JP2022058582A - Resin composition, resin layer-attached support, prepreg, laminate, multilayer printed board and printed wiring board for millimeter wave radar - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that has excellent high frequency properties (low relative dielectric constants and low dielectric loss tangents) and also has high levels of heat resistance and adhesion to a conductor, and a resin layer-attached support, a prepreg, a laminate, a multilayer printed board and a printed wiring board for millimeter wave radars.

SOLUTION: A resin composition has: (A) a compound having a maleimide group and a divalent group binding to the maleimide group, the divalent group containing a saturated or unsaturated divalent hydrocarbon group binding to the maleimide group, and at least two imide groups other than the maleimide group; (B) a compound having a silyl group, and (C) a compound having a maleimide group. The (B) component is a compound other than the (A) component and the (C) component, and the (C) component is a compound other than the (A) component.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a resin composition, a support with a resin layer, a prepreg, a laminated board, a multilayer printed wiring board, and a printed wiring board for a millimeter wave radar.

The speed and capacity of signals used in mobile communication devices such as mobile phones, their base station devices, servers, network infrastructure devices such as routers, and electronic devices such as large computers are increasing year by year. Along with this, the printed wiring boards mounted on these electronic devices need to be compatible with high frequencies, and there is a demand for a substrate material having a low relative permittivity and a low dielectric loss tangent that can reduce transmission loss. In recent years, as applications that handle such high-frequency signals, in addition to the above-mentioned electronic devices, practical application and practical planning of new systems that handle high-frequency wireless signals in the ITS field (automobiles, transportation system-related) and indoor short-range communication fields. Is progressing. In the future, it is expected that low transmission loss substrate materials will be further required for printed wiring boards mounted on these applications.

Further, due to recent environmental problems, mounting of electronic components by lead-free solder and flame retardancy by halogen-free are required. Therefore, the material for printed wiring boards is required to have higher heat resistance and flame retardancy than before.

Conventionally, a polyphenylene ether (PPE) -based resin has been used as a heat-resistant thermoplastic polymer exhibiting excellent high-frequency characteristics in a printed wiring board that requires low transmission loss. As for the use of the polyphenylene ether-based resin, for example, a method of using the polyphenylene ether and the thermosetting resin in combination has been proposed, and specifically, a resin composition containing the polyphenylene ether and the epoxy resin (for example, Patent Document). 1), a resin composition in which polyphenylene ether and a cyanate ester resin having a low relative dielectric constant among thermosetting resins are used in combination (see, for example, Patent Document 2) and the like are disclosed.

Further, by forming a semi-IPN at the production stage (A stage stage) of the resin composition based on the polyphenylene ether resin and the polybutadiene resin, compatibility, heat resistance, thermal expansion characteristics, adhesion to the conductor, etc. can be improved. A resin composition that can be improved has been proposed (see, for example, Patent Document 3).

Further, it is also considered to use a maleimide compound as a material for a printed wiring board. For example, Patent Document 4 describes a maleimide compound having at least two maleimide skeletons, an aromatic diamine compound having at least two amino groups and having an aromatic ring structure, and the maleimide compound and the aromatic diamine compound. A resin composition comprising a catalyst having a basic group and a phenolic hydroxyl group and silica, which promotes a reaction, is disclosed.

Japanese Unexamined Patent Publication No. 58-69046 Special Publication No. 61-18937 Japanese Unexamined Patent Publication No. 2008-95061 Japanese Unexamined Patent Publication No. 2012-255059

However, the substrate material for printed wiring boards used in the high frequency band in recent years is required to have high frequency characteristics in a higher frequency region.

In view of the current situation, the present invention comprises a resin composition having excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent), and also having a high level of adhesion to a conductor and heat resistance. It is an object of the present invention to provide a support with a resin layer, a prepreg, a laminated board, a multilayer printed wiring board, and a printed wiring board for a millimeter wave radar manufactured by using the resin composition.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by a specific resin composition, and have completed the present invention.

That is, the present invention is (A) a compound having a maleimide group and a divalent group bonded to a maleimide group, and at least other than a saturated or unsaturated divalent hydrocarbon group and a maleimide group bonded to the maleimide group. It contains a compound containing two imide groups, a compound having (B) a silyl group, and a compound having (C) a maleimide group, and the component (B) is other than the components (A) and (C). A resin composition (hereinafter, referred to as “first resin composition” for convenience), which is a compound and the component (C) is a compound other than the component (A), is provided.

According to the first resin composition, it is intended to provide a resin composition having excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent), and also having high level of adhesiveness and heat resistance to a conductor. Can be done. Further, it is possible to provide a resin composition having excellent low thermal expansion characteristics.

In the first resin composition, the component (C) preferably contains a maleimide group and a compound having an aromatic group bonded to the maleimide group, and more preferably contains a compound represented by the following formula (VI). preferable. By using such a component (C), the low thermal expansion characteristics of the resin composition can be further improved, and the moldability of the resin composition can be improved.

［式（ＶＩ）中、Ａ^４は下記式（ＶＩＩ）、（ＶＩＩＩ）、（ＩＸ）又は（Ｘ）で表される基を示し、Ａ^５は下記式（ＸＩ）で表される基を示す。］

[In the formula (VI), A ⁴ indicates a group represented by the following formula (VII), (VIII), (IX) or (X), and A ⁵ indicates a group represented by the following formula (XI). .. ]

［式（ＶＩＩ）中、Ｒ^１０は各々独立に、水素原子、炭素数１～５の脂肪族炭化水素基又はハロゲン原子を示す。］

[In formula (VII), R ¹⁰ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom. ]

［式（ＶＩＩＩ）中、Ｒ^１１及びＲ^１２は各々独立に、水素原子、炭素数１～５の脂肪族炭化水素基又はハロゲン原子を示し、Ａ^６は炭素数１～５のアルキレン基若しくはアルキリデン基、エーテル基、スルフィド基、スルホニル基、ケトン基、単結合又は下記式（ＶＩＩＩ－１）で表される基を示す。］

[In formula (VIII), R ¹¹ and R ¹² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁶ is an alkylene group having 1 to 5 carbon atoms or alkylidene. A group, an ether group, a sulfide group, a sulfonyl group, a ketone group, a single bond or a group represented by the following formula (VIII-1) is shown. ]

［式（ＶＩＩＩ－１）中、Ｒ^１３及びＲ^１４は各々独立に、水素原子、炭素数１～５の脂肪族炭化水素基又はハロゲン原子を示し、Ａ^７は炭素数１～５のアルキレン基、イソプロピリデン基、エーテル基、スルフィド基、スルホニル基、ケトン基又は単結合を示す。］

[In the formula (VIII-1), R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁷ is an alkylene group having 1 to 5 carbon atoms. , Isopropyridene group, ether group, sulfide group, sulfonyl group, ketone group or single bond. ]

［式（ＩＸ）中、ｉは１～１０の整数を表す。］

[In the formula (IX), i represents an integer from 1 to 10. ]

［式（Ｘ）中、Ｒ^１５及びＲ^１６は各々独立に、水素原子又は炭素数１～５の脂肪族炭化水素基を示し、ｊは１～８の整数を表す。］

[In the formula (X), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and j represents an integer of 1 to 8. ]

［式（ＸＩ）中、Ｒ^１７及びＲ^１８は各々独立に、水素原子、炭素数１～５の脂肪族炭化水素基、炭素数１～５のアルコキシ基、水酸基又はハロゲン原子を示し、Ａ^８は炭素数１～５のアルキレン基若しくはアルキリデン基、エーテル基、スルフィド基、スルホニル基、ケトン基、フルオレニレン基、単結合、下記式（ＸＩ－１）で表される基又は下記式（ＸＩ－２）で表される基を示す。］

[In the formula (XI), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom, and ^A8 . Is an alkylene group or an alkylidene group having 1 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a ketone group, a fluorenylene group, a single bond, a group represented by the following formula (XI-1) or the following formula (XI-2). ) Indicates a group. ]

［式（ＸＩ－１）中、Ｒ^１９及びＲ^２０は各々独立に、水素原子、炭素数１～５の脂肪族炭化水素基又はハロゲン原子を示し、Ａ^９は炭素数１～５のアルキレン基、イソプロピリデン基、ｍ－フェニレンジイソプロピリデン基、ｐ－フェニレンジイソプロピリデン基、エーテル基、スルフィド基、スルホニル基、ケトン基又は単結合を示す。］

[In the formula (XI-1), R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁹ is an alkylene group having 1 to 5 carbon atoms. , Isopropyridene group, m-phenylenediisopropyridene group, p-phenylenediisopropyridene group, ether group, sulfide group, sulfonyl group, ketone group or single bond. ]

［式（ＸＩ－２）中、Ｒ^２１は各々独立に、水素原子、炭素数１～５の脂肪族炭化水素基又はハロゲン原子を示し、Ａ^１０及びＡ^１１は各々独立に、炭素数１～５のアルキレン基、イソプロピリデン基、エーテル基、スルフィド基、スルホニル基、ケトン基又は単結合を示す。］

[In the formula (XI-2), R ²¹ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ¹⁰ and A ¹¹ independently represent 1 to 1 carbon atoms, respectively. 5 shows an alkylene group, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond. ]

In the first resin composition, the total content of the component (A) and the component (C) is preferably 98% by mass or less based on the total mass of the resin composition. As a result, the low thermal expansion characteristics of the resin composition can be further improved, and the heat resistance of the resin composition can be enhanced.

Further, the present invention is (A) a compound having a maleimide group and a divalent group bonded to the maleimide group, and the divalent group is saturated or unsaturated having 8 to 300 carbon atoms bonded to the maleimide group. Compounds containing at least two imide groups other than the divalent hydrocarbon group and maleimide group of (B) amino group, vinyl group, epoxy group, styryl group, methacryloyl group, isocyanul group, ureido group, mercapto group, A resin composition containing at least one functional group selected from the group consisting of a sulfide group and an isocyanate group and a compound having a silyl group, and the component (B) is a compound other than the component (A). , For the sake of convenience, the "second resin composition") is provided.

According to the second resin composition, it is intended to provide a resin composition having excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent), and also having high level of adhesiveness and heat resistance to a conductor. Can be done.

Further, the present invention is (A) a compound having a maleimide group and a divalent group bonded to the maleimide group, wherein the divalent group is a saturated or unsaturated divalent hydrocarbon group bonded to the maleimide group. And a compound containing at least two imide groups other than the maleimide group, and (B) a compound having a silyl group, and the component (B) is a compound other than the component (A) between layers of a printed wiring board. Provided is a resin composition used for forming an insulating layer (hereinafter, referred to as “third resin composition” for convenience).

