JP2021014544A - Resin composition - Google Patents

Abstract

To provide: a resin composition that can suppress a curing shrinkage rate, and gives a cured product with an excellent dielectric constant; a resin sheet containing the resin composition; and a printed wiring board, a multilayer flexible substrate and a semiconductor device having an insulating layer formed using the resin composition.SOLUTION: A resin composition contains (A) a compound containing an aromatic ester skeleton and an unsaturated bond, and (B) a polyimide resin. The (B) component content is 10 mass% or more and 50 mass% or less when a nonvolatile content in the resin composition is 100 mass%.SELECTED DRAWING: None

Description

The present invention relates to resin compositions. Furthermore, the present invention relates to a resin sheet, a printed wiring board, a multilayer flexible substrate, and a semiconductor device obtained by using the resin composition.

As a manufacturing technique for a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known.

As an insulating material for a printed wiring board used for such an insulating layer, for example, Patent Document 1 discloses a resin composition.

JP-A-2019-6869

In recent years, further improvement in the dielectric constant of the insulating layer has been required. Further, as the demand for thinning is increasing with the spread of smartphones and the like, thinning of the insulating layer is required. Since warpage tends to occur when the insulating layer is made thin, it is required to suppress the curing shrinkage rate of the insulating layer.

An object of the present invention is a resin composition capable of suppressing a curing shrinkage rate and obtaining a cured product having an excellent dielectric constant; a resin sheet containing the resin composition; an insulating layer formed by using the resin composition. It is an object of the present invention to provide a printed wiring board and a semiconductor device.

As a result of diligent studies on the above problems, the present inventors can solve the above problems by containing (A) an aromatic ester skeleton, an unsaturated bond-containing compound, and a predetermined amount (B) a polyimide resin. The present invention has been completed.

（一般式（Ａ−１）中、Ａｒ^１１は、それぞれ独立に、置換基を有していてもよい１価の芳香族炭化水素基を表し、Ａｒ^１２は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基を表し、Ａｒ^１３は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基、置換基を有していてもよい２価の脂肪族炭化水素基、酸素原子、硫黄原子、又はこれらの組み合わせからなる２価の基を表す。ｎは０〜１０の整数を表す。）

（一般式（Ａ−２）中、Ａｒ^２１は、置換基を有していてもよいｍ価の芳香族炭化水素基を表し、Ａｒ^２２は、それぞれ独立に置換基を有していてもよい１価の芳香族炭化水素基を表す。ｍは、２又は３の整数を表す。）
［３］ （Ａ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、０．１質量％以上３０質量％以下である、［１］又は［２］に記載の樹脂組成物。
［４］ さらに、（Ｃ）無機充填材を含有する、［１］〜［３］のいずれかに記載の樹脂組成物。
［５］ （Ｃ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、３０質量％以上である、［４］に記載の樹脂組成物。
［６］ さらに、（Ｄ）熱硬化性樹脂を含有する、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］ 絶縁層形成用である、［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ 導体層を形成するための絶縁層形成用である、［１］〜［７］のいずれかに記載の樹脂組成物。
［９］ 支持体と、該支持体上に設けられた、［１］〜［８］のいずれかに記載の樹脂組成物を含む樹脂組成物層とを含む、樹脂シート。
［１０］ ［１］〜［８］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、プリント配線板。
［１１］ ［１］〜［８］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、多層フレキシブル基板。
［１２］ ［１０］に記載のプリント配線板を含む、半導体装置。
［１３］ ［１１］に記載の多層フレキシブル基板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition containing (A) an aromatic ester skeleton, an unsaturated bond-containing compound, and (B) a polyimide resin.
A resin composition in which the content of the component (B) is 10% by mass or more and 50% by mass or less when the non-volatile component in the resin composition is 100% by mass.
[2] The resin according to [1], wherein the component (A) is either a compound represented by the following general formula (A-1) or a compound represented by the following general formula (A-2). Composition.

(In the general formula (A-1), Ar ¹¹ represents a monovalent aromatic hydrocarbon group which may independently have a substituent, and Ar ¹² has a substituent independently. Represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ may independently have a divalent aromatic hydrocarbon group and a substituent which may have a substituent. It represents a good divalent aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. N represents an integer of 0 to 10.)

(In the general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent, and Ar ²² may have a substituent independently of each other. Represents a monovalent aromatic hydrocarbon group. M represents an integer of 2 or 3.)
[3] The content of the component (A) is 0.1% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass, according to [1] or [2]. Resin composition.
[4] The resin composition according to any one of [1] to [3], which further contains (C) an inorganic filler.
[5] The resin composition according to [4], wherein the content of the component (C) is 30% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[6] The resin composition according to any one of [1] to [5], which further contains (D) a thermosetting resin.
[7] The resin composition according to any one of [1] to [6], which is used for forming an insulating layer.
[8] The resin composition according to any one of [1] to [7], which is used for forming an insulating layer for forming a conductor layer.
[9] A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [8].
[10] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [8].
[11] A multilayer flexible substrate including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [8].
[12] A semiconductor device including the printed wiring board according to [10].
[13] A semiconductor device including the multilayer flexible substrate according to [11].

According to the present invention, a resin composition capable of suppressing a curing shrinkage rate and obtaining a cured product having an excellent dielectric constant; a resin sheet containing the resin composition; an insulating layer formed by using the resin composition. A printed wiring board, a multilayer flexible substrate, and a semiconductor device can be provided.

FIG. 1 is a schematic view showing an example of a resin sheet when measuring the curing shrinkage rate.

Hereinafter, the present invention will be described in detail according to its preferred embodiment. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof. The dielectric constant represents the relative permittivity unless otherwise specified.

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) an aromatic ester skeleton, an unsaturated bond-containing compound, and (B) a polyimide resin, and the content of the component (B) is the resin composition. When the non-volatile component in the product is 100% by mass, it is 10% by mass or more and 50% by mass or less. In the present invention, by containing the component (A) and further containing a predetermined amount of the component (B), the curing shrinkage rate can be suppressed, and a cured product having an excellent dielectric constant can be obtained. In addition, it is usually possible to obtain a cured product having excellent dielectric loss tangent.

The resin composition may further contain any component in combination with the components (A) to (B). Examples of the optional component include (C) an inorganic filler, (D) a thermosetting resin, (E) a curing accelerator, and (F) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Aromatic ester skeleton and unsaturated bond-containing compound>
The resin composition contains (A) an aromatic ester skeleton and an unsaturated bond-containing compound as the component (A). By incorporating the component (A) in the resin composition, the curing shrinkage rate can be suppressed, and a cured product having an excellent dielectric constant can be obtained. The component (A) may be used alone or in combination of two or more.

The component (A) has an aromatic ester skeleton. The aromatic ester skeleton represents a skeleton having an ester bond and an aromatic ring bonded to one end or both ends of the ester bond. Of these, those having aromatic rings at both ends of the ester bond are preferable. Examples of the group having such a skeleton include an arylcarbonyloxy group, an aryloxycarbonyl group, an arylenecarbonyloxy group, an aryleneoxycarbonyl group, an arylcarbonyloxyarylene group, an aryloxycarbonylarylene group, and an arylenecarbonyloxyarylene group. The arylene oxycarbonylarylene group and the like can be mentioned. The number of carbon atoms of the group having such a skeleton is preferably 7 to 20, more preferably 7 to 15, and even more preferably 7 to 11. Aromatic hydrocarbon groups such as aryl groups and arylene groups may have substituents.

As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. Examples of such an aryl group include a phenyl group, a furanyl group, a pyrrolyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridinyl group, a pyrimidinyl group, a pyridadinyl group and a pyrazinyl group. A monocyclic aromatic compound such as a group or a triazinyl group from which one hydrogen atom has been removed; a naphthyl group, an anthracenyl group, a phenalenyl group, a phenylanthrenyl group, a quinolinyl group, an isoquinolinyl group, a quinazolyl group, a phthalazinyl group, a pteridinyl group, a cumlinyl group. A group in which one hydrogen atom is removed from a fused ring aromatic compound such as a group, an indol group, a benzoimidazolyl group, a benzofuranyl group, and an acridinyl group; and the like.

As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is further preferable. Such arylene group include a phenylene group, naphthylene group, anthracenylene group, biphenylene group _{(-C 6 H 4 -C 6 H} 4 -) , and the like.

The component (A) contains an unsaturated bond. As a result, the dielectric constant of the cured product becomes excellent. In addition, the unsaturated bond contributes to the curing reaction of the resin composition. Since the unsaturated bond contributes to the curing reaction, it is suppressed that a part of the ester moiety of the aromatic ester skeleton is used in the curing reaction, and as a result, the curing shrinkage rate is suppressed.

This unsaturated bond is preferably a carbon-carbon unsaturated bond. As the unsaturated bond, it is preferable to have it as a substituent having at least one unsaturated bond. Examples of the unsaturated bond include an unsaturated hydrocarbon group having 2 to 30 carbon atoms and an alkynyl group having 2 to 30 carbon atoms. The unsaturated bond is preferably provided as a substituent of the terminal aromatic hydrocarbon group, and more preferably as a substituent of the aromatic hydrocarbon group at both ends.

Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and 1-hexenyl. Group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group, 1-undecenyl group, 1-pentadecenyl group, 3-pentadecenyl group, 7-pentadecenyl Group, 1-octadecenyl group, 2-octadecenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, 1,3-butadienyl group, 1,4-butadienyl group, hexa-1,3-dienyl group, hexa-2, Examples thereof include a 5-dienyl group, a pentadeca-4,7-dienyl group, a hexa-1,3,5-trienyl group and a pentadeca-1,4,7-trienyl group.

