TW202144499A - Resin composition capable of obtaining a cured product having a low dielectric loss tangent and a high glass transition temperature - Google Patents

Abstract

The object of the present invention is to provide a resin composition capable of obtaining a cured product having a low dielectric loss tangent and a high glass transition temperature. The solution of the present invention is a resin composition containing: (A) a maleimide compound, (B) an epoxy resin, and (C) an active ester-based curing agent, wherein (A) the maleimide compound contains (A-1) a maleimide compound containing a trimethylindan skeleton.

Description

resin composition

The present invention relates to resin compositions. Furthermore, the present invention relates to a cured product of the resin composition, and a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

As a manufacturing technique of a printed wiring board, the manufacturing method of the build-up method by alternately stacking insulating layers and conductor layers is known. In the manufacturing method of the build-up method, generally, the insulating layer is formed by curing the resin composition. As such a resin composition, the resin composition disclosed in patent document 1 is known, for example. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2020-29494

[Problems to be solved by the invention]

The cured product formed by curing the resin composition is used as an insulating layer of a printed wiring board of a semiconductor device. Therefore, it is required to reduce the dielectric tangent of the cured product. In addition, from the viewpoint of improving heat resistance, it is desirable that the glass transition temperature of the cured product be high.

The present invention was made in view of the aforementioned problems, and an object of the present invention is to provide: a resin composition capable of obtaining a cured product with a low dielectric tangent and a high glass transition temperature; a cured product of the resin composition; and a resin composition comprising the resin composition A layered resin sheet; a printed wiring board comprising an insulating layer formed of a cured product of the resin composition; and a semiconductor device comprising the printed wiring board. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention have diligently examined and found a resin composition comprising (A) a maleimide compound, (B) an epoxy resin, and (C) an active ester-based hardener, wherein (A) The maleimide compound containing (A-1) the maleimide compound containing a trimethylindenane skeleton can solve the above-mentioned problems, thereby completing the present invention. That is, the present invention includes the following.

(式(A4)中， Ar^a1 表示可具有取代基之2價芳香族烴基； R^a1 各自獨立地表示碳原子數1～10的烷基、碳原子數1～10的烷氧基、碳原子數1～10的烷硫基、碳原子數6～10的芳基、碳原子數6～10的芳氧基、碳原子數6～10的芳硫基、碳原子數3～10的環烷基、鹵素原子、硝基、羥基或巰基； R^a2 各自獨立地表示碳原子數1～10的烷基、碳原子數1～10的烷氧基、碳原子數1～10的烷硫基、碳原子數6～10的芳基、碳原子數6～10的芳氧基、碳原子數6～10的芳硫基、碳原子數3～10的環烷基、鹵素原子、羥基或巰基； R^a3 各自獨立地表示2價脂肪族烴基； n_a1 表示正之整數； n_a2 各自獨立地表示0～4之整數； n_a3 各自獨立地表示0～3之整數； R^a1 的烷基、烷氧基、烷硫基、芳基、芳氧基、芳硫基及環烷基的氫原子可被鹵素原子所取代； R^a2 的烷基、烷氧基、烷硫基、芳基、芳氧基、芳硫基及環烷基的氫原子可被鹵素原子所取代； n_a2 為2～4時，R^a1 係在同一環內可相同或相異； n_a3 為2～3時，R^a2 係在同一環內可相同或相異)。 [3] 如[1]或[2]記載之樹脂組成物，其中相對於樹脂組成物中的樹脂成分100質量%，(A-1)成分之量為0.5質量%以上70質量%以下。 [4] 如[1]～[3]中任一項記載之樹脂組成物，其中相對於樹脂組成物中的樹脂成分100質量%，(A)成分之量為0.5質量%以上70質量%以下。 [5] 如[1]～[4]中任一項記載之樹脂組成物，其中相對於樹脂組成物中的樹脂成分100質量%，(B)成分之量為3質量%以上50質量%以下。 [6] 如[1]～[5]中任一項記載之樹脂組成物，其中相對於樹脂組成物中的樹脂成分100質量%，(C)成分之量為6質量%以上80質量%以下。 [7] 如[1]～[6]中任一項記載之樹脂組成物，其進一步包含(D)無機填充材。 [8] 如[7]記載之樹脂組成物，其中相對於樹脂組成物中的不揮發成分100質量%，(D)成分之量為20質量%以上90質量%以下。 [9] 如[1]～[8]中任一項記載之樹脂組成物，其係絕緣層形成用。 [10] 一種如[1]～[9]中任一項記載之樹脂組成物之硬化物。 [11] 一種樹脂薄片，其具備支撐體與在該支撐體上之以如[1]～[9]中任一項記載之樹脂組成物所形成的樹脂組成物層。 [12] 一種印刷配線板，其包含以如[1]～[9]中任一項記載之樹脂組成物之硬化物所形成之絕緣層。 [13] 一種半導體裝置，其包含如[12]記載之印刷配線板。 [發明的效果][1] A resin composition comprising (A) a maleimide compound, (B) an epoxy resin and (C) an active ester-based hardener, (A) the maleimide compound comprising (A-1) ) maleimide compounds containing a trimethylindenane skeleton. [2] The resin composition according to [1], wherein the component (A-1) contains a structure represented by the following formula (A4);

