JP7117498B2 - Thermosetting resin composition, resin sheet, resin-coated metal foil, metal-clad laminate, and printed wiring board - Google Patents

Description

The present disclosure generally relates to thermosetting resin compositions, resin sheets, resin-coated metal foils, metal-clad laminates, and printed wiring boards. Specifically, a resin comprising a thermosetting resin composition, a resin sheet containing a dried or semi-cured product of this thermosetting resin composition, and a resin layer containing a semi-cured product of this thermosetting resin composition a metal foil, a metal-clad laminate comprising an insulating layer containing the cured product of the thermosetting resin composition, and a printed wiring board comprising an insulating layer containing the cured product of the thermosetting resin composition. .

The speed of information transmission continues to advance. Along with this, in order to obtain a printed wiring board capable of processing high-speed signals, it is required to reduce the dielectric constant and the dielectric loss tangent of the insulating layer of the printed wiring board.

For example, Patent Literature 1 discloses a thermosetting adhesive composition used for producing an insulating layer of a printed wiring board. In the composition of Patent Document 1, a vinyl compound having a polyphenylene ether skeleton, a maleimide resin having two or more maleimide groups, and an elastomer having a polyphenylene skeleton as a main component and being a copolymer of a polyolefin block and a polystyrene block are combined in a predetermined manner. included in proportion. Patent Document 1 discloses that an insulating layer formed from a thermosetting adhesive composition is excellent in low dielectric constant, low dielectric loss tangent, adhesive strength to LCP films and copper foils, and heat resistance.

International Publication No. 2016/117554

Printed wiring boards for in-vehicle use are required to have high connection reliability, specifically, high flame resistance. The thermosetting adhesive composition of Patent Document 1 has insufficient flame resistance of the cured product.

The object of the present disclosure is a thermosetting resin composition whose cured product has a low dielectric constant and a low dielectric loss tangent while having excellent flame resistance, and a dried or semi-cured product of this thermosetting resin composition. a resin sheet containing, a metal foil with resin comprising a resin layer containing a semi-cured product of the thermosetting resin composition, a metal-clad laminate comprising an insulating layer containing a cured product of the thermosetting resin composition, The object of the present invention is to provide a printed wiring board provided with an insulating layer containing a cured product of this thermosetting resin composition.

A thermosetting resin composition according to one embodiment of the present disclosure includes an ethylene-propylene-diene copolymer (A) and a terminal-modified polyphenylene ether compound (B), and includes an olefin unit and a styrene unit. It further contains at least one of an elastomer (C) which is a copolymer and an inorganic filler (D) surface-treated with a surface-treating agent having a polymerizable unsaturated bond.

A resin sheet according to an embodiment of the present disclosure includes a dried product or a semi-cured product of the thermosetting resin composition.

A resin-coated metal foil according to an embodiment of the present disclosure includes a metal foil and a resin layer overlapping the metal foil, and the resin layer includes a dried or semi-cured material of the thermosetting resin composition.

A metal-clad laminate according to an embodiment of the present disclosure includes an insulating layer and a metal foil, and the insulating layer contains a cured product of the thermosetting resin composition.

A printed wiring board according to an embodiment of the present disclosure includes an insulating layer and conductor wiring, and the insulating layer includes a cured product of the thermosetting resin composition.

According to the present disclosure, the cured product includes a thermosetting resin composition having excellent flame resistance while having a low dielectric constant and a low dielectric loss tangent, and a dried or semi-cured product of this thermosetting resin composition. A resin sheet, a resin-coated metal foil comprising a resin layer containing a semi-cured product of the thermosetting resin composition, a metal-clad laminate comprising an insulating layer containing the cured product of the thermosetting resin composition, and the and a printed wiring board comprising an insulating layer containing a cured product of the thermosetting resin composition.

Each of FIGS. 1A and 1B is a schematic diagram showing an example of a resin-coated metal foil according to an embodiment of the present invention. 2A, 2B, 2C and 2D are schematic diagrams showing examples of metal-clad laminates according to embodiments of the present invention. 3A, 3B, 3C, and 3D are schematic diagrams illustrating examples of printed wiring boards according to embodiments of the present invention.

1. Overview A thermosetting resin composition according to an embodiment of the present disclosure includes an ethylene-propylene-diene copolymer (A) (hereinafter also referred to as copolymer (A)) and a terminal-modified polyphenylene ether compound (B) (hereinafter also referred to as compound (B)). The thermosetting resin composition comprises an elastomer (C) (hereinafter also referred to as elastomer (C)), which is a copolymer containing an olefin unit and a styrene unit, and a surface treatment agent having a polymerizable unsaturated bond. and at least one of a treated inorganic filler (D).

The thermosetting resin composition of the present embodiment can have excellent flame resistance while the cured product thereof has a low dielectric constant and a low dielectric loss tangent. Therefore, the thermosetting resin composition is suitable as a material for producing an insulating layer of a metal-clad laminate and a printed wiring board. Good high frequency characteristics and good reliability can be imparted.

2. Details The thermosetting resin composition of the present embodiment will be described in detail below.

2-1. Thermosetting Resin Composition As described above, the thermosetting resin composition of the present embodiment contains an ethylene-propylene-diene copolymer (A) and a terminal-modified polyphenylene ether compound (B). The thermosetting resin composition comprises an elastomer (C) containing an olefin unit and a styrene unit, and an inorganic filler (D) surface-treated with a surface treatment agent having a polymerizable unsaturated bond (hereinafter referred to as an inorganic filler (Also referred to as (D)). The thermosetting resin composition can further contain an organic compound (E) containing a polymerizable unsaturated group (hereinafter also referred to as an organic compound (E)). The thermosetting resin composition may further contain a flame retardant (F) containing bromine or phosphorus (hereinafter also referred to as flame retardant (F)). In addition, the thermosetting resin composition contains components other than the copolymer (A), the compound (B), the elastomer (C), the inorganic filler (D), the organic compound (E), and the flame retardant (F) ( hereinafter, may also be referred to as component (G)). Components that may be included in the thermosetting resin composition of the present embodiment are described in detail below.

(i) Ethylene-propylene-diene copolymer As described above, the thermosetting resin composition contains an ethylene-propylene-diene copolymer (A). Copolymer (A) is also commonly called EPDM rubber (ethylene-propylene-diene monomer rubber).

The copolymer (A) comprises a structural unit derived from ethylene (hereinafter referred to as an ethylene unit), a structural unit derived from propylene (hereinafter referred to as a propylene unit) and a structural unit derived from a diene (hereinafter referred to as a diene unit). have. The diene unit preferably contains a structural unit derived from 5-ethylidene-2-norbornene (hereinafter referred to as a 5-ethylidene-2-norbornene unit). That is, for example, the ethylene-propylene-diene copolymer (A) preferably contains a component represented by the following formula (1). In formula (1), each of n, m and l is a natural number and indicates the number of structural units in formula (1). Therefore, formula (1) is a composition formula showing the ratio of structural units. That is, the formula (1) means that the copolymer (A) contains n mol of ethylene units, m mol of propylene units, and 1 mol of diene units. A 5-ethylidene-2-norbornene unit, which is a diene unit, can contribute to improving the curing reaction speed of the thermosetting resin composition, and can shorten the time required for curing the thermosetting resin composition. Structural units included in the diene unit are not limited to the 5-ethylidene-2-norbornene unit. For example, the diene unit contains at least one structural unit selected from the group consisting of a dicyclopentadiene unit and a 1,4-hexadiene unit.

The mass ratio of the diene unit to the entire copolymer (A) is preferably 3% or more. This can contribute to improving the heat resistance of the cured product. It is more preferable if the ratio of the diene unit is 3% or more and 15% or less.

