chloride (AGCSEIMICHEMICAL CO., LTD., "CMS-P"), 1,600g of methylene chloride, 6.2g of benzyldimethylamine, 199.5g of pure water, and 83.6g of a 30.5 mass% aqueous NaOH solution were put into a reactor equipped with a stirrer, a thermometer, and a reflux tube, and stirred at a reaction temperature of 40 ℃. After stirring for 24 hours, the organic layer was washed with a 1N hydrochloric acid aqueous solution, followed by pure water. The resulting solution was concentrated by an evaporator, and was added dropwise to methanol to solidify it, and the solid was recovered by filtration and dried under vacuum to obtain modified polyphenylene ether 450.1. The modified polyphenylene ether had a number average molecular weight of 2250 in terms of polystyrene obtained by GPC, a weight average molecular weight of 3920 in terms of polystyrene obtained by GPC, and a vinyl equivalent of 1189 g/vinyl.

< Properties of the Filler Material >

"BA-S", manufactured by JGC Catalysts and Chemicals Ltd: hollow silica having a number of bubbles of 1 to 10, a water absorption of 0.02 to 0.1%, a bubble content of 15 to 30%, a median particle diameter (D50) of 2.0 to 3.0 [ mu ] m, and a density of 1.5 to 1.9g/cm ³

"SC4500SQ", ADMATECHS co, ltd: spherical fused silica having a bubble number of 0, a water absorption of 0.02 to 0.1%, a bubble content of 0%, a median diameter (D50) of 0.5 μm, and a density of 2.2g/cm ³

"BA-1", manufactured by JGC Catalysts and Chemicals Ltd: hollow silica having a number of bubbles of 1 to 10, a water absorption of 0.02 to 0.1%, a bubble content of 77%, a median particle diameter (D50) of 16.0 [ mu ] m, and a density of 0.5g/cm ³

The number of bubbles represents D in formula (i). The water absorption rate is a value obtained when the sample is treated at 85 ℃ and a relative humidity of 85% for 48 hours.

< Water absorption of Metal-clad laminate >

The water absorption was calculated from the weight change of a sample obtained by cutting the metal-clad laminate obtained in each example and each comparative example to 30mm × 30mm after treatment at 121 ℃ and 2 atmospheres according to JIS C6481 using a Pressure Cooker (PCT) tester for 1 hour, 3 hours, and 5 hours. In Table 1-1, 1 hour corresponds to the water absorption after 1 hour of treatment, 3 hours corresponds to the water absorption after 3 hours of treatment, and 5 hours corresponds to the water absorption after 5 hours of treatment.

The pressure cooker tester used was PC-3 model manufactured by Hill corporation.

< glass transition temperature >

The glass transition temperature (Tg) of the resin composition was measured by a DMA method using a dynamic viscoelasticity analyzer (manufactured by taistmumets) according to JIS C6481 after removing copper foil on both sides of the obtained 8 stacked metal-foil-clad laminate by etching. In Table 1-1 below, E "represents the loss modulus, and tan. Delta. Represents the loss tangent.

< coefficient of thermal expansion (CTE XY) >

The glass transition temperatures of the 8 stacked metal-clad laminate sheets obtained in each of examples and comparative examples were measured by a DMA method using a dynamic viscoelasticity analyzer (manufactured by taistments) according to JIS C6481.

Next, with respect to the metal-clad laminate, the thermal expansion coefficient in the longitudinal direction of the glass cloth was measured with respect to the insulating layer of the laminate by the TMA method (Thermo-mechanical analysis) specified in JIS C6481, and the value thereof was obtained. Specifically, after removing the copper foils on both sides of the metal-clad laminate obtained above by etching, the temperature was raised from 40 ℃ to 340 ℃ at 10 ℃ per minute by using a thermomechanical analyzer (manufactured by TA INSTRUMENTS), and the linear thermal expansion coefficient (ppm/. Degree. C.) was measured. ppm is volume ratio. Alpha 1 is calculated from the tilt rate of 60 ℃ to 120 ℃. For this sample,. Alpha.2 was calculated from the value at 280 to 300 ℃.

