JP7121354B2 - Resin composition, prepreg, resin sheet, laminated resin sheet, laminate, metal foil-clad laminate, and printed wiring board - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition, a prepreg, a resin sheet, a laminated resin sheet, a laminate, a metal foil-clad laminate, and a printed wiring board.

In recent years, as semiconductor packages, which are widely used in electronic devices, communication devices, personal computers, etc., have become more sophisticated and smaller, the integration and high-density mounting of each component for semiconductor packages has accelerated in recent years. ing. Along with this, warping of semiconductor plastic packages caused by a difference in coefficient of thermal expansion between a semiconductor element and a printed wiring board for semiconductor plastic packages has become a problem, and various countermeasures have been taken.

One of the countermeasures is to reduce the thermal expansion of insulating layers used in printed wiring boards. This is a method of suppressing warpage by bringing the coefficient of thermal expansion of a printed wiring board closer to that of a semiconductor element, and is currently being actively pursued (see Patent Documents 1 to 3, for example).

In addition to lowering the thermal expansion of the printed wiring board, methods for suppressing warping of semiconductor plastic packages include increasing the rigidity of the laminate (high rigidity) and increasing the glass transition temperature of the laminate (high Tg (for example, see Patent Documents 4 and 5).

JP 2013-216884 A Japanese Patent No. 3173332 Japanese Patent Application Laid-Open No. 2009-035728 JP 2013-001807 A JP 2011-178992 A

However, the reduction in thermal expansion of printed wiring boards by the conventional techniques described in Patent Documents 1 to 3 is already approaching its limit, and further reduction in thermal expansion is becoming difficult.

High rigidity of the laminate can be achieved by filling the resin composition used for the laminate with a high filler or by using an inorganic filler with a high elastic modulus such as alumina. However, the use of an inorganic filler such as alumina deteriorates the coefficient of thermal expansion of the laminate. Therefore, increasing the rigidity of the laminate has not sufficiently suppressed the warpage of the semiconductor plastic package.

In addition, since the method of increasing the Tg of the laminated plate improves the elastic modulus during reflow, it is effective in reducing the warpage of the semiconductor plastic package. However, the technique of increasing Tg causes deterioration of moisture absorption and heat resistance due to an increase in cross-linking density, and the generation of voids due to deterioration of moldability. often a problem. Therefore, a technique to solve these problems is desired.

Furthermore, the insulating layer of the printed wiring board is required to have high elastic modulus retention rate, high copper foil peel strength, and excellent plating peel strength at the same time. However, there has been no report on a resin composition that gives a cured product that satisfies all these problems.

The present invention has been made in view of the above problems, and provides a resin composition that gives a cured product having excellent copper foil peel strength and plating peel strength, and a prepreg, a resin sheet, and a laminate using the resin composition. An object of the present invention is to provide a resin sheet, a laminate, a metal foil-clad laminate, and a printed wiring board.

The inventors of the present invention have made intensive studies in order to solve the above problems. As a result, the inventors have found that the above problems can be solved by using predetermined amounts of the cyanate ester compound (A) and the maleimide compound (B), and have completed the present invention.

（式（１）中、Ｒ¹は、各々独立して、水素原子又は炭素数１～４のアルキル基を表し、Ｒ²は、各々独立して、置換基としてシアン酸エステル基、ヒドロキシル基及びアリル基からなる群より選ばれる少なくとも１つを有してもよいフェニル基、水素原子、アリル基、シアン酸エステル基、又は、エポキシ基を表し、ｎ１は１以上の整数であり、ｍは１～４の整数である。）

（式（２）中、Ｒ³は、各々独立して、水素原子又は炭素数１～４のアルキル基を表し、ｎ２は１以上の整数である。）
〔３〕
シアン酸エステル化合物（Ａ）のシアン酸エステル基当量が、１００～２２０ｇ／ｅｑ．である、
〔１〕又は〔２〕に記載の樹脂組成物。
〔４〕
前記シアン酸エステル化合物（Ａ）が、下記一般式（１’’）で表される化合物を含む、
〔１〕～〔３〕のいずれかに記載の樹脂組成物。

（式（１’’）中、Ｒ¹は、各々独立して、水素原子又は炭素数１～４のアルキル基を表し、ｎ１は１以上の整数である。）
〔５〕
前記シアン酸エステル化合物（Ａ）が、下記一般式（３）で表される化合物を含む、
〔１〕～〔４〕のいずれかに記載の樹脂組成物。

〔６〕
前記マレイミド化合物（Ｂ）が、ビス（４－マレイミドフェニル）メタン、２，２－ビス｛４－（４－マレイミドフェノキシ）－フェニル｝プロパン、ビス（３－エチル－５－メチル－４－マレイミドフェニル）メタン、及び下記式（４）で表されるマレイミド化合物からなる群より選ばれる少なくとも１種を含む、
〔１〕～〔５〕のいずれかに記載の樹脂組成物。

（式中、Ｒ⁴は、各々独立して、水素原子又はメチル基を表し、ｎ３は１以上の整数を表す。）
〔７〕
前記比（〔α／β〕）が、０．４５～１．０である、
〔１〕～〔６〕のいずれかに記載の樹脂組成物。
〔８〕
無機充填材（Ｃ）をさらに含む、
〔１〕～〔７〕のいずれかに記載の樹脂組成物。
〔９〕
前記無機充填材（Ｃ）の含有量が、樹脂固形分１００質量部に対して、２５～７００質量部である、
〔８〕に記載の樹脂組成物。
〔１０〕
前記無機充填材（Ｃ）が、シリカ、ベーマイト、及びアルミナからなる群より選択される少なくとも１種類を含む、
〔８〕又は〔９〕に記載の樹脂組成物。
〔１１〕
基材と、
該基材に含浸又は塗布された〔１〕～〔１０〕のいずれか一項に記載の樹脂組成物と、を有する、
プリプレグ。
〔１２〕
〔１〕～〔１０〕のいずれか一項に記載の樹脂組成物をシート状に形成してなる、
樹脂シート。
〔１３〕
シート基材と、該シート基材の片面又は両面に配された〔１〕～〔１０〕のいずれか一項に記載の樹脂組成物と、を有する、
積層樹脂シート。
〔１４〕
〔１１〕に記載のプリプレグ、〔１２〕に記載の樹脂シート、及び〔１３〕に記載の積層樹脂シートからなる群より選択される少なくとも１種を１枚以上有する、
積層板。
〔１５〕
〔１１〕に記載のプリプレグ、〔１２〕に記載の樹脂シート、及び〔１３〕に記載の積層樹脂シートからなる群より選択される少なくとも１種と、
前記プリプレグ、前記樹脂シート、及び前記積層樹脂シートの片面又は両面に配された金属箔と、を有する、
金属箔張積層板。
〔１６〕
絶縁層と、該絶縁層の片面又は両面に形成された導体層と、を有し、
前記絶縁層が、〔１〕～〔１０〕のいずれか一項に記載の樹脂組成物を含む、
プリント配線板。 That is, the present invention is as follows.
[1]
containing a cyanate ester compound (A) and a maleimide compound (B),
The ratio ([α/β]) of the cyanate ester group amount (α) of the cyanate ester compound (A) to the maleimide group amount (β) of the maleimide compound (B) is 0.30 or more.
Resin composition.
[2]
The cyanate ester compound (A) contains a compound represented by the following general formula (1) and / or the following general formula (2),
The resin composition according to [1].

