JP2016204639A - Resin composition, laminate and multilayer printed board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that has excellent high frequency properties (low relative dielectric constant and low dielectric loss tangent) and also has low thermal expansion properties and conductor adhesion properties at high levels.SOLUTION: This invention relates to a resin composition comprising (A) a maleimide compound having a saturated or unsaturated divalent hydrocarbon group, and (B) an aromatic maleimide compound.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a laminated board, and a multilayer printed wiring board.

  In mobile communication devices typified by mobile phones, base station devices, network infrastructure devices such as servers and routers, and electronic devices such as large computers, the speed and capacity of signals used are increasing year by year. Along with this, printed wiring boards mounted on these electronic devices are required to cope with high frequencies, and a substrate material having a low relative dielectric constant and a low dielectric loss tangent that can reduce transmission loss is required. In recent years, practical applications and practical plans for new systems that handle high-frequency radio signals in the ITS field (related to automobiles and transportation systems) and indoor short-distance communication fields in addition to the above-described electronic devices are available as applications that handle such high-frequency signals. In the future, it is expected that a low transmission loss substrate material will be further required for printed wiring boards mounted on these devices.

  In addition, due to recent environmental problems, mounting of electronic components with lead-free solder and flame-retardant with halogen-free has been required, so printed circuit board materials have higher heat resistance and flame resistance than before. Sex is needed.

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

  In addition, the present inventors use a polyphenylene ether resin and a polybutadiene resin as a base to make a semi-IPN at the resin composition production stage (A stage stage), thereby providing compatibility, heat resistance, thermal expansion characteristics, and adhesion to a conductor. The resin composition which can improve property etc. is proposed (for example, refer patent document 3).

  Furthermore, the use of a maleimide compound as a printed wiring board material has been studied. For example, Patent Document 4 discloses 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 that promotes a reaction and silica is disclosed.

JP 58-69046 A Japanese Patent Publication No. 61-18937 JP 2008-95061 A JP 2012-255059 A

  However, printed circuit board materials used in recent high-frequency bands are required to be further excellent in various properties such as a low coefficient of thermal expansion in addition to high-frequency properties and high adhesion to conductors.

  For example, the adhesiveness to the conductor is 0.6 kN / m in terms of the peel strength of the copper foil when using a low profile copper foil (Rz: 1 to 2 μm) having a very low surface roughness on the side of the adhesive surface with the resin. The above is desired. Moreover, as a low thermal expansion characteristic, it is desired that a thermal expansion coefficient (Z direction, Tg or less) is 45 ppm / ° C. or less.

  Of course, as the high frequency characteristics, excellent dielectric characteristics in a higher frequency band are required. For example, the relative dielectric constant of a substrate material when a general E glass base material is combined is 3.7 or less, and Is desired to be 3.6 or less. In addition to the conventional dielectric characteristic values at 1 to 5 GHz, there is an increasing need to satisfy the above-mentioned required values in a high frequency band of 10 GHz band or higher.

  In view of the present situation, the present invention provides a resin composition having excellent high frequency characteristics (low relative dielectric constant, low dielectric loss tangent), low thermal expansion characteristics and high adhesion to conductors, and An object of the present invention is to provide a laminated board and a multilayer printed wiring board which are manufactured using the resin composition and have good appearance and handleability.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a compound having a specific structure and a resin composition containing an aromatic maleimide compound different from the compound. It came to be completed.

That is, the present invention includes the following aspects.
[1] A resin composition comprising (A) a maleimide compound having a saturated or unsaturated divalent hydrocarbon group, and (B) an aromatic maleimide compound.
[2] The resin composition according to [1], wherein the (B) aromatic maleimide compound has a structure in which a maleimide group is bonded to an aromatic ring.
[3] The resin composition according to [1] or [2], wherein the saturated or unsaturated divalent hydrocarbon group has 8 to 100 carbon atoms.
[4] The resin composition according to [1] or [2], wherein the saturated or unsaturated divalent hydrocarbon group is a group represented by the following formula (II).

［式（ＩＩ）中、Ｒ_２及びＲ_３はそれぞれ独立に炭素数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 represents 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. An alkyl group is shown. ]

[5] Any of [1] to [4], wherein the maleimide compound (A) having a saturated or unsaturated divalent hydrocarbon group further has a divalent group having at least two imide bonds. The resin composition as described.
[6] The resin composition according to [1], wherein the divalent group having at least two imide bonds is a group represented by the following formula (I).

［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. ]

[7] The resin composition according to any one of [1] to [5], wherein the (B) aromatic maleimide compound is a compound represented by the following formula (VI).

［式（ＶＩ）中、Ａ_４は下記式（ＶＩＩ）、（ＶＩＩＩ）、（ＩＸ）又は（Ｘ）で表される残基を示し、Ａ_５は下記式（ＸＩ）で表される残基を示す。］

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

［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), each R ₁₀ 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）で表される残基を示す。］

[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 represents an alkylene group or alkylidene having 1 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a ketone group, a single bond or a residue represented by the following formula (VIII-1); ]

［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 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 represents an alkylene group having 1 to 5 carbon atoms. , An isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond. ]

［式（ＩＸ）中、ｉは１〜１０の整数である。］

[In formula (IX), i is an integer of 1-10. ]

［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の整数である。］

[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 is 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）で表される残基又は下記式（ＸＩ−２）で表される残基を示す。］

Wherein _(XI), each independently _{R 17} and _{R 18} represents 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, _{A 8} Is an alkylene group having 1 to 5 carbon atoms or an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group, a fluorenylene group, a single bond, a residue represented by the following formula (XI-1), or the following formula (XI- The residue represented by 2) is shown. ]

［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 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 represents an alkylene group having 1 to 5 carbon atoms. , Isopropylidene group, m-phenylene diisopropylidene group, p-phenylene diisopropylidene 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 formula (XI-2), each 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 are alkylene groups having 1 to 5 carbon atoms. , An isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond. ]

[8] The resin composition according to any one of [1] to [7], wherein the (A) maleimide compound having a saturated or unsaturated divalent hydrocarbon group has a weight average molecular weight of 500 to 10,000. .
[9] A laminate having a resin layer containing a cured product of the resin composition according to any one of [1] to [8] and a conductor layer.
[10] A multilayer printed wiring board comprising a resin layer containing a cured product of the resin composition according to any one of [1] to [8] and a circuit layer.