Examples of the alkynyl group having 2 to 30 carbon atoms include an ethynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, and a 1,3-butadinyl group. The group etc. can be mentioned.

Of these, the unsaturated bond is preferably an alkenyl group having 2 to 30 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms. Is even more preferable, an allyl group, an isopropenyl group, and a 1-propenyl group are even more preferable, and an allyl group is particularly preferable.

The component (A) may have any of an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, and a group consisting of a combination thereof, in addition to the aromatic ester skeleton. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring, and the aromatic ring may be a monocyclic ring, a polycyclic ring, or a heterocyclic ring.

As the aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferable, an arylene group and an aralkylene group are more preferable, and an arylene group is further preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is further preferable. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group and the like. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferable, an aralkylene group having 7 to 20 carbon atoms is more preferable, and an aralkylene group having 7 to 15 carbon atoms is further preferable. Of these, a phenylene group is preferable.

As the aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferable, a divalent saturated aliphatic hydrocarbon group is more preferable, and an alkylene group and a cycloalkylene group are further preferable. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group and a 1,2-dimethylethylene group. Examples thereof include a group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group and a hexylene group.

As the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferable, a cycloalkylene group having 3 to 15 carbon atoms is more preferable, and a cycloalkylene group having 5 to 10 carbon atoms is further preferable. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, a cycloalkylene group represented by the following formulas (a) to (d), and the like. Can be mentioned. In the formulas (a) to (d), "*" represents a bond.

The aromatic ester skeleton, aromatic hydrocarbon group, aliphatic hydrocarbon group, and unsaturated hydrocarbon group may have a substituent. Examples of the substituent include an unsaturated hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom and the like. The substituent may be contained alone or in combination of two or more.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and isopentyl. Group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group. Examples include a group and a cyclononyl group.

The alkoxy group having 1 to 10 carbon atoms is not particularly limited, but is limited to a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group and an octyloxy group. , Nonyloxy group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The above-mentioned substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). The unsaturated hydrocarbon group is as described above. Unless otherwise specified, the same as the above-mentioned substituent may be used as the secondary substituent.

（一般式（Ａ−１）中、Ａｒ^１１は、それぞれ独立に、置換基を有していてもよい１価の芳香族炭化水素基を表し、Ａｒ^１２は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基を表し、Ａｒ^１３は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基、置換基を有していてもよい２価の脂肪族炭化水素基、酸素原子、硫黄原子、又はこれらの組み合わせからなる２価の基を表す。ｎは０〜１０の整数を表す。）

（一般式（Ａ−２）中、Ａｒ^２１は、置換基を有していてもよいｍ価の芳香族炭化水素基を表し、Ａｒ^２２は、それぞれ独立に置換基を有していてもよい１価の芳香族炭化水素基を表す。ｍは、２又は３の整数を表す。） The component (A) is preferably either a compound represented by the following general formula (A-1) or a compound represented by the following general formula (A-2).

(In the general formula (A-1), Ar ¹¹ represents a monovalent aromatic hydrocarbon group which may independently have a substituent, and Ar ¹² has a substituent independently. Represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ may independently have a divalent aromatic hydrocarbon group and a substituent which may have a substituent. It represents a good divalent aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. N represents an integer of 0 to 10.)

(In the general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent, and Ar ²² may have a substituent independently of each other. Represents a monovalent aromatic hydrocarbon group. M represents an integer of 2 or 3.)

In the general formula (A-1), Ar ¹¹ independently represents a monovalent aromatic hydrocarbon group which may have a substituent. Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a furanyl group, a pyrrolyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridinyl group, a pyrimidinyl group and a pyridadinyl group. A monocyclic aromatic compound such as a group, a pyrazinyl group, or a triazinyl group from which one hydrogen atom has been removed; a naphthyl group, an anthracenyl group, a phenalenyl group, a phenanthrenyl group, a quinolinyl group, an isoquinolinyl group, a quinazolyl group, a phthalazinyl group, a pteridinyl group. One hydrogen atom is removed from a fused ring aromatic compound such as a group, a coumarinyl group, an indol group, a benzoimidazolyl group, a benzofuranyl group, and an acridinyl group; and the like, among which the viewpoint of obtaining the effect of the present invention remarkably is mentioned. Therefore, a phenyl group is preferable. The monovalent aromatic hydrocarbon group represented by Ar ¹¹ may have a substituent. The substituents are the same as the substituents that the aromatic ester skeleton may have. Above all, the substituent of Ar ¹¹ preferably contains an unsaturated bond.

In the general formula (A-1), Ar ¹² represents a divalent aromatic hydrocarbon group which may independently have a substituent. Examples of the divalent aromatic hydrocarbon group include an arylene group and an aralkylene group, and an arylene group is preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is further preferable. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group and the like. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferable, an aralkylene group having 7 to 20 carbon atoms is more preferable, and an aralkylene group having 7 to 15 carbon atoms is further preferable. Of these, a phenylene group is preferable.

The divalent aromatic hydrocarbon group represented by Ar ¹² may have a substituent. The substituents are the same as the substituents that the aromatic ester skeleton may have.

In the general formula (A-1), Ar ¹³ independently has a divalent aromatic hydrocarbon group which may have a substituent and a divalent aliphatic hydrocarbon which may have a substituent. It represents a divalent group consisting of a hydrogen group, an oxygen atom, a sulfur atom, or a combination thereof, and a divalent group consisting of a combination thereof is preferable. The divalent aromatic hydrocarbon group is the same as the divalent aromatic hydrocarbon group represented by Ar ¹² .

As the divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is more preferable, an alkylene group and a cycloalkylene group are preferable, and a cycloalkylene group is more preferable.

As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group and a 1,2-dimethylethylene group. Examples thereof include a group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group and a hexylene group.

As the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferable, a cycloalkylene group having 3 to 15 carbon atoms is more preferable, and a cycloalkylene group having 5 to 10 carbon atoms is further preferable. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and a cycloalkylene group represented by the above formulas (a) to (d). The cycloalkylene group represented by the formula (c) is preferable.

As the divalent group composed of these combinations, a divalent aromatic hydrocarbon group which may have a substituent and a divalent aliphatic hydrocarbon group which may have a substituent are combined. A divalent group is preferable, a plurality of divalent aromatic hydrocarbon groups which may have a substituent, and a plurality of divalent aliphatic hydrocarbon groups which may have a substituent. A divalent group in which the above are alternately combined is more preferable. Specific examples of the above-mentioned divalent groups include the following divalent groups (A1) to (A8). In the formula, a1 to a8 represent an integer of 0 to 10, preferably an integer of 0 to 5. “*” Indicates a bond, and the wavy line indicates a structure obtained by reacting an aromatic compound, an acid halide of an aromatic compound, or an esterified compound of an aromatic compound used in synthesizing the component (A). Represent.

The divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group represented by Ar ¹³ may have a substituent. The substituents are the same as the substituents that the aromatic ester skeleton may have.

In the general formula (A-1), n represents an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3. When the compound represented by the general formula (A-1) is an oligomer or a polymer, n represents the average value thereof.

In the general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent. As the m-valent aromatic hydrocarbon group, an m-valent aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, and an m-valent aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable. An aromatic hydrocarbon group having an m-valent carbon atom number of 6 to 10 is more preferable. The m-valent aromatic hydrocarbon group represented by Ar ²¹ may have a substituent. The substituents are the same as the substituents that the aromatic ester skeleton may have.

In the general formula (A-2), Ar ²² represents a monovalent aromatic hydrocarbon group which may have a substituent independently of each other. Ar ²² is the same as the aromatic hydrocarbon group represented by Ar ¹¹ in the general formula (A-1). The monovalent aromatic hydrocarbon group represented by Ar ²² may have a substituent. The substituents are the same as the substituents that the aromatic ester skeleton may have.

In the general formula (A-2), m represents an integer of 2 or 3, and 2 is preferable.

Specific examples of the component (A) include the following compounds. Specific examples of the component (A) include the compounds described in paragraphs 0068 to 0071 of International Publication No. 2018/235424 and paragraphs 0113 to 0115 of International Publication No. 2018/235425. However, the component (A) is not limited to these specific examples. In the formula, s represents an integer of 0 or 1 or more, and r represents an integer of 1 to 10.

As the component (A), one synthesized by a known method may be used. The synthesis of the component (A) can be carried out, for example, by the method described in International Publication No. 2018/235424 or International Publication No. 2018/235425.

The weight average molecular weight of the component (A) is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, preferably 3000 or less, and more preferably 2000, from the viewpoint of remarkably obtaining the effect of the present invention. Below, it is more preferably 1500 or less. The weight average molecular weight of the component (A) is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The unsaturated bond equivalent of the component (A) is preferably 50 g / eq or more, more preferably 100 g / eq, from the viewpoint of obtaining the effect of the present invention remarkably. Above, more preferably 150 g / eq. It is preferably 2000 g / eq. Hereinafter, more preferably 1000 g / eq. Below, more preferably 500 g / eq. It is as follows. The unsaturated bond equivalent is the mass of component (A) containing 1 equivalent of the unsaturated bond.

The content of the component (A) is 0.1% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining a cured product having an excellent dielectric constant and which can suppress the curing shrinkage rate. Yes, preferably 1% by mass or more, more preferably 3% by mass or more, 30% by mass or less, preferably 28% by mass or less, still more preferably 25% by mass or less, 20% by mass or less, 15% by mass or less. , Or 10% by mass or less.

<(B) Polyimide resin>
The resin composition contains (B) polyimide resin as the (B) component. By including the component (B) in the resin composition, the cured product becomes flexible, and as a result, the curing shrinkage rate can be suppressed, and a cured product having an excellent dielectric constant can be obtained.