According to the third resin composition, it is intended to provide a resin composition having excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent), and also having high level of adhesion to a conductor and heat resistance. Therefore, it is possible to provide a resin composition useful for forming an interlayer insulating layer of a printed wiring board.

In the second and third resin compositions, the content of the component (A) is preferably 98% by mass or less based on the total mass of the resin composition. This makes it possible to improve the low thermal expansion characteristics of the resin composition and further enhance the heat resistance of the resin composition.

In the first to third resin compositions, it is preferable that the divalent group contains a group having two imide groups represented by the following formula (I). By including the component (A) having such a structure, the mechanical strength of the resin film or the like produced from the resin composition can be increased.

［式（Ｉ）中、Ｒ^１は４価の有機基を示す。］

[In formula (I), R ¹ represents a tetravalent organic group. ]

The component (A) preferably contains a compound represented by the following formula (XIII). By including such a component (A), the mechanical strength of a resin film or the like produced from a resin composition can be more effectively increased.

［式（ＸＩＩＩ）中、Ｒは飽和又は不飽和の２価の炭化水素基を示し、Ｒ^１は４価の有機基を示し、ｎは１～１０の整数を表す。］

[In formula (XIII), R represents a saturated or unsaturated divalent hydrocarbon group, R ¹ represents a tetravalent organic group, and n represents an integer from 1 to 10. ]

In the first to third resin compositions, the saturated or unsaturated divalent hydrocarbon group is preferably a group represented by the following formula (II). By including the component (A) having such a structure, high frequency characteristics, low thermal expansion characteristics, adhesiveness with a conductor, heat resistance and low hygroscopicity can be more effectively enhanced.

［式（ＩＩ）中、Ｒ^２及びＲ^３は各々独立に炭素数４～５０のアルキレン基を示し、Ｒ^４は炭素数４～５０のアルキル基を示し、Ｒ^５は炭素数２～５０のアルキル基を示す。］

[In formula (II), R ² and R ³ each independently represent an alkylene group having 4 to 50 carbon atoms, R ⁴ represents an alkyl group having 4 to 50 carbon atoms, and R ⁵ represents an alkyl group having 2 to 50 carbon atoms. Indicates an alkyl group. ]

The present invention provides a resin composition having a relative permittivity of 3.6 or less at 10 GHz of the cured product of the first to third resin compositions. When the relative permittivity is in the above range, more excellent high-frequency characteristics can be obtained, and a cured product suitable for electronic devices that handle high-frequency signals can be obtained.

The present invention provides a support with a resin layer, comprising a support base material and a resin layer containing the first to third resin compositions provided on the support base material. Since the support with a resin layer according to the present invention is formed by using each of the resin compositions according to the present invention, the same effect as each resin composition according to the present invention can be obtained.

The present invention provides a prepreg comprising a fiber base material and a resin layer containing the first to third resin compositions impregnated in the fiber base material. Since the prepreg according to the present invention is formed by using each of the resin compositions according to the present invention, the same effect as that of each resin composition according to the present invention can be obtained.

The present invention provides a laminated board including a conductor layer and a cured resin layer containing a cured product of the first to third resin compositions provided on the conductor layer. Since the laminated board according to the present invention is formed by using each of the resin compositions according to the present invention, the same effect as each resin composition according to the present invention can be obtained.

The present invention is a multi-layer printed wiring board comprising at least three circuit layers and two or more layers of interlayer insulating layers provided between adjacent sets of circuit layers, among the interlayer insulating layers. Provided is a multilayer printed wiring board in which at least one layer is a cured resin layer containing a cured product of the first to third resin compositions. The number of circuit layers can be 3 to 20 layers. Since the multilayer printed wiring board according to the present invention is formed by using each of the resin compositions according to the present invention, the same effect as that of each resin composition according to the present invention can be obtained.

The present invention provides an application for manufacturing a millimeter-wave radar of the multilayer printed wiring board according to the present invention. The present invention also provides a printed wiring board for a millimeter-wave radar, comprising a circuit layer and a cured resin layer containing a cured product of the first to third resin compositions provided on the circuit layer. .. As described above, the multilayer printed wiring board according to the present invention can obtain the same effect as each resin composition according to the present invention, and thus can provide an application for manufacturing a millimeter wave radar. , Useful as a printed wiring board for millimeter-wave radar.

According to the present invention, a resin composition having excellent high frequency characteristics (low relative permittivity, low dielectric loss tangent), and having a high level of adhesion to a conductor and heat resistance, and the resin composition. It is possible to provide a support with a resin layer, a prepreg, a laminated board, a multilayer printed wiring board, and a printed wiring board for a millimeter wave radar manufactured using the same.

It is a schematic diagram which shows the manufacturing process of the multilayer printed wiring board which concerns on this embodiment. It is a schematic diagram which shows the manufacturing process of the inner layer circuit board. It is a schematic diagram which shows the manufacturing process of the multilayer printed wiring board which concerns on this embodiment. It is a schematic diagram which shows the manufacturing process of the conventional multilayer printed wiring board.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, the high frequency region refers to the region of 0.3 GHz to 300 GHz, and the frequency region particularly used for the millimeter wave radar refers to the region of 3 GHz to 300 GHz.

[Resin composition]
The resin composition according to the present embodiment is (A) a compound having a maleimide group and a divalent group bonded to the maleimide group, and the divalent group is a saturated or unsaturated divalent group bonded to the maleimide group. A compound containing at least two imide groups other than the hydrocarbon group and the maleimide group of (B), and (B) a compound having a silyl group.

<(A) Maleimide group and compound having a divalent group bonded to the maleimide group>
A compound having a maleimide group and a divalent group bonded to a maleimide group according to the present embodiment, wherein the divalent group is a saturated or unsaturated divalent hydrocarbon group and a maleimide group bonded to the maleimide group. A compound containing at least two imide groups other than the above may be referred to as "component (A)". Further, among the components (A), the maleimide group is "structure (a)", the divalent group bonded to the maleimide group is "structure (b)", and the saturated or unsaturated divalent carbonic acid bonded to the maleimide group is carbonized. The hydrogen group may be referred to as "structure (b1)" and at least two imide groups other than the maleimide group may be referred to as "structure (b2)". By using the component (A), a resin composition having high frequency characteristics and high adhesiveness to a conductor can be obtained.

The structure (a) is not particularly limited and is a general maleimide group. The structure (a) is bonded to the structure (b1) of the structure (b) described later, but the bonding position with the structure (b1) in the structure (a) is not limited. Examples of the bond position with the structure (b1) in the structure (a) include the nitrogen atom of the maleimide group as represented by the following formula (XIV). In the following formula (XIV), (b1) represents the structure (b1).

The structure (b) includes a structure (b1) and a structure (b2). Of these, the structure (b1) is combined with the above structure (a).

The saturated or unsaturated divalent hydrocarbon group in the structure (b1) is not particularly limited, and is a saturated or unsaturated divalent linear hydrocarbon group or a saturated or unsaturated divalent branched hydrocarbon. It may be either a group and a saturated or unsaturated divalent cyclic hydrocarbon group. Further, the unsaturated divalent cyclic hydrocarbon group may be an aromatic group. The saturated or unsaturated divalent hydrocarbon group may have 8 to 300 carbon atoms, 8 to 250 carbon atoms, 8 to 200 carbon atoms or 8 to 100 carbon atoms. The structure (b1) is preferably an alkylene group having branches of 8 to 300, 8 to 250, 8 to 200 or 8 to 100 carbon atoms, and has branches of 10 to 70 carbon atoms. It is more preferably an alkylene group which may be present, and further preferably an alkylene group which may have a branch having 15 to 50 carbon atoms. Since the component (A) has the structure (b1), the flexibility of the resin composition according to the present embodiment is improved, and the handleability (tackiness, cracking, powder removal) of the resin film produced from the resin composition is improved. Etc.) and the strength can be increased. Further, the structure having the number of carbon atoms (b1) is preferable because the molecular structure can be easily made three-dimensional and the free volume of the polymer can be increased to reduce the density, that is, the dielectric constant.

The structure (b1) includes, for example, an alkylene group such as a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, an octadecylene group and a nonadesilene group; an arylene group such as a benzylene group, a phenylene group and a naphthylene group; An arylene alkylene group such as a phenylene methylene group, a phenylene ethylene group, a benzyl propylene group, a naphthylene methylene group and a naphthylene ethylene group; an allylene alkylene group such as a phenylenedi methylene group and a phenylenedi ethylene group can be mentioned.

From the viewpoints of high frequency characteristics, low thermal expansion characteristics, adhesiveness to conductors, heat resistance and low hygroscopicity, the group represented by the following formula (II) as the structure (b1) is particularly preferable.

In formula (II), R ² and R ³ each independently represent an alkylene group having 4 to 50 carbon atoms. From the viewpoint of further improvement of flexibility and easiness of synthesis, R ² and R ³ are each independently preferably an alkylene group having 5 to 25 carbon atoms, and preferably an alkylene group having 6 to 10 carbon atoms. More preferably, it is an alkylene group having 7 to 10 carbon atoms.

In formula (II), R ⁴ represents an alkyl group having 4 to 50 carbon atoms. From the viewpoint of further improvement of flexibility and easiness of synthesis, ^R4 is preferably an alkyl group having 5 to 25 carbon atoms, more preferably an alkyl group having 6 to 10 carbon atoms, and 7 to 7 carbon atoms. It is more preferably 10 alkyl groups.

In formula (II), R ⁵ represents an alkyl group having 2 to 50 carbon atoms. From the viewpoint of further improvement of flexibility and easiness of synthesis, R5 is preferably an alkyl group having ³ to 25 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and 5 to 10 carbon atoms. It is more preferably an alkyl group of 8.

From the viewpoint of fluidity and circuit embedding property, it is preferable that a plurality of structures (b1) are present in the component (A). In that case, the structures (b1) may be the same or different. For example, it is preferable that 2 to 40 structures (b1) are present in the component (A), more preferably 2 to 20 structures (b1) are present, and 2 to 10 structures (b1) are present. Is even more preferable.

The structure (b2) is not particularly limited, and examples thereof include a group represented by the following formula (I).

In formula (I), R ¹ represents a tetravalent organic group. R ¹ is not particularly limited as long as it is a tetravalent organic group, but may be, for example, a hydrocarbon group having 1 to 100 carbon atoms or a hydrocarbon group having 2 to 50 carbon atoms from the viewpoint of handleability. It may be a hydrocarbon group having 4 to 30 carbon atoms.

R ¹ may be substituted and may contain a substituted or unsubstituted siloxane group. Examples of the siloxane group include groups derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, and the like.