  According to the present invention, a resin composition having excellent high-frequency characteristics (low relative dielectric constant, low dielectric loss tangent), low thermal expansion characteristics, and high adhesion to a conductor, and the resin composition A laminated board and a multilayer printed wiring board manufactured using can be provided.

  Moreover, in the conventional resin film, when the reinforcing base material is not arranged in the resin composition, the handleability of the resin film is deteriorated, and the strength tends to be not sufficiently maintained. On the other hand, the resin film produced using the resin composition of the present invention is excellent in appearance and handleability (tackiness, cracking, powder falling, etc.) without having a reinforcing substrate.

  Since the laminated board and multilayer printed wiring board of the present invention are formed using the resin composition of the present invention, they have excellent dielectric properties such that the relative dielectric constant and dielectric loss tangent are both low in the high frequency region.

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

  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 a region of 0.3 GHz to 300 GHz, and particularly 3 GHz to 300 GHz.

[Resin composition]
The resin composition of this embodiment contains (A) a maleimide compound having a saturated or unsaturated divalent hydrocarbon group, and (B) an aromatic maleimide compound.

<(A) Maleimide compound having a saturated or unsaturated divalent hydrocarbon group>
The maleimide compound having a saturated or unsaturated divalent hydrocarbon group according to this embodiment may be referred to as component (A). The component (A) is a compound having (a) a maleimide group and (c) a saturated or unsaturated divalent hydrocarbon group. (A) The maleimide group may be referred to as structure (a), and (c) a saturated or unsaturated divalent hydrocarbon group may be referred to as structure (c). By using the component (A), it is possible to obtain a resin composition having high frequency characteristics and high adhesiveness with a conductor.

  In addition to the structure (a) and the structure (c), the component (A) may further include (b) a divalent group having at least two imide bonds. (B) A divalent group having at least two imide bonds may be referred to as structure (b).

  (A) The maleimide group is not particularly limited, and is a general maleimide group. (A) The maleimide group may be bonded to an aromatic ring or an aliphatic chain, but from the viewpoint of dielectric properties, a long-chain aliphatic chain (for example, saturated carbonization having 8 to 100 carbon atoms) It is preferably bonded to a hydrogen group. Since the component (A) has a structure in which the (a) maleimide group is bonded to a long-chain aliphatic chain, the high-frequency characteristics of the resin composition can be further improved.

  Although it does not specifically limit as a structure (b), For example, group represented by following formula (I) is mentioned.

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. For example, from the viewpoint of handleability, R ₁ may be a hydrocarbon group having 1 to 100 carbon atoms, or a hydrocarbon group having 2 to 50 carbon atoms. It may be a hydrocarbon group having 4 to 30 carbon atoms.

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

When R ₁ is substituted, examples of the substituent include 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 (R x) 2, -OC (O) -N (R x) 2, like acyl groups, oxyacyl group, a carboxyl group, a carbamate group, a sulfonamido group or the like It is done. Here, R _x represents a hydrogen atom or an alkyl group. These substituents can be selected from one type or two or more types according to the purpose and application.

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 to an acid anhydride group (—C (═O) OC (= A tetravalent group excluding two O)-) is preferred. Examples of the acid anhydride include compounds as described below.

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

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

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

  The structure (c) is not particularly limited, and may be linear, branched or cyclic. From the viewpoint of high-frequency characteristics, the structure (c) is preferably an aliphatic hydrocarbon group. Moreover, 8-100 may be sufficient as carbon number of a saturated or unsaturated divalent hydrocarbon group. The structure (c) is preferably an alkylene group which may have a branch having 8 to 100 carbon atoms, more preferably an alkylene group which may have a branch having 10 to 70 carbon atoms, More preferably, it is an alkylene group which may have a branch having 15 to 50 carbon atoms. When the structure (c) is an alkylene group which may have a branch having 8 or more carbon atoms, the molecular structure can be easily three-dimensional, and the free volume of the polymer can be increased to reduce the density. That is, since the dielectric constant can be reduced, the high frequency characteristics of the resin composition can be easily improved. In addition, since the component (A) has the structure (c), the flexibility of the resin composition according to this embodiment is improved, and the handleability of the resin film produced from the resin composition (tackiness, cracking, And the strength can be increased.

  As the structure (c), 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 or a nonadecylene group; an arylene group such as a benzylene group, a phenylene group or a naphthylene group; Examples include arylene alkylene groups such as phenylenemethylene group, phenyleneethylene group, benzylpropylene group, naphthylenemethylene group, and naphthyleneethylene group; and arylenealkylene groups such as phenylenedimethylene group and phenylenediethylene group.

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

In formula (II), R ₂ and R ₃ each independently represents an alkylene group having 4 to 50 carbon atoms. From the viewpoint of further improvement in flexibility and ease 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 a C7-10 alkylene group.

In formula (II), R ₄ represents an alkyl group having ₄ to 50 carbon atoms. From the viewpoint of further improving flexibility and ease of synthesis, R ₄ 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. More preferably, it is 10 alkyl groups.

In formula (II), R ₅ represents an alkyl group having 2 to 50 carbon atoms. From the viewpoint of further improvement in flexibility and ease of synthesis, R ₅ 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 5 carbon atoms. More preferably, it is an alkyl group of 8.

  From the viewpoint of fluidity and circuit embedding properties, it is preferable that a plurality of structures (c) exist in the component (A). In that case, the structures (c) may be the same or different. For example, the component (A) preferably has 2 to 40 structures (c), more preferably 2 to 20 structures (c), and more preferably 2 to 10 structures (c). More preferably.

  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) is preferably 2 to 98% by mass, more preferably 10 to 50% by mass, and more preferably 10 to 30% by mass with respect to the total mass of the resin composition. % Is more preferable.

  The molecular weight of the component (A) is not particularly limited. The weight average molecular weight (Mw) of the component (A) is preferably 500 to 10,000, more preferably 1000 to 9000, and 1500 to 9000 from the viewpoints of handleability, fluidity, and circuit embedding properties. Is more preferable, it is still more preferable that it is 1500-7000, and it is especially preferable that it is 1700-5000.

