KR20210025526A - Resin composition and its application - Google Patents

Abstract

Resin composition excellent in various performances such as heat resistance and excellent in electrical properties, and cured product, prepreg, metal foil-clad laminate, resin sheet, printed wiring board, method of manufacturing resin composition, dielectric constant and/or dielectric loss tangent reduction agent Offer of. A resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by formula (1); Formula (1) of, X represents an organic group of carbon number ^{1 ~ 12, R 1 ~ R} 3 are, each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 3, a is independently an integer of 0 to 4, respectively, Show.

Description

Resin composition and its application

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 an agent for reducing dielectric constant and/or dielectric loss tangent using the resin composition.

2. Description of the Related Art In recent years, high integration and miniaturization of semiconductors used in electronic devices, communication devices, personal computers, and the like are accelerating more and more. Along with this, various properties required for a semiconductor package laminate (for example, a metal foil clad laminate, etc.) used in a printed wiring board are becoming more and more stringent. As a required characteristic, low dielectric constant, low dielectric loss tangent, low thermal expansion, heat resistance, etc. are mentioned, for example. Among them, an insulator material having a large dielectric constant and a dielectric loss tangent requires a material having a small dielectric constant and a dielectric loss tangent because the electrical signal is attenuated and reliability is impaired.

In order to obtain a printed wiring board in which these various characteristics are improved, studies are being conducted on a material used as a material for a printed wiring board. For example, in Patent Document 1, as a composition having excellent varnish storage stability, and improved electrical properties, peel strength, and thermal decomposition resistance without reducing multilayer moldability and heat resistance after moisture absorption, a specific polyphenylene ether skeleton is used. It is disclosed that a difunctional vinylbenzyl compound to be contained, a specific maleimide compound, a specific cyanate ester resin, and a specific epoxy resin are combined as constituent components in a predetermined ratio.

On the other hand, in Patent Document 2, bismaleimide having a specific structure, (b) one or more liquid co-reactants, which may optionally contain other additives, and (c) a prepreg composed of structural fibers. There is a description of. However, there is no description of the electrical characteristics or the like.

Japanese Patent Laid-Open Publication No. 2010-138364 Japanese Patent Laid-Open Publication No. Hei 05-25298

As described above, a resin composition containing a cyanate ester compound and a maleimide compound having excellent electrical properties is known. However, with recent technological innovations, further improvement of electrical properties is required. Moreover, even if it is excellent in electrical characteristics, if other performance is inferior, usefulness is insufficient.

An object of the present invention is to solve such a problem, as a resin composition containing a cyanate ester compound and a maleimide compound, excellent in various performances such as heat resistance, and a resin composition having excellent electrical properties, and It is an object of the present invention to provide a cargo, a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, a method for producing a resin composition, and an agent for reducing dielectric constant and/or dielectric loss tangent.

Under the above subject, as a result of investigation by the present inventors, it was found that by using a bismaleimide compound having a specific structure, a resin composition having excellent various performances such as heat resistance and improved electrical properties can be obtained, and the present invention Came to complete. Specifically, the said subject was solved by the following means <1>, Preferably it is by <2>-<18>.

The resin composition containing the <1> cyanic acid ester compound (A) and the bismaleimide compound (B) represented by the following formula (1);

[Formula 1]

Formula (1) of, X represents an organic group of carbon number ^{1 ~ 12, R 1 ~ R} 3 are, each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 3, a is independently an integer of 0 to 4, respectively, Show.

<2> formula (1), X is an alkylene group of carbon number ^{1 ~ 3, R 1 ~ R} 3 are, each independently represents a hydrogen atom, a methyl group or an ethyl group, a is an integer of 0 to 2, each independently The resin composition as described in <1> which is shown.

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

[Formula 2]

<4> The resin composition in any one of <1>-<3> which contains a solvent further.

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

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

<7> Maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, compounds having a polymerizable unsaturated group, carbon-carbon unsaturated double bonds (except maleimide The resin according to any one of <1> to <6>, further containing at least one selected from the group consisting of a modified polyphenylene ether, an elastomer, and an active ester compound terminally modified by a substituent containing). Composition.

<8> The resin composition in any one of <1>-<7> which contains a filler (C) further.

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

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

The cured product of the resin composition in any one of <11> <1>-<10>.

A prepreg formed from a <12> 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 one prepreg according to <12>, and a metal foil disposed on one or both surfaces of the layer formed from the prepreg.

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

A printed wiring board comprising a <15> insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer is a layer formed from the resin composition according to any one of <1> to <10>, and <12> A printed wiring board comprising at least one of the layers formed from the prepreg described in.

As a production method of a resin composition containing a <16> cyanic acid ester compound (A) and a bismaleimide compound (B) represented by the following formula (1), a cyanate ester compound (A) and a bismaleimide compound (B ) And a solvent, and the content of the bismaleimide compound (B) is 0.1 to 30 mass% of the resin composition;

[Formula 3]

Formula (1) of, X represents an organic group of carbon number ^{1 ~ 12, R 1 ~ R} 3 are, each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 3, a is independently an integer of 0 to 4, respectively, Show.

<17> Further, maleimide compounds other than the bismaleimide compound (B), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group, a carbon-carbon unsaturated double bond (male The method for producing a resin composition according to <16>, containing at least one selected from the group consisting of a modified polyphenylene ether, an elastomer, and an active ester compound terminally modified by a substituent containing).

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

[Formula 4]

Formula (1) of, X represents an organic group of carbon number ^{1 ~ 12, R 1 ~ R} 3 are, each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 3, a is independently an integer of 0 to 4, respectively, Show.

Advantageous Effects of Invention According to the present invention, as a resin composition containing a cyanate ester compound and a maleimide compound, it has become possible to provide a resin composition excellent in various performances such as heat resistance and excellent in electrical properties. Further, it has become possible to provide an excellent cured product, a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, a method for producing a resin composition, and an agent for reducing dielectric constant and/or dielectric loss tangent.

Hereinafter, the content of the present invention will be described in detail. In addition, in this specification, "-" is used for the meaning including the numerical value described before and after that as a lower limit value and an upper limit value.

The resin composition according to the present invention is characterized in that it is a resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1).

[Formula 5]

Formula (1) of, X represents an organic group of carbon number ^{1 ~ 12, R 1 ~ R} 3 are, each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 3, a is independently an integer of 0 to 4, respectively, Show.

By blending the bismaleimide compound (B) represented by formula (1) in the cyanate ester compound (A), while maintaining various properties (low water absorption, low heat loss, good appearance of varnish), the dielectric constant (Dk) and It becomes possible to lower the dielectric loss tangent Df. In addition, high levels of peel strength, heat resistance, flame retardancy, and the like can be maintained in the appearance when prepreg is formed and when the metal foil-clad laminate is formed.

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 compound (A)>

The cyanate ester compound (A) in this embodiment is not specifically determined as long as it is a compound having a cyanate structure.

As the cyanate ester compound (A), for example, a naphthol aralkyl type cyanate compound (naphthol aralkyl type cyanate), a naphthylene ether type cyanate ester compound, a xylene resin type cyanate ester compound, and trisphenol At least one selected from the group consisting of a methane type cyanate ester compound and an adamantane skeleton type cyanate ester compound can be mentioned. Among these, from the viewpoint of further improving plating adhesion and low water absorption, at least selected from the group consisting of a naphthol aralkyl type cyanate ester compound, a naphthylene ether type cyanate ester compound, and a xylene resin type cyanate ester compound It is preferable that it is 1 type, and it is more preferable that it is a naphthol aralkyl type cyanate ester compound. These cyanate ester compounds may be prepared by a known method, or a commercial item may be used. In addition, a cyanate ester compound having a naphthol aralkyl skeleton, a naphthylene ether skeleton, a xylene skeleton, a trisphenolmethane skeleton, or an adamantane skeleton has a relatively large number of functional group equivalents and fewer unreacted cyanate ester groups. Therefore, the water absorbency tends to be further lowered. Further, mainly due to having an aromatic skeleton or an adamantane skeleton, there is a tendency for the plating adhesion to be further improved.

It is preferable that it is 200 g/eq or more, and, as for the equivalent weight of the cyanate group of a cyanate ester compound (A), it is preferable that it is 400 g/eq or less. When a plurality of types of cyanate ester compounds (A) are included, it is set as the weighted average equivalent of cyanate groups in consideration of the mass of each cyanate ester compound contained in the resin composition.

The lower limit of the content of the cyanate ester compound (A) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more with respect to 100 parts by mass of the total amount of the resin component in the resin composition. And, it is still more preferable that it is 30 mass parts or more, and 40 mass parts or more may be sufficient. When the content of the cyanate ester compound is 1 part by mass or more, more preferably 10 parts by mass or more, heat resistance, combustion resistance, chemical resistance, low dielectric constant, low dielectric loss tangent, and insulation 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, even more preferably 70 parts by mass or less, based on 100 parts by mass of the total amount of the resin component in the resin composition. It is even more preferable that it is less than a mass part.

The resin composition in this embodiment may contain only one type of cyanate ester compound, and may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

<bismaleimide compound (B) represented by formula (1)>

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

[Formula 6]

Formula (1) of, X represents an organic group of carbon number ^{1 ~ 12, R 1 ~ R} 3 are, each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 3, a is independently an integer of 0 to 4, respectively, Show.

In formula (1), X represents an organic group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an isopropylene group. Two Xs may be the same or different. It is preferably the same.

Each of R ¹ to R ³ 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.

It is preferable that a represents the integer of 0-2 each independently, 0 or 1 is more preferable, and 0 is still more preferable.

It is preferable that the said bismaleimide compound (B) is represented by formula (1-2).

[Formula 7]

Equation (1-2), X is C 1 -C 12 represents an organic group of, R ¹ to R ³ are, each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 3, a is independently 0 to 4 Represents an integer.