(In formula (A4), Ar ^a1 represents a divalent aromatic hydrocarbon group which may have a substituent; R ^a1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carbon atom Alkylthio group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, arylthio group having 6 to 10 carbon atoms, cycloalkane having 3 to 10 carbon atoms group, halogen atom, nitro group, hydroxyl group or mercapto group; R ^a2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, aryl group with 6-10 carbon atoms, aryloxy group with 6-10 carbon atoms, arylthio group with 6-10 carbon atoms, cycloalkyl group with 3-10 carbon atoms, halogen atom, hydroxyl or mercapto group; R ^a3 each independently represents a divalent aliphatic hydrocarbon group; n _a1 represents a positive whole number; n _a2 each independently represent an integer of 0 to 4 of; n _a3 each independently represent an integer of 0 to 3, of; R ^a1 is an alkyl group, an alkoxy Hydrogen atoms of radicals, alkylthio groups, aryl groups, aryloxy groups, arylthio groups and cycloalkyl groups may be substituted by halogen atoms; the alkyl, alkoxy, alkylthio, aryl, aryloxy groups of ^{R a2} , arylthio and cycloalkyl hydrogen atoms can be substituted by halogen atoms; when n _a2 is 2-4, R ^a1 can be the same or different in the same ring; when n _a3 is 2-3, R ^a2 is can be the same or different within the same ring). [3] The resin composition according to [1] or [2], wherein the amount of the component (A-1) is 0.5 mass % or more and 70 mass % or less with respect to 100 mass % of the resin component in the resin composition. [4] The resin composition according to any one of [1] to [3], wherein the amount of (A) component is 0.5 mass % or more and 70 mass % or less with respect to 100 mass % of the resin component in the resin composition . [5] The resin composition according to any one of [1] to [4], wherein the amount of (B) component is 3 mass % or more and 50 mass % or less with respect to 100 mass % of the resin component in the resin composition . [6] The resin composition according to any one of [1] to [5], wherein the amount of (C) component is 6 mass % or more and 80 mass % or less with respect to 100 mass % of the resin component in the resin composition . [7] The resin composition according to any one of [1] to [6], further comprising (D) an inorganic filler. [8] The resin composition according to [7], wherein the amount of the component (D) is 20% by mass or more and 90% by mass or less with respect to 100% by mass of the nonvolatile content in the resin composition. [9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer. [10] A cured product of the resin composition according to any one of [1] to [9]. [11] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [9] on the support. [12] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [9]. [13] A semiconductor device comprising the printed wiring board according to [12]. [Effect of invention]

According to the present invention, there can be provided: a resin composition capable of obtaining a cured product with a low dielectric tangent and a high glass transition temperature; a cured product of the resin composition; a resin sheet including a resin composition layer comprising the resin composition; comprising A printed wiring board having an insulating layer formed of a cured product of the resin composition; and a semiconductor device including the printed wiring board.

[The form of carrying out the invention]

Hereinafter, the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented with arbitrary modifications without departing from the scope of the invention claimed in the present invention and the scope of its equivalents.

[1. Outline of resin composition] The resin composition which concerns on one Embodiment of this invention contains (A) a maleimide compound, (B) an epoxy resin, and (C) an active ester type hardening|curing agent. Moreover, (A) maleimide compound contains (A-1) the maleimide compound containing a trimethylindanane skeleton.

With such a resin composition, a cured product having a low dielectric tangent and a high glass transition temperature can be obtained. Moreover, the hardened|cured material of the said resin composition can reduce a dielectric constant normally. Furthermore, when the insulating layer is formed from the cured product of the resin composition, the surface roughness of the insulating layer is usually reduced, and the plating peeling strength can be improved.

The said resin composition may further contain arbitrary components, such as (D) an inorganic filler, (E) arbitrary hardener, (F) hardening accelerator, as needed.

[2. (A) Maleimide compound] The maleimide compound as the component (A) contained in the resin composition means a compound containing one or more maleimide groups in the molecule. The maleimide group is represented by the following formula (A2). In formula (A2), * represents a bond. (A) The number of maleimide groups contained in one molecule of the maleimide compound is usually 1 or more, preferably 2 or more. The upper limit is not particularly limited, and may be, for example, 22 or less, 10 or less, 6 or less, 4 or less, or 3 or less.

The (A) maleimide compound contained in the resin composition of the present embodiment includes (A-1) the maleimide compound containing a trimethylindan skeleton. In the following description, the "maleimide compound containing a trimethylindenane skeleton" is also referred to as a "specific maleimide compound". The trimethylindenane skeleton represents a skeleton represented by the following formula (A3).

A substituent may be bonded to the benzene ring contained in the trimethylindenane skeleton. As a substituent, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a halogen atom, a hydroxyl group, and a mercapto group are mentioned, for example. The number of carbon atoms in the alkyl group is preferably 1-10. As an alkyl group, a methyl group, an ethyl group, a propyl group, a n-butyl group, a tertiary butyl group, etc. are mentioned, for example. The number of carbon atoms of the alkoxy group is preferably 1-10. As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. are mentioned, for example. The number of carbon atoms in the alkylthio group is preferably 1-10. As an alkylthio group, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, etc. are mentioned, for example, The number of carbon atoms in the aryl group is preferably 6-10. As an aryl group, a phenyl group, a naphthyl group, etc. are mentioned, for example. The number of carbon atoms of the aryloxy group is preferably 6-10. As an aryloxy group, a phenoxy group, a naphthoxy group, etc. are mentioned, for example. The number of carbon atoms in the arylthio group is preferably 6-10. As an arylthio group, a phenylthio group, a naphthylthio group, etc. are mentioned, for example. The number of carbon atoms in the cycloalkyl group is preferably 3-10. As a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc. are mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, an iodine atom, etc. are mentioned, for example.

Among the aforementioned substituents, the hydrogen atom of the alkyl group, the alkoxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group and the cycloalkyl group may be substituted with a halogen atom.

The number of substituents bonded to one benzene ring contained in the trimethylindenane skeleton may be one or two or more. The number of substituents bonded to the benzene ring contained in the trimethylindenane skeleton is usually 0 or more and 3 or less. When the number of substituents is 2 or more, those 2 or more substituents may be the same or different. Among them, it is preferable that the benzene ring contained in the trimethylindenane skeleton does not bind a substituent.