When R ¹ is substituted, the substituents include, for example, an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, an alkoxy group, a mercapto group, a cycloalkyl group, a substituted cycloalkyl group, a heterocyclic group, and a substituted heterocyclic group. , Aryl group, substituted aryl group, heteroaryl group, substituted heteroaryl group, aryloxy group, substituted aryloxy group, halogen atom, haloalkyl group, cyano group, nitro group, nitroso group, amino group, amide group, -C ( O) H, -NR ^X C (O) -N (RX) ₂ , -OC (O) -N ( ^RX ) ₂ , acyl group, ^oxyacyl group, carboxyl group, carbamate group, sulfonamide group and the like. Be done. Here, ^RX represents a hydrogen atom or an alkyl group. One type or two or more types of these substituents can be selected according to the purpose, application and the like.

As R ¹ , for example, a tetravalent residue of an acid anhydride having two or more anhydride rings in one molecule, that is, an acid anhydride group (−C (= O) OC (=). It is preferably a tetravalent group excluding two O)-). Examples of the acid anhydride include compounds as described below.

From the viewpoint of mechanical strength, R ¹ is preferably an aromatic group, and more preferably a residue obtained by removing two acid anhydride groups from pyromellitic anhydride. That is, it is more preferable that the structure (b2) is a group represented by the following formula (III).

From the viewpoint of fluidity and circuit embedding property, it is preferable that a plurality of structures (b2) are present in the component (A). In that case, the structures (b2) may be the same or different. (A) The number of structures (b2) in the component is preferably 2 to 40, more preferably 2 to 20, and even more preferably 2 to 10.

From the viewpoint of the dielectric property, the structure (b2) may be a group represented by the following formula (IV) or the following formula (V).

The component (A) may be, for example, a compound represented by the following formula (XIII).

In the formula (XIII), R represents a saturated or unsaturated divalent hydrocarbon group, and the saturated or unsaturated divalent hydrocarbon group having the same structure as the above structure (b1) can be used. R ¹ represents a tetravalent organic group similar to R ¹ in the formula (I), and n represents an integer of 1 to 10.

As the component (A), a commercially available compound can also be used. Examples of commercially available compounds include products manufactured by Digigner Moleculars Incorporated, and specifically, BMI-1500, BMI-1700, BMI-3000, BMI-5000, and BMI-9000 ( All of them are product names) and the like. From the viewpoint of obtaining better high frequency characteristics, it is more preferable to use BMI-3000 as the component (A).

The content of the component (A) in the resin composition is not particularly limited. From the viewpoint of heat resistance, the content of the component (A) may be 2% by mass or more or 10% by mass or more based on the total mass of the resin composition. Further, from the viewpoint of the low coefficient of thermal expansion, the content of the component (A) may be 98% by mass or less, 50% by mass or less, 30% by mass or less, or 20% by mass or less based on the total mass of the resin composition. .. From the viewpoint of heat resistance, the content of the component (A) is preferably 2 to 98% by mass, more preferably 10 to 50% by mass, and 10 to 30% by mass based on the total mass of the resin composition. % Is more preferable.

The molecular weight of the component (A) is not particularly limited. From the viewpoint of fluidity, the lower limit of the weight average molecular weight (Mw) of the component (A) may be 500 or more, 1000 or more, 1500 or more, 1700 or more, 2000 or more, 2500 or more, or 3000 or more. Further, from the viewpoint of handleability, the upper limit of Mw of the component (A) may be 10,000 or less, 9000 or less, 7,000 or less, or 5,000 or less. From the viewpoint of handleability, fluidity, and circuit embedding property, the Mw of the component (A) is preferably 500 to 10000, more preferably 1000 to 9000, and further preferably 1500 to 9000. It is even more preferably 7,000 to 7,000, and particularly preferably 1700 to 5,000.

The Mw of the component (A) can be measured by a gel permeation chromatography (GPC) method.

The measurement conditions of GPC are as follows.

Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Guard column and column: TSK Guardcolum HHR-L + TSKgel G4000HHR + TSKgel G2000HHR [All manufactured by Tosoh Corporation, product name]
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Flow rate: 1.00 mL / min Measurement temperature: 40 ° C

(A) The method for producing the component is not limited. The component (A) may be prepared, for example, by reacting an acid anhydride with a diamine to synthesize an amine-terminated compound, and then reacting the amine-terminated compound with an excess of maleic anhydride.

Examples of the acid anhydride include pyromellitic anhydride, maleic anhydride, succinic anhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyl. Examples thereof include tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride and the like. These acid anhydrides may be used alone or in combination of two or more depending on the purpose, use and the like. As described above, as R ₁ of the above formula (I), a tetravalent organic group derived from an acid anhydride as described above can be used. From the viewpoint of better dielectric properties, the acid anhydride is preferably pyromellitic anhydride.

Examples of the diamine include diamine diamine, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (4-aminophenoxy) benzene, and 4,4'-bis (4-amino). Phenoxy) biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4) -Aminophenyl) -2-propyl] benzene, polyoxyalkylenediamine, [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene and the like. These may be used alone or in combination of two or more depending on the purpose, application and the like.

<(B) Compound having a silyl group>
The compound having a (B) silyl group according to the present embodiment may be referred to as a component (B). By using the component (B), a resin composition having high frequency characteristics and high adhesiveness to a conductor can be obtained. The compound that can correspond to both the component (A) and the component (B) is attributed to the component (A).

Examples of the silyl group include a silyl group represented by -SiR _a R _b R _c (in the formula, R _a , R _b and R _c each independently represent a monovalent organic group).

Examples of R _a , R _b and R _c include a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group and a hexyl group; cyclopentyl. Cycloalkyl group such as group, cyclohexyl group, methylcyclohexyl group; aryl group such as phenyl group, methylphenyl (tolyl) group, ethylphenyl group, dimethylphenyl (xysilyl) group, naphthyl group, methylnaphthyl group; benzyl group, phenethyl Aralkyl groups such as a group and a phenylpropyl group; alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group and a third butoxy group can be mentioned. R _a , R _b and R _c may be further substituted with one or more other substituents (eg, alkoxy groups, etc.).

Examples of the silyl group include a trialkylsilyl group, a triarylsilyl group, an alkyldiarylsilyl group, an aryldialkylsilyl group, a triaralkylsilyl group, a trialkoxysilyl group, and an alkyldialkoxysilyl group. Among these, from the viewpoint of easy availability, the silyl group is preferably at least one selected from the group consisting of a trialkoxysilyl group and an alkyldialkoxysilyl group, and is preferably a methyldimethoxysilyl group or a trimethoxysilyl group. More preferably, it is at least one selected from the group consisting of a group and a triethoxysilyl group.

The compound having a silyl group is at least selected from the group consisting of an amino group, a vinyl group, an epoxy group, a styryl group, a methacryloyl group, an isocyanul group, a ureido group, a mercapto group, a sulfide group and an isocyanate group, in addition to the silyl group. It may have one kind of functional group. Among these, compounds having a silyl group are amino groups from the viewpoint of reactivity with the above component (A) and, if necessary, the component (C) described later and an inorganic filler, and higher adhesion to a conductor. It is preferable to have at least one functional group selected from the group consisting of an epoxy group and an amino group, and it is more preferable to have an amino group. By using a compound having an amino group and a silyl group, silanol produced by hydrolysis is adsorbed on the surface of the metal substrate in a hydrogen-bonded manner, and the action of the amino group enhances the adhesion between the resin and the metal substrate. Therefore, it is considered that higher adhesion to the conductor can be obtained.

The amino group may be present in one or more than one in the compound having a silyl group, and may be any of a primary amino group, a secondary amino group and a tertiary amino group. Above all, the amino group is preferably a primary amino group and / or a secondary amino group from the viewpoint of higher adhesion to the conductor, and is a primary amino group from the viewpoint of facilitating the control of reactivity. Is more preferable.

Examples of the compound having an amino group and a silyl group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-amino. Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Partial hydrolysis of propylamine, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine partial addition Examples thereof include decomposition products, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, and these may be hydrochlorides. From the viewpoint of reactivity with the above component (A) and, if necessary, the component (C) described later and an inorganic filler and higher adhesion to the conductor, the compound having an amino group and a silyl group is N-phenyl- It is preferably at least one selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

The content of the component (B) in the resin composition is not particularly limited. From the viewpoint of adhesiveness, the content of the component (B) may be 0.05% by mass or more, 0.1% by mass or more, or 0.2% by mass or more based on the total mass of the resin composition. Further, from the viewpoint of the dielectric property, the content of the component (B) may be 3% by mass or less, 2% by mass or less, or 1% by mass or less based on the total mass of the resin composition. From the viewpoint of adhesiveness, the content of the component (B) is preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, based on the total mass of the resin composition. It is more preferably 0.2 to 1% by mass.

<(C) Compound having maleimide group>
The resin composition of the present embodiment can further contain (C) a compound having a maleimide group. The compound (C) having a maleimide group according to this embodiment may be referred to as a component (C). The compound that can correspond to both the component (A) and the component (C) is attributed to the component (A). Further, the compound that can correspond to both the component (B) and the component (C) described above shall belong to the component (C). By using the component (C), the resin composition is particularly excellent in low thermal expansion characteristics. That is, the resin composition of the present embodiment can further improve the low thermal expansion property and the like while maintaining good dielectric properties by using the component (A) and the component (C) in combination. The reason for this is that the cured product obtained from the resin composition containing the component (A) and the component (C) has a structural unit composed of the component (A) having a low dielectric property and a component (C) having a low thermal expansion property. It is presumed that it contains a polymer having a structural unit consisting of.

The component (C) preferably has a lower coefficient of thermal expansion than the component (A). The component (C) having a lower coefficient of thermal expansion than the component (A) includes, for example, a compound having a smaller molecular weight than the component (A), a compound having more aromatic rings than the component (A), and a main chain (A). ) Compounds shorter than the component can be mentioned.

The content of the component (C) in the resin composition is not particularly limited. From the viewpoint of low thermal expansion characteristics, the lower limit of the content of the component (C) is 1% by mass or more, 2% by mass or more, 3% by mass or more, or 5% by mass or more based on the total mass of the resin composition. May be good. Further, from the viewpoint of the dielectric property, the upper limit of the content of the component (C) may be 95% by mass or less, 90% by mass or less, or 85% by mass or less based on the total mass of the resin composition. From the viewpoint of low thermal expansion characteristics, the content of the component (C) is preferably 1 to 95% by mass, more preferably 3 to 90% by mass, based on the total mass of the resin composition, and 5 to 85. It is more preferably by mass%.