In the formula (1-2), X, R ¹ ~ R ³ and a are, respectively, the same meanings as the X, R ¹ ~ R ³ and a in the formula (1), are also the same preferable range. By using the bismaleimide compound represented by formula (1-2), the electrical properties and heat resistance (in particular, suppression of heating loss) of the resin composition tend to be more improved.

It is preferable that the bismaleimide compound (B) represented by formula (1) is further represented by the following formula (2).

[Formula 8]

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

[Formula 9]

It is preferable that it is 200 g/eq or more, and, as for the equivalent of the unsaturated imide group of the bismaleimide compound (B), it is preferable that it is 400 g/eq or less. In the case of containing a plurality of types of bismaleimide compounds (B), the weight of each bismaleimide compound (B) contained in the resin composition is taken into consideration, and the weighted average is the equivalent of an unsaturated imide group.

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, and still more preferably 5 parts by mass or more with respect to 100 parts by mass of the total amount of the resin component in the resin composition. Further, it may be 8 parts by mass or more, 10 parts by mass or more, and 15 parts by mass or more. When the content of the bismaleimide compound (B) is 1 part by mass or more, the flame resistance tends to be improved. In addition, the upper limit of the content of the bismaleimide compound (B), when containing the bismaleimide compound (B), is preferably 90 parts by mass or less with respect to 100 parts by mass of the total amount of the resin components in the resin composition, and 75 parts by mass. It is more preferably less than or equal to parts, still more preferably less than or equal to 60 parts by mass, still more preferably less than or equal to 45 parts, still more preferably less than or equal to 35 parts by mass, and still more preferably less than or equal to 30 parts by mass.

Moreover, it is preferable that content of a bismaleimide compound (B) is 0.1-30 mass% of a 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 with respect to the solid content (components other than the solvent). Do. As an upper limit, it is preferable that it is 90 mass% or less, it is more preferable that it is 70 mass% or less, and it is still more preferable that it is 50 mass% or less.

Moreover, it is preferable that content of a bismaleimide compound (B) is 0.1-30 mass% in the resin composition (in a resin composition containing a solvent) after diluting with a solvent. 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. As an upper limit, it is preferable that it is 25 mass% or less, it is more preferable that it is 20 mass% or less, and it is still more preferable that it is 17.5 mass% or less.

By setting it as such a range, it is possible to further improve the appearance of the varnish and, furthermore, the appearance of a prepreg, and the electrical properties of the laminate.

The resin composition according to the present embodiment may contain only one type or two or more types of the bismaleimide compound (B). When two or more types are included, it is preferable that the total amount falls within the above range.

The content ratio of the cyanate ester compound (A) and the bismaleimide compound (B) in the resin composition according to the present embodiment is the unsaturated imide group of the bismaleimide compound (B) and the cyanate ester compound (A ) Of the cyanate group (equivalent of unsaturated imide group/equivalent of cyanate group), and is preferably 0.01 or more and less than 1.1. The lower limit of the equivalence ratio is more preferably 0.05 or more, still more preferably 0.1 or more, and even more preferably 0.3 or more. Moreover, as for the upper limit of the said equivalent ratio, it is more preferable that it is 0.9 or less, it is still more preferable that it is 0.7 or less, and it is still more preferable that it is 0.5 or less. By setting it as such a range, the effects of water absorption rate, electrical properties, and thermal properties are exhibited more effectively.

<Other resin components>

The resin composition according to the present embodiment may contain other resin components other than the cyanate ester compound (A) and the bismaleimide compound (B). Other resin components include maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, compounds having a polymerizable unsaturated group, and carbon-carbon unsaturated double bonds (maleimide Excluding)) at least one selected from the group consisting of a modified polyphenylene ether, an elastomer and an active ester compound terminally modified by a substituent containing, and maleimide compounds other than the bismaleimide compound (B), It is preferably at least one selected from the group consisting of an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group, and at least a maleimide compound other than the bismaleimide compound (B) It is more preferable to include. By blending such other resin components, while further improving the appearance, other properties can be made more favorable.

<<maleimide compounds other than bismaleimide compound (B)>>

A maleimide compound other than the bismaleimide compound (B) (hereinafter, also referred to as another maleimide compound) is a maleimide compound other than the bismaleimide compound (B) and is a compound having two or more maleimide groups in the molecule. Not limited. In particular, by using a maleimide compound having high solubility in a solvent, it is possible to improve the appearance of the varnish and, furthermore, the appearance of the prepreg obtained from the varnish while improving the electrical properties. Other maleimide compounds used in the present embodiment, for example, have a solubility in methyl ethyl ketone at 25° C. of 5% by mass or more, more preferably 10% by mass or more, and 20% by mass or more. More preferable. Since methyl ethyl ketone has a relatively low boiling point, the drying temperature can be lowered when drying the solvent, and unnecessary curing of the resin component during drying can be effectively suppressed.

As an example of another maleimide compound, a maleimide compound represented by formula (1-3) can be mentioned. By using the maleimide compound represented by formula (1-3), when used for a printed wiring board material (e.g., a laminated plate, a metal foil-clad laminate) or the like, excellent heat resistance can be imparted, while peeling strength, low water absorption, and Desmear resistance and flame resistance can be improved.

[Formula 10]

In the formula (1-3), a plurality of R's each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n is an average value and represents 1<n≦5.

In the formula (1-3), a plurality of R is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group , Isobutyl group, t-butyl group, n-pentyl group, etc.), or a phenyl group. Among these, from the viewpoint of further improving the 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 furthermore desirable.

In said formula (1-3), n is an average value, and 1<n<5 is represented. From the viewpoint of more excellent solvent solubility, n is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. Two or more types of compounds from which n is different may be contained.

The maleimide compound represented by the above formula (1-3) may be prepared by a known method, or a commercial item may be used. As a commercial item, "MIR-3000" manufactured by Nippon Explosives Co., Ltd. is mentioned, for example.

Further, in addition to the above, as other maleimide compounds, 4,4'-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3 -Maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, polyphenylmethane maleimide, and prepolymers thereof, and prepolymers of maleimide and amine thereof, and the like.

It is preferable that it is 200 g/eq or more, and, as for the equivalent weight of the unsaturated imide group of another maleimide compound, it is preferable that it is 400 g/eq or less. In the case of containing a plurality of different maleimide compounds, the weight of the weighted average unsaturated imide group in consideration of the mass of each other maleimide compound contained in the resin composition is used.

The lower limit of the content of the other maleimide compound is, in the case of containing the other maleimide compound, preferably 1 part by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the total amount of the resin component in the resin composition. It is more preferable that it is more than a mass part. When the content of the other maleimide compound is 1 part by mass or more, the flame resistance of the resin composition tends to be improved. In addition, the upper limit of the content of the other maleimide compound is preferably 90 parts by mass or less, and more preferably 85 parts by mass or less when the total amount of the resin component in the resin composition is 100 parts by mass, when other maleimide compounds are contained. And, it is still more preferably 75 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, still more preferably 55 parts by mass or less, and particularly more preferably 45 parts by mass or less. When the content of the other maleimide compound is 90 parts by mass or less, peel strength and low water absorption tend to be improved.

In particular, it is preferable that the resin composition in this embodiment contains both a bismaleimide compound represented by formula (1) and a maleimide compound represented by formula (1-3). In the resin composition, the mass ratio of the bismaleimide compound represented by formula (1) and the maleimide compound represented by formula (1-3) is preferably 1:0.1 to 2.0, and 1:1.0 to 2.0. It is more preferable, it is still more preferable that it is 1:1.2-1.8, and it is still more preferable that it is 1:1.4-1.6. By setting it as such a ratio, the external appearance of the varnish obtained and the electrical property of a hardened|cured material can be made compatible in a high dimension.

The resin composition in this embodiment may contain only 1 type, and may contain 2 or more types of other maleimide compounds. When two or more types are included, it is preferable that the total amount falls within the above range.

<<epoxy resin>>

The epoxy resin is not particularly limited as long as it is a compound or resin having two or more epoxy groups in one molecule.

Epoxy resin is, for example, 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 novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy Resin, naphthalene skeleton modified novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, phosphorus Compounds obtained by epoxidating a double bond such as a containing epoxy resin, glycidylamine, glycidyl ester, and butadiene, and a compound obtained by reaction of a hydroxyl group-containing silicone resin with epichlorohydrin. Among these, from the viewpoint of further improving flame retardancy and heat resistance, a biphenyl aralkyl type epoxy resin, a naphthylene ether type epoxy resin, a polyfunctional phenol type epoxy resin, a naphthalene type epoxy resin is preferable, and a biphenyl aralkyl type It is more preferable that it is an epoxy resin.

It is preferable to contain the epoxy resin within a range that does not impair the effect of the present invention. From the viewpoint of moldability and adhesiveness, the lower limit of the content of the epoxy resin is preferably 0.1 parts by mass or more, and 1 part by mass or more, when the total amount of the resin component in the resin composition is 100 parts by mass when the epoxy resin is contained. More preferably, it is more preferably 2 parts by mass or more. When the content of the epoxy resin is 0.1 parts by mass or more, the metal foil (copper foil) peel strength and toughness tend to improve. 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, and 20 parts by mass or less, when the total amount of the resin component in the resin composition is 100 parts by mass when containing an epoxy resin. It is more preferable that it is more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. When the content of the epoxy resin is 50 parts by mass or less, the electrical properties tend to be improved.

The resin composition in this embodiment may contain only one type of epoxy resin, and may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

Moreover, the resin composition in this embodiment can also be made into the structure which does not contain an epoxy resin substantially. Substantially not included means that the content of the epoxy resin is less than 0.1 parts by mass with respect 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 two or more phenolic hydroxy groups in one molecule.

The phenolic resin is, for example, 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, biphenylaralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton Modified novolak type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, And hydroxyl group-containing silicone resins. Among these, from the viewpoint of further improving the flame resistance, it is preferably at least one selected from the group consisting of a biphenyl aralkyl type phenol resin, a naphthol aralkyl type phenol resin, a phosphorus-containing phenol resin, and a hydroxyl group-containing silicone resin.

