CN118019799A

CN118019799A - Resin composition, prepreg, metal foil-clad laminate, resin composite sheet, printed wiring board, and semiconductor device

Info

Publication number: CN118019799A
Application number: CN202280064980.4A
Authority: CN
Inventors: 中岛祐司; 桥口和弘; 平野俊介; 长谷部惠一
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2021-09-27
Filing date: 2022-07-22
Publication date: 2024-05-10
Also published as: WO2023047782A1; JP7380943B2; JPWO2023047782A1; JP2024003007A; TW202323426A

Abstract

The invention provides a resin composition which maintains excellent dielectric characteristics and has excellent moisture absorption and heat resistance, and a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed circuit board and a semiconductor device. A resin composition comprising: a polymer (A) having a structural unit represented by the formula (V), and a compound (B) having a molecular weight of less than 1000 and containing 1 organic group containing a carbon-carbon unsaturated bond in the molecule. In the formula (V), ar represents an aromatic hydrocarbon linking group. * Indicating the bonding location.

Description

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

Technical Field

The present invention relates to a resin composition, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device.

Background

In recent years, high integration and miniaturization of semiconductor elements used in electronic devices, communication devices, and the like, including portable terminals, are being accelerated. With this, a technology capable of high-density mounting of semiconductor elements is demanded, and improvement of a printed circuit board occupying its important position is demanded.

On the other hand, applications of electronic devices and the like are diversified and continue to expand. In this regard, various characteristics required for printed circuit boards, metal foil-clad laminates used for the same, prepregs, and the like are diversified and strict. In order to obtain a printed circuit board improved while taking such required characteristics into consideration, various materials and processing methods have been proposed. One of them is improvement and development of a resin material constituting a prepreg or a resin composite sheet.

For example, patent document 1 discloses a novel soluble polyfunctional vinyl aromatic copolymer having improved heat resistance, compatibility, transparency and toughness, a method for producing the same, and a curable composition containing the copolymer.

Prior art literature

Patent literature

Patent document 1: international publication No. 2017/115813

Disclosure of Invention

Problems to be solved by the invention

As described above, the applications of electronic devices and the like are diversified and continue to expand, and new materials are also required for resin materials constituting prepregs and the like. In particular, further material development is required for resin compositions which maintain excellent dielectric characteristics and are excellent in moisture absorption and heat resistance.

The present invention has been made to solve the above problems, and an object thereof is to provide a resin composition, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device, which maintain excellent dielectric characteristics and excellent moisture and heat resistance.

Solution for solving the problem

Based on the above-mentioned problems, the present inventors have studied and found that the above-mentioned problems can be solved by blending a compound (B) having a molecular weight of less than 1000 and containing 1 organic group containing a carbon-carbon unsaturated bond in the molecule with a predetermined aromatic vinyl compound.

Specifically, the above problems are solved by the following means.

<1> A resin composition comprising:

a polymer (A) having a structural unit represented by the formula (V), and

A compound (B) having a molecular weight of less than 1000 and containing 1 organic group containing carbon-carbon unsaturated bond in the molecule.

( In the formula (V), ar represents an aromatic hydrocarbon linking group; * Indicating the bonding location. )

<2> The resin composition according to <1>, wherein the weight average molecular weight of the polymer (A) is 1,000 ～ 160,000.

<3> The resin composition according to <1> or <2>, wherein the content of the polymer (A) is 5 to 70 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

<4> The resin composition according to any one of <1> to <3>, wherein the organic group containing a carbon-carbon unsaturated bond has a structure of CH ₂ =c (X) -and X is a hydrogen atom or a methyl group.

<5> The resin composition according to any one of <1> to <4>, wherein the organic group containing a carbon-carbon unsaturated bond is 1 selected from the group consisting of vinyl group, allyl group, acrylic group, and methacrylic group.

<6> The resin composition according to any one of <1> to <5>, wherein the molecular weight of the compound (B) is 70 to 500.

<7> The resin composition according to any one of <1> to <6>, wherein the boiling point of the compound (B) is 110 to 300 ℃.

<8> The resin composition according to any one of <1> to <7>, wherein the content of said compound (B) is 1 to 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

<9> The resin composition according to any one of <1> to <8>, wherein the mass ratio of the polymer (a) to the compound (B) in the resin composition is 1:0.025 to 0.7.

<10> The resin composition according to any one of <1> to <9>, further comprising another thermosetting compound (C) not belonging to the polymer (A) and the compound (B).

<11> The resin composition according to <10>, wherein the other thermosetting compound (C) contains at least 1 selected from the group consisting of maleimide compounds, polyphenylene ether compounds containing 2 or more carbon-carbon unsaturated double bonds, cyanate ester compounds, epoxy compounds, phenol compounds, alkenyl-substituted nadic imide compounds, oxetane resins, and benzoxazine compounds.

<12> The resin composition according to <10>, wherein the other thermosetting compound (C) comprises at least 1 selected from the group consisting of a compound (M1) represented by formula (M1), a compound represented by formula (M3), a compound represented by formula (M5), and a compound represented by formula (OP-1).

( In the formula (M1), R ^M1、R^M2、R^M3 and R ^M4 each independently represent a hydrogen atom or an organic group. R ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group. Ar ^M represents a 2-valent aromatic group. A is an alicyclic group having 4 to 6 membered ring. R ^M7 and R ^M8 are each independently alkyl. mx is 1 or 2 and lx is 0 or 1.R ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group. R ^M11、R^M12、R^M13 and R ^M14 each independently represent a hydrogen atom or an organic group. R ^M15 is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 1 to 10 carbon atoms, an arylthio group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group. px represents an integer of 0 to 3. nx is an integer of 1 to 20. )

(In the formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer of 1 to 10 inclusive.)

(In the formula (M5), R ⁵⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, R ⁵⁹ each independently represents a hydrogen atom or a methyl group, and n ₆ represents an integer of 1 or more.)

(In the formula (OP-1), X represents an aromatic group, - (Y-O) n ₂ -represents a polyphenylene ether structure, R ¹、R² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, n ₁ represents an integer of 1 to 6, n ₂ represents an integer of 1 to 100, and n ₃ represents an integer of 2 to 4.)

<13> The resin composition according to <10>, wherein the other thermosetting compound (C) comprises at least 1 selected from the group consisting of a compound (M1) represented by the formula (M1), a compound represented by the formula (M3), and a compound represented by the formula (OP-1).

<14> The resin composition according to <10>, wherein the content of the thermosetting compound (C) is 5 to 95 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

<15> The resin composition according to <10>, wherein the other thermosetting compound (C) contains at least 1 selected from the group consisting of compounds represented by the formula (OP-1) and the content thereof is 3 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

<16> The resin composition according to any one of <1> to <15>, further comprising a filler (D).

<17> The resin composition according to <16>, wherein the filler (D) is contained in an amount of 10 to 500 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

<18> The resin composition according to any one of <1> to <17>, wherein the content of the polymer (a) is 5 to 70 parts by mass and the content of the compound (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

<19> The resin composition according to any one of <1> to <18>, which is substantially free of a polymerization initiator.

<20> The resin composition according to <1>, wherein the weight average molecular weight of the polymer (A) is 1,000 ～ 160,000,

The content of the polymer (A) is 5 to 70 parts by mass per 100 parts by mass of the resin solid content in the resin composition,

The organic group containing a carbon-carbon unsaturated bond is 1 selected from the group consisting of a vinyl group, an allyl group, an acrylic group, and a methacrylic group,

The molecular weight of the compound (B) is 70-500,

The boiling point of the compound (B) is 110-300 ℃,

The content of the compound (B) is 1 to 10 parts by mass per 100 parts by mass of the resin solid content in the resin composition,

The mass ratio of the polymer (a) to the compound (B) in the resin composition is 1:0.025 to 0.7 percent of the total weight of the composite material,

The resin composition further comprises other thermosetting compound (C) not belonging to the polymer (A) and the compound (B),

The other thermosetting compound (C) contains at least 1 selected from the group consisting of maleimide compounds, polyphenylene ether compounds having 2 or more carbon-carbon unsaturated double bonds, cyanate ester compounds, epoxy compounds, phenol compounds, alkenyl-substituted nadic imide compounds, oxetane resins, and benzoxazine compounds,

The content of the thermosetting compound (C) is 5 to 95 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

<21> The resin composition according to <20>, wherein the other thermosetting compound (C) contains at least 1 selected from the group consisting of compounds represented by the formula (OP-1) and the content thereof is 3 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

<22> The resin composition according to <21>, which is substantially free of a polymerization initiator.

<23> A prepreg formed of a base material, and the resin composition of any one of <1> to <22 >.

<24> A metal foil-clad laminate comprising at least 1 layer formed of the prepreg of <23>, and a metal foil disposed on one or both sides of the layer formed of the prepreg.

<25> A resin composite sheet comprising a support and a layer formed of the resin composition according to any one of <1> to <22> disposed on the surface of the support.

<26> A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer comprises a layer formed of the resin composition of any one of <1> to <22 >.

<27> A semiconductor device comprising the printed circuit board of <26 >.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a resin composition, a prepreg, a metal foil-clad laminate, a resin composite sheet, a printed wiring board, and a semiconductor device, which are excellent in moisture absorption and heat resistance while maintaining excellent dielectric characteristics.

Detailed Description

The mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.

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

In the present specification, various physical property values and characteristic values are values at 23 ℃ unless otherwise specified.

In the expression of the group (radical) in the present specification, the expression of substitution and non-substitution is not described to include a group (radical) having no substituent and a group (radical) having a substituent. For example, "alkyl" means to include not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the expression of substitution and non-substitution is not described, and non-substitution is preferable.

In the present specification, the relative permittivity means a ratio of permittivity to vacuum permittivity of a substance. In this specification, the relative permittivity may be simply referred to as "permittivity".

In the present specification, "(meth) acrylic acid" means both or either of acrylic acid and methacrylic acid.

In the case where the standards shown in the present specification differ depending on the method of measuring the content of the sample by the year, unless otherwise specified, the standards at the time point of 2021, 1 month and 1 day are used as references.

In the present specification, the resin solid component means a component other than the filler (D) and the solvent, and is characterized by comprising: a polymer (A) having a structural unit represented by the formula (V), a compound (B) having a molecular weight of less than 1000 and containing 1 organic group containing a carbon-carbon unsaturated bond in the molecule, and other thermosetting compounds (C), elastomers, silane coupling agents, and other resin additive components (additives such as flame retardants) compounded as required.

The resin composition of the present embodiment is characterized by comprising: a polymer (A) having a structural unit represented by the formula (V), and a compound (B) having a molecular weight of less than 1000 and containing 1 organic group containing a carbon-carbon unsaturated bond in the molecule (hereinafter, sometimes simply referred to as "compound (B)").

( In the formula (V), ar represents an aromatic hydrocarbon linking group. * Indicating the bonding location. )

With such a constitution, a resin composition having excellent moisture absorption and heat resistance while maintaining excellent dielectric characteristics can be provided.

The polymer (a) having the structural unit represented by the formula (V) has excellent dielectric characteristics, but tends to be poor in moisture absorption and heat resistance. This is presumably because the polymer (a) having the structural unit represented by the formula (V) is a polymer and has a large amount of vinyl groups in the molecular chain. That is, if the vinyl group remains unreacted during curing, the moisture absorption and heat resistance are deteriorated. In this embodiment, it is presumed that by compounding the compound (B), the unreacted vinyl group of the polymer (a) having the structural unit represented by the formula (V) can be blocked. As a result, it is presumed that the unreacted vinyl groups in the obtained cured product are reduced, and the moisture absorption heat resistance is greatly improved. In addition, it is presumed that since the compound (B) is a small molecule having a molecular weight of less than 1000, the mobility and the diffusivity are high, and the probability of reacting with unreacted vinyl groups is also improved.

Regarding the blocking effect as described above, it is presumed that the moisture absorption heat resistance is improved as long as the functional group is one which blocks the vinyl group in the polymer (a) in addition to the organic group containing a carbon-carbon unsaturated bond. However, it is also envisaged that the following is present: depending on the kind of functional group, a highly polar part remains even after the end capping, and thus the dielectric properties of the cured product are adversely affected. In contrast, in this embodiment, it is presumed that the use of a compound having an organic group containing a carbon-carbon unsaturated bond makes it difficult to impart polarity to the obtained cured product.

< Polymer (A) having structural unit represented by formula (V) >)

The resin composition of the present embodiment includes a polymer (a) having a structural unit represented by formula (V). By the polymer (a) having the structural unit represented by the formula (V), a resin composition excellent in low dielectric characteristics (low dielectric constant, low dielectric loss tangent) can be obtained.

The aromatic hydrocarbon linking group may be a group composed of only an aromatic hydrocarbon optionally having a substituent, or may be a group composed of a combination of an aromatic hydrocarbon optionally having a substituent and another linking group, and is preferably a group composed of only an aromatic hydrocarbon optionally having a substituent. Examples of the substituent optionally contained in the aromatic hydrocarbon include substituent Z (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a halogen atom, and the like). The aromatic hydrocarbon preferably has no substituent.

The aromatic hydrocarbon linking group is typically a 2-valent linking group.

Specific examples of the aromatic hydrocarbon linking group include optionally substituted phenylene, naphthalenediyl, anthracenediyl, phenanthrediyl, biphenyldiyl and fluorenediyl, and among these, optionally substituted phenylene is preferable. The substituent Z may be exemplified by the above substituents, but the above groups such as phenylene group are preferably unsubstituted.