The content of the component (B) is 10% by mass or more, preferably 13% by mass or more, more preferably 13% by mass or more, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of suppressing the curing shrinkage rate. It is 15% by mass or more, more preferably 20% by mass or more. The upper limit is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

The component (B) is not particularly limited as long as it is a resin having an imide bond in the repeating unit. The component (B) generally includes those obtained by an imidization reaction of a diamine compound and an acid anhydride. The component (B) also includes a modified polyimide resin such as a siloxane-modified polyimide resin. The component (B) may be used alone or in combination of two or more.

The diamine compound for preparing the component (B) is not particularly limited, and examples thereof include an aliphatic diamine compound and an aromatic diamine compound.

Examples of the aliphatic diamine compound include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, and 1,5-diaminopentane. , 1,10-Diaminodecane and other linear aliphatic diamine compounds; 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5- Branched chain aliphatic diamine compounds such as diaminopentane; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexyl) An alicyclic diamine compound such as amine); dimer acid type diamine (hereinafter, also referred to as “dimer diamine”) and the like can be mentioned, and among them, dimer acid type diamine is preferable.

The diamine-type diamine is a diamine compound obtained by substituting two terminal carboxylic acid groups (-COOH) of dimer acid with an aminomethyl group (-CH _2- NH ₂ ) or an amino group (-NH ₂ ). means. Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those having 11 to 22 carbon atoms, particularly preferably those having 18 carbon atoms), and its industrial production process is almost the same in the industry. It is standardized. As the dimer acid, a dimer acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid and linoleic acid, which are particularly inexpensive and easily available, can be easily obtained. Further, the dimer acid may contain an arbitrary amount of monomeric acid, trimer acid, other polymerized fatty acids and the like depending on the production method, the degree of purification and the like. In addition, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in the present specification, hydrogenated substances whose degree of unsaturation is lowered by further hydrogenation reaction are also included in dimer acid. Commercially available products of the dimer acid type diamine are available, and examples thereof include "PRIAMINE 1073", "PRIAMINE 1074", and "PRIAMINE 1075" manufactured by Croda Japan; "Versamine 551" and "Versamine 552" manufactured by Cognis Japan. ..

Examples of the aromatic diamine compound include a phenylenediamine compound, a naphthalenediamine compound, a dianiline compound and the like.

The phenylenediamine compound means a compound composed of a benzene ring having two amino groups, and the benzene ring here may optionally have 1 to 3 substituents. The substituents here are the same as the substituents that the aromatic ester skeleton in the component (A) may have. Examples of the phenylenediamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, and 3,5-diaminobiphenyl. Examples thereof include 2,4,5,6-tetrafluoro-1,3-phenylenediamine.

The naphthalene diamine compound means a compound composed of a naphthalene ring having two amino groups, and the naphthalene ring here may optionally have 1 to 3 substituents. The substituents here are the same as the substituents that the aromatic ester skeleton in the component (A) may have. Examples of the naphthalenediamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 2,3-diaminonaphthalene and the like.

The dianiline compound means a compound containing two aniline structures in the molecule, and each of the two benzene rings in the two aniline structures further optionally has 1 to 3 substituents. Can be done. The substituents here are the same as the substituents that the aromatic ester skeleton in the component (A) may have. The two aniline structures in the dianiline compound are directly bonded and / or bonded via one or two linker structures having 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur and nitrogen atoms. Can be. Dianiline compounds also include those in which two aniline structures are bound by two bonds.

Specific examples of the "linker structure" in the dianiline compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH _2- , -CH ₂ CH _2- , -CH ₂ CH ₂ CH _{2- , -CH 2 CH 2 CH 2 CH} 2 -, - CH 2 CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 - , -CH = CH-, -O-, -S-, -CO-, -SO _2- , -NH-, -Ph-, -Ph-Ph-, -C (CH ₃ ) ₂ -Ph-C ( CH ₃ ) _2- , -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C (CH ₃ ) ₂ -Ph -O-, -Ph-CO-O-Ph-, -C (CH ₃ ) ₂ -Ph-C (CH ₃ ) _2- , groups represented by the following formulas (I) and (II), and these. Examples include a group consisting of a combination. In the present specification, "Ph" indicates a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group.

In one embodiment, the dianiline compound specifically includes 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-. Diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfide, 4-aminophenyl4-aminobenzoate, 1,3-bis (3-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenyl) propane, 4,4'-(hexafluoroisopropi) Liden) dianiline, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, α, α-bis [4- (4-Aminophenoxy) Phenyl] -1,3-diisopropylbenzene, α, α-bis [4- (4-Aminophenoxy) Phenyl] -1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene) Dianiline, 2,2-bis (3-methyl-4-aminophenyl) propane, 2,2-bis (3-methyl-4-aminophenyl) benzene, 4,4'-diamino-3,3'-dimethyl- 1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis (3-methyl-4-aminophenyl) fluorene, 5- (4) −Aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindan and the like, preferably 5- (4-aminophenoxy) -3- [4- ( 4-Aminophenoxy) Phenyl] -1,1,3-trimethylindan.

In another embodiment, examples of the dianiline compound include a diamine compound represented by the following formula (B-1).

（式（Ｂ−１）中、Ｒ^１〜Ｒ^８は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、−Ｘ^９−Ｒ^９、又は−Ｘ^１０−Ｒ^１０を示し、Ｒ^１〜Ｒ^８のうち少なくとも１つが、−Ｘ^１０−Ｒ^１０であり、Ｘ^９は、それぞれ独立して、単結合、−ＮＲ^９’−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ_２−、−ＮＲ^９’ＣＯ−、−ＣＯＮＲ^９’−、−ＯＣＯ−、又は−ＣＯＯ−を示し、Ｒ^９は、それぞれ独立して、置換又は無置換のアルキル基、又は置換又は無置換のアルケニル基を示し、Ｒ^９’は、それぞれ独立して、水素原子、置換又は無置換のアルキル基、又は置換又は無置換のアルケニル基を示し、Ｘ^１０は、それぞれ独立して、単結合、−（置換又は無置換のアルキレン基）−、−ＮＨ−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ_２−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＯＣＯ−、又は−ＣＯＯ−を示し、Ｒ^１０は、それぞれ独立して、置換又は無置換のアリール基、又は置換又は無置換のヘテロアリール基を示す。）

(In formula (B-1), R ^{1 to} R ⁸ independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ^9- R ⁹ , or -X ^10- R ¹⁰ . at least one of R ¹ to R ^8, a -X ^{10 -R} 10, ^{X 9} are each independently a single ^{bond, -NR 9 '-, - O} -, - S -, - CO-, ^{_{-SO 2 -, - NR 9 '}} CO -, - CONR 9' -, - OCO-, or -COO- are shown, ^{R 9} are each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted a substituted alkenyl group, R 9 ^'are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, X ¹⁰ are each independently a single bond ,-(Substituted or unsubstituted alkylene group)-, -NH-, -O-, -S-, -CO-, -SO _2- , -NHCO-, -CONH-, -OCO-, or -COO- , And R ¹⁰ independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.)

Alkyl group represented by the formula R ⁹ and R ⁹ of the (B-1) in ^'refers to a straight-chain, branched or cyclic, monovalent aliphatic saturated hydrocarbon group. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a cyclopentyl group. Cyclohexyl group and the like can be mentioned.

Alkenyl group represented by the formula R ⁹ and R ⁹ of the (B-1) ^'in at least one carbon - refers to a straight, branched or cyclic monovalent unsaturated hydrocarbon group having a carbon-carbon double bond .. As the alkenyl group, an alkenyl group having 2 to 6 carbon atoms is preferable, and an alkenyl group having 2 or 3 carbon atoms is more preferable. Examples of such an alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group and a 3-methyl group. -2-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, Examples thereof include a 2-cyclohexenyl group. The substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" is not particularly limited, but for example, a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group and a nitro group. , Hydroxyl group, carboxy group, sulfo group and the like. The number of substituents is preferably 1 to 3, and more preferably 1.

The substituent of the alkyl group in the "substituted or unsubstituted alkyl group" and the substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, but for example, a halogen atom or a cyano. Examples thereof include a group, an alkoxy group, an amino group, a nitro group, a hydroxy group, a carboxy group and a sulfo group. The number of substituents is preferably 1 to 3, and more preferably 1.

The alkoxy group refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferable, and an alkoxy group having 1 to 3 carbon atoms is more preferable. Examples of such an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and the like.

The alkylene group represented by X ¹⁰ in the formula (B-1) refers to a linear, branched or cyclic divalent aliphatic saturated hydrocarbon group, preferably an alkylene group having 1 to 6 carbon atoms, and carbon. An alkylene group having 1 to 3 atoms is more preferable. As the alkylene group, _{e.g., -CH 2 -, - CH 2} -CH 2 -, - CH (CH 3) -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) -, _{-CH (CH 3) -CH 2 -} , - C (CH 3) 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH (CH 3) -, - CH _{2 -CH (CH 3) -CH 2} -, - CH (CH 3) -CH 2 -CH 2 -, - CH 2 -C (CH 3) 2 -, - C (CH 3) 2 -CH 2 - , etc. Can be mentioned. The substituent of the alkylene group in the "substituted or unsubstituted alkylene group" is not particularly limited, but for example, a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group and a nitro group. , Hydroxyl group, carboxy group, sulfo group and the like. The number of substituents is preferably 1 to 3, and more preferably 1.

As the aryl group represented by R ¹⁰ in the formula (B-1), an aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. Examples of such an aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, and a phenyl group is preferable. The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, but for example, a halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group and an amino group. , Nitro group, hydroxy group, carboxy group, sulfo group and the like. The number of substituents is preferably 1 to 3, and more preferably 1.