The mass ratio of ethylene units to the entire copolymer (A) is preferably 50% or more. In this case, the thermosetting resin composition can be easily formed into a sheet. More preferably, the ratio of ethylene units is 50% or more and 75% or less.

The Mooney viscosity ML(1+4) 100° C. defined by JIS K6300-1:2013 of the copolymer (A) is preferably 10 or more. Also in this case, the thermosetting resin composition can be easily formed into a sheet, and the tackiness of the sheet can be reduced. More preferably, the Mooney viscosity ML(1+4) 125° C. defined by JIS K6300-1:2013 of the copolymer (A) is 80 or less. When it is 80 or less, the melt viscosity of the copolymer (A) does not become too high, and the moldability of the cured product can be improved.

The Mooney viscosity of the copolymer (A) increases as the molecular weight of the copolymer (A) increases. For this reason, the molecular weight of the molecules contained in the copolymer (A) can be adjusted, or the mixture ratio can be adjusted by mixing and containing molecules with different molecular weights in the copolymer (A). The Mooney viscosity can be adjusted by adjusting the molecule contained in A) into a branched structure.

The amount of the copolymer (A) is preferably 50 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the compound (B) described later. When the amount of the copolymer (A) is 50 parts by mass or more, it becomes easier to form a film from the thermosetting resin composition. Furthermore, the dielectric constant of the cured product of the thermosetting resin composition can be lowered. When the amount of the copolymer (A) is 200 parts by mass or less, the thermal expansion coefficient of the cured product of the thermosetting resin composition can be lowered, and therefore the heat resistance can be improved.

(ii) Terminal-Modified Polyphenylene Ether Compound As described above, the thermosetting resin composition contains the terminal-modified polyphenylene ether compound (B). Compound (B) is not particularly limited as long as it is a polyphenylene ether terminally modified with a substituent having a carbon-carbon unsaturated double bond. That is, compound (B) has, for example, a polyphenylene ether chain and a substituent having a carbon-carbon unsaturated double bond bonded to the end of the polyphenylene ether chain.

Examples of substituents having a carbon-carbon unsaturated double bond include substituents represented by the following formula (2).

In formula (2), n represents 0-10. Moreover, Z represents an arylene group. R ₁ to R ₃ each independently represent a hydrogen atom or an alkyl group.

In formula (2), when n is 0, Z is directly bonded to the end of the polyphenylene ether chain.

This arylene group is not particularly limited. Specifically, the arylene group is, for example, a monocyclic aromatic group such as a phenylene group, or a polycyclic aromatic group such as a naphthylene group. Further, at least one hydrogen atom bonded to the aromatic ring in this arylene group may be substituted with a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. good. The alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, or the like.

Further, the substituent having a carbon-carbon unsaturated double bond is, more specifically, a vinylbenzyl group (ethenylbenzyl group) such as p-ethenylbenzyl group, m-ethenylbenzyl group, vinylphenyl group , an acrylate group, or a methacrylate group. The substituent preferably has a vinylbenzyl group, a vinylphenyl group, or a methacrylate group. If the substituent having a carbon-carbon unsaturated double bond has an allyl group, the reactivity of compound (B) tends to be low. Also, if the substituent having a carbon-carbon unsaturated double bond has an acrylate group, the reactivity of compound (B) tends to be too high.

Preferred specific examples of substituents having a carbon-carbon unsaturated double bond include functional groups containing a vinylbenzyl group. Specifically, the substituent represented by the formula (2) is, for example, a substituent represented by the following formula (3) or (4).

Substituents with carbon-carbon unsaturated double bonds may be (meth)acrylate groups. A (meth)acrylate group is represented, for example, by the following formula (5).

In formula (5), _R4 represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, for example, the alkyl group is a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, or the like.

Compound (B) also has a polyphenylene ether chain in its molecule. A polyphenylene ether chain has, for example, a repeating unit represented by the following formula (6).

Also, in formula (6), m represents 1 to 50. Each of R ₅ to R ₈ independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferred.

Specific examples of the functional groups mentioned for R ₅ to R ₈ include the following.

Although the alkyl group is not particularly limited, for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, or the like.

Although the alkenyl group is not particularly limited, for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specifically, the alkenyl group is, for example, a vinyl group, an allyl group, a 3-butenyl group, or the like.

Although the alkynyl group is not particularly limited, for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specifically, the alkynyl group is, for example, an ethynyl group, a prop-2-yn-1-yl group (propargyl group), or the like.

The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group. For example, an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable. . Specifically, the alkylcarbonyl group is, for example, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, a cyclohexylcarbonyl group, or the like.

The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group. For example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable. . Specifically, the alkenylcarbonyl group is, for example, an acryloyl group, a methacryloyl group, a crotonoyl group, or the like.

The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group. For example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable. . Specifically, an alkynylcarbonyl group is, for example, a propioloyl group and the like.

The weight average molecular weight (Mw) of compound (B) is not particularly limited, but is preferably 500 to 5,000, more preferably 500 to 2,000, and even more preferably 1,000 to 2,000. Here, the weight average molecular weight may be measured by a general molecular weight measurement method, and specifically, it is measured using gel permeation chromatography (GPC), and the value converted to polystyrene is mentioned. be done. Further, when the modified polyphenylene ether compound has a repeating unit represented by formula (6) in the molecule, m is a numerical value such that the weight average molecular weight of the modified polyphenylene ether compound falls within such a range. is preferably Specifically, m is preferably 1 or more and 50 or less.

When the weight average molecular weight of the compound (B) is within such a range, the compound (B) imparts excellent dielectric properties to the cured product of the thermosetting resin composition due to the polyphenylene ether chain, and furthermore, the cured product It is possible to improve the heat resistance and moldability of. The reason for this is as follows. Ordinary polyphenylene ethers with a weight-average molecular weight of about 500 to 5,000 have a relatively low molecular weight, and tend to lower the heat resistance of the cured product. On the other hand, since compound (B) has an unsaturated double bond at the terminal, it is thought that the heat resistance of the cured product can be enhanced. Further, when the weight average molecular weight of the compound (B) is 5000 or less, the moldability of the thermosetting resin composition is considered to be excellent because of its relatively low molecular weight. Therefore, it is considered that the compound (B) can not only improve the heat resistance of the cured product, but also improve the moldability of the thermosetting resin composition. When the weight average molecular weight of compound (B) is 500 or more, the glass transition temperature of the cured product is less likely to decrease, and thus the cured product tends to have good heat resistance. Furthermore, since the polyphenylene ether chain in the compound (B) is less likely to be shortened, the excellent dielectric properties of the cured product due to the polyphenylene ether chain are likely to be maintained. Moreover, when the weight average molecular weight is 5000 or less, the compound (B) is easily dissolved in a solvent, and the storage stability of the thermosetting resin composition is less likely to deteriorate. In addition, the compound (B) does not easily increase the viscosity of the thermosetting resin composition, so that the thermosetting resin composition can easily obtain good moldability.

The average number of substituents having a carbon-carbon unsaturated double bond (the number of terminal functional groups) per molecule of the compound (B) is not particularly limited, but is preferably 1 to 5. More preferably 3, more preferably 1.5 to 3. In this case, the heat resistance of the cured product of the thermosetting resin composition can be easily ensured, and excessive increase in reactivity and viscosity of the compound (B) can be suppressed. In addition, it is possible to prevent unreacted unsaturated double bonds from remaining after the thermosetting resin composition is cured. The number of terminal functional groups of the compound (B) includes, for example, a numerical value representing the average value of substituents per molecule in 1 mol of the compound (B). The number of terminal functional groups is, for example, when polyphenylene ether is modified to synthesize compound (B), the number of hydroxyl groups in compound (B) is measured, and the number of hydroxyl groups in compound (B) is the number of polyphenylenes before modification. It can be measured by calculating the amount of decrease from the number of hydroxyl groups of the ether. The decrease from the number of hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups. The number of hydroxyl groups remaining in compound (B) is determined by measuring the UV absorbance of a mixed solution obtained by adding a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with hydroxyl groups to a solution of compound (B). can ask.