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

The measurement conditions for GPC are as follows.
Pump: L-6200 [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Guard column and column: TSK Guardcolumn HHR-L + TSKgel G4000HHR + TSKgel G2000HHR [All trade names, manufactured by Tosoh Corporation]
Column size: 6.0 × 40 mm (guard column), 7.8 × 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

  The method for producing the component (A) is not limited. The component (A) may be produced, for example, by reacting an acid anhydride and 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′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl. Examples thereof include tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride. These acid anhydrides may be used alone or in combination of two or more depending on the purpose and application. Incidentally, as described above, as R ₁ of the formula (I), can be used a tetravalent organic group derived from acid anhydrides such as those listed above. From the viewpoint of better dielectric properties, the acid anhydride is preferably pyromellitic anhydride.

  Examples of the diamine include dimer diamine, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (4-aminophenoxy) benzene, 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 according to the purpose and application.

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

In the formula, R and Q each independently represent a divalent organic group. R can be the same as in the above structure (c), and Q can be the same as the above R ₁ . N represents an integer of 1 to 10.

  As the component (A), a commercially available compound can also be used. As a commercially available compound, for example, Designer Molecules Inc. Specific examples include BMI-1500, BMI-1700, BMI-3000, BMI-5000, BMI-9000 (all are trade 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).

<(B) Aromatic maleimide compound>
The (B) aromatic maleimide compound according to this embodiment may be referred to as the (B) component. The component (B) is a maleimide compound different from the component (A). In addition, although the compound applicable to both (A) component and (B) component shall belong to (A) component, the compound applicable to both (A) component and (B) component is 2 When two or more types are included, one of them belongs to the component (A), and the other compounds belong to the component (B). By using the component (B), 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 characteristics and the like while maintaining good dielectric characteristics by using the component (A) and the component (B) in combination. The reason for this is that the cured product obtained from the resin composition containing the component (A) and the component (B) is a structural unit composed of the component (A) having low dielectric properties and the component (B) having low thermal expansion. This is presumably because it contains a polymer having a structural unit consisting of

  That is, (B) preferably has a lower thermal expansion coefficient than component (A). As the component (B) having a lower thermal expansion coefficient than the component (A), for example, a maleimide group-containing compound having a lower molecular weight than the component (A), a maleimide group-containing compound having more aromatic rings than the component (A), Examples thereof include maleimide group-containing compounds having a main chain shorter than the component (A).

  The content of the component (B) in the resin composition is not particularly limited. From the viewpoint of low thermal expansion and dielectric properties, the content of the component (B) is preferably 1 to 95% by mass, more preferably 3 to 90% by mass, with respect to the total mass of the resin composition. More preferably, it is -85 mass%.

  The blending ratio of the component (A) and the component (B) in the resin composition is not particularly limited. From the viewpoint of dielectric properties and a low thermal expansion coefficient, the mass ratio (B) / (A) of the component (A) to the component (B) is preferably 0.01 to 3, and preferably 0.03 to 2. More preferably, it is 0.05-1 more preferably.

  The component (B) is not particularly limited as long as it has an aromatic ring. Since the aromatic ring is rigid and has low thermal expansion, the thermal expansion coefficient of the resin composition can be reduced by using the component (B) having an aromatic ring. The maleimide group may be bonded to an aromatic ring or an aliphatic chain, but is preferably bonded to an aromatic ring from the viewpoint of low thermal expansion. The component (B) is also preferably a polymaleimide compound containing two or more maleimide groups.

  Specific examples of the component (B) include 1,2-dimaleimidoethane, 1,3-dimaleimidopropane, bis (4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis ( 3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,7-dimaleimidofluorene, N, N ′-(1,3-phenylene) bismaleimide, N, N ′-(1,3- (4 -Methylphenylene)) bismaleimide, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ether, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (3- (3-maleimidophenoxy) phenoxy) benzene, bis (4-maleimidophenyl) ketone, 2,2-bi (4- (4-maleimidophenoxy) phenyl) propane, bis (4- (4-maleimidophenoxy) phenyl) sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, 4,4′-bis (3- Maleimidophenoxy) biphenyl, 1,3-bis (2- (3-maleimidophenyl) propyl) benzene, 1,3-bis (1- (4- (3-maleimidophenoxy) phenyl) -1-propyl) benzene, bis (Maleimidocyclohexyl) methane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis (maleimidophenyl) 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-maleimidophenyl) methane is preferably used from the viewpoint of further reducing the hygroscopicity and the thermal expansion coefficient. From the viewpoint of further increasing the breaking strength and the metal foil peeling strength of the resin film formed from the resin composition, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane is used as the component (B). It is preferable to use it.

  From the viewpoint of moldability, as the component (B), for example, a compound represented by the following formula (VI) is preferable.

In the formula (VI), A ₄ represents a residue represented by the following formula (VII), (VIII), (IX) or (X), and A ₅ represents a residue represented by the following formula (XI). Show. From the viewpoint of low thermal expansibility, A ₄ is preferably a residue represented by the following formula (VII), (VIII) or (IX).

In formula (VII), each R ₁₀ 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 represents an alkylene group or alkylidene group having 1 to 5 carbon atoms. , An ether group, a sulfide group, a sulfonyl group, a ketone group, a single bond, or a residue 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, A ₇ is an alkylene group having 1 to 5 carbon atoms, An isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond is shown.

  In formula (IX), i is an integer of 1-10.

In formula (X), R ₁₅ and R ₁₆ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and j is 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 A ₈ represents , An alkylene group having 1 to 5 carbon atoms or an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group, a fluorenylene group, a single bond, a residue represented by the following formula (XI-1), or the following formula (XI- The residue represented by 2) is shown.

In 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 represents an alkylene group having 1 to 5 carbon atoms. , Isopropylidene group, m-phenylene diisopropylidene group, p-phenylene diisopropylidene group, ether group, sulfide group, sulfonyl group, ketone group or single bond.

In formula (XI-2), R ₂₁ each 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 each independently represent 1 to 5 carbon atoms. An alkylene group, an isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond.

  The component (B) is preferably used as a polyaminobismaleimide compound from the viewpoints of solubility in an organic solvent, high frequency characteristics, high adhesion to a conductor, moldability of a prepreg, and the like. The polyamino bismaleimide compound can be obtained, for example, by 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. 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 and the like. These may be used alone or in combination of two or more.