< dielectric constant (Dk) and dielectric loss tangent (Df) >)

Using samples obtained by removing the copper foil of the metal-clad laminates obtained in each example and each comparative example by etching, the dielectric constant (Dk) and dielectric loss tangent (Df) at 10GHz and 2GHz were measured by a perturbation method cavity resonator (Agilent Technologies Japan, ltd. Product, agilent8722 ES).

The perturbation method cavity resonator uses Agilent Technologies Japan, ltd.

< comparative example 1 >

30 parts by mass of a naphthol aralkyl type cyanate ("SNCN" synthesized according to the description in paragraph 0074 to 0077 of jp 2018-035327 a), 30 parts by mass of a biphenyl aralkyl type polymaleimide compound ("MIR-3000", manufactured by japan chemical co., ltd.), 5 parts by mass of a biphenyl aralkyl type epoxy resin ("NC-3000 FH", manufactured by japan chemical co., ltd.), 35 parts by mass of the modified polyphenylene ether (OPE-2 St) obtained in the above synthesis example 1, and 1.50 parts by mass in total of a wetting dispersant ("disperbyk-2009 (BYK chemie japan co., ltd." 0.75 parts by mass, "disperbyk-161 (BYK chemie japan co., ltd.," ltd.) "0.75 parts by mass), and manganese octoate (" Oct-Mn ", 0.10 part by mass of a curing accelerator manufactured by Nippon chemical Co., ltd.) and 0.5 part by mass of TPIZ (2,4,5-triphenylimidazole, a curing accelerator) were dissolved and mixed with methyl ethyl ketone to obtain a varnish, and each of the above amounts of addition represents a solid content, the varnish was diluted with methyl ethyl ketone, impregnated and coated on a NE glass woven fabric (product No." N2013 "manufactured by Nidoku corporation) having a thickness of 0.1mm, and heat-dried at 150 ℃ for 5 minutes to obtain a prepreg, the thickness of the obtained prepreg was 100 μm, and the surface of the prepreg had a glossy appearance.

The obtained prepreg was stacked in 8 sheets, and electrolytic copper foil (3 EC-M3-VLP, manufactured by Mitsui Metal Co., ltd.) having a thickness of 12 μ M was disposed on the upper and lower sides thereof under a pressure of 30kgf/cm ² And laminated at 220 ℃ for 120 minutes to obtain a metal-clad laminate having an insulating layer thickness of 0.8 mm. The obtained metal-clad laminate was evaluated for water absorption, glass transition temperature, CTE XY (α 1), (α 2), dk, and Df. The evaluation results are shown in Table 1-1.

< example 1 >

Comparative example 1 was carried out in the same manner as above except that 40.9 parts by mass of hollow silica ("BA-S", manufactured by JGC Catalysts and Chemicals Ltd.) was further compounded and the compounding amount of manganese octoate ("Oct-Mn") was changed to 0.050 parts by mass. The thickness of the resulting prepreg was 100. Mu.m. In addition, the prepreg surface had gloss and a good appearance was obtained. The evaluation results are shown in Table 1-1.

< example 2 >

Comparative example 1 was carried out in the same manner as above except that 122.7 parts by mass of hollow silica ("BA-S", manufactured by JGC Catalysts and Chemicals Ltd.) was further compounded and the compounding amount of manganese octoate ("Oct-Mn") was changed to 0.040 parts by mass. The thickness of the resulting prepreg was 100. Mu.m. In addition, the prepreg surface had gloss and a good appearance was obtained. The evaluation results are shown in Table 1-1.

< comparative example 2 >

Comparative example 1 was carried out in the same manner except that 50.0 parts by mass of spherical fused silica ("SC 4500SQ", ADMATECHS co., ltd. System, water absorption rate 0.02 to 0.1%) was further compounded and the compounding amount of manganese octoate ("Oct-Mn") was changed to 0.050 parts by mass. The thickness of the resulting prepreg was 100. Mu.m. In addition, the prepreg surface had gloss and a good appearance was obtained. The evaluation results are shown in Table 1-1.