Moreover, the intrinsic viscosity of the compound (B) is not particularly limited. Specifically, the intrinsic viscosity of compound (B) may be 0.03 to 0.12 dl/g, preferably 0.04 to 0.11 dl/g, and more preferably 0.06 to 0.095 dl. /g is more preferred. In this case, the dielectric constant and dielectric loss tangent of the cured product of the thermosetting resin composition can be easily lowered. Moreover, sufficient fluidity can be imparted to the thermosetting resin composition, and the moldability of the cured product can be improved.

The intrinsic viscosity here is the intrinsic viscosity measured in methylene chloride at 25° C. More specifically, for example, compound (B) is dissolved in methylene chloride at a concentration of 0.18 g/45 ml. Viscosity at 25° C. of the prepared solution. This viscosity is measured with a viscometer such as Schott's AVS500 Visco System.

The method for synthesizing compound (B) is not particularly limited as long as a modified polyphenylene ether compound terminally modified with a substituent having a carbon-carbon unsaturated double bond can be synthesized. Specifically, a method of reacting a polyphenylene ether with a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded can be mentioned.

Examples of compounds in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include p-chloromethylstyrene and m-chloromethylstyrene.

Moreover, the polyphenylene ether as a raw material is not particularly limited as long as it can finally synthesize the compound (B). Specifically, polyphenylene ether such as poly(2,6-dimethyl-1,4-phenylene oxide) and polyphenylene ether composed of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol. and the like as a main component. Moreover, a bifunctional phenol is a phenol compound having two phenolic hydroxyl groups in the molecule, and examples thereof include tetramethylbisphenol A and the like. A trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in the molecule.

Further, the method for synthesizing the compound (B) specifically includes dissolving a polyphenylene ether and a compound in which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are combined in a solvent, followed by stirring. . By doing so, the polyphenylene ether reacts with the compound in which the substituent having a carbon-carbon unsaturated double bond and the halogen atom are bonded to obtain the compound (B).

(iii) Elastomer which is a copolymer containing an olefin unit and a styrene unit As described above, the thermosetting resin composition contains an elastomer (C) which is a copolymer containing an olefin unit and a styrene unit. can be done. In this case, compatibility between the copolymer (A) and the compound (B) in the thermosetting resin composition can be improved. In addition, the B-stage film-forming ability of the thermosetting resin composition can be improved, and the B-stage toughness can be improved. The olefin unit means a structural unit derived from an olefin monomer, and the styrene unit means a structural unit derived from a styrene monomer. The styrene monomer is at least one selected from the group consisting of styrene and styrene having a substituent. Substituents are, for example, alkyl groups such as methyl groups. In particular, the styrene monomer preferably contains at least one of styrene and methylstyrene.

Elastomer (C) may be a random copolymer or a block copolymer.

When the elastomer (C) is a random copolymer, the elastomer (C) is a copolymer in which a plurality of olefin units and a plurality of styrene units are randomly arranged.

When the elastomer (C) is a block copolymer, the elastomer (C) is a copolymer in which one or more olefin blocks and one or more styrene blocks are arranged. An olefin block consists of multiple olefin units, and a styrene block consists of multiple styrene units.

The plurality of olefin units in the elastomer (C) are one or more selected from the group consisting of ethylene units, propylene units, butylene units, α-olefin units, butadiene units, hydrogenated butadiene units, isoprene units and hydrogenated isoprene units. is preferably included. It is particularly preferred that the olefin units include hydrogenated isoprene units. In this case, the stability of the thermosetting resin composition can be improved.

In the elastomer (C), the mass ratio of olefin units to styrene units is preferably in the range of 30:70 to 90:10, more preferably in the range of 60:40 to 85:15. In this case, compatibility between the copolymer (A) and the compound (B) can be improved.

When the elastomer (C) is a random copolymer, the elastomer (C) can be produced, for example, by polymerizing an olefin monomer and a styrene monomer by emulsion polymerization or solution polymerization.

When the elastomer (C) is a block copolymer, the elastomer (C) is produced, for example, by block-polymerizing the olefin monomer and the styrene monomer in an inert solvent in the presence of a lithium catalyst. be able to.

When the thermosetting resin composition in the present disclosure contains an elastomer (C), the amount of the elastomer (C) is 5 parts by mass or more with respect to a total of 100 parts by mass of the copolymer (A) and the compound (B). It is preferably 50 parts by mass or less. When the amount of the elastomer (C) is 5 parts by mass or more, the compatibility between the copolymer (A) and the compound (B) can be sufficiently ensured, thereby improving the thermosetting resin composition. can improve the flame resistance of When the amount of the elastomer (C) is 50 parts by mass or less, it is possible to suppress an increase in the coefficient of thermal expansion of the cured product of the thermosetting resin composition and to improve heat resistance and flame resistance.

(iv) Inorganic filler surface-treated with a surface-treating agent having a polymerizable unsaturated bond As described above, the thermosetting resin composition in the present disclosure is surface-treated with a surface-treating agent having a polymerizable unsaturated bond. It can contain an inorganic filler (D). Also in this case, compatibility between the copolymer (A) and the compound (B) can be improved in the thermosetting resin composition. Furthermore, the coefficient of thermal expansion of the cured product of the thermosetting resin composition can be lowered, the heat resistance and flame resistance of the cured product can be improved, and in particular, the coefficient of thermal expansion can be reduced.

Inorganic fillers (D) are, for example, silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, boron nitride, forsterite, zinc oxide, magnesium oxide and calcium carbonate. It can contain at least one material selected from the group consisting of

The inorganic filler (D) is surface-treated with a surface-treating agent having a polymerizable unsaturated bond, as described above. Examples of polymerizable unsaturated bonds include vinyl groups, allyl groups, methacrylate groups, styryl groups, acryloyl groups, methacryloyl groups, and malemiddle groups. Examples of surface treatment agents include silane coupling agents having polymerizable unsaturated bonds.

The inorganic filler (D) can contribute to improving dielectric properties, improving heat resistance, improving flame resistance, improving toughness, and reducing the coefficient of thermal expansion of the cured product. Moreover, since the inorganic filler (D) is surface-treated with a surface treatment agent, it has a polymerizable unsaturated bond on its surface. Therefore, when curing the thermosetting resin composition, the polymerizable unsaturated bond of the inorganic filler (D), the copolymer (A), and the compound (B) can react, thereby The crosslink density of the cured product can be increased. As a result, the inorganic filler (D) can particularly contribute to improving the flame resistance of the cured product.

When the thermosetting resin composition in the present disclosure contains an inorganic filler (D), the amount of the inorganic filler (D) is, with respect to a total of 100 parts by mass of the copolymer (A) and the compound (B), It is preferably 30 parts by mass or more and 500 parts by mass or less. When the amount of the inorganic filler (D) is 30 parts by mass or more, the compatibility between the copolymer (A) and the compound (B) can be sufficiently ensured in the thermosetting resin composition. As a result, the heat resistance of the cured product of the thermosetting resin can be improved. When the amount of the inorganic charging agent (D) is 500 parts by mass or less, an increase in the coefficient of thermal expansion of the cured product of the thermosetting resin composition can be suppressed.