  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 is preferred. These may be used alone or in combination of two or more according to the purpose and application.

  The organic solvent used in producing the polyaminobismaleimide compound is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone 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, And nitrogen-containing compounds such as N-dimethylacetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more. 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 according to the present embodiment may further contain a catalyst for promoting the curing of the component (A). Although content of a catalyst is not specifically limited, 0.1-5 mass% may be sufficient with respect to the total mass of a 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-dioxide. (T-Butylperoxy) hexane, bis (tert-butylperoxyisopropyl) benzene, and tert-butyl hydroperoxide. Examples of the azo compound include 2,2'-azobis (2-methylpropanenitrile), 2,2'-azobis (2-methylbutanenitrile), and 1,1'-azobis (cyclohexanecarbonitrile).

<(C) Thermosetting resin>
The resin composition of this embodiment can further contain a thermosetting resin (C) different from the component (A) and the component (B). In addition, the compound which can correspond to (A) component or (B) component shall not belong to (C) thermosetting resin. (C) As a thermosetting resin, an epoxy resin, cyanate ester resin, etc. are mentioned, for example. (C) By including a thermosetting resin, the low thermal expansion characteristic etc. of a resin composition can further be improved.

  (C) When an epoxy resin is contained as the thermosetting resin, it is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain Epoxy resin, 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, etc. Biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, dihydroanthracene type epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more. Among these, it is preferable to use a naphthalene skeleton containing type epoxy resin or a biphenyl aralkyl type epoxy resin from the viewpoint of high frequency characteristics and thermal expansion characteristics.

  (C) When cyanate ester resin is contained as the thermosetting resin, it is not particularly limited. For example, 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, bis (3 , 5-Dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4 -Cyanatophenyl) -m-diisopropylbenzene, cyanate ester compound of phenol-added dicyclopentadiene polymer, phenol novolak type cyanate ester compound, cresol novolak type cyanate ester compound and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use 2,2-bis (4-cyanatophenyl) propane in consideration of the low cost, the high-frequency characteristics, and the overall balance of other characteristics.

(Curing agent)
The resin composition of this embodiment may further contain (C) a curing agent for a thermosetting resin. Thereby, the reaction at the time of obtaining the cured product of the resin composition can be smoothly advanced, and the physical properties of the cured product of the obtained resin composition can be appropriately adjusted.

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

  When the cyanate ester resin is used, the curing agent is not particularly limited, and examples thereof include various monophenol compounds, various polyphenol compounds, various amine compounds, various alcohol compounds, various acid anhydrides, various carboxylic acid compounds, and the like. These may be used alone or in combination of two or more.

(Curing accelerator)
You may further mix | blend a hardening accelerator with the resin composition of this embodiment according to the kind of (C) thermosetting resin. Examples of the epoxy resin curing accelerator include various imidazoles which are latent thermosetting agents, BF ₃ amine complexes, phosphorus curing accelerators, and the like. When a curing accelerator is blended, imidazoles and phosphorus 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 this embodiment may further contain an inorganic filler. By arbitrarily containing an appropriate inorganic filler, it is possible to improve low thermal expansion characteristics, high elastic modulus, heat resistance, flame retardancy, and the like of the resin composition. The inorganic filler is not particularly limited. For example, silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, Examples thereof include aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, and silicon carbide. 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 diameter means an average particle diameter, and is a particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the particles being 100%. The average particle diameter can be measured with a particle size distribution measuring apparatus using a laser diffraction scattering method.

  When the inorganic filler is used, the amount used is not particularly limited. For example, the content of the inorganic filler is preferably 3 to 75% by volume based on the solid content in the resin composition, and preferably 5 to 70 volume. % Is more preferable. When the content ratio of the inorganic filler in the resin composition is in the above range, good curability, moldability, and chemical resistance are easily obtained.

  When an inorganic filler is used, a coupling agent can be used in combination as necessary for the purpose of improving the dispersibility of the inorganic filler and the adhesion with the organic component. It does not specifically limit as a coupling agent, For example, various silane coupling agents, a titanate coupling agent, etc. can be used. These may be used alone or in combination of two or more. Moreover, the usage-amount of a coupling agent is not specifically limited, For example, it is good also as 0.1-5 mass parts with respect to 100 mass parts of inorganic fillers to be used, and good also as 0.5-3 mass parts. If it is this range, there will be little fall of various characteristics and it will become easy to exhibit the feature by use of an inorganic filler effectively.

  When a coupling agent is used, it may be a so-called integral blend treatment method in which an inorganic filler is added to the resin composition and then the coupling agent is added, but the coupling agent is added to the inorganic filler in advance. A method using an inorganic filler surface-treated with a dry method or a wet method is preferable. By using this method, the characteristics of the inorganic filler can be expressed more effectively.

(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. Although the kind of thermoplastic resin is not specifically limited and molecular weight is also not limited, It is preferable that a number average molecular weight (Mn) is 200-60000 from the point which improves compatibility with (A) component.

  From the viewpoint of film formability and moisture absorption resistance, the thermoplastic resin is preferably a thermoplastic elastomer. Examples of the thermoplastic elastomer include saturated thermoplastic elastomers, and examples of the saturated thermoplastic elastomer include chemically modified saturated thermoplastic elastomers and non-modified saturated thermoplastic elastomers. Examples of the chemically-modified saturated thermoplastic elastomer include styrene-ethylene-butylene copolymer modified with maleic anhydride. Specific examples of the chemically modified saturated thermoplastic elastomer include Tuftec M1911, M1913, M1943 (all trade names, manufactured by Asahi Kasei Chemicals Corporation). On the other hand, examples of the non-modified saturated thermoplastic elastomer include non-modified styrene-ethylene-butylene copolymer. Specific examples of the unmodified saturated thermoplastic elastomer include Tuftec H1041, H1051, H1043, and H1053 (all trade names, manufactured by Asahi Kasei Chemicals Corporation).

  From the viewpoint of film formability, dielectric properties, and moisture absorption resistance, the saturated thermoplastic elastomer preferably has a styrene unit in the molecule. In this specification, the styrene unit refers to a unit derived from a styrene monomer in a polymer, and the saturated thermoplastic elastomer refers to an aliphatic hydrocarbon portion other than the aromatic hydrocarbon portion of the styrene unit. Are all having a structure constituted by a saturated bonding group.