It is preferable to contain the phenol resin within a range that does not impair the effect of the present invention. When the content of the phenol resin contains a phenol resin, when the total amount of the resin component in the resin composition is 100 parts by mass, it is preferably 0.1 parts by mass or more, and preferably 50 parts by mass or less.

The resin composition in this embodiment may contain only one type of phenol resin, and may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

Moreover, the resin composition in this embodiment can also be made into the structure which does not contain a phenol resin substantially. Substantially not included means that the content of the phenol resin is less than 0.1 parts by mass with respect 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 two or more oxetanyl groups.

As the oxetane resin, for example, oxetane, alkyloxetane (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.) , 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type Oxetane, OXT-101 (manufactured by Toa Synthesis Co., Ltd.), OXT-121 (manufactured by Toa Synthesis Co., Ltd.), and the like.

It is preferable to contain the oxetane resin in a range that does not impair the effect of the present invention. The lower limit of the content of the oxetane resin is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and 2 parts by mass, when the total amount of the resin component in the resin composition is 100 parts by mass, when containing an oxetane resin. More preferably, it is more than one part. When the content of the oxetane resin is 0.1 parts by mass or more, the metal foil (copper foil) peel strength and toughness tend to be improved. The upper limit of the content of the oxetane resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, more preferably 20 parts by mass, when the total amount of the resin component in the resin composition is 100 parts by mass, when it contains an oxetane resin. It is more preferable that it is less than a part, and it is still more preferable that it is 10 mass parts or less, and it is still more preferable that it is 8 mass parts or less. When the content of the oxetane resin is 50 parts by mass or less, the electrical properties of the resin composition tend to be further improved.

The resin composition in this embodiment may contain only one type of oxetane resin, and may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

Moreover, the resin composition in this embodiment can also be made into the structure which does not contain oxetane resin substantially. Substantially not included means that the content of the oxetane resin is less than 0.1 parts by mass with respect 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 two or more dihydrobenzoxazine rings in one molecule.

Examples of the benzoxazine compound include bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), and bisphenol S type Benzooxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.), etc. are mentioned.

It is preferable to contain the benzoxazine compound in a range that does not impair the effect of the present invention. When the benzoxazine compound is contained, the content of the benzoxazine compound is preferably 0.1 parts by mass or more, and preferably 50 parts by mass or less, when the total amount of the resin component in the resin composition is 100 parts by mass.

The resin composition in this embodiment may contain only 1 type of benzoxazine compound, and may contain 2 or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

Moreover, the resin composition in this embodiment can also be made into the structure which does not contain a benzoxazine compound substantially. Substantially not included means that the content of the benzoxazine compound is less than 0.1 parts by mass with respect to 100 parts by mass of the total amount of the resin component in the resin composition.

<<compound having a polymerizable unsaturated group>>

The compound having a polymerizable unsaturated group is not particularly limited, and a compound having two or more polymerizable unsaturated groups may be used.

Compounds having a polymerizable unsaturated group include, for example, vinyl compounds (e.g., ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl, etc.), acrylates (e.g., methyl (meth)acrylate). Etc.), mono or polyalcohol (meth)acrylates (e.g., 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropanedi(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 resin, and the like.

It is preferable to contain the compound which has a polymerizable unsaturated group in the range which does not impair the effect of this invention. The content of the compound having a polymerizable unsaturated group is preferably 0.1 parts by mass or more, and preferably 50 parts by mass or less, when the total amount of the resin component in the resin composition is 100 parts by mass when the same compound is contained.

The resin composition in this embodiment may contain only 1 type, and may contain 2 or more types of the compound which has a polymerizable unsaturated group. When two or more types are included, it is preferable that the total amount falls within the above range.

Moreover, the resin composition in this embodiment can also be made into the structure which does not contain a compound which has a polymerizable unsaturated group substantially. Substantially not included means that the content of the compound having a polymerizable unsaturated group is less than 0.1 parts by mass with respect to 100 parts by mass of the total amount of the resin component in the resin composition.

<<modified polyphenylene ether terminally modified by a substituent containing a carbon-carbon unsaturated double bond (excluding maleimide)>>

In the modified polyphenylene ether terminal modified by a substituent containing a carbon-carbon unsaturated double bond (excluding maleimide), for example, all or part of the terminal of the polyphenylene ether is a carbon-carbon unsaturated double bond. It is a modified product terminally modified by a substituent having a bond. Although it does not specifically limit as long as it is other than a maleimide group as a substituent which has a carbon-carbon unsaturated double bond, an ethylenic unsaturated group is mentioned, for example. Examples of the ethylenically unsaturated group include alkenyl groups such as ethenyl group, allyl group, acrylic group, methacrylic group, propenyl group, butenyl group, hexenyl group and octenyl group, cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group, Alkenyl aryl groups such as a vinyl benzyl group and a vinyl naphthyl group, and a vinyl benzyl group is preferable. The "polyphenylene ether" used in the present specification refers to a compound having a phenylene ether skeleton represented by the following formula (X1).

[Formula 11]

(In formula (X1), R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be the same or different, and represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom.)

Modified polyphenylene ether is formula (X2):

[Formula 12]

(In formula (X2), R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , and R ³⁵ may be the same or different, and are an alkyl group or a phenyl group having 6 or less carbon atoms. R ³¹ , R ³² , and R ³³ are, They may be the same or different, and they are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

The repeating unit represented by and/or formula (X3):

[Formula 13]

(In formula (X3), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ may be the same or different, and a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group -A- is a C20 or less linear, branched or cyclic divalent hydrocarbon group) and may further contain a repeating unit represented by.

As for the modified polyphenylene ether, a modified polyphenylene ether functionalized with an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxyl group, and a silyl group may be used. These may be used alone or in combination of two or more.

The method for producing the modified polyphenylene ether is not particularly limited as long as the effect of the present invention is obtained. For example, what has been functionalized with a vinylbenzyl group can be prepared by dissolving a bifunctional phenylene ether oligomer and vinylbenzyl chloride in a solvent, reacting by adding a base under heating and stirring, and solidifying the resin. What is functionalized with a carboxyl group is produced by melt-kneading an unsaturated carboxylic acid or a functionalized derivative thereof with polyphenylene ether, for example, in the presence or absence of a radical initiator, and reacting. Alternatively, it is prepared by dissolving polyphenylene ether and an unsaturated carboxylic acid or its organoleptic derivative in an organic solvent in the presence or absence of a radical initiator, and reacting in a solution.

It is preferable that the modified polyphenylene ether contains a modified polyphenylene ether having an ethylenic unsaturated group at both ends (hereinafter, it may be referred to as "modified polyphenylene ether (g)"). Examples of the ethylenically unsaturated group include alkenyl groups such as ethenyl group, allyl group, acrylic group, methacrylic group, propenyl group, butenyl group, hexenyl group and octenyl group, cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group, Alkenyl aryl groups such as a vinyl benzyl group and a vinyl naphthyl group, and a vinyl benzyl group is preferable. The two ethylenically unsaturated groups at both ends may be the same functional group or different functional groups.

As a modified polyphenylene ether (g) having an ethylenically unsaturated group at the terminal (hereinafter, it may be simply referred to as a modified polyphenylene ether (g)), a structure represented by the formula (G1) can be mentioned.

[Formula 14]

(In formula (G1), X represents an aromatic group, (Y) m represents a polyphenylene ether moiety, and R ^G1 , R ^G2 , R ^G3 each independently represent 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 and R ^G3 are hydrogen atoms.)

Preferably n is an integer of 1 or more and 4 or less, more preferably n is 1 or 2, and even more preferably n is 1. Moreover, preferably q is an integer of 1 or more and 3 or less, more preferably q is 1 or 2, and still more preferably q is 2.

It is preferable that the modified polyphenylene ether (g) in this embodiment is represented by formula (G2).

[Formula 15]

Here, -(O-X-O)- is the formula (G3):

[Formula 16]

(In formula (G3), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , and R ¹¹ may be the same or different, and are an alkyl group or a phenyl group having 6 or less carbon atoms. R ⁷ , R ⁸ , and R ⁹ are the same. Or they may be different, and they are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

And/or Equation (G4):

[Formula 17]

(In formula (G4), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ may be the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a C20 or less linear, branched, or cyclic divalent hydrocarbon group.)

In addition, -(Y-O)- is the formula (G5):

[Formula 18]

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

a and b represent an integer of 0 to 100 in which at least one of them is not 0. When a and b are integers of 2 or more, -(YO)-a or -(YO)-b may be arranged in a structure represented by one type of formula (G5), or a structure represented by two or more types of formula (G5). May be arranged randomly.

As -A- in formula (G4), for example, methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene) , 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, 1-phenylethylidene, and other divalent organic groups may be mentioned. no.

In the modified polyphenylene ether (g), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ²⁰ , R ²¹ are an alkyl group having 3 or less carbon atoms, and R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²² , R ²³ are preferably polyphenylene ethers in which hydrogen atoms or alkyl groups having 3 or less carbon atoms are preferred, and in particular formula (G3 ) Or -(OXO)- represented by Formula (G4) is Formula (9), Formula (10), and/or Formula (11), and -(YO)- represented by Formula (G5) is Formula (12) ) Or formula (13). When a and b are integers of 2 or more, -(YO)-a or -(YO)-b is a structure in which Equation (12) or Equation (13) is arranged, or Equations (12) and (13) are It is preferable that the structure is arranged randomly.

[Formula 19]

[Formula 20]

(In formula (10), R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ may be the same or different, and are a hydrogen atom or a methyl group. -B- is a C20 or less linear, branched or ring It is a divalent hydrocarbon group of type.)

As for -B-, what is the same as the specific example of -A- in formula (G4) is mentioned as a specific example.

[Formula 21]

(In formula (11), -B- is a C20 or less linear, branched, or cyclic divalent hydrocarbon group.)

As for B-, what is the same as the specific example of -A- in formula (G4) is mentioned as a specific example.