More preferably, the structural unit represented by the formula (V) includes at least 1 of the structural unit represented by the following formula (V1), the structural unit represented by the following formula (V2), and the structural unit represented by the following formula (V3). In addition, the following formula represents a bonding position. In the following, the structural units represented by the formulae (V1) to (V3) may be collectively referred to as "structural unit (a)".

In the formulae (V1) to (V3), L ¹ is an aromatic hydrocarbon linking group (carbon number is preferably 6 to 22, more preferably 6 to 18, still more preferably 6 to 10). Specifically, a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, or a fluorenediyl group which may be substituted, is exemplified, and among these, a phenylene group which may be substituted is preferable. The substituent Z may be exemplified by the above substituents, but the above groups such as phenylene group are preferably unsubstituted.

The compound forming the structural unit (a) is preferably a divinyl aromatic compound, and examples thereof include divinylbenzene, bis (1-methylvinyl) benzene, divinyl naphthalene, divinyl anthracene, divinyl biphenyl, and divinyl phenanthrene. Of these, divinylbenzene is particularly preferable. These divinyl aromatic compounds may be used in an amount of 1 kind or 2 or more kinds as required.

The polymer (a) having the structural unit represented by the formula (V) may be a homopolymer of the structural unit (a) or a copolymer with the structural unit derived from another monomer as described above.

When the polymer (a) having the structural unit represented by the formula (V) is a copolymer, the copolymerization ratio of the structural unit (a) is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and may be 15 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, still more preferably 70 mol% or less, still more preferably 60 mol% or less, still more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 30 mol% or less, still more preferably 25 mol% or less, or 20 mol% or less.

As the structural unit derived from the other monomer, a structural unit (b) derived from an aromatic compound having 1 vinyl group (monovinyl aromatic compound) can be exemplified.

The structural unit (b) derived from a monovinylaromatic compound is preferably a structural unit represented by the following formula (V4).

In the formula (V4), L ² is an aromatic hydrocarbon linking group, and specific examples of preferable groups include the above-mentioned examples of L ¹.

R ^V1 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group). When R ^V1 is a hydrocarbon group, the carbon number is preferably 1 to 6, more preferably 1 to 3.R ^V1 and L ² may have the above substituent Z.

When the polymer (a) having a structural unit represented by the formula (V) is a copolymer containing a structural unit (b) derived from a monovinylaromatic compound, examples of the monovinylaromatic compound include vinylaromatic compounds such as styrene, vinylnaphthalene, and vinylbiphenyl; nuclear alkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, methylvinylbiphenyl, and ethylvinylbiphenyl. The monovinylaromatic compounds exemplified here may suitably have the substituents Z mentioned above. In addition, 1 kind of the monovinylaromatic compound may be used, or 2 or more kinds may be used.

When the polymer (a) having the structural unit represented by the formula (V) is a copolymer containing the structural unit (b), the copolymerization ratio of the structural unit (b) is preferably 10 mol% or more, more preferably 15 mol% or more, and further may be 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 75 mol% or more. The upper limit is preferably 98 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less.

The polymer (a) having the structural unit represented by the formula (V) may have other structural units than the structural unit (a) and the structural unit (b). Examples of the other structural unit include a structural unit (c) derived from a cycloolefin compound. Examples of the cycloolefin compound include hydrocarbons having a double bond in the ring structure. Specifically, there may be mentioned monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene and cyclooctene, compounds having a norbornene ring structure such as norbornene and dicyclopentadiene, and cycloolefin compounds obtained by condensing aromatic rings such as indene and acenaphthylene. Examples of the norbornene compound include norbornene compounds described in paragraphs 0037 to 0043 of Japanese patent application laid-open No. 2018-39995, the contents of which are incorporated herein. The cycloolefin compound exemplified herein may further have the substituent Z.

When the polymer (a) having the structural unit represented by the formula (V) is a copolymer containing the structural unit (c), the copolymerization ratio of the structural unit (c) is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and may be 50 mol% or less, or may be 30 mol% or less.

In the polymer (a) having a structural unit represented by the formula (V), a structural unit (d) derived from a different polymerizable compound (hereinafter, also referred to as another polymerizable compound) may be further incorporated. As the other polymerizable compound (monomer), a compound containing 3 vinyl groups is exemplified. Specifically, 1,3, 5-trivinylbenzene, 1,3, 5-trivinylnaphthalene, and 1,2, 4-trivinylcyclohexane are exemplified. Or ethylene glycol diacrylate, butadiene, etc. may be mentioned. The copolymerization ratio of the structural unit (d) derived from another polymerizable compound is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10mol% or less.

As one embodiment of the polymer (a) having a structural unit represented by the formula (V), there can be exemplified: it is necessary to include the structural unit (a) and at least 1 of the structural units (b) to (d). Further, it is possible to exemplify: the total of the structural units (a) to (d) is 95 mol% or more, and further 98 mol% or more of the total structural units.

In another embodiment of the polymer (a) having the structural unit represented by the formula (V), the polymer having the structural unit (a) and having 90 mol% or more of the structural unit including an aromatic ring in all the structural units except the terminal is preferable, and 95 mol% or more is more preferable, and 100 mol% or more is also preferable.

When the mole% relative to the total structural units is calculated, 1 structural unit refers to a structural unit derived from 1 molecule of a monomer (for example, a divinyl aromatic compound, a monovinyl aromatic compound, or the like) used in the production of the polymer (a) having the structural unit represented by the formula (V).

The method for producing the polymer (a) having the structural unit represented by the formula (V) is not particularly limited, and examples thereof may include: a starting material comprising a divinylaromatic compound (optionally together with a monovinylaromatic compound, a cycloolefin compound, etc.) is polymerized in the presence of a Lewis acid catalyst. As the lewis acid catalyst, a metal fluoride such as boron trifluoride or a complex thereof can be used.

The structure of the chain end of the polymer (a) having the structural unit represented by the formula (V) is not particularly limited, and the group derived from the above-mentioned divinylaromatic compound may be a structure represented by the following formula (E1). In addition, L ¹ in the formula (E1) is the same as defined in the above formula (V1). * Indicating the bonding location.

*-CH＝CH-L¹-CH＝CH₂(E1)

When the group derived from the monovinylaromatic compound is a chain end, a structure represented by the following formula (E2) is used. Wherein L ² and R ^V1 have the same meanings as defined in the above formula (V4). * Indicating the bonding location.

*-CH＝CH-L²-R^V1(E2)

The molecular weight of the polymer (a) having the structural unit represented by the formula (V) is preferably 300 or more, more preferably 500 or more, still more preferably 1,000 or more, and still more preferably 1,500 or more, in terms of the number average molecular weight Mn. The upper limit is preferably 130,000 or less, more preferably 120,000 or less, still more preferably 110,000 or less, and still more preferably 100,000 or less.

The molecular weight of the polymer (a) having the structural unit represented by the formula (V) is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, still more preferably 2,500 or more, still more preferably 3,000 or more, and may be 3,500 or more, and may be 4,000 or more, in terms of the weight average molecular weight Mw. By setting the lower limit value or more, the cured product of the resin composition can effectively exhibit excellent low dielectric characteristics, particularly, df and dielectric characteristics after moisture absorption, of the polymer (a) having the structural unit represented by the formula (V). The upper limit is preferably 160,000 or less, more preferably 150,000 or less, still more preferably 140,000 or less, still more preferably 130,000 or less, and may be 120,000 or less, or may be 110,000 or less. When the upper limit value is set to be less than or equal to the above-described upper limit value, a land filling failure tends to be less likely to occur when the prepreg or the resin sheet is laminated on the circuit forming board.

The monodispersity (Mw/Mn) expressed as a ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, and further preferably 20 or less. The lower limit value is practically 1.1 or more, but may be 5 or more and 7 or more, and even 10 or more, the required performance is satisfied.

The Mw and Mn were measured as described in examples to be described later.

When the resin composition of the present embodiment contains 2 or more polymers (a) having structural units represented by formula (V), the Mw, mn, and Mw/Mn of the mixture preferably satisfy the above ranges.

The equivalent of vinyl group of the polymer (A) having the structural unit represented by the formula (V) is preferably 200g/eq. Or more, more preferably 230g/eq. Or more, still more preferably 250g/eq. Or more, or 300g/eq. Or more, or 350g/eq. Or more. The equivalent of the vinyl group is preferably 1200g/eq or less, more preferably 1000g/eq or less, and further, 800g/eq or less, 600g/eq or less, 500g/eq or less, 400g/eq or less, or 350g/eq or less. When the lower limit value is set to be equal to or larger than the above lower limit value, the storage stability of the resin composition tends to be improved, and the fluidity of the resin composition tends to be improved. Therefore, the formation of voids is less likely to occur when prepregs or the like are formed, and a printed wiring board with higher reliability tends to be obtained. On the other hand, setting the upper limit value or less tends to improve the heat resistance of the obtained cured product.

The polymer (a) having a structural unit represented by the formula (V) used in the present embodiment preferably has excellent low dielectric characteristics as a cured product thereof. For example, the cured product of the polymer (a) having the structural unit represented by the formula (V) used in the present embodiment preferably has a relative dielectric constant (Dk) of 2.80 or less, more preferably 2.60 or less, still more preferably 2.50 or less, and still more preferably 2.40 or less at 10GHz as measured by the cavity disturbance method. It is practical that the lower limit value of the relative dielectric constant is, for example, 1.80 or more. The dielectric loss tangent (Df) at 10GHz, as measured by the cavity resonator disturbance method, of the cured product of the polymer (a) having the structural unit represented by the formula (V) used in the present embodiment is preferably 0.0030 or less, more preferably 0.0020 or less, and still more preferably 0.0010 or less. It is practical that the lower limit value of the dielectric loss tangent is, for example, 0.0001 or more.

The relative permittivity (Dk) and the dielectric loss tangent (Df) were measured by the method described in examples below.

In this specification, regarding the polymer (a) having a structural unit represented by the formula (V), reference may be made to a compound described in paragraphs 0029 to 0058 of international publication No. 2017/115813, a compound described in paragraphs 0013 to 0058 of japanese patent application laid-open publication No. 2018-039995, a compound described in paragraphs 0008 to 0043 of japanese patent application laid-open publication No. 2018-168343, a compound described in paragraphs 0014 to 0042 of japanese patent application laid-open publication No. 2006-070136, a compound described in paragraphs 0014 to 0061 of japanese patent application laid-open publication No. 2006-089683, a compound described in paragraphs 0014 to 0061 of japanese patent application laid-open publication No. 2008-248001, a compound described in paragraphs 0008 to 0036 of japanese patent application laid-open publication No. 2018-168343, a compound described in terms of synthetic reaction condition, and the like, and the contents of the present specification.

In the resin composition of the present embodiment, the content of the polymer (a) having the structural unit represented by the formula (V) is preferably 5 to 70 parts by mass when the resin solid content in the resin composition is set to 100 parts by mass. The lower limit value of the content of the polymer (a) having the structural unit represented by the formula (V) is more preferably 7 parts by mass or more, still more preferably 9 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more, when the resin solid content in the resin composition is set to 100 parts by mass. By setting the content of the polymer (a) having the structural unit represented by the formula (V) to the above lower limit value or more, low dielectric characteristics, particularly low relative permittivity, can be effectively achieved. On the other hand, when the resin solid content in the resin composition is set to 100 parts by mass, the upper limit value of the content of the polymer (a) having the structural unit represented by the formula (V) is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, further preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, and also 20 parts by mass or less. By setting the upper limit value or less, the peel strength of the metal foil of the obtained cured product can be effectively improved.

The polymer (a) having the structural unit represented by the formula (V) may be contained in the resin composition in an amount of 1 or 2 or more. When the content is 2 or more, the total amount is preferably within the above range.

< Compound (B) having a molecular weight of less than 1000 and containing 1 organic group containing carbon-carbon unsaturated bond in the molecule >

The resin composition of the present embodiment contains a compound (B) (compound (B)) having a molecular weight of less than 1000 and containing 1 organic group containing a carbon-carbon unsaturated bond in a molecule. It is presumed that the carbon-carbon unsaturated bond of the compound (B) reacts with the vinyl group of the polymer (a) having the structural unit represented by the formula (V), and the moisture absorption heat resistance of the obtained cured product is improved.

The carbon-carbon unsaturated bond constituting the aforementioned organic group containing a carbon-carbon unsaturated bond does not contain a group contained as a part of an aromatic ring. On the other hand, the aromatic compound contains a carbon-carbon unsaturated bond contained as a part of a non-aromatic ring. Examples of the carbon-carbon unsaturated bond contained as a part of the non-aromatic ring include cyclohexenyl in a molecule, and the like. The organic compound also contains a part other than the terminal end of the linear or branched organic group, that is, a carbon-carbon unsaturated bond contained in the linear or branched organic group.

In this embodiment, the organic group containing a carbon-carbon unsaturated bond preferably has a structure of CH ₂ =c (X) - (X are hydrogen atoms or methyl groups). By using a compound containing a carbon-carbon unsaturated bond at the end of the molecule in this manner, it is possible to more effectively react with the vinyl group of the polymer (a) having the structural unit represented by formula (V).

The organic group containing a carbon-carbon unsaturated bond is more preferably 1 selected from the group consisting of vinyl group, allyl group, acrylic group, and methacrylic group, and further preferably vinyl group.