(In formula (1), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, each R ² independently represents a cyanate ester group, a hydroxyl group and a a phenyl group which may have at least one selected from the group consisting of allyl groups, a hydrogen atom, an allyl group, a cyanate ester group, or an epoxy group; n1 is an integer of 1 or more; m is 1; is an integer between ~4.)

(In formula (2), each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n2 is an integer of 1 or more.)
[3]
The cyanate ester group equivalent of the cyanate ester compound (A) is 100 to 220 g/eq. is
The resin composition according to [1] or [2].
[4]
The cyanate ester compound (A) contains a compound represented by the following general formula (1''),
[1] The resin composition according to any one of [3].

(In formula (1''), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1 is an integer of 1 or more.)
[5]
The cyanate ester compound (A) contains a compound represented by the following general formula (3),
[1] The resin composition according to any one of [4].

[6]
The maleimide compound (B) is bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl ) containing at least one selected from the group consisting of methane and a maleimide compound represented by the following formula (4),
[1] The resin composition according to any one of [5].

(In the formula, each R ⁴ independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.)
[7]
The ratio ([α/β]) is 0.45 to 1.0,
[1] The resin composition according to any one of [6].
[8]
further comprising an inorganic filler (C),
[1] The resin composition according to any one of [7].
[9]
The content of the inorganic filler (C) is 25 to 700 parts by mass with respect to 100 parts by mass of the resin solid content.
The resin composition according to [8].
[10]
The inorganic filler (C) contains at least one selected from the group consisting of silica, boehmite, and alumina,
The resin composition according to [8] or [9].
[11]
a substrate;
and the resin composition according to any one of [1] to [10] impregnated or applied to the substrate,
prepreg.
[12]
[1] to [10] formed by forming the resin composition according to any one of the sheet,
resin sheet.
[13]
Having a sheet substrate and the resin composition according to any one of [1] to [10] arranged on one or both sides of the sheet substrate,
Laminated resin sheet.
[14]
At least one selected from the group consisting of the prepreg described in [11], the resin sheet described in [12], and the laminated resin sheet described in [13].
laminated board.
[15]
at least one selected from the group consisting of the prepreg described in [11], the resin sheet described in [12], and the laminated resin sheet described in [13];
a metal foil disposed on one or both sides of the prepreg, the resin sheet, and the laminated resin sheet;
Metal foil clad laminate.
[16]
Having an insulating layer and a conductor layer formed on one side or both sides of the insulating layer,
The insulating layer contains the resin composition according to any one of [1] to [10],
printed wiring board.

According to the present invention, a resin composition that gives a cured product having excellent copper foil peel strength and plating peel strength, and a prepreg, a resin sheet, a laminated resin sheet, a laminate, and a metal foil clad laminate using the resin composition Boards and printed wiring boards can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail, but the present invention is not limited to this, and various modifications can be made without departing from the scope of the invention. is possible.

[Resin composition]
The resin composition of the present embodiment contains a cyanate ester compound (A) and a maleimide compound (B), and the cyanate ester compound (A ) has a ratio ([α/β]) of cyanate ester groups (α) of 0.30 or more.

[Cyanate ester compound (A)]
The cyanate ester compound (A) is not particularly limited as long as it is a compound having at least one cyanate ester group. The cyanate ester compound (A) may or may not have a reactive functional group other than the cyanate ester group.

Examples of reactive functional groups other than cyanate ester groups include, but are not limited to, allyl groups, hydroxyl groups, epoxy groups, amino groups, isocyanate groups, glycidyl groups, and phosphoric acid groups. Among these, at least one selected from the group consisting of an allyl group, a hydroxyl group and an epoxy group is preferable, and an allyl group is more preferable. Having such a reactive functional group tends to further improve the bending strength, bending elastic modulus, glass transition temperature, and coefficient of thermal expansion of the resin composition.

One type of the cyanate ester compound (A) may be used alone, or two or more types may be used in combination. When two or more types are used in combination, one having a reactive functional group other than a cyanate ester and one not having it may be used in combination, and two or more types of reactive substituents other than a cyanate ester group. may be used together. At that time, the reactive functional groups other than the cyanate ester group may be the same or different. Among these, it is preferable that the cyanate ester compound (A) contains at least a cyanate ester compound having a reactive functional group other than a cyanate ester group. The use of such a cyanate ester compound (A) tends to further improve the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention rate of the resulting cured product.

The cyanate ester compound (A) as described above is not particularly limited. ester), novolak-type cyanate, biphenylaralkyl-type cyanate, bis(3,5-dimethyl-4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1 ,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2 ,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis(4-cyanatophenyl) ether, bis(4-cyanato phenyl)thioether, bis(4-cyanatophenyl)sulfone, and 2,2′-bis(4-cyanatophenyl)propane; prepolymers of these cyanate esters. These may be used individually by 1 type, and may use 2 or more types together. Among them, a compound represented by the following general formula (1) and a compound represented by the following general formula (2) are more preferable.

（式（１）中、Ｒ¹は、各々独立して、水素原子又は炭素数１～４のアルキル基を表し、Ｒ²は、各々独立して、置換基としてシアン酸エステル基、ヒドロキシル基及びアリル基からなる群より選ばれる少なくとも１つを有してもよいフェニル基、水素原子、アリル基、シアン酸エステル基、又は、エポキシ基を表し、ｎ１は１以上の整数であり、ｍは１～４の整数である。）

（式（１’）中、Ｒ¹は、各々独立して、水素原子又は炭素数１～４のアルキル基を表し、Ｒ²は、各々独立して、置換基としてシアン酸エステル基、ヒドロキシル基及びアリル基からなる群より選ばれる少なくとも１つを有してもよいフェニル基、水素原子、アリル基、シアン酸エステル基、又は、エポキシ基を表し、ｎ１は１以上の整数である。）

（式（１’’）中、Ｒ¹は、各々独立して、水素原子又は炭素数１～４のアルキル基を表し、ｎ１は１以上の整数である。） Among the cyanate ester compounds (A), the compound having a reactive functional group other than a cyanate ester group is not particularly limited. A compound represented by the formula (1′) is more preferable, and a compound represented by the following general formula (1″) is even more preferable. Including such a cyanate ester compound (A) tends to further improve the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention rate of the resulting cured product.