The heteroaryl group represented by R ¹⁰ in the formula (B-1) refers to an aromatic heterocyclic group having 1 to 4 heteroatoms selected from an oxygen atom, a nitrogen atom and a sulfur atom. The heteroaryl group is preferably a 5- to 12-membered (preferably 5- or 6-membered) monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group. Examples of such a heteroaryl group include a fryl group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isooxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, 1,2,3-oxadiazolyl group, 1,2. , 4-Oxaziazolyl group, 1,3,4-oxadiazolyl group, Frazanyl group, 1,2,3-thiadiazolyl group, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, 1,2,3 -Triazolyl group, 1,2,4-triazolyl group, tetrazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group and the like can be mentioned. The substituent of the heteroaryl group in the "substituted or unsubstituted heteroaryl group" is the same as the substituent of the aryl group in the "substituted or unsubstituted aryl group".

R ^{1 to} R ⁸ independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ^9- R ⁹ , or -X ^10- R ¹⁰ . R ^{1 to} R ⁸ are preferably hydrogen atoms or −X ¹⁰ −R ¹⁰ independently of each other.

At least one of R ^{1 to} R ⁸ is −X ¹⁰ −R ¹⁰ . Preferably, one or two of R ^{1 to} R ⁸ is -X ^10- R ¹⁰ , and more preferably one or two of R ^{5 to} R ⁸ is -X ^10- R ^10. Preferably, one or two of R ⁵ and R ⁷ are -X ^10- R ¹⁰ .

In one embodiment, preferably one or two of R ^{1 to} R ⁸ are -X ^10- R ¹⁰ , and the other of R ^{1 to} R ⁸ is a hydrogen atom, more preferably R ⁵ One or two of ~ R ⁸ are -X ^10- R ¹⁰ , and the other of R ^{1 to} R ⁸ are hydrogen atoms, more preferably one or 2 of R ⁵ and R ^7. One is −X ¹⁰ −R ¹⁰ , and the other of R ^{1 to} R ⁸ is a hydrogen atom.

X ⁹ are each independently a single ^{bond, -NR 9 '-, - O} -, - S -, - CO -, - SO 2 -, - NR 9' CO -, - CONR 9 '-, - OCO -Or -COO- is indicated. R ⁹ independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. X ⁹ is preferably a single bond.

R ^{9'independently} represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. R ⁹ is preferably a substituted or unsubstituted alkyl group.

X ¹⁰ are independently single-bonded,-(substituted or unsubstituted alkylene group)-, -NH-, -O-, -S-, -CO-, -SO _2- , -NHCO-,- Indicates CONH-, -OCO-, or -COO-. X ¹⁰ is preferably a single bond.

R ¹⁰ independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ¹⁰ is preferably a substituted or unsubstituted aryl group.

（式中、Ｒ^１〜Ｒ^６及びＲ^８は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、−Ｘ^９−Ｒ^９を示し、その他の記号は式（Ｂ−１）と同様である。）

In one embodiment, the diamine compound represented by the formula (B-1) is preferably a compound represented by the following formula (B-2), and the compound represented by the following formula (B-3) ( 4-Aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl) is more preferred.

(In the formula, R ^{1 to} R ⁶ and R ⁸ independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, and -X ^9- R ⁹ , and other symbols are in the formula (B-1). Is the same as.)

As the diamine compound, a commercially available one may be used, or a compound synthesized by a known method may be used. For example, the diamine compound represented by the formula (B-1) can be synthesized by the synthetic method described in Japanese Patent No. 6240798 or a method similar thereto. The diamine compound may be used alone or in combination of two or more.

The acid anhydride for preparing the component (B) is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, diphthalic acid dianhydride and the like, and preferred examples thereof. It is a diphthalic dianhydride.

The benzenetetracarboxylic dianhydride means a benzene dianhydride having 4 carboxy groups, and the benzene ring here may optionally have 1 to 3 substituents. Here, as the substituent, a halogen atom, a cyano group, and ^-X 13 ^{-R 13} those selected from (as defined by the following formula (B-4)) is preferable. Specific examples of the benzenetetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

The naphthalenetetracarboxylic dianhydride means a naphthalene dianhydride having 4 carboxy groups, and the naphthalene ring here may optionally have 1 to 3 substituents. Here, as the substituent, a halogen atom, a cyano group, and ^-X 13 ^{-R 13} those selected from (as defined by the following formula (B-4)) is preferable. Specific examples of the naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.

The anthracene tetracarboxylic dianhydride means an anthracene dianhydride having 4 carboxy groups, and the anthracene ring here may optionally have 1 to 3 substituents. Here, as the substituent, a halogen atom, a cyano group, and ^-X 13 ^{-R 13} those selected from (as defined by the following formula (B-4)) is preferable. Specific examples of the anthracene tetracarboxylic dianhydride include 2,3,6,7-anthracene tetracarboxylic dianhydride.

The diphthalic anhydride means a compound containing two phthalic anhydrides in the molecule, and the two benzene rings in the two phthalic anhydrides are optionally 1 to 3 rings, respectively. It may have a substituent. Here, as the substituent, a halogen atom, a cyano group, and ^-X 13 ^{-R 13} those selected from (as defined by the following formula (B-4)) is preferable. The two phthalic anhydrides in the diphthalic dianhydride can be bonded directly or via a linker structure having 1 to 100 skeleton atoms selected from carbon, oxygen, sulfur and nitrogen atoms.

（式中、Ｒ^１１及びＲ^１２は、それぞれ独立して、ハロゲン原子、シアノ基、ニトロ基、又は−Ｘ^１３−Ｒ^１３を示し、
Ｘ^１３は、それぞれ独立して、単結合、−ＮＲ^１３’−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ_２−、−ＮＲ^１３’ＣＯ−、−ＣＯＮＲ^１３’−、−ＯＣＯ−、又は−ＣＯＯ−を示し、
Ｒ^１３は、それぞれ独立して、置換又は無置換のアルキル基、又は置換又は無置換のアルケニル基を示し、
Ｒ^１３’は、それぞれ独立して、水素原子、置換又は無置換のアルキル基、又は置換又は無置換のアルケニル基を示し、
Ｙは、単結合、或いは炭素原子、酸素原子、硫黄原子及び窒素原子から選ばれる１〜１００個の骨格原子を有するリンカー構造を示し、
ｎ１及びｍ１は、それぞれ独立して、０〜３の整数を示す。） Examples of the diphthalic dianhydride include a compound represented by the formula (B-4).

(In the formula, R ¹¹ and R ¹² each independently represent a halogen atom, a cyano group, a nitro group, or -X ^13- R ¹³ .
X ¹³ are each independently a single ^{bond, -NR 13 '-, - O} -, - S -, - CO -, - SO 2 -, - NR 13' CO -, - CONR 13 '-, - OCO -Or -COO-, indicating
R ¹³ independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group.
R ^{13'independently} represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group.
Y represents a single bond or a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.
n1 and m1 each independently represent an integer of 0 to 3. )

Y is preferably a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. n1 and m1 are preferably 0.

The "linker structure" in Y has 1 to 100 skeletal atoms selected from carbon, oxygen, sulfur and nitrogen atoms. The "linker structure" is preferably − [A—Ph] _a −A− [Ph—A] _b − [in the formula, A is a single bond, − (substituted or unsubstituted alkylene group, respectively). ) -, - O -, - S -, - CO -, - SO 2 -, - CONH -, - NHCO -, - COO-, or -OCO- indicates, a and b are each independently 0 Indicates an integer of ~ 2 (preferably 0 or 1). ] Is a divalent group represented by.

"Linker structure" in Y, _{specifically, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH ₂ CH ₂ CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -O-, -CO-, -SO _2- , -Ph-, -O-Ph-O-,- Examples thereof include O-Ph-SO ₂ -Ph-O-, -O-Ph-C (CH ₃ ) ₂ -Ph-O-, and the like.

Specific examples of the diphthalic acid dianhydride include 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 3,. 3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride Anhydroide, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether Tetetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfone Tetracarboxylic dianhydride 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfonate dianhydride, methylene-4, 4'-diphthalic acid dianhydride, 1,1-ethinilidene-4,4'-diphthalic acid dianhydride, 2,2-propylidene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4 , 4'-Diphthalic dianhydride, 1,3-trimethylethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-penta Methylene-4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) benzene dianhydride , 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 2,2-bis (2,3-di) Carboxiphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 4,4'-(4,5pyridenediphenoxy) bisphthalic dianhydride, etc. Can be mentioned.

As the aromatic tetracarboxylic dianhydride, a commercially available product may be used, or a product synthesized by a known method or a method similar thereto may be used. The aromatic tetracarboxylic dianhydride may be used alone or in combination of two or more.

In one embodiment, the acid anhydride for producing the component (B) may contain other acid anhydrides in addition to the aromatic tetracarboxylic dianhydride.

Specific examples of other acid anhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexane-1,2,3,4-tetracarboxylic acid. Dianoxide, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, 3,3', 4,4'-bicyclohexyltetracarboxylic acid dianhydride, carbonyl-4,4'-bis (cyclohexane) -1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis (cyclohexane-1) , 2-Dicarboxylic acid) dianhydride, oxy-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) Examples thereof include aliphatic tetracarboxylic acid dianhydrides such as dianhydride and sulfonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride.

The content of the structure derived from the aromatic tetracarboxylic dianhydride in the entire structure derived from the acid anhydride constituting the component (B) is preferably 10 mol% or more, preferably 30 mol% or more. More preferably, it is more preferably 50 mol% or more, further preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 100 mol%. ..