(v) Organic Compound Containing Polymerizable Unsaturated Group As described above, the thermosetting resin composition preferably contains an organic compound (E) having a polymerizable unsaturated group. In this case, deterioration in heat resistance and flame resistance of the cured product of the thermosetting resin composition can be suppressed.

The polymerizable unsaturated group contained in the organic compound (E) contains, for example, at least one group selected from the group consisting of a vinyl group, an allyl group, a methacryl group, a styryl group, a meth(acryl) group, and a maleimide group. When the thermosetting resin composition contains the organic compound (E), the physical properties of the thermosetting resin composition and the cured product can be controlled by selecting the components contained in the organic compound (E). For example, when the organic compound (E) contains a monofunctional compound having one polymerizable unsaturated group, the monofunctional compound can reduce the melt viscosity of the thermosetting resin composition and improve moldability. Moreover, when the organic compound (E) contains a polyfunctional compound having a plurality of polymerizable unsaturated groups, the polyfunctional compound can increase the crosslink density of the cured product. As a result, the polyfunctional compound can contribute to improving the toughness of the cured product, improving the glass transition point and accompanying heat resistance, reducing the coefficient of linear expansion, and improving adhesion. The organic compound (E) is, as a polyfunctional compound, one or more selected from the group consisting of divinylbenzene, trivinylcyclohexane, triallyl isocyanurate (TAIC), dicyclopentadiene dimethanol dimethacrylate, and nonanediol dimethacrylate. preferably included. In this case, the flame resistance of the cured product of the thermosetting resin composition can be improved. Further, the organic compound (E) includes polyfunctional compounds such as 4,4′-diphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyletherbismaleimide, 3,3′-dimethyl-5,5′-diethyl-4, containing one or more bismaleimides selected from the group consisting of 4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide and 1,6-bismaleimido-(2,2,4-trimethyl)hexane; You can stay. The organic compound (E) preferably includes BMI-689 or BMI-3000 (trade name, manufactured by DESIGNER MOLECULES) as a commercially available bismaleimide. In this case, the flame resistance of the cured product of the thermosetting resin composition can be improved.

When the thermosetting resin composition contains the organic compound (E), the amount of the organic compound (E) is 5 parts by mass or more with respect to the total 100 parts by mass of the copolymer (A) and the compound (B). 50 parts by mass or less is preferable. When the amount of the organic compound (E) is 5 parts by mass or more, the heat resistance of the cured product of the thermosetting resin composition can be improved. When the amount of the organic compound (E) is 50 parts by mass or less, the dielectric constant and dielectric loss tangent of the cured product of the thermosetting resin composition can be lowered, and the occurrence of tack can be suppressed.

(vi) Bromine- or Phosphorus-Containing Flame Retardant As described above, the thermosetting resin composition may contain a bromine- or phosphorus-containing flame retardant (F). In this case, it is possible to improve the flame resistance while lowering the dielectric constant of the cured product of the thermosetting resin composition. The flame retardant (F) can contain at least one of a bromine-containing flame retardant (F1) and a phosphorus-containing flame retardant (F2).

The flame retardant (F1) preferably contains, for example, an aromatic bromine compound. The flame retardant (F1) preferably contains at least one selected from the group consisting of decabromodiphenylethane, 4,4-dibromobiphenyl, and ethylenebistetrabromophthalimide.

When the thermosetting resin composition contains the flame retardant (F1), the amount of bromine in the thermosetting resin composition is 8% by mass or more and 20% by mass or less with respect to the thermosetting resin composition. Preferably. In this case, the flame retardancy of the cured product of the thermosetting resin composition can be improved, and dissociation of bromine can be suppressed during heating of the cured product.

The flame retardant (F2) preferably contains, for example, at least one of an incompatible phosphorus compound and a compatible phosphorus compound.

The flame retardant (F2) preferably contains, for example, a phosphine oxide compound having two or more diphenylphosphine oxide groups in the molecule as an incompatible phosphorus compound. The melting point of this phosphine oxide compound is preferably 280° C. or higher. The phosphine oxide compound has a structure in which two or more diphenylphosphine oxide groups are linked by one or more linking groups selected from the group consisting of phenylene group, xylylene group, biphenylene group, naphthylene group, methylene group and ethylene group. preferably contains a compound of

The flame retardant (F2) preferably contains, for example, at least one selected from the group consisting of a phosphate ester compound, a phosphazene compound, a phosphite ester compound, and a phosphine compound as a compatible phosphorus compound.

When the thermosetting resin composition contains the flame retardant (F2), the amount of phosphorus in the flame retardant (F2) is 1.8% by mass or more and 5.2% by mass with respect to the thermosetting resin composition. The following are preferable. In this case, the flame retardancy of the cured product of the thermosetting resin composition can be improved, and dissociation of phosphorus can be suppressed during heating of the cured product.

(vii) Component (G)
As described above, the thermosetting resin composition includes a copolymer (A), a compound (B), an elastomer (C), an inorganic filler (D), an organic compound (E), and a flame retardant other than (F). A component (G) may be included.

Component (G) includes, for example, thermal radical polymerization initiators, solvents, antifoaming agents such as silicone antifoaming agents and acrylic acid ester antifoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes, pigments, It contains at least one component selected from the group consisting of lubricants and dispersants such as wetting and dispersing agents.

A thermal radical polymerization initiator can accelerate curing when the thermosetting resin composition is heated. If the thermosetting resin composition contains a component that easily generates active species when heated, the thermosetting resin composition may not contain a thermal radical polymerization initiator. The thermal radical polymerization initiator preferably contains an organic peroxide such as α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di (t-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl , t-butyl peroxyisopropyl monocarbonate, t-amyl peroxyneodecanoate, t-amyl peroxypivalate, t-amyl peroxy-2-ethylhexanoate, t-amyl peroxy normal octoate, t -amyl peroxyacetate, t-amyl peroxy isononanoate, t-amyl peroxybenzoate, t-amyl peroxyisopropyl carbonate, di-t-amyl peroxide, 1,1-di(t-amylperoxy)cyclohexane and at least one component selected from the group consisting of azobisisobutyronitrile. The amount of the thermal radical polymerization initiator is, for example, 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of thermosetting components in the thermosetting resin composition, but is not limited thereto. . The thermosetting component here includes the copolymer (A) and the compound (B), and when the thermosetting resin composition contains the organic compound (E), the organic compound (E) is also included. include.

The solvent preferably contains at least one component selected from the group consisting of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents and ketone solvents. In this case, moldability is improved when the thermosetting resin composition is molded into a sheet.

2-2. Resin Sheet The resin sheet according to this embodiment includes a dried product or a semi-cured product of the thermosetting resin composition. The resin sheet can be applied as a material for producing laminates and printed wiring boards. That is, using a resin sheet, a laminate provided with an insulating layer containing a cured product of a resin sheet (that is, an insulating layer containing a cured product of the thermosetting resin composition), and an insulating layer containing a cured product of a resin sheet ( That is, a printed wiring board provided with an insulating layer containing a cured product of the thermosetting resin composition can be produced.

In order to produce a resin sheet, for example, the thermosetting resin composition is formed into a sheet by a coating method or the like, and then dried or semi-cured by heating. Thereby, a resin sheet containing the dried or semi-cured material of the thermosetting resin composition is obtained. The temperature during heating may be a temperature at which the solvent contained in the thermosetting resin composition can be dried and the resin component can be semi-cured. minutes or more and 10 minutes or less.

