CN112313265B

CN112313265B - Resin composition and use thereof

Info

Publication number: CN112313265B
Application number: CN201980042158.6A
Authority: CN
Inventors: 杉山源希; 高野健太郎
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2018-06-27
Filing date: 2019-06-20
Publication date: 2024-04-23
Anticipated expiration: 2039-06-20
Also published as: CN112313265A; KR20210025526A; JPWO2020004211A1; TWI830741B; WO2020004211A1; TW202000784A; JP7363781B2

Abstract

Providing: resin composition having excellent heat resistance and other properties and excellent electrical properties, cured product, prepreg, metal foil-clad laminate, resin sheet, printed wiring board, method for producing resin composition, and agent for reducing dielectric constant and/or dielectric loss tangent. A resin composition comprising: a cyanate ester compound (A) and a bismaleimide compound (B) represented by formula (1); in the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ¹～R³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a each independently represents an integer of 0 to 4.

Description

Resin composition and use thereof

Technical Field

The present invention relates to a resin composition. Further, the present invention relates to a cured product, a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, a method for producing a resin composition, and a reducing agent for dielectric constant and/or dielectric loss tangent, each of which uses the resin composition.

Background

In recent years, the integration and miniaturization of semiconductors used in electronic devices, communication devices, personal computers, and the like have been accelerated. With this, various characteristics required for a laminate for a semiconductor package (for example, a metal foil-clad laminate) used for a printed circuit board are becoming more stringent. Examples of the required characteristics include low dielectric constant, low dielectric loss tangent, low thermal expansion, and heat resistance. Among them, in an insulator material having a large dielectric constant and dielectric loss tangent, an electric signal is attenuated, and in order not to deteriorate reliability, a material having a small dielectric constant and dielectric loss tangent is required.

In order to obtain a printed wiring board having these improved characteristics, studies have been made on a material used as a material for a printed wiring board. For example, patent document 1 discloses, as a composition which is excellent in varnish storage stability and is improved in electrical characteristics, peel strength and thermal decomposition resistance without deteriorating multilayer moldability and heat resistance after moisture absorption, the following composition: the modified polyphenylene ether resin composition comprises a 2-functional vinylbenzyl compound containing a specific polyphenylene ether skeleton, a specific maleimide compound, a specific cyanate ester resin and a specific epoxy resin as constituent components, which are combined in a predetermined ratio.

On the other hand, patent document 2 describes a prepreg comprising: a bismaleimide having a specific structure, optionally (b) 1 or more liquid coreactants with other additives added thereto, and (c) structural fibers. However, there is no description about electrical characteristics and the like.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2010-138364

Patent document 2: japanese patent laid-open No. 05-25298

Disclosure of Invention

Problems to be solved by the invention

As described above, a resin composition containing a cyanate ester compound and a maleimide compound, which is excellent in electrical characteristics, is known. However, with recent technological innovations, further improvement in electrical characteristics is demanded. Further, even if the electrical characteristics are excellent, if other performances are poor, the usefulness is lacking.

The present invention has been made to solve the above problems, and an object of the present invention is to provide: a resin composition which contains a cyanate ester compound and a maleimide compound, has excellent heat resistance and other properties, and has excellent electrical properties; and cured products, prepregs, metal foil-clad laminates, resin sheets, printed wiring boards, methods for producing resin compositions, and dielectric constant and/or dielectric loss tangent reducing agents.

Solution for solving the problem

Based on the foregoing, the present inventors have studied and found that: the present invention has been completed by the completion of the present invention, in which a bismaleimide compound having a specific structure is used to obtain a resin composition having various excellent properties such as heat resistance and improved electrical characteristics. Specifically, the above-described problems can be solved by the following means <1 >, preferably <2 > <18 >.

<1> A resin composition comprising:

Cyanate ester compound (A), and

A bismaleimide compound (B) represented by the following formula (1);

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ¹～R³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a each independently represents an integer of 0 to 4.

<2> The resin composition according to <1>, wherein in the formula (1), X is an alkylene group having 1 to 3 carbon atoms, R ¹～R³ each independently represents a hydrogen atom, a methyl group or an ethyl group, and a each independently represents an integer of 0 to 2.

<3> The resin composition according to <1>, wherein the aforementioned bismaleimide compound (B) is represented by the following formula (2).

<4> The resin composition according to any one of <1> to <3>, further comprising a solvent.

<5> The resin composition according to <4>, wherein the content of the bismaleimide compound (B) is 0.1 to 30% by mass of the resin composition.

<6> The resin composition according to any one of <1> to <5>, wherein the content ratio of the cyanate ester compound (A) and the bismaleimide compound (B) is 0.01 or more and less than 1.1 as expressed by the equivalent ratio of the unsaturated imide group of the bismaleimide compound (B) to the cyanate ester group of the cyanate ester compound (A) (equivalent of unsaturated imide group/equivalent of cyanate ester group).

<7> The resin composition according to any one of <1> to <6>, further comprising 1 or more selected from the group consisting of maleimide compounds other than the aforementioned bismaleimide compound (B), epoxy resins, phenolic resins, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, modified polyphenylene ethers having terminal-modified substituents having a carbon-carbon unsaturated double bond (other than maleimide), elastomers and active ester compounds.

<8> The resin composition according to any one of <1> to <7>, further comprising a filler (C).

<9> The resin composition according to <8>, wherein the content of the filler (C) is 50 to 1600 parts by mass based on 100 parts by mass of the total amount of the resin components in the resin composition.

<10> The resin composition according to any one of <1> to <9>, which is a low dielectric constant material and/or a low dielectric loss tangent material.

<11> Is a cured product of the resin composition according to any one of <1> to <10 >.

<12> A prepreg formed of a base material and the resin composition according to any one of <1> to <10 >.

<13> A metal foil-clad laminate comprising: a layer formed from at least 1 sheet of the prepreg of <12 >; and a metal foil disposed on one or both surfaces of the layer formed of the prepreg.

<14> A resin sheet comprising: a support body; and a layer formed of the resin composition according to any one of <1> to <10> disposed on the surface of the support.

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

The insulating layer includes: at least one of a layer formed of the resin composition of any one of <1> to <10> and a layer formed of the prepreg of <12 >.

<16> A method for producing a resin composition comprising a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1),

The manufacturing method comprises the following steps: mixing a cyanate ester compound (A), a bismaleimide compound (B) and a solvent, wherein the content of the bismaleimide compound (B) is 0.1-30% by mass of the resin composition;

<17> The method for producing a resin composition according to <16>, wherein the resin composition further comprises 1 or more selected from the group consisting of maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenolic resins, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, modified polyphenylene ethers having a substituent having a carbon-carbon unsaturated double bond (other than maleimide), elastomers and active ester compounds.

<18> A dielectric constant and/or dielectric loss tangent reducing agent comprising a bismaleimide compound (B) represented by the following formula (1);

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there may be provided: a resin composition which comprises a cyanate ester compound, a maleimide compound, and a heat-resistant resin and has excellent electrical properties. Further, it is possible to provide: excellent cured product, prepreg, metal foil-clad laminate, resin sheet, printed wiring board, method for producing resin composition, and agent for reducing dielectric constant and/or dielectric loss tangent.

Detailed Description

Hereinafter, the present invention will be described in detail. In the present specification, "to" is used in a sense including the numerical values described before and after the "to" as the lower limit value and the upper limit value.

The resin composition of the present invention is characterized by comprising a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1).

By compounding the bismaleimide compound (B) represented by the formula (1) with the cyanate ester compound (a), various properties (low water absorption, low loss on heating, good appearance of varnish) can be maintained, and dielectric constant (Dk) and dielectric loss tangent (Df) can be reduced. Further, the appearance when forming the prepreg, peel strength, heat resistance, flame retardancy, and the like can be maintained at high levels when forming the metal foil-clad laminate.

Hereinafter, the present invention will be described in detail using an embodiment of the present invention (hereinafter, also referred to as "the present embodiment") as an example.

< Cyanate ester Compound (A) >)

The cyanate ester compound (a) in the present embodiment is not particularly limited as long as it is a compound having a cyanate ester structure.

The cyanate ester compound (a) includes, for example, 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, xylene resin type cyanate ester compounds, triphenol methane type cyanate ester compounds, and adamantane skeleton type cyanate ester compounds. Among these, from the viewpoint of further improvement of coating adhesion and low water absorption, 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 can be prepared by a known method, and commercially available products can be used. The cyanate ester compound having a naphthol aralkyl skeleton, a naphthylene ether skeleton, a xylene skeleton, a triphenol methane skeleton, or an adamantane skeleton has a large equivalent number of functional groups, and the number of unreacted cyanate groups decreases, so that the water absorption tends to be further lowered. Further, since the coating composition mainly has an aromatic skeleton or an adamantane skeleton, the coating adhesion tends to be further improved.

The equivalent weight of the cyanate group of the cyanate ester compound (A) is preferably 200g/eq or more, and further preferably 400g/eq or less. When the plurality of cyanate compounds (a) are contained, the equivalent weight of the cyanate groups on a weighted average taking into consideration the mass of each cyanate compound contained in the resin composition is regarded as.