The blending ratio of the component (A) and the component (C) in the resin composition is not particularly limited. From the viewpoint of the dielectric property and the low coefficient of thermal expansion, the mass ratio (C) / (A) of the component (A) to the component (C) is preferably 0.01 to 3, preferably 0.03 to 2. It is more preferably 0.05 to 1, and even more preferably 0.05 to 1.

The total content of the component (A) and the component (C) in the resin composition is not particularly limited. From the viewpoint of heat resistance, the lower limit of the total content of the component (A) and the component (C) may be 2% by mass or more or 10% by mass or more based on the total mass of the resin composition. Further, from the viewpoint of the low coefficient of thermal expansion, the upper limit of the total content of the component (A) and the component (C) is 98% by mass or less, 50% by mass or less, and 30% by mass or less based on the total mass of the resin composition. Alternatively, it may be 20% by mass or less. From the viewpoint of heat resistance, the total content of the component (A) and the component (C) is preferably 2 to 98% by mass, preferably 10 to 50% by mass, based on the total mass of the resin composition. Is more preferable, 10 to 30% by mass is further preferable, and 10 to 20% by mass is even more preferable.

Such a component (C) is not particularly limited, and may contain a compound having an aromatic group bonded to a maleimide group, an aliphatic group bonded to a maleimide group, or the like, in addition to the maleimide group. From the viewpoint of more effectively reducing the coefficient of thermal expansion, the component (C) preferably contains a maleimide group and a compound having an aromatic group bonded to the maleimide group. Since the aromatic group is rigid and has a low thermal expansion, the coefficient of thermal expansion can be further reduced by using a maleimide group and a compound having an aromatic group bonded to the maleimide group. Further, the compound having a maleimide group is preferably a polymaleimide compound having two or more maleimide groups.

Specific examples of the compound having a maleimide group as the component (C) include 1,2-dimaleimideethane, 1,3-dimaleimidepropane, bis (4-maleimidephenyl) methane, and bis (3-ethyl-4-4). Maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, 2,7-dimaleimidefluorene, N, N'-(1,3-phenylene) bismaleimide, N, N'- (1,3- (4-Moleimidephenyl)) bismaleimide, bis (4-maleimidephenyl) sulfone, bis (4-maleimidephenyl) sulfide, bis (4-maleimidephenyl) ether, 1,3-bis ( 3-Maleimidephenoxy) benzene, 1,3-bis (3- (3-maleimidephenoxy) phenoxy) benzene, bis (4-maleimidephenyl) ketone, 2,2-bis (4- (4-maleimidephenoxy) phenyl) Propane, bis (4- (4-maleimidephenoxy) phenyl) sulfone, bis [4- (4-maleimidephenoxy) phenyl] sulfoxide, 4,4'-bis (3-maleimidephenoxy) biphenyl, 1,3-bis ( 2- (3-Maleimidephenyl) propyl) benzene, 1,3-bis (1- (4- (3-maleimidephenoxy) phenyl) -1-propyl) benzene, bis (maleimidecyclohexyl) methane, 2,2-bis [4- (3-Maleimidephenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis (maleimidephenyl) thiophene and the like can be mentioned. These may be used alone or in combination of two or more. Among these, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane is preferably used from the viewpoint of further lowering the hygroscopicity and the coefficient of thermal expansion. From the viewpoint of further increasing the breaking strength and the metal leaf peeling strength of the resin film formed from the resin composition, it is preferable to use 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane. From the viewpoint of low dielectric property, it is preferable to use bis (4-maleimidephenyl) methane.

From the viewpoint of moldability, the component (C) preferably contains, for example, a polyaminobismaleimide compound represented by the following formula (VI).

^In the formula (VI), A4 represents a group represented by the following formula (VII), (VIII), (IX) or (X), and A5 represents a group represented by the following formula ⁽ XI).

In formula (VII), R ¹⁰ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom.

In formula (VIII), R ¹¹ and R ¹² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁶ is an alkylene group or an alkylidene group having 1 to 5 carbon atoms. , Ether group, sulfide group, sulfonyl group, ketone group, single bond or group represented by the following formula (VIII-1).

In formula (VIII-1), R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁷ is an alkylene group having 1 to 5 carbon atoms. Shows an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond.

In equation (IX), i represents an integer from 1 to 10.

In formula (X), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and j represents an integer of 1 to 8.

In formula (XI), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom, and ^A8 is , An alkylene group or an alkylidene group having 1 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a ketone group, a fluorenylene group, a single bond, a group represented by the following formula (XI-1) or the following formula (XI-2). ) Indicates a group.

In the formula (XI-1), R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁹ is an alkylene group having 1 to 5 carbon atoms. , Isopropyridene group, m-phenylenediisopropyridene group, p-phenylenediisopropyridene group, ether group, sulfide group, sulfonyl group, ketone group or single bond.

In formula (XI-2), R ²¹ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ¹⁰ and A ¹¹ independently represent 1 to 5 carbon atoms, respectively. Shows an alkylene group, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond.

The component (C) is preferably used as a polyaminobismaleimide compound represented by the above formula (VI) from the viewpoints of solubility in an organic solvent, high frequency characteristics, high adhesiveness to a conductor, moldability of a prepreg, and the like. .. The polyaminobismaleimide compound is obtained, for example, by carrying out a Michael addition reaction of a compound having two maleimide groups at the terminal and an aromatic diamine compound having two primary amino groups in the molecule in an organic solvent.

The aromatic diamine compound having two primary amino groups in the molecule is not particularly limited, and is, for example, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 2,2. '-Dimethyl-4,4'-diaminobiphenyl, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline , 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene and the like. These may be used alone or in combination of two or more.

In addition, from the viewpoint of high solubility in organic solvents, high reaction rate during synthesis, and high heat resistance, 4,4'-diaminodiphenylmethane and 4,4'-diamino-3,3'-dimethyl -Diphenylmethane or 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene is preferred. These may be used alone or in combination of two or more depending on the purpose, application and the like.

The organic solvent used in producing the polyaminobismaleimide compound is not particularly limited, and for example, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, and methyl. Ketones such as isobutylketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and mesitylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate and ethyl acetate; N, N-dimethylformamide, N, Examples thereof include nitrogen-containing compounds such as N-dimethylacetamide and N-methyl-2-pyrrolidone. One of these may be used alone, or two or more thereof may be mixed and used. Among these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide and N, N-dimethylacetamide are preferable from the viewpoint of solubility.

(catalyst)
The resin composition of the present embodiment may further contain a catalyst for accelerating the curing of the component (A). The content of the catalyst is not particularly limited, but may be 0.1 to 5% by mass based on the total mass of the resin composition. As the catalyst, for example, a peroxide, an azo compound or the like can be used.

Examples of the peroxide include dicumyl peroxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di. Examples thereof include bis (tert-butylperoxyisopropyl) benzene and tert-butylhydroperoxide such as (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene. Examples of the azo compound include 2,2'-azobis (2-methylpropanenitrile), 2,2'-azobis (2-methylbutanenitrile) and 1,1'-azobis (cyclohexanecarbonitrile).

(Thermosetting resin)
The resin composition of the present embodiment can further contain a thermosetting resin different from the component (A) and the component (C). The compound corresponding to the component (A) or the component (C) shall not belong to the thermosetting resin. Examples of the thermosetting resin include epoxy resin and cyanate ester resin. By including the thermosetting resin, the low thermal expansion characteristics of the resin composition can be further improved.

When the epoxy resin is contained as the thermosetting resin, it is not particularly limited, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, etc. Naphthalene skeleton-containing epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, bifunctional biphenyl type epoxy Examples thereof include a resin, a biphenyl aralkyl type epoxy resin, a dicyclopentadiene type epoxy resin, and a dihydroanthracene type epoxy resin. These may be used alone or in combination of two or more. Among these, from the viewpoint of high frequency characteristics and thermal expansion characteristics, it is preferable to use a naphthalene skeleton-containing epoxy resin or a biphenyl aralkyl type epoxy resin.

When the cyanate ester resin is contained as the thermosetting resin, it is not particularly limited, and for example, 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, and bis (3,5-). Dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α'-bis (4-cyanato) Examples thereof include phenyl) -m-diisopropylbenzene, a cyanate ester compound of a phenol-added dicyclopentadiene polymer, a phenol novolac type cyanate ester compound, and a cresol novolac type cyanate ester compound. These may be used alone or in combination of two or more. Among these, 2,2-bis (4-cyanatophenyl) propane is preferably used in consideration of its low cost and the overall balance of high frequency characteristics and other characteristics.

(Hardener)
The resin composition of the present embodiment may further contain a curing agent for the thermosetting resin. This makes it possible to smoothly proceed with the reaction when obtaining a cured product of the resin composition, and to appropriately adjust the physical characteristics of the cured product of the obtained resin composition.

When an epoxy resin is used as the thermosetting resin, the curing agent is not particularly limited, and for example, polyamine compounds such as diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, m-phenylenediamine, and dicyandiamide; bisphenol A, phenol novolac resin, and cresol. Examples thereof include polyphenol compounds such as novolak resin, bisphenol A novolak resin, and phenol aralkyl resin; acid anhydrides such as phthalic anhydride and pyromellitic anhydride; various carboxylic acid compounds; and various active ester compounds.

When a cyanate ester resin is used as the thermosetting resin, the curing agent is not particularly limited, but for example, various monophenol compounds, various polyphenol compounds, various amine compounds, various alcohol compounds, various acid anhydrides, various carboxylic acid compounds, etc. Can be mentioned. These may be used alone or in combination of two or more.

(Curing accelerator)
The resin composition of the present embodiment may further contain a curing accelerator depending on the type of the thermosetting resin. Examples of the curing accelerator of the epoxy resin include various imidazoles which are latent thermosetting agents, a _BF3 amine complex, a phosphorus-based curing accelerator and the like. When a curing accelerator is blended, imidazoles and phosphorus-based curing accelerators are preferable from the viewpoints of storage stability of the resin composition, handleability of the semi-cured resin composition, and solder heat resistance.

(Inorganic filler)
The resin composition of the present embodiment may further contain an inorganic filler. By arbitrarily containing an appropriate inorganic filler, the low thermal expansion property, high elastic modulus, heat resistance, flame retardancy and the like of the resin composition can be more effectively improved. The inorganic filler is not particularly limited, but for example, silica, alumina, titanium oxide, mica, verilia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, etc. Examples thereof include aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, silicon carbide and the like. These may be used alone or in combination of two or more.

There are no particular restrictions on the shape and particle size of the inorganic filler. The particle size of the inorganic filler may be, for example, 0.01 to 20 μm or 0.1 to 10 μm. Here, the particle size refers to the average particle size, and is the particle size at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the particles as 100%. The average particle size can be measured by a particle size distribution measuring device or the like using a laser diffraction / scattering method.