(A-1) The number of trimethylindanane skeletons contained in one molecule of the specific maleimide compound may be one, or two or more. The upper limit may be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

(A-1) It is preferable that the specific maleimide compound further contains an aromatic ring skeleton in addition to the above-mentioned trimethylindan skeleton. The number of carbon atoms constituting the ring of the aromatic ring skeleton is preferably 6-10. As an aromatic ring skeleton, a benzene ring skeleton, a naphthalene ring skeleton, etc. are mentioned, for example. (A-1) The number of the aromatic ring skeleton contained in one molecule of the specific maleimide compound is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 4 or less, Particularly preferred is 3 or less. (A-1) When the specific maleimide compound contains two or more aromatic ring skeletons in addition to the trimethylindenane skeleton, those aromatic ring skeletons may be the same or different.

A substituent may be bonded to the aromatic ring contained in the above-mentioned aromatic ring skeleton. As a substituent, the said substituent and a nitro group as a substituent which can be bonded to the benzene ring contained in a trimethylindenane skeleton are mentioned, for example. The number of substituents bonded to one aromatic ring may be one or two or more. The number of substituents bonded to the aromatic ring is usually 0 or more and 4 or less. When the number of substituents is 2 or more, those 2 or more substituents may be the same or different.

(A-1) It is preferable that the specific maleimide compound further contains a divalent aliphatic hydrocarbon group in addition to the above-mentioned trimethylindenane skeleton. In particular, when the specific maleimide compound (A-1) contains an aromatic ring skeleton other than the benzene ring contained in the trimethylindan skeleton, the specific maleimide compound (A-1) preferably contains Divalent aliphatic hydrocarbon group. In this case, the divalent aliphatic hydrocarbon group is preferably connected between the benzene ring and the aromatic ring skeleton contained in the trimethylindenane skeleton. Moreover, it is preferable that a divalent aliphatic hydrocarbon group connects between aromatic ring skeletons.

The number of carbon atoms of the divalent aliphatic hydrocarbon group is preferably 1 or more, more preferably 12 or less, particularly preferably 8 or less, and particularly preferably 5 or less. The divalent aliphatic hydrocarbon group is more preferably an alkylene group of a saturated aliphatic hydrocarbon group. Examples of the divalent aliphatic hydrocarbon group include straight-chain alkylene groups such as methylene, ethylidene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; ethylene (-CH (CH ₃ )-), propylene (-CH(CH ₂ CH ₃ )-), isopropylidene (-C(CH ₃ ) ₂ -), ethylmethylmethylene (-C(CH _{3 )} )(CH ₂ CH ₃ )-), diethylmethylene (-C(CH ₂ CH ₃ ) ₂ -) and other branched alkylenes, etc. (A-1) When the specific maleimide compound contains two or more divalent aliphatic hydrocarbon groups in addition to the trimethylindenane skeleton, those divalent aliphatic hydrocarbon groups may be the same or different.

(A-1) The specific maleimide compound preferably has a structure represented by the following formula (A4). (A-1) The whole of the specific maleimide compound may have the structure represented by the formula (A4), and the part of the (A-1) specific maleimide compound may have the structure represented by the formula (A4) .

(In formula (A4), Ar ^a1 represents a divalent aromatic hydrocarbon group which may have a substituent; R ^a1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carbon atom Alkylthio group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, arylthio group having 6 to 10 carbon atoms, cycloalkane having 3 to 10 carbon atoms group, halogen atom, nitro group, hydroxyl group or mercapto group; R ^a2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, aryl group with 6-10 carbon atoms, aryloxy group with 6-10 carbon atoms, arylthio group with 6-10 carbon atoms, cycloalkyl group with 3-10 carbon atoms, halogen atom, hydroxyl or mercapto group; R ^a3 each independently represents a divalent aliphatic hydrocarbon group; n _a1 represents a positive whole number; n _a2 each independently represent an integer of 0 to 4 of; n _a3 each independently represent an integer of 0 to 3, of; R ^a1 is an alkyl group, an alkoxy Hydrogen atoms of radicals, alkylthio groups, aryl groups, aryloxy groups, arylthio groups and cycloalkyl groups may be substituted by halogen atoms; alkyl, alkoxy, alkylthio, aryl, aryloxy groups of ^{R a2} , arylthio and cycloalkyl hydrogen atoms can be replaced by halogen atoms; when n _a2 is 2-4, R ^a1 can be the same or different in the same ring; when n _a3 is 2-3, R ^a2 is can be the same or different within the same ring).

In formula (A4), Ar ^a1 represents a divalent aromatic hydrocarbon group which may have a substituent. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 or more, more preferably 20 or less, and particularly preferably 16 or less. As a divalent aromatic hydrocarbon group, a phenylene group and a naphthylene group are mentioned, for example. Examples of the substituent which the divalent aromatic hydrocarbon group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a carbon atom An aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group. The hydrogen atom of each substituent may be further substituted by a halogen atom. Moreover, as a specific example of such a substituent, the thing similar to the substituent which can be bonded to the benzene ring contained in a trimethylindenane skeleton is mentioned, for example. When the divalent aromatic hydrocarbon group has a substituent, the number of the substituents is preferably 1 to 4. When the number of the substituents the divalent aromatic hydrocarbon group has is 2 or more, the 2 or more substituents may be the same, or can be different. Among them, Ar ^{a1 is} preferably an unsubstituted divalent aromatic hydrocarbon group.