  The content ratio of the styrene unit in the saturated thermoplastic elastomer is not particularly limited, but is preferably 10 to 80% by mass with respect to the total mass of the saturated thermoplastic elastomer, preferably 10 to 80% by mass, and 20 to 70% by mass. More preferably. 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. A styrene-ethylene-butylene copolymer can be obtained, for example, by hydrogenating an unsaturated double bond of a structural unit derived from butadiene of a 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, and 0.3 to 10% by mass. % Is more preferable, and 0.5 to 5% by mass is still more preferable.

(Flame retardants)
You may further mix | blend a flame retardant with the resin composition of this embodiment. Although it does not specifically limit as a flame retardant, A bromine flame retardant, a phosphorus flame retardant, a metal hydroxide, etc. are used suitably. Brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resins and brominated phenol novolac type epoxy resins; hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, 2,4, Brominated flame retardants such as 6-tris (tribromophenoxy) -1,3,5-triazine; tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type Methacrylate, pentabromobenzyl acrylate, and unsaturated double bond group brominated reactive flame retardants containing brominated styrene. These flame retardants may be used alone or in combination of two or more.

  Phosphorus flame retardants include aromatic phosphoric acids such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate) Ester; Phosphonic acid ester such as divinyl phenylphosphonate, diallyl phenylphosphonate, bis (1-butenyl) phenylphosphonate; phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phos Phosphinic acid esters such as faphenanthrene-10-oxide derivatives; phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene; melamine phosphate, melamine pyrophosphate, poly Phosphate melamine, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds, such as phosphorus-based flame retardant of red phosphorus and the like. Examples of the metal hydroxide flame retardant include magnesium hydroxide and aluminum hydroxide. These flame retardants may be used alone or in combination of two or more.

  The resin composition of this embodiment can be obtained by uniformly dispersing and mixing the above-described components, and the preparation means, conditions, and the like are not particularly limited. For example, after stirring and mixing various components of a predetermined blending amount sufficiently uniformly with a mixer, etc., the mixture is kneaded using a mixing roll, an extruder, a kneader, a roll, an extruder, etc., and the obtained kneaded product is cooled and The method of pulverizing is mentioned. The kneading type is not particularly limited.

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

  From the viewpoint of suppressing warpage of the laminate, the thermal expansion coefficient of the cured product of the resin composition of the present embodiment is preferably 10 to 90 ppm / ° C, more preferably 10 to 45 ppm / ° C. More preferably, it is ˜40 ppm / ° C. The thermal expansion coefficient can be measured according to IPC-TM-650 2.4.24.

[Resin film]
In the present embodiment, a resin film can be produced using the above resin composition. The resin film refers to an uncured or semi-cured film-shaped resin composition.

  Although the manufacturing method of a resin film is not limited, For example, it can obtain by drying the resin layer formed by apply | coating a resin composition on a support base material. Specifically, after coating the resin composition on a supporting substrate using a kiss coater, roll coater, comma coater, etc., the temperature is, for example, 70 to 250 ° C., preferably 70 to 200 ° C. in a heating and drying furnace. And may be dried for 1 to 30 minutes, preferably 3 to 15 minutes. Thereby, the resin film in the state in which the resin composition is semi-cured can be obtained.

  In addition, the resin film in the semi-cured state is further cured in a heating furnace, for example, by heating at a temperature of 170 to 250 ° C., preferably 185 to 230 ° C. for 60 to 150 minutes. it can.

  Although the thickness of the resin film which concerns on this embodiment is not specifically limited, It is preferable that it is 1-200 micrometers, It is more preferable that it is 2-180 micrometers, It is still more preferable that it is 3-150 micrometers. By setting the thickness of the resin film in the above range, it is easy to achieve both a reduction in thickness of the printed wiring board obtained by using the resin film according to the present embodiment and good high frequency characteristics.

  The support substrate is not particularly limited, but is preferably at least one selected from the group consisting of glass, metal foil, and PET film. When a resin film is provided with a support base material, it exists in the tendency for the storage property and the handleability at the time of using for manufacture of a printed wiring board to become favorable. That is, the resin film according to the present embodiment can take the form of a support with a resin layer including a resin layer containing the resin composition of the present embodiment and a support base material, and when used, a support base. It may be peeled from the material.

[Prepreg]
The prepreg according to the present embodiment can be obtained, for example, by applying the resin composition of the present embodiment to a fiber base material that is a reinforcing base material and drying the applied resin composition. Further, the prepreg of the present embodiment may be obtained by impregnating the fiber base material into the resin composition of the present embodiment and then drying the impregnated resin composition. Specifically, the prepreg in which the resin composition is semi-cured is obtained by heating and drying the fiber base material to which the resin composition is adhered, usually in a drying oven at a temperature of 80 to 200 ° C. for 1 to 30 minutes. It is done. From the viewpoint of good moldability, it is preferable to apply or impregnate the resin composition with respect to the fiber substrate so that the resin content in the prepreg after drying is 30 to 90% by mass.

  Although it does not limit as a reinforcement base material of a prepreg, a sheet-like fiber base material is preferable. As a sheet-like fiber base material, the well-known thing used for the laminated board for various electrical insulation materials is used, for example. Examples of the material include inorganic fibers such as E glass, NE glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene. As the sheet-like fiber base material, those having a shape such as woven fabric, non-woven fabric, and chopped strand mat can be used. Moreover, the thickness in particular of a sheet-like fiber base material is not restrict | limited, For example, a 0.02-0.5 mm thing can be used. In addition, as the sheet-like fiber base material, what is surface-treated with a coupling agent or the like, or mechanically subjected to fiber opening treatment is impregnated with a resin composition, heat resistance when used as a laminate, It is preferable from the viewpoint of moisture absorption resistance and processability.

[Laminated board]
According to this embodiment, the laminated board which has the resin layer containing the hardened | cured material of the above-mentioned resin composition, and a conductor layer can be provided. For example, a metal-clad laminate can be produced using the resin film or the prepreg.