By heating and curing the resin sheet, an insulating layer containing the cured product of the thermosetting resin composition can be produced. The temperature during heating is, for example, 160° C. or higher and 200° C. or lower, preferably 180° C. or higher and 200° C. or lower, and the heating time is, for example, 30 minutes or longer and 120 minutes or shorter, preferably 60 minutes or longer and 120 minutes or shorter. The resin sheet of the present disclosure can also be used as a bonding sheet for attaching multiple layers. Specifically, first, the thermosetting resin composition is applied to a support film, formed into a sheet, and dried or semi-cured to form a resin sheet. Next, after the resin sheet is attached to a substrate or the like, the support film is peeled off. Next, another substrate or the like is adhered onto the dried or semi-cured material formed on the substrate. Thereby, a plurality of substrates can be attached using the dried or semi-cured material of the thermosetting resin composition contained in the resin sheet.

2-3. Resin-coated Metal Foil A resin-coated metal foil 1 according to this embodiment includes a metal foil 10 and a resin layer 20 overlapping the metal foil 10, as shown in FIG. 1A. The resin layer 20 contains a dried product or a semi-cured product of the thermosetting resin composition. When producing a metal-clad laminate or a printed wiring board from the resin-coated metal foil 1 , an insulating layer is produced from the resin layer 20 . In this case, it is possible to achieve a low dielectric constant and a low dielectric loss tangent of the insulating layer.

The metal foil 10 is, for example, copper foil. The thickness of the metal foil 10 is, for example, 2 μm or more and 105 μm or less, preferably 5 μm or more and 35 μm or less. The metal foil 10 may be a copper foil, for example in a 2 μm thick copper foil with an 18 μm thick copper carrier foil.

The resin layer 20 shown in FIG. 1A includes a first resin layer 21 overlapping the metal foil 10 and a second resin layer 22 overlapping the first resin layer 21 . That is, an insulating layer is produced from the first resin layer 21 and the second resin layer 22 . In this case, a low dielectric constant and a low dielectric loss tangent of the insulating layer can be achieved, and good flexibility can be imparted to the cured product of the first resin layer 21 . Further, the flexibility of the cured product of the first resin layer 21 is less likely to be hindered by the cured product of the second resin layer 22 . Therefore, a flexible metal-clad laminate or printed wiring board can be produced from the resin-coated metal foil 1 .

The thickness of the first resin layer 21 is, for example, 1 μm or more and 50 μm or less. The thickness of the second resin layer 22 is, for example, 5 μm or more and 200 μm or less, preferably 10 μm or more and 150 μm or less.

The first resin layer 21 preferably contains at least one component selected from the group consisting of liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluorine resins and polyphenylene ether resins. That is, the first resin layer 21 is made of a resin liquid or a sheet material containing at least one component selected from the group consisting of liquid crystal polymer resin, polyimide resin, polyamideimide resin, fluororesin and polyphenylene ether resin. is preferred. The sheet material may have a base material such as glass cloth inside and be reinforced with this base material. The sheet material may be, for example, prepreg. The first resin layer 21 can be produced, for example, by applying a resin liquid to the metal foil 10 and then drying it, or by stacking a sheet material on the metal foil 10 and then hot-pressing it.

Liquid crystal polymer resins include, for example, polycondensates of ethylene terephthalate and parahydroxybenzoic acid, polycondensates of phenol and phthalic acid and parahydroxybenzoic acid, and polycondensates of 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid. It can contain at least one component selected from the group consisting of polycondensates. When the first resin layer 21 contains a liquid crystal polymer resin, for example, the first resin layer 21 can be produced by producing a sheet material from the liquid crystal polymer resin and stacking this sheet material on a metal foil.

A polyimide resin can be produced, for example, by the following method. First, a polyamic acid is produced by polycondensation of a tetracarboxylic dianhydride and a diamine component. The tetracarboxylic dianhydride preferably contains 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride. The diamine component is selected from the group consisting of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminodiphenyl ether, and bis[4-(4-aminophenoxy)phenyl]sulfone. can contain at least one component that Next, polyamic acid is heated in a solvent and imidized by a reduction reaction. This produces a polyimide resin. The solvent can contain at least one component selected from components consisting of, for example, N-methyl-2-pyrrolidone, methyl ethyl ketone, toluene, dimethylacetamide, dimethylformamide, and methoxypropanol. The heating temperature is, for example, 60° C. or more and 250° C. or less, preferably 100° C. or more and 200° C. or less, and the heating time is, for example, 0.5 hours or more and 50 hours or less. When the first resin layer 21 contains a polyimide resin, for example, the first resin layer 21 can be produced by applying a resin liquid containing a polyimide resin to the metal foil 10 and then heating and drying it.

A polyamide-imide resin can be produced, for example, by the following method. First, trimellitic anhydride, 4,4′-diisocyanato-3,3′-dimethylbiphenyl, tolylene 2,4-diisocyanate, diazabicycloundecene, and N,N-dimethylacetamide are mixed to prepare a mixture. do. Next, by heating and reacting this mixture, a mixed liquid containing polyamideimide is obtained. Next, after cooling the liquid mixture, bismaleimide is blended. Thereby, a resin liquid containing polyamide-imide is obtained. When the first resin layer 21 contains a polyamide-imide resin, for example, a resin solution containing the polyamide-imide resin is applied onto the metal foil 10 and then heated and dried to form the first resin layer 21. can be made.

Fluororesins include, for example, polytetrafluoroethylene.

The polyphenylene ether resin preferably has a terminal substituent having a carbon-carbon double bond. When the first resin layer 21 contains polyphenylene ether resin, the first resin layer 21 preferably further contains a cross-linking agent having a carbon-carbon double bond. Cross-linking agents are, for example, from the group consisting of divinylbenzene, polybutadiene, alkyl (meth)acrylates, tricyclodecanol (meth)acrylates, fluorene (meth)acrylates, isocyanurate (meth)acrylates, and trimethylolpropane (meth)acrylates. It can contain at least one selected component. The amount of the polyphenylene ether resin is, for example, 65% by mass or more and 95% by mass or less with respect to the total amount of the polyphenylene ether resin and the cross-linking agent. When the first resin layer 21 contains a polyphenylene ether resin, for example, a resin liquid containing a polyphenylene ether resin and a cross-linking agent is applied onto the metal foil 10 and then thermally cured to form the first resin layer. 21 can be made.

The first resin layer 21 may be a single layer as shown in FIG. 1A, or may be composed of a plurality of layers. For example, the first resin layer 21 may include a first layer 211 and a second layer 212 having different compositions, as shown in FIG. 1B.

For example, each of the first layer 211 and the second layer 212 contains at least one component selected from the group consisting of liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluororesins and polyphenylene ether resins, and has compositions that are different from each other. different.

The first layer 211 and the second layer 212 can be produced, for example, by sequentially producing the first layer 211 and the second layer 212 on the metal foil 10 in the same manner as described above. Specifically, first, the first layer 211 is produced by applying a resin liquid containing the components of the first layer 211 to the metal foil 10 and drying it. Next, a resin liquid containing components of the second layer 212 is applied to the first layer 211 and dried to form the second layer 212 . The first layer 211 and the second layer 212 may be made of sheet material instead of liquid resin.

The second resin layer 22 preferably contains a dried or semi-cured material of the thermosetting resin composition. Therefore, the second resin layer 22 can be produced by applying the thermosetting resin composition to the first resin layer 21 and then drying or semi-curing it. In this case, the heating conditions for the thermosetting resin composition are preferably, for example, a heating temperature of 100° C. or higher and 160° C. or lower, and a heating time of 5 minutes or longer and 10 minutes or shorter. The second resin layer 22 may be produced by stacking a resin sheet containing a dried or semi-cured thermosetting resin composition on the first resin layer 21. .