[Formula 22]

[Formula 23]

It is preferable that the number average molecular weight of the modified polyphenylene ether in terms of polystyrene by the GPC method is 500 or more and 3000 or less. When the number average molecular weight is 500 or more, stickiness when the resin composition according to the present embodiment is used as a coating film tends to be further suppressed. When the number average molecular weight is 3000 or less, the solubility in the solvent tends to be further improved.

Further, the weight average molecular weight of the modified polyphenylene ether in terms of polystyrene by GPC is preferably 800 or more and 10000 or less, and more preferably 800 or more and 5000 or less. By setting it as more than the said lower limit, the dielectric constant and dielectric loss tangent tend to become lower, and by setting it as the said upper limit or less, solubility in a solvent, a low viscosity, and moldability in a solvent tend to be improved more.

In addition, the carbon-carbon unsaturated double bond equivalent at the terminal of the modified polyphenylene ether is preferably 400 to 5000 g per one carbon-carbon unsaturated double bond, and more preferably 400 g to 2500 g. By setting it as more than the said lower limit, the dielectric constant and dielectric loss tangent tend to become lower. By setting it as the above upper limit or less, the solubility in a solvent, low viscosity, and moldability tend to be further improved.

The preparation method (production method) of the modified polyphenylene ether represented by formula (2) in the present embodiment is not particularly limited, and, for example, a bifunctional phenol compound and a monofunctional phenol compound are oxidatively coupled. And a step of obtaining a bifunctional phenylene ether oligomer (oxidation coupling step) and a step of converting the terminal phenolic hydroxyl group of the resulting bifunctional phenylene ether oligomer into vinylbenzyl ether (vinylbenzyl etherification step). I can. Moreover, as such a modified polyphenylene ether, Mitsubishi Gas Chemical Co., Ltd. make (OPE-2St1200 etc.) can be used, for example.

In the oxidative coupling step, for example, a bifunctional phenol compound, a monofunctional phenol compound, and a catalyst are dissolved in a solvent, and oxygen is blown under heating and stirring to obtain a bifunctional phenylene ether oligomer. It does not specifically limit as a bifunctional phenol compound, For example, 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenol)-4,4'- The group consisting of diol, 4,4'-methylenebis(2,6-dimethylphenol), 4,4'-dihydroxyphenylmethane, and 4,4'-dihydroxy-2,2'-diphenylpropane At least 1 type selected from is mentioned. It does not specifically limit as a monofunctional phenol compound, For example, 2,6-dimethylphenol and/or 2,3,6-trimethylphenol are mentioned. The catalyst is not particularly limited, and examples include copper salts (eg, CuCl, CuBr, CuI, CuCl ₂ , CuBr _2, etc.), amines (eg, di-n-butylamine, n-butyl Dimethylamine, N,N'-di-t-butylethylenediamine, pyridine, N,N,N',N'-tetramethylethylenediamine, piperidine, imidazole, etc.) etc. are mentioned. It does not specifically limit as a solvent, For example, at least 1 type selected from the group consisting of toluene, methanol, methyl ethyl ketone, and xylene is mentioned.

In the vinyl benzyl etherification process, for example, the bifunctional phenylene ether oligomer obtained by the oxidation coupling process and vinyl benzyl chloride are dissolved in a solvent, and a base is added to react under heating and stirring, and then the resin is solidified. can do. The vinyl benzyl chloride is not particularly limited, and examples thereof include at least one selected from the group consisting of o-vinyl benzyl chloride, m-vinyl benzyl chloride, and p-vinyl benzyl chloride. The base is not particularly limited, and examples thereof include at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide. In the vinyl benzyl etherification process, an acid may be used to neutralize the base remaining after the reaction, and the acid is not particularly limited, for example, selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and nitric acid. At least 1 type to be used can be mentioned. The solvent is not particularly limited, and for example, at least 1 selected from the group consisting of toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, methylene chloride, and chloroform. It can be a bell. As a method of solidifying a resin, a method of evaporating a solvent to dryness, a method of mixing a reaction liquid with a poor solvent, and reprecipitating, etc. are mentioned, for example.

The lower limit of the content of the modified polyphenylene ether is preferably 1 part by mass or more, and more preferably 5 parts by mass or more, when the total amount of the resin component in the resin composition is 100 parts by mass when it contains modified polyphenylene ether. And, it is more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more. The upper limit of the content of the modified polyphenylene ether is preferably 90 parts by mass or less, and more preferably 85 parts by mass or less when the total amount of the resin component in the resin composition is 100 parts by mass, when the modified polyphenylene ether is contained. And, it is more preferable that it is 70 mass parts or less, and it is still more preferable that it is 60 mass parts or less. When the content of the modified polyphenylene ether is within the above range, the low dielectric loss tangent and reactivity tend to be further improved.

The resin composition in this embodiment may contain only one type of modified polyphenylene ether, and may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

<<Elastomer>>

The elastomer is not particularly limited, and a known elastomer can be widely used.

As an elastomer, for example, polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butadiene styrene, styrene propylene styrene, styrene ethylene propylene styrene , Fluorine rubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and at least one selected from the group consisting of copolymers thereof. Among these, from the viewpoint of excellent electrical properties, styrene butadiene, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butadiene styrene, styrene propylene styrene, styrene ethylene propylene styrene, hydrogenated compounds thereof, alkyl compounds thereof, and It is preferably at least one selected from the group consisting of their copolymers, and from the viewpoint of further excellent compatibility with modified polyphenylene ether, at least one selected from the group consisting of styrene butadiene rubber, butadiene rubber, and isoprene rubber It is more preferable that it is a species.

From the viewpoint of excellent electrical properties, the elastomer in the present embodiment ^{preferably has an SP value of 9 (cal/cm 3) 1/2} or less. The SP value is called a dissolution parameter, and is calculated from ^{the square root (cal/cm 3) 1/2} of the heat of evaporation required to evaporate a 1 cm 3 liquid. In general, the smaller this value, the lower the polarity, and the closer this value is, the higher the affinity between the two components is. If the SP value of the elastomer is 9 (cal/cm3) ^1/2 or less, it is used for printed wiring boards for high frequency applications. Electrical properties more suitable for the resin composition to be obtained are obtained.

When the elastomer in the present embodiment has a weight average molecular weight of 80000 or more in terms of polystyrene by the GPC method, and is solid at 25°C, when used for a material for a printed wiring board (for example, a laminated plate, a metal foil coated laminate), or the like, It is preferable because the crack resistance is further improved. On the other hand, if the weight average molecular weight in terms of polystyrene by the GPC method is 40000 or less, and if it is liquid at 25°C, the warpage when bonding the film applied to the substrate becomes small, so it is particularly suitable as a build-up material for a printed wiring board. do.

It is preferable to contain the elastomer in a range that does not impair the effect of the present invention. The lower limit of the content of the elastomer, when containing an elastomer, is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more with respect to 100 parts by mass of the total amount of the resin component in the resin composition. Do. When the content of the elastomer is 5 parts by mass or more, the electrical properties tend to be further improved. The upper limit of the content of the elastomer is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, based on 100 parts by mass of the total amount of the resin component in the resin composition when the elastomer is contained. And, it is still more preferable that it is 60 mass parts or less, and it is still more preferable that it is 50 mass parts or less. When the content of the elastomer is 20 parts by mass or less, the combustion resistance tends to be improved.

The resin composition in this embodiment may contain only one type of elastomer, and may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

Moreover, the resin composition in this embodiment can also be made into the structure which does not contain an elastomer substantially. Substantially not included means that the content of the elastomer is less than 1 part by mass with respect 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 a compound having two or more active ester groups per molecule.

The active ester compound may be a linear or 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, a hydroxy compound and/or a thiol compound is preferable, and a carboxylic acid compound and, An active ester compound obtained by reacting at least one compound selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferable, and is obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group, 1 Aromatic compounds having two or more active ester groups in the molecule are more preferred, obtained by reacting a compound having two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group, and having two or more active ester groups in one molecule Aromatic compounds having an ester group are particularly preferred. Examples of the carboxylic acid compound include one 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. Among these, heat resistance From the viewpoint of further improving, at least one selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid is preferred, and at least one selected from the group consisting of isophthalic acid and terephthalic acid is It is more preferable. Examples of the thiocarboxylic acid compound include one or more selected from the group consisting of thioacetic acid and thiobenzoic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, tree One or more selected from the group consisting of hydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol, and phenol novolac, and heat resistance and solvent solubility. From the viewpoint of further improvement, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloglusine, benzenetriol, dicyclopentadienyldiphenol, Phenol novolac is preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetra At least one selected from the group consisting of hydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol, and phenol novolac is more preferable, and 1,5-dihydroxynaphthalene, 1, Selected from the group consisting of 6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolac More preferably, at least one of dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and at least one selected from the group consisting of phenol novolac (preferably At least one selected from the group consisting of dicyclopentadienyldiphenol and phenol novolac, More preferably, dicyclopentadienyldiphenol) is particularly preferred. Examples of the thiol compound include one or more selected from the group consisting of benzenedithiol and triazinedithiol. In addition, from the viewpoint of further improving the compatibility with the epoxy resin, the active ester compound is preferably a compound having two or more carboxylic acids in one molecule and containing an aliphatic chain, and further improving heat resistance. In, it is preferable that it is a compound having an aromatic ring. As a more specific active ester compound, the active ester compound described in Unexamined-Japanese-Patent No. 2004-277460 can be mentioned.

A commercially available product may be used as the active ester compound, or may be prepared by a known method. Commercially available products include compounds containing a dicyclopentadienyldiphenol structure (e.g., EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all manufactured by DIC Corporation), etc.), and acetylated products of phenol novolacs (e.g. For example, DC808 (manufactured by Mitsubishi Chemical Co., Ltd.), and benzoylates of phenol novolac (e.g., YLH1026, YLH1030, YLH1048 (all manufactured by Mitsubishi Chemical Co., Ltd.)) are mentioned. From the viewpoint of further improving the storage stability of the varnish and the low thermal expansion coefficient of the cured product, EXB9460S is preferable.