When the inorganic filler is used, the amount used is not particularly limited, but for example, the content ratio of the inorganic filler is preferably 3 to 75% by volume with the solid content in the resin composition as the total amount, and 5 to 70% by volume. % Is more preferable. When the content ratio of the inorganic filler in the resin composition is within the above range, good curability, moldability and chemical resistance can be easily obtained.

When an inorganic filler is used, a coupling agent can be used in combination as needed for the purpose of improving the dispersibility of the inorganic filler and the adhesion with the organic component. The coupling agent is not particularly limited, and for example, a titanate coupling agent, various silane coupling agents, and the like can be used. These may be used alone or in combination of two or more. Further, the amount of the coupling agent used is not particularly limited, and may be, for example, 0.1 to 5 parts by mass or 0.5 to 3 parts by mass with respect to 100 parts by mass of the inorganic filler used. Within this range, there is little deterioration in various properties, and it becomes easy to effectively demonstrate the features of the use of the inorganic filler.

When a coupling agent is used, a so-called integral blend treatment method may be used in which the inorganic filler is mixed in the resin composition and then the coupling agent is added. However, the coupling agent is previously added to the inorganic filler. A method using a dry or wet surface-treated inorganic filler is preferable. By using this method, the features of the above-mentioned inorganic filler can be exhibited more effectively. When the coupling agent is added by the integral blend treatment method, the coupling agent to be used shall be a coupling agent other than the above component (B), and the surface may be treated with the coupling agent in advance. When a filler is used, a coupling agent corresponding to the above component (B) can also be used.

(Thermoplastic resin)
The resin composition of the present embodiment may further contain a thermoplastic resin from the viewpoint of improving the handleability of the resin film. The type of the thermoplastic resin is not particularly limited, and the molecular weight is not limited, but the number average molecular weight (Mn) is preferably 200 to 60,000 from the viewpoint of further enhancing the compatibility with the component (A).

From the viewpoint of film formability and hygroscopicity, the thermoplastic resin is preferably a thermoplastic elastomer. Examples of the thermoplastic elastomer include a saturated thermoplastic elastomer, and examples of the saturated thermoplastic elastomer include a chemically modified saturated thermoplastic elastomer and a non-modified saturated thermoplastic elastomer. Examples of the chemically modified saturated thermoplastic elastomer include a styrene-ethylene-butylene copolymer modified with maleic anhydride. Specific examples of the chemically modified saturated thermoplastic elastomer include Tuftec M1911, M1913, M1943 (all manufactured by Asahi Kasei Chemicals Co., Ltd., trade name) and the like. On the other hand, examples of the non-denatured saturated thermoplastic elastomer include a non-denatured styrene-ethylene-butylene copolymer and the like. Specific examples of the non-denatured saturated thermoplastic elastomer include Tuftec H1041, H1051, H1043, H1053 (all manufactured by Asahi Kasei Chemicals Co., Ltd., trade name) and the like.

From the viewpoint of film formability, dielectric properties and hygroscopicity, the saturated thermoplastic elastomer preferably has a styrene unit in the molecule. In the present specification, the styrene unit refers to a unit derived from a styrene monomer in a polymer, and the saturated thermoplastic elastoma refers to an aliphatic hydrocarbon portion other than the aromatic hydrocarbon portion of the styrene unit. However, all of them have a structure composed of saturated bond groups.

The content ratio of the styrene unit in the saturated thermoplastic elastomer is not particularly limited, but the mass percentage of the styrene unit to the total mass of the saturated thermoplastic elastomer is preferably 10 to 80% by mass, preferably 20 to 70% by mass. It is more preferable to have it. When the content ratio of the styrene unit is within the above range, the film appearance, heat resistance and adhesiveness tend to be excellent.

Specific examples of the saturated thermoplastic elastomer having a styrene unit in the molecule include a styrene-ethylene-butylene copolymer. The styrene-ethylene-butylene copolymer can be obtained, for example, by hydrogenating the unsaturated double bond of the structural unit derived from butadiene of the styrene-butadiene copolymer.

The content of the thermoplastic resin is not particularly limited, but from the viewpoint of further improving the dielectric properties, the total solid content of the resin composition is preferably 0.1 to 15% by mass, preferably 0.3 to 10% by mass. %, More preferably 0.5 to 5% by mass.

(Flame retardants)
A flame retardant may be further added to the resin composition of the present embodiment. The flame retardant is not particularly limited, but a brominated flame retardant, a phosphorus flame retardant, a metal hydroxide and the like are preferably used. Examples of the bromine-based flame retardant include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolak type epoxy resin; hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), and ethylenebistetrabromophthalimide. , 1,2-Dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, 2,4 6-Tris (tribromophenoxy) -1,3,5-triazine and other brominated flame retardants; tribromophenylmaleimide, tribromophenylacrylate, tribromophenylmethacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromo Examples thereof include a brominated reaction type flame retardant containing an unsaturated double bond group such as benzyl acrylate and brominated styrene. One of these flame retardants may be used alone, or two or more of these flame retardants may be used in combination.

Examples of the phosphorus-based flame retardant include aromatic phosphoric acids such as triphenyl phosphate, tricresyl phosphate, trixilenyl phosphate, cresyldiphenyl phosphate, cresyldi-2,6-xylenyl phosphate, and resorcinolbis (diphenyl phosphate). Esters; Phosphonate esters such as divinyl phenylphosphonate, diallyl phenylphosphonate, bis (1-butenyl) phenylphosphonate; phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phos Phosphonate esters such as fafenanthrene-10-oxide derivatives; phosphazenic compounds such as bis (2-allylphenoxy) phosphazene, dicresylphosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, Examples thereof include phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus. Examples of the metal hydroxide flame retardant include magnesium hydroxide and aluminum hydroxide. One of these flame retardants may be used alone, or two or more of these flame retardants may be used in combination.

The resin composition of the present embodiment can be obtained by uniformly dispersing and mixing each of the above-mentioned components with a solvent, if necessary, and the preparation means, conditions and the like thereof are not particularly limited. For example, after sufficiently uniformly stirring and mixing various components in a predetermined blending amount with a mixer or the like, the mixture is kneaded using a mixing roll, an extruder, a kneader, a roll, an extruder or the like, and the obtained kneaded product is further cooled and mixed. A method of crushing can be mentioned. The kneading format is also not particularly limited. The solvent is not particularly limited, but toluene, xylene, mesitylene, methyl isobutyl ketone, cyclohexanone and the like are preferably used.

The relative permittivity of the cured product of the resin composition of the present embodiment is not particularly limited, but the relative permittivity at 10 GHz is preferably 3.6 or less, preferably 3.1 or less, from the viewpoint of suitable use in the high frequency band. Is more preferable, and 3.0 or less is further preferable. The lower limit of the relative permittivity is not particularly limited, but may be, for example, about 1.0. Further, from the viewpoint of suitable use in the high frequency band, the dielectric loss tangent of the cured product of the resin composition of the present embodiment is preferably 0.004 or less, more preferably 0.003 or less. The lower limit of the relative permittivity is not particularly limited, and may be, for example, about 0.0001. The relative permittivity and the dielectric loss tangent can be measured by the methods shown in the following examples.

From the viewpoint of suppressing warpage of the laminated board, the upper limit of the coefficient of thermal expansion of the cured product of the resin composition of the present embodiment is preferably 90 ppm / ° C. or lower, more preferably 45 ppm / ° C. or lower. It is more preferably 40 ppm / ° C. or less. The lower limit of the coefficient of thermal expansion is not particularly limited, but may be, for example, 10 ppm / ° C. or higher. The coefficient of thermal expansion can be measured according to IPC-TM-650 2.4.24.

The peeling strength of the cured product of the resin composition of the present embodiment is not particularly limited, but from the viewpoint of adhesiveness to the conductor, the low profile copper foil having a very small surface roughness on the adhesive surface side with the resin. The lower limit of the copper foil peeling strength at the time of use is preferably 0.6 kN / m or more, more preferably 0.7 kN / m or more, and further preferably 0.8 kN / m or more. preferable. The upper limit of the copper foil peeling strength is not particularly limited, but may be, for example, 5 kN / m or less. The peeling strength of the copper foil can be measured in accordance with the copper-clad laminate test standard JIS-C-6481.

The resin composition of the present embodiment has excellent high-frequency characteristics (low relative permittivity, low dielectric loss tangent), and also has high levels of adhesiveness and heat resistance to conductors. It is particularly useful as a resin composition used for forming an insulating layer.

[Support with resin layer]
In the present embodiment, the support with a resin layer can be manufactured by using the above resin composition. The support with a resin layer includes a support base material and a resin layer containing the above-mentioned resin composition provided on the support base material. The resin layer refers to a film-like, uncured or semi-cured resin composition, and is also referred to as a resin film.

The method for producing the support with the resin layer is not limited, and for example, it can be obtained by applying the resin composition on the support base material and drying the formed resin layer. Specifically, after applying the above resin composition on a supporting substrate using a kiss coater, a roll coater, a comma coater or the like, the temperature is, for example, 70 to 250 ° C., preferably 70 to 200 ° C. in a heating / drying furnace or the like. Then, it may be dried for 1 to 30 minutes, preferably 3 to 15 minutes. This makes it possible to obtain a support with a resin layer in a state where the resin layer is semi-cured.

The semi-cured resin layer is further heated in a heating furnace at a temperature of, for example, 170 to 250 ° C, preferably 185 to 230 ° C for 60 to 150 minutes to thermally cure the resin layer and cure the resin. You can get a layer.

The thickness of the resin layer according to the present embodiment is not particularly limited, but is preferably 1 to 200 μm, more preferably 2 to 180 μm, and even more preferably 3 to 150 μm. By setting the thickness of the resin layer within the above range, it is easy to achieve both thinness of the printed wiring board obtained by using the support with the resin layer according to the present embodiment and good high frequency characteristics.

The supporting base material is not particularly limited, but is preferably at least one selected from the group consisting of glass, metal foil and PET film. Since the support with the resin layer is provided with the support base material, the storability and the handleability when used in the manufacture of the printed wiring board tend to be good. The support with a resin layer according to the present embodiment may be peeled off from the support base material when used.

[Prepreg]
The prepreg of the present embodiment includes a fiber base material and the above-mentioned resin composition impregnated in the fiber base material. Such a prepreg can be obtained, for example, by impregnating a fiber base material as a reinforcing base material with the resin composition of the present embodiment and drying the impregnated resin composition.