（一般式（Ｂ）中、Ｒ^５１は、単結合又は酸無水物に由来する残基を表し、Ｒ^５２は、単結合又はジアミン化合物に由来する残基を表す。） The component (B) preferably has a structural unit represented by the following general formula (B).

(In the general formula (B), R ⁵¹ represents a residue derived from a single bond or an acid anhydride, and R ⁵² represents a residue derived from a single bond or a diamine compound.)

R ⁵¹ represents a residue derived from a single bond or an acid anhydride, and is preferably a residue derived from an acid anhydride. The residue derived from the acid anhydride represented by R ⁵¹ refers to a divalent group obtained by removing two oxygen atoms from the acid anhydride. The acid anhydride is as described above.

R ⁵² represents a residue derived from a single bond or a diamine compound, and is preferably a residue derived from a diamine compound. The residue derived from the diamine compound represented by R ⁵² refers to a divalent group obtained by removing two amino groups from the diamine compound. The diamine compound is as described above.

The component (B) can be prepared by a conventionally known method. Known methods include, for example, a method of heating and reacting a mixture of a diamine compound, an acid anhydride and a solvent. The mixing amount of the diamine compound can be, for example, usually 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents, relative to the acid anhydride.

As the solvent used for preparing the component (B), amide-based solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, and N-methyl-2-pyrrolidone; acetone and methyl ethyl ketone. Examples thereof include ketone solvents such as (MEK) and cyclohexanone; ester solvents such as γ-butyrolactone; and hydrocarbon solvents such as cyclohexane and methylcyclohexane. Further, for the preparation of the component (B), an imidization catalyst, an azeotropic dehydration solvent, an acid catalyst or the like may be used, if necessary. Examples of the imidization catalyst include tertiary amines such as triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N, N-dimethyl-4-aminopyridine and pyridine. Examples of the azeotropic dehydration solvent include toluene, xylene, ethylcyclohexane and the like. Examples of the acid catalyst include acetic anhydride and the like. Those skilled in the art can appropriately set the amount of the imidization catalyst, azeotropic dehydration solvent, acid catalyst and the like to be used. The reaction temperature for the preparation of the component (B) is usually 100-250 ° C.

The weight average molecular weight of the component (B) is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, preferably 100,000 or less, more preferably 70,000 or less, still more preferably 50,000 or less. Is.

The content of the component (A) when the non-volatile component in the resin composition is 100% by mass is a1, and the content of the component (B) is b1 when the non-volatile component in the resin composition is 100% by mass. When, a1 / b1 is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, preferably 1 or less, more preferably 0.5 or less, still more preferably. It is 0.3 or less. By adjusting a1 / b1 so as to be within such a range, the effect of the present invention can be remarkably obtained.

<(C) Inorganic filler>
In addition to the above-mentioned components, the resin composition may contain an inorganic filler as an arbitrary component and further as a component (C).

An inorganic compound is used as the material of the inorganic filler. Examples of materials for inorganic fillers are silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , Barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Of these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more.

Commercially available products of the component (C) include, for example, "UFP-30" manufactured by Denka Corporation; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C" manufactured by Admatex Corporation. "YA050C", "YA050C-MJE", "YA010C"; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO" manufactured by Admatex -C4 "," SO-C2 "," SO-C1 "; and the like.

The specific surface area of the component (C) is preferably 1 m ² / g or more, more preferably 2 m ² / g or more, and particularly preferably 3 m ² / g or more. The upper limit is not particularly limited, but is preferably 60 m ² / g or less, 50 m ² / g or less, or 40 m ² / g or less. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. ..

The average particle size of the component (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 0.1 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is 5 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less.

The average particle size of the component (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the wavelengths of the light sources used were blue and red, and the volume-based particle size distribution of component (C) was measured by the flow cell method, and the obtained particle size distribution was obtained. The average particle size can be calculated as the median diameter from. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.

The component (C) is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of the surface treatment agent include vinylsilane-based coupling agents, (meth) acrylic-based coupling agents, fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, and mercaptosilane-based coupling agents. Examples thereof include silane-based coupling agents, alkoxysilanes, organosilazane compounds, and titanate-based coupling agents. Of these, vinylsilane-based coupling agents, (meth) acrylic-based coupling agents, and aminosilane-based coupling agents are preferable from the viewpoint of remarkably obtaining the effects of the present invention. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Examples of commercially available surface treatment agents include "KBM1003" (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM503" (3-methacryloxypropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. , "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyl) manufactured by Shin-Etsu Chemical Co., Ltd. (Trimethoxysilane), "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane coupling agent), "KBM-7103" manufactured by Shin-Etsu Chemical Co., Ltd. (3,3,3-trifluoropropyltrimethoxysilane) And so on.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of a surface treatment agent, and 0.2 parts by mass to 3 parts by mass is surface-treated. It is preferable that the surface is treated with 0.3 parts by mass to 2 parts by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further preferable. preferable.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

The content of the component (C) is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 40% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of lowering the dielectric constant. It is preferably 50% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.

The content of the component (A) when the non-volatile component in the resin composition is 100% by mass is a1, and the content of the component (B) is b1 when the non-volatile component in the resin composition is 100% by mass. When the content of the component (C) is c1 when the non-volatile component in the resin composition is 100% by mass, (a1 + b1) / c1 preferably exceeds 0.4, more preferably 0. It is 43 or more, more preferably 0.45 or more, preferably 1 or less, more preferably 0.6 or less, still more preferably 0.55 or less. By adjusting (a1 + b1) / c1 so as to be within such a range, the effect of the present invention can be remarkably obtained.

<(D) Thermosetting resin>
In addition to the above-mentioned components, the resin composition may contain a thermosetting resin as an arbitrary component and further as a component (D). However, those corresponding to the components (A) to (B) are excluded. Examples of the thermosetting resin include epoxy resin, phenolic resin, naphthol resin, benzoxazine resin, active ester resin, cyanate ester resin, carbodiimide resin, amine resin, and acid anhydride type. Examples include resin. As the component (D), one type may be used alone, or two or more types may be used in combination at an arbitrary ratio. Hereinafter, the resin composition reacts with an epoxy resin, such as a phenol-based resin, a naphthol-based resin, a benzoxazine-based resin, an active ester-based resin, a cyanate ester-based resin, a carbodiimide-based resin, an amine-based resin, and an acid anhydride-based resin. Resins that can cure objects are sometimes collectively referred to as "curing agents".

Examples of the epoxy resin as the component (D) include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and dicyclopentadiene type epoxy resin. Trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester Type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy Examples thereof include resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the component (D). From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass with respect to 100% by mass of the non-volatile component of the component (D). As mentioned above, it is more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as "liquid epoxy resin") or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as "solid epoxy resin"). ). The resin composition may contain only the liquid epoxy resin as the component (D), may contain only the solid epoxy resin, or may contain a combination of the liquid epoxy resin and the solid epoxy resin. Good.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are more preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", "825", and "Epicoat" manufactured by Mitsubishi Chemical Co., Ltd. 828EL (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical's "630", "630LSD" (glycidylamine type epoxy resin); "ZX1059" manufactured by Nittetsu Chemical & Materials Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); manufactured by Nagase ChemteX. "EX-721" (glycidyl ester type epoxy resin); "Selokiside 2021P" manufactured by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel Co., Ltd. (epoxy resin having a butadiene structure) Examples thereof include "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nittetsu Chemical & Materials Co., Ltd. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene ether type epoxy resin. Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC. Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), manufactured by DIC "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN" manufactured by Nippon Kayakusha -502H "(Trisphenol type epoxy resin)," NC7000L "(Naftor novolac type epoxy resin)," NC3000H "," NC3000 "," NC3000L "," NC3100 "(biphenyl type epoxy resin); Nittetsu Chemical & Materials Co., Ltd. "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin); "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy) manufactured by Mitsubishi Chemical Co., Ltd. Resin), "YX8800" (anthracene type epoxy resin); "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "YL7800" (Fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (D), their quantity ratio (liquid epoxy resin: solid epoxy resin) is a mass ratio, preferably 1: 0.1: 1: 20, more preferably 1: 0.3 to 1:15, and particularly preferably 1: 1 to 1:10. When the amount ratio of the liquid epoxy resin to the solid epoxy resin is within such a range, the desired effect of the present invention can be remarkably obtained. Furthermore, usually, when used in the form of a resin sheet, moderate adhesiveness is provided. In addition, when used in the form of a resin sheet, sufficient flexibility is usually obtained and handleability is improved. Further, usually, a cured product having sufficient breaking strength can be obtained.

The epoxy equivalent of the epoxy resin as the component (D) is preferably 50 g / eq. ~ 5000 g / eq. , More preferably 50 g / eq. ~ 3000 g / eq. , More preferably 80 g / eq. ~ 2000g / eq. , Even more preferably 110 g / eq. ~ 1000 g / eq. Is. Within this range, the crosslinked density of the cured product of the resin composition can provide a sufficiently cured product. Epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin as the component (D) is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effect of the present invention. is there. The weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The content of the epoxy resin as the component (D) is preferably 10% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability. As mentioned above, it is more preferably 15% by mass or more, still more preferably 20% by mass or more. The upper limit of the content of the epoxy resin is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

The amount ratio of the epoxy resin to the component (A) as the component (D) is the ratio of [total number of epoxy groups of the epoxy resin]: [total number of unsaturated bonds of the component (A)] to be 1: 0. The range of 01 to 1: 5 is preferable, 1: 0.03 to 1: 3 is more preferable, and 1: 0.05 to 1: 1 is even more preferable. Here, the "number of epoxy groups of the epoxy resin" is a total value obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. The "number of unsaturated bonds of the component (A)" is a total value obtained by dividing the mass of the non-saturated component of the component (A) present in the resin composition by the unsaturated bond equivalent. By setting the amount ratio of the epoxy resin to the component (A) within such a range, the effect of the present invention can be remarkably obtained.