(In formula (1), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, each R ² independently represents a cyanate ester group, a hydroxyl group and a a phenyl group which may have at least one selected from the group consisting of allyl groups, a hydrogen atom, an allyl group, a cyanate ester group, or an epoxy group; n1 is an integer of 1 or more; m is 1; is an integer between ~4.)

(In formula (1′), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each R ² independently represents a cyanate ester group or a hydroxyl group as a substituent. and an allyl group, a phenyl group, a hydrogen atom, an allyl group, a cyanate ester group, or an epoxy group, and n1 is an integer of 1 or more.)

(In formula (1''), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n1 is an integer of 1 or more.)

In formula (1), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a methyl group. In addition, each R ² is independently a phenyl group optionally having at least one substituent selected from the group consisting of a cyanate ester group, a hydroxyl group and an allyl group, a hydrogen atom, an allyl group, cyanic acid It represents an ester group or an epoxy group, preferably a hydrogen atom or an allyl group. Further, n1 is an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-5. Further, m is an integer of 1-4, preferably an integer of 1-2.

In formulas (1′) and (1″), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably methyl represents a group. Use of a compound having a bisphenol A skeleton in which R ¹ is a methyl group tends to further improve copper foil peel strength, plating peel strength, and glass transition temperature. Further, having an allyl group tends to further improve flexibility and moldability. Furthermore, in the formulas (1′) and (1″), n1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably 1 be.

Although the compound represented by the general formula (1'') is not particularly limited, for example, a compound represented by the following formula (3) is more preferable. By containing such a cyanate ester compound (A), the copper foil peel strength, plating peel strength, glass transition temperature, elastic modulus retention rate, flexibility, and moldability of the obtained cured product tend to be further improved. It is in.

（式（２）中、Ｒ³は、各々独立して、水素原子又は炭素数１～４のアルキル基を表し、ｎ２は１以上の整数である。） On the other hand, among the cyanate ester compound (A), the compound having no reactive functional group other than a cyanate ester group is not particularly limited, but for example, a compound represented by the following general formula (2) is preferable. . Including such a cyanate ester compound (A) tends to further improve the copper foil peel strength and the plating peel strength of the obtained cured product.

(In formula (2), each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n2 is an integer of 1 or more.)

In formula (2), each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. Also, n2 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5.

The number of cyanate ester groups in one molecule of the cyanate ester compound (A) is not particularly limited, but is preferably 1-50, more preferably 2-12, still more preferably 2-6. When the number of cyanate ester groups in one molecule of the cyanate ester compound (A) is within the above range, the obtained cured product has copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention rate. tend to improve.

In addition, the number of reactive functional groups other than the cyanate ester group in one molecule of the cyanate ester compound (A) is not particularly limited, but is preferably 1 to 50, more preferably 2 to 12, and further 2 to 6 are preferred. When the number of reactive functional groups other than the cyanate ester group in one molecule of the cyanate ester compound (A) is within the above range, the obtained cured product has copper foil peel strength, plating peel strength, glass transition temperature, And the elastic modulus retention rate tends to be further improved.

The cyanate ester group amount (α) of the cyanate ester compound (A) is not particularly limited, but is preferably 0.075 to 0.5, more preferably 0.085 to 0.4, and still more preferably. is between 0.095 and 0.3. When the cyanate ester group amount (α) of the cyanate ester compound (A) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention rate of the resulting cured product are increased. tend to improve. The cyanate ester group amount (α) is obtained by dividing the content (parts by mass) of the cyanate ester compound (A) with respect to 100 parts by mass of the resin solid content by the cyanate ester group equivalent of the cyanate ester compound (A). can ask. In the present specification, unless otherwise specified, the term "resin solid content" refers to the components of the resin composition excluding the solvent and the inorganic filler (C), and "100 parts by mass of resin solid content". It means that the total of the components excluding the solvent and the inorganic filler (C) in the resin composition is 100 parts by mass.

Although the content of the cyanate ester compound (A) is not particularly limited, it is preferably 10 to 65 parts by mass, more preferably 15 to 60 parts by mass, and still more preferably 100 parts by mass of the resin solid content. is 15 to 55 parts by mass. When the content of the cyanate ester compound (A) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention of the obtained cured product tend to be further improved.

The cyanate ester group equivalent of the cyanate ester compound (A) is preferably 100 to 290 g/eq. and more preferably 120 to 270 g/eq. and more preferably 150 to 220 g/eq. is. When the cyanate ester group equivalent of the cyanate ester compound (A) is within the above range, the copper foil peel strength and the plating peel strength of the resulting cured product tend to be further improved.

（式中、Ｒ⁴は、各々独立して、水素原子又はメチル基を表し、ｎ３は１以上の整数を表す。） [Maleimide compound (B)]
The maleimide compound (B) is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Examples include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane , bis(3,5-diethyl-4-maleimidophenyl)methane, maleimide compounds represented by the following formula (4), prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. Among these, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, and At least one selected from the group consisting of maleimide compounds represented by the following formula (4) is preferred. Including such a maleimide compound (B) tends to further improve copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention rate of the resulting cured product. Among the above-mentioned compounds, maleimide compounds represented by the following formula (4) are more preferable from the viewpoint of high glass transition temperature (high Tg).

(In the formula, each R ⁴ independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.)

In formula (4), R ⁴ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Moreover, in Formula (4), n3 represents an integer greater than or equal to 1. n3 is preferably 10 or less, more preferably 7 or less.

The maleimide group amount (β) of the maleimide compound (B) is not particularly limited, but is preferably 0.175 to 0.6, more preferably 0.185 to 0.5, and still more preferably 0.195. ~0.4. When the maleimide group amount (β) of the maleimide compound (B) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention of the obtained cured product tend to be further improved. be. The maleimide group content (β) can be obtained by dividing the content (parts by mass) of the maleimide compound (B) with respect to 100 parts by mass of the resin solid content by the maleimide group equivalent of the maleimide compound (B).

The content of the maleimide compound (B) is not particularly limited, but is preferably 30 to 80 parts by mass, more preferably 35 to 75 parts by mass, and still more preferably 40 parts by mass relative to 100 parts by mass of the resin solid content. ~72 parts by mass. When the content of the maleimide compound (B) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention rate of the obtained cured product tend to be further improved.

The maleimide group equivalent of the maleimide compound (B) is preferably 100 to 350 g/eq. and more preferably 150 to 300 g/eq. is. When the maleimide group equivalent of the maleimide compound (B) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention of the obtained cured product tend to be further improved.

In the resin composition of the present embodiment, the ratio ([α/β]) of the cyanate ester group amount (α) of the cyanate ester compound (A) to the maleimide group amount (β) of the maleimide compound (B) is 0. 0.30 or more, preferably 0.30 to 2.0, more preferably 0.40 to 1.1, and particularly preferably 0.45 to 1.0. When the ratio ([α/β]) is within the above range, the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention of the obtained cured product tend to be further improved.