< comparative example 3 >

Comparative example 1 was carried out in the same manner except that 150.0 parts by mass of spherical fused silica ("SC 4500SQ", ADMATECHS co., ltd.) was further compounded and the compounding amount of manganese octanoate ("Oct-Mn") was changed to 0.040 parts by mass. The thickness of the resulting prepreg was 100. Mu.m. In addition, the prepreg surface had gloss and a good appearance was obtained. The evaluation results are shown in Table 1-1.

< comparative example 4 >

Comparative example 1 was carried out in the same manner as above except that 150.0 parts by mass of hollow silica ("BA-1", manufactured by JGC Catalysts and Chemicals Ltd.) was further compounded and the compounding amount of manganese octanoate ("Oct-Mn") was changed to 0.040 parts by mass. The thickness of the resulting prepreg was 100. Mu.m. The prepreg obtained was found to have a remarkably poor appearance, in which silica aggregates were observed, and foreign matter and silica particles were observed to protrude. Therefore, other properties were not evaluated.

< example 4 >

The procedure was carried out in the same manner as in example 2 except that the amount of hollow silica ("BA-S") was changed to 20.5 parts by mass and that 25 parts by mass of spherical fused silica ("SC 4500 SQ") was added. The thickness of the resulting prepreg was 100. Mu.m. In addition, the prepreg surface had gloss and a good appearance was obtained. The evaluation results are shown in Table 1-2.

< example 5 >

The procedure was carried out in the same manner as in example 2 except that the amount of hollow silica ("BA-S") was changed to 61.4 parts by mass and spherical fused silica ("SC 4500 SQ") was compounded in an amount of 75 parts by mass. The thickness of the resulting prepreg was 100. Mu.m. In addition, the prepreg surface had gloss and a good appearance was obtained. The evaluation results are shown in Table 1-2.

[ tables 1-1]

[ tables 1-2]

The above-described examples 1 and comparative examples 2 were compounded in such a manner that the volume ratio of silica in the composition was the same. This is because hollow silica has a low specific gravity as compared with conventional silica.

The same applies to example 2 and comparative example 3.

As is clear from the results in table 1, df and Dk can be reduced by using hollow silica in the resin composition of the present embodiment (examples 1 and 2).

Fig. 2 is a graph obtained by plotting Dk in examples 1 and 2 and comparative examples 1 to 3. The triangles (solid lines) indicate Dk (10 GHz) of comparative examples 1, 2 and 3, respectively, and the diamonds (broken lines) indicate examples 1 and 2, respectively.

In addition, the resin composition of the present embodiment can also reduce the water absorption rate.

In addition, the same tendency was observed in the systems using both hollow silica and conventional silica (examples 4 and 5).

< example 3 >

In example 1 of jp 2017-75270 a, a resin composition was prepared by changing hollow silica (ADMATECHS co., ltd.) to the same parts by mass of hollow silica (JGC Catalysts and Chemicals ltd.), as a filler, and measuring the dielectric constant according to the description of the document. The results are shown in Table 2.

In example 1 of jp 2017-75270 a, hollow silica (ADMATECHS co., ltd) is silica having a large number of bubbles, which is much larger than 10, as a filler.

< comparative example 5 >

A resin composition was prepared as described in example 1 of Japanese patent application laid-open No. 2017-75270, and the dielectric constant was measured as described in the above publication. The results are shown in Table 2.

< comparative example 6 >

In comparative example 5, a resin composition was prepared by changing the amount of hollow silica (ADMATECHS co., ltd.) to be blended, and the dielectric constant was measured according to the description of the publication. The results are shown in Table 2.

This corresponds to a comparative example in which the volume ratio of silica was adjusted in the same manner as in example 3 described above.