The lower limit of the content of the cyanate ester compound (a) may be 40 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition, preferably 1 part by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more. The cyanate ester compound content is 1 part by mass or more, more preferably 10 parts by mass or more, and thus the heat resistance, the combustion resistance, the chemical resistance, the low dielectric constant, the low dielectric loss tangent, and the insulation property tend to be improved. The upper limit of the content of the cyanate ester compound is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, and still more preferably 60 parts by mass or less, relative to 100 parts by mass of the total amount of the resin components in the resin composition.

The resin composition in the present embodiment may contain only 1 kind of cyanate ester compound, or may contain 2 or more kinds of cyanate ester compounds. When the content is 2 or more, the total amount is preferably within the above range.

< Bismaleimide Compound (B) >, represented by formula (1)

The resin composition of the present embodiment contains a bismaleimide compound (B) represented by the following formula (1).

In the formula (1), X represents an organic group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, more preferably an isopropylidene group. The 2X's may be the same or different. Preferably the same.

R ¹～R³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom.

A preferably each independently represents an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

The aforementioned bismaleimide compound (B) is preferably represented by the formula (1-2).

In the formula (1-2), X represents an organic group having 1 to 12 carbon atoms, R ¹～R³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a each independently represents an integer of 0 to 4.

The X, R ¹～R³ and a in the formula (1-2) have the same meanings as X, R ¹～R³ and a in the formula (1), respectively, and the preferable ranges are the same. By using the bismaleimide compound represented by the formula (1-2), the electrical characteristics and heat resistance (particularly, suppression of weight loss on heating) of the resin composition tend to be further improved.

The bismaleimide compound (B) represented by the formula (1) is also preferably represented by the following formula (2).

The bismaleimide compound (B) used in the present embodiment is more preferably any of the following.

The equivalent weight of the unsaturated imide group of the bismaleimide compound (B) is preferably 200g/eq or more and further preferably 400g/eq or less. When a plurality of bismaleimide compounds (B) are contained, the equivalent weight of the unsaturated imide groups of the weighted average of the mass of each bismaleimide compound (B) contained in the resin composition is considered.

The lower limit of the content of the bismaleimide compound (B) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and further may be 8 parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more, relative to 100 parts by mass of the total amount of the resin components in the resin composition. The content of the bismaleimide compound (B) is 1 part by mass or more, and thus the flame resistance tends to be improved. In addition, when the bismaleimide compound (B) is contained, the upper limit of the content of the bismaleimide compound (B) is preferably 90 parts by mass or less, more preferably 75 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 45 parts by mass or less, still more preferably 35 parts by mass or less, still more preferably 30 parts by mass or less, based on 100 parts by mass of the total amount of the resin components in the resin composition.

The content of the bismaleimide compound (B) is preferably 0.1 to 30% by mass of the resin composition.

In particular, the lower limit of the content of the bismaleimide compound (B) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more, relative to the solid component (component other than the solvent). The upper limit is preferably 90 mass% or less, more preferably 70 mass% or less, and still more preferably 50 mass% or less.

The content of the bismaleimide compound (B) in the resin composition diluted with the solvent (in the resin composition containing the solvent) is preferably 0.1 to 30% by mass. The lower limit of the content of the bismaleimide compound (B) is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 17.5% by mass or less.

By setting the range as described above, the appearance of the varnish can be further improved, the appearance when the prepreg is formed, and the electrical characteristics of the laminate can be further improved.

The resin composition of the present embodiment may contain only 1 kind of bismaleimide compound (B), or may contain 2 or more kinds of bismaleimide compounds (B). When the content is 2 or more, the total amount is preferably within the above range.

The content ratio of the cyanate ester compound (a) and the bismaleimide compound (B) in the resin composition of the present embodiment is preferably 0.01 or more and less than 1.1, expressed as the equivalent ratio of the unsaturated imide group of the bismaleimide compound (B) to the cyanate ester group of the cyanate ester compound (a) (equivalent of the unsaturated imide group/equivalent of the cyanate ester group). The lower limit of the equivalent ratio is more preferably 0.05 or more, still more preferably 0.1 or more, and still more preferably 0.3 or more. The upper limit of the equivalent ratio is more preferably 0.9 or less, still more preferably 0.7 or less, and still more preferably 0.5 or less. When the content is within this range, the effects of water absorption, electrical characteristics, and thermal properties can be more effectively exhibited.

< Other resin component >)

The resin composition of the present embodiment may contain other resin components than the cyanate ester compound (a) and the bismaleimide compound (B). As the other resin component, 1 or more selected from the group consisting of maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenolic resins, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, modified polyphenylene ethers having terminal-modified substituents other than maleimide, elastomers and active ester compounds, preferably 1 or more selected from the group consisting of maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenolic resins, oxetane resins, benzoxazine compounds, and compounds having polymerizable unsaturated groups, more preferably maleimide compounds other than the bismaleimide compound (B), can be exemplified. By compounding such other resin components, the appearance can be further improved, and other characteristics become more favorable.

Maleimide Compounds other than bismaleimide Compound (B)

The maleimide compounds other than the bismaleimide compound (B) (hereinafter, also referred to as other maleimide compounds) are not particularly limited as long as they are maleimide compounds other than the bismaleimide compound (B) and have 2 or more maleimide groups in the molecule. In particular, by using a maleimide compound having high solubility in a solvent, the electrical characteristics can be improved, and the appearance of the varnish can be improved, and the appearance of a prepreg obtained from the varnish can be further improved. For the other maleimide compound used in the present embodiment, for example, the solubility of methyl ethyl ketone at 25 ℃ is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. Since methyl ethyl ketone has a low boiling point, the drying temperature can be reduced when the solvent is dried, and unnecessary curing of the resin component during drying can be effectively suppressed.

Examples of the other maleimide compound include maleimide compounds represented by the formula (1-3). The use of the maleimide compound represented by the formula (1-3) can provide excellent heat resistance and improve peel strength, low water absorption, surface stain removal resistance and flame resistance when used in a material for a printed wiring board (for example, a laminate, a metal foil-clad laminate) or the like.

In the above formula (1-3), R's each 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 as an average value.

In the above formula (1-3), each of a plurality of R's present independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, etc.), or phenyl group. Among these, from the viewpoint of further improving flame resistance and peel strength, 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 further preferable.

In the above formula (1-3), n is an average value and is 1<n.ltoreq.5. From the viewpoint of further excellent solvent solubility, n is preferably 4 or less, more preferably 3 or less, and further preferably 2 or less. More than 2 different compounds of n may be included.

The maleimide compound represented by the above formula (1-3) may be prepared by a known method or commercially available ones may be used. As a commercial product, for example, "MIR-3000" manufactured by Kagaku Kogyo Co., ltd.

In addition, other maleimide compounds other than the above include 4,4' -5,5' -diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1, 6-bismaleimide- (2, 4-trimethyl) hexane, 4' -diphenylether bismaleimide, 4' -diphenylsulfone bismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, polyphenylmethane maleimide, prepolymers thereof, prepolymers of these maleimides and amines, and the like.

The equivalent weight of the unsaturated imide group of the other maleimide compound is preferably 200g/eq or more, and further preferably 400g/eq or less. When a plurality of other maleimide compounds are contained, the equivalent weight of the unsaturated imide groups on a weighted average is considered in consideration of the mass of each of the other maleimide compounds contained in the resin composition.

When the other maleimide compound is contained, the lower limit of the content of the other maleimide compound is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition. The content of the other maleimide compound is 1 part by mass or more, and the flame resistance of the resin composition tends to be improved. When the total amount of the resin components in the resin composition is 100 parts by mass or less, the upper limit of the content of the other maleimide compound is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, still more preferably 75 parts by mass or less, still more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 55 parts by mass or less, and particularly preferably 45 parts by mass or less. The content of the other maleimide compound is 90 parts by mass or less, and thus the peel strength and low water absorption tend to be improved.

The resin composition of the present embodiment particularly preferably contains both the bismaleimide compound represented by formula (1) and the maleimide compound represented by formulas (1-3). The mass ratio of the bismaleimide compound represented by the formula (1) to the maleimide compound represented by the formula (1-3) in the resin composition is preferably 1:0.1 to 2.0, more preferably 1:1.0 to 2.0, more preferably 1:1.2 to 1.8, more preferably 1:1.4 to 1.6. By setting the ratio as described above, the appearance of the varnish obtained and the electrical characteristics of the cured product can be both achieved in a high dimension.

The resin composition in this embodiment may contain only 1 kind of other maleimide compound, or may contain 2 or more kinds of other maleimide compounds. When the content is 2 or more, the total amount is preferably within the above range.

Epoxy resin

The epoxy resin 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 include: bisphenol a type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol a novolac type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyhydric alcohol type epoxy resin, phosphorus containing epoxy resin, a compound obtained by the reaction of a hydroxyl group-containing silicone resin with epichlorohydrin, and the like. Among these, from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, naphthalene type epoxy resins are preferable, and biphenyl aralkyl type epoxy resins are more preferable.