The prepreg of the present embodiment may be obtained by applying the resin composition of the present embodiment to the fiber base material and then drying the coated resin composition. Specifically, the fiber substrate to which the resin composition is attached is heated and dried in a drying oven at a temperature of usually 80 to 200 ° C. for 1 to 30 minutes to obtain a prepreg in which the resin composition is semi-cured. Be done. From the viewpoint of good moldability, it is preferable to coat or impregnate the resin composition so that the amount of the resin composition adhered to the fiber substrate is 30 to 90% by mass as the resin content in the prepreg after drying.

The fiber base material is not limited, but a sheet-shaped fiber base material is preferable. As the sheet-shaped fiber base material, for example, known materials used for laminated boards for various electric insulating materials are used. Examples of the material include inorganic fibers such as E glass, NE glass, S glass and Q glass; and organic fibers such as polyimide, polyester and tetrafluoroethylene. As the sheet-shaped fiber base material, those having a shape such as a woven fabric, a non-woven fabric, and a chopped strand mat can be used. Further, the thickness of the sheet-shaped fiber base material is not particularly limited, and for example, one having a thickness of 0.02 to 0.5 mm can be used. Further, as the sheet-like fiber base material, those surface-treated with a coupling agent or the like or those subjected to mechanically opening treatment have the impregnation property of the resin composition and the heat resistance when formed into a laminated board. It is preferable from the viewpoint of moisture absorption resistance and processability.

[Laminate board]
The laminated board of the present embodiment includes a conductor layer and a cured resin layer containing a cured product of the above resin composition provided on the conductor layer. For example, the metal-clad laminate can be manufactured by using the support with the resin layer or the prepreg.

The method for manufacturing the metal-clad laminate is not limited, but for example, one or a plurality of resin layers or prepregs from which the support base material is peeled off from the support with the resin layer of the present embodiment are laminated, and a conductor layer is formed on at least one surface. A resin layer to be an insulating layer by arranging a metal leaf, for example, by heating and pressurizing at a temperature of 170 to 250 ° C., preferably 185 to 230 ° C. and a pressure of 0.5 to 5.0 MPa for 60 to 150 minutes. Alternatively, a metal-clad laminate having a metal leaf on at least one surface of the prepreg can be obtained. The heating and pressurization can be performed, for example, under the condition that the degree of vacuum is 10 kPa or less, preferably 5 kPa or less, and it is preferable to perform the heating and pressurization in a vacuum from the viewpoint of improving efficiency. The heating and pressurization are preferably carried out from 30 minutes from the start to the end time of molding.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present embodiment includes at least three circuit layers and two or more interlayer insulating layers provided between adjacent sets of circuit layers, respectively, and at least one of the interlayer insulating layers. The layer is a cured resin layer containing a cured product of the above resin composition. The number of circuit layers is not particularly limited, and may be 3 to 20 layers. The multilayer printed wiring board can also be manufactured by using, for example, the above-mentioned support with a resin layer, a prepreg, or a metal-clad laminate.

The method for manufacturing the multilayer printed wiring board is not particularly limited, but for example, first, a support with a resin layer is arranged on one side or both sides of the circuit-formed core board, or between a plurality of core boards. After arranging a support with a resin layer and performing pressurization and heat laminating molding, or pressurization and heat press molding to bond each layer, laser drilling, drilling, metal plating, metal etching, etc. By performing circuit forming processing, a multilayer printed wiring board can be manufactured. The supporting base material of the support with the resin layer can be peeled off before being placed on the core substrate or between the core substrates, or can be peeled off after the resin layer is attached to the core substrate.

A method for manufacturing a multilayer printed wiring board according to the present embodiment will be described with reference to FIG. FIG. 1 is a diagram schematically showing a manufacturing process of a multilayer printed wiring board according to the present embodiment. The method for manufacturing a multilayer printed wiring board according to the present embodiment includes (a) a step of laminating a resin film on an inner layer circuit board to form a resin layer (hereinafter referred to as "step (a)") and (b) a resin. A step of heating and pressurizing the layer to cure it (hereinafter referred to as "step (b)") and (c) a step of forming an antenna circuit layer on the cured resin layer (hereinafter referred to as "step (c)"). And have.

As shown in FIG. 1A, in the step (a), the resin film 12 according to the present embodiment is laminated on the inner layer circuit board 11 to form a resin layer made of the resin film 12.

The laminating method is not particularly limited, and examples thereof include a multi-stage press, a vacuum press, a normal pressure laminator, a method of laminating using a laminator that heats and pressurizes under vacuum, and a method that uses a laminator that heats and pressurizes under vacuum is preferable. .. As a result, even if the inner layer circuit board 11 has a fine wiring circuit on the surface, there are no voids and the circuits can be embedded with resin. The laminating conditions are not particularly limited, but it is preferable that the crimping temperature is 70 to 130 ° C., the crimping pressure is 1 to 11 kgf / cm ² , and the laminating is performed under reduced pressure or vacuum. The laminating may be a batch type or a continuous type in a roll.

The inner layer circuit board 11 is not particularly limited, and a glass epoxy board, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, or the like can be used. The circuit surface of the surface on which the resin film of the inner layer circuit board 11 is laminated may be roughened in advance.

The number of circuit layers of the inner layer circuit board 11 is not limited. In FIG. 1, a 6-layer inner circuit board is used, but the number of layers is not limited. For example, when manufacturing a printed wiring board for a millimeter-wave radar, 2 to 20 layers can be freely selected according to the design. can do. The multilayer printed wiring board of this embodiment can be applied to the production of a millimeter wave radar. That is, it is possible to manufacture a printed wiring board for a millimeter-wave radar including a resin layer containing a cured product of the resin composition of the present embodiment and a circuit layer.

When the antenna circuit layer 14 described later is formed on the resin layer 12a by etching, the metal foil 13 may be further laminated on the resin film 12 to form the metal layer 13a. Examples of the metal foil include copper, aluminum, nickel, zinc and the like, and copper is preferable from the viewpoint of conductivity. The metal foil may be an alloy, and examples of the copper alloy include high-purity copper alloys to which a small amount of beryllium or cadmium is added. The thickness of the metal foil is preferably 3 to 200 μm, more preferably 5 to 70 μm.

As shown in FIG. 1 (b), in the step (b), the inner layer circuit board 11 and the resin layer 12a laminated in the step (a) are heated and pressed to be thermally cured. The conditions are not particularly limited, but are preferably in the range of a temperature of 100 ° C. to 250 ° C., a pressure of 0.2 to 10 MPa, and a time of 30 to 120 minutes, more preferably 150 ° C. to 220 ° C.

As shown in FIG. 1 (c), in the step (c), the antenna circuit layer 14 is formed on the resin layer 12a. The method for forming the antenna circuit layer 14 is not particularly limited, and may be formed by, for example, an etching method such as a subtractive method, a semi-additive method, or the like.

In the subtractive method, an etching resist layer having a shape corresponding to a desired pattern shape is formed on the metal layer 13a, and the metal layer of the portion from which the resist has been removed is dissolved and removed with a chemical solution by a subsequent development process. This is a method of forming a desired circuit. As the chemical solution, for example, a copper chloride solution, an iron chloride solution, or the like can be used.

In the semi-additive method, a metal film is formed on the surface of the resin layer 12a by an electroless plating method, a plating resist layer having a shape corresponding to a desired pattern is formed on the metal film, and then the metal layer is formed by an electrolytic plating method. After forming, the unnecessary electroless plating layer is removed with a chemical solution or the like to form a desired circuit layer.

Further, holes such as via holes 15 may be formed in the resin layer 12a, if necessary. The method of forming holes is not limited, but NC drills, carbon dioxide lasers, UV lasers, YAG lasers, plasmas and the like can be applied.

Here, the inner layer circuit board 11 can also be manufactured by the steps (p) to (r) shown in FIG. FIG. 2 is a diagram schematically showing a manufacturing process of an inner layer circuit board. That is, the method for manufacturing a multilayer printed wiring board according to the present embodiment includes steps (p), steps (q), steps (r), steps (a), steps (b), and steps (c). May be good. Hereinafter, steps (p) to (r) will be described.

First, as shown in FIG. 2 (p), in the step (p), the core substrate 41 and the prepreg 42 are laminated. As the core substrate, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or the like can be used. Examples of the prepreg include "GWA-900G", "GWA-910G", "GHA-679G", "GHA-679G (S)", "GZA-71G" and "GEA-75G" manufactured by Hitachi Kasei Co., Ltd. Also product name) etc. can be used.

Next, as shown in FIG. 2 (q), in the step (q), the laminate of the core substrate 41 and the prepreg 42 obtained in the step (p) is heated and pressed. The heating temperature is not particularly limited, but is preferably 120 to 230 ° C, more preferably 150 to 210 ° C. The pressure to be pressurized is not particularly limited, but is preferably 1 to 5 MPa, more preferably 2 to 4 MPa. The heating time is not particularly limited, but is preferably 30 to 120 minutes. As a result, it is possible to obtain an inner layer circuit board having excellent dielectric properties, mechanical and electrical connection reliability in high temperature and high humidity.

Further, as shown in FIG. 2 (r), in the step (r), a through hole 43 is formed in the inner layer circuit board as needed. The method for forming the through hole 43 is not particularly limited, and may be the same as the step for forming the antenna circuit layer described above, or a known method may be used.

By the above steps, the multilayer printed wiring board of the present embodiment can be manufactured. Further, the steps (a) to (c) may be further repeated using the printed wiring board manufactured through the above steps as an inner layer circuit board.

FIG. 3 is a diagram schematically showing a manufacturing process of a multilayer printed wiring board using a multilayer printed wiring board manufactured by the process shown in FIG. 1 as an inner layer circuit board. FIG. 3A and FIG. 1A correspond to FIG. 3B and FIG. 1B, and FIG. 3C and FIG. 1C correspond to each other.

Specifically, in FIG. 3A, the resin film 22 is laminated on the inner layer circuit board 21 to form the resin layer 22s, and the metal foil 23 is laminated on the resin film 22 as needed to form the metal layer 23a. Is the process of forming. FIG. 3B is a step of heating and pressurizing the resin layer 22a to cure the resin layer 22a, and FIG. 3C is a step of forming the antenna circuit layer 24 on the cured resin layer.

In FIGS. 1 and 3, the number of resin layers laminated on the inner circuit board is set to one or two for the purpose of forming an antenna circuit pattern or the like, but the number is not limited to this, and the number of layers is not limited to this, depending on the antenna circuit design. The number of layers may be three or more. By making the antenna circuit layer multi-layered, it becomes easy to design an antenna having a wide band characteristic and an antenna in which the angle change of the antenna radiation pattern is small (beam tiltless) in the frequency band used.