[Inorganic filler (C)]
The resin composition of the present embodiment may further contain an inorganic filler (C). Examples of the inorganic filler (C) include, but are not limited to, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, Metal oxides such as magnesium oxide and zirconium oxide; Metal nitrides such as boron nitride, agglomerated boron nitride, silicon nitride and aluminum nitride; Metal sulfates such as barium sulfate; metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc such as zinc borate and zinc stannate Compound; alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M -Glass G20, glass short fibers (including fine glass powders such as E glass, T glass, D glass, S glass, Q glass, etc.), hollow glass, spherical glass, and the like. An inorganic filler (C) may be used individually by 1 type, or may use 2 or more types together.

Among these, it is preferable to include at least one selected from the group consisting of silica, boehmite, and alumina. By using such an inorganic filler (C), the flexural strength, flexural modulus and coefficient of thermal expansion tend to be further improved.

The content of the inorganic filler (C) is preferably 25 to 700 parts by mass, more preferably 50 to 500 parts by mass, and still more preferably 75 to 300 parts by mass with respect to 100 parts by mass of the resin solid content. is. When the content of the inorganic filler (C) is within the above range, the copper foil peel strength and the plating peel strength of the obtained cured product tend to be further improved.

[Silane coupling agent and wetting and dispersing agent]
The resin composition of this embodiment may further contain a silane coupling agent and a wetting and dispersing agent. By containing the silane coupling agent and the wetting and dispersing agent, the dispersibility of the inorganic filler (C), the resin component, the inorganic filler (C), and the adhesive strength of the substrate described below tend to be further improved.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent that is generally used for surface treatment of inorganic substances. - aminosilane compounds such as aminopropyltrimethoxysilane; epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; acrylsilane compounds such as γ-acryloxypropyltrimethoxysilane; cationic silane compounds such as vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; and phenylsilane compounds. A silane coupling agent may be used individually by 1 type, or may use 2 or more types together.

The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints. , W9010, W903, and the like.

[Other resins, etc.]
The resin composition of the present embodiment may further contain epoxy resin (D), alkenyl-substituted nadimide compound (E), and amine-modified silicone compound (F), if necessary. By containing such other resins, etc., the copper foil peel strength, bending strength, and bending elastic modulus tend to be further improved, and the coefficient of linear thermal expansion tends to decrease.

[Epoxy resin (D)]
The resin composition of this embodiment may further contain an epoxy resin (D). Further containing the epoxy resin (D) tends to further improve the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention rate of the resulting cured product. In the case where the cyanate ester compound (A) has an epoxy group, when the epoxy resin (D) is used, the epoxy resin (D) is a compound other than the cyanate ester compound (A) having an epoxy group. shall say.

The epoxy resin (D) is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, glycidyl ester type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, aralkyl novolac type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, isocyanurate ring-containing epoxy resin, or these Halides are mentioned. Among them, at least one selected from the group consisting of naphthol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins is preferable.

The content of the epoxy resin (D) is preferably 2.5 to 20 parts by mass, more preferably 5.0 to 17.5 parts by mass, and still more preferably 7.5 to 15 parts by mass. When the content of the epoxy resin (D) is within the above range, the flexibility, copper foil peel strength, chemical resistance, and desmear resistance of the obtained cured product tend to be further improved.

（式中、Ｒ⁵は、各々独立して、水素原子、又は炭素数１～６のアルキル基を示し、Ｒ⁶は、炭素数１～６のアルキレン基、フェニレン基、ビフェニレン基、ナフチレン基、又は下記式（６）若しくは（７）で表される基を示す。）

（式中、Ｒ⁷は、メチレン基、イソプロピリデン基、又は、ＣＯ、Ｏ、Ｓ、若しくはＳＯ₂で表される置換基を示す。）

（式中、Ｒ⁸は、各々独立して、炭素数１～４のアルキレン基、又は炭素数５～８のシクロアルキレン基を示す。） [Alkenyl-substituted nadimide compound (E)]
The alkenyl-substituted nadimide compound (E) is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadimide groups in the molecule. Among these, a compound represented by the following formula (5) is preferable. By using such an alkenyl-substituted nadimide compound (E), the copper foil peel strength, plating peel strength, glass transition temperature, and elastic modulus retention of the obtained cured product tend to be further improved.

(In the formula, each R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁶ represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (6) or (7).)

( _In the formula, ^R7 represents a methylene group, an isopropylidene group, or a substituent represented by CO, O, S, or SO2.)

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

The alkenyl-substituted nadimide compound (E) is preferably a compound represented by the following formulas (9) and/or (10). By using such an alkenyl-substituted nadimide compound (E), the thermal expansion coefficient of the resulting cured product tends to be further lowered and the heat resistance tends to be further improved.

In addition, a commercially available alkenyl-substituted nadimide compound (E) can also be used. Commercially available products are not particularly limited, but for example, BANI-M (Maruzen Petrochemical Co., Ltd., compound represented by formula (9)), BANI-X (Maruzen Petrochemical Co., Ltd., compounds represented by the formula (10)) and the like. These may be used singly or in combination of two or more.

Although the content of the alkenyl-substituted nadimide compound (E) is not particularly limited, it is preferably 20 to 45 parts by mass, more preferably 25 to 40 parts by mass, and still more preferably 100 parts by mass of the resin solid content. is 30 to 35 parts by mass. When the content of the alkenyl-substituted nadimide compound (E) is within the above range, the copper foil peel strength and plating peel strength of the obtained cured product tend to be further improved.

[Amine-modified silicone compound (F)]
Amine-modified silicone compound (F) is not particularly limited as long as it is a compound having one or more amino groups in the molecule. Specific examples thereof include compounds represented by the following general formula (11).

In formula (11), each R ⁸ independently represents a hydrogen atom, a methyl group or a phenyl group, with a methyl group being preferred. Each R ⁹ independently represents a single bond, an alkylene group having 1 to 8 carbon atoms and/or an arylene group. As R ⁹ , an alkylene group having 1 to 8 carbon atoms and an arylene group may be linked to form a divalent group. Among these, R ⁹ is preferably an alkylene group having 2 to 4 carbon atoms. In formula (11), each n ₄ independently represents an integer of 1 or more.

The amino group equivalent weight of the amine-modified silicone compound (F) is preferably 130-6000, more preferably 400-3000, even more preferably 600-2500. By using such an amine-modified silicone compound (F), it is possible to obtain a resin composition having a good elastic modulus retention rate and a lower coefficient of thermal expansion.

The content of the amine-modified silicone compound (F) is not particularly limited, but is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, based on 100 parts by mass of the resin solid content. Yes, more preferably 5 to 20 parts by mass. When the content of the amine-modified silicone compound (F) is within the above range, the elastic modulus retention rate and thermal expansion coefficient of the resulting cured product tend to be further improved.