The epoxy resin is preferably contained within a range that does not impair the effects of the present invention. In terms of moldability and adhesion, the lower limit of the content of the epoxy resin is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition when the epoxy resin is contained. The content of the epoxy resin is 0.1 part by mass or more, and thus the peel strength and toughness of the metal foil (copper foil) tend to be improved. When the epoxy resin is contained, the upper limit of the content of the epoxy resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, based on 100 parts by mass of the total amount of the resin components in the resin composition. The epoxy resin content is 50 parts by mass or less, and thus the electric characteristics tend to be improved.

The resin composition in the present embodiment may contain only 1 kind of epoxy resin, or may contain 2 or more kinds of epoxy resins. When the content is 2 or more, the total amount is preferably within the above range.

The resin composition of the present embodiment may be substantially free of epoxy resin. Substantially free means that the content of the epoxy resin is less than 0.1 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition.

Phenolic resin

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

Examples of the phenolic resin 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, polyfunctional phenol resin, naphthol novolac resin, polyfunctional 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-containing silicone resin, and the like. Among these, at least 1 selected from the group consisting of biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl-containing silicone resins is preferable from the viewpoint of further improving flame resistance.

The phenolic resin is preferably contained within a range that does not impair the effects of the present invention. When the phenolic resin is contained, the total amount of the resin components in the resin composition is preferably 0.1 parts by mass or more and preferably 50 parts by mass or less, based on 100 parts by mass of the total amount of the resin components.

The resin composition in the present embodiment may contain only 1 kind of phenolic resin, or may contain 2 or more kinds of phenolic resins. When the content is 2 or more, the total amount is preferably within the above range.

The resin composition of the present embodiment may be substantially free of phenolic resin. Substantially free means that the content of the phenolic resin is less than 0.1 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition.

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 oxetanes (e.g., 2-methyl oxetane, 2-dimethyl oxetane, 3-methyl oxetane, 3-dimethyl oxetane, etc.), 3-methyl-3-methoxymethyl oxetane, 3-bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3-bis (chloromethyl) oxetane, biphenyl oxetane, OXT-101 (manufactured by Toyama Synthesis Co., ltd.), OXT-121 (manufactured by Toyama Synthesis Co., ltd.), and the like.

The oxetane resin is preferably contained within a range that does not impair the effects of the present invention. When the oxetane resin is contained, 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 still more preferably 2 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition. The oxetane resin content is 0.1 part by mass or more, and thus the peel strength and toughness of the metal foil (copper foil) tend to be improved. When the amount of the oxetane resin is contained, the upper limit of the amount of the oxetane resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, based on 100 parts by mass of the total amount of the resin components in the resin composition. The oxetane resin content is 50 parts by mass or less, and the electric characteristics of the resin composition tend to be further improved.

The resin composition in this embodiment may contain only 1 kind of oxetane resin, or may contain 2 or more kinds of oxetane resins. When the content is 2 or more, the total amount is preferably within the above range.

The resin composition of the present embodiment may be substantially free of oxetane resin. By substantially free, it is meant that the content of the oxetane resin is less than 0.1 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition.

Benzoxazine compound

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

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

The benzoxazine compound is preferably contained within a range that does not impair the effects of the present invention. When the benzoxazine compound is contained, the total amount of the resin components in the resin composition is preferably 0.1 parts by mass or more and preferably 50 parts by mass or less, based on 100 parts by mass of 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 of benzoxazine compounds. When the content is 2 or more, the total amount is preferably within the above range.

The resin composition of the present embodiment may be substantially free of benzoxazine compounds. Substantially free means that the content of the benzoxazine compound is less than 0.1 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition.

Compounds having polymerizable unsaturated groups

The compound having a polymerizable unsaturated group is not particularly limited as long as it is a compound having 2 or more polymerizable unsaturated groups.

Examples of the compound having a polymerizable unsaturated group include: vinyl compounds (e.g., ethylene, propylene, styrene, divinylbenzene, etc.), acrylic esters (e.g., methyl (meth) acrylate, etc.), (meth) acrylic esters 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 type epoxy (meth) acrylate, etc.), benzocyclobutene resins, etc.

The compound having a polymerizable unsaturated group is preferably contained within a range that does not impair the effects of the present invention. When the content of the compound having a polymerizable unsaturated group is 100 parts by mass or more, preferably 0.1 parts by mass or more and 50 parts by mass or less, based on the total amount of the resin components in the resin composition, in the case of containing the same compound.

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

The resin composition of the present embodiment may be formed so as to be substantially free of a compound having a polymerizable unsaturated group. By substantially free, it is meant that the content of the compound having a polymerizable unsaturated group is less than 0.1 part by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition.

Modified polyphenylene ether terminal-modified with substituent containing carbon-carbon unsaturated double bond (except maleimide)

The modified polyphenylene ether terminal-modified with a substituent having a carbon-carbon unsaturated double bond (other than maleimide) is, for example, a modified product in which all or part of the terminal end of the polyphenylene ether is terminal-modified with a substituent having a carbon-carbon unsaturated double bond. The substituent having a carbon-carbon unsaturated double bond is not particularly limited as long as it is a maleimide group, and examples thereof include an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include alkenyl groups such as vinyl, allyl, acryl, methacryl, propenyl, butenyl, hexenyl and octenyl, cycloalkenyl groups such as cyclopentenyl and cyclohexenyl, and alkenylaryl groups such as vinylbenzyl and vinylnaphthyl, and vinylbenzyl is preferred. The term "polyphenylene ether" as used herein refers to a compound having a phenylene ether skeleton represented by the following formula (X1).

(In the formula (X1), R ²⁴、R²⁵、R²⁶ and R ²⁷ are optionally the same or different and each represents an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom or a hydrogen atom.)

The modified polyphenylene ether 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、R²⁹、R³⁰、R³⁴、R³⁵ is optionally the same or different and is an alkyl group having 6 or less carbon atoms or a phenyl group. R ³¹、R³²、R³³ is optionally the same or different and is a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. )

( In the formula (X3), R ³⁶、R³⁷、R³⁸、R³⁹、R⁴⁰、R⁴¹、R⁴²、R⁴³ is optionally the same or different and is 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 may be one in which a part of the terminal is functionalized with an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxyl group, a silyl group or the like. They may be used in combination of 1 or 2 or more.

The method for producing the modified polyphenylene ether is not particularly limited as long as the effects of the present invention can be obtained. For example, those functionalized with vinylbenzyl groups can be produced as follows: the 2-functional phenylene ether oligomer and vinylbenzyl chloride are dissolved in a solvent, and the resin is solidified after a base is added thereto under heating and stirring to react the mixture. The carboxyl functionalized product can be produced as follows: for example, an unsaturated carboxylic acid or a derivative thereof functionalized is melt-kneaded with polyphenylene ether in the presence or absence of a radical initiator, and reacted to produce the polymer. Or may be manufactured as follows: the polyphenylene ether and the unsaturated carboxylic acid, or functional derivative thereof, are dissolved in an organic solvent in the presence or absence of a radical initiator, and reacted in the presence of a solution to produce the polyphenylene ether-unsaturated carboxylic acid copolymer.

The modified polyphenylene ether preferably contains a modified polyphenylene ether having an ethylenically unsaturated group at both ends (hereinafter, sometimes referred to as "modified polyphenylene ether (g)"). Examples of the ethylenically unsaturated group include alkenyl groups such as vinyl, allyl, acryl, methacryl, propenyl, butenyl, hexenyl and octenyl, cycloalkenyl groups such as cyclopentenyl and cyclohexenyl, and alkenylaryl groups such as vinylbenzyl and vinylnaphthyl, and vinylbenzyl is preferred. The 2 ethylenically unsaturated groups at both ends may be the same functional group or may be different functional groups.

The modified polyphenylene ether (G) having an ethylenically unsaturated group at the terminal (hereinafter sometimes simply referred to as modified polyphenylene ether (G)) may have a structure represented by the formula (G1).

( In the formula (G1), X represents an aromatic group, (Y) m represents a polyphenylene ether moiety, R ^G1、R^G2、R^G3 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 ^G1、R^G2、R^G3 is a hydrogen atom. )

Preferably, n is an integer of 1 to 4, more preferably, n is 1 or 2, and still more preferably, n is 1. It is preferable that q is 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 the formula (G2).

Here, - (O-X-O) -is preferably represented by the formula (G3) and/or the formula (G4).

( In the formula (G3), R ⁴、R⁵、R⁶、R¹⁰、R¹¹ is optionally the same or different and is an alkyl group having 6 or less carbon atoms or a phenyl group. R ⁷、R⁸、R⁹ is optionally the same or different and is a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. )

( In the formula (G4), R ¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹ is optionally the same or different and is 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. )

In addition, - (Y-O) -is preferably represented by the formula (G5).

( In the formula (G5), R ²² and R ²³ are optionally the same or different and are alkyl or phenyl groups having 6 or less carbon atoms. R ²⁰ and R ²¹ are optionally the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. )

A. b represents an integer of 0 to 100, at least one of which is not 0. a. When b is an integer of 2 or more, the- (Y-O) -a or- (Y-O) -b may be arranged in 1 structure represented by formula (G5), or may be arranged randomly in 2 or more structures represented by formula (G5).

Examples of the-A-in the formula (G4) include 2-valent organic groups such as methylene, ethylidene, 1-methylethylidene, 1-propylidene, 1, 4-phenylenedi (1-methylethylidene), 1, 3-phenylenedi (1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene and 1-phenylenedi, but are not limited thereto.