In the formula (A4), R ^a1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or an alkyl group having 6 to 10 carbon atoms. aryl group, aryloxy group with 6-10 carbon atoms, arylthio group with 6-10 carbon atoms, cycloalkyl group with 3-10 carbon atoms, halogen atom, nitro group, hydroxyl group or mercapto group. The hydrogen atom of the alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group and cycloalkyl group may be substituted with a halogen atom. As a specific example of these groups, the thing similar to the substituent which can be bonded to the benzene ring contained in a trimethylindenane skeleton is mentioned, for example. Among them, R ^{a1 is more} preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. , particularly preferably an alkyl group having 1 to 4 carbon atoms.

In formula (A4), R ^a2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or an alkylthio group having 6 to 10 carbon atoms. aryl group, aryloxy group with 6-10 carbon atoms, arylthio group with 6-10 carbon atoms, cycloalkyl group with 3-10 carbon atoms, halogen atom, hydroxyl or mercapto group. The hydrogen atom of the alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group and cycloalkyl group may be substituted with a halogen atom. As a specific example of these groups, the thing similar to the substituent which can be bonded to the benzene ring contained in a trimethylindenane skeleton is mentioned, for example. Among them, R ^{a2 is more} preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. .

In formula (A4), R ^a3 each independently represents a divalent aliphatic hydrocarbon group. The preferred range of the divalent aliphatic hydrocarbon group is as described above.

In formula (A4), n _a1 represents a positive integer. n _{a1 is} preferably 1 or more, more preferably 10 or less, particularly preferably 8 or less.

In formula (A4), n _a2 each independently represents an integer of 0 to 4. n _{a2 is} preferably 2 or 3, more preferably 2. The plural n _a2 may be different, but are preferably the same. When n _a2 is 2 or more, plural R ^a1 series may be the same or different in the same ring.

In formula (A4), n _a3 each independently represents an integer of 0 to 3. The plural n _a3 may be different, but are preferably the same. n _{a3 is} preferably 0.

(A-1) It is particularly preferable that the specific maleimide compound has a structure represented by the following formula (A5). (A-1) The entirety of the specific maleimide compound may have the structure represented by the formula (A5), or (A-1) a part of the specific maleimide compound may have the structure represented by the formula (A5) .

(In formula (A5), R ^b1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkyl group having 6 to 10 carbon atoms. 10 aryl groups, aryloxy groups with 6 to 10 carbon atoms, arylthio groups with 6 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, halogen atoms, nitro groups, hydroxyl groups or mercapto groups; R ^b2 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryl group having 6 carbon atoms. Aryloxy group of ~10, arylthio group of carbon number of 6 to 10, cycloalkyl group of carbon number of 3 to 10, halogen atom, hydroxyl or mercapto group; n _b1 represents a positive integer; n _b2 independently represents 0 to an integer of 4; n _b3 each independently represent an integer of 0 to 3 of the .R ^b1 alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group and a cycloalkyl group may be a halogen atom hydrogen The hydrogen atom of the alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group and cycloalkyl group of ^{R b2} _{can be substituted by halogen atom. When n b2} is 2-4, R ^b1 may be the same or different within the same ring. When n _b3 is 2 to 3, R ^b2 may be the same or different within the same ring).

In formula (A5), R ^b1 , R ^b2 , n _b1 , n _b2 and n _b3 are each the same as R ^a1 , R ^a2 , n _a1 , n _a2 and n _{a3 in} formula (A4).

(A-1) The specific maleimide compound may further include a structure represented by the following formula (A6).

In formula (A6), R ^c1 , R ^c2 , n _c2 and n _c3 ^{are the same as R a1} , R ^a2 , n _a2 and n _{a3 in} formula (A4), respectively. Moreover, in Formula (A6), n _c1 is the number of repeating units, and represents an integer of 1-20. In addition, in formula (A6), * represents a bond. For example, the specific maleimide compound (A-1) is in the formula (A4), n _a2 is 3 or less, and the maleimide group of the benzene ring to which the maleimide group is bonded In the ortho position and the para position, when two or more of them are not bonded to R ^a1 , the structure represented by the above-mentioned formula (A6) can be included in combination with the structure represented by the formula (A4). Also, for example, the specific maleimide compound (A-1) is in the formula (A5), n _b2 is 3 or less, and the maleimide group of the benzene ring bonded to the maleimide group In the ortho position and the para position, when two or more of them are not bonded to R ^b1 , the structure represented by the aforementioned formula (A6) can be included in combination with the structure represented by the formula (A5).

As the (A-1) specific maleimide compound as the component (A-1), one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