The preparation method of the active ester compound can be prepared by a known method, and can be obtained, for example, by a condensation reaction of a carboxylic acid compound and a hydroxy compound. As a specific example, (a) a carboxylic acid compound or a halide thereof, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound, per 1 mole of the carboxy group or acid halide group of (a), (b) A method of reacting at a ratio of 0.05 to 0.75 moles of phenolic hydroxyl groups and (c) 0.25 to 0.95 moles is mentioned.

It is preferable to contain the active ester compound in a range that does not impair the effect 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 with respect 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 type, and may contain 2 or more types of active ester compounds. When two or more types are included, it is preferable that the total amount falls within the above range.

Moreover, the resin composition in this embodiment can also be made into the structure which does not contain an active ester compound substantially. Substantially not included means that the content of the active ester compound is less than 1 part by mass with respect to 100 parts by mass of the total amount of the resin components in the resin composition.

When the resin composition in this embodiment does not contain or substantially does not contain the filler (C) described later, the total amount of the resin component is preferably 70% by mass or more of the component excluding the solvent of the resin composition. It is more preferable that it is 80 mass% or more, and it is still more preferable that it is 90 mass% or more.

When the resin composition in this embodiment contains the filler (C) described later, the total amount of the resin component is preferably 30% by mass or more of the components excluding the solvent of the resin composition, and preferably 35% by mass or more. It is more preferable that it is 40 mass% or more. As an upper limit, it is preferable that it is 70 mass% or less, it is more preferable that it is 65 mass% or less, and it is still more preferable that it is 60 mass% or less.

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

<Filling material (C)>

The resin composition according to the present embodiment preferably contains a filler (C) in order to improve low dielectric constant, low dielectric loss tangent, flame resistance, and low thermal expansion properties. As the filler (C) used in the present embodiment, a known filler can be appropriately used, and its kind is not particularly limited, and those generally used in the art can be suitably used. Specifically, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosol and hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, agglomerated boron nitride , Silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat treatment product (a part of the crystal water is reduced by heat treatment of aluminum hydroxide), metal hydrates such as boehmite, magnesium hydroxide, molybdenum oxide or zinc molybdate Molybdenum compounds such as, zinc borate, zinc stannate, alumina, 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, short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, spherical shape (球狀) In addition to inorganic fillers such as glass, organic fillers such as styrene type, butadiene type, and acrylic type rubber powder, core shell type rubber powder, silicone resin powder, silicone rubber powder, and silicone composite powder, etc. may be mentioned.

Among these, one or two or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide, and magnesium hydroxide are suitable, and silica is more preferable. As for silica, spherical silica is preferable. The spherical silica may also be hollow silica.

By using these fillers (C), properties such as thermal expansion properties, dimensional stability, and flame retardancy of the resin composition are improved.

The content of the filler (C) in the resin composition according to the present embodiment can be appropriately set depending on the desired properties, and is not particularly limited, but when the total amount of the resin component in the resin composition is 100 parts by mass, 10 parts by mass It is preferably at least 20 parts by mass, more preferably at least 30 parts by mass, even more preferably at least 50 parts by mass, and even more preferably at least 75 parts by mass. As the upper limit, it is preferably 1600 parts by mass or less, more preferably 1200 parts by mass or less, even more preferably 1000 parts by mass or less, even more preferably 750 parts by mass or less, even more preferably 500 parts by mass or less, and 300 It is still more preferable that it is not more than 250 parts by mass, even more preferably not more than 250 parts by mass, and it may be not more than 200 parts by mass.

The resin composition in this embodiment may contain only one type of filler (C), and may contain two or more types. When two or more types are included, it is preferable that the total amount falls within the above range.

On the other hand, in this embodiment, the resin composition may have a structure which does not contain the said filler (C) substantially. Substantially not included means that the content of the filler (C) is less than 1% by mass of the content of the resin component, and is preferably 0.1% by mass or less.

In using the filler (C) here, it is preferable to use a silane coupling agent and/or a wet dispersant in combination. As the silane coupling agent, those generally used for surface treatment of inorganic substances can be suitably used, and the kind is not particularly limited. Specifically, aminosilanes such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-( Epoxysilanes such as 3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxypropyltrimethoxysilane, vinyl-tri(β-methoxyethoxy)silane, N- and cationic silane systems such as β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, and phenylsilane systems. The silane coupling agent may be used alone or in combination of two or more. Moreover, as a wet dispersing agent, what is generally used for a paint can be used suitably, and its kind is not specifically limited. Preferably, a copolymer-based wetting dispersant is used, and as a specific example thereof, Disperbyk-110, 111, 161, 180, 2009, 2152, BYK-W996, BYK-W9010 manufactured by Vickemi Japan Co., Ltd. , BYK-W903, BYK-W940, etc. are mentioned. Wet dispersants may be used alone or in combination of two or more.

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

<hardening accelerator>

The resin composition according to the present embodiment may further contain a curing accelerator. Although it does not specifically limit as a hardening accelerator, For example, Imidazoles, such as triphenylimidazole; Organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl-di-perphthalate; Azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine Tertiary amines such as triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; Phenols such as phenol, xylenol, cresol, resorcin, and catechol; Organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, manganese octylate, tin oleate, dibutyl tin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; What is formed by dissolving these organometallic salts in a hydroxyl group-containing compound such as phenol and bisphenol; Inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; Organotin compounds such as dioctyl tin oxide, other alkyl tin, and alkyl tin oxide; And the like.

Preferred curing accelerators are imidazoles and organometallic salts, and it is more preferred to use both imidazoles and organometallic salts in combination.

When the content of the curing accelerator contains a curing accelerator, the lower limit is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and 0.1 parts by mass with respect to 100 parts by mass of the total amount of the resin component in the resin composition. It is more preferable that it is above. Further, 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 with respect to 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 two or more. When two or more types are used, the total amount falls within the above range.

<Solvent>

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

When the resin composition according to the present embodiment contains a solvent, the content thereof is not particularly determined, but for example, it may be 1% by mass or more of the resin composition, and may be 10% by mass or more, or 30% by mass or more, It may be 40 mass% or more. Moreover, as an upper limit, it can be made into 99 mass% or less, 80 mass% or less may be sufficient, 70 mass% or less, 60 mass% or less may be sufficient as it.

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

In the resin composition according to the present embodiment, the solid content in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, even more preferably 30% by mass or more, and 40 It may be mass% or more and 50 mass% or more. Further, the upper limit of the solid content is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and may be 60% by mass or less.

In addition, the solid content means a component excluding a solvent in a resin composition.

<Other ingredients>

The resin composition according to the present embodiment may contain, in addition to the above components, various polymer compounds such as a thermoplastic resin, and oligomers thereof, and various additives within a range that does not impair the effects of the present invention. As additives, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, flow modifiers, lubricants, antifoaming agents, dispersants, leveling agents, brightening agents, polymerization prohibition And my back. These additives can be used alone or in combination of two or more.

In addition, the resin composition according to the present embodiment can also be configured to contain substantially no flame retardant. Substantially not included means that the content of the flame retardant is less than 0.01 parts by mass based on 100 parts by mass of the total amount of the resin composition, and is preferably 0 parts by mass. The resin composition in this embodiment is valuable in that it can maintain high flame retardancy even if it has a structure which does not contain a flame retardant substantially. Specifically, the resin composition in the present embodiment has a flame retardancy of a material (printed wiring board, etc.) molded to a thickness of 0.8 mm (and 0.4 mm) according to UL (Underwriters Laboratories Inc.) standards. It can be 0. Flame retardancy is measured according to the description of Examples to be described later.

<Specific form of resin composition>

Below, a more specific form of this embodiment is described. Needless to say, this embodiment is not limited to these.

In the first specific example of the resin composition according to the present embodiment, the solid content in the resin composition contains 90% by mass or more (preferably 95% by mass or more) of the resin component. In this embodiment, it is preferable that a resin component contains a cyanic acid ester compound (A), a bismaleimide compound (B) represented by Formula (1), and another maleimide compound.

In the resin composition of the first specific example, the dielectric constant (Dk) in 10 GHz of the test piece molded to a thickness of 0.8 mm can be 3.0 or less, and may be 2.8 or less. The lower limit of the dielectric constant is 0 or more, but 2.0 or more is practical. Moreover, in the resin composition of 1st specific example, the dielectric loss tangent (Df) in 10 GHz of the test piece molded to a thickness of 0.8 mm can be 0.0050 or less, can be less than 0.0045, and can be 0.0044 or less. As for the lower limit of the dielectric constant, 0 is ideal, but 0.0020 or more is practical. The permittivity and dielectric loss tangent are measured by the method described in Examples to be described later.

In the resin composition of the first specific example, the 1% mass reduction temperature of the test piece molded to a thickness of 0.8 mm can be 370°C or higher, or 380°C or higher. The upper limit of the 1% mass reduction temperature is not particularly determined, but 420°C or less is practical.

In the resin composition of the first specific example, the mass reduction ratio at 450°C of the test piece molded to a thickness of 0.8 mm can be 19.0% or less, or 18.0% or less. The lower limit of the mass reduction rate at 450°C is ideally 0%, but 10% or more is practical.

In the second specific example of the resin composition according to the present embodiment, the solid content in the resin composition is 5 to 70 mass% (preferably 20 to 60 mass%) of the resin component, and 95 to 30 mass% (preferably 80). It is a form containing a filler of -40 mass%). In this embodiment, it is preferable that a resin component contains a cyanic acid ester compound (A), a bismaleimide compound (B) represented by Formula (1), and another maleimide compound. The filler is preferably spherical silica.

<Production method of resin composition>

The production method of the 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), as a method for producing a cyanate ester compound (A ), a bismaleimide compound (B) and a solvent are mixed, and the content of the bismaleimide compound (B) is 0.1 to 30 mass% (preferably 0.1 to 20 mass%) of the resin composition.