Among the modified polyphenylene ethers (G), polyphenylene ethers in which R ⁴、R⁵、R⁶、R¹⁰、R¹¹、R²⁰、R²¹ is an alkyl group 、R⁷、R⁸、R⁹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²²、R²³ having 3 or less carbon atoms or an alkyl group having 3 or less carbon atoms are preferable, particularly preferred is a compound represented by the formula (G3) or the formula (G4) - (O-X-O) -represented by the formula (9), the formula (10) and/or the- (Y-O) -represented by the formula (11) and the formula (G5) is the formula (12) or the formula (13). a. When b is an integer of 2 or more, - (Y-O) -a or- (Y-O) -b is preferably a structure in which the formula (12) or the formula (13) is arranged, or a structure in which the formula (12) and the formula (13) are arranged randomly.

( In formula (10), R ⁴⁴、R⁴⁵、R⁴⁶、R⁴⁷, which are optionally the same or different, are a hydrogen atom or a methyl group. -B-is a linear, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms. )

The term "B" is the same as the specific example of the term "A" in the formula (G4).

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

The modified polyphenylene ether preferably has a number average molecular weight of 500 to 3000 in terms of polystyrene by GPC. When the number average molecular weight is 500 or more, tackiness tends to be further suppressed when the resin composition of the present embodiment is 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 weight average molecular weight of the modified polyphenylene ether in terms of polystyrene by GPC is preferably 800 to 10000, more preferably 800 to 5000. When the dielectric constant and the dielectric loss tangent are set to the lower limit or more, the dielectric constant and the dielectric loss tangent tend to be lower, and when the dielectric loss tangent is set to the upper limit or less, the solubility in a solvent, the low viscosity and the moldability tend to be further improved.

Further, the equivalent weight of the carbon-carbon unsaturated double bond at the terminal of the modified polyphenylene ether is preferably 400 to 5000g, more preferably 400 to 2500g, per 1 carbon-carbon unsaturated double bond. When the dielectric constant and the dielectric loss tangent are set to the lower limit or more, the dielectric constant and the dielectric loss tangent tend to be lower. When the viscosity is equal to or lower than the upper limit, the solubility in a solvent, low viscosity and moldability tend to be further improved.

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

In the oxidative coupling step, for example, the 2-functional phenol compound, the 1-functional phenol compound, and the catalyst are dissolved in a solvent, and oxygen is blown under heating and stirring, thereby obtaining the 2-functional phenylene ether oligomer. The 2-functional phenol compound is not particularly limited, and examples thereof include at least 1 selected from the group consisting of 2,2', 3', 5' -hexamethyl- (1, 1' -biphenol) -4,4' -diol, 4' -methylenebis (2, 6-dimethylphenol), 4' -dihydroxyphenyl methane, 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、CuBr₂), amines (e.g., di-N-butylamine, N-butyldimethylamine, N, N ' -di-t-butylethylenediamine, pyridine, N, N, N ', N ' -tetramethylethylenediamine, piperidine, imidazole, and the like). 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 ether process, for example, it can be produced as follows: the 2-functional phenylene ether oligomer and the vinylbenzyl chloride obtained in the oxidative coupling step are dissolved in a solvent, and after a base is added under heating and stirring to react, the resin is solidified to produce 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 alkali 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 ether step, an acid may be used to neutralize the base remaining after the reaction, and 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, methylene chloride, and chloroform. Examples of the method for solidifying the resin include: a method of evaporating the solvent and drying it, a method of mixing the reaction solution with a poor solvent and reprecipitating it, and the like.

When the modified polyphenylene ether is contained in the resin composition, the lower limit value of the content of the modified polyphenylene ether is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition. When the modified polyphenylene ether is contained, the upper limit of the content of the modified polyphenylene ether is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, still more preferably 70 parts by mass or less, and still more preferably 60 parts by mass or less, based on 100 parts by mass of the total amount of the resin components in the resin composition. When the content of the modified polyphenylene ether is within 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 modified polyphenylene ether or may contain 2 or more modified polyphenylene ethers. When the content is 2 or more, the total amount is preferably within the above range.

Elastomer

The elastomer is not particularly limited, and known elastomers 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 these, 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 from the viewpoint of excellent electrical characteristics, and at least 1 selected from the group consisting of styrene butadiene rubber, and isoprene rubber is more preferable from the viewpoint of further excellent compatibility with the modified polyphenylene ether.

In the elastomer of the present embodiment, the SP value is preferably 9 (cal/cm ³)^1/2 or less because the SP value is called a dissolution parameter, and therefore, the SP value is calculated from the square root of the evaporation heat required for evaporation of a liquid of 1cm ³ (cal/cm ³)^1/2. Generally, the smaller the value, the closer the polarity is, the higher the affinity between 2 components is, and the SP value of the elastomer is 9 (cal/cm ³)^1/2 or less), whereby the electrical characteristics of the resin composition more suitable for use in a printed wiring board for high-frequency applications can be obtained.

The elastomer in this embodiment is preferable because crack resistance is further improved when it is used as a material for a printed wiring board (for example, a laminated board or a metal foil-clad laminated board) or the like if it has a polystyrene-equivalent weight average molecular weight of 80000 or more by GPC and is solid at 25 ℃. On the other hand, if the weight average molecular weight in terms of polystyrene by GPC is 40000 or less and is liquid at 25 ℃, warpage when a film-coated member is bonded to a substrate becomes small, and therefore, the film is particularly suitable as a laminate for a printed circuit board.

The elastomer is preferably contained within a range that does not impair the effects of the present invention. When the elastomer is contained, the lower limit value of the content of the elastomer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition. When the content of the elastomer is 5 parts by mass or more, the electric characteristics tend to be further improved. When the elastomer is contained, the upper limit value of the content of the elastomer is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, based on 100 parts by mass of the total amount of the resin components 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 this embodiment may contain only 1 kind of elastomer, or may contain 2 or more kinds of elastomer. When the content is 2 or more, the total amount is preferably within the above range.

The resin composition of the present embodiment may be substantially free of an elastomer. By substantially free, it is meant that the content of the elastomer is less than 1 part by mass relative to 100 parts by mass of the total amount of the resin components 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 these, from the viewpoint of further improving heat resistance, 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 is preferable, 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 is more preferable, 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 is more preferable, and an aromatic compound having 2 or more active ester groups in 1 molecule obtained by reacting a compound having 2 or more carboxylic acids in 1 molecule with an aromatic compound having a phenolic hydroxyl group is particularly preferable. 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 these, 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 from the viewpoint of further improving heat resistance. The thiocarboxylic acid compound is 1 or more selected from the group consisting of thioacetic acid and thiobenzoic acid. Examples of the phenol compound or the naphthol compound 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, triol, dicyclopentadiene diphenol, and phenol novolac, 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, dicyclopentadiene diphenol, phenol novolak, 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, glycerol, dicyclopentadiene diphenol and phenol novolak, further preferably 1 or more selected from the group consisting of 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene diphenol and phenol novolak, particularly preferably 1 or more selected from the group consisting of dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene diphenol and phenol novolac (preferably 1 or more selected from the group consisting of dicyclopentadiene diphenol and phenol novolac, more preferably dicyclopentadiene diphenol). The thiol compound may be 1 or more selected from the group consisting of a benzenedithiol and a triazinedichiol. In addition, the active ester compound is preferably a compound having 2 or more carboxylic acids in 1 molecule and containing an aliphatic chain from the viewpoint of improving compatibility with the epoxy resin, and is preferably a compound having an aromatic ring from the viewpoint of improving heat resistance. More specific examples of the active ester compound include those described in JP-A-2004-277460.

The active ester compound may be used as a commercially available product, or may be prepared by a known method. Examples of the commercial products include: compounds having a dicyclopentadiene-based diphenol structure (e.g., EXB9451, EXB9460S, HPC-8000-65T (all available from DIC corporation), etc.), the acetylation of phenol novolacs (e.g., DC808 (available from mitsubishi chemical corporation)), and the benzoylation of phenol novolacs (e.g., YLH1026, YLH1030, YLH1048 (all available from mitsubishi chemical corporation)). EXB9460S is preferable from the viewpoint of further improving the storage stability of the varnish and the low thermal expansion coefficient of the cured product.

The method for producing the active ester compound can be produced by a known method, and can be obtained, for example, by a condensation reaction of a carboxylic acid compound with a hydroxy compound. Specific examples thereof include the following methods: the carboxylic acid compound (a) or its acid halide, (b) the hydroxyl compound (c) and the aromatic monohydroxy compound (c) are reacted in a ratio of 0.05 to 0.75 mole of phenolic hydroxyl groups (b) to 1 mole of carboxyl groups or acid halide groups (a) and 0.25 to 0.95 mole of (c).

The active ester compound is preferably contained within a range that does not 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 relative to 100 parts by mass of the total amount of the resin components in the resin composition.

The resin composition in this embodiment may contain only 1 kind of active ester compound, or may contain 2 or more kinds of active ester compounds. When the content is 2 or more, the total amount is preferably within the above range.

The resin composition of the present embodiment may be substantially free of active ester compounds. By substantially free, it is meant 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 resin components in the resin composition.