(A-1) The maleimide group equivalent of the specific maleimide compound is preferably 50 g/eq. or more, more preferably 100 g/eq. or more, particularly preferably 200 g/eq. or more, and more preferably It is 2000 g/eq. or less, more preferably 1000 g/eq. or less, and particularly preferably 800 g/eq. or less. The maleimide group equivalent means the mass of the maleimide group per 1 equivalent of the maleimide compound. (A-1) When the maleimide group equivalent of the specific maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the (A-1) specific maleimide compound in the resin composition is based on 100% by mass of the nonvolatile matter in the resin composition, preferably 0.1% by mass or more, more preferably 0.5% by mass or more , 1 mass % or more is particularly preferable, and 70 mass % or less is preferable, 60 mass % or less is more preferable, and 50 mass % or less is particularly preferable. (A-1) When the amount of the specific maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of (A-1) the specific maleimide compound in the resin composition is based on 100% by mass of the resin component in the resin composition, preferably 0.5% by mass or more, more preferably 1% by mass or more, 2 mass % or more is especially preferable, 70 mass % or less is preferable, 60 mass % or less is more preferable, and 50 mass % or less is especially preferable. The resin component in the resin composition refers to components other than the (D) inorganic filler among the nonvolatile components in the resin composition. (A-1) When the amount of the specific maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the (A-1) specific maleimide compound in the resin composition is 100% by mass, preferably 60% by mass or more, based on 100% by mass of the (B) radically polymerizable aromatic resin in the resin composition, 80 mass % or more is more preferable, 100 mass % or more is especially preferable, 200 mass % or less is preferable, 180 mass % or less is more preferable, and 160 mass % or less is especially preferable. (A-1) When the amount of the specific maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A-1) Ratio of the total number of maleimide groups of the specific maleimide compound to the total number of epoxy groups of the epoxy resin (B) (maleimide group/epoxy group) It is preferable to be in a specific range. The aforementioned ratio (maleimide group/epoxy group) is preferably 0.01 or more, more preferably 0.3 or more, particularly preferably 0.5 or more, and preferably 5 or less, more preferably 3 or less, and particularly preferably 2 the following. "(A-1) The total number of maleimide groups of the specific maleimide compound" means the nonvolatile content of the (A-1) specific maleimide compound present in the resin composition. The value obtained by dividing the mass of the maleimide group by the equivalent of the maleimide group was calculated as the total value. In addition, "(B) the total number of epoxy groups of the epoxy resin" is a value obtained by dividing the mass of the nonvolatile components of the epoxy resin present in the resin composition by the epoxy equivalent, and summing all of them. value. When the aforementioned ratio (maleimide group/epoxy group) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the (A-1) specific maleimide compound in the resin composition is based on 100% by mass of the (C) active ester-based hardener in the resin composition, preferably 10% by mass or more, more preferably It is 20 mass % or more, particularly preferably 30 mass % or more, preferably 160 mass % or less, more preferably 130 mass % or less, and particularly preferably 110 mass % or less. (A-1) When the amount of the specific maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A-1) Ratio of the total number of maleimide groups of the specific maleimide compound to the total number of active ester groups of the (C) active ester-based hardener (maleimide group/active ester) The group is preferably within a specific range. The aforementioned ratio (maleimide group/active ester group) is preferably 0.01 or more, more preferably 0.3 or more, particularly preferably 0.5 or more, and preferably 5 or less, more It is preferably at most 3, particularly preferably at most 2. The term "(C) the total number of active ester groups of the active ester-based curing agent" refers to the sum of the nonvolatile components of the (C) active-ester-based curing agent present in the resin composition. The value obtained by dividing the mass by the active ester equivalent is calculated as the total value. When the aforementioned ratio (maleimide group/active ester group) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the (A-1) specific maleimide compound in the resin composition is 100% by mass relative to the total amount of the (A) maleimide compound, preferably 30% by mass to 100% by mass , more preferably 40% by mass to 100% by mass, and particularly preferably 50% by mass to 100% by mass. (A-1) When the amount of the specific maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A-1) The production method of the specific maleimide compound is not particularly limited. (A-1) The specific maleimide compound can be produced, for example, by the method described in JIS Kokai Publication No. 2020-500211. According to the production method described in the Japanese Inventor's Association Kokai Publication No. 2020-500211, a maleimide compound having a distribution in the number of repeating units of the trimethylindanane skeleton can be obtained. The maleimide compound obtained by this method has a structure represented by the following formula (A1). Therefore, (A) the maleimide compound may include the maleimide compound having the structure represented by the formula (A1).

(In formula (A1), R ¹ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkyl group having 6 to 10 carbon atoms. 10 aryl group, aryloxy group with 6-10 carbon atoms, arylthio group with 6-10 carbon atoms, cycloalkyl group with 3-10 carbon atoms, halogen atom, nitro group, hydroxyl group or mercapto group; R ² Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryl group having 6 carbon atoms. Aryloxy group of ~10, arylthio group of carbon number of 6 to 10, cycloalkyl group of carbon number of 3 to 10, halogen atom, hydroxyl or mercapto group; n ₁ represents the average number of repeating units of 0.95 to 10.0; n ₂ each independently represent an integer of 0 to 4; _n-3 each independently represent an integer of 0 to 3 of the .R ^alkyl group, an alkoxy group, an alkylthio group, aryl group, aryloxy group, arylthio group and a cycloalkyl group ^{The hydrogen atoms of R 2} can be replaced by halogen atoms. The hydrogen atoms of the alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio and cycloalkyl groups of _{R 2 can be replaced by halogen atoms. n 2 When n 3} is 2-4, R ¹ can be the same or different in the same ring. When n 3 is 2-3, R ² can be the same or different in the same ring).

In formula (A1), R ¹ , R ² , n ₂ and n ₃ ^{are the same as R a1} , R ^a2 , n _a2 and n _{a3 in} formula (A4), respectively.

In formula (A1), n ₁ represents the average number of repeating units, and the range thereof is 0.95 to 10.0. According to the production method described in JIS Publication No. 2020-500211, a maleimide compound containing a group of structures represented by formula (A1) can be obtained. As can be seen from the fact that the average number of repeating units n ₁ in the formula (A1) can be less than 1.00, the maleimide compound having the structure represented by (A1) obtained in this way may contain repeating trimethylindanane skeletons. A maleimide compound having 0 units. Therefore, from the maleimide compound having the structure represented by the formula (A1), the maleimide compound in which the number of repeating units of the trimethylindanane skeleton is 0 is purified to obtain (A-1) ) specific maleimide compound, the resin composition may contain only (A-1) specific maleimide compound obtained therefrom. However, the effects of the present invention can be obtained even when the maleimide compound in which the number of repeating units of the trimethylindenane skeleton is 0 is contained in the resin composition. In addition, when purification is omitted, cost can be suppressed. Therefore, a maleimide compound having a repeating unit number of 0 without removing the trimethylindenane skeleton is preferable, and the resin composition contains the maleimide compound having the structure represented by the formula (A1).