In metal foil 1 with resin shown in FIG. 1B, first resin layer 21 includes two layers (first layer 211 and second layer 212), but may include three or more layers. For example, the first resin layer 21 may include a first layer, a second layer, and a third layer, and these layers may be laminated in this order. In this case, the first layer and the second layer have different compositions, and the second layer and the third layer have different compositions, but the first layer and the third layer may have different compositions. , may have the same composition.

The resin layer 20 may be a single layer containing the dried or semi-cured material of the thermosetting resin composition. In this case, for example, the resin layer 20 can be produced by forming the thermosetting resin composition on the metal foil 10 into a sheet shape by a coating method or the like, and then drying or semi-curing the sheet by heating. In this case, the heating conditions for the thermosetting resin composition are preferably, for example, a heating temperature of 100° C. or higher and 160° C. or lower, and a heating time of 5 minutes or longer and 10 minutes or shorter.

2-4. Metal-clad laminate The metal-clad laminate 2 according to this embodiment will be described.

The metal-clad laminate 2 includes an insulating layer 30 and a metal foil 10, as shown in FIGS. 2A to 2D.

The metal-clad laminate 2 has a metal foil 10 as its outermost layer. The metal-clad laminate 2 may include one metal foil 10 or multiple metal foils 10 . When the metal-clad laminate 2 includes a plurality of metal foils 10, the metal-clad laminate 2 includes one of the plurality of metal foils 10 in its outermost layer.

The insulating layer 30 contains a cured product of the thermosetting resin composition. The insulating layer 30 preferably contains at least one component selected from the group consisting of liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluorine resins and polyphenylene ether resins.

The metal-clad laminate 2 may have only one insulating layer 30 as shown in FIGS. 2A and 2B, or may have two or more insulating layers 30 as shown in FIGS. 2C and 2D.

When the metal-clad laminate 2 includes only one insulating layer 30, the insulating layer 30 includes, for example, only a layer containing a cured product of the thermosetting resin composition, or a cured product of the thermosetting resin composition. and a layer other than that. For example, the insulating layer 30 includes a layer containing a cured product of the thermosetting resin composition, and at least one component selected from the group consisting of liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluororesins, and polyphenylene ether resins. and a layer comprising. In this case, for example, the insulating layer 30 may comprise a first layer 301 and a second layer 302 overlapping the first layer 301 . The first layer 301 contains at least one component selected from the group consisting of liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluororesins and polyphenylene ether resins. The second layer 302 contains a cured product of the thermosetting resin composition. The thickness of the first layer 301 is, for example, 1 μm or more and 50 μm or less. The thickness of the second layer 302 is, for example, 5 μm or more and 50 μm or less.

When the metal-clad laminate 2 includes two or more insulating layers 30, the two or more insulating layers 30 may include the insulating layer 30 containing the cured product of the thermosetting resin composition, liquid crystal polymer resin, polyimide resin , polyamideimide resin, fluororesin, and polyphenylene ether resin. The two or more insulating layers 30 are composed of a cured product of the thermosetting resin composition and at least one component selected from the group consisting of liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluororesins and polyphenylene ether resins. It is also preferred to include an insulating layer 30 comprising. In this case, at least one of the two or more insulating layers 30 may be a layer comprising the first layer 301 and the second layer 302 overlapping the first layer 301 . More preferably, each of the two or more insulating layers 30 contains at least one component selected from the group consisting of liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluorine resins and polyphenylene ether resins.

As the metal foil 10, the same material and thickness as those of the metal foil 10 described in "2-3. Resin-coated metal foil" can be used.

By providing the metal-clad laminate 2 with the insulating layer 30 containing the cured product of the thermosetting resin composition, it is possible to achieve a low dielectric constant and a low dielectric loss tangent of the insulating layer 30 . Also, the insulating layer 30 can have high heat resistance. Furthermore, since the cured product of the thermosetting resin composition has high adhesion to resin and metal, the insulating layer 30 and the layer in contact therewith can have high adhesion.

When the insulating layer 30 of the metal-clad laminate 2 includes the first layer 301 and the second layer 302, the dielectric constant and the dielectric loss tangent of the insulating layer 30 can be further lowered. Also, the insulating layer 30 can have high heat resistance. Furthermore, since the cured product of the thermosetting resin composition has high adhesion to resin and metal, the second layer 302 and the layer in contact therewith can have high adhesion.

The metal-clad laminate 2 shown in FIGS. 2A to 2D will be described in more detail.

The metal-clad laminate 2 shown in FIG. 2A includes a metal foil 10, a first layer 301 and a second layer 302, which are laminated in this order. The metal-clad laminate 2 shown in FIG. 2A includes, for example, a metal foil 10, a sheet material containing the components of the first layer 301, and a resin sheet containing a dried or semi-cured material of the thermosetting resin composition. , can be manufactured by stacking them in this order and then hot-pressing them.

In addition, in the metal-clad laminate 2 shown in FIG. 2A, the metal foil 10, the second layer 302 and the first layer 301 may be laminated in this order. That is, the first layer 301 and the second layer 302 may be laminated in the reverse order of the example shown in FIG. 1A. Also, the first layer 301 may comprise two or more layers. In that case, the two layers in direct contact within the first layer 301 have different compositions. Two layers in the first layer 301 that are not in direct contact with each other may have the same composition or different compositions.

The metal-clad laminate 2 shown in FIG. 2B includes a metal foil 10 (first metal foil 11), an insulating layer 30, and a metal foil 10 (second metal foil 12), which are laminated in this order. . That is, the metal-clad laminate 2 shown in FIG. 2B has the same configuration as the metal-clad laminate 2 shown in FIG. 2A except that the second metal foil 12 is further provided. The metal-clad laminate 2 shown in FIG. 2B includes, for example, the first metal foil 11, the sheet material containing the components of the first layer 301, the sheet material containing the components of the second layer 302, and the second metal It can be manufactured by preparing the foil 12, laminating them in this order, and then hot-pressing them.

The metal-clad laminate 2 shown in FIG. 2C includes a metal foil 10 (first metal foil 11), an insulating layer 30 (first insulating layer 31), a conductor layer 50, and an insulating layer 30 (second insulating layer 30). layer 32) are laminated in this order. The first insulating layer 31 comprises a first layer 301 and a second layer 302 . The configuration of the first insulating layer 31 may be the same as that of the insulating layer 30 in the metal-clad laminate 2 shown in FIG. 2A. The second insulating layer 32 preferably contains at least one component selected from the group consisting of thermosetting resin compositions, liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluororesins and polyphenylene ether resins. The conductor layer 50 is, for example, metal foil or conductor wiring. The metal-clad laminate 2 shown in FIG. 2C includes, for example, a metal foil 10 (first metal foil 11), a sheet material containing the components of the first layer 301, a sheet material containing the components of the second layer 302, It can be manufactured by preparing a sheet material containing the components of the conductor layer 50 and the second insulating layer 32, stacking them in this order, and hot-pressing them.

The metal-clad laminate 2 shown in FIG. 2D includes a metal foil 10 (first metal foil 11), an insulating layer 30 (first insulating layer 31), a conductor layer 50, and an insulating layer 30 (second insulating layer 32). and metal foil 10 (second metal foil 12) are laminated in this order. The first insulating layer 31 comprises a first layer 301 and a second layer 302 . That is, the metal-clad laminate 2 shown in FIG. 2D has the same configuration as the metal-clad laminate 2 shown in FIG. 2C except that the second metal foil 12 is further provided. The metal-clad laminate 2 shown in FIG. 2D includes, for example, the first metal foil 11, the sheet material containing the components of the first layer 301, the sheet material containing the components of the second layer 302, the conductor layer 50, the It can be manufactured by preparing a sheet material containing the components of the two insulating layers and the second metal foil 12, laminating them in this order, and hot-pressing them. The conductor layer 50 is a metal foil.