In the case where the resin composition of the present embodiment does not contain the filler (C) described later or does not substantially contain the filler (C) described later, the total amount of the resin components is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more of the components of the resin composition other than the solvent.

When the resin composition according to the present embodiment contains a filler (C) described later, the total amount of the resin components is preferably 30 mass% or more, more preferably 35 mass% or more, and still more preferably 40 mass% or more of the components of the resin composition other than the solvent. The upper limit is preferably 70 mass% or less, more preferably 65 mass% or less, and still more preferably 60 mass% or less.

In any of the above cases, it is preferable that 90 mass% or more of the resin component is composed of the cyanate ester compound (a), the bismaleimide compound (B) represented by the formula (1), and other maleimide compounds.

< Filler (C) >)

In order to improve the flame resistance and the low thermal expansion property, the resin composition of the present embodiment preferably contains the filler (C) for low dielectric constant, low dielectric loss tangent. As the filler (C) used in the present embodiment, a known one can be suitably used, and the kind thereof is not particularly limited, and one commonly used in the art can be suitably used. Specifically, there may be mentioned: inorganic filler such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica, etc., white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide heat-treated product (obtained by heat-treating aluminum hydroxide with a part of crystal water being reduced), metal hydrate such as boehmite, magnesium hydroxide, molybdenum compound such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, aluminum oxide, 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 G20, glass short fibers (glass fine powder such as E glass, T glass, D glass, S glass, Q glass, etc.), hollow glass, spherical glass, etc.; and organic filler such as styrene-type, butadiene-type, acrylic-type, etc., core-shell-type rubber powder, silicone resin powder, silicone rubber powder, silicone composite powder, etc.

Of these, 1 or 2 or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide are suitable, and silica is more preferable. The silica is preferably spherical silica. The spherical silica may be hollow silica.

By using these filler (C), the thermal expansion characteristics, dimensional stability, flame retardancy and other characteristics of the resin composition are improved.

The content of the filler (C) in the resin composition of the present embodiment is not particularly limited, and may be appropriately set according to the desired characteristics, and is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, still more preferably 75 parts by mass or more, based on 100 parts by mass of the total amount of the resin components in the resin composition. The upper limit 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, still more preferably 750 parts by mass or less, still more preferably 500 parts by mass or less, still more preferably 300 parts by mass or less, still more preferably 250 parts by mass or less, and may be 200 parts by mass or less.

The resin composition in the present embodiment may contain only 1 filler (C), or may contain 2 or more fillers (C). When the content is 2 or more, the total amount is preferably within the above range.

On the other hand, in the present embodiment, the resin composition may be substantially free of the filler (C). Substantially free means that the content of the filler (C) is less than 1 mass% of the content of the resin component, preferably 0.1 mass% or less.

When the filler (C) is used here, a silane coupling agent and/or a wetting dispersant are preferably used in combination. The silane coupling agent may be suitably used as a surface treatment agent commonly used for inorganic substances, and the kind thereof is not particularly limited. Specifically, there may be mentioned: aminosilanes such as γ -aminopropyl triethoxysilane, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, epoxysilanes such as γ -glycidoxypropyl trimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, vinylsilanes such as γ -methacryloxypropyl trimethoxysilane and vinyl-tris (β -methoxyethoxy) silane, and cationic silanes such as N- β - (N-vinylbenzyl aminoethyl) - γ -aminopropyl trimethoxysilane hydrochloride, phenylsilanes, and the like. The silane coupling agent may be used alone or in combination of 2 or more. The wetting dispersant is not particularly limited in kind, and is usually used for paint users. As concrete examples of the wetting dispersant based on the copolymer, disperbyk-110, 111, 161, 180, 2009, 2152, BYK-W996, BYK-W9010, BYK-W903, BYK-W940, etc. manufactured by BYK Chemie Japan Co., ltd. The wetting and dispersing agent may be used alone or in combination of 2 or more.

The content of the silane coupling agent is not particularly limited, and may be about 1 to 5 parts by mass based on 100 parts by mass of the total amount of the resin components in the resin composition. The content of the dispersant (particularly, the wet dispersant) is not particularly limited, and may be, for example, about 0.5 to 5 parts by mass based on 100 parts by mass of the total amount of the resin components in the resin composition.

< 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, and di-tert-butyl peroxyphthalate; azo compounds such as azodinitrile; tertiary amines such as N, N-dimethylbenzylamine, N-dimethylaniline, N-dimethylbenzylamine, 2-N-ethylphenylaminoethanol, 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 octoate, manganese octoate, tin oleate, dibutyl tin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetonate; these 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; organotin compounds such as dioctyltin oxide, other alkyl tin, and alkyl tin oxide; etc.

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

When the content of the curing accelerator is contained, the lower limit value thereof 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 amount of the resin components 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 amount of the resin components in the resin composition.

The curing accelerator may be used alone or in combination of 2 or more. When 2 or more types are used, the total amount falls within the above range.

< Solvent >

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

When the resin composition of the present embodiment contains a solvent, the content thereof is not particularly limited, and may be, for example, 1 mass% or more, 10 mass% or more, 30 mass% or more, or 40 mass% or more of the resin composition. The upper limit may be 99 mass% or less, 80 mass% or less, or 70 mass% or less, or 60 mass% or less.

The solvent may be used alone or in combination of 2 or more. When 2 or more types are used, the total amount falls within the above range.

The resin composition of the present embodiment preferably has a solid content of 10 mass% or more, more preferably 15 mass% or more, still more preferably 20 mass% or more, still more preferably 30 mass% or more, and may be 40 mass% or more, 50 mass% or more. The upper limit of the amount of the solid component is preferably 90 mass% or less, more preferably 80 mass% or less, still more preferably 70 mass% or less, and may be 60 mass% or less.

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

< Other Components >

The resin composition of the present embodiment may contain various polymer compounds such as thermoplastic resins and oligomers thereof, and various additives, in addition to the aforementioned components, within a range that does not hinder the effects of the present invention. Examples of the additives include flame retardants, ultraviolet absorbers, oxidation inhibitors, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, antifoaming agents, dispersants, leveling agents, gloss agents, and polymerization inhibitors. These additives may be used singly or in combination of 2 or more.

The resin composition of the present embodiment may be substantially free of flame retardant. Substantially free means that the content of the flame retardant is less than 0.01 parts by mass, preferably 0 parts by mass, relative to 100 parts by mass of the total resin composition. The resin composition according to the present embodiment is valuable in that it can maintain high flame retardancy even in a composition substantially free of flame retardant. Specifically, the resin composition in this embodiment can be molded to have a flame retardancy of V-0 in a material (printed wiring board or the like) having a thickness of 0.8mm (further 0.4 mm) in UL (Underwriters Laboratories inc.) standard. The flame retardancy was measured according to the description of examples described later.

< Concrete mode of resin composition >

Hereinafter, a more specific embodiment of the present embodiment will be described. The present embodiment is not limited to these.

The first specific example of the resin composition of the present embodiment is a resin composition in which the solid content in the resin composition contains 90 mass% or more (preferably 95 mass% or more) of the resin component. In the present embodiment, the resin component preferably contains a cyanate ester compound (a), a bismaleimide compound (B) represented by formula (1), and another maleimide compound.

The resin composition of the first specific example may have a dielectric constant (Dk) of 3.0 or less or 2.8 or less at 10GHz, which is formed into a test piece having a thickness of 0.8 mm. The lower limit of the dielectric constant is preferably 0, but it is practically 2.0 or more. The resin composition of the first specific example may have a dielectric loss tangent (Df) at 10GHz, which is a test piece molded to a thickness of 0.8mm, of 0.0050 or less, or less than 0.0045, or 0.0044 or less. It is practical that the lower limit of the dielectric constant is preferably 0,0.0020 or more. The dielectric constant and the dielectric loss tangent were measured by the methods described in examples described below.

The resin composition of the first specific example may have a mass reduction temperature of at least 370℃or at least 380% at 1% in a test piece molded to a thickness of 0.8 mm. The upper limit of the 1% mass reduction temperature is not particularly limited, and 420℃or lower is practical.

The resin composition of the first specific example may have a mass reduction rate at 450℃of 19.0% or less, or may have a mass reduction rate of 18.0% or less, in a test piece molded to a thickness of 0.8 mm. The lower limit of the mass reduction rate at 450℃is preferably 0% or more, and is practically 10% or more.

The second specific example of the resin composition of the present embodiment is a resin composition in which the solid content of the resin composition contains 5 to 70 mass% (preferably 20 to 60 mass%) of the resin component and 95 to 30 mass% (preferably 80 to 40 mass%) of the filler. In the present embodiment, the resin component preferably contains a cyanate ester compound (a), a bismaleimide compound (B) represented by formula (1), and another maleimide compound. The filler material is preferably spherical silica.

< Method for producing resin composition >

The method for producing a resin composition according to the present embodiment is a method for producing a resin composition containing a cyanate ester compound (a) and a bismaleimide compound (B) represented by formula (1), and the method comprises the steps of: the cyanate ester compound (a) is mixed with the bismaleimide compound (B) in an amount of 0.1 to 30 mass% (preferably 0.1 to 20 mass%) of the resin composition, and the solvent.