The compound (B) used in the present embodiment is preferably composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, oxygen atoms and silicon atoms.

The compound (B) used in this embodiment may or may not have a polar group. The compound (B) used in this embodiment preferably has no polar group. Examples of the polar group include an amino group, a carboxyl group, a hydroxyl group, and a nitro group.

In this embodiment, the molecular weight of the compound (B) is preferably 70 or more, more preferably 80 or more, and further preferably 90 or more. By setting the lower limit value or more, volatilization of the compound (B) derived from the resin composition, the cured product thereof, or the like of the present embodiment tends to be suppressed. The upper limit of the molecular weight of the compound (B) is preferably 500 or less, more preferably 400 or less, still more preferably 300 or less, still more preferably 200 or less, and may be 150 or less. When the ratio is equal to or less than the upper limit, the effect of improving the reactivity with the polymer (a) having the structural unit represented by the formula (V) tends to be more improved.

When the resin composition of the present embodiment contains 2 or more kinds of compounds (B), the average molecular weight value of the compounds (B) is preferably within the above-mentioned range, and more preferably the molecular weight of each compound is within the above-mentioned preferred range.

In this embodiment, the boiling point of the compound (B) is preferably 110℃or higher, more preferably 115℃or higher, and still more preferably 120℃or higher. By setting the lower limit value or more, volatilization of the compound (B) at the time of thermosetting the resin composition can be suppressed, and the vinyl group of the polymer (a) having the structural unit represented by the formula (V) can be more effectively reacted with the compound (B). The boiling point of the compound (B) is preferably 300℃or lower, more preferably 250℃or lower, and still more preferably 200℃or lower. Setting the upper limit value or less makes it difficult for the solvent to remain in the cured product as a residual solvent.

When the resin composition of the present embodiment contains 2 or more compounds (B), the average boiling point value may fall within the above-mentioned range, and the boiling point of each compound is preferably within the above-mentioned preferred range.

The compound (B) may be exemplified by a (meth) acrylate compound, an aromatic vinyl compound (preferably a styrene compound), a saturated fatty acid vinyl ester compound, a vinyl cyanide compound, an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, an ethylenically unsaturated dicarboxylic acid monoalkyl ester, an ethylenically unsaturated carboxamide, a vinyl silane compound (e.g., a vinyltrialkoxysilane or the like), an acrylic silane compound (e.g., an acrylic trialkoxysilane or the like), a methacrylic silane compound (e.g., a methacrylic trialkoxysilane or the like), a styryl silane compound (e.g., a styryltrialkoxysilane or the like), or the like, and preferably at least 1 selected from the group consisting of (meth) acrylate compounds, aromatic vinyl compounds, saturated fatty acid vinyl ester compounds, vinyl silane compounds, acrylic silane compounds, methacrylic silane compounds, styryl silane compounds, and the like, and more preferably aromatic vinyl compounds and/or vinyl silane compounds.

Specific examples of the compound (B) include methylstyrene, ethylvinylbenzene, vinyltrimethoxysilane and vinyltriethoxysilane.

In the resin composition of the present embodiment, the content of the compound (B) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 2.5 parts by mass or more, based on 100 parts by mass of the resin solid content. When the lower limit is not less than the above-mentioned lower limit, unreacted functional groups in the obtained cured product tend to be reduced, and the moisture absorption heat resistance tends to be significantly improved. The upper limit of the content of the compound (B) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, and still more preferably 5 parts by mass or less, based on 100 parts by mass of the resin solid content. When the upper limit value is not more than the above, the low dielectric characteristics (Dk and/or Df) of the obtained cured product tend to be improved.

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

In the resin composition of the present embodiment, the mass ratio of the polymer (a) to the compound (B) is preferably 0.025 or more, more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.15 or more, and may be 0.2 or more, with respect to the polymer (a) 1. When the lower limit is set to the above lower limit or more, unreacted functional groups in the obtained cured product tend to be reduced, and moisture absorption and heat resistance tend to be improved greatly. The upper limit of the mass ratio of the polymer (a) to the compound (B) is preferably 0.7 or less, more preferably 0.5 or less, still more preferably 0.4 or less, still more preferably 0.3 or less, and may be 0.25 or less, relative to the polymer (a) 1. When the upper limit value is not more than the above, the low dielectric characteristics (Dk and/or Df) of the obtained cured product tend to be improved.

The resin composition in the present embodiment may have the following composition: a compound (B') which contains substantially no organic group having a molecular weight of less than 1000 and contains 2 or more structures of CH ₂ =c (X) - (X being a hydrogen atom or a methyl group) in the molecule. Specific examples of the compound (B') include aromatic divinyl compounds, particularly divinylbenzene. The substantial absence of the aforementioned compound (B ') means that the content of the aforementioned compound (B') is less than 1 part by mass, preferably less than 0.1 part by mass, more preferably less than 0.01 part by mass, and even more preferably less than 0.001 part by mass, relative to 100 parts by mass of the resin solid content in the resin composition.

< Other thermosetting Compound (C) >)

The resin composition of the present embodiment preferably further comprises a thermosetting compound (C) other than the polymer (a) and the compound (B). By including such components, other desired properties required of the printed circuit board can be more effectively exerted.

In particular, in the present embodiment, the weight average molecular weight of the other thermosetting compound (C) is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more. The upper limit of the weight average molecular weight of the other thermosetting compound (C) is preferably 5,000 or less, more preferably 4,000 or less. The equivalent weight of the functional group of the other thermosetting compound (C) is preferably 100g/eq. Or more, more preferably 150g/eq. Or more, and still more preferably 200g/eq. Or more. The upper limit of the equivalent weight of the functional group of the other thermosetting compound (C) is preferably 1,500g/eq. Or less, more preferably 1,300g/eq. Or less.

In this embodiment, in particular, it is preferable that the other thermosetting compound (C) satisfies the weight average molecular weight and the equivalent weight of the functional group. Such other thermosetting compound (C) tends to have a smaller weight average molecular weight than the polymer (A) having the structural unit represented by the formula (V), and the functional group concentration is higher, so that the crosslinking point is more increased, and the moisture absorption heat resistance of the obtained cured product can be more effectively improved.

In this embodiment, the other thermosetting compound (C) preferably contains at least 1 selected from the group consisting of a maleimide compound, a polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds, a cyanate ester compound, an epoxy compound, a phenol compound, an alkenyl-substituted nadimide compound, an oxetane resin, and a benzoxazine compound, and more preferably contains: the maleimide compound and/or the polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds further preferably contains at least 1 selected from the group consisting of the compound (M1) represented by the formula (M1), the compound represented by the formula (M3), the compound represented by the formula (M5), and the compound represented by the formula (OP-1), and further preferably contains at least 1 selected from the group consisting of the compound (M1) represented by the formula (M1), the compound represented by the formula (M3), and the compound represented by the formula (OP-1), and still further preferably contains the compound (M1) represented by the formula (M1) from the viewpoint of low dielectric characteristics.

/>

Maleimide compound

The resin composition of the present embodiment may contain a maleimide compound. The resin composition of the present embodiment is not particularly limited as long as it is a compound having 1 or more maleimide groups in 1 molecule (preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2), and a compound generally used in the field of printed wiring boards can be widely used.

In this embodiment, the compound represented by the formulae (M0) to (M5) is preferable, the compound represented by the formulae (M1) to (M4) is more preferable, the compound represented by the formulae (M1) and/or (M3) is more preferable, and the compound (M1) represented by the formula (M1) is more preferable. When these maleimide compounds are used for a material for a printed wiring board (for example, a metal foil-clad laminate), excellent heat resistance can be imparted. In particular, when the compound (M1) represented by the formula (M1) is used, low dielectric characteristics tend to be more effectively achieved.

(In the formula (M0), R ⁵¹ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, R ⁵² each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.)

R ⁵¹ is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or phenyl, more preferably one of a hydrogen atom and methyl, and still more preferably a hydrogen atom.

R ⁵² is preferably methyl.

N ₁ is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably an integer of 1 to 3, still more preferably 1 or 2, still more preferably 1.

The compound represented by the formula (M0) may be a mixture of 2 or more compounds other than 1. Examples of the mixture include a mixture of compounds having different n ₁ groups, a mixture of compounds having different types of substituents R ⁵¹ and/or R ⁵² groups, a mixture of compounds having different bonding positions (meta, para, ortho) of maleimide groups and oxygen atoms to the benzene ring, and a mixture of compounds having 2 or more of the foregoing different groups. The same applies to the compounds represented by the formulae (M1) to (M5).

/>

Wherein R ^M1、R^M2、R^M3 and R ^M4 each independently represent a hydrogen atom or an organic group. The organic group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group or a butyl group, and particularly preferably a methyl group. R ^M1 and R ^M3 are preferably each independently an alkyl group, and R ^M2 and R ^M4 are preferably hydrogen atoms.

R ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group or a butyl group, and particularly preferably a methyl group.

Ar ^M represents a 2-valent aromatic group, preferably phenylene, naphthalenediyl, phenanthrylene or anthracenediyl, more preferably phenylene, and still more preferably m-phenylene. Ar ^M may have a substituent, and as a substituent, an alkyl group is preferable, an alkyl group having 1 to 12 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, a methyl group, an ethyl group, a propyl group, a butyl group is more preferable, and a methyl group is particularly preferable. However, ar ^M is preferably unsubstituted.

A is an alicyclic group having 4 to 6 membered rings, more preferably a 5 membered alicyclic group (preferably a group which forms an indane ring together with a benzene ring). R ^M7 and R ^M8 are each independently an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group.

Mx is 1 or 2, preferably 2.

Lx is 0 or 1, preferably 1.

R ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group, more preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group or a butyl group, and particularly preferably a methyl group.

R ^M11、R^M12、R^M13 and R ^M14 each independently represent a hydrogen atom or an organic group. The organic group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group or a butyl group, and particularly preferably a methyl group. R ^M12 and R ^M13 are preferably each independently an alkyl group, and R ^M11 and R ^M14 are preferably hydrogen atoms.

R ^M15 independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 1 to 10 carbon atoms, an arylthio group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group, preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

Px represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

Nx is an integer of 1 to 20. nx may be an integer of 10 or less.

The resin composition of the present embodiment may contain only 1 kind of compound (M1) represented by the formula (M1) and at least 2 kinds or more of compounds having different values of nx. When 2 or more are contained, the average value (average number of repeating units) n of nx in the compound (M1) represented by the formula (M1) in the resin composition is preferably 0.92 or more, more preferably 0.95 or more, still more preferably 1.0 or more, still more preferably 1.1 or more, in order to obtain a low melting point (low softening point), low melt viscosity and excellent handleability. N is preferably 10.0 or less, more preferably 8.0 or less, still more preferably 7.0 or less, still more preferably 6.0 or less, and may be 5.0 or less. The same applies to the formula (M1-1) and the like described below.

The compound (M1) represented by the formula (M1) is preferably a compound represented by the following formula (M1-1).

( In the formula (M1-1), R ^M21、R^M22、R^M23 and R ^M24 each independently represent a hydrogen atom or an organic group. R ^M25 and R ^M26 each independently represent a hydrogen atom or an alkyl group. R ^M27、R^M28、R^M29 and R ^M30 each independently represent a hydrogen atom or an organic group. R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group. R ^M33、R^M34、R^M35 and R ^M36 each independently represent a hydrogen atom or an organic group. R ^M37、R^M38 and R ^M39 each independently represent a hydrogen atom or an alkyl group. nx is an integer of 1 to 20 inclusive. )

Wherein R ^M21、R^M22、R^M23 and R ^M24 each independently represent a hydrogen atom or an organic group. The organic group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. R ^M21 and R ^M23 are preferably alkyl groups, and R ^M22 and R ^M24 are preferably hydrogen atoms.

R ^M25 and R ^M26 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group or a butyl group, and particularly preferably a methyl group.

R ^M27、R^M28、R^M29 and R ^M30 each independently represent a hydrogen atom or an organic group, preferably a hydrogen atom. The organic group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group or a butyl group, and particularly preferably a methyl group.

R ^M33、R^M34、R^M35 and R ^M36 each independently represent a hydrogen atom or an organic group. The organic group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

R ^M33 and R ^M36 are preferably hydrogen atoms, and R ^M34 and R ^M35 are preferably alkyl groups.

R ^M37、R^M38、R^M39 each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group or a butyl group, and particularly preferably a methyl group.

Nx is an integer of 1 to 20 inclusive. nx may be an integer of 10 or less.

The compound represented by the formula (M1-1) is preferably a compound represented by the following formula (M1-2).

( In the formula (M1-2), R ^M21、R^M22、R^M23 and R ^M24 each independently represent a hydrogen atom or an organic group. R ^M25 and R ^M26 each independently represent a hydrogen atom or an alkyl group. R ^M27、R^M28、R^M29 and R ^M30 each independently represent a hydrogen atom or an organic group. R ^M31 and R ^M32 each independently represent a hydrogen atom or an alkyl group. R ^M33、R^M34、R^M35 and R ^M36 each independently represent a hydrogen atom or an organic group. R ^M37、R^M38 and R ^M39 each independently represent a hydrogen atom or an alkyl group. nx is an integer of 1 to 20 inclusive. )

,R^M21、R^M22、R^M23、R^M24、R^M25、R^M26、R^M27、R^M28、R^M29、R^M30、R^M31、R^M32、R^M33、R^M34、R^M35、R^M36、R^M37、R^M38、R^M39 And nx in the formula (M1-2) have the same meanings as R^M21、R^M22、R^M23、R^M24、R^M25、R^M26、R^M27、R^M28、R^M29、R^M30、R^M31、R^M32、R^M33、R^M34、R^M35、R^M36、R^M37、R^M38、R^M39 and nx in the formula (M1-1), and the preferable ranges are the same.