In the method for producing a multilayer printed wiring board according to the present embodiment, a resin composition containing a maleimide group, a divalent group having at least two imide bonds, and a compound having a saturated or unsaturated divalent hydrocarbon group is used. Since the resin layer is formed by using the resin layer, it is possible to produce a laminated body without providing an adhesive layer in addition to the layer having excellent high frequency characteristics. As a result, the effect of simplifying the process and further improving the high frequency characteristics can be obtained.

The support with a resin layer, the prepreg, the laminated board, and the multilayer printed wiring board using the resin composition of the present embodiment as described above can be suitably used for an electronic device that handles a high frequency signal of 1 GHz or more, and particularly 10 GHz. It can be suitably used for electronic devices that handle the above high-frequency signals.

Although the preferred embodiments of the present invention have been described above, these are examples for explaining the present invention, and the scope of the present invention is not limited to these embodiments. The present invention can be carried out in various embodiments different from the above embodiments without departing from the gist thereof.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the present invention is not limited to the following examples.

[Resin composition]
Various resin compositions were prepared according to the following procedure. The amounts (parts by mass) of the raw materials used for preparing the resin compositions of Examples 1 to 12 and Comparative Examples 1 and 2 are collectively shown in Tables 1 and 2.

Put each component shown in Table 1 or 2 into a 300 mL four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, stir at 25 ° C. for 1 hour, and then # 200 nylon mesh (opening 75 μm). Was filtered to obtain a resin composition.

The abbreviations and the like of each material in Tables 1 and 2 are as follows.
(1) BMI-3000 [Mw: about 3000, Designer Moles Inc. Made, product name]
(2) BMI-5000 [Mw: about 5000, Designer Moleculars Inc. Made, product name]
(3) BMI-1000 [Bis (4-maleimidephenyl) methane, manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name)
(4) BMI-4000 [2,2-bis (4- (4-maleimide phenoxy) phenyl) propane, manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name]
(5) KBM-602 [N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd., trade name]
(6) KBM-603 [N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd., trade name]
(7) KBE-903 [3-aminopropyltriethoxysilane, manufactured by Shinetsu Silicone Co., Ltd., trade name]
(8) KBM-903 [3-aminopropyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd., trade name]
(9) KBM-573 [N-Phenyl-3-aminopropyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd., trade name]
(10) KBM-403 [3-glycid kyripropyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd., trade name]
(11) Bisaniline M [1,3-bis (2- (4-aminophenyl) -2-propyl) benzene, manufactured by Mitsui Kagaku Fine Chemicals Co., Ltd., trade name]
(12) Silica slurry [Spherical molten silica, surface treatment: phenylaminosilane coupling agent (1% by mass / total solid content in the slurry), dispersion medium: methyl isobutyl ketone (MIBK), solid content concentration: 70% by mass, average Particle size: 0.5 μm, density: 2.2 g / cm ³ , manufactured by Admatex Co., Ltd., trade name "SC-2050KNK"]
(13) Perbutyl P [1,4-bis (tert-butylperoxyisopropyl) benzene, manufactured by NOF CORPORATION, trade name]

The presumed structure of the compounds (BMI-3000 and BMI-5000) used as the component (A) is as shown in the following formula (XII-3). In the formula (XII-3), n represents an integer of 1 to 10.

[Support with resin layer]
The resin compositions obtained in Examples and Comparative Examples were coated on a 38 μm-thick PET film (G2-38, manufactured by Teijin Co., Ltd.) as a supporting base material using a comma coater (drying temperature: 130). ℃), a support with a resin layer provided with a semi-cured resin layer (semi-cured resin film) on a PET film was produced. The thickness of the resin layer of the support with the resin layer was 50 μm.

[Evaluation of support with resin layer]
The appearance and handleability of the support with a resin layer of Examples and Comparative Examples were evaluated. The results are shown in Tables 3 and 4.

The appearance was visually evaluated according to the following criteria.
A: There is no unevenness, streaks, etc. on the surface of the semi-cured resin film.
B: The surface of the semi-cured resin film has some unevenness, streaks, etc., and lacks surface smoothness.

The handleability was evaluated by the following criteria by visual inspection and tactile sensation.
(1) Presence or absence of surface stickiness (tack) at 25 ° C.
(2) Presence or absence of resin cracking or powder falling in the state when cutting with a cutter knife.
A: Neither (1) nor (2) above.
B: It is also one of the above (1) and (2).

[Multilayer printed wiring board]
Using the above-mentioned support with a resin layer, a multilayer printed wiring board was produced by the following procedure.

A glass cloth base material epoxy resin copper-clad laminated board on which a circuit pattern is formed is used as an inner layer circuit board, and one semi-cured resin film obtained by peeling a PET film from the support with the resin layer is placed on both sides thereof. After arranging an electrolytic copper foil with a thickness of 12 μm (manufactured by Nippon Denkai Co., Ltd., trade name “YGP-12”), a mirror plate is placed on it, and heating and applying under press conditions of 200 ° C / 3.0 MPa / 70 minutes. A four-layer printed wiring board was produced by pressure molding.

Next, the copper foil of the outermost layer of the produced 4-layer printed wiring board was etched, and the circuit embedding property (multilayer formability) was evaluated. The multi-layer moldability was visually evaluated according to the following criteria.
A: There are no voids or blurs in the circuit.
B: There are some voids and cassoulet.

[Double-sided metal-clad cured resin film]
After stacking two semi-cured resin films from which the PET film was peeled off from the above-mentioned support with a resin layer, low-profile copper foil with a thickness of 18 μm (M surface Rz: 3 μm, manufactured by Furukawa Denki Kogyo Co., Ltd.) was placed on both sides thereof. The product name "F3-WS") is placed so that its roughened surface (M surface) is in contact with the roughened surface (M surface), a mirror plate is placed on it, and heat and pressure molding are performed under press conditions of 200 ° C./3.0 MPa/70 minutes. A double-sided metal-clad cured resin film (thickness: 0.1 mm) was prepared.

The above-mentioned double-sided metal-clad cured resin film was evaluated for handleability (bending resistance), dielectric properties, copper foil peeling strength, and solder heat resistance. The evaluation results are shown in Tables 3 and 4. The method for evaluating the characteristics of the double-sided metal-clad cured resin film is as follows.

[Handling (bending resistance)]
The handleability (bending resistance) was evaluated according to the following criteria by bending an etched outer layer copper foil of a double-sided metal-clad cured resin film by 180 degrees.
A: No cracks or cracks occur when bent.
B: When bent, some cracks or cracks occur.

[Dielectric characteristics]
For the relative permittivity and dielectric loss tangent, which are the dielectric properties, the outer layer copper foil of the double-sided metal-clad cured resin film is etched and cut into a length of 60 mm, a width of 2 mm, and a thickness of about 1 mm. It was measured. The vector network analyzer E8364B manufactured by Agilent Technologies is used for the measuring instrument, CP129 (10 GHz band resonator) and CP137 (20 GHz band resonator) manufactured by Kanto Denshi Applied Development Co., Ltd. are used for the cavity resonator, and CPMA-V2 is used for the measurement program. I used each. The conditions were a frequency of 10 GHz and a measurement temperature of 25 ° C.

[Copper foil peeling strength]
The peeling strength of the copper foil was measured in accordance with the copper-clad laminate test standard JIS-C-6481. The measurement temperature was 25 ° C.

[Solder heat resistance]
For solder heat resistance, a copper foil on one side of a double-sided metal-clad cured resin film is etched and cut into 50 mm squares as a test piece, and the normal condition and pressure cooker test (PCT) device (condition: 121 ° C., 2.2). After being treated for a predetermined time (1, 3, 5 hours) at atmospheric pressure), it was floated on molten solder at 288 ° C. for 20 seconds, and the appearance of each of the three cured resin films having different treatment times was determined according to the following criteria. It was evaluated visually. In Tables 3 and 4, the one that has been processed for 1 hour is referred to as PCT-1h, the one that has been processed for 3 hours is referred to as PCT-3h, and the one that has been processed for 5 hours. Is expressed as PCT-5h. Further, in Tables 3 and 4, the notation "A (3/3)" indicates that all three of the three cured resin films were evaluated as A.
A: No swelling or measling occurs inside the film or between the film and the copper foil.
B: Occurrence of swelling or measling is observed inside the film and between the film and the copper foil.

[Coefficient of thermal expansion (CTE)]
The coefficient of thermal expansion (in the plate thickness direction) is the thermomechanical analyzer TMA (TA Instrument Co., Ltd., Q400), which is a test piece obtained by etching copper foil on both sides of a double-sided metal-clad cured resin film and cutting it into 5 mm squares. ) (Temperature range: 30 to 150 ° C., load: 5 g) and measured in accordance with the IPC standard (IPC-TM-650 2.4.24).

As is clear from the results shown in Tables 3 and 4, the semi-curable resin films produced by using the resin compositions of Examples 1 to 12 have an appearance (surface uniformity) and handleability (tackability). , Cracking, powder falling, etc.), and it was confirmed that the multi-layer moldability was also good. In addition, the cured resin films, which are the cured products of the resin compositions of Examples 1 to 12, are both excellent in relative permittivity and dielectric loss tangent, and are also excellent in solder heat resistance and copper foil peeling strength. rice field.

On the other hand, as is clear from the results shown in Tables 3 and 4, the cured resin film which is the cured product of the resin composition of Comparative Example 1 was inferior to that of the example in terms of the copper foil peeling strength. .. Further, the semi-cured resin film of the resin composition of Comparative Example 2 had resin cracking, and the film handleability was poor. Further, the cured resin film, which is the cured product, was inferior to that of the examples in terms of relative permittivity and dielectric loss tangent.

[Printed wiring board for millimeter-wave radar]
(Example 13)
After the inner layer circuit board 11 is manufactured in the process shown in FIG. 2, the resin composition of Example 1 is used in the process shown in FIG. 1 to print a millimeter-wave radar having a total of 7 layers including one millimeter-wave antenna circuit layer. A wiring board was produced.

First, in the step (p), a glass cloth base material epoxy copper-clad laminate with a thickness of 0.1 mm, in which copper foil with a thickness of 18 μm is bonded on both sides (manufactured by Hitachi Kasei Co., Ltd., trade name “MCL-E-75G” After etching and removing unnecessary copper foil to prepare an inner layer circuit board, a 0.1 mm glass cloth base material epoxy prepreg (manufactured by Hitachi Kasei Co., Ltd., trade name "GEA-75G") is coated with a copper-clad laminate. The structure was prepared by arranging them on top of each other. Next, in step (q), the structure produced in step (p) was heat-press molded under press conditions of 180 ° C./3.0 MPa/60 minutes to form an integrated substrate. Then, in the step (r), a hole was drilled at a desired position in the integrated substrate produced in the step (q), and copper plating was performed in the hole to prepare the inner layer circuit board 11.