By setting the content of the bismaleimide compound (B) to the above range, the bismaleimide compound (B) can be properly dissolved in a solvent, whereby the appearance of the varnish and the appearance of the prepreg can be further improved. In particular, the use of the bismaleimide compound represented by the above formula (1-2) as the bismaleimide compound represented by the formula (1) can further improve the appearance.

Further, the method for producing a resin composition according to the present embodiment preferably further contains 1 or more selected from the group consisting of maleimide compounds other than bismaleimide compound (B), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, modified polyphenylene ethers having a substituent containing a carbon-carbon unsaturated double bond (other than maleimide), elastomers and active ester compounds, more preferably further contains 1 or more selected from the group consisting of maleimide compounds other than bismaleimide compound (B), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, and compounds having polymerizable unsaturated groups. By compounding such other resin components, the appearance can be further improved and other characteristics can be further improved.

< Use >

The resin composition of the present embodiment is used as a cured product. Specifically, the resin composition of the present embodiment can be suitably used as a low dielectric constant material and/or a low dielectric loss tangent material, and can be suitably used as an insulating layer of a printed wiring board or a material for a semiconductor package. The resin composition of the present embodiment can be suitably used as a prepreg, a metal foil-clad laminate using the prepreg, a resin sheet, and a material constituting a printed circuit board.

The resin composition of the present embodiment is used as a material for a layered (including film-like, sheet-like, and the like) molded product such as an insulating layer, prepreg, and resin sheet of a printed wiring board, and when the layered molded product is formed, the thickness thereof is preferably 5 μm or more, more preferably 10 μm or more. The upper limit of the thickness of the molded article is preferably 200 μm or less, more preferably 180 μm or less. For example, in the case where the resin composition of the present embodiment is impregnated into a substrate such as glass cloth, the thickness of the layered molded article is the thickness including the substrate.

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

Prepreg

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

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

Metal foil-clad laminate

The metal foil-clad laminate of the present embodiment includes: a layer formed from 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 (preferably, 2 or more prepregs) according to this embodiment is arranged, and metal foils are arranged on one or both surfaces of the prepreg to be laminated and molded. 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 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 used as 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 1.5 μm or more, and may be about 2 to 70 μm. The molding method includes a method generally used for molding a laminate and a multilayer board for a printed wiring board, and more specifically includes the following method: using a multistage pressurizing machine, a multistage vacuum pressurizing machine, a continuous molding machine, an autoclave molding machine, etc., and performing lamination molding at a temperature of about 180-350 ℃ for about 100-300 minutes and a surface pressure of about 20-100 kg/cm ². The prepreg of the present embodiment may be combined with a separately manufactured wire board for an inner layer (also referred to as an inner layer circuit board) and laminated to form a multilayer board. As a method for producing a multilayer board, for example, a multilayer board can be produced by disposing metal foils (copper foils) of about 35 μm on both sides of 1 sheet of prepreg according to the present embodiment, laminating the metal foils by the above-described molding method, forming an inner layer circuit, blackening the circuit to form an inner layer circuit board, disposing 1 sheet of the inner layer circuit board alternately with the prepreg according to the present embodiment, disposing metal foils (copper foils) on the outermost layers, and laminating and molding the metal foils under the above-described conditions, preferably under vacuum. The metal foil-clad laminate of the present embodiment can be suitably used as a printed circuit board.

Printed circuit board

The printed circuit board of the present embodiment is a printed circuit board including an insulating layer and a conductor layer disposed on a surface of the insulating layer, the insulating layer including: at least one of the layer formed of the resin composition of the present embodiment and the layer formed of the prepreg of the present embodiment. Such a printed circuit board can be manufactured according to a conventional method, and the manufacturing method thereof is not particularly limited. Hereinafter, an example of a method for manufacturing a printed circuit board is shown. First, a metal foil-clad laminate such as the above-described copper foil-clad laminate is prepared. Then, the surface of the metal foil-clad laminate was subjected to etching treatment to form an inner layer circuit, thereby producing an inner layer substrate. The inner layer circuit surface of the inner layer substrate is subjected to surface treatment for improving the adhesive strength as needed, and then the prepreg is laminated on the inner layer circuit surface in a desired number, and further a metal foil for the outer layer circuit is laminated on the outer side thereof, and the inner layer circuit is heated and pressed to be integrally molded. Thus, a multilayer laminated board having a base material and an insulating layer formed of a cured product of a thermosetting resin composition formed between metal foils for inner and outer circuits was produced. Then, after the multilayer laminated board is subjected to a through-hole and an opening for a via hole, a plated metal film for making the inner layer circuit and the outer layer circuit conductive is formed on the wall surface of the hole, and further, the outer layer circuit is formed by performing an etching process on the outer layer circuit metal foil.

The printed circuit board obtained in the foregoing manufacturing example has an insulating layer; and a conductor layer formed on the surface of the insulating layer, wherein the insulating layer is composed of the resin composition of the present embodiment. 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 formed of the resin composition in the metal foil-clad laminate of the present embodiment serve as the insulating layer of the present embodiment.

Resin sheet

The resin sheet of the present embodiment includes: a support body; and a layer formed of the resin composition of the present embodiment, which is disposed on the surface of the support. The resin sheet can be used as a laminate film or a dry film solder resist. The method for producing the resin sheet is not particularly limited, and examples thereof include the following methods: the solution in which the resin composition of the present embodiment is dissolved in the solvent is applied (coated) to a support and dried, thereby obtaining a resin sheet.

Examples of the support used herein include: the sheet-like support such as polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, release film having a release agent coated on the surface of these films, organic film base material such as polyimide film, conductor foil such as copper foil and aluminum foil, glass plate, SUS plate, FRP, etc. is not particularly limited.

Examples of the coating method (coating method) include the following methods: the solution in which the resin composition of the present embodiment is dissolved in the solvent is applied to the support by a bar coater, a die coater, a doctor blade, a baking applicator, or the like. After drying, the support may be peeled off from the resin sheet in which the support and the resin composition are laminated or etched, thereby forming a single-layer sheet. The solution in which the resin composition according to the present embodiment is dissolved in the solvent is supplied into a mold having a cavity in the form of a sheet, and dried, etc., to be molded into a sheet, whereby a single-layer sheet may be obtained without using a support.

In the production of the single-layer sheet or the resin sheet according to the present embodiment, the drying condition for removing the solvent is not particularly limited, but the solvent is liable to remain in the resin composition if the temperature is low, and the curing of the resin composition proceeds if the temperature is high, and therefore, the temperature is preferably from 1 to 90 minutes at 20 to 200 ℃. In the single-layer sheet or the resin 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-staged) state as needed. Further, the thickness of the resin layer of the single layer or the resin sheet of the present embodiment is not particularly limited, and may be adjusted according to the concentration of the solution of the resin composition and the thickness of the coating, but in general, if the thickness of the coating becomes thicker, the solvent tends to remain during drying, and therefore, 0.1 to 500 μm is preferable.

< Agent for decreasing dielectric constant and/or dielectric loss tangent >)

The agent for reducing the dielectric constant and/or dielectric loss tangent of the present embodiment contains a bismaleimide compound (B) represented by formula (1). By blending the bismaleimide compound represented by the formula (1) with a maleimide compound other than the cyanate compound (a) and the bismaleimide compound (B) and other resin components, the dielectric constant and/or dielectric loss tangent of the resin composition can be reduced. The dielectric constant and/or dielectric loss tangent reducing agent of the present embodiment is particularly effective as a dielectric loss tangent reducing agent. The preferable range of the bismaleimide compound represented by the formula (1) is the same as that described above.

Examples

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

Synthesis example 1 Synthesis of naphthol aralkyl cyanate ester Compound (SNCN)

300G (1.28 mol in terms of OH group) of 1-naphthol aralkyl resin (manufactured by Nippon Kagaku Co., ltd.) and 194.6g (1.92 mol) of triethylamine (1.5 mol relative to 1mol of hydroxyl group) were dissolved in 1800g of methylene chloride to prepare a solution 1.

While stirring 125.9g (2.05 mol) of cyanogen chloride (1.6 mol relative to 1mol of hydroxyl group), 293.8g of methylene chloride, 194.5g (1.92 mol) of 36% hydrochloric acid (1.5 mol relative to 1mol of hydroxyl group) and 1205.9g of water, the solution 1 was injected over 30 minutes while maintaining the liquid temperature at-2 to-0.5 ℃. After the completion of the injection of the solution 1, a solution (solution 2) in which 65g (0.64 mol) of triethylamine (0.5 mol to 1mol of hydroxyl group) was dissolved in 65g of methylene chloride was injected over 10 minutes after stirring at the same temperature for 30 minutes. After the injection of the solution 2 was completed, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

The reaction solution was then allowed to stand to separate the organic phase and the aqueous phase. The resulting organic phase was washed 5 times with 1300g of water. The conductivity of the wastewater from the 5 th washing was 5. Mu.S/cm, and it was confirmed that the ionic compound to be removed was sufficiently removed by washing with water.