The compound represented by the formula (M1-1) is more preferably a compound represented by the following formula (M1-3), and still more preferably a compound represented by the following formula (M1-4).

(In the formula (M1-3), nx represents an integer of 1 to 20 inclusive.)

Nx may be an integer of 10 or less.

(In the formula (M1-4), nx represents an integer of 1 to 20 inclusive.)

The molecular weight of the compound (M1) represented by the formula (M1) is preferably 500 or more, more preferably 600 or more, and further preferably 700 or more. When the lower limit value is set to be equal to or larger than the above-mentioned lower limit value, the low dielectric characteristics and low water absorption properties of the obtained cured product tend to be improved. The molecular weight of the compound (M1) represented by the formula (M1) is preferably 10000 or less, more preferably 9000 or less, further preferably 7000 or less, further preferably 5000 or less, further preferably 4000 or less. When the upper limit value is not more than the above, the heat resistance and the handleability of the obtained cured product tend to be improved.

(In the formula (M2), R ⁵⁴ each independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more.)

N ₄ is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably an integer of 1 to 3, still more preferably 1 or 2.

R ⁵⁵ is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or phenyl, more preferably one of a hydrogen atom and methyl, and still more preferably a hydrogen atom.

N ₅ is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2.

(In the formula (M4), R ⁵⁶ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ⁵⁷ each independently represents a hydrogen atom or a methyl group.)

R ⁵⁸ is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or phenyl, more preferably one of a hydrogen atom and methyl, and still more preferably a hydrogen atom.

R ⁵⁹ is preferably methyl.

N ₆ is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably an integer of 1 to 3, still more preferably 1 or 2, and may be 1.

The compound represented by the formula (M5) may be a mixture of compounds having different n ₆, and is preferably a mixture. The compound represented by the formula (M0) may be a mixture of compounds having different portions as described in the above description.

The maleimide compound may be produced by a known method, or commercially available maleimide compounds may be used. As a commercially available product, for example, a compound represented by the formula (M0), the formula KI chemical Co., ltd. "BMI-80"; as the compound (M1) represented by the formula (M1), there may be mentioned "NE-X-9470S" manufactured by DIC Co., ltd; as the compound represented by the formula (M2), there may be mentioned "BMI-2300" manufactured by Daikovia chemical Co., ltd; as the compound represented by the formula (M3), there may be mentioned "MIR-3000-70MT" manufactured by Nippon Kagaku Co., ltd; as the compound represented by the formula (M4), there may be mentioned "BMI-70" manufactured by KI chemical Co., ltd; as the compound represented by the formula (M5), MIR-5000, manufactured by Japanese chemical Co., ltd.

Examples of maleimide compounds other than the above include N-phenylmaleimide, oligomers of phenylmethane maleimide, m-phenylene bismaleimide, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, 4-methyl-1, 3-phenylene bismaleimide, 1, 6-bismaleimide- (2, 4-trimethyl) hexane, 4 '-diphenyl ether bismaleimide, 4' -diphenyl sulfone bismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, prepolymers thereof, prepolymers of these maleimides and amines, and the like.

When the resin composition of the present embodiment contains a maleimide compound, the lower limit value of the content of the maleimide compound is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the maleimide compound is 1 part by mass or more, the flame resistance of the obtained cured product tends to be improved. The upper limit of the content of the maleimide compound is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and may be 40 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition. When the content of the maleimide compound is 70 parts by mass or less, the peel strength and low water absorption of the metal foil tend to be improved.

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

The resin composition of the present embodiment may be configured to contain substantially no maleimide compound, in particular, to contain substantially no monofunctional maleimide compound. Substantially not including means that the monofunctional maleimide compound and further the maleimide compound content is less than 1 part by mass, preferably less than 0.1 part by mass, more preferably less than 0.01 part by mass, relative to 100 parts by mass of the resin solid content in the resin composition. By containing substantially no monofunctional maleimide, the reaction between vinyl groups is preferentially performed as compared with the reaction between the maleimide group of the maleimide compound and the vinyl groups of the polymer (a) having a structural unit represented by the formula (V) or the inorganic filler (B), and a cured product having more excellent low dielectric characteristics tends to be obtained. In addition, if the reaction between vinyl groups is preferentially performed, the degree of curing after heating tends to be improved from the viewpoint of steric hindrance.

Polyphenylene ether Compound containing more than 2 carbon-carbon unsaturated double bonds

The resin composition of the present embodiment may contain a polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds.

The polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds is preferably a polyphenylene ether compound having 2 or more groups selected from the group consisting of a (meth) acrylic group, a maleimide group, and a vinylbenzyl group at the terminal. By using these polyphenylene ether compounds, dielectric characteristics of printed wiring boards and the like tend to be improved more effectively, such as low water absorption.

Details thereof are described below.

Examples of the polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds include compounds having a phenylene ether skeleton represented by the following formula (X1).

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

The polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds may further contain a repeating unit represented by the formula (X2) and/or a repeating unit represented by the formula (X3):

( In the formula (X2), R ²⁸、R²⁹、R³⁰、R³⁴ and R ³⁵ may be the same or different and each represents an alkyl group having 6 or less carbon atoms or a phenyl group. R ³¹、R³² and R ³³ may be the same or different and each is a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. )

( In the formula (X3), R ³⁶、R³⁷、R³⁸、R³⁹、R⁴⁰、R⁴¹、R⁴² and R ⁴³ may be the same or different and each represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A-is a straight-chain, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms. )

The polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds is preferably a modified polyphenylene ether compound obtained by functionalizing a part or the whole of the terminal with an ethylenically unsaturated group (hereinafter, sometimes referred to as "modified polyphenylene ether compound (g)"), more preferably a modified polyphenylene ether compound having 2 or more groups selected from the group consisting of (meth) acrylic groups, maleimide groups, and vinylbenzyl groups at the terminal. By using such a modified polyphenylene ether compound (g), the dielectric loss tangent (Df) of the cured product of the resin composition can be made smaller, and the low water absorption property and the peel strength of the metal foil can be improved. These may be used in combination of 1 or more than 2.

The modified polyphenylene ether compound (g) is a compound represented by the formula (OP-1).

In the case where n ₂ is an integer of 2 or more, and n ₃,n₂ structural units (Y-O) and/or n ₃ structural units may be the same or different. n ₃ is preferably 2.

The modified polyphenylene ether compound (g) of the present embodiment is preferably a compound represented by the formula (OP-2).

Here, - (O-X-O) -is preferably represented by the formula (OP-3) and/or the formula (OP-4):

( In the formula (OP-3), R ⁴、R⁵、R⁶、R¹⁰ and R ¹¹ may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group. R ⁷、R⁸ and R ⁹ may be the same or different and each is a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. )

( In the formula (OP-4), R ¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸ and R ¹⁹ may be the same or different and each represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A-is a straight-chain, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms. )

In addition, - (Y-O) -is preferably represented by the formula (OP-5):

( In the formula (OP-5), R ²⁰、R²¹ may be the same or different and is an alkyl group having 6 or less carbon atoms or a phenyl group. R ²²、R²³ may be the same or different and is a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. )

In the formula (OP-2), at least one of a and b is not 0 and represents an integer of 0 to 100, preferably an integer of 0 to 50, and more preferably an integer of 1 to 30. When a and/or b are integers of 2 or more, 2 or more- (Y-O) -groups may be each independently arranged in 1 structure, or may be arranged in 2 or more structure blocks or randomly.

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

Among the above-mentioned modified polyphenylene ether compounds (g), polyphenylene ether compounds in which R ⁴、R⁵、R⁶、R¹⁰、R¹¹、R²⁰ and R ²¹ are alkyl groups having 3 or less carbon atoms and R⁷、R⁸、R⁹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²² and R ²³ are hydrogen atoms or alkyl groups having 3 or less carbon atoms are preferable, in particular, it is preferable that- (O-X-O) -represented by the formula (OP-3) or the formula (OP-4) is represented by the formula (OP-9), the formula (OP-10), and/or the formula (OP-11), and- (Y-O) -represented by the formula (OP-5) is the formula (OP-12) or the formula (OP-13). When a and/or b are integers of 2 or more, 2 or more- (Y-O) -may each independently have a structure in which 2 or more formulae (OP-12) and/or (OP-13) are arranged, or a structure in which formulae (OP-12) and (OP-13) are block-or randomly arranged.

( In the formula (OP-10), R ⁴⁴、R⁴⁵、R⁴⁶ and R ⁴⁷ may be the same or different and are a hydrogen atom or a methyl group. -B-is a straight, branched or cyclic 2-valent hydrocarbon group having 20 or less carbon atoms. )

As the specific example of-B-is mentioned the same one as the specific example of-A-in the formula (OP-4).

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

/>

In addition, details of the polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds can be found in Japanese patent application laid-open No. 2018-016709, the contents of which are incorporated herein by reference.

The number average molecular weight of the polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds (preferably the modified polyphenylene ether compound (g)) in terms of polystyrene by GPC (gel permeation chromatography) is preferably 500 or more and 3,000 or less. When the number average molecular weight is 500 or more, tackiness tends to be further suppressed when the resin composition of the present embodiment is formed into a film. When the number average molecular weight is 3,000 or less, the solubility in a solvent tends to be improved.

The weight average molecular weight of the polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds (preferably the modified polyphenylene ether compound (g)) in terms of polystyrene by GPC is preferably 800 or more and 10,000 or less, more preferably 800 or more and 5,000 or less. When the lower limit value is set to be equal to or higher than the upper limit value, the relative permittivity (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower, and when the lower limit value is set to be equal to or lower than the upper limit value, the solubility in a solvent, low viscosity and moldability of the resin composition tend to be improved even more in the production of a varnish or the like described later.

Further, in the case of the modified polyphenylene ether compound (g), the equivalent weight of the terminal carbon-carbon unsaturated double bond is preferably 400 to 5000g, more preferably 400 to 2500g, per 1 carbon-carbon unsaturated double bond. When the lower limit value is set to be equal to or higher than the above-mentioned lower limit value, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be low. When the upper limit value is less than or equal to the above, the solubility in a solvent, low viscosity and moldability of the resin composition tend to be improved.

When the resin composition of the present embodiment contains a polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds, the lower limit value of the content of the polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, still more preferably 7 parts by mass or more, and still more preferably 10 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. When the lower limit value is set to be equal to or larger than the above-mentioned lower limit value, the low water absorption and low dielectric properties (Dk and/or Df) of the obtained cured product tend to be improved. The upper limit of the content of the polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, still more preferably 25 parts by mass or less, and may be 20 parts by mass or less, based on 100 parts by mass of the solid resin component in the resin composition. When the upper limit value is less than or equal to the above, the heat resistance and chemical resistance of the obtained cured product tend to be improved.

The resin composition in this embodiment may contain only 1 type of polyphenylene ether compound having 2 or more carbon-carbon unsaturated double bonds, or may contain 2 or more types of polyphenylene ether compounds. When the content is 2 or more, the total amount is preferably within the above range.

Cyanate ester compound

The resin composition of the present embodiment may contain a cyanate ester compound.

The cyanate ester compound is not particularly limited as long as it contains 1 or more cyanate ester groups (cyanate groups) (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) in 1 molecule, and compounds generally used in the field of printed wiring boards can be widely used. The cyanate ester compound is preferably a compound in which a cyanate ester group is directly bonded to an aromatic skeleton (aromatic ring).

The cyanate ester compound includes at least 1 selected from the group consisting of phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds (naphthol aralkyl type cyanate esters), naphthylene ether type cyanate ester compounds, biphenyl aralkyl type cyanate ester compounds, xylene resin type cyanate ester compounds, triphenol methane type cyanate ester compounds, adamantane skeleton type cyanate ester compounds, bisphenol M type cyanate ester compounds, bisphenol a type cyanate ester compounds, and diallyl bisphenol a type cyanate ester compounds. Among them, from the viewpoint of improving the low water absorbability of the obtained cured product, at least 1 selected from the group consisting of phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, xylene resin type cyanate ester compounds, bisphenol M type cyanate ester compounds, bisphenol a type cyanate ester compounds, and diallyl bisphenol a type cyanate ester compounds are preferable, at least 1 selected from the group consisting of phenol novolac type cyanate ester compounds, and naphthol aralkyl type cyanate ester compounds are more preferable, and naphthol aralkyl type cyanate ester compounds are still more preferable. These cyanate ester compounds can be prepared by a known method, and commercially available products can be used. Since the cyanate ester compound having a naphthol aralkyl skeleton, a naphthylene ether skeleton, a xylene skeleton, a triphenol methane skeleton, or an adamantane skeleton has a large equivalent number of functional groups, the number of unreacted cyanate ester groups decreases, and thus the cured product of a resin composition using them tends to be more excellent in low water absorption. In addition, since the coating composition has mainly an aromatic skeleton or an adamantane skeleton, the coating adhesion tends to be further improved.