In formula (A1), the average number of repeating units n _{1 is} preferably 0.95 or more, more preferably 0.98 or more, particularly preferably 1.0 or more, particularly preferably 1.1 or more, and preferably 10.0 or less, more preferably 8.0 or less, especially Preferably, it is 7.0 or less, and particularly preferably, it is 6.0 or less. When the average repeating unit number n _{1 is} within the aforementioned range, the effect of the present invention can be remarkably obtained. In particular, the glass transition temperature of the resin composition can be effectively increased.

As an example of the structure represented by Formula (A1), the following are mentioned.

The maleimide compound containing the structure represented by the formula (A1) may further contain the structure represented by the aforementioned formula (A6). For example, in the maleimide compound having the structure represented by the formula (A1), in the formula (A1), n ₂ is 3 or less, and relative to the ratio of the benzene ring to which the maleimide group is bonded In the maleimide group, in the ortho position and the para position, when two or more of them are not bonded to R ¹ , they can be combined with the structure represented by the formula (A1) to include the structure represented by the formula (A6) .

The maleimide compound containing the structure represented by the formula (A1) preferably has a molecular weight distribution Mw/Mn calculated by gel permeation chromatography (GPC) measurement within a specific range. The molecular weight distribution is a value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and is represented by "Mw/Mn". Specifically, the molecular weight distribution Mw/Mn of the maleimide compound having the structure represented by the formula (A1) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, particularly preferably 1.2 to 3.6, particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw/Mn of the maleimide compound having the structure represented by the formula (A1) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

In the maleimide compound having the structure represented by the formula (A1), the amount of the maleimide compound having an average repeating unit number n ₁ of 0 is preferably within a specific range. When the maleimide compound containing the structure represented by the formula (A1) is subjected to the aforementioned GPC measurement, the amount of the maleimide compound having an average repeating unit number n ₁ of 0 can be determined according to the result of the GPC measurement as The area is expressed in %. _{Specifically, in the chromatogram obtained by the aforementioned GPC measurement, the average number of repeating units n 1} is 0 based on the total area of the peaks of the maleimide compound having the structure represented by the formula (A1). The ratio (area %) of the area of the peak of the maleimide compound can represent the amount of the maleimide compound in which the _{average repeating unit number n 1 is 0. Specifically, the amount of the maleimide compound having an average repeating unit number n 1} of 0 is preferably 32 area % with respect to 100 area % of the total amount of the maleimide compound having the structure represented by the formula (A1). % or less, more preferably 30 area % or less, particularly preferably 28 area % or less. When the amount of the maleimide compound in which the average number of repeating units n ₁ is 0 is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The maleimide group equivalent of the maleimide compound having the structure represented by the formula (A1) is preferably the maleimide group equivalent of the above-mentioned (A-1) specific maleimide compound the same range. When the maleimide group equivalent of the maleimide compound having the structure represented by the formula (A1) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the maleimide compound containing the structure represented by the formula (A1) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the nonvolatile matter in the resin composition, 1 mass % or more is especially preferable, 70 mass % or less is preferable, 60 mass % or less is more preferable, and 50 mass % or less is especially preferable. When the amount of the maleimide compound containing the structure represented by the formula (A1) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the maleimide compound containing the structure represented by the formula (A1) is based on 100% by mass of the resin component in the resin composition, preferably 0.5% by mass or more, more preferably 1% by mass or more, especially 2 mass % or more is preferable, and 70 mass % or less is preferable, 60 mass % or less is more preferable, and 50 mass % or less is especially preferable. When the amount of the maleimide compound containing the structure represented by the formula (A1) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the maleimide compound containing the structure represented by the formula (A1) is based on 100 mass % of the epoxy resin (B) in the resin composition, preferably 60 mass % or more, more preferably 80 mass % % or more, particularly preferably 100 mass % or more, preferably 200 mass % or less, more preferably 180 mass % or less, and particularly preferably 160 mass % or less. When the amount of the maleimide compound containing the structure represented by the formula (A1) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

Ratio of the total number of maleimide groups in the maleimide compound having the structure represented by the formula (A1) to the total number of epoxy groups in the epoxy resin (B) (maleimide groups/ epoxy group) is preferably within a specific range. The aforementioned ratio (maleimide group/epoxy group) is preferably 0.01 or more, more preferably 0.3 or more, particularly preferably 0.5 or more, and preferably 5 or less, more preferably 3 or less, and particularly preferably 2 the following. The "total number of maleimide groups of the maleimide compound having the structure represented by the formula (A1)" means the total number of maleimide groups having the structure represented by the formula (A1) existing in the resin composition. The value obtained by dividing the mass of the non-volatile content of the imide compound by the equivalent of the maleimide group was calculated as the total value. When the aforementioned ratio (maleimide group/epoxy group) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the maleimide compound containing the structure represented by the formula (A1) is based on 100% by mass of the (C) active ester-based hardener in the resin composition, preferably 10% by mass or more, more preferably 100% by mass or more 20 mass % or more, particularly preferably 30 mass % or more, preferably 160 mass % or less, more preferably 130 mass % or less, and particularly preferably 110 mass % or less. When the amount of the maleimide compound containing the structure represented by the formula (A1) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The ratio of the total number of maleimide groups of the maleimide compound having the structure represented by the formula (A1) to the total number of active ester groups of the (C) active ester-based hardener (maleimide group/active ester group) is preferably within a specific range. The aforementioned ratio (maleimide group/active ester group) is preferably 0.01 or more, more preferably 0.3 or more, particularly preferably 0.5 or more, and preferably 5 or less, more preferably 3 or less, particularly preferably 2 the following. When the aforementioned ratio (maleimide group/active ester group) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the maleimide compound containing the structure represented by the formula (A1) is 100% by mass relative to the total amount of the maleimide compound (A), preferably 30% by mass to 100% by mass, More preferably, it is 40 mass % - 100 mass %, Especially preferably, it is 50 mass % - 100 mass %. When the amount of the maleimide compound containing the structure represented by the formula (A1) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A) The maleimide compound can be combined with the above-mentioned (A-1) specific maleimide compound, and further includes any maleimide compound which does not contain a trimethylindan skeleton. As arbitrary maleimide compounds, for example, (A-2) biphenyl-type maleimide compounds and (A-3) aliphatic maleimide compounds are mentioned. Arbitrary maleimide compounds may be used individually by 1 type, and may be used in combination of 2 or more types in arbitrary ratios.