The configuration of the metal-clad laminate 2 is not limited to the specific examples shown in FIGS. 2A to 2D. For example, the metal-clad laminate 2 may include one or more metal foils 10 , two or more conductor layers 50 and three or more insulating layers 30 . The conductor layer 50 is interposed between two adjacent insulating layers 30 . The metal foil 10 is the outermost layer of the metal-clad laminate 2 . At least one of the three or more insulating layers 30 contains a cured product of the thermosetting resin composition. At least one of the three or more insulating layers 30 preferably contains at least one component selected from the group consisting of liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluorine resins and polyphenylene ether resins.

2-5. Printed Wiring Board The printed wiring board 3 according to the present embodiment includes an insulating layer 30 and conductor wiring 60, as shown in FIGS. 3A to 3D. The printed wiring board 3 has conductor wiring 60 on its outermost layer. The insulating layer 30 contains a cured product of the thermosetting resin composition. In this case, a low dielectric constant and a low dielectric loss tangent of the insulating layer 30 can be achieved, and high heat resistance and flame resistance can be imparted to the insulating layer 30 . Furthermore, the adhesion between the insulating layer 30 and the layer in direct contact with the insulating layer 30 can be improved.

The printed wiring board 3 may include one insulating layer 30 as shown in FIGS. 3A and 3B, or may include a plurality of insulating layers 30 as shown in FIGS. 3C and 3D. When the printed wiring board 3 includes a plurality of insulating layers 30, at least one insulating layer 30 includes the thermosetting resin composition. At least one insulating layer 30 contains at least one component selected from the group consisting of liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluororesins and polyphenylene ether resins, which is different from the thermosetting resin composition. is preferred. In particular, the printed wiring board 3 shown in FIGS. 3C and 3D is also the multilayer printed wiring board 4 because it includes one or more conductor wirings 60 and two or more insulating layers 30 .

The insulating layer 30 may be composed of a single layer, or may be composed of a plurality of layers. A printed wiring board 3 shown in FIGS. 3A to 3D includes an insulating layer 30 composed of a first layer 301 and a second layer 302 overlapping the first layer 301 . The structure of the insulating layer 30 is the same as that of the insulating layer 30 described above in “2-4. Metal-clad laminate”.

The printed wiring board 3 shown in FIGS. 3A to 3D will be described in more detail.

The printed wiring board 3 shown in FIG. 3A includes conductor wiring 60, a first layer 301, and a second layer 302, which are laminated in this order. This printed wiring board 3 has the same configuration as the metal-clad laminate 2 shown in FIG. This printed wiring board 3 can be manufactured by, for example, removing unnecessary portions of the metal foil 10 in the metal-clad laminate 2 shown in FIG.

The printed wiring board 3 shown in FIG. 3B includes a conductor wiring 60, an insulating layer 30, and a conductor layer 50 laminated in this order. This printed wiring board 3 includes a conductor wiring 60 instead of the first metal foil 11, and a conductor layer 50 (second conductor layer 52) instead of the second metal foil 12, as shown in FIG. has the same configuration as the metal-clad laminate 2 shown in FIG. For this reason, the printed wiring board 3 is produced by, for example, removing an unnecessary portion of the first metal foil 11 in the metal-clad laminate 2 shown in FIG. It can be manufactured by applying a metal foil for the second conductor layer 52 instead of 12 .

The printed wiring board 3 shown in FIG. 3C includes a conductor wiring 60, an insulating layer 30 (first insulating layer 31), a conductor layer 50, and an insulating layer 30 (second insulating layer 32) laminated in this order. ing. This printed wiring board 3 has the same configuration as the metal-clad laminate 2 shown in FIG. This printed wiring board 3 can be manufactured, for example, by removing unnecessary portions of the metal foil 10 in the metal-clad laminate 2 shown in FIG.

The printed wiring board 3 shown in FIG. 3D includes conductor wiring 60, insulation layer 30 (first insulation layer 31), conductor layer 50 (first conductor layer 51), insulation layer 30 (second insulation layer 32), and a conductor layer 50 (second conductor layer 52) laminated in this order. This printed wiring board 3 includes a conductor wiring 60 instead of the first metal foil 11, and a conductor layer 50 (second conductor layer 52) instead of the second metal foil 12, as shown in FIG. 2D. has the same configuration as the metal-clad laminate 2 shown in FIG. For this printed wiring board 2, for example, an unnecessary portion of the first metal foil 11 in the metal-clad laminate 2 shown in FIG. Alternatively, it can be manufactured by applying a metal foil for the second conductor layer 52 .

The printed wiring board 3 shown in FIGS. 3C and 3D has two insulating layers 30, but is not limited to this. For example, the printed wiring board 3 may have three or more insulating layers 30 .

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. It should be noted that the present invention is not limited only to this embodiment.

1. Preparation of resin sheet By dissolving the components shown in the “Composition” column in Tables 1 and 2 in toluene, heat curing of Examples 1 to 21 with a solid content concentration of 25% by mass and Comparative Examples 1 to 3 A flexible resin composition was obtained.

Using a comma coater and a dryer connected thereto, a thermosetting resin composition is applied onto a polyethylene terephthalate film having a thickness of 38 μm, and then the thermosetting resin composition is heated at 110° C. for 5 minutes. A resin sheet having a thickness of 25 μm was prepared on a polyethylene terephthalate film. Thus, resin sheets of Examples 1 to 21 and Comparative Examples 1 to 3 were produced.
Copolymer 1: ethylene-propylene-diene copolymer, Mooney viscosity (ML (1 + 4) 100 ° C.) 15, ethylene content 72%, diene content 3.6%, manufactured by Mitsui Chemicals, Inc., product number X- 3012P.
Copolymer 2: ethylene-propylene-diene copolymer, Mooney viscosity (ML(1+4) 125° C.) 25, ethylene content 70%, diene content 4.9%, manufactured by Dow, part number NORDEL IP4725P.
Copolymer 3: ethylene-propylene-diene copolymer, Mooney viscosity (ML (1+4) 100° C.) 20, ethylene content 77%, diene content 10.4%, manufactured by Mitsui Chemicals, product number K-9720.
· PPE: terminal-modified polyphenylene ether compound, manufactured by Mitsubishi Gas Chemical Co., Ltd., product number OPE-2St.
• Elastomer 1: Product name Septon V9827 manufactured by Kuraray.
• Elastomer 2: Product name Septon 8007 manufactured by Kuraray.
· Inorganic filler 1: Spherical silica surface-treated with vinylsilane, manufactured by Admatechs Co., Ltd., product number 0.5 μm SV-CT1 (slurry containing 25% toluene).
Inorganic filler 2: Spherical silica surface-treated with methacrylsilane, Admatechs Co., Ltd., product number 0.5 μm SM-CT1 (slurry containing 25% toluene).
- Organic compound 1 having a polymerizable unsaturated group: triallyl isocyanurate, manufactured by Mitsubishi Chemical Corporation, product number TAIC.
• Organic compound 2 having a polymerizable unsaturated group: triallyl trimellitate, product number TRIAM-705 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• Organic compound 3 having a polymerizable unsaturated group: divinylbenzene.
• Organic compound 4 having a polymerizable unsaturated group: trivinylcyclohexane.
• Organic compound 5 having a polymerizable unsaturated group: Tricyclodecanedimethanol dimethacrylate, product number DCP, manufactured by Shin-Nakamura Chemical.
• Organic compound 6 having a polymerizable unsaturated group: Bismaleimide, manufactured by DESIGNER MOLECULES, product number BMI-689.
- Flame retardant 1: bromine-containing flame retardant, melting point 350°C, bromine content 82%, manufactured by Albemarle Co., Ltd., product name SAYTEX8010.
- Flame retardant 2: Phosphorus-containing flame retardant, manufactured by Daihachi Chemical Industry Co., Ltd., product number PX-200.
・ Flame retardant 3: Phosphorus-containing flame retardant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product number PQ-60
- Thermal radical polymerization initiator: product name Perbutyl P manufactured by NOF Corporation.