The naphthol aralkyl type cyanate ester compound is more preferably a compound represented by the following formula (1).

(In the formula (1), R ³ each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.)

In the formula (1), R ³ each independently represents a hydrogen atom or a methyl group, among which a hydrogen atom is preferable.

In the formula (1), n3 is an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and still more preferably an integer of 1 to 6.

The novolak type cyanate ester compound is not particularly limited, and is preferably a compound represented by the following formula (VII), for example.

(In the formula (VII), R ⁶ each independently represents a hydrogen atom or a methyl group, and n7 represents an integer of 1 or more.)

In the formula (VII), R ⁶ each independently represents a hydrogen atom or a methyl group, among which a hydrogen atom is preferable.

In the formula (VII), n7 is an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and still more preferably an integer of 1 to 6.

As the bisphenol a type cyanate ester compound, 1 or more selected from the group consisting of 2, 2-bis (4-cyanooxyphenyl) propane and prepolymers of 2, 2-bis (4-cyanooxyphenyl) propane can be used.

The resin composition of the present embodiment preferably contains a cyanate ester compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a cyanate ester compound, the lower limit value of the content thereof is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, and even more preferably 0.5 part by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the cyanate ester compound is 0.1 part by mass or more, the heat resistance, the flame resistance, the chemical resistance, the low relative permittivity, the low dielectric loss tangent, and the insulation properties of the obtained cured product tend to be improved. When the resin composition of the present embodiment contains a cyanate ester compound, the upper limit value of the content of the cyanate ester compound is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, or may be 10 parts by mass or less, or 5 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.

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

Epoxy compound

The resin composition of the present embodiment may contain an epoxy compound.

The epoxy compound is not particularly limited as long as it is a compound or resin having 1 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) epoxy groups in 1 molecule, and a compound generally used in the field of printed wiring boards can be widely used.

Examples of the epoxy compound include bisphenol a type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol a novolac type epoxy resin, glycidyl ester type epoxy resin, aralkyl novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene ether type epoxy resin, cresol novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyhydric alcohol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidylester, a compound obtained by epoxidation of a double bond of butadiene or the like, a compound obtained by reaction of a hydroxyl-containing silicone resin with epichlorohydrin, and the like. By using these, moldability and adhesion of the resin composition are improved. Among them, from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resins, naphthalene ether type epoxy resins, polyfunctional phenol type epoxy resins, naphthalene type epoxy resins are preferable, and biphenyl aralkyl type epoxy resins are more preferable.

The resin composition of the present embodiment preferably contains an epoxy compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains an epoxy compound, the content thereof is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the epoxy compound is 0.1 part by mass or more, the peel strength and toughness of the metal foil tend to be improved. When the resin composition of the present embodiment contains an epoxy compound, the upper limit value of the content of the epoxy compound is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, further preferably 8 parts by mass or less, further still further preferably 5 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the epoxy compound is 50 parts by mass or less, the electrical characteristics of the obtained cured product tend to be improved.

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

The resin composition in the present embodiment may be a composition substantially containing no epoxy compound. Substantially not including means that the content of the epoxy compound is less than 0.1 part by mass, preferably less than 0.01 part by mass, and further, may be less than 0.001 part by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

Phenol compound

The resin composition of the present embodiment may contain a phenol compound.

The phenol compound is not particularly limited as long as it is a phenol compound containing 1 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) phenolic hydroxyl groups in1 molecule, and a compound generally used in the field of printed wiring boards can be widely used.

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

The resin composition of the present embodiment preferably contains a phenol compound in a range that does not impair the effects of the present invention. When the phenol compound is contained in the resin composition of the present embodiment, the content thereof is preferably 0.1 part by mass or more and further preferably 50 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition.

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

The resin composition in the present embodiment may be a composition substantially free of phenol compounds. Substantially not including means that the content of the phenol compound is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

Alkenyl substituted nadic imide compounds

The alkenyl-substituted nadic imide compound is not particularly limited as long as it is a compound having 1 or more alkenyl-substituted nadic imide groups in the molecule. Among them, preferred is a compound represented by the formula (AN-1). By using such an alkenyl-substituted nadic imide compound, the thermal expansion coefficient of the obtained cured product tends to be further reduced, and the heat resistance tends to be further improved.

(In the formula (AN-1), R ₁ independently represents a hydrogen atom or AN alkyl group having 1 to 6 carbon atoms, R ₂ represents AN alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, a group represented by the formula (AN-2), or a group represented by the formula (AN-3))

(In the formula (AN-2), R ₃ represents methylene, isopropylidene, -C (=O) -, -O-, -S-, or-S (=O) ₂ -)

(In the formula (AN-3), R ₄ each independently represents AN alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

Among the compounds represented by the formula (AN-1), the compounds represented by the formula (AN-4) and the compounds represented by the formula (AN-5) are preferable. By using such an alkenyl-substituted nadic imide compound, the thermal expansion coefficient of the obtained cured product tends to be further reduced, and the heat resistance tends to be further improved.

In addition, commercially available products can be used as the alkenyl-substituted nadic imide compound. Examples of the commercial products include, but are not limited to, BANI-M (a compound represented by formula (AN-4) manufactured by Wash petro-chemical Co., ltd.), BANI-X (a compound represented by formula (AN-5) manufactured by Wash petro-chemical Co., ltd.), and the like.

The resin composition of the present embodiment preferably contains an alkenyl-substituted nadic imide compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains an alkenyl-substituted nadic imide compound, the content thereof is preferably 0.1 part by mass or more and preferably 50 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

The resin composition in this embodiment may contain only 1 kind of alkenyl-substituted nadic imide compound, or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.

The resin composition in the present embodiment may be a composition substantially free of an alkenyl-substituted nadic imide compound. Substantially not including means that the content of the alkenyl-substituted nadic imide compound is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

Oxetane resins

The resin composition of the present embodiment may contain an oxetane resin.

The oxetane resin is not particularly limited as long as it is a compound having 1 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) oxetanyl groups, and compounds generally used in the field of printed wiring boards can be widely used.

Examples of the oxetane resin include: oxetane, alkyl oxetanes (e.g., 2-methyl oxetane, 2-dimethyl oxetane, 3-methyl oxetane, 3-dimethyl oxetane, etc.), 3-methyl-3-methoxymethyl oxetane, 3-bis (trifluoromethyl) oxetane, 2-chloromethyloxetane, 3-bis (chloromethyl) oxetane, biphenyl oxetane, OXT-101 (manufactured by east Asia Synthesis Co., ltd.), OXT-121 (manufactured by east Asia Synthesis Co., ltd.), etc.

The resin composition of the present embodiment preferably contains an oxetane resin within a range that does not impair the effects of the present invention. When the oxetane resin is contained in the resin composition of the present embodiment, the content thereof is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition. When the content of the oxetane resin is 0.1 part by mass or more, the peel strength and toughness of the metal foil tend to be improved. When the resin composition of the present embodiment contains an oxetane resin, the upper limit value of the content of the oxetane resin is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, still further preferably 8 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. When the content of the oxetane resin is 50 parts by mass or less, the electrical characteristics of the obtained cured product tend to be improved.

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

The resin composition in the present embodiment may be a composition substantially containing no oxetane resin. Substantially not including means that the content of the oxetane resin is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

Benzoxazine compound

The resin composition of the present embodiment may contain a benzoxazine compound.

The benzoxazine compound is not particularly limited as long as it is a compound having 2 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) dihydrobenzoxazine rings in 1 molecule, and a compound generally used in the field of printed circuit boards can be widely used.

Examples of the benzoxazine compound include: bisphenol A-type benzoxazine BA-BXZ (manufactured by Xiao xi chemical Co., ltd.), bisphenol F-type benzoxazine BF-BXZ (manufactured by Xiao xi chemical Co., ltd.), bisphenol S-type benzoxazine BS-BXZ (manufactured by Xiao xi chemical Co., ltd.), and the like.

The resin composition of the present embodiment preferably contains a benzoxazine compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a benzoxazine compound, the content thereof is preferably 0.1 parts by mass or more, and preferably 50 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition.

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

The resin composition in the present embodiment may be a composition substantially containing no benzoxazine compound. Substantially not including means that the content of the benzoxazine compound is less than 0.1 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

When the resin composition of the present embodiment contains the thermosetting compound (C), the content (total amount) thereof is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, relative to 100 parts by mass of the resin solid content. When the lower limit value is set to be equal to or larger than the above-mentioned lower limit value, heat resistance, plating adhesion, low thermal expansion and the like tend to be more improved. The upper limit of the content of the thermosetting compound (C) is preferably 95 parts by mass or less, more preferably 85 parts by mass or less, still more preferably 75 parts by mass or less, still more preferably 65 parts by mass or less, still more preferably 50 parts by mass or less, based on 100 parts by mass of the resin solid content. When the upper limit value is less than or equal to the above-mentioned upper limit value, the low dielectric characteristics and the low water absorption tend to be improved.

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

Filling material (D) >, and

The resin composition of the present embodiment preferably contains a filler (D). By including the filler (D), the resin composition and its cured product can be further improved in properties such as dielectric characteristics (low dielectric constant, low dielectric loss tangent, etc.), flame resistance, and low thermal expansion.

The filler (D) used in the present embodiment is more preferably excellent in low dielectric characteristics. For example, the filler (D) used in the present embodiment preferably has a relative dielectric constant (Dk) of 8.0 or less, more preferably 6.0 or less, and even more preferably 4.0 or less, as measured by the cavity perturbation method. It is practical that the lower limit value of the relative dielectric constant is 2.0 or more, for example. The dielectric loss tangent (Df) of the filler (D) used in the present embodiment, as measured by the cavity disturbance method, is preferably 0.05 or less, and more preferably 0.01 or less. It is practical that the lower limit value of the dielectric loss tangent is, for example, 0.0001 or more.

The type of the filler (D) used in the present embodiment is not particularly limited, and a filler generally used in the technical field can be suitably used. Specifically, examples thereof include silica types such as natural silica, fused silica, synthetic silica, amorphous silica, AEROSIL, and hollow silica; metal oxides such as alumina, white carbon, titanium white, titanium oxide, zinc oxide, magnesium oxide, and zirconium oxide; composite oxides such as zinc borate, zinc stannate, forsterite, barium titanate, strontium titanate, and calcium titanate; nitrides such as boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride; aluminum hydroxide, aluminum hydroxide heat-treated products (products obtained by heat-treating aluminum hydroxide to reduce a part of crystal water), metal hydroxides (including hydrates) such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; inorganic fillers such as barium sulfate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including glass fine powders such as E glass, T glass, D glass, S glass, Q glass, etc.), hollow glass, and spherical glass; rubber powders of styrene type, butadiene type, acrylic type and the like, core-shell rubber powders, silicone resin powders, silicone rubber powders, silicone composite powders and the like.

In this embodiment, the inorganic filler is preferably 1 or more selected from the group consisting of silica, aluminum hydroxide, aluminum nitride, boron nitride, forsterite, titanium oxide, barium titanate, strontium titanate, and calcium titanate, more preferably 1 or more selected from the group consisting of silica and aluminum hydroxide, and even more preferably silica, from the viewpoint of low dielectric characteristics. By using these inorganic fillers, the heat resistance, dielectric characteristics, thermal expansion characteristics, dimensional stability, flame retardancy and the like of the cured product of the resin composition are further improved.

The content of the filler (D) in the resin composition of the present embodiment is not particularly limited, and is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 40 parts by mass or more, still more preferably 60 parts by mass or more, and still more preferably 80 parts by mass or more, based on 100 parts by mass of the resin solid content in the resin composition, which can be appropriately set according to the desired characteristics. When the lower limit value is set to be equal to or larger than the above-mentioned lower limit value, low thermal expansion and low dielectric loss tangent tend to be improved. The upper limit of the content of the filler (D) is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, still more preferably 200 parts by mass or less, still more preferably 150 parts by mass or less, and still more preferably 120 parts by mass or less, based on 100 parts by mass of the resin solid content. When the upper limit value is set to be equal to or less than the above-described upper limit value, moldability tends to be improved.

In the resin composition of the present embodiment, as an example of a preferred embodiment, a mode in which the content of the filler (D) is 30 to 80% by mass of the component from which the solvent is removed is exemplified.

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

In the resin composition of the present embodiment, when the filler (D), in particular, the inorganic filler is used, a silane coupling agent may be further contained. By including the silane coupling agent, dispersibility of the filler (D) and adhesive strength between the resin component and the filler (D) and between the resin component and a substrate to be described later tend to be improved.

The silane coupling agent is not particularly limited, and examples thereof include an aminosilane compound (for example, γ -aminopropyl triethoxysilane, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, etc.), an epoxysilane compound (for example, γ -glycidoxypropyl trimethoxysilane, etc.), a vinylsilane compound (for example, vinyltrimethoxysilane, etc.), a styrylsilane compound, an acrylic silane compound (for example, γ -acryloxypropyl trimethoxysilane, etc.), a cationic silane compound (for example, N- β - (N-vinylbenzyl aminoethyl) - γ -aminopropyl trimethoxysilane hydrochloride, etc.), and a phenylsilane compound. The silane coupling agent is used alone or in combination of 2 or more.

The content of the silane coupling agent is not particularly limited, and may be 0.1 to 5.0 parts by mass per 100 parts by mass of the resin solid component.