[Curing accelerator]
The resin composition of this embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include organic peroxides such as triphenylimidazole, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl-di-perphthalate. azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline , N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine and other tertiary amines; phenol, xylenol, cresol, resorcinol, catechol and other phenols; lead naphthenate, stearic acid Organometallic salts such as lead, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; organic tin compounds such as dioctyltin oxide, other alkyltins and alkyltin oxides; Among these, triphenylimidazole is particularly preferred because it accelerates the curing reaction and tends to have excellent glass transition temperature and thermal expansion coefficient.

〔solvent〕
The resin composition of this embodiment may further contain a solvent. By containing a solvent, the viscosity of the resin composition during preparation tends to be lowered, and the handling property is further improved, and the impregnation property to the substrate described later tends to be further improved.

The solvent is not particularly limited as long as it can dissolve some or all of the resin components in the resin composition. Examples include ketones such as acetone, methyl ethyl ketone and methyl cellosolve; group hydrocarbons; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate; A solvent may be used individually by 1 type, or may use 2 or more types together.

[Glass transition temperature (Tg)]
The glass transition temperature of the resin composition of the present embodiment is preferably 270 to 360°C, more preferably 290 to 355°C, still more preferably 310 to 350°C. The glass transition temperature can be measured by the method described in Examples.

[Retention rate of elastic modulus]
The elastic modulus retention rate of the resin composition of the present embodiment is preferably 75 to 99%, more preferably 80 to 95%, still more preferably 85 to 95%. The “elastic modulus retention rate” refers to the flexural modulus at 27°C and 260°C measured according to JIS C6481, and the obtained flexural modulus (a) at 27°C and the hot flexural modulus at 260°C. is calculated by the following formula. In addition, excellent elastic modulus retention means that the difference between the bending elastic modulus at 27° C. and the bending elastic modulus at 260° C. (thermal elastic modulus) is small, for example.
Elastic modulus retention = [(b)/(a)] x 100

[Method for producing resin composition]
The method for producing the resin composition of the present embodiment is not particularly limited, but an example thereof includes a method in which each component is sequentially blended in a solvent and thoroughly stirred. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing and kneading treatment can be performed. Specifically, the dispersibility of the inorganic filler (C) in the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank equipped with a stirrer having an appropriate stirring capacity. The above stirring, mixing, and kneading treatments can be appropriately performed using, for example, a device for mixing purposes such as a ball mill or bead mill, or a known device such as a revolution or rotation type mixing device.

In addition, an organic solvent can be used as necessary during the preparation of the resin composition of the present embodiment. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. A specific example thereof is as described above.

[Use]
The resin composition of the present embodiment can be suitably used as a prepreg, a resin sheet, a laminated resin sheet, a laminate, a metal foil-clad laminate, or a printed wiring board. The prepreg, resin sheet, laminated resin sheet, laminate, metal foil-clad laminate, or printed wiring board will be described below.

[Prepreg]
The prepreg of the present embodiment has a base material and the resin composition impregnated or applied to the base material. A method for producing the prepreg is not particularly limited and can be carried out according to a conventional method. For example, after impregnating or applying the resin component in the present embodiment to the base material, semi-curing (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes, etc. The prepreg of this embodiment can be produced.

The content of the resin composition (including the inorganic filler (C)) is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, preferably 40% by mass, relative to the total amount of the prepreg. ~80% by mass. When the content of the resin composition is within the above range, moldability tends to be further improved.

The substrate is not particularly limited, and known substrates used in various printed wiring board materials can be appropriately selected and used depending on the intended use and performance. Specific examples of fibers constituting the base material are not particularly limited, but glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; Inorganic fibers other than glass; polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene/3,4'oxydiphenylene terephthalamide (Technora (registered trademark), Teijin Techno Products Co., Ltd.) 2,6-hydroxynaphthoic acid/parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), Zexion (registered trademark, manufactured by KB SEIREN), etc.; polyesters such as polyparaphenylene Organic fibers such as benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.) and polyimide can be mentioned. Among these, at least one selected from the group consisting of E-glass cloth, T-glass cloth, S-glass cloth, Q-glass cloth, and organic fibers is preferable from the viewpoint of low thermal expansion coefficient. One of these substrates may be used alone, or two or more thereof may be used in combination.

The shape of the substrate is not particularly limited, but examples thereof include woven fabrics, nonwoven fabrics, rovings, chopped strand mats, and surfacing mats. The weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave, etc. are known, and it is possible to appropriately select and use from these known ones depending on the intended use and performance. . In addition, glass woven fabrics surface-treated with a silane coupling agent or the like are preferably used. The thickness and mass of the base material are not particularly limited, but usually about 0.01 to 0.3 mm is suitably used. In particular, from the viewpoint of strength and water absorption, the substrate is preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g/m ² or less. more preferred.

[Resin sheet]
The resin sheet of the present embodiment is obtained by molding the above resin composition into a sheet. The method for producing the resin sheet is not particularly limited and can be carried out according to a conventional method. For example, in the method for producing a laminated resin sheet described below, a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied onto the sheet substrate and dried, and then the sheet substrate is peeled or etched from the laminated resin sheet. method. In addition, a sheet base material is used by molding a solution obtained by dissolving the resin composition of the present embodiment in a solvent into a sheet by supplying it into a mold having a sheet-like cavity and drying it. A single-layer resin sheet (resin sheet) can also be obtained without

[Laminated resin sheet]
The laminated resin sheet of the present embodiment has a sheet substrate and the resin composition laminated on one side or both sides of the sheet substrate. A laminated resin sheet is used as one means of thinning the sheet. ) can be applied and dried.

The sheet base material is not particularly limited, but known ones used for various printed wiring board materials can be used. Examples include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, aluminum foil, copper foil, and gold foil. Among them, electrolytic copper foil and PET film are preferable.

Examples of the coating method include a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is coated on the sheet substrate using a bar coater, die coater, doctor blade, baker applicator, or the like.

The laminated resin sheet is preferably obtained by applying the above resin composition to a sheet base material and then semi-curing (to B-stage) the resin composition. Specifically, for example, after the resin composition is applied to a sheet substrate such as a copper foil, it is semi-cured by a method such as heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes, and the laminated resin sheet. and the like. The amount of the resin composition attached to the sheet substrate is preferably in the range of 1 to 300 μm in terms of resin thickness of the laminated resin sheet.

[Laminate]
The laminated plate of the present embodiment has one or more sheets of at least one selected from the group consisting of the prepreg, the resin sheet, and the laminated resin sheet.

[Metal foil clad laminate]
The metal foil-clad laminate of the present embodiment includes at least one selected from the group consisting of the prepreg, the resin sheet, and the laminated resin sheet, and one side or one side of the prepreg, the resin sheet, and the laminated resin sheet and a metal foil disposed on both sides. That is, the metal foil-clad laminate of the present embodiment is obtained by laminating and curing at least one selected from the group consisting of the prepreg, the resin sheet, and the laminated resin sheet, and a metal foil. is.