(A-2) Biphenyl-type maleimide compound means a maleimide compound containing a biphenyl skeleton. When the (A-2) biphenyl-type maleimide compound and the (A-1) specific maleimide compound are used in combination, the plating peel strength can be effectively improved.

One or more substituents may be bonded to the benzene ring of the biphenyl skeleton contained in the (A-2) biphenyl-type maleimide compound. Examples of the substituent include a halogen atom, -OH, -OC _1-10 alkyl group, -N(C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6-10 aryl group, -NH ₂ , -CN, -C(O)OC _1-10 alkyl, -COOH, -C(O)H, -NO ₂ and the like. Here, the term "C _xy " (x and y are positive integers and satisfy x<y) means that the number of carbon atoms of the organic group described immediately after the term is x to y. For example, _{the expression "C 1-10} alkyl group" means an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring. The aforementioned rings also include spiro or condensed rings. The above-mentioned substituent may further have a substituent (hereinafter also referred to as a "secondary substituent"). As the secondary substituent, the same ones as those described above can be used. Among them, it is preferable that a substituent is not bonded to the benzene ring of the biphenyl skeleton contained in the (A-2) biphenyl-type maleimide compound.

(A-2) Biphenyl-type maleimide compound, preferably combined in a biphenyl skeleton, containing either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably one having an aliphatic hydrocarbon group and an aromatic hydrocarbon group both. As a preferable (A-2) biphenyl-type maleimide compound, the maleimide compound represented by following formula (A7) is mentioned.

(In formula (A7), R ^d1 each independently represents an alkylene group; R ^d2 each independently represents an optionally substituted alkyl group or an optionally substituted aryl group; R ^d3 each independently represents a substituent; n _d1 Represents an integer of 1 to 100; n _d2 independently represents an integer of 0 to 2; n _d3 independently represents an integer of 0 to 4).

In formula (A7), R ^d1 each independently represents an alkylene group. The number of carbon atoms in the alkylene group is preferably 1-10, more preferably 1-6, still more preferably 1-3. As the alkylene group, a straight-chain alkylene group is preferable, and a methylene group is more preferable.

In formula (A7), R ^d2 each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent. The number of carbon atoms of the alkyl group is preferably 1-10, more preferably 1-6, particularly preferably 1-3. The alkyl group may be any of linear, branched or cyclic. Moreover, as a substituent which an alkyl group may have, the thing similar to the above-mentioned thing as a substituent which can be bonded to the benzene ring of a biphenyl skeleton is mentioned, for example. The number of carbon atoms in the aryl group is preferably 6-20, more preferably 6-15, particularly preferably 6-10. As a substituent which an aryl group may have, the thing similar to the above-mentioned thing as a substituent which can be bonded to the benzene ring of a biphenyl skeleton is mentioned, for example.

In formula (A7), R ^d3 each independently represents a substituent. As this substituent, the same example as the above-mentioned thing as a substituent which can be bonded to the benzene ring of a biphenyl skeleton is mentioned, for example.

In formula (A7), n _d1 represents an integer of 1-100, preferably 1-50, more preferably 1-20, more preferably 1-5.

In formula (A7), n _d2 each independently represents an integer of 0 to 2, preferably 0.

In formula (A7), n _d3 each independently represents an integer of 0 to 4, preferably 0 to 3, more preferably 0 or 1, particularly preferably 0.

Examples of the (A-2) biphenyl-type maleimide compound represented by the formula (A7) include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. (main component: the following formula (A8) compounds). In the following formula (A8), n _d4 represents 1 or 2.

(A-2) The amount of the biphenyl-type maleimide compound is based on 100% by mass of the nonvolatile content in the resin composition, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably It is 1.0 mass % or more, and preferably 10.0 mass % or less, more preferably 6.0 mass % or less, and particularly preferably 4.0 mass % or less. (A-2) When the amount of the biphenyl-type maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A-2) The amount of the biphenyl-type maleimide compound is based on 100% by mass of the resin component in the resin composition, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1.0 mass % or more, and preferably 20 mass % or less, more preferably 15 mass % or less, and particularly preferably 10 mass % or less. (A-2) When the amount of the biphenyl-type maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A-3) Aliphatic maleimide compound means a maleimide compound containing an aliphatic hydrocarbon group having 5 or more carbon atoms. When the (A-3) aliphatic maleimide compound and the (A-1) specific maleimide compound are used in combination, the plating peel strength can be effectively improved.

(A-3) The number of carbon atoms of the aliphatic hydrocarbon group contained in the aliphatic maleimide compound is usually 5 or more, preferably 6 or more, more preferably 8 or more, and preferably 50 or less, more preferably 45 or less, preferably 40 or less.