  Although the manufacturing method of a metal-clad laminated board is not limited, For example, the resin film or prepreg which concerns on this embodiment is laminated | stacked 1 sheet or multiple sheets, the metal foil used as a conductor layer is arrange | positioned on at least one surface, for example, 170- A metal foil is applied to at least one surface of a resin layer or a prepreg serving as an insulating layer by heating and pressing at 250 ° C., preferably 185 to 230 ° C. and a pressure of 0.5 to 5.0 MPa for 60 to 150 minutes. A metal-clad laminate provided is obtained. The heating and pressurization can be performed, for example, under a condition where the degree of vacuum is 10 kPa or less, preferably 5 kPa or less, and is preferably performed in vacuum from the viewpoint of increasing efficiency. It is preferable to carry out the heating and pressurization from the start for 30 minutes to the molding end time.

[Multilayer printed wiring board]
According to this embodiment, a multilayer printed wiring board provided with the resin layer containing the hardened | cured material of the above-mentioned resin composition and a circuit layer can be provided. The upper limit of the number of circuit layers is not particularly limited, and may be 3 to 20 layers. A multilayer printed wiring board can also be manufactured using the said resin film, a prepreg, or a metal-clad laminated board, for example.

  The method for producing a multilayer printed wiring board is not particularly limited. For example, first, a resin film is disposed on one or both sides of a core substrate subjected to circuit formation processing, or a resin film is disposed between a plurality of core substrates. Place and apply pressure and heat laminate molding, or press and heat press molding to bond each layer, then perform circuit formation processing by laser drilling, drilling, metal plating, metal etching, etc. Thus, a multilayer printed wiring board can be manufactured. When the resin film has a supporting base, the supporting base is peeled off before placing the resin film on the core substrate or between the core substrates, or after the resin layer is attached to the core substrate. Can be peeled off.

  The manufacturing method of the multilayer printed wiring board using the resin film which concerns on this embodiment is demonstrated along 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 producing a multilayer printed wiring board according to the present embodiment includes (a) a step of forming a resin layer by laminating a resin film on an inner layer circuit board (hereinafter referred to as “step (a)”), and (b) a resin. A step of curing the layer by heating and pressing (hereinafter referred to as “step (b)”), and 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 step (a), the resin film 12 according to this 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, an atmospheric laminator, a method of laminating using a laminator that is heated and pressurized under vacuum, and a method using a laminator that is heated and pressurized under vacuum is preferable. . Thereby, even if the inner circuit board 11 has a fine wiring circuit on the surface, there is no void and the circuit can be filled with the resin. Lamination conditions are not particularly limited, but the pressure bonding temperature is 70 to 130 ° C., the pressure bonding pressure is 1 to 11 kgf / cm ² , and the lamination is preferably performed under reduced pressure or vacuum. The laminate 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 board, a polyester board, a polyimide board, a BT resin board, a thermosetting polyphenylene ether board, 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, the inner circuit board has six layers. However, the number of layers is not limited. For example, when a printed wiring board for millimeter wave radar is manufactured, it can be freely selected from 2 to 20 layers depending on the design. can do. The multilayer printed wiring board of this embodiment can be applied to the production of millimeter wave radar. That is, a millimeter-wave radar printed wiring board including a resin layer containing a cured product of the resin film according to the present embodiment and a circuit layer can be produced.

  When the antenna circuit layer 14 described later is formed on the resin layer 12a by etching, a 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. Examples of the copper alloy include a high purity copper alloy 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. 1B, in the step (b), the inner layer circuit board 11 and the resin layer 12a laminated in the step (a) are heated and pressurized to be thermally cured. The conditions are not particularly limited, but a temperature range of 100 ° C. to 250 ° C., a pressure of 0.2 to 10 MPa, and a time of 30 to 120 minutes are preferable, and 150 ° C. to 220 ° C. is more preferable.

  As shown in FIG. 1C, in 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 for example, the antenna circuit layer 14 may be formed by an etching method such as a subtractive method or a semi-additive method.

  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 a portion of the metal layer from which the resist has been removed is dissolved and removed by a chemical solution by subsequent development processing. Thus, a desired circuit is formed. 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 the formation, an unnecessary electroless plating layer is removed with a chemical solution or the like to form a desired circuit layer.

  Moreover, you may form holes, such as the via hole 15, as needed in the resin layer 12a. The hole forming method is not limited, but an NC drill, carbon dioxide laser, UV laser, YAG laser, plasma, or the like can be applied.

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

  First, as shown in FIG. 2P, 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. As the prepreg, for example, “GWA-900G”, “GWA-910G”, “GHA-679G”, “GHA-679G (S)”, “GZA-71G”, “GEA-75G” (manufactured by Hitachi Chemical Co., Ltd.) In either case, the trade name) can be used.

  Next, as shown in FIG. 2 (q), in the step (q), the laminated body of the core substrate 41 and the prepreg 42 obtained in the step (p) is heated and pressurized. Although the temperature to heat is not specifically limited, 120-230 degreeC is preferable and 150-210 degreeC is more preferable. Moreover, the pressure to pressurize is not particularly limited, but is preferably 1 to 5 MPa, and 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 characteristics, mechanical and electrical connection reliability under high temperature and high humidity.

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

  The multilayer printed wiring board of this embodiment can be manufactured by the above steps. Moreover, you may repeat process (a)-(c) further by making the printed wiring board manufactured through the said process into an inner layer circuit board.

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

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

  1 and 3, the number of resin layers laminated on the inner circuit board is one or two for the purpose of forming an antenna circuit pattern or the like. However, the number of resin layers is not limited to this. 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 used frequency band.

  In the method for producing a multilayer printed wiring board according to the present embodiment, since the resin layer is formed using the resin film containing the component (A) and the component (B), an adhesive layer in addition to the layer having excellent high frequency characteristics. A laminated body can be manufactured without providing. Thereby, the simplification of a process and the further improvement effect of a high frequency characteristic are acquired.

  The resin composition, resin film, prepreg, laminate, and multilayer printed wiring board according to the present embodiment as described above can be suitably used for electronic devices that handle high-frequency signals of 1 GHz or higher, particularly high-frequency signals of 10 GHz or higher. It can be suitably used for electronic equipment that handles.