2. Evaluation (I) B-stage film property A flexibility test was performed on the resin sheets of Examples 1 to 21 and Comparative Examples 1 to 3 based on JIS K5600-5-1 (flexibility (cylindrical mandrel)). gone. The results were evaluated according to the following criteria. The results are shown in Tables 1 and 2.
A: No crack occurred.
B: A crack occurred at φ10 mm.
C: A crack occurred at φ20 mm.
-: Unevaluated (II) Flame Resistance Test pieces were prepared from the resin sheets of Examples 1 to 21 and Comparative Examples 1 and 2, and a flame retardancy test according to the UL94 vertical method was performed. As a result of the flame retardancy test, those satisfying the V-0 flammability class were evaluated as "A", and those not satisfying the V-0 flammability class were evaluated as "B". The results are shown in Tables 1 and 2.
(III) Thermal expansion coefficient The resin sheets of Examples 1 to 21 and Comparative Examples 1 and 2 were subjected to tensile measurement using a thermomechanical analyzer (“TMA/SS6100” manufactured by SII Nanotechnology Co., Ltd.). did The measurement conditions of the thermomechanical analyzer were a chuck-to-chuck length of 15 mm, a load of 10 g, and a heating rate of 10° C./min up to 350° C. The thermal expansion coefficient of each resin sheet from room temperature to a temperature below the glass transition temperature was obtained from the TMA curve showing the measurement results of the tensile measurement of each resin sheet. The results are shown in Tables 1 and 2.
(IV) Dielectric properties (relative permittivity and dielectric loss tangent)
Two copper foils having a thickness of 18 μm were arranged so that their glossy surfaces faced each other, and a resin sheet was arranged between the two copper foils. A sample was prepared by hot-pressing these under conditions of 200° C. and 2 MPa for 1 hour. This sample was subjected to an etching treatment to remove the copper foils on both sides, thereby preparing test pieces of the cured resin sheets of Examples 1 to 21 and Comparative Examples 1 and 2. The dielectric constant and dielectric loss tangent of this test piece at a test frequency of 10 GHz were measured according to IPC TM-650 2.5.5.5.
(V) Resistance to Soldering Heat Two substrates each having a 12 μm-thick copper foil and a 3 μm-thick insulating layer made of polyamideimide were prepared. Two substrates were arranged so that the insulating layers faced each other, and a resin sheet was arranged between the insulating layers. The samples of Examples 1 to 21 and Comparative Examples 1 and 2 were prepared by hot-pressing these under conditions of 200° C. and 2 MPa for 1 hour. A test piece was produced from this sample based on JIS C6471. The test piece was floated in solder baths at 260° C., 288° C. and 300° C. for 3 minutes and pulled up, and then the appearance of the test piece was observed. As a result, "A" indicates that no abnormality such as swelling or peeling is observed at any of the solder bath temperatures of 260°C, 288°C, and 300°C, and no abnormality is observed at the solder bath temperature of 260°C. When the solder bath temperature was 288°C, it was evaluated as "B", and when the solder bath temperature was 260°C, 288°C, or 300°C, it was evaluated as "C".

The thermosetting resin compositions of Examples 1 to 21 were able to form films, but Comparative Example 1, which does not contain the copolymer (A), could not form films.

Compared to the thermosetting resin compositions of Examples 1 to 21 containing the compound (B), in Comparative Example 2 containing no compound (B), the thermal expansion coefficient of the cured product increased and the solder heat resistance decreased. .

Example 14 in which the amount of the copolymer (A) to the compound (B) is less than 50 parts by mass has a lower B-stage film crack evaluation than Example 1 in which the amount is 50 parts by mass or more. ing. In addition, in Example 15, in which the amount greatly exceeded 100 parts by mass, the flame resistance was lowered.

Example 19, in which the amount of the elastomer (C) greatly exceeds 50 parts by mass with respect to 100 parts by mass of the total amount of the copolymer (A) and the compound (B), is compared with the other examples that do not greatly exceed 50 parts by mass. , solder heat resistance and flame resistance are lowered.

Examples in which the amount of the inorganic filler (D) with respect to 100 parts by mass of the total amount of the copolymer (A) and the compound (B) is less than 30 parts by mass compared to Examples 1 to 15 in which the amount is 30 parts by mass or more In No. 16, the solder heat resistance of the cured product was slightly lowered. In Example 18, which did not contain the inorganic filler (D), the solder heat resistance of the cured product was further lowered. In Example 17, in which the amount of the inorganic filler (D) exceeded 500 parts by mass, the evaluation of B-stage film properties (cracks) was lowered.

Example 20 containing no organic compound (E) corresponds to Examples 1 to 14 in which the amount of the organic compound (E) is 10 parts by mass or more relative to the total amount of 100 parts by mass of the copolymer (A) and the compound (B). , 16 to 18, the flame resistance decreased.

Claims (12)

an ethylene-propylene-diene copolymer (A);
A terminally modified polyphenylene ether compound (B) terminally modified with a substituent having a carbon-carbon unsaturated double bond ,
At least one of an elastomer (C) which is a copolymer containing an olefin unit and a styrene unit and an inorganic filler (D) surface-treated with a surface treatment agent having a polymerizable unsaturated bond is further added. include,
A thermosetting resin composition. The amount of the copolymer (A) is 50 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the compound (B).
The thermosetting resin composition according to claim 1. including the elastomer (C),
The amount of the elastomer (C) is 5 parts by mass or more and 50 parts by mass or less with respect to the total amount of 100 parts by mass of the copolymer (A) and the compound (B).
The thermosetting resin composition according to claim 1 or 2. including the inorganic filler (D),
The amount of the inorganic filler (D) is 30 parts by mass or more and 500 parts by mass or less with respect to the total amount of 100 parts by mass of the copolymer (A) and the compound (B).
The thermosetting resin composition according to any one of claims 1 to 3. Containing an organic compound (E) containing a polymerizable unsaturated group,
The thermosetting resin composition according to any one of claims 1 to 4. The amount of the organic compound (E) is 5 parts by mass or more and 50 parts by mass or less with respect to the total amount of 100 parts by mass of the copolymer (A) and the compound (B).
The thermosetting resin composition according to claim 5. a flame retardant (F) containing bromine or phosphorus,
The thermosetting resin composition according to any one of claims 1 to 6. Including a dried or semi-cured product of the thermosetting resin composition according to any one of claims 1 to 7,
resin sheet. metal foil;
and a resin layer overlapping the metal foil,
The resin layer comprises a dried or semi-cured product of the thermosetting resin composition according to any one of claims 1 to 7,
Metal foil with resin. The resin layer includes a first resin layer overlapping the metal foil and a second resin layer overlapping the first resin layer,
The first resin layer contains at least one component selected from the group consisting of liquid crystal polymer resins, polyimide resins, polyamideimide resins, fluororesins and polyphenylene ether resins,
The second resin layer contains a dried or semi-cured product of the thermosetting resin composition,
The metal foil with resin according to claim 9. an insulating layer;
a metal foil;
The insulating layer comprises a cured product of the thermosetting resin composition according to any one of claims 1 to 7,
Metal clad laminate. an insulating layer;
comprising conductor wiring and
The insulating layer comprises a cured product of the thermosetting resin composition according to any one of claims 1 to 7,
printed wiring board.

Images