Thus, by setting the content of the bismaleimide compound (B) in the above range, it becomes possible to appropriately dissolve in a solvent, and the appearance of the varnish, and furthermore, the appearance when used as a prepreg can be further improved. In particular, the appearance can be further improved by using the bismaleimide compound represented by the above-described formula (1-2) as the bismaleimide compound represented by formula (1).

In addition, the production method of the resin composition according to the present embodiment is a maleimide compound other than the bismaleimide compound (B), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group, and carbon. -It is preferable to further contain at least one selected from the group consisting of modified polyphenylene ethers, elastomers and active ester compounds terminally modified by a substituent containing a carbon unsaturated double bond (excluding maleimide), It further contains at least one selected from the group consisting of maleimide compounds other than the bismaleimide compound (B), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group. It is more preferable. By blending such other resin components, while further improving the appearance, other properties can be made more favorable.

<use>

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

The resin composition according to the present embodiment is used as a material for a molded article in the form of a layer (to the effect of including a film form, a sheet form, etc.) such as an insulating layer, a prepreg, and a resin sheet of a printed wiring board. In this case, the thickness is preferably 5 µm or more, and more preferably 10 µm or more. The upper limit of the thickness of the molded article is preferably 200 µm or less, and more preferably 180 µm or less. In addition, the thickness of the said layered molded article means the thickness including a base material, for example, when the resin composition concerning this embodiment is impregnated with a base material, such as a glass cloth.

The material formed from the resin composition according to the present embodiment may be used for an application of forming a pattern by exposure development, or may be used for an application not subject to exposure development. In particular, it is suitable for use in which exposure is not developed.

<<Prepreg>>

The prepreg of this embodiment is formed from a substrate (prepreg substrate) and a resin composition according to the present embodiment. The prepreg of this embodiment is, for example, after applying (for example, impregnation or coating) the resin composition according to the present embodiment to a substrate, and heating (for example, at 120 to 220°C for 2 to 15 minutes) It is obtained by semi-curing by a method of drying, etc.). In this case, the amount of adhesion of the resin composition (including the cured product of the resin composition) to the substrate, that is, the amount of the resin composition (including the filler) relative to the total amount of the prepreg after semi-curing, is in the range of 20 to 99% by mass. desirable.

The base material is not particularly limited as long as it is a base material used for various printed wiring board materials. As the material of the substrate, for example, inorganic fibers other than glass fiber (e.g., E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, etc.) (For example, quartz, etc.), organic fibers (for example, polyimide, polyamide, polyester, liquid crystal polyester, etc.) are mentioned. The form of the substrate is not particularly limited, and includes a substrate composed of layered fibers such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. In particular, a substrate composed of long fibers such as glass cloth is preferable. Here, the long fibers mean, for example, those having a number average fiber length of 6 mm or more. These substrates can be used alone or in combination of two or more. Among these substrates, from the viewpoint of dimensional stability, woven fabrics subjected to super-opening treatment and fine weaving treatment are preferred, and from the viewpoint of moisture absorption and heat resistance, silane couples such as epoxysilane treatment and aminosilane treatment A glass woven fabric surface-treated with a ring agent or the like is preferable, and from the viewpoint of electrical properties, a low-dielectric glass cloth made of glass fibers exhibiting low dielectric constant and low dielectric loss tangent such as L-glass, NE-glass, and Q-glass desirable. The thickness of the substrate 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 at least one layer formed from the prepreg of the present embodiment, and a metal foil disposed on one or both sides of the layer formed from the prepreg. The metal foil-clad laminate of the present embodiment is manufactured by, for example, a method of placing at least one prepreg of the present embodiment (preferably overlapping two or more sheets), and placing a metal foil on one or both sides of the prepreg and forming a laminate. can do. In more detail, it can be manufactured by placing a metal foil, such as copper or aluminum, on one or both sides of a prepreg and laminating and molding it. As the number of prepregs, 1-10 sheets are preferable, 2-10 sheets are more preferable, and 2-7 sheets are still more preferable. The metal foil is not particularly limited as long as it is used for a material for printed wiring boards, and examples thereof include copper foils such as rolled copper foil and electrolytic copper foil. The thickness of the metal foil (copper foil) is not particularly limited, and may be 1.5 µm or more, and further, about 2 to 70 µm. As a molding method, a method commonly used when molding a laminated board and a multilayer board for printed wiring boards is mentioned, and more specifically, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. are used, and a temperature of 180 About -350 degreeC, the heating time is about 100-300 minutes, and the method of lamination-molding about 20-100 kg/cm<2> of surface pressure is mentioned. In addition, a multilayer board can also be obtained by combining the prepreg of the present embodiment and a separately manufactured wiring board for an inner layer (also referred to as an inner layer circuit board) and laminating and molding. As a manufacturing method of a multilayer board, for example, after disposing a metal foil (copper foil) of about 35 μm on both sides of one prepreg of the present embodiment, laminating and forming by the above molding method, an inner layer circuit is formed. , This circuit was subjected to a blackening treatment to form an inner circuit board, after which the inner circuit board and the prepreg of the present embodiment were alternately arranged one by one, and a metal foil (copper foil) was further disposed on the outermost layer, under the above conditions. Preferably, a multilayer plate can be manufactured by laminating and molding under vacuum. The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board.

<<printed wiring board>>

The printed wiring board of this embodiment is a printed wiring board comprising an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer is a layer formed from the resin composition according to the present embodiment, and free of the present embodiment. And at least one of the layers formed from the preg. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited. Hereinafter, an example of the manufacturing method of a printed wiring board is shown. First, a metal foil-clad laminate such as the above-described copper clad laminate is prepared. Next, the surface of the metal foil-clad laminate is subjected to an etching treatment to form an inner layer circuit, and an inner layer substrate is manufactured. The inner circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, and then the required number of prepregs is superimposed on the inner circuit surface, and a metal foil for an outer layer circuit is further formed on the outer side of the inner circuit surface. It is laminated, heated and pressurized to form an integral piece. In this way, a multilayer laminate is produced in which an insulating layer made of a substrate and a cured product of a thermosetting resin composition is formed between the inner circuit and the metal foil for the outer circuit. Subsequently, the multilayer laminate was subjected to hole drilling for through holes or via holes, and then a plated metal film was formed on the wall of the hole to conduct the metal foil for the inner circuit and the outer circuit, and additionally, the metal foil for the outer circuit was formed. A printed wiring board is manufactured by performing an etching treatment on the outer layer circuit to form an outer layer circuit.

The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer has a configuration including the resin composition according to the present embodiment described above. That is, in the prepreg of the present embodiment described above (for example, a prepreg formed from a substrate and the resin composition according to the present embodiment impregnated or applied thereto), and the metal foil-clad laminate according to the present embodiment described above. The layer formed from the resin composition becomes the insulating layer of the present embodiment.

<<resin sheet>>

The resin sheet of this embodiment includes a support and a layer formed from the resin composition according to the present embodiment disposed on the surface of the support. The resin sheet can be used as a build-up film or a dry film solder resist. Although it does not specifically limit as a manufacturing method of a resin sheet, For example, a method of obtaining a resin sheet by applying (coating) a solution obtained by dissolving the resin composition according to the present embodiment in a solvent to a support and drying it is mentioned. have.

As a support used here, for example, a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and a release film coated with a release agent on the surface of these films, polyee Although organic film substrates, such as a mid film, conductor foils, such as copper foil and aluminum foil, plate-like thing, such as a glass plate, SUS plate, and FRP, are mentioned, It is not specifically limited.

As the coating method (coating method), for example, a solution obtained by dissolving the resin composition according to the present embodiment in a solvent is applied on a support with a bar coater, die coater, doctor blade, or baker applicator. have. Further, after drying, the support may be peeled off or etched from the resin sheet on which the support and the resin composition are laminated to obtain a single-layered sheet. Further, a single-layer sheet can be obtained without using a support by supplying a solution obtained by dissolving the resin composition according to the present embodiment in a solvent into a mold having a sheet-like cavity and drying it into a sheet shape.

In addition, in the production of the single-layer sheet or resin sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited, but at low temperatures, the solvent is likely to remain in the resin composition, and at high temperatures, curing of the resin composition proceeds. Therefore, 1 to 90 minutes is preferable at a temperature of 20°C to 200°C. Moreover, in a single-layer sheet or a resin sheet, the resin composition may be used in an uncured state in which only the solvent has been dried, or may be used in a state of semi-curing (B-stage formation) as necessary. In addition, the thickness of the single layer of the present embodiment or the resin layer of the resin sheet can be adjusted by the concentration of the solution of the resin composition according to the present embodiment and the coating thickness, and is not particularly limited, but generally, when the coating thickness is increased Since the solvent tends to remain during drying, 0.1 to 500 µm is preferable.

<Dielectric constant and/or dielectric loss tangent lowering agent>

The agent for reducing the dielectric constant and/or the dielectric loss tangent of the present embodiment contains a bismaleimide compound (B) represented by formula (1). By blending the bismaleimide compound represented by formula (1) with a maleimide compound other than the cyanate ester compound (A) or bismaleimide compound (B), and other resin components, the dielectric constant and/or dielectric loss tangent of the resin composition It becomes possible to decrease. In particular, the agent for reducing the dielectric constant and/or the dielectric loss tangent of the present embodiment is effective as an agent for reducing the dielectric loss tangent. The preferred range of the bismaleimide compound represented by formula (1) is the same as described above.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. Materials, amounts used, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed as long as they do not deviate 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 type cyanate ester compound (SNCN)>

1-naphthol aralkyl resin (manufactured by Shinnittetsu Keum Chemical Co., Ltd.) 300 g (1.28 mol in terms of OH group) and 194.6 g (1.92 mol) of triethylamine (1.5 mol with respect to 1 mol of hydroxy group) to 1800 g of dichloromethane It dissolved, and this was made into solution 1.