  The preferred embodiments of the present invention have been described above, but these are examples for explaining the present invention, and the scope of the present invention is not intended to be limited to these embodiments. The present invention can be implemented in various modes different from the above-described 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.

[Preparation of resin composition]
Various resin compositions were prepared according to the following procedures. Tables 1 and 2 collectively show the amounts (parts by mass) of the raw materials used in the preparation of the resin compositions of Examples 1 to 8, Reference Examples 1 to 4 and Comparative Examples 1 to 4.

  Each component shown in Table 1 or 2 was put into a 300 mL four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, stirred at 25 ° C. for 1 hour, and then # 200 nylon mesh (opening 75 μm). Filtration gave a resin composition.

In addition, the symbol of each material in Tables 1 and 2 is as follows.
(1) BMI-1500 [Mw: about 1500, Designer Molecules Inc. Product name
(2) BMI-1700 [Mw: about 1700, Designer Moleculars Inc. Product name
(3) BMI-3000 [Mw: about 3000, Designer Moleculars Inc. Product name
(4) BMI-5000 [Mw: about 5000, Designer Moleculars Inc. Product name
(5) BMI-1000 [bis (4-maleimidophenyl] methane, manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name)
(6) BMI-4000 [2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name]
(7) BMI-2300 [polyphenylmethanemaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name]
(8) MIR-3000 [biphenyl aralkyl type maleimide, manufactured by Nippon Kayaku Co., Ltd., trade name]
(9) B-3000 [Butadiene homopolymer, Mn: about 3000, manufactured by Nippon Soda Co., Ltd., trade name]
(10) PPO640 [polyphenylene ether, Mn: about 16000, manufactured by SABIC Innovative Plastics, trade name]
(11) NC-3000H [Biphenyl aralkyl type epoxy resin, Nippon Kayaku Co., Ltd., trade name]
(12) BADCY [2,2-bis (4-cyanatophenyl) propane, manufactured by Lonza, trade name]
(13) KA1165 [Novolac type phenolic resin, manufactured by DIC Corporation, trade name]
(14) PCP [p-cumylphenol, Wako Pure Chemical Industries, Ltd., trade name]
(15) H1041 [hydrogenated product of styrene-butadiene copolymer having a Mn of less than 60,000, styrene content ratio: 30%, Mn: 58000, manufactured by Asahi Kasei Chemicals Corporation, trade name “Tuftec H1041”]
(16) Silica slurry [spherical fused silica, surface treatment: phenylaminosilane coupling agent (1 mass% / total solid content in slurry), dispersion medium: methyl isobutyl ketone (MIBK), solid content concentration: 70 mass%, average Particle size: 0.5 μm, density: 2.2 g / cm ³ , manufactured by Admatechs Co., Ltd., trade name “SC-2050KNK”]
(17) Perhexine 25B [2,5-dimethyl-2,5-di (t-butylperoxy) hexane, manufactured by NOF Corporation, trade name]
(18) 2E4MZ [2-ethyl-4-methyl-imidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name]
(19) Zinc naphthenate [Tokyo Chemical Industry Co., Ltd.]

  In addition, the presumed structure of the compound used as said (A) component is as follows. The following formulas (XII-1) to (XII-3) correspond to the above (1) to (3), respectively, (4) has the structure of the formula (XII-3), and has a weight larger than (3) Has an average molecular weight. In formulas (XII-1) to (XII-3), n represents an integer of 1 to 10.

[Production of resin film having semi-cured resin layer]
The resin compositions obtained in Examples, Reference Examples and Comparative Examples were coated on a PET film (G2-38, manufactured by Teijin Ltd.) having a thickness of 38 μm as a supporting substrate using a comma coater (drying). Temperature: 130 ° C.), a semi-cured resin film with a PET film provided with a semi-cured resin layer was produced. The thickness of the semi-cured resin film (resin layer) was 50 μm.

[Evaluation of resin film]
The appearance and handleability of the semi-cured resin films of Examples 1 to 8, Reference Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated. The results are shown in Tables 3 and 4.

The appearance was evaluated visually according to the following criteria.
○: There is no unevenness, streaks, etc. on the surface of the semi-cured resin film.
X: The surface of the semi-cured resin film is somewhat uneven, streaks, and lacks surface smoothness.

The handleability was evaluated according to the following criteria by visual and tactile sensations.
(1) Presence or absence of tackiness (tack) on the surface at 25 ° C.
(2) Presence or absence of resin cracking or powder falling when cut with a cutter knife.
○: None of the above (1) and (2).
X: It exists in any one of said (1) and (2).

[Multilayer printed wiring board]
Using the above-mentioned semi-cured resin film with a PET film, a multilayer printed wiring board was produced by the following procedure.
A glass cloth base epoxy resin copper clad laminate with a circuit pattern formed thereon is used as an inner layer circuit board, and a semi-cured resin film from which a PET film is peeled is placed on both sides thereof, and an electrolytic copper foil having a thickness of 12 μm is placed thereon. (Nippon Electrolytic Co., Ltd., trade name “YGP-12”) is placed, and then a mirror plate is placed thereon, and heated and pressure-molded under press conditions of 200 ° C./3.0 MPa / 70 minutes to form four layers. A printed wiring board was produced.

Subsequently, the copper foil of the outermost layer of the produced four-layer printed wiring board was etched, and circuit embedding property (multilayered formability) was evaluated. The multilayer formability was visually evaluated according to the following criteria.
○: There are no voids or blurs in the circuit.
X: Voids and blurring are present to some extent.

[Double-sided metal-clad cured resin film]
After stacking two resin films from which the PET film was peeled from the semi-cured resin film with PET film described above, a low profile copper foil (M surface Rz: 3 μm, manufactured by Furukawa Electric Co., Ltd.) (Product name “F3-WS”) is placed so that the roughened surface (M surface) is in contact with it, a mirror plate is placed on it, and it is heated and pressure-molded under press conditions of 200 ° C./3.0 MPa / 70 minutes. Thus, a double-sided metal-clad cured resin film (thickness: 0.1 mm) was produced.

  About the above-mentioned double-sided metal-clad cured resin film, handleability (bending resistance), dielectric properties, copper foil peeling strength, solder heat resistance, water absorption rate and insulation reliability were evaluated. The evaluation results are shown in Tables 3 and 4. The characteristic evaluation method of the double-sided metal-clad cured resin film is as follows.