The insulating layer may be the resin composition, one-layer prepreg, resin sheet, or laminated resin sheet, or may be formed by laminating two or more layers of the resin composition, prepreg, resin sheet, or laminated resin sheet. good too.

The conductor layer can be a metal foil such as copper or aluminum. The metal foil used here is not particularly limited as long as it is used for printed wiring board materials, but known copper foils such as rolled copper foil and electrolytic copper foil are preferred. The thickness of the conductor layer is not particularly limited, but preferably 1 to 70 μm, more preferably 1.5 to 35 μm.

The molding method and molding conditions for the metal foil-clad laminate are not particularly limited, and general techniques and conditions for printed wiring board laminates and multilayer boards can be applied. For example, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when molding a metal foil-clad laminate. In molding metal foil-clad laminates, the temperature is generally 100 to 300° C., the pressure is 2 to 100 kgf/cm ² , and the heating time is generally 0.05 to 5 hours. Furthermore, if desired, post-curing can be performed at a temperature of 150-300°C. Moreover, it is also possible to form a multi-layer board by combining the above-mentioned prepreg and a wiring board for an inner layer separately prepared and performing lamination molding.

[Printed wiring board]
A printed wiring board of the present embodiment is a printed wiring board including an insulating layer and a conductor layer formed on the surface of the insulating layer, wherein the insulating layer includes the resin composition. The metal foil-clad laminate described above can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The above metal foil-clad laminate has a low coefficient of thermal expansion, good moldability and chemical resistance, and is particularly effectively used as a printed wiring board for semiconductor packages that require such performance. can be done.

Specifically, the printed wiring board of this embodiment can be produced, for example, by the following method. First, the aforementioned metal foil-clad laminate (metal foil-clad laminate, etc.) is prepared. An inner layer circuit is formed by subjecting the surface of the metal foil-clad laminate to an etching treatment to prepare an inner layer substrate. The surface of the inner layer circuit of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, and then the required number of prepregs are laminated on the surface of the inner layer circuit, and a metal foil for the outer layer circuit is laminated on the outer side. Then, heat and pressurize to integrally mold. In this manner, a multilayer laminate is produced in which an insulating layer composed of the base material and the cured product of the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling holes for through holes and via holes in this multilayer laminate, desmear treatment is performed to remove smear, which is a resin residue derived from the resin component contained in the cured product layer. . After that, a plated metal film is formed on the wall surface of this hole to connect the metal foil for the inner layer circuit and the outer layer circuit, and the metal foil for the outer layer circuit is etched to form the outer layer circuit, and the printed wiring board is manufactured. be done.

For example, the above-mentioned prepreg (base material and the above-mentioned resin composition attached thereto) and the resin composition layer (layer made of the above-mentioned resin composition) of the metal foil-clad laminate contain the above-mentioned resin composition. It constitutes an insulating layer.

In the case where a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer to form a circuit on the prepreg, the laminated resin sheet, or the resin composition. At this time, an electroless plating technique can be used to form the conductor layer.

In the printed wiring board of the present embodiment, the above-described insulating layer maintains an excellent elastic modulus even under the reflow temperature during semiconductor mounting, thereby effectively suppressing warping of the semiconductor plastic package. It can be used particularly effectively as a printed wiring board.

Hereinafter, the present invention will be described more specifically using examples and comparative examples. The present invention is by no means limited by the following examples.

[Synthesis Example 1: Synthesis of diallyl bisphenol A-type cyanate ester compound]
Diallyl bisphenol A 700 g (hydroxyl group equivalent 154.2 g / eq.) (OH group conversion 4.54 mol) (DABPA, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and triethylamine 459.4 g (4.54 mol) (per 1 mol of hydroxyl group 1.0 mol) was dissolved in 2100 g of dichloromethane to obtain Solution 1.

474.4 g (7.72 mol) of cyanogen chloride (1.7 mol per 1 mol of hydroxyl group), 1106.9 g of dichloromethane and 735.6 g (7.26 mol) of 36% hydrochloric acid (1.7 mol per 1 mol of hydroxyl group). 6 mol) and 4560.7 g of water were poured into Solution 1 over 90 minutes while maintaining the liquid temperature at -2 to -0.5°C under stirring. After pouring solution 1, the mixture was stirred at the same temperature for 30 minutes, and then a solution of 459.4 g (4.54 mol) of triethylamine (1.0 mol per 1 mol of hydroxyl group) dissolved in 459.4 g of dichloromethane ( Solution 2) was poured over 25 minutes. After pouring solution 2, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

After that, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The obtained organic phase was washed with 2 L of 0.1N hydrochloric acid and then washed with 2000 g of water six times. The electric conductivity of the wastewater after the sixth washing was 20 μS/cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.

The organic phase after washing with water is concentrated under reduced pressure, and finally concentrated to dryness at 90° C. for 1 hour to give the desired diallyl bisphenol A-type cyanate compound (DABPA-CN, cyanate ester group equivalent: 179 g/ eq.) was obtained as a pale yellow liquid. The IR spectrum of the obtained DABPA-CN showed an absorption at 2264 cm ^-1 (cyanate ester group) and no hydroxyl group absorption.

[Synthesis Example 2: Synthesis of α-naphthol aralkyl-type cyanate ester compound]
In the reactor, α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g/eq., manufactured by Nippon Steel Chemical Co., Ltd.: Naphthol aralkyl repeating unit number n is 1 to 5.) 0 .47 mol (as OH group) was dissolved in 500 mL of chloroform, and 0.7 mol of triethylamine was added to this solution. While maintaining the temperature at −10° C., 300 g of a chloroform solution of 0.93 mol of cyanogen chloride was dropped into the reactor over 1.5 hours, and after the dropping was completed, the mixture was stirred for 30 minutes. After that, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise into the reactor and stirred for 30 minutes to complete the reaction. After the by-produced triethylamine hydrochloride was filtered off from the reaction solution, the resulting filtrate was washed with 500 mL of 0.1N hydrochloric acid, and then washed with 500 mL of water four times. This was dried with sodium sulfate, evaporated at 75° C., and degassed under reduced pressure at 90° C. to obtain a brown solid α-naphthol aralkyl cyanate resin (SNCN). Analysis of the obtained α-naphthol aralkyl-type cyanate ester resin (SN495-V-CN, cyanate ester group equivalent: 261 g/eq.) by infrared absorption spectrum revealed that cyanate ester groups near 2264 cm ^-1 Absorption was confirmed.