Elastomer >

The resin composition of the present embodiment may contain an elastomer.

In the present embodiment, the elastomer is not particularly limited, and at least 1 selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, fluororubber, silicone rubber, hydrogen compounds thereof, alkyl compounds thereof, and copolymers thereof may be used.

The thermoplastic elastomer may be a thermoplastic elastomer or a thermosetting elastomer, but is preferably a thermoplastic elastomer.

The number average molecular weight of the elastomer used in the present embodiment is preferably 5 ten thousand or more. When the number average molecular weight is 5 ten thousand or more, the low dielectric properties of the obtained cured product tend to be more excellent. The number average molecular weight is preferably 6 ten thousand or more, more preferably 7 ten thousand or more, and still more preferably 8 ten thousand or more. The upper limit of the number average molecular weight of the thermal elastomer is preferably 40 ten thousand or less, more preferably 35 ten thousand or less, and still more preferably 30 ten thousand or less. When the upper limit value is not more than the above, the solubility of the elastomer component in the resin composition tends to be improved.

When the resin composition of the present embodiment contains 2 or more kinds of elastomers, the number average molecular weight of the mixture thereof preferably satisfies the above range.

In the present embodiment, the elastomer is preferably a thermoplastic elastomer (hereinafter referred to as "thermoplastic elastomer (E)") containing a styrene monomer unit and a conjugated diene monomer unit. By using such a thermoplastic elastomer (E), the low dielectric characteristics of the obtained cured product are more excellent.

The thermoplastic elastomer (E) contains styrene monomer units. By containing a styrene monomer unit, the solubility of the thermoplastic elastomer (E) in the resin composition is improved. Examples of the styrene monomer include styrene, α -methylstyrene, p-methylstyrene, divinylbenzene (vinyl styrene), N-dimethyl-p-aminoethyl styrene, N-diethyl-p-aminoethyl styrene, and the like, and among these, 1 or more selected from the group consisting of styrene, α -methylstyrene, and p-methylstyrene are preferable from the viewpoint of availability and productivity. Among them, styrene is particularly preferable.

The content of the styrene monomer unit in the thermoplastic elastomer (E) is preferably in the range of 10 to 50% by mass, more preferably in the range of 13 to 45% by mass, and even more preferably in the range of 15 to 40% by mass of the total monomer units. When the content of the styrene monomer unit is 50 mass% or less, the adhesion to a substrate or the like and the adhesiveness are improved. In addition, if the content is 10 mass% or more, the adhesion is preferably suppressed from being too strong, the generation of residual glue and stay marks is less likely to occur, and the easy peeling between the adhesion surfaces is likely to be good.

The thermoplastic elastomer (E) may contain only 1 kind of styrene monomer unit or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.

The method for measuring the content of the styrene monomer unit in the thermoplastic elastomer (E) can be described in International publication No. 2017/126469, the contents of which are incorporated herein by reference. The same applies to conjugated diene monomer units and the like described later.

The thermoplastic elastomer (E) contains conjugated diene monomer units. By containing conjugated diene monomer units, the solubility of the thermoplastic elastomer (E) in the resin composition is improved. The conjugated diene monomer is not particularly limited as long as it is a diene having 1 pair of conjugated double bonds. Examples of the conjugated diene monomer include 1, 3-butadiene, 2-methyl-1, 3-butadiene (isoprene), 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, 2-methyl-1, 3-pentadiene, 1, 3-hexadiene, and farnesene, preferably 1, 3-butadiene, and/or isoprene, and more preferably 1, 3-butadiene.

The thermoplastic elastomer (E) may contain only 1 conjugated diene monomer unit or may contain 2 or more.

In the thermoplastic elastomer (E), the mass ratio of the styrene monomer unit to the conjugated diene monomer unit is preferably in the range of styrene monomer unit/conjugated diene monomer unit=5/95 to 80/20, more preferably in the range of 7/93 to 77/23, and still more preferably in the range of 10/90 to 70/30. When the mass ratio of the styrene monomer unit to the conjugated diene monomer unit is in the range of 5/95 to 80/20, the adhesion is suppressed from becoming too strong and the high adhesive force is maintained. The peelability between the adhesive faces becomes good.

In the thermoplastic elastomer (E), all or a part of the conjugated diene bond of the thermoplastic elastomer may be hydrogenated, or may be unhydrogenated.

The thermoplastic elastomer (E) may contain other monomer units in addition to the styrene monomer unit and the conjugated diene monomer unit, or may not contain other monomer units. Examples of the other monomer units include aromatic vinyl compound units other than styrene monomer units.

In the thermoplastic elastomer (E), the total of the styrene monomer units and the conjugated diene monomer units is preferably 90 mass% or more, more preferably 95 mass% or more, still more preferably 97 mass% or more, and still more preferably 99 mass% or more of the total monomer units.

The thermoplastic elastomer (E) may contain only 1 kind of styrene monomer unit and conjugated diene monomer unit, or may contain 2 or more kinds of styrene monomer units. When the content is 2 or more, the total amount is preferably within the above range.

The thermoplastic elastomer (E) may be a block polymer or a random polymer. The hydrogenated elastomer may be one in which the conjugated diene monomer units are hydrogenated, one in which the conjugated diene monomer units are not hydrogenated, or one in which the conjugated diene monomer units are partially hydrogenated.

In one embodiment of the present embodiment, the thermoplastic elastomer (E) is a hydrogenated elastomer. Here, the hydrogenated elastomer refers to, for example, an elastomer in which double bonds of a conjugated diene monomer unit are hydrogenated in a thermoplastic elastomer, and includes 80% or more of an elastomer in addition to an elastomer having a hydrogenation rate (Hydrogenation rate) of 100%. The hydrogenation rate of the hydrogenated elastomer is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. In this embodiment, the hydrogenation rate is calculated from the result of ¹ H-NMR spectroscopy.

In one embodiment of the present embodiment, the thermoplastic elastomer (E) is an unhydrogenated elastomer. The unhydrogenated elastomer means an elastomer having a hydrogenation ratio (Hydrogenation rate) of 20% or less, which is a ratio of hydrogenated double bonds based on conjugated diene monomer units in the elastomer. The hydrogenation rate of the unhydrogenated elastomer is preferably 15% or less, more preferably 10% or less, and still more preferably 5% or less.

On the other hand, a partially hydrogenated elastomer means an elastomer in which a part of double bonds based on conjugated diene monomer units in a thermoplastic elastomer is hydrogenated, and generally means that the hydrogenation ratio (Hydrogenation rate) is less than 80% and more than 20%.

Examples of the commercial products of the thermoplastic elastomer (E) used in the present embodiment include SEPTON (registered trademark) 2104 manufactured by colali corporation, s.o.e. (registered trademark) S1606, S1613, S1609, S1605 manufactured by asahi chemical corporation, DYNARON (registered trademark) 9901P, TR2250 manufactured by JSR corporation, and the like.

When the resin composition of the present embodiment contains an elastomer (preferably, the thermoplastic elastomer (E)), the content thereof is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, relative to 100 parts by mass of the resin solid content. When the lower limit value is not less than the above-mentioned lower limit value, the low dielectric characteristics tend to be improved. The upper limit of the content of the elastomer is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, further preferably 35 parts by mass or less, further preferably 32 parts by mass or less, further preferably 28 parts by mass or less, based on 100 parts by mass of the solid content of the resin. When the temperature is not higher than the upper limit, the heat resistance tends to be improved.

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

< Active ester Compounds >

The resin composition of the present embodiment may contain an active ester compound.

The active ester compound is not particularly limited, and examples thereof include compounds having 2 or more (preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 or 3, still more preferably 2) active ester groups in 1 molecule.

The active ester compound may be a linear or branched or cyclic compound. Among them, from the viewpoint of further improving the heat resistance of the obtained cured product, an active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound is preferable, an active ester compound obtained by reacting a carboxylic acid compound with 1 or more compounds selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferable, an aromatic compound having 2 or more active ester groups in 1 molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is more preferable, and an aromatic compound having 2 or more active ester groups in 1 molecule obtained by reacting a compound having 2 or more carboxylic acids in 1 molecule with an aromatic compound having a phenolic hydroxyl group is particularly preferable.

The carboxylic acid compound is preferably 1 or more selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid, and among these, 1 or more selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid is more preferably 1 or more selected from the group consisting of isophthalic acid and terephthalic acid, from the viewpoint of improving the heat resistance of the obtained cured product.

The thiocarboxylic acid compound is 1 or more selected from thioacetic acid and thiobenzoic acid.

Examples of the phenol compound or naphthol compound include at least 1 selected from the group consisting of hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene diphenol, and phenol novolac, and from the viewpoint of further improving the heat resistance and solvent solubility of the obtained cured product, preferably bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, alpha-naphthol, beta-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene-based diphenol, phenol novolak, more preferably 1 or more selected from the group consisting of catechol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene-based diphenol, and phenol novolak, still more preferably 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-based diphenol, and 1 or more selected from the group consisting of phenol novolacs, particularly preferably 1 or more selected from the group consisting of dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene diphenol, and phenol novolacs (preferably 1 or more selected from the group consisting of dicyclopentadiene diphenol and phenol novolacs, more preferably dicyclopentadiene diphenol).

The thiol compound may be 1 or more selected from the group consisting of a benzenedithiol and a triazinedichiol.

The active ester compound is preferably a compound having 2 or more carboxylic acids in 1 molecule and containing an aliphatic chain, from the viewpoint of improving the compatibility with the epoxy compound, and is preferably a compound having an aromatic ring from the viewpoint of improving the heat resistance. More specific examples of the active ester compound include the active ester compounds described in JP-A-2004-277460.

The active ester compound may be prepared by a known method, using commercially available products. Examples of the commercial products include compounds having a dicyclopentadiene-based diphenol structure (for example, EXB9451, EXB9460S, HPC-8000-65T (both manufactured by DIC Co.), and the like), an acetyl compound of a phenol novolac (for example, DC808 (manufactured by Mitsubishi chemical Co.), and a benzoyl compound of a phenol novolac (for example, YLH1026, YLH1030, YLH1048 (both manufactured by Mitsubishi chemical Co.), and EXB9460S is preferable from the viewpoint of further improving the storage stability of the varnish and the low thermal expansion property at the time of curing the resin composition (cured product).

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

The active ester compound is preferably contained within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains an active ester compound, the resin composition is preferably 1 part by mass or more and preferably 90 parts by mass or less based on 100 parts by mass of the resin solid content in the resin composition.

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

The resin composition in the present embodiment may be a composition substantially containing no active ester compound. Substantially not including means that the content of the active ester compound is less than 1 part by mass, preferably less than 0.1 part by mass, and more preferably less than 0.01 part by mass, relative to 100 parts by mass of the resin solid content in the resin composition.

< Flame retardant >)

The resin composition of the present embodiment may contain a flame retardant. Examples of the flame retardant include phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, and silicone flame retardants, and phosphorus flame retardants are preferable.

Examples of the flame retardant include known flame retardants, such as brominated epoxy resins, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol a, pentabromobenzyl (meth) acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1, 2-pentabromophenyl ethane, chlorinated polystyrene, and chlorinated paraffin; phosphorus flame retardants such as red phosphorus, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tri (xylyl) phosphate, trialkyl phosphate, dialkyl phosphate, tri (chloroethyl) phosphate, phosphazene, bis (2, 6-di (xylyl) 1, 3-phenylene phosphate, and 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, partial boehmite, zinc borate, and antimony trioxide; silicone flame retardants such as silicone rubber and silicone resin.

In this embodiment, among these compounds, bis (2, 6-di (xylyl)) 1, 3-phenylene phosphate is preferable because it does not impair low dielectric characteristics.

When the resin composition of the present embodiment contains a flame retardant, the content thereof is preferably 1 part by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. The lower limit of the content of the flame retardant is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.

The flame retardant may be used alone in an amount of 1 or in a combination of 2 or more. When 2 or more kinds are used, the total amount is within the above range.

< Dispersant >)

The resin composition of the present embodiment may contain a dispersant. As the dispersant, a dispersant which is generally used for paint applications can be suitably used, and the kind thereof is not particularly limited. As the dispersant, a wet dispersant of a copolymer base is preferably used, and specific examples thereof include DISPERBYK (registered trademark) -110, 111, 161, 180, 2009, 2152, 2155, BYK (registered trademark) -W996, W9010, W903, W940, and the like, manufactured by BYK Japan corporation.

When the resin composition of the present embodiment contains a dispersant, the lower limit value of the content thereof is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and may be 0.3 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. The upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition.

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

< Curing accelerator >)

The resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include imidazoles such as 2-ethyl-4-methylimidazole and triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, and di-tert-butyl di-peroxyphthalate; azo compounds such as azobisisobutyronitrile; tertiary amines such as N, N-dimethylbenzylamine, N-dimethylaniline, N-dimethylbenzylamine, 2-N-ethylphenylaminoethanol, tri-N-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, catechol, and the like; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, manganese octoate, tin oleate, dibutyl tin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetonate; a substance obtained by dissolving these organic metal salts in a hydroxyl group-containing compound such as phenol or bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; organotin compounds such as dioctyltin oxide, other alkyltin, and alkyltin oxide.

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

The resin composition of the present embodiment may be configured to contain substantially no organic peroxide (for example, an organic peroxide having a molecular weight of 30 to 500). Substantially not included means that the amount of the resin is less than 0.1 parts by mass, preferably 0.01 parts by mass or less based on 100 parts by mass of the resin solid content contained in the resin composition of the present embodiment. By setting the range as described above, various cured products having more excellent properties can be obtained.