[ Table 2]

From the above results, it is understood that when silica having many bubbles inside is used as in example 1 of jp 2017-75270 a, the dielectric constant is high (comparative examples 5 and 6). In particular, in comparative example 6, although the same volume of silica as in example 3 was used, a clear significant difference in Dk was observed.

Claims

1. A resin composition comprising a thermosetting resin (A) and a filler (B),

the filler (B) contains hollow particles (B) satisfying the following formula (i) and having an average particle diameter of 0.01 to 10 [ mu ] m,

the hollow particles (b) have a water absorption of 3.0% or less when treated at 85 ℃ under an atmosphere having a relative humidity of 85% for 48 hours,

the hollow particles (b) are 1 or more selected from the group consisting of silica, alumina, aluminum hydroxide, boehmite, and boron nitride,

the thermosetting resin (A) is at least 1 resin selected from the group consisting of a maleimide compound (C), an epoxy resin (D), a phenolic resin (E), a cyanate ester compound (F) and a modified polyphenylene ether (G) having an ethylenically unsaturated group at the end, the ethylenically unsaturated group excluding maleimide,

the thermosetting resin (A) contains at least a maleimide compound (C) in an amount of 50% by mass or more based on the thermosetting resin (A),

the resin composition is used for a copper clad laminate, a prepreg or a resin composite sheet for a printed wiring board, the resin composite sheet comprises a copper foil and a layer formed of the resin composition and disposed on the surface of the copper foil,

d is more than or equal to 1 and less than or equal to 10. Formula (i)

2. The resin composition according to claim 1, wherein the maleimide compound (C) is contained in an amount of 1 to 90 parts by mass based on 100 parts by mass of the total amount of the thermosetting resin (A) in the resin composition.

3. The resin composition according to claim 1 or 2, wherein the cyanate ester compound (F) is contained in an amount of 1 to 90 parts by mass based on 100 parts by mass of the total amount of the thermosetting resins (a) in the resin composition.

4. The resin composition according to claim 1 or 2, wherein the modified polyphenylene ether (G) is contained in an amount of 1 to 90 parts by mass based on 100 parts by mass of the total of the thermosetting resins (A) in the resin composition.

5. The resin composition according to claim 1 or 2, wherein the content of the epoxy resin (D) in the resin composition is less than 0.1 part by mass with respect to 100 parts by mass of the total of the thermosetting resins (a) in the resin composition.

6. The resin composition according to claim 1 or 2, wherein the filler (B) is contained in an amount of 40 to 1600 parts by mass based on 100 parts by mass of the total amount of the thermosetting resin (a) in the resin composition.

7. A resin composition comprising a thermosetting resin (A) and a filler (B),

the thermosetting resin (A) is at least 1 resin selected from the group consisting of a maleimide compound (C), an epoxy resin (D), a phenolic resin (E), a cyanate ester compound (F), and a modified polyphenylene ether (G) having an ethylenically unsaturated group at the end, the ethylenically unsaturated group excluding maleimide, the modified polyphenylene ether (G) accounting for at least 50 mass% of the thermosetting resin (A),

d is more than or equal to 1 and less than or equal to 10. Formula (i)

8. A prepreg formed from a substrate and the resin composition of any one of claims 1 to 7.

9. A prepreg according to claim 8 wherein the prepreg has a thickness of from 5 to 200 μm.

10. A prepreg according to claim 8 or 9 wherein the substrate is a glass cloth.

11. A copper clad laminate comprising: a layer comprising at least 1 sheet of the prepreg according to any one of claims 8 to 10, and a copper foil disposed on one or both surfaces of the layer.

12. A resin composite sheet comprising a copper foil and a layer formed of the resin composition according to any one of claims 1 to 7 disposed on a surface of the copper foil.

13. The resin composite sheet according to claim 12, wherein the thickness of the resin composite sheet is 5 to 200 μm.

14. A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer,

the insulating layer comprises a layer formed from the resin composition according to any one of claims 1 to 7.