The organic phase after washing was concentrated under reduced pressure, and finally concentrated at 90℃for 1 hour to give 331g of the objective naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous substance). The mass average molecular weight of SNCN obtained was 600. Further, the IR spectrum of SNCN shows the absorption of 2250cm ^-1 (cyanate group) and does not show the absorption of hydroxyl groups. The equivalent weight of the cyanate ester group of SNCN obtained was 256g/eq.

< Synthesis example 2 Synthesis of bismaleimide Compound (BMI-Bisanilin-M) >)

A flask equipped with a stirrer, a nitrogen inlet pipe, a dean-Stark trap, a condenser, and a thermometer was charged with 17.23g (50.0 mmol) of 1, 3-bis [2- (4-aminophenyl) -2-propyl ] benzene manufactured by Tokyo chemical Co., ltd, and 120.0g of N, N-dimethylformamide as a solvent, and the mixture was dissolved by stirring while charging nitrogen. To this solution, 10.8g (110 mmol) of maleic anhydride was added, and stirred overnight at room temperature. Thereafter, 0.951g (5.00 mmol) of p-toluenesulfonic acid monohydrate as a catalyst and 60g of toluene as a dehydrated azeotropic solvent were charged, and azeotropic stirring was performed for 6 hours. At this time, evaporation of toluene and water occurs, and a part of them is condensed in a condenser. After separating the water and toluene captured by the dean-stark trap, only toluene was refluxed into the system, and a part of the toluene was distilled off from the upper part of the cooling tube to the outside of the system by passing nitrogen gas.

After cooling the reaction mixture, toluene was distilled off in an evaporator. Thereafter, the obtained solution was poured into a1 mass% aqueous sodium bicarbonate solution, and the excessive maleic anhydride and p-toluenesulfonic acid were removed. The crude product obtained was dissolved in N, N-dimethylformamide, reprecipitated by adding methanol, filtered to obtain a precipitate and dried. This operation was repeated 3 times to obtain 4,4' -bismaleimide diphenyl ether (yield: 70%).

The equivalent weight of the maleimide group of BMI-Bisanilin-M obtained was 252.3g/eq.

< Synthesis example 3 Synthesis of bismaleimide Compound (BMI-Bisanilin-P) >)

A flask equipped with a stirrer, a nitrogen inlet pipe, a dean-Stark trap, a condenser, and a thermometer was charged with 17.23g (50.0 mmol) of 1, 4-bis [2- (4-aminophenyl) -2-propyl ] benzene manufactured by Tokyo chemical Co., ltd, and 120.0g of N, N-dimethylformamide as a solvent, and the mixture was dissolved by stirring while charging nitrogen. To this solution, 10.8g (110 mmol) of maleic anhydride was added, and stirred overnight at room temperature. Thereafter, 0.951g (5.00 mmol) of p-toluenesulfonic acid monohydrate as a catalyst and 60g of toluene as a dehydrated azeotropic solvent were charged, and azeotropic stirring was performed for 6 hours. At this time, evaporation of toluene and water occurs, and a part of them is condensed in a condenser. After separating the water and toluene captured by the dean-stark trap, only toluene was refluxed into the system, and a part of the toluene was distilled off from the upper part of the cooling tube to the outside of the system by passing nitrogen gas.

The functional group equivalent of BMI-Bisanilin-P obtained was 252.3g/eq.

Example 1>

Using methyl ethyl ketone as a solvent, SNCN parts by mass of the BMI-Bisanilin-M20 parts by mass obtained in Synthesis example 1, 30 parts by mass of a biphenylaralkyl type polymaleimide compound ("MIR-3000", manufactured by Kagaku Co., ltd., equivalent of maleimide group: 275 g/eq), 0.5 part by mass of TPIZ (2, 4, 5-triphenylimidazole, curing accelerator), and 0.10 part by mass of zinc octoate ("Oct-Zn", manufactured by Kagaku Co., ltd., curing accelerator) were dissolved so that the solid content concentration became 50% by mass, and mixed to obtain a varnish. The content of each component represents the amount of the solid component. The appearance of the obtained varnish was evaluated according to the method described below.

Methyl ethyl ketone was evaporated from the obtained varnish to be distilled off, whereby a mixed resin powder was obtained. The mixed resin powder was filled into a mold having a thickness of 0.8mm at a side of 1, and vacuum-pressurized at a temperature of 230℃and a pressure of 40kg/cm ² for 120 minutes to obtain a test piece of a cured product having a thickness of 0.8mm at a side of 1.

The water absorption, electrical characteristics (Dk and Df) and heating loss were measured according to the following methods for the obtained test piece having a thickness of 0.8 mm.

Appearance of varnish

The appearance of the obtained varnish was evaluated visually as follows. The evaluations A to C were at practical level.

A: even and no precipitate was observed.

B: no precipitate was observed uniformly and substantially.

C: slightly uneven, and some precipitates were confirmed.

D: non-uniformity and a large amount of precipitate were observed.

Water absorption rate >)

The water absorption was calculated from the weight change after the water vapor treatment at 120℃for 0.1MPa and 5 hours using the test piece having a thickness of 0.8mm obtained by using a Pressure Cooker (PCT) tester in accordance with JIS C6481. In JIS C6481, the sample size was changed to 30mm by 30mm for a test piece having a thickness of 0.8 mm.

The autoclave tester was a product of Pingshan Kagaku Co., ltd., PC-3.

The results are shown in table 1 below.

Electric characteristics (Dk and Df) >, of

The dielectric constant (Dk) and dielectric loss tangent (Df) at 10GHz were measured on the obtained test piece having a thickness of 0.8mm using a cavity resonator by a perturbation method.

The perturbation method cavity resonator uses Agilent Technologies, inc.

The results are shown in table 1 below.

Heating loss

The thermal analysis of the cured product was performed using a thermal analyzer under a nitrogen atmosphere at a heating rate of 10 ℃/min.

The calorimeter was used SII Nanotechnology, inc. under the heading "TGA5200".

The results are shown in table 1 below.

Example 2>

The procedure was carried out in the same manner as in example 1 except that BMI-Bisanilin-M was changed to BMI-Bisanilin-P obtained in Synthesis example 3 in the same amount. The results are shown in table 1 below.

Comparative example 1>

The procedure was carried out in the same manner as in example 1 except that BMI-Bisanilin-M was not used and MIR-3000 was contained in an amount of 50 parts by mass. The results are shown in table 1 below.

Comparative example 2>

The procedure was carried out in the same manner as in example 1 except that SNCN and MIR-3000 were not used and the content of BMI-Bisanilin-M was set to 100 parts by mass. The results are shown in table 1 below.

Comparative example 3 >

The procedure was carried out in the same manner as in example 1 except that SNCN, MIR-3000 and BMI-Bisanilin-M were not used and the content of BMI-Bisanilin-P was set to 100 parts by mass. The results are shown in table 1 below.

TABLE 1

From the results described above, it was revealed that the resin compositions of examples 1 and 2 maintained good varnish appearance and low water absorption as in comparative example 1, and further, the weight loss under heating was smaller than in comparative example 1, and further, the electrical characteristics were improved. In particular, df is significantly reduced. In comparative examples 2 and 3, the varnish appearance was D, and the varnish was not practically usable.

Example 3 >

Using methyl ethyl ketone as a solvent, SNCN parts by mass of the BMI-Bisanilin-M20 parts by mass obtained in Synthesis example 1, 30 parts by mass of a biphenylaralkyl type polymaleimide compound ("MIR-3000", manufactured by Kagaku Co., ltd.), 100 parts by mass of spherical silica (SC 2050-MB, manufactured by Admatechs Co., ltd., average particle size: 0.5 μm), 0.5 parts by mass of TPIZ (2, 4, 5-triphenylimidazole, curing accelerator), and 0.10 parts by mass of zinc octoate ("Oct-Zn", manufactured by Kagaku Co., ltd., curing accelerator) were dissolved so that the solid content concentration became 50% by mass, and mixed to obtain a varnish. The above-mentioned respective contents represent the amounts of solid components. The appearance of the obtained varnish was evaluated according to the method described below.

The varnish obtained was impregnated and coated on an E glass cloth having a thickness of 0.1mm, and then dried by heating at 165℃for 5 minutes using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Kyowa Kagaku Co., ltd.) to obtain a prepreg having 50% by mass of the resin composition and 50% by mass of the glass cloth. The appearance of the obtained prepreg was evaluated according to the method described below.

A copper foil laminate with a thickness of 0.4mm and 0.8mm was obtained by placing 12 μm copper foil (3 EC-M3-VLP, manufactured by Mitsui Metal mineral Co., ltd.) on both sides of the prepreg in a state where 4 or 8 sheets of the prepreg were stacked, and vacuum-pressurizing the prepreg at a pressure of 40kg/cm ² and a temperature of 220℃for 120 minutes.

The resulting copper-clad laminate was measured for peel strength, flexural physical properties, water absorption, electrical properties (Dk and Df), glass transition temperature, flame retardancy, thermal expansion coefficient, weight loss under heating, and thermal conductivity.

Appearance of varnish

A: even and no precipitate was observed.

B: no precipitate was observed uniformly and substantially.

C: slightly uneven, and some precipitates were confirmed.

D: non-uniformity and a large amount of precipitate were observed.

Prepreg appearance

The obtained prepreg was visually evaluated for appearance as follows. The evaluations A to C were at practical level.