When the non-volatile component in the resin composition is 100% by mass, the content of the component (A) is a1, and the non-volatile component in the resin composition is 100% by mass, the epoxy resin as the component (D). When the content is d1, d1 / a1 is preferably 1 or more, more preferably 3 or more, still more preferably 4 or more, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. .. By adjusting d1 / a1 so as to be within such a range, the effect of the present invention can be remarkably obtained.

As the active ester resin as the component (D), a resin having one or more active ester groups in one molecule can be used. Among them, the active ester-based resin has two or more ester groups with high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. Resin is preferred. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Preferred specific examples of the active ester-based resin include an active ester-based resin containing a dicyclopentadiene-type diphenol structure, an active ester-based resin containing a naphthalene structure, an active ester-based resin containing an acetylated product of phenol novolac, and a benzoyl of phenol novolac. Examples thereof include active ester-based resins containing compounds. Of these, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of the active ester resin include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester resins containing a dicyclopentadiene type diphenol structure. "65TM", "EXB-8000L-65TM" (manufactured by DIC); "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-" as active ester resins containing a naphthalene structure. 8150-62T ”(manufactured by DIC);“ DC808 ”(manufactured by Mitsubishi Chemical) as an active ester resin containing an acetylated product of phenol novolac;“ YLH1026 ”(Mitsubishi Chemical) as an active ester resin containing a benzoylated product of phenol novolac. (Manufactured by Mitsubishi Chemical Co., Ltd.); "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester resin which is an acetylated product of phenol novolac; (Manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.); "EXB-8500-65T" (manufactured by DIC Co., Ltd.); and the like.

As the phenolic resin and the naphthol resin as the component (D), those having a novolak structure are preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based resin is more preferable.

Specific examples of the phenolic resin and the naphthol resin include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. , "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel Chemical & Materials Co., Ltd. , DIC Corporation "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and the like.

Specific examples of the benzoxazine-based resin as the component (D) include "JBZ-OD100" (benzoxazine ring equivalent 218), "JBZ-OP100D" (benzoxazine ring equivalent 218), and "ODA-" manufactured by JFE Chemical Co., Ltd. "BOZ" (benzoxazine ring equivalent 218); "Pd" (benzoxazine ring equivalent 217), "FA" (benzoxazine ring equivalent 217) manufactured by Shikoku Kasei Kogyo Co., Ltd .; "HFB2006M" manufactured by Showa Polymer Co., Ltd. (Benzooxazine ring equivalent 432) and the like.

Examples of the cyanate ester-based resin as the component (D) include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), and 4,4'-methylenebis (2,6-dimethylphenylcyanate). ), 4,4'-Etilidendiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-) 3,5-Dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, etc. Bifunctional cyanate resin; polyfunctional cyanate resin derived from phenol novolac, cresol novolac, etc .; prepolymer in which these cyanate resins are partially triazine; and the like. Specific examples of the cyanate ester resin include "PT30", "PT30S" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin) manufactured by Ronza Japan. Examples thereof include "BA230" and "BA230S75" (prepolymer in which part or all of bisphenol A disyanate is triazined to form a trimer).

Specific examples of the carbodiimide-based resin as the component (D) include carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216, V-05 (carbodiimide group equivalent: 216)) and V-07 (registered trademark) manufactured by Nisshinbo Chemical Co., Ltd. Carbodiimide group equivalent: 200); V-09 (carbodiimide group equivalent: 200); Stavaxol® P (carbodiimide group equivalent: 302) manufactured by Rheinchemy.

Examples of the amine-based resin as the component (D) include resins having one or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, and aromatics. Examples thereof include amines, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. The amine-based resin is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of amine-based resins include 4,4'-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-. Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine , 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-Aminophenoxy) Benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-Aminophenoxy) phenyl) sulfone, etc. may be mentioned. Commercially available products may be used as the amine resin, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard AB", "Kayahard" manufactured by Nippon Kayaku Corporation. Examples include "AS" and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

Examples of the acid anhydride-based resin as the component (D) include a resin having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydroanhydride, methylnadic acid anhydride, and methylnadic hydride anhydride. Trialkyltetrahydrophthalic anhydride, succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimerit anhydride Acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenyl Sulphontetracarboxylic hydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1, Examples thereof include 3-dione, ethylene glycol bis (anhydrotrimeritate), and polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized.

When the epoxy resin and the curing agent are contained as the component (D), the amount ratio of the epoxy resin to all the curing agents is [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the curing agent]. The ratio is preferably in the range of 1: 0.01 to 1: 5, more preferably 1: 0.3 to 1: 3, and even more preferably 1: 0.5 to 1: 2. Here, the "number of epoxy groups of the epoxy resin" is a total value obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. The "number of active groups of the curing agent" is a total value obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active group equivalent. By setting the amount ratio of the epoxy resin and the curing agent within such a range as the component (D), a cured product having excellent flexibility can be obtained.

The content of the curing agent as the component (D) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, based on 100% by mass of the non-volatile component in the resin composition from the viewpoint of obtaining a cured product having excellent flexibility. It is 0.5% by mass or more, more preferably 1% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.

The content of the component (D) is preferably 5% by mass or more, more preferably 10% by mass or more, and further, with respect to 100% by mass of the non-volatile component in the resin composition, from the viewpoint of obtaining a cured product having excellent flexibility. It is preferably 15% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

<(E) Curing accelerator>
In addition to the above-mentioned components, the resin composition may contain a curing accelerator as an arbitrary component and further as a component (E). By containing the component (E), it becomes possible to further promote polymerization by heat.

Examples of the component (E) include epoxy resin curing accelerators such as phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators; peroxide-based components. Examples thereof include thermal polymerization curing accelerators such as curing accelerators. The component (E) may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned, with dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene being preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

Examples of the peroxide-based curing accelerator include di-butyl peroxide, t-butyl cumyl peroxide, t-butyl peroxyacetate, α, α'-di (t-butyl peroxy) diisopropylbenzene, and t. Peroxides such as −butylperoxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butylperoxybenzoate can be mentioned.

Examples of commercially available peroxide-based curing accelerators include "Perhexyl D", "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", and "Perbutyl O" manufactured by NOF CORPORATION. Examples thereof include "perbutyl ND", "perbutyl Z", "park mill P", and "park mill D".

The content of the component (E) is preferably 0.1% by mass or more, more preferably 0, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. .2% by mass or more, more preferably 0.3% by mass or more, preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less.

<(F) Other additives>
In addition to the above-mentioned components, the resin composition may further contain other additives as arbitrary components. Examples of such an additive include a thermoplastic resin other than the component (B), a thickener, a defoaming agent, a leveling agent, a resin additive such as an adhesion imparting agent, and the like. These additives may be used alone or in combination of two or more. Each content can be appropriately set by those skilled in the art.

The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a solvent or the like to the compounding components as necessary and mixing and dispersing them using a rotary mixer or the like.

<Physical characteristics and uses of resin composition>
The resin composition contains the component (A) and a predetermined amount of the component (B). As a result, the curing shrinkage rate can be suppressed, and a cured product having an excellent dielectric constant can be obtained. In addition, it is usually possible to obtain a cured product having excellent dielectric loss tangent.

A cured product obtained by thermosetting the resin composition at 190 ° C. for 90 minutes exhibits a characteristic of low curing shrinkage rate. That is, curing shrinkage is suppressed, thereby providing an insulating layer capable of suppressing warpage. The curing shrinkage rate is preferably 0.35% or less, more preferably 0.34% or less, still more preferably 0.33% or less. The lower limit of the curing shrinkage rate is not particularly limited, but may be 0.01% or more. The curing shrinkage rate can be measured according to the method described in Examples described later.

A cured product obtained by thermosetting the resin composition at 190 ° C. for 90 minutes exhibits a characteristic of low dielectric constant. Therefore, the cured product provides an insulating layer having a low dielectric constant. The dielectric constant is preferably 3.0 or less, more preferably 2.9 or less, still more preferably 2.85 or less. The lower limit of the dielectric constant may be 0.001 or more. The dielectric constant can be measured according to the method described in Examples described later.

A cured product obtained by thermosetting the resin composition at 190 ° C. for 90 minutes exhibits a characteristic of low dielectric loss tangent. Therefore, the cured product provides an insulating layer having a low dielectric loss tangent. The dielectric loss tangent is preferably 0.01 or less, more preferably 0.007 or less, still more preferably 0.005 or less. The lower limit of the dielectric loss tangent may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in Examples described later.

The resin composition of the present invention can suppress the curing shrinkage rate and can provide an insulating layer having an excellent dielectric constant. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating applications. Specifically, a resin composition for forming the insulating layer for forming the conductor layer (including the rewiring layer) formed on the insulating layer (resin for forming the insulating layer for forming the conductor layer). It can be suitably used as a composition).

Further, in the multilayer printed wiring board described later, a resin composition for forming an insulating layer of the multilayer printed wiring board (resin composition for forming an insulating layer of the multilayer printed wiring board) and an interlayer insulating layer of the printed wiring board are formed. (Resin composition for forming an interlayer insulating layer of a printed wiring board), and a resin composition for forming an insulating layer of a flexible substrate (resin composition for forming an insulating layer of a flexible substrate). be able to.