[Bending resistance]
Bending resistance was evaluated according to the following criteria by bending 180 ° of the outer layer copper foil of the double-sided metal-clad cured resin film.
○: No cracking or cracking occurs when bent.
X: When bent, some cracks or cracks occur.

[Dielectric properties]
The dielectric constant and dielectric loss tangent, which are dielectric properties, are obtained by etching the outer layer copper foil of a double-sided metal-clad cured resin film and cutting it into a length of 60 mm, a width of 2 mm, and a thickness of about 1 mm by a cavity resonator perturbation method. It was measured. Vector type network analyzer E8364B manufactured by Agilent Technologies Co., Ltd., CP129 (10 GHz band resonator) and CP137 (20 GHz band resonator) manufactured by Kanto Electronics Application Co., Ltd., and CPMA-V2 for the measurement program. Each was used. The conditions were frequencies of 10 GHz and 20 GHz, and a measurement temperature of 25 ° C.

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

[Solder heat resistance]
Solder heat resistance is determined by etching a copper foil on one side of a double-sided metal-clad cured resin film and cutting it into 50 mm squares, using the test pieces as normal and pressure cooker test (PCT) equipment (conditions: 121 ° C., 2.2 At atmospheric pressure), after processing for a predetermined time (1, 3, 5 hours), float on molten solder at 288 ° C. for 20 seconds, and visually evaluate the appearance of each cured resin film with different processing times according to the following criteria did. Three test pieces were evaluated for the same processing time, and the number of samples that were ○ according to the following criteria is shown in Tables 3 and 4. In Tables 3 and 4, what was processed for 1 hour was expressed as PCT-1h, and what was processed for 3 hours was expressed as PCT-3h and processed for 5 hours Is represented as PCT-5h.
○: No occurrence of swelling or measling inside the film or between the film and the copper foil.
X: Generation | occurrence | production of the swelling or mead ring in the film inside and between a film and copper foil is seen.

[Water absorption rate]
The water absorption is determined by etching the copper foils on both sides of the double-sided metal-clad cured resin film and cutting them into 50 mm squares, using the test pieces as normal and pressure cooker test (PCT) equipment (conditions: 121 ° C., 2.2 atm. ) Was measured for a predetermined time (5 hours), and the mass before and after the treatment was measured to calculate the increase rate (% by weight) before and after the treatment.

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

As is apparent from the results shown in Table 3, according to the semi-cured resin films of Examples 1 to 8, there are no problems in appearance (surface uniformity) and handleability (tackiness, cracking, powder falling, etc.). Further, it was confirmed that the multilayer formability was also good.
In addition, the cured resin films produced using the semi-cured resin films of Examples 1 to 8 are both excellent in relative dielectric constant and dielectric loss tangent, and have high thermal expansion characteristics, solder heat resistance, and copper foil peeling strength. The thickness and water absorption were also excellent.

  Further, when the component (A) and the component (B) are used in combination (Examples 1 to 8), the case where the component (A) is used alone (Reference Examples 1 to 4) achieves a lower thermal expansion coefficient. did it.

  Since the resin composition of the present invention expresses various characteristics required for printed wiring boards and excellent high-frequency characteristics, an electronic device, a mobile communication device, a base station device, and a server that handle high-frequency signals of 1 GHz or more or 10 GHz or more It is useful as a member / part for printed wiring boards used in network-related electronic devices such as routers and various electronic devices such as large computers.

  11, 21 ... inner layer circuit board, 12, 22 ... resin film, 12a, 22a ... resin layer, 13, 23 ... metal foil, 13a, 23a ... metal layer, 14, 24 ... antenna circuit layer, 15 ... via hole, 42 ... Prepreg, 41 ... core substrate, 43 ... through hole.

Claims (10)

  (A) A resin composition containing a maleimide compound having a saturated or unsaturated divalent hydrocarbon group and (B) an aromatic maleimide compound.   The resin composition according to claim 1, wherein the (B) aromatic maleimide compound has a structure in which a maleimide group is bonded to an aromatic ring.   The resin composition according to claim 1 or 2, wherein the saturated or unsaturated divalent hydrocarbon group has 8 to 100 carbon atoms. The resin composition according to claim 1 or 2, 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 represents 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. An alkyl group is shown. ]   The resin according to any one of claims 1 to 4, wherein the maleimide compound (A) having a saturated or unsaturated divalent hydrocarbon group further has a divalent group having at least two imide bonds. Composition. The resin composition according to claim 5, wherein the divalent group having at least two imide bonds is a group represented by the following formula (I).

[In Formula (I), R ₁ represents a tetravalent organic group. ] The resin composition as described in any one of Claims 1-6 whose said (B) aromatic maleimide compound is a compound represented by following formula (VI).

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

[In Formula (VII), each R ₁₀ 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 represents an alkylene group or alkylidene having 1 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a ketone group, a single bond or a residue 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 represents an alkylene group having 1 to 5 carbon atoms. , An isopropylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group or a single bond. ]

[In formula (IX), i is an integer of 1-10. ]

[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 is an integer of 1 to 8. ]

Wherein _(XI), each independently _{R 17} and _{R 18} represents 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, _{A 8} Is an alkylene group having 1 to 5 carbon atoms or an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a ketone group, a fluorenylene group, a single bond, a residue represented by the following formula (XI-1), or the following formula (XI- The residue represented by 2) is shown. ]

[In 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 represents an alkylene group having 1 to 5 carbon atoms. , Isopropylidene group, m-phenylene diisopropylidene group, p-phenylene diisopropylidene group, ether group, sulfide group, sulfonyl group, ketone group or single bond. ]

[In formula (XI-2), each 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 each independently represent 1 to 5 shows an alkylene group, isopropylidene group, ether group, sulfide group, sulfonyl group, ketone group or single bond. ]   The resin composition according to any one of claims 1 to 7, wherein the (A) maleimide compound having a saturated or unsaturated divalent hydrocarbon group has a weight average molecular weight of 500 to 10,000.   The laminated board which has a resin layer containing the hardened | cured material of the resin composition as described in any one of Claims 1-8, and a conductor layer.   A multilayer printed wiring board comprising a resin layer containing a cured product of the resin composition according to claim 1 and a circuit layer.

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