A: even and no precipitate was observed.

B: no precipitate was observed uniformly and substantially.

C: slightly uneven, and some precipitates were confirmed.

D: non-uniformity and a large amount of precipitate were observed.

Peel strength >

The copper foil peel strength was measured 3 times using a test piece (30 mm. Times.150 mm. Times.0.8 mm in thickness) obtained by cutting the copper-clad laminate having a thickness of 0.8mm obtained as described above, according to the test method (see 5.7 peel strength) for a copper-clad laminate for a printed wiring board of JIS C6481, and the average value of the lower limit values was used as a measured value. The results are shown in Table 2.

Bending physical property

The copper foil on the surface layer of the copper-clad laminate having a thickness of 0.8mm obtained as described above was removed by etching, and both end portions of the test piece were supported by a fulcrum using an Autograph tester according to JIS K6911 to form both end supporting beads, and the maximum bending stress when a concentrated load was applied from above to the center portion was measured to obtain bending strength.

Further, using a test piece from which the copper foil of the copper-clad laminate was removed, the deformation resistance of the test piece to the bending stress of the straight line portion of the load deflection curve within the elastic limit was measured as the bending stress per unit strain using an Autograph tester according to JIS K6911, and the flexural modulus was obtained.

An Autograph tester was used as AG-Xplus manufactured by Shimadzu corporation.

The results are shown in Table 2.

Water absorption rate >)

The resulting copper-clad laminate sheet of 0.8mm thickness was cut into a sample of 30mm. Times.30 mm, and the water absorption was calculated from the weight change after the treatment at 120℃for 0.1MPa and 5 hours by using a Pressure Cooker (PCT) tester in accordance with JIS C6481.

The autoclave tester was a product of Pingshan Kagaku Co., ltd., PC-3.

The results are shown in Table 2.

Electric property >

The dielectric constants (Dk) and dielectric loss tangents (Df) at 2GHz and 10GHz were measured, respectively, using samples from which the resulting copper foil of the copper-clad laminate having a thickness of 0.4mm and a thickness of 0.8mm were removed by etching.

The perturbation method cavity resonator uses Agilent Technologies, inc.

The results are shown in Table 2.

Glass transition temperature

The glass transition temperature (Tg) was determined as follows: after removing copper foil on both sides of the obtained copper-clad laminate having a thickness of 0.8mm by etching, the resultant was measured by a dynamic mechanical analysis (DMA, dynamic Mechanical Analysis) method using a dynamic viscoelasticity analysis apparatus in accordance with JIS C6481. In table 2 below, E "represents loss modulus, and tan δ represents loss tangent.

Dynamic viscoelasticity analysis device a device manufactured by TA Instruments was used.

The results are shown in Table 2.

Flame retardance >)

The copper foil on both sides of the metal foil-clad laminate obtained in each example and comparative example was removed by etching. Then, using the test piece from which the copper foil on both sides was removed, a flame retardancy test was performed according to the UL94 vertical burn test method.

The results are shown in Table 2.

Thermal expansion rate

Using a sample from which the copper foil of the obtained copper-clad laminate having a thickness of 0.8mm was removed by etching, the thermal expansion coefficient (x direction, y direction, and z direction) of the glass cloth was measured for the insulating layer of the laminate by the TMA method (Thermo-mechanical analysis ) specified in JlS C6481, and the value was obtained. Specifically, copper foil on both sides of the copper-clad laminate obtained as described above was etched and removed, and then an evaluation substrate of 4.5mm×16mm was produced, and the thermal expansion coefficients (ppm/K) in the x-direction, y-direction and z-direction were measured at 60 to 120 ℃ by heating from 40 ℃ to 340 ℃ at 10 ℃ per minute using a thermo-mechanical analyzer (manufactured by TA Instruments).

The results are shown in Table 2.

Heating loss

The thermal analysis of the sample from which the copper foil of the obtained copper-clad laminate having a thickness of 0.8mm was removed by etching was performed using a thermal measurement device under a nitrogen atmosphere at a temperature rising rate of 10 ℃/min.

The calorimeter was used SII Nanotechnology, inc. under the heading "TGA5200".

The results are shown in Table 2.

Thermal conductivity

The density and specific heat of the copper-clad laminate obtained in each of examples and comparative examples were measured.

Specific heat was determined using a type Q100 DSC of TA Instruments.

Further, the thermal diffusivity of the copper-clad laminate in the thickness direction of the copper-clad laminate was measured.

Thermal diffusivity was measured using a xenon flash analyzer (Bruker: LFA447 Nanoflash). The thermal conductivity was calculated according to the following formula.

Thermal conductivity (W/m.K)

=Density (kg/m ³) ×specific heat (kJ/kg·k) ×thermal diffusivity (m ²/S) ×1000

The results are shown in Table 2.

Example 4 >

The procedure was carried out in the same manner as in example 3 except that BMI-Bisanilin-M was changed to BMI-Bisanilin-P obtained in Synthesis example 3 in the same amount. The results are shown in table 2 below.

Comparative example 4 >

The procedure was carried out in the same manner as in example 3 except that BMI-Bisanilin-M was not used and MIR-3000 was contained in an amount of 50 parts by mass. The results are shown in table 2 below.

TABLE 2

From the foregoing results, it was revealed that the copper-clad laminate of examples 3 and 4 maintained good varnish appearance, good prepreg appearance, high peel strength, high flexural physical properties, low water absorption, low thermal expansion and thermal conductivity equivalent to those of comparative example 4, and achieved higher Tg and less thermal weight loss than that of comparative example 4, and further improved electrical characteristics (low Dk and low Df).

Claims

1. A resin composition comprising:

Naphthol aralkyl type cyanate ester compound (A), and

A bismaleimide compound (B) represented by the following formula (1);

in the formula (1), X represents an organic group having 1 to 12 carbon atoms, R ¹～R³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a each independently represents an integer of 0 to 4,

The resin composition further comprises a filler (C), wherein the dielectric loss tangent (Df) at 10GHz of a test piece formed from the resin composition to a thickness of 0.8mm is 0.0050 or less,

The content ratio of the naphthol aralkyl type cyanate ester compound (A) and the bismaleimide compound (B) is 0.01 or more and less than 1.1 in terms of the equivalent ratio of the unsaturated imide group of the bismaleimide compound (B) to the cyanate ester group of the naphthol aralkyl type cyanate ester compound (A), that is, the equivalent of the unsaturated imide group/the equivalent of the cyanate ester group.

2. The resin composition according to claim 1, wherein in the formula (1), X is an alkylene group having 1 to 3 carbon atoms, R ¹～R³ each independently represents a hydrogen atom, a methyl group or an ethyl group, and a each independently represents an integer of 0 to 2.

3. The resin composition according to claim 1, wherein the bismaleimide compound (B) is represented by the following formula (2),

4. The resin composition according to any one of claims 1 to 3, further comprising a solvent.

5. The resin composition according to claim 4, wherein the content of the bismaleimide compound (B) is 0.1 to 30% by mass of the resin composition.

6. The resin composition according to any one of claims 1 to 3, further comprising 1 or more selected from the group consisting of maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenolic resins, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, modified polyphenylene ethers having terminal-modified substituents containing a carbon-carbon unsaturated double bond other than maleimide groups, elastomers and active ester compounds, wherein the compounds having polymerizable unsaturated groups are 1 or more selected from the group consisting of ethylene, propylene, styrene, divinylbenzene, acrylic esters and benzocyclobutene resins.

7. The resin composition according to any one of claims 1 to 3, wherein the content of the filler (C) is 50 to 1600 parts by mass relative to 100 parts by mass of the total amount of resin components in the resin composition.

8. The resin composition according to any one of claims 1 to 3, which is a low dielectric constant material and/or a low dielectric loss tangent material.

9. A cured product of the resin composition according to any one of claims 1 to 8.

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

11. A metal foil-clad laminate comprising: a layer formed from at least 1 sheet of the prepreg of claim 10; and a metal foil disposed on one or both sides of the layer formed of the prepreg.

12. A resin sheet, comprising: a support body; and a layer formed of the resin composition according to any one of claims 1 to 8, which is disposed on the surface of the support.

13. A printed circuit board, comprising: an insulating layer, and a conductor layer disposed on a surface of the insulating layer,

The insulating layer includes: at least one of a layer formed of the resin composition according to any one of claims 1 to 8 and a layer formed of the prepreg according to claim 10.

14. The method for producing a resin composition according to any one of claims 1 to 8, which comprises a naphthol aralkyl type cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1),

The manufacturing method comprises the following steps: mixing a naphthol aralkyl type cyanate ester compound (A), a bismaleimide compound (B) and a solvent, wherein the content of the bismaleimide compound (B) is 0.1-30% by mass of the resin composition;

15. The method for producing a resin composition according to claim 14, wherein the resin composition further contains 1 or more selected from the group consisting of maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups, modified polyphenylene ether having a substituent containing a carbon-carbon unsaturated double bond other than maleimide groups, elastomers and active ester compounds, and the compound having a polymerizable unsaturated group is 1 or more selected from the group consisting of ethylene, propylene, styrene, divinylbenzene, acrylic esters and benzocyclobutene resins.