The resin composition of the present embodiment may be configured to substantially not include an azo compound (for example, an azo compound having a molecular weight of 30 to 500). Substantially not included means that the amount of the resin is less than 0.1 parts by mass, preferably 0.01 parts by mass or less based on 100 parts by mass of the resin solid content contained in the resin composition of the present embodiment. By setting the range as described above, various cured products having more excellent properties can be obtained.

When the resin composition of the present embodiment contains a curing accelerator, the lower limit value of the content thereof is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. The upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition.

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

< Solvent >

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

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

< Other Components >)

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

The resin composition of the present embodiment may be a composition substantially containing no polymerization initiator. Substantially not including means that the content of the polymerization initiator is less than 0.1 parts by mass, preferably 0.01 parts by mass or less relative to 100 parts by mass of the resin solid content contained in the resin composition of the present embodiment. By setting the range as described above, various cured products having more excellent properties can be obtained.

< Usage >

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

The resin composition of the present embodiment preferably has a low relative dielectric constant (Dk) when molded into a cured plate having a thickness of 0.8 mm. Specifically, the relative dielectric constant (Dk) of the cured plate at 10GHz, as measured by the cavity disturbance method, is preferably 2.50 or less, and more preferably 2.45 or less. The lower limit of the relative dielectric constant (Dk) is not particularly limited, but is, for example, practically 0.01 or more.

In addition, the resin composition of the present embodiment preferably has a low dielectric loss tangent (Df) when molded into a cured plate having a thickness of 0.8 mm. Specifically, the dielectric loss tangent (Df) at 10GHz measured by the cavity resonator disturbance method is preferably 0.0020 or less, and more preferably 0.0018 or less. The lower limit of the dielectric loss tangent (Df) is not particularly limited, and is practically 0.0001 or more, for example.

The relative permittivity (Dk) and the dielectric loss tangent (Df) of the cured plate were measured by the method described in examples described later.

The resin composition of the present embodiment can be used as a layered material (including films, sheets, and the like) such as a prepreg or a resin composite sheet which is an insulating layer of a printed wiring board, and the thickness thereof is preferably 5 μm or more, more preferably 10 μm or more when the layered material is produced. The upper limit of the thickness is preferably 200 μm or less, more preferably 180 μm or less. The thickness of the layered material refers to a thickness including glass cloth when, for example, the resin composition of the present embodiment is impregnated into glass cloth or the like.

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

Prepreg

The prepreg of the present embodiment is formed of a base material (prepreg base material) and the resin composition of the present embodiment. The prepreg according to the present embodiment can be obtained, for example, by applying (e.g., impregnating and/or coating) the resin composition according to the present embodiment to a substrate, and then semi-curing the resin composition by heating (e.g., drying at 120 to 220 ℃ for 2 to 15 minutes). In this case, the amount of the resin composition to be adhered to the substrate, that is, the amount of the resin composition (including the filler (D)) to the total amount of the prepreg after half curing is preferably in the range of 20 to 99 mass%, more preferably in the range of 20 to 80 mass%.

The substrate is not particularly limited as long as it is a substrate used for various printed wiring board materials. Examples of the material of the substrate include glass fibers (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.), inorganic fibers other than glass (e.g., quartz, etc.), organic fibers (e.g., polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the substrate is not particularly limited, and examples thereof include: woven fabrics, non-woven fabrics, roving, short glass fiber mats, surfacing mats and the like. These substrates may be used alone or in combination of 2 or more. Among these base materials, a fabric subjected to a super-open treatment or a caulking treatment is preferable from the viewpoint of dimensional stability, a glass fabric having a thickness of 200 μm or less and a mass of 250g/m ² or less is preferable from the viewpoint of strength and low water absorption, and a glass fabric subjected to a surface treatment with a silane coupling agent such as epoxy silane or amino silane is preferable from the viewpoint of moisture absorption and heat resistance. From the viewpoint of electrical characteristics, a low dielectric glass cloth composed of glass fibers such as L-glass, NE-glass, Q-glass, etc. exhibiting a low relative permittivity and a low dielectric loss tangent is more preferable.

Examples of the low-relative-permittivity substrate include substrates having a relative permittivity of 5.0 or less (preferably 3.0 to 4.9). Examples of the low dielectric loss tangent substrate include a substrate having a dielectric loss tangent of 0.006 or less (preferably 0.001 to 0.005). The relative dielectric constant and dielectric loss tangent are measured at 10GHz using a cavity resonator by perturbation method.

Metal foil laminated board

The metal foil-clad laminate of the present embodiment includes: at least 1 layer formed of the prepreg of the present embodiment, and a metal foil disposed on one or both sides of the layer formed of the prepreg. As a method for producing the metal foil-clad laminate of the present embodiment, for example, a method of disposing at least 1 prepreg of the present embodiment (preferably, 2 or more prepregs are stacked) and disposing metal foils on one side or both sides thereof to perform lamination molding is exemplified. More specifically, the prepreg can be produced by disposing a metal foil such as copper or aluminum on one or both surfaces of the prepreg and laminating the metal foil. The number of sheets of the prepreg is preferably 1 to 10, more preferably 2 to 10, and still more preferably 2 to 9. The metal foil is not particularly limited as long as it is used as a material for a printed circuit board, and examples thereof include: rolled copper foil, electrolytic copper foil, and the like. The thickness of the metal foil (preferably copper foil) is not particularly limited and may be about 1.5 to 70 μm. The molding method includes a method generally used for molding a laminate for a printed circuit board, and more specifically, a method of performing lamination molding using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 180 to 350 ℃ for a heating time of about 100 to 300 minutes and a surface pressure of about 20 to 100kg/cm ². The prepreg of the present embodiment and a separately produced circuit board for an inner layer are combined and laminated to form a multilayer board. As a method for producing a multilayer board, for example, a multilayer board can be produced by laminating 1 prepreg of the present embodiment on both sides with copper foil of about 35 μm, forming an inner layer circuit after lamination molding by the molding method described above, blackening the circuit to form an inner layer circuit board, alternately disposing the inner layer circuit board and the prepreg of the present embodiment one by one 1 prepreg, and further disposing copper foil on the outermost layer, under the conditions described above, preferably by lamination molding under vacuum. The metal foil-clad laminate of the present embodiment can be suitably used as a printed circuit board.

As described above, the cured product of the resin composition for electronic materials obtained by using the resin composition of the present embodiment (resin composition containing a combination of specific components) has excellent dielectric characteristics (low dielectric loss tangent), moisture absorption heat resistance, crack resistance, appearance of the cured product, and low thermal expansion.

Printed circuit board

The printed wiring board of the present embodiment includes an insulating layer and a conductor layer disposed on a surface of the insulating layer, and the insulating layer includes at least one of a layer formed of the resin composition of the present embodiment and a layer formed of the prepreg of the present embodiment. Such a printed circuit board can be manufactured according to a usual method, and the manufacturing method thereof is not particularly limited. Hereinafter, an example of a method for manufacturing a printed circuit board is shown. First, a metal foil-clad laminate such as the metal foil-clad laminate described above is prepared. Then, an etching process is performed on the surface of the metal foil-clad laminate to form an inner layer circuit, thereby producing an inner layer substrate. The surface of the inner layer circuit of the inner layer substrate is subjected to a surface treatment for improving the adhesive strength as required, and then the prepreg having a desired number of sheets is laminated on the surface of the inner layer circuit, and further a metal foil for the outer layer circuit is laminated on the outer side thereof, and the resultant is heated and pressed to be molded into a body. In this way, a multilayer laminated board having an insulating layer formed of a base material and a cured product of a resin composition formed between metal foils for inner and outer circuits is produced. Then, after the multilayer laminated board is subjected to a hole forming process for a through hole or a via hole, a plated metal film for making the metal foil for the inner layer circuit and the outer layer circuit conductive is formed on the wall surface of the hole, and further, the metal foil for the outer layer circuit is subjected to an etching process to form the outer layer circuit, thereby manufacturing a printed circuit board.

The printed circuit board obtained in the above manufacturing example was constituted as follows: the insulating layer contains the resin composition and/or the cured product thereof according to the present embodiment. That is, the insulating layer of the present embodiment is a layer formed of the prepreg of the present embodiment (for example, a prepreg formed of a base material and the resin composition of the present embodiment impregnated into or applied to the base material) and a layer formed of the resin composition of the metal foil-clad laminate of the present embodiment.

The present embodiment also relates to a semiconductor device including the printed circuit board. Details of the semiconductor device can be referred to the descriptions of paragraphs 0200 to 0202 of japanese patent application laid-open No. 2021-021027, and these are incorporated into the present specification.

Resin composite sheet

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

Examples of the support used herein include, but are not particularly limited to, polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, release films obtained by coating the surfaces of these films with a release agent, organic film substrates such as polyimide films, conductor foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless (stainless steel for steel)) plates, and plate-like supports such as FRP (Fiber-Reinforced Plastics (Fiber reinforced plastic)).

Examples of the coating method (coating method) include: a method of applying a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a support using a bar coater, a die coater, a doctor blade, a Baker coater, or the like. After drying, the support may be peeled off from the resin composite sheet obtained by laminating the support and the resin composition or etched to prepare a single-layer sheet. The resin composition of the present embodiment may be molded into a sheet by supplying a solution obtained by dissolving the resin composition in a solvent into a mold having a sheet-shaped cavity, and drying the mold, thereby obtaining a single-layer sheet without using a support.

In the case of producing the single-layer sheet or the resin composite sheet according to the present embodiment, the drying condition at the time of removing the solvent is not particularly limited, and since the solvent is liable to remain in the resin composition at a low temperature and the curing of the resin composition proceeds at a high temperature, it is preferable to perform the curing at a temperature of 20 to 200 ℃ for 1 to 90 minutes. The single-layer sheet or the resin composite sheet may be used in an uncured state after drying only the solvent, or may be used in a semi-cured (B-staged) state as needed. The thickness of the resin layer in the single-layer sheet or the resin composite sheet of the present embodiment can be adjusted according to the concentration of the solution of the resin composition of the present embodiment used in coating (application) and the thickness of the applied layer, and is not particularly limited, but in general, the thickness of the applied layer is preferably 0.1 to 500 μm because the solvent is easily remained at the time of drying when the applied layer is thickened.

Examples

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

When the measurement equipment and the like used in the examples are difficult to obtain due to stoppage of production and the like, measurement can be performed using other equipment having equivalent performance.

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

An α -naphthol aralkyl resin (SN 495V, OH base equivalent: 236g/eq., manufactured by new japanese iron chemical Co., ltd.; resin containing 1 to 5 repeating units of naphthol aralkyl) was dissolved in 500mL of chloroform by 0.47 mol (in terms of OH group), and 0.7 mol of triethylamine was added to the solution to prepare a solution 1. While maintaining the temperature at-10 ℃, solution 1 was added dropwise over 1.5 hours to 300g of a 0.93 mol cyanogen chloride chloroform solution charged into the reactor, and after the completion of the addition, the mixture was stirred for 30 minutes. Then, a mixed solution of 0.1 mol of triethylamine and 30g of chloroform was further added dropwise to the reactor, followed by stirring for 30 minutes to complete the reaction. The hydrochloride of triethylamine to be produced was filtered from the reaction solution, and the obtained filtrate was washed with 500mL of 0.1N hydrochloric acid, followed by repeated 4 times of washing with 500mL of water. After drying it over sodium sulfate, evaporation was performed at 75 ℃, and then degassing was performed at 90 ℃ under reduced pressure, whereby a naphthol aralkyl type cyanate ester compound represented by the formula (S1) (wherein R ^C1～R^C4 in the formula is a hydrogen atom and n ^c is a mixture of 1 to 5) was obtained as a brown solid. After the obtained naphthol aralkyl type cyanate ester compound was analyzed by infrared absorption spectrum, absorption of cyanate ester group was confirmed in the vicinity of 2264cm ^-1.

Synthesis example 2 Synthesis of modified polyphenylene ether Compound

Synthesis of 2-functional phenylene ether oligomers

A mixed solution of CuBr ₂ 9.36.36 g (42.1 mmol), N ' -di-t-butylethylenediamine 1.81g (10.5 mmol), N-butyldimethylamine 67.77g (671.0 mmol) and toluene 2,600g was charged into a 12L lengthwise reactor equipped with a stirrer, a thermometer, an air inlet tube and a baffle plate, and stirred at a reaction temperature of 40℃to prepare a mixed gas of 2,2', 3', 5' -hexamethyl- (1, 1' -biphenol) -4,4' -diol 129.32g (0.48 mol), 2, 6-dimethylphenol 878.4g (7.2 mol), N ' -di-t-butylethylenediamine 1.22g (7.2 mmol) and N-butyldimethylamine 26.35g (260.9 mmol) dissolved in 2,300g of methanol, which was mixed with nitrogen and air at a flow rate of 5.2L/min was bubbled while stirring for 230 minutes. After completion of the dropwise addition, 1,500g of water (48.06 g, 126.4 mmol) in which tetrasodium ethylenediamine tetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 1N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated to 50% by mass with an evaporator to obtain 1981g of a toluene solution of a 2-functional phenylene ether oligomer (resin "A"). The resin "A" had a number average molecular weight in terms of polystyrene obtained by GPC of 1975, a weight average molecular weight in terms of polystyrene obtained by GPC of 3514, and a hydroxyl equivalent of 990.