Cyan chloride 125.9 g (2.05 mol) (1.6 mol with respect to 1 mol of hydroxy group), dichloromethane 293.8 g, 36% hydrochloric acid 194.5 g (1.92 mol) (1.5 mol with respect to 1 mol of hydroxy group), water 1205.9 g , Solution 1 was poured over 30 minutes while maintaining the liquid temperature at -2 to -0.5°C under stirring. After the completion of one week of solution, after stirring at the same temperature for 30 minutes, 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxy group) was dissolved in 65 g of dichloromethane (solution 2). It was commented over a minute. After the completion of the solution 2 weeks or less, the reaction was completed by stirring at the same temperature for 30 minutes.

After that, the reaction solution was allowed to stand and the organic phase and the aqueous phase were separated. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater at the fifth time of washing with water was 5 µS/cm, and it was confirmed that the ionic compounds that can be removed were sufficiently removed by washing with water.

The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90° C. for 1 hour to obtain 331 g of the target naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous substance). The mass average molecular weight of the obtained SNCN was 600. Moreover, the IR spectrum of SNCN showed absorption of 2250 cm ^-1 (cyanate ester group), and absorption of a hydroxy group was not shown. The equivalent weight of the cyanate group of the obtained SNCN was 256 g/eq.

<Synthesis Example 2 Synthesis of bismaleimide compound (BMI-Bisanilin-M)>

To a flask equipped with a stirrer, a nitrogen introduction tube, Dean Stark, a cooler and a thermometer, 17.23 g (50.0 mmol) of 1,3-bis[2-(4-aminophenyl)-2-propyl] manufactured by Tokyo Chemical Industry Co., Ltd. Benzene and 120.0 g of N,N-dimethylformamide were charged as a solvent, and the mixture was stirred and dissolved while passing through nitrogen gas. To this solution, 10.8 g (110 mmol) of maleic anhydride was added, and the mixture was stirred at room temperature overnight. Then, 0.951 g (5.00 mmol) of p-toluenesulfonic acid monohydrate as a catalyst and 60 g of toluene as a dehydration azeotropic solvent were charged, and azeotropic stirring was performed for 6 hours. At this time, evaporation of toluene and water occurred, and some of them were condensed with a cooler. After separating the water and toluene trapped in Dean Stark, only toluene was refluxed into the system, and part of it was distilled off from the upper part of the cooling pipe by the flow of nitrogen gas.

After cooling the reaction mixture, toluene was distilled off with an evaporator. Thereafter, the obtained solution was poured into 1% by mass of sodium bicarbonate water to remove excess maleic anhydride and p-toluenesulfonic acid. The obtained crude product was dissolved in N,N-dimethylformamide, methanol was added to reprecipitate, and the precipitate was collected by filtration 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 the obtained BMI-Bisanilin-M was 252.3 g/eq.

[Formula 24]

<Synthesis Example 3 Synthesis of bismaleimide compound (BMI-Bisanilin-P)>

To a flask equipped with a stirrer, a nitrogen introduction tube, Dean Stark, a cooler and a thermometer, 17.23 g (50.0 mmol) of 1,4-bis[2-(4-aminophenyl)-2-propyl] manufactured by Tokyo Chemical Industry Co., Ltd. Benzene and 120.0 g of N,N-dimethylformamide were charged as a solvent, and the mixture was stirred and dissolved while passing through nitrogen gas. To this solution, 10.8 g (110 mmol) of maleic anhydride was added, and the mixture was stirred at room temperature overnight. Then, 0.951 g (5.00 mmol) of p-toluenesulfonic acid monohydrate as a catalyst and 60 g of toluene as a dehydration azeotropic solvent were charged, and azeotropic stirring was performed for 6 hours. At this time, evaporation of toluene and water occurred, and some of them were condensed with a cooler. After separating the water and toluene trapped in Dean Stark, only toluene was refluxed into the system, and part of it was distilled off from the upper part of the cooling pipe by the flow of nitrogen gas.

After cooling the reaction mixture, toluene was distilled off with an evaporator. Thereafter, the obtained solution was poured into 1% by mass of sodium bicarbonate water to remove excess maleic anhydride and p-toluenesulfonic acid. The obtained crude product was dissolved in N,N-dimethylformamide, methanol was added to reprecipitate, and the precipitate was collected by filtration and dried. This operation was repeated 3 times to obtain 4,4'-bismaleimide diphenyl ether (yield 70%).

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

[Formula 25]

<Example 1>

50 parts by mass of SNCN obtained in Synthesis Example 1, 20 parts by mass of BMI-Bisanilin-M obtained in Synthesis Example 2, a biphenylaralkyl type polymaleimide compound ("MIR-3000", manufactured by Nippon Explosives Co., Ltd., equivalent of maleimide group) Silver 275 g/eq) 30 parts by mass, TPIZ (2,4,5-triphenylimidazole, curing accelerator) 0.5 parts by mass, zinc octylate ("Oct-Zn", manufactured by Nippon Chemical Industries, Ltd., curing accelerator) 0.10 The mass part was dissolved and mixed so as to obtain a solid content concentration of 50% by mass using methyl ethyl ketone as a solvent to obtain a varnish. In addition, the content of each component represents the amount of solid content. The appearance of the obtained varnish was evaluated according to the method described later.

A mixed resin powder was obtained by evaporating and distilling methyl ethyl ketone from the obtained varnish. The mixed resin powder was filled into a mold having a side of 100 mm and a thickness of 0.8 mm, vacuum pressing was performed at a pressure of 40 kg/cm 2 and a temperature of 230°C for 120 minutes, and a cured product having a side of 100 mm and a thickness of 0.8 mm A test piece was obtained.

About the obtained 0.8 mm-thick test piece, the water absorption rate, electrical properties (Dk and Df), and heating loss were measured according to the following method.

<<varnish appearance>>

About the obtained varnish, the appearance was evaluated visually as follows. Evaluations A to C are practical levels.

A: It was uniform and no precipitate was observed.

B: It was uniform and hardly a precipitate was confirmed.

C: It was slightly non-uniform, and a precipitate was somewhat confirmed.

D: It was non-uniform, and a lot of precipitates were confirmed.

<<water absorption>>

Using the obtained 0.8 mm-thick test piece, in accordance with JIS C6481, a pressure cooker (PCT) tester was used, and the water absorption was calculated from the change in weight after water vapor treatment at 120° C., 0.1 MPa, and 5 hours. However, in JIS C6481, as for the sample size, the test piece having a thickness of 0.8 mm was changed to 30 mm x 30 mm.

The pressure cooker tester was manufactured by Hirayama Manufacturing Co., Ltd., PC-3 type.

The results are shown in Table 1 below.

<<Electrical Characteristics (Dk and Df)>>

About the obtained 0.8 mm-thick test piece, the dielectric constant (Dk) and the dielectric loss tangent (Df) at 10 GHz were measured using a perturbation cavity resonator.

As the perturbation cavity resonator, Agilent 8722ES, manufactured by Agilent Technologies, was used.

The results are shown in Table 1 below.

<<heating loss>>

Using a thermogravimetric measuring device, thermogravimetric analysis of the cured product was performed under conditions of a temperature increase rate of 10°C/min in a nitrogen atmosphere.

As the thermogravimetric measuring device, "TGA5200" manufactured by SI Nanotechnology Co., Ltd. was used.

The results are shown in Table 1 below.

<Example 2>

In Example 1, BMI-Bisanilin-M was changed to BMI-Bisanilin-P obtained in Synthesis Example 3 in an equivalent amount, and other things were carried out in the same manner. The results are shown in Table 1 below.

<Comparative Example 1>

In Example 1, the same was carried out except that BMI-Bisanilin-M was not used and the content of MIR-3000 was 50 parts by mass. The results are shown in Table 1 below.

<Comparative Example 2>

In Example 1, SNCN and MIR-3000 were not used, except that the content of BMI-Bisanilin-M was set to 100 parts by mass. The results are shown in Table 1 below.

<Comparative Example 3>

In Example 1, SNCN, MIR-3000, and BMI-Bisanilin-M were not used, except that the content of BMI-Bisanilin-P was set to 100 parts by mass. The results are shown in Table 1 below.

As is clear from the above results, the resin compositions of Examples 1 and 2 maintain a good varnish appearance and low water absorption, which are equivalent to those of Comparative Example 1, and, compared with Comparative Example 1, the amount of heating loss is reduced, and further, Electrical properties have been improved. In particular, Df was remarkably lowered. In Comparative Example 2 and Comparative Example 3, the appearance of the varnish became D, resulting in a result that could not be used practically.

<Example 3>

50 parts by mass of SNCN obtained in Synthesis Example 1, 20 parts by mass of BMI-Bisanilin-M obtained in Synthesis Example 2, 30 parts by mass of a biphenylaralkyl-type polymaleimide compound ("MIR-3000", manufactured by Nippon Explosives Co., Ltd.), spherical shape 100 parts by mass of silica (SC2050-MB, manufactured by Admatex, average particle diameter 0.5 µm), 0.5 parts by mass of TPIZ (2,4,5-triphenylimidazole, curing accelerator), zinc octylate ("Oct -Zn", manufactured by Nippon Chemical Industries, Ltd., curing accelerator) 0.10 parts by mass was dissolved in a solvent so as to have a solid content concentration of 50% by mass using methyl ethyl ketone, and mixed to obtain a varnish. In addition, each of the above contents represents a solid content. The appearance of the obtained varnish was evaluated according to the method described later.

The obtained varnish was impregnated and coated on an E glass cloth having a thickness of 0.1 mm, and heated and dried at 165° C. for 5 minutes using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Co., Ltd.), and 50% by mass of a resin composition, A glass cloth 50 mass% prepreg was obtained. The appearance of the obtained prepreg was evaluated according to the method described later.

In a state where 4 or 8 sheets of the obtained prepreg were stacked, a 12 µm copper foil (3EC-M3-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) was placed on both sides for 120 minutes at a pressure of 40 kg/cm 2 and a temperature of 220°C. Vacuum pressing was performed to obtain a copper foil-clad laminate having a thickness of 0.4 mm and 0.8 mm.