In the step (a), a semi-curable resin film (thickness 130 μm) prepared by using the resin composition of Example 1 is temporarily adhered to the surface of the inner layer circuit board 11 with a vacuum laminator, and further, a row having a thickness of 18 μm is obtained. A profile copper foil (manufactured by Furukawa Denki Kogyo Co., Ltd., trade name "F3-WS") was placed to prepare a structure. Next, in the step (b), a mirror plate was placed on the structure produced in the step (a), and heat and pressure molding was performed under press conditions of 200 ° C./3.0 MPa/70 minutes. Then, in the step (c), the structure produced in the step (b) is subjected to plating and etching after removing unnecessary resin and forming a via hole (IVH) at a desired position with a laser. The antenna circuit layer 14 was formed, and a multi-layer printed wiring board having a total of 7 layers including one millimeter-wave antenna circuit layer was obtained.

(Example 14)
Using the resin composition of Example 2, a printed wiring board for a millimeter-wave radar having a total of eight layers including two millimeter-wave antenna circuit layers was produced in the process shown in FIG.

In the step (a), the printed wiring board for millimeter wave radar produced in Example 1 is used as the inner layer circuit board 21, and the semi-cured resin film (thickness) produced by using the resin composition of Example 2 on the surface thereof. After temporarily adhering 130 μm) with a vacuum laminator, “F3-WS” was placed to prepare a structure. Next, in step (b), a mirror plate was placed on the structure produced in step (a), and heat and pressure molding was performed under press conditions of 200 ° C./3.0 MPa/70 minutes. Then, in the step (c), the structure produced in the step (b) is subjected to plating and etching after removing unnecessary resin and forming a via hole (IVH) at a desired position with a laser. The antenna circuit layer 24 was formed, and a printed wiring board for a millimeter-wave radar having a total of eight layers including two layers of millimeter-wave antenna circuits was obtained.

(Comparative Example 3)
A total including two millimeter-wave antenna circuit layers in the process shown in FIG. 4, which is a conventional method, using a fluororesin material (manufactured by Rogers, trade name “RO3003”) instead of the resin composition of Example 2. A printed wiring board for a millimeter-wave radar having an eight-layer structure was produced.

First, in the step (a') of FIG. 4, 0.1 mm glass cloth base material epoxy prepreg (GEA-75G) 33 and 0. A structure was prepared by stacking and arranging copper-clad laminates 32 from which unnecessary copper foil of a 13 mm fluororesin-based copper-clad laminate (manufactured by Rogers, trade name "RO-3003") was removed by etching. Next, in the step (b'), the structure produced in the step (a') was heat-press molded under the press conditions of 180 ° C./3.0 MPa/60 minutes, and a total of 7 including one layer of the antenna circuit was formed. A multi-layer wiring board with a layered structure was produced. Next, in the step (c'), a 0.1 mm glass cloth base material epoxy prepreg (GEA-75G) 33 and a 0.13 mm fluororesin group were placed on the multilayer wiring board produced in the step (b'). A structure was produced by stacking and arranging copper-clad laminates 32 from which unnecessary copper foil of the copper-clad laminate (RO-3003) was removed by etching. Then, in the step (d'), the structure produced in the step (c') is heat-press molded under the press conditions of 180 ° C./3.0 MPa/60 minutes, and then through-hole drilling-plating-etching. A desired circuit was formed by the above method, and a printed wiring board for a millimeter-wave radar having a total of eight layers including two layers of antenna circuits was obtained.

According to the method of Comparative Example 3, it is possible to form an antenna circuit having a multi-layer structure even by using a fluororesin-based copper-clad laminate, but an adhesive layer such as a prepreg is required between the fluororesins. At that time, since the adhesive layer such as a general prepreg has a poor relative permittivity and dielectric loss tangent in the millimeter wave band as compared with the fluororesin material, the presence of the adhesive layer between the fluororesins causes an antenna having a multilayer structure. Circuit characteristics are prone to deterioration.

On the other hand, in the method of Example 14, since the antenna circuit having a multilayer structure is composed only of the material having excellent relative permittivity and dielectric loss tangent in the millimeter wave band, the characteristics are excellent as compared with Comparative Example 3. An antenna circuit having a multi-layer structure can be formed.

Since the resin composition of the present invention exhibits various characteristics required for a printed wiring board and excellent high-frequency characteristics, electronic devices, mobile communication devices and their base station devices, servers that handle high-frequency signals of 1 GHz or higher or 10 GHz or higher are exhibited. It is useful as a member / component of a printed wiring board used in network-related electronic devices such as routers and various electronic devices such as large computers.

11,21,31 ... Inner layer circuit board, 12,22 ... Resin film, 12a, 22a ... Resin layer, 13,23 ... Metal leaf, 13a, 23a ... Metal layer, 14,24 ... Antenna circuit layer, 15 ... Via hole, 32 ... Copper-clad laminate, 33, 42 ... Prepreg, 41 ... Core substrate, 43 ... Through hole.

Claims (18)

(A) A compound having a maleimide group and a divalent group bonded to the maleimide group, wherein the divalent group is a saturated or unsaturated divalent hydrocarbon group and a maleimide group bonded to the maleimide group. Compounds containing at least two imide groups other than
(B) A compound having a silyl group and
(C) Containing a compound having a maleimide group and
The resin composition, wherein the component (B) is a compound other than the component (A) and the component (C), and the component (C) is a compound other than the component (A). The resin composition according to claim 1, wherein the component (C) contains a maleimide group and a compound having an aromatic group bonded to the maleimide group. The resin composition according to claim 1, wherein the component (C) contains a compound represented by the following formula (VI).

[ ^In the formula (VI), A4 indicates a group represented by the following formula (VII), (VIII), (IX) or (X), and A5 indicates a group represented by the following formula ⁽ XI). .. ]

[In formula (VII), R ¹⁰ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom. ]

[In formula (VIII), R ¹¹ and R ¹² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁶ is an alkylene group having 1 to 5 carbon atoms or alkylidene. A group, an ether group, a sulfide group, a sulfonyl group, a ketone group, a single bond or a group represented by the following formula (VIII-1) is shown. ]

[In the formula (VIII-1), R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁷ is an alkylene group having 1 to 5 carbon atoms. , Isopropyridene group, ether group, sulfide group, sulfonyl group, ketone group or single bond. ]

[In the formula (IX), i represents an integer from 1 to 10. ]

[In the formula (X), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and j represents an integer of 1 to 8. ]

[In the formula (XI), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom, and ^A8 . Is an alkylene group or an alkylidene group having 1 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a ketone group, a fluorenylene group, a single bond, a group represented by the following formula (XI-1) or the following formula (XI-2). ) Indicates a group. ]

[In the formula (XI-1), R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ⁹ is an alkylene group having 1 to 5 carbon atoms. , Isopropyridene group, m-phenylenediisopropyridene group, p-phenylenediisopropyridene group, ether group, sulfide group, sulfonyl group, ketone group or single bond. ]

[In the formula (XI-2), R ²¹ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and A ¹⁰ and A ¹¹ independently represent 1 to 1 carbon atoms, respectively. 5 shows an alkylene group, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond. ] The resin composition according to any one of claims 1 to 3, wherein the total content of the component (A) and the component (C) is 98% by mass or less based on the total mass of the resin composition. thing. (A) A saturated or unsaturated divalent compound having a maleimide group and a divalent group bonded to the maleimide group, wherein the divalent group has 8 to 300 carbon atoms bonded to the maleimide group. A compound containing at least two imide groups other than the hydrocarbon group and the maleimide group of
(B) It has at least one functional group and a silyl group selected from the group consisting of an amino group, a vinyl group, an epoxy group, a styryl group, a methacryloyl group, an isocyanul group, a ureido group, a mercapto group, a sulfide group and an isocyanate group. Containing with compounds,
The resin composition, wherein the component (B) is a compound other than the component (A). (A) A compound having a maleimide group and a divalent group bonded to the maleimide group, wherein the divalent group is a saturated or unsaturated divalent hydrocarbon group and a maleimide group bonded to the maleimide group. Compounds containing at least two imide groups other than
(B) Containing a compound having a silyl group and
The component (B) is a resin composition used for forming an interlayer insulating layer of a printed wiring board, which is a compound other than the component (A). The resin composition according to claim 5 or 6, wherein the content of the component (A) is 98% by mass or less based on the total mass of the resin composition. The resin composition according to any one of claims 1 to 7, wherein the divalent group contains a group having two imide groups represented by the following formula (I).

[In formula (I), R ¹ represents a tetravalent organic group. ] The resin composition according to claim 8, wherein the component (A) contains a compound represented by the following formula (XIII).

[In formula (XIII), R represents a saturated or unsaturated divalent hydrocarbon group, R ¹ represents a tetravalent organic group, and n represents an integer from 1 to 10. ] The resin composition according to any one of claims 1 to 9, wherein the saturated or unsaturated divalent hydrocarbon group is a group represented by the following formula (II).

[In formula (II), R ² and R ³ each independently represent an alkylene group having 4 to 50 carbon atoms, R ⁴ represents an alkyl group having 4 to 50 carbon atoms, and R ⁵ represents an alkyl group having 2 to 50 carbon atoms. Indicates an alkyl group. ] The resin composition according to any one of claims 1 to 10, wherein the cured product of the resin composition has a relative permittivity of 3.6 or less at 10 GHz. A support with a resin layer comprising a support base material and a resin layer containing the resin composition according to any one of claims 1 to 11 provided on the support base material. A prepreg comprising a fiber base material and the resin composition according to any one of claims 1 to 11 impregnated in the fiber base material. A laminated board comprising a conductor layer and a cured resin layer containing a cured product of the resin composition according to any one of claims 1 to 11 provided on the conductor layer. A multilayer printed wiring board comprising at least three circuit layers and two or more layers of interlayer insulating layers provided between adjacent sets of circuit layers, and at least one of the interlayer insulating layers. A multilayer printed wiring board in which the layer is a cured resin layer containing a cured product of the resin composition according to any one of claims 1 to 11. The multilayer printed wiring board according to claim 15, wherein the number of circuit layers is 3 to 20 layers. An application for manufacturing a millimeter wave radar of the multilayer printed wiring board according to claim 15 or 16. A printed wiring board for a millimeter-wave radar, comprising a circuit layer and a cured resin layer containing a cured product of the resin composition according to any one of claims 1 to 11 provided on the circuit layer.

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