[Example 1]
48.3 parts by mass of DABPA-CN obtained in Synthesis Example 1, 27 parts by mass of a novolac-type maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd., maleimide group equivalent: 186 g/eq.), and bismaleimide 14.7 parts by mass of a compound (BMI-80, manufactured by Daiwa Kasei Kogyo Co., Ltd., maleimide group equivalent: 285 g / eq.), an amine-modified silicone compound (X-22-161B, manufactured by Shin-Etsu Chemical Co., Ltd., functional Base equivalent: 1500 g / eq.) 10 parts by mass, slurry silica (SC-5050MOB, average particle size 1.5 μm, Admatechs Co., Ltd.) 100 parts by mass, wetting and dispersing agent (DISPERBYK-161, BYK Chemie Japan Co., Ltd.), 0.05 parts by mass of leveling agent (BYK-Chemie Japan Co., Ltd., "BYK-310"), curing accelerator (2,4,5-triphenylimidazole, Tokyo Kasei Kogyo Co., Ltd.) was mixed to obtain a varnish. This varnish was diluted with methyl ethyl ketone, impregnated and applied to a 0.1 mm thick T-glass woven fabric, and dried by heating at 140° C. for 3 minutes to obtain a prepreg having a resin content of 44% by mass. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.270, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is 0.270. /maleimide group equivalent) was 0.197 and the ratio ([α/β]) was 1.37.

[Example 2]
A prepreg was obtained in the same manner as in Example 1, except that the amount of DABPA-CN used was 40.3 parts by mass and the amount of BMI-2300 used was 35 parts by mass. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.225, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is 0.225. /maleimide group equivalent) was 0.240, and the ratio ([α/β]) was 0.94.

[Example 3]
A prepreg was obtained in the same manner as in Example 1, except that the amount of DABPA-CN used was 27.3 parts by mass and the amount of BMI-2300 used was 48 parts by mass. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.153, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is 0.153. /maleimide group equivalent) was 0.310, and the ratio ([α/β]) was 0.49.

[Example 4]
A prepreg was obtained in the same manner as in Example 1, except that the amount of DABPA-CN used was 19.3 parts by mass and the amount of BMI-2300 used was 56 parts by mass. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.108, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is 0.108. /maleimide group equivalent) was 0.353, and the ratio ([α/β]) was 0.31.

[Comparative Example 1]
A prepreg was obtained in the same manner as in Example 1, except that the amount of DABPA-CN used was 14.3 parts by mass and the amount of BMI-2300 used was 61 parts by mass. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.080, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is 0.080. /maleimide group equivalent) was 0.380, and the ratio ([α/β]) was 0.21.

[Example 5]
52.7 parts by mass of SN495-V-CN obtained in Synthesis Example 2, and 37.3 parts by mass of a novolac-type maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd., maleimide group equivalent: 186 g/eq.). Part, biphenyl aralkyl type epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290 g / eq.) 10 parts by mass, slurry silica (SC-5050MOB, average particle size 1.5 μm, Admatex Co., Ltd.) is 100 parts by mass, a wetting and dispersing agent (DISPERBYK-161, BYK-Chemie Japan Co., Ltd.) is 1 part by mass, and a leveling agent (BYK-Chemie Japan Co., Ltd., "BYK-310") is 0. 0.05 part by mass and 0.5 part by mass of a curing accelerator (2,4,5-triphenylimidazole, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed to obtain a varnish. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1 mm-thick T-glass fabric, and dried by heating at 140° C. for 3 minutes to obtain a prepreg having a resin content of 48% by mass. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.202, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is 0.202. /maleimide group equivalent) was 0.201, and the ratio ([α/β]) was 1.01.

[Comparative Example 2]
A prepreg was obtained in the same manner as in Example 5, except that the amount of SN495-V-CN used was 25.3 parts by mass and the amount of BMI-2300 used was 64.7 parts by mass. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.097, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is 0.097. /maleimide group equivalent) was 0.348, and the ratio ([α/β]) was 0.28.

[Example 6]
24.9 parts by mass of SN495-V-CN obtained in Synthesis Example 2, and 43.3 parts by mass of a novolak-type maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd., maleimide group equivalent: 186 g/eq.). part, 31.8 parts by mass of bisallyl nadimide (manufactured by Maruzen Petrochemical Co., Ltd., "BANI-M"), slurry silica (SC-5050MOB, average particle size 1.5 μm, Admatechs Co., Ltd.) 200 mass parts Part, wetting and dispersing agent (DISPERBYK-161, BYK-Chemie Japan Co., Ltd.) 1 part by mass, leveling agent (BYK-Chemie Japan Co., Ltd., "BYK-310") 0.05 parts by mass, curing accelerator 0.5 part by mass of (2,4,5-triphenylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed to obtain a varnish. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1 mm-thick T-glass fabric, and dried by heating at 140° C. for 3 minutes to obtain a prepreg having a resin content of 48% by mass. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.095, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is 0.095. /maleimide group equivalent) was 0.233, and the ratio ([α/β]) was 0.41.

[Comparative Example 3]
The amount of SN495-V-CN used was 5 parts by mass, the amount of BMI-2300 used was 49 parts by mass, the amount of BANI-M used was 36 parts by mass, and a biphenylaralkyl type epoxy compound (NC-3000H, Nippon Kayaku A prepreg was obtained in the same manner as in Example 6, except that 10 parts by mass of Yaku Co., Ltd., functional group equivalent: 290 g/eq.) was used. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.019, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is 0.019. /maleimide group equivalent) was 0.263, and the ratio ([α/β]) was 0.07.

[Example 7]
Bisphenol A type cyanate ester compound (CA210, Mitsubishi Gas Chemical Co., Ltd., cyanate equivalent: 139 g / eq.) 40.5 parts by mass, maleimide compound (BMI-70, maleimide group equivalent 221 g / eq, K-I Kasei Co., Ltd.) 29.8 parts by mass, biphenyl aralkyl type epoxy compound (NC-3000H, Nippon Kayaku Co., Ltd., functional group equivalent: 290 g / eq.) 15 parts by mass, bismaleimide compound (BMI-80, Daiwa Kasei Kogyo Co., Ltd., maleimide group equivalent: 285 g / eq.) 14.7 parts by mass, slurry silica (SC-5050MOB, average particle size 1.5 μm, Admatechs Co., Ltd.) 100 parts by mass, wet 1 part by mass of a dispersant (DISPERBYK-161, manufactured by BYK-Chemie Japan Co., Ltd.), 0.05 parts by mass of a leveling agent (manufactured by BYK-Chemie Japan Co., Ltd., "BYK-310"), and a curing accelerator (2, 0.5 part by mass of 4,5-triphenylimidazole, manufactured by Tokyo Kasei Kogyo Co., Ltd. was mixed to obtain a varnish. This varnish was diluted with methyl ethyl ketone, impregnated and applied to a 0.1 mm thick T-glass woven fabric, and dried by heating at 140° C. for 3 minutes to obtain a prepreg having a resin content of 44% by mass. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.291, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is 0.291. /maleimide group equivalent) was 0.186 and the ratio ([α/β]) was 1.56.