For the obtained copper clad laminate, peel strength, bending properties, water absorption, electrical properties (Dk and Df), glass transition temperature, flame retardancy, thermal expansion coefficient, heating loss, and thermal conductivity were measured.

<<varnish appearance>>

About the obtained varnish, the appearance was evaluated visually as follows. Evaluations A to C are practical levels.

A: It was uniform and no precipitate was observed.

B: It was uniform and hardly a precipitate was confirmed.

C: It was slightly non-uniform, and a precipitate was somewhat confirmed.

D: It was non-uniform, and a lot of precipitates were confirmed.

<<the appearance of prepreg>>

About the obtained prepreg, the external appearance was evaluated visually as follows. Evaluations A to C are practical levels.

A: It was uniform and no precipitate was observed.

B: It was uniform and hardly a precipitate was confirmed.

C: It was slightly non-uniform, and a precipitate was somewhat confirmed.

D: It was non-uniform, and a lot of precipitates were confirmed.

<<Peel strength>>

Using the test piece (30 mm × 150 mm × 0.8 mm thick) obtained by cutting the 0.8 mm-thick copper clad laminate obtained above, according to JIS C6481's copper-clad laminate test method for printed wiring boards (refer to 5.7 Peel strength.) The peel strength of the copper foil was measured three times, and the average value of the lower limit was made into the measurement value. Table 2 shows the results.

<<bending properties>>

The copper foil on the surface layer of the 0.8 mm-thick copper clad laminate obtained above was removed by etching, and using an autograph tester according to JIS K6911, both ends of the test piece were supported at a point to form a support beam at both ends. , The maximum bending stress when a concentrated load was applied from the upper portion to the central portion was measured, and the bending strength was obtained.

In addition, using the test piece from which the copper foil of the copper clad laminate was removed, and using an autograph tester in accordance with JIS K6911, the degree of deformation resistance of the test piece against the bending stress in the straight portion of the load bending curve within the elastic limit was measured per unit deformation. It measured by bending stress, and obtained the bending elastic modulus.

The autograph tester used AG-Xplus manufactured by Shimadzu Corporation.

Table 2 shows the results.

<<water absorption>>

A sample obtained by cutting the obtained 0.8 mm-thick copper clad laminate into 30 mm × 30 mm, according to JIS C6481, using a pressure cooker (PCT) tester, from a weight change after treatment at 120° C., 0.1 MPa, and 5 hours. , The absorption rate was calculated.

The pressure cooker tester was manufactured by Hirayama Manufacturing Co., Ltd., PC-3 type.

Table 2 shows the results.

<<Electrical Characteristics>>

The dielectric constant (Dk) and the dielectric loss tangent (Df) at 2 GHz and 10 GHz were measured, respectively, using a sample obtained by removing the copper foil of the copper foil-clad laminate having a thickness of 0.4 mm and a thickness of 0.8 mm by etching.

As the perturbation cavity resonator, Agilent 8722ES, manufactured by Agilent Technologies, was used.

Table 2 shows the results.

<<glass transition temperature>>

The glass transition temperature (Tg) was measured by DMA (Dynamic Mechanical Analysis) method with a dynamic viscoelasticity analyzer in accordance with JIS C6481 after removing the copper foil on both sides of the obtained 0.8 mm thick copper clad laminate by etching. In Table 2 below, E'' represents a loss modulus, and tan δ represents a loss tangent.

As the dynamic viscoelasticity analyzer, the one manufactured by TA Instruments was used.

Table 2 shows the results.

<<flame retardant>>

Copper foils on both sides of the metal foil-clad laminate obtained in each Example and Comparative Example were removed by etching. Next, using a sample from which copper foil on both sides was removed, a flame retardancy test was performed in accordance with the UL94 vertical combustion test method.

Table 2 shows the results.

<<Coefficient of thermal expansion>>

Using a sample from which the copper foil of the obtained 0.8 mm thick copper clad laminate was removed by etching, the thermal expansion coefficient of the glass cloth (x direction) with respect to the insulating layer of the laminate by the TMA method (Thermo-mechanical analysis) specified in JlS C 6481. , y direction and z direction) were measured, and the values were obtained. Specifically, after removing the copper foil on both sides of the copper clad laminate obtained above by etching, a 4.5 mm x 16 mm evaluation substrate was prepared, and then from 40°C to 340°C every minute with a thermomechanical analysis device (manufactured by TA Instruments). The temperature was raised to 10°C, and the coefficients of thermal expansion (ppm/K) in the x direction, y direction, and z direction in 60°C to 120°C were measured, respectively.

Table 2 shows the results.

<<heating loss>>

Using a thermogravimetric measuring device, thermogravimetric analysis of a sample in which the copper foil of the obtained 0.8 mm-thick copper foil-clad laminate was removed by etching under a nitrogen atmosphere and conditions of a temperature increase rate of 10°C/min.

As the thermogravimetric measuring device, "TGA5200" manufactured by SI Nanotechnology Co., Ltd. was used.

Table 2 shows the results.

<<heat conductivity>>

The density and specific heat of the copper clad laminate obtained in each Example and Comparative Example were measured.

The specific heat was measured by a Q100 type DSC manufactured by TA Instruments.

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

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

Thermal conductivity (W/m·K)

= Density (kg/㎥) × Specific heat (kJ/kg·K) × Thermal diffusion rate (㎡/S) × 1000

Table 2 shows the results.

<Example 4>

In Example 3, BMI-Bisanilin-M was changed to BMI-Bisanilin-P obtained in Synthesis Example 3 in an equivalent amount, and others were carried out in the same manner. The results are shown in Table 2 below.

<Comparative Example 4>

In Example 3, it carried out similarly except having not used BMI-Bisanilin-M and having set the content of MIR-3000 to 50 parts by mass. The results are shown in Table 2 below.

As is clear from the above results, the copper clad laminates of Examples 3 and 4 maintain a good varnish appearance, good prepreg appearance, high peel strength, high bending properties, low water absorption, low coefficient of thermal expansion, and thermal conductivity equivalent to those of Comparative Example 4. While, compared with Comparative Example 4, higher Tg and less heating loss were achieved, and electrical properties (lower Dk and lower Df) were also improved.

Claims (18)

Cyanic acid ester compound (A) and
Bismaleimide compound (B) represented by the following formula (1)
Resin composition containing;

Formula (1) of, X represents an organic group of carbon number ^{1 ~ 12, R 1 ~ R} 3 are, each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 3, a is each independently an integer of 0 to 4 Represents. The method of claim 1,
Formula (1), X is an alkylene group of carbon number ^{1 ~ 3, R 1 ~ R} 3 are, each independently represents a hydrogen atom, a methyl group or an ethyl group, a is a resin each independently represent an integer of 0 to 2 Composition. The method of claim 1,
The resin composition in which the bismaleimide compound (B) is represented by the following formula (2).

The method according to any one of claims 1 to 3,
A resin composition containing a solvent further. The method of claim 4,
The resin composition, wherein the content of the bismaleimide compound (B) is 0.1 to 30 mass% of the resin composition. The method according to any one of claims 1 to 5,
The content ratio of the cyanate ester compound (A) and the bismaleimide compound (B) is an equivalent ratio of the unsaturated imide group of the bismaleimide compound (B) and the cyanate group of the cyanate ester compound (A) ( The resin composition represented by the equivalent weight of an unsaturated imide group/equivalent weight of a cyanate group), and is 0.01 or more and less than 1.1. The method according to any one of claims 1 to 6,
Maleimide compounds other than the bismaleimide compound (B), an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound, a compound having a polymerizable unsaturated group, and a carbon-carbon unsaturated double bond (excluding maleimide). A resin composition further containing at least one selected from the group consisting of a modified polyphenylene ether, an elastomer, and an active ester compound terminally modified by the contained substituent. The method according to any one of claims 1 to 7,
The resin composition further containing a filler (C). The method of claim 8,
The resin composition, wherein the content of the filler (C) is 50 to 1600 parts by mass with respect to 100 parts by mass of the total amount of the resin component in the resin composition. The method according to any one of claims 1 to 9,
A resin composition which is a low dielectric constant material and/or a low dielectric loss tangent material. A cured product of the resin composition according to any one of claims 1 to 10. A prepreg formed from a substrate and the resin composition according to any one of claims 1 to 10. A metal foil-clad laminate comprising a layer formed from at least one prepreg according to claim 12 and a metal foil disposed on one side or both sides of the layer formed from the prepreg. A resin sheet comprising a support and a layer formed from the resin composition according to any one of claims 1 to 10 disposed on the surface of the support. A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer,
A printed wiring board including at least one of a layer formed from the resin composition according to any one of claims 1 to 10 and a layer formed from the prepreg according to claim 12. As a method for producing a resin composition containing a cyanate ester compound (A) and a bismaleimide compound (B) represented by the following formula (1),
A method for producing a resin composition comprising mixing a cyanic acid ester compound (A), a bismaleimide compound (B) and a solvent, wherein the content of the bismaleimide compound (B) is 0.1 to 30 mass% of the resin composition ;

Formula (1) of, X represents an organic group of carbon number ^{1 ~ 12, R 1 ~ R} 3 are, each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 3, a is independently an integer of 0 to 4, respectively, Show. The method of claim 16,
In addition, maleimide compounds other than the bismaleimide compound (B), epoxy resins, phenol resins, oxetane resins, benzoxazine compounds, compounds having a polymerizable unsaturated group, carbon-carbon unsaturated double bonds (except maleimide A method for producing a resin composition containing at least one selected from the group consisting of a modified polyphenylene ether, an elastomer, and an active ester compound terminally modified by a substituent containing). An agent for reducing the dielectric constant and/or dielectric loss tangent containing the bismaleimide compound (B) represented by the following formula (1);

Formula (1) of, X represents an organic group of carbon number ^{1 ~ 12, R 1 ~ R} 3 are, each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 3, a is independently an integer of 0 to 4, respectively, Show.