Synthesis of modified polyphenylene ether Compound

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

Determination of weight average molecular weight and number average molecular weight

The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by Gel Permeation Chromatography (GPC). The reaction was carried out using a liquid feed pump (LC-20 AD, manufactured by Shimadzu corporation), a differential refractive index detector (RID-10A, manufactured by Shimadzu corporation), a GPC column (GPC KF-801, 802, 803, 804, manufactured by Showa electrician corporation), tetrahydrofuran as a solvent at a flow rate of 1.0ml/min and a column temperature of 40℃using a standard curve obtained using monodisperse polystyrene.

Synthesis example 3 Synthesis of Polymer (va) having structural unit represented by the formula (V)

2.25 Mol (292.9 g) of divinylbenzene, 1.32 mol (172.0 g) of ethylvinylbenzene, 11.43 mol (1190.3 g) of styrene and 15.0 mol (1532.0 g) of n-propyl acetate were charged into the reactor, and 600 mmol of a diethyl ether complex of boron trifluoride was added at 70℃to react for 4 hours. After stopping the reaction with an aqueous sodium hydrogencarbonate solution, the oil layer was washed 3 times with pure water and devolatilized under reduced pressure at 60℃to recover a polymer (va) having a structural unit represented by the formula (V). The obtained polymer (va) having the structural unit represented by the formula (V) was weighed, and 860.8g of the obtained polymer (va) having the structural unit represented by the formula (V) was confirmed.

The polymer (va) having a structural unit represented by the formula (V) obtained had a number average molecular weight Mn of 2,060, a weight average molecular weight Mw of 30,700 and a monodispersity Mw/Mn of 14.9. By performing ¹³ C-NMR and ¹ H-NMR analyses, resonance lines from each monomer unit used as a raw material in the polymer (va) having the structural unit represented by the formula (V) were observed. Based on the NMR measurement result and the GC analysis result, the ratio of each monomer unit (structural unit derived from each raw material) in the polymer (va) having the structural unit represented by formula (V) was calculated as follows.

Structural units derived from divinylbenzene: 20.9 mol% (24.3 mass%)

Structural units derived from ethylvinylbenzene: 9.1 mol% (10.7 mass%)

Structural units derived from styrene: 70.0 mol% (65.0 mass%)

In addition, the structural unit having a residual vinyl group derived from divinylbenzene was 16.7 mol% (18.5 mass%).

Example 1

30 Parts by mass of a maleimide compound (ma) (product of DIC, "NE-X-9470S", product of formula (M1)), 1 part by mass of a maleimide compound (MIR-3000-70 MT, product of Japanese chemical Co., ltd.), 1 part by mass of a cyanate ester compound (naphthol aralkyl type cyanate ester compound (SNCN) obtained in Synthesis example 1), 15 parts by mass of a modified polyphenylene ether compound obtained in Synthesis example 2, 15 parts by mass of a phosphorus flame retardant (PX-200, product of Daba chemical industries Co., ltd.), 25 parts by mass of an unhydrogenated styrene thermoplastic elastomer (SBS, TR2250, mn115000, product of JSR Co., ltd.), 10 parts by mass of a polymer (va) having a structural unit represented by formula (V) obtained in Synthesis example 3, 3 parts by boiling point 175 ℃ C.), 0.005 parts by mass of manganese, TPIZ, 4-triphenyl imidazole, catalyst (6, product of methyl ethyl ketone, product of MZ catalyst (2, product of MZ), and 0.2 are dissolved. The above amounts of the respective additives represent the amounts of the solid components.

Maleimide compound (ma)

N is an integer of 1 to 20.

Production of test piece of cured plate having thickness of 0.8mm

The solvent was distilled off by evaporation from the obtained varnish to obtain a mixed resin powder. The mixed resin powder was filled into a mold having a side length of 100mm and a thickness of 0.8mm, and a copper foil (3 EC-M2S-VLP, manufactured by Mitsui metal mining Co., ltd.) having a thickness of 12 μm was placed on both sides, and vacuum-pressed at a pressure of 30kg/cm ² and a temperature of 220℃for 120 minutes to obtain a cured plate having a side length of 100mm and a thickness of 0.8 mm.

The obtained cured plate was used to evaluate the relative dielectric constant (Dk), dielectric loss tangent (Df), and moisture absorption heat resistance. The evaluation results are shown in table 1.

< Measurement method and evaluation method >)

(1) Relative permittivity (Dk) and dielectric loss tangent (Df)

The copper foil of the cured plate was removed by etching, and after drying at 120℃for 60 minutes, the relative dielectric constant (Dk) and dielectric loss tangent (Df) after drying at 10GHz were measured using a cavity resonator by a perturbation method. The measurement temperature was set at 23 ℃.

The perturbation cavity resonator used was Agilent8722ES manufactured by Agilent Technologies.

Relative permittivity (Dk)

A:2.45 or less

B: more than 2.45 and less than 2.50

C: exceeding 2.50

Dielectric tangent (Df)

A: less than 0.0018

B: exceeding 0.0018 and less than 0.0020

C: exceeding 0.0020

(2) Moisture and heat resistance

The cured plate was cut into 50mm×50mm pieces (reduced in size), all of the copper foil on one side was removed by etching, and half of the copper foil on the other side was removed by etching, to obtain a sample for moisture and heat resistance measurement. The obtained sample was dried at 120℃for 60 minutes, and then allowed to stand for 5 hours in the presence of saturated steam at 121℃and 2 atm using a pressure cooker tester, followed by impregnating (dip) the sample in a solder bath at 260℃for 30 seconds to visually observe the presence or absence of abnormality of the change in appearance. The pressure cooker test machine was a PC-3 model manufactured by Pingshan manufacturing company. Each measurement was performed on 3 pieces, and among the 3 pieces, the evaluation was "a" when the appearance abnormality was 0 pieces, the evaluation was "B" when the appearance abnormality was found to be 1 to 2 pieces, and the evaluation was "C" when the appearance abnormality was found to be 3 pieces. The observation of the appearance was performed by 5 experts, determined by majority voting.

Example 2

The procedure was repeated except that the 4-methylstyrene of example 1 was changed to vinyltrimethoxysilane (KBM-1003, manufactured by Xinyue chemical industries, ltd., boiling point 123 ℃ C.) in the same amount.

Example 3

The procedure was carried out in the same manner as in example 1 except that the content of the polymer (va) having the structural unit represented by the formula (V) obtained in Synthesis example 3 was changed to 20 parts by mass, and the content of the maleimide compound (ma) (product of DIC corporation, "NE-X-9470S", compound represented by the formula (M1)) was changed to 20 parts by mass.

Comparative example 1

The procedure was carried out in the same manner as in example 1 except that 4-methylstyrene was not mixed and the content of maleimide compound (MIR-3000-70 MT, corresponding to the compound represented by the formula (M3)) was changed to 4 parts by mass.

Comparative example 2

The procedure was carried out in the same manner as in comparative example 1 except that the content of the polymer (va) having the structural unit represented by the formula (V) obtained in Synthesis example 3 was changed to 20 parts by mass, and the content of the maleimide compound (ma) (product of DIC, inc., "NE-X-9470S", compound represented by the formula (M1)) was changed to 20 parts by mass.

Comparative example 3

In comparative example 1, the same procedure was conducted except that the polymer (va) having the structural unit represented by the formula (V) obtained in Synthesis example 3 was not compounded, and the content of the modified polyphenylene ether compound obtained in Synthesis example 2 was changed to 25 parts by mass.

Comparative example 4

The procedure was carried out in the same manner as in example 1 except that 3 parts by mass of 3-glycidoxypropyl trimethoxysilane (manufactured by Shin-Etsu Silicones, "KBM-403") was not blended.

TABLE 1

Example 1

Example 2

Example 3

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

Dk 10GHz[-]

A

B

A

C

A

Df 10GHz[-]

B

A

B

A

C

B

Moisture and heat resistance

A

C

A

C

Claims

1. A resin composition comprising:

a polymer (A) having a structural unit represented by the formula (V), and

A compound (B) having a molecular weight of less than 1000 and containing 1 organic group containing a carbon-carbon unsaturated bond in the molecule;

In the formula (V), ar represents an aromatic hydrocarbon linking group; * Indicating the bonding location.

2. The resin composition according to claim 1, wherein the weight average molecular weight of the polymer (a) is 1,000 ～ 160,000.

3. The resin composition according to claim 1, wherein the content of the polymer (a) is 5 to 70 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

4. The resin composition according to claim 1, wherein the organic group containing a carbon-carbon unsaturated bond has a structure of CH ₂ =c (X) -where X is a hydrogen atom or a methyl group.

5. The resin composition according to claim 1, wherein the organic group containing a carbon-carbon unsaturated bond is 1 selected from the group consisting of a vinyl group, an allyl group, an acrylic group, and a methacrylic group.

6. The resin composition according to claim 1, wherein the molecular weight of the compound (B) is 70 to 500.

7. The resin composition according to claim 1, wherein the boiling point of the compound (B) is 110 to 300 ℃.

8. The resin composition according to claim 1, wherein the content of the compound (B) is 1 to 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

9. The resin composition according to claim 1, wherein a mass ratio of the polymer (a) to the compound (B) in the resin composition is 1:0.025 to 0.7.

10. The resin composition according to claim 1, further comprising other thermosetting compound (C) not belonging to the polymer (a) and the compound (B).

11. The resin composition according to claim 10, wherein the other thermosetting compound (C) contains at least 1 selected from the group consisting of maleimide compounds, polyphenylene ether compounds containing 2 or more carbon-carbon unsaturated double bonds, cyanate ester compounds, epoxy compounds, phenol compounds, alkenyl-substituted nadimide compounds, oxetane resins, and benzoxazine compounds.

12. The resin composition according to claim 10, wherein the other thermosetting compound (C) comprises at least 1 selected from the group consisting of a compound (M1) represented by formula (M1), a compound represented by formula (M3), a compound represented by formula (M5), and a compound represented by formula (OP-1);

In the formula (M1), R ^M1、R^M2、R^M3 and R ^M4 each independently represent a hydrogen atom or an organic group; r ^M5 and R ^M6 each independently represent a hydrogen atom or an alkyl group; ar ^M represents a 2-valent aromatic group; a is alicyclic group of 4-6 membered ring; r ^M7 and R ^M8 are each independently alkyl; mx is 1 or 2, lx is 0 or 1; r ^M9 and R ^M10 each independently represent a hydrogen atom or an alkyl group; r ^M11、R^M12、R^M13 and R ^M14 each independently represent a hydrogen atom or an organic group; r ^M15 independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 1 to 10 carbon atoms, an arylthio group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group; px represents an integer of 0 to 3; nx represents an integer of 1 to 20;

In the formula (M3), R ⁵⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, and n ₅ represents an integer of 1 to 10 inclusive;

In the formula (M5), R ⁵⁸ independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group, R ⁵⁹ independently represents a hydrogen atom or a methyl group, and n ₆ represents an integer of 1 or more;

In the formula (OP-1), X represents an aromatic group, - (Y-O) n ₂ -represents a polyphenylene ether structure, R ¹、R² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, n ₁ represents an integer of 1 to 6, n ₂ represents an integer of 1 to 100, and n ₃ represents an integer of 2 to 4.

13. The resin composition according to claim 10, wherein the other thermosetting compound (C) comprises at least 1 selected from the group consisting of a compound (M1) represented by formula (M1), a compound represented by formula (M3), and a compound represented by formula (OP-1);

14. The resin composition according to claim 10, wherein the content of the thermosetting compound (C) is 5 to 95 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

15. The resin composition according to claim 10, wherein the other thermosetting compound (C) contains at least 1 selected from the group consisting of compounds represented by the formula (OP-1) and is contained in an amount of 3 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition;

16. The resin composition according to claim 1, further comprising a filler material (D).

17. The resin composition according to claim 16, wherein the filler (D) is contained in an amount of 10 to 500 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

18. The resin composition according to claim 1, wherein the content of the polymer (a) is 5 to 70 parts by mass and the content of the compound (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

19. The resin composition of claim 1, which is substantially free of polymerization initiator.

20. The resin composition according to claim 1, wherein the weight average molecular weight of the polymer (A) is 1,000 ～ 160,000,

The molecular weight of the compound (B) is 70-500,

The boiling point of the compound (B) is 110-300 ℃,

21. The resin composition according to claim 20, wherein the other thermosetting compound (C) contains at least 1 selected from the group consisting of compounds represented by the formula (OP-1) and is contained in an amount of 3 to 50 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition;

22. The resin composition of claim 21, which is substantially free of polymerization initiator.

23. A prepreg formed from a substrate, and the resin composition of any one of claims 1 to 22.

24. A metal foil-clad laminate comprising at least 1 layer formed from the prepreg of claim 23, and a metal foil disposed on one or both sides of the layer formed from the prepreg.

25. A resin composite sheet comprising a support and a layer formed of the resin composition according to any one of claims 1 to 22 disposed on a surface of the support.

26. A printed circuit board comprising an insulating layer, and a conductor layer disposed on a surface of the insulating layer, the insulating layer comprising a layer formed of the resin composition of any one of claims 1 to 22.

27. A semiconductor device comprising the printed circuit board of claim 26.