[Comparative Example 4]
The amount of bisphenol A cyanate ester compound (CA210, manufactured by Mitsubishi Gas Chemical Co., Ltd., cyanate equivalent: 139 g/eq.) was set to 12 parts by mass, and the maleimide compound (BMI-70, maleimide group equivalent: 221 g/eq, silica · A prepreg was obtained in the same manner as in Example 7, except that the amount of 58.3 parts by mass of Ai Kasei Co., Ltd. was used. The cyanate ester group amount (α) (parts by mass/cyanate ester group equivalent) of the cyanate ester compound (A) is 0.086, and the maleimide group amount (β) (parts by mass) of the maleimide compound (B) is /maleimide group equivalent) was 0.315, and the ratio ([α/β]) was 0.27.

[Preparation of metal foil-clad laminate]
Four or eight sheets of the obtained prepreg were stacked and 12 μm thick electrolytic copper foils (3EC ^- VLP, manufactured by Mitsui Kinzoku Mining Co., Ltd.) were placed on top and bottom. Lamination molding was performed for minutes to obtain metal foil-clad laminates having insulating layer thicknesses of 0.4 mm and 0.8 mm. Using the obtained metal foil-clad laminate, the glass transition temperature (Tg), linear thermal expansion coefficient, and copper foil peel strength were measured as described below.

[Copper foil peel strength]
The copper foil peel strength (kg/cm) was measured according to JIS C6481 using the obtained metal foil-clad laminate (insulating layer thickness: 0.8 mm).

[Plating peel strength]
The surface layer copper foil of the obtained metal foil clad laminate (insulation layer thickness 0.4 mm) was removed by etching, and electroless copper plating process manufactured by Uemura Kogyo Co., Ltd. (chemical names used: MCD-PL, MDP-2, MAT -SP, MAB-4-C, MEL-3-APEA ver.2), electroless copper plating of about 0.5 μm was applied, and drying was performed at 130° C. for 1 hour. Subsequently, electrolytic copper plating was applied so that the thickness of the plated copper was 18 μm, and drying was performed at 180° C. for 1 hour. Thus, a printed wiring board sample was produced in which a conductor layer (plated copper) with a thickness of 18 μm was formed on an insulating layer with a thickness of 0.4 mm. Using a printed wiring board sample having an insulating layer thickness of 0.4 mm produced by the above procedure, the adhesive strength of plated copper was measured three times according to JIS C6481, and the average value (kg/cm) was obtained.

[Glass transition temperature (Tg)]
After cutting the obtained metal foil-clad laminate (insulating layer thickness: 0.8 mm) into a size of 12.7×2.5 mm with a dicing saw, the copper foil on the surface was removed by etching to obtain a sample for measurement. Using this measurement sample, the glass transition temperature was measured by the DMA method with a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481 (average value of n=3).

[Retention rate of elastic modulus]
Using the obtained metal foil clad laminate (insulation layer thickness 0.8 mm) from which the copper foil was removed as a sample, Autograph (manufactured by Shimadzu Corporation) was used according to the method specified in JIS C 6481. AG-Xplus), the flexural modulus was measured at 27° C. and 260° C. respectively. From the flexural modulus (a) at 27° C. and the hot flexural modulus (b) at 260° C. measured as described above, the elastic modulus retention rate was calculated by the following formula.
Elastic modulus retention rate = (b) / (a) x 100

[Flexibility]
The obtained prepreg is wound around a bar of a predetermined diameter and bent at 180°, and the bent portion of the prepreg is observed. If the prepreg is damaged, it is regarded as damaged, and if it is not damaged, it is regarded as not damaged. was evaluated.
A: No damage to the prepreg with a diameter of 3 mm.
B: No damage to the prepreg at 5 mmφ.
C: No breakage in the prepreg at 10 mmφ.
D: The prepreg was damaged at 10 mmφ.

This application is based on a Japanese patent application (Japanese Patent Application No. 2016-92758) filed with the Japan Patent Office on May 2, 2016, the contents of which are incorporated herein by reference.

The resin composition of the present invention has industrial applicability as a material for prepregs, resin sheets, laminated resin sheets, metal foil-clad laminates, and printed wiring boards.

Claims (15)

containing a cyanate ester compound (A), a maleimide compound (B), and an amine-modified silicone (F),
The ratio ([α/β]) of the cyanate ester group amount (α) of the cyanate ester compound (A) to the maleimide group amount (β) of the maleimide compound (B) is 0.30 or more,
The cyanate ester compound (A) contains a compound represented by the following formula (2),

(In formula (2), each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n2 is an integer of 1 or more.)
Resin composition. The cyanate ester compound (A) further includes a compound represented by the following general formula (1),
The resin composition according to claim 1.

(In formula (1), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, each R ² independently represents a cyanate ester group, a hydroxyl group and a a phenyl group which may have at least one selected from the group consisting of allyl groups, a hydrogen atom, an allyl group, a cyanate ester group, or an epoxy group; n1 is an integer of 1 or more; m is 1; is an integer between ~4.) The cyanate ester group equivalent of the cyanate ester compound (A) is 100 to 220 g/eq. is
The resin composition according to claim 1 or 2. The cyanate ester compound (A) further includes a compound represented by the following general formula (3),
A resin composition according to any one of claims 1 to 3 .

The maleimide compound (B) is bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl ) containing at least one selected from the group consisting of methane and a maleimide compound represented by the following formula (4),
The resin composition according to any one of claims 1-4 .

(In the formula, each R ⁴ independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or more.) The ratio ([α/β]) is 0.45 to 1.0,
A resin composition according to any one of claims 1 to 5 . further comprising an inorganic filler (C),
The resin composition according to any one of claims 1-6 . The content of the inorganic filler (C) is 25 to 700 parts by mass with respect to 100 parts by mass of the resin solid content.
The resin composition according to claim 7 . The inorganic filler (C) contains at least one selected from the group consisting of silica, boehmite, and alumina,
The resin composition according to claim 7 or 8 . a substrate;
and the resin composition according to any one of claims 1 to 9 impregnated or applied to the substrate,
prepreg. Forming the resin composition according to any one of claims 1 to 9 into a sheet,
resin sheet. A sheet substrate and the resin composition according to any one of claims 1 to 9 arranged on one or both sides of the sheet substrate,
Laminated resin sheet. At least one selected from the group consisting of the prepreg according to claim 10 , the resin sheet according to claim 11 , and the laminated resin sheet according to claim 12 .
laminated board. at least one selected from the group consisting of the prepreg according to claim 10 , the resin sheet according to claim 11 , and the laminated resin sheet according to claim 12 ;
a metal foil arranged on one or both sides of the prepreg, the resin sheet, and the laminated resin sheet;
Metal foil clad laminate. Having an insulating layer and a conductor layer formed on one side or both sides of the insulating layer,
The insulating layer contains the resin composition according to any one of claims 1 to 9 ,
printed wiring board.