(A-3) The aliphatic hydrocarbon group contained in the aliphatic maleimide compound may be saturated or unsaturated, and among them, a saturated aliphatic hydrocarbon group is preferred. In addition, the aliphatic hydrocarbon group may be a chain group or a cyclic group. In addition, the aliphatic hydrocarbon group may be a monovalent group or a divalent group.

Examples of the aliphatic hydrocarbon group contained in the (A-3) aliphatic maleimide compound include alkyl groups such as pentyl, hexyl, heptyl, octyl, nonyl, and decyl; Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, heptadecyl, hexadecyl, with octyl- An alkylene group such as a group having a cyclohexylene structure, a group having a octylene-cyclohexylene-octylene structure, a group having a propylidene-cyclohexylene-octylene structure, and the like.

A substituent may be bonded to the aliphatic hydrocarbon group contained in the (A-3) aliphatic maleimide compound. Examples of the substituent include the same examples as those described above as the substituent which can be bonded to the benzene ring of the biphenyl skeleton in the description of the (A-2) biphenyl-type maleimide compound. Among these, it is preferable that a substituent is not bonded to the aliphatic hydrocarbon group contained in the (A-3) aliphatic maleimide compound.

The (A-3) aliphatic maleimide compound preferably contains a polyimide structure. As a preferable (A-3) aliphatic maleimide compound, the maleimide-terminated polyimide compound represented by the following formula (A9) is mentioned.

(In formula (A9), R ^e1 each independently represents a divalent aliphatic hydrocarbon group having 5 or more carbon atoms which may have a substituent; R ^e2 each independently represents a divalent linking group; n _e1 represents an integer of 1 to 10) .

In formula (A9), R ^e1 each independently represents a divalent aliphatic hydrocarbon group having 5 or more carbon atoms which may have a substituent. R ^e1 preferably represents an optionally substituted alkylene group, alkenylene group or polyalkylene group having 5 or more carbon atoms (more preferably, the number of double bonds is 2). R ^a1 preferably includes an optionally substituted alkylene group having 5 or more carbon atoms, and in this case, the alkylene group having 5 or more carbon atoms may be a part of an alkenylene group or a polyalkenylene group. Specifically, the number of carbon atoms of R ^e1 is usually 5 or more, preferably 6 or more, more preferably 8 or more, and preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less. As a substituent which a divalent aliphatic hydrocarbon group such as an alkylene group, an alkenylene group, and a polyalkylene alkenyl group may have, for example, in the description of the (A-2) biphenyl-type maleimide compound, the The above-mentioned example of the substituent which can couple|bond with the benzene ring of a biphenyl skeleton is the same. Among them, R ^{e1 is} preferably an unsubstituted divalent aliphatic hydrocarbon group, and more preferably an unsubstituted alkylene group.

In formula (A9), R ^e2 each independently represents a divalent linking group. As a divalent linking group, a divalent group consisting of an oxygen atom, an arylidene group, an alkylene group, or a combination of two or more of these groups is preferable. The number of carbon atoms in the aryl extended group is preferably 6-24, more preferably 6-18, particularly preferably 6-14, particularly preferably 6-10. As a preferable arylidene group, a phenylene group, a naphthylene group, an anthracene group, etc. are mentioned, for example. The number of carbon atoms in the alkylene group is preferably 1-50, more preferably 1-45, still more preferably 1-40. The alkylene group may be linear, branched, or cyclic. As preferable alkylene groups, for example, methyl ethylidene, cyclohexylene, pentylene, hexylene, heptyl, octyl, nonyl, decyl, unundecyl, Tendodecyl, threeteenthyl, seventeen, thirty sixteen, bases with a structure of octyl-cyclohexylene, bases with a structure of octyl-cyclohexylene-octylene, bases with Propylidene-cyclohexylidene-octylidene structure, etc. Among these, as ^Re2 , an oxygen atom is preferable.

In formula (A9), n _e1 represents an integer of 1-10.

Examples of the (A-3) aliphatic maleimide compound represented by the formula (A9) include "BMI-1500" (a compound of the formula (A10) and a compound of the formula (A12) manufactured by Designer Molecules) ), "BMI-1700" (compound of formula (A11), compound of formula (A13)). In the following formula (A10), formula (A11), formula (A12), and formula (A13), n _e2 , n _e3 , n _e4 and n _e5 each independently represent an integer of 1 to 10.

(A-3) The amount of the aliphatic maleimide compound is based on 100% by mass of the nonvolatile content in the resin composition, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1.0 mass % or more, and preferably 10.0 mass % or less, more preferably 6.0 mass % or less, and particularly preferably 4.0 mass % or less. (A-3) When the amount of the aliphatic maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A-3) The amount of the aliphatic maleimide compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1.0% by mass relative to 100% by mass of the resin component in the resin composition. The mass % or more is preferably 20 mass % or less, more preferably 15 mass % or less, and particularly preferably 10 mass % or less. (A-3) When the amount of the aliphatic maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A-2) Maleimide group equivalent of any maleimide compound such as biphenyl-type maleimide compound and (A-3) aliphatic maleimide compound, preferably It is in the same range as the maleimide group equivalent of the above-mentioned (A-1) specific maleimide compound. When the maleimide group equivalent of any maleimide compound is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A) The amount of the maleimide compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more with respect to 100% by mass of the nonvolatile content in the resin composition. , and preferably 70 mass % or less, more preferably 60 mass % or less, and particularly preferably 50 mass % or less. When the amount of the maleimide compound (A) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A) The amount of the maleimide compound is based on 100% by mass of the resin component in the resin composition, preferably 0.5% by mass or more, more preferably 1% by mass or more, particularly preferably 2% by mass or more, And it is preferable that it is 70 mass % or less, It is more preferable that it is 60 mass % or less, and it is especially preferable that it is 50 mass