Further, for example, when the semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is for a rewiring forming layer as an insulating layer for forming the rewiring layer. Can also be suitably used as a resin composition (resin composition for forming a rewiring forming layer) and a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When the semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) A process of laminating a temporary fixing film on a base material,
(2) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(3) Step of forming a sealing layer on a semiconductor chip,
(4) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(5) A step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off, and (6) a rewiring layer as a conductor layer is formed on the rewiring forming layer. The process of forming

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer provided on the support and formed of the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulating properties even if the cured product of the resin composition is a thin film. It is preferably 40 μm or less, more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 5 μm or more.

Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, and a film made of a plastic material and a metal leaf are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyethylene. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The surface of the support to be joined to the resin composition layer may be matted, corona-treated, or antistatic-treated.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples thereof include "AL-5" and "AL-7", "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Corporation, and "Unipee" manufactured by Unitika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

In one embodiment, the resin sheet may further contain other layers, if desired. Examples of such other layers include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and the like to the surface of the resin composition layer and scratches.

For the resin sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like and further dried to form a resin composition layer. It can be manufactured by.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol and the like. Carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.

The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[Printed circuit board]
The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

The printed wiring board can be manufactured, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II).
(I) A step of laminating the resin composition layer of the resin sheet on the inner layer substrate so as to be bonded to the inner layer substrate (II) A step of thermosetting the resin composition layer to form an insulating layer.

The "inner layer substrate" used in the step (I) is a member that becomes a substrate of a printed wiring board, and is, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. And so on. Further, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board". Further, an intermediate product in which an insulating layer and / or a conductor layer should be formed when the printed wiring board is manufactured is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable to press the heat-bonded member not directly on the resin sheet but through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the resin sheet may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

After laminating, the laminated resin sheet may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

The support may be removed between steps (I) and step (II) or after step (II).

In step (II), the resin composition layer is thermoset to form an insulating layer. The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions usually adopted when forming the insulating layer of the printed wiring board may be used.

For example, the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but the curing temperature is preferably 120 ° C. to 240 ° C., more preferably 150 ° C. to 220 ° C., still more preferably 170 ° C. to 210. ℃. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, prior to thermosetting the resin composition layer, the resin composition layer is heated at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

In manufacturing the printed wiring board, (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after the step (II), the removal of the support is performed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

The step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out by using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the hole may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also performed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P", "Swelling Dip Securigans SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. Be done. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. to 100 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. Further, the neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be carried out by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 1 minute to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and further preferably 50 nm or more. The arithmetic mean roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

The step (V) is a step of forming the conductor layer, and forms the conductor layer on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed from a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single copper layer is preferable. A metal layer is more preferred.

The conductor layer may have a single-layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the desired printed wiring board design.

In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern, and the semi-additive can be manufactured from the viewpoint of ease of manufacture. It is preferably formed by the method. Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[Multilayer flexible substrate]
The multilayer flexible substrate includes an insulating layer formed by a cured product of the resin composition of the present invention. The multilayer flexible substrate may include any member in combination with the insulating layer. Examples of the optional member include an electronic component, a coverlay film, and the like.

The multilayer flexible substrate can be manufactured by a manufacturing method including a method of manufacturing a laminated sheet produced by laminating and curing a plurality of resin composition layers. Therefore, the multilayer flexible substrate can be manufactured by a manufacturing method including (a) a step of preparing a resin sheet and (b) a step of laminating and curing a plurality of resin composition layers using the resin sheet.

The method for manufacturing the multilayer flexible substrate may further include an arbitrary step in combination with the above steps. For example, a method for manufacturing a multilayer flexible substrate including electronic components may include a step of joining electronic components to a laminated sheet. As the joining condition between the laminated sheet and the electronic component, any condition can be adopted in which the terminal electrode of the electronic component and the conductor layer as wiring provided on the laminated sheet can be connected by a conductor. Further, for example, a method for manufacturing a multilayer flexible substrate including a coverlay film may include a step of laminating a laminated sheet and a coverlay film.

The multilayer flexible substrate can be usually used by being bent so that one surface of the laminated sheet included in the multilayer flexible substrate faces each other. For example, a multilayer flexible substrate is housed in a housing of a semiconductor device in a state of being bent to reduce its size. Further, for example, a multilayer flexible substrate is provided in a movable portion of a semiconductor device having a bendable movable portion.

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board or the multilayer flexible substrate of the present invention. The semiconductor device of the present invention can be manufactured by using the printed wiring board or the multilayer flexible substrate of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conduction point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The mounting method of the semiconductor chip in manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer. Examples thereof include a mounting method using (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

<Synthesis Example 1: Synthesis of Polyimide Resin 1>
9.13 g (30 mmol) of 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl (compound of formula (B-3)) in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer. ), 4,4'-(4,4'-isopropyridene diphenoxy) bisphthalic acid dianhydride 15.61 g (30 mmol), N-methyl-2-pyrrolidone 94.64 g, pyridine 0.47 g (6 mmol) , 10 g of toluene was added, and the imidization reaction was carried out at 180 ° C. under a nitrogen atmosphere for 4 hours while looking out of the system on the way to obtain a polyimide solution (nonvolatile content 20% by mass) containing the polyimide resin 1. No precipitation of the synthesized polyimide resin 1 was observed in the polyimide solution. The weight average molecular weight of the polyimide resin 1 was 45,000.

<Synthesis Example 2: Synthesis of Polyimide Resin 2>
Aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan, 4,4'-(4,4') in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. -Isopropyridenediphenoxy) bisphthalic dianhydride) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g were charged, and the solution was heated to 60 ° C. Next, 43.7 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 5.4 g of 1,3-bis (aminomethyl) cyclohexane were added dropwise, and then an imidization reaction was carried out at 140 ° C. for 1 hour. As a result, a polyimide solution containing the polyimide resin 2 (nonvolatile content: 30% by mass) was obtained. The weight average molecular weight of the polyimide resin 2 was 25,000.

<Synthesis Example 3: Synthesis of Polyimide Resin 3>
A 500 mL separable flask equipped with a moisture metering receiver connected to a reflux condenser, a nitrogen introduction pipe, and a stirrer was prepared. In this flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) [Phenyl] -1,1,3-trimethylindan 29.6 g was added, and the reaction was carried out by stirring at 45 ° C. for 2 hours under a nitrogen stream. Next, the temperature of the reaction solution was raised and the condensed water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. It was confirmed that a predetermined amount of water had accumulated in the moisture metering receiver and that no outflow of water was observed. After confirmation, the temperature of the reaction solution was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Then, it was cooled to obtain a polyimide solution (nonvolatile content 20% by mass) containing a polyimide resin 3 having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin 3 had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight average molecular weight of the polyimide resin 3 was 12,000.

<Synthesis Example 4: Synthesis of aromatic ester skeleton and unsaturated bond-containing compound A (Compound A)>
89 parts by mass of orthoallylphenol, 110 parts by mass of dicyclopentadiene-phenol copolymer resin (softening point 85 ° C., hydroxyl group equivalent of about 165 g / eq.), And 1000 parts by mass of toluene were charged in the reaction vessel, and the inside of the vessel was replaced with nitrogen under reduced pressure. It was dissolved while. Subsequently, 135 parts by mass of isophthalic acid chloride was charged and dissolved. Next, 0.5 g of tetrabutylammonium bromide was added, and 309 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while purging the inside of the container with nitrogen. At that time, the temperature in the system was controlled to 60 ° C. or lower. Then, it was stirred for 1 hour and reacted. After completion of the reaction, the reaction product was separated and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and toluene and the like were distilled off under heating and reduced pressure conditions to obtain an aromatic ester skeleton and an unsaturated bond-containing compound A. The unsaturated bond equivalent of the obtained aromatic ester skeleton and the unsaturated bond-containing compound A was calculated from the charging ratio to be 428 g / eq. Met. Compound A is represented by the following formula, s represents an integer of 0 or 1 or more, and the average value of r calculated from the charging ratio is 1. The wavy line is a structure obtained by reacting isophthalic acid chloride and a polyaddition reaction resin of phenol and / or orthoallylphenol.

<Synthesis Example 5: Synthesis of aromatic ester skeleton and unsaturated bond-containing compound B (Compound B)>
201 parts by mass of orthoallylphenol and 1000 parts by mass of toluene were charged in the reaction vessel, and the inside of the vessel was dissolved while being replaced with nitrogen under reduced pressure. Subsequently, 152 parts by mass of isophthalic acid chloride was charged and dissolved. While purging the inside of the container with nitrogen, 309 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. At that time, the temperature in the system was controlled to 60 ° C. or lower. Then, it was stirred for 1 hour and reacted. After completion of the reaction, the reaction product was separated and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and toluene and the like were distilled off under heating and reduced pressure conditions to obtain an aromatic ester skeleton and an unsaturated bond-containing compound B. The unsaturated bond equivalent of the obtained aromatic ester skeleton and the unsaturated bond-containing compound B was calculated from the charging ratio to be 199 g / eq. Met. Compound B has a structure represented by the following formula.

<Example 1: Preparation of resin composition 1>
Bixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent about 185g / eq.) 5 parts, Naphthalene type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 332g / eq.), 5 parts, Bisphenol AF type epoxy resin (Mitsubishi Chemical "YL7760", epoxy equivalent about 238 g / eq.) 10 parts, cyclohexane type epoxy resin (Mitsubishi Chemical "ZX1658GS", epoxy equivalent about 135 g / eq.), Synthetic It was dissolved by heating in a mixed solvent of 100 parts of the epoxy resin 1 (20% by mass of the non-volatile component) obtained in Example 1 and 10 parts of cyclohexanone while stirring. After cooling to room temperature, 5 parts of the compound A obtained in Synthesis Example 4, a triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151 g / eq., Solid content) was added thereto. 4 parts of 50% 2-methoxypropanol solution), spherical silica ("SC2500SQ" manufactured by Admatex, average particle size 0.5 μm, specific surface area 11.2 m ² / g, N-phenyl-3 per 100 parts of silica -Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., surface-treated with 1 part of KBM573) 50 parts, amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) 0.2 parts, and peroxide 0.03 parts of a physical curing accelerator (“Perbutyl C” manufactured by Nichiyu Co., Ltd.) is mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to form a resin composition. Object 1 was prepared.

<Example 2: Preparation of resin composition 2>
In Example 1, 5 parts of compound A was changed to 10 parts of compound B (50% by mass of non-volatile component). A resin composition 2 was prepared in the same manner as in Example 1 except for the above items.

<Example 3: Preparation of resin composition 3>
In Example 1, 100 parts of the polyimide resin 1 (non-volatile component 20% by mass) obtained in Synthesis Example 1 was changed to 66.7 parts of the polyimide resin 2 (non-volatile component 30% by mass) obtained in Synthesis Example 2. A resin composition 3 was prepared in the same manner as in Example 1 except for the above items.

<Example 4: Preparation of resin composition 4>
In Example 1, 100 parts of the polyimide resin 1 (non-volatile component 20% by mass) obtained in Synthesis Example 1 was changed to 100 parts of the polyimide resin 3 (non-volatile component 20% by mass) obtained in Synthesis Example 3. A resin composition 4 was prepared in the same manner as in Example 1 except for the above items.

<Comparative Example 1: Preparation of Resin Composition 5>
In Example 1, 5 parts of Compound A obtained in Synthesis Example 4 was mixed with an active ester-based curing agent (“EXB-8000L-65TM” manufactured by DIC), an active group equivalent of about 220 g / eq., And a toluene having a non-volatile component of 65% by mass. : 1: 1 solution of MEK) 7.7 parts. A resin composition 5 was prepared in the same manner as in Example 1 except for the above items.

<Comparative Example 2: Preparation of Resin Composition 6>
In Example 1, 5 parts of the compound A obtained in Synthesis Example 4 was mixed with an active ester-based curing agent (“EXB-8150-62T” manufactured by DIC), an active group equivalent of about 230 g / eq., And a toluene having a non-volatile component of 62% by mass. Solution) changed to 8.1 parts. A resin composition 6 was prepared in the same manner as in Example 1 except for the above items.

<Measurement of average particle size of inorganic filler>
100 mg of an inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasonic waves for 10 minutes. Using a laser diffraction type particle size distribution measuring device (“LA-960” manufactured by Horiba Seisakusho Co., Ltd.), the wavelengths of the light sources used were blue and red, and the particle size distribution of the inorganic filler was measured on a volume basis by the flow cell method. From the obtained particle size distribution, the average particle size of the inorganic filler was calculated as the median diameter.

<Measurement of specific surface area of inorganic filler>
Using a BET fully automatic specific surface area measuring device (Maxorb HM-1210 manufactured by Mountech), nitrogen gas is adsorbed on the sample surface, and the specific surface area is calculated using the BET multipoint method to calculate the specific surface area of the inorganic filler. Was measured.

<Measurement of curing shrinkage rate>
(1-1) Preparation of Resin Sheet The resin composition of each Example and Comparative Example is dried on a release-treated surface of a PET film (thickness 38 μm) treated with an alkyd-based release agent. The layer was uniformly applied with a die coater so that the thickness of the layer was 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 6 minutes to obtain a resin sheet 1.

(1-2) Preparation of Polyimide Film with Resin After processing this resin sheet 1 into a 200 mm square, a resin composition is used using a batch type vacuum pressure laminator (Nichigo Morton, 2-stage build-up laminator, CVP700). A polyimide film with resin was obtained by laminating on one side so that the material layer was in contact with the center of the smooth surface of the polyimide film (UPIREX 25S manufactured by Ube Kosan Co., Ltd., 25 μm thickness, 240 mm square). Lamination was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(1-3) Measurement of initial length The obtained polyimide film with resin is punched from the support of the resin sheet into a portion of 200 mm square resin about 4 to 20 mm with a through hole (diameter about 6 mm). Four holes are formed (the holes are tentatively referred to as A, B, C, and D in a clockwise direction), and after the support of the resin sheet is peeled off, the length L ( _LAB , _LBC) between the centers of the formed holes is L. L _CD , L _DA , L _AC , L _BD ) (see FIG. 1) were measured with a non-contact image measuring device (Mitutoyo, Quick Vision model: QVH1X606-PRO III_BHU2G). In FIG. 1, X and Y represent the vertical direction and the horizontal direction of the resin sheet.

(1-4) Thermosetting of Resin Composition Layer The polyimide film surface of the resin-attached polyimide film whose length has been measured is a glass cloth base material epoxy resin double-sided copper-clad laminate (0.7 mm thick, Matsushita) having a size of 255 mm × 255 mm. It was installed on "R5715ES" manufactured by Denko Co., Ltd., and its four sides were fixed with a polyimide adhesive tape (width 10 mm) and heated at 190 ° C. for 90 minutes to heat-cure the resin composition layer to obtain a cured product layer. ..

(1-5) Measurement of Thermosetting Shrinkage Rate After thermosetting, the polyimide adhesive tape is peeled off, the polyimide film with a cured product layer is removed from the laminated plate, and the cured product layer is further peeled off from the polyimide film (1-3). The length L'(L' _AB , L' _BC , L' _CD , L' _DA , L' _AC , L' _BD ) between the centers of the holes formed in is non-contact like L. It was measured with a polyimide measuring device.

Hole A, the shrinkage _{s1 AB} after curing of the length _{L AB} between the hole B was determined by the following equation (1). Was determined _{L BC, L CD, L DA} , L AC and _L shrinkage _s1 BC after curing of the _{BD, s1 CD, s1 DA,} s1 AC and _{s1 DA} in the same manner.
_{s1 AB = (L AB -L '} AB) / L AB (1)

The curing shrinkage rate of the cured product layer was determined by the following formula (2).
Curing shrinkage rate [shrinkage rate in the xy direction: S1] (%)
= {(S1 _AB + s1 _BC + s1 _CD + s1 _DA + s1 _AC + s1 _DA ) / 6} x 100 (2)

The curing shrinkage rate of the cured product layer was evaluated according to the following criteria.
◯: Curing shrinkage rate is 0.35% or less ×: Curing shrinkage rate exceeds 0.35%

<Measurement of dielectric properties (dielectric constant, dielectric loss tangent)>
The resin sheet 1 produced in (1-1) above was used as a laminated plate (MCL-E-700G manufactured by Hitachi Kasei Co., Ltd.) using a batch type vacuum pressurizing laminator (“MVLP-500” manufactured by Meiki Co., Ltd.). It was laminated on a copper foil etched out product). The laminate was depressurized for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimped at 120 ° C. for 30 seconds at a pressure of 0.74 MPa. Then, the PET film was peeled off, and the resin composition layer was cured under curing conditions of 190 ° C. for 90 minutes to obtain a cured product sample.

The cured sample was cut into test pieces having a width of 2 mm and a length of 80 mm. With respect to the test piece, the dielectric constant and the dielectric loss tangent were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using "HP8362B" manufactured by Azilent Technologies. Measurements were made on the three test pieces, and the average value was calculated. The dielectric constant was evaluated according to the following criteria.
◯: Dielectric constant is 3.0 or less ×: Dielectric constant exceeds 3.0

＊表中、「（Ａ）成分の含有量」は、樹脂組成物中の不揮発成分を１００質量％とした場合の（Ａ）成分の含有量を表し、「（Ｂ）成分の含有量」は、樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｂ）成分の含有量を表し、「（Ｃ）成分の含有量」は、樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｃ）成分の含有量を表す。

* In the table, "content of component (A)" represents the content of component (A) when the non-volatile component in the resin composition is 100% by mass, and "content of component (B)" is Represents the content of the component (B) when the non-volatile component in the resin composition is 100% by mass, and the "content of the component (C)" is 100% by mass of the non-volatile component in the resin composition. The content of the component (C) in the case is represented.

In Examples 1 to 4, it has been confirmed that even when the components (C) to (E) are not contained, the same result as in the above-mentioned Examples is obtained, although the degree is different.

Claims (13)

A resin composition containing (A) an aromatic ester skeleton, an unsaturated bond-containing compound, and (B) a polyimide resin.
A resin composition in which the content of the component (B) is 10% by mass or more and 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein the component (A) is either a compound represented by the following general formula (A-1) or a compound represented by the following general formula (A-2).

(In the general formula (A-1), Ar ¹¹ represents a monovalent aromatic hydrocarbon group which may independently have a substituent, and Ar ¹² has a substituent independently. Represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ may independently have a divalent aromatic hydrocarbon group and a substituent which may have a substituent. It represents a good divalent aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. N represents an integer of 0 to 10.)

(In the general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent, and Ar ²² may have a substituent independently of each other. Represents a monovalent aromatic hydrocarbon group. M represents an integer of 2 or 3.) The resin composition according to claim 1 or 2, wherein the content of the component (A) is 0.1% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 3, further comprising (C) an inorganic filler. The resin composition according to claim 4, wherein the content of the component (C) is 30% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 5, further comprising (D) a thermosetting resin. The resin composition according to any one of claims 1 to 6, which is used for forming an insulating layer. The resin composition according to any one of claims 1 to 7, which is used for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 8. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 8. A multilayer flexible substrate including an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 8. A semiconductor device including the printed wiring board according to claim 10. A semiconductor device including the multilayer flexible substrate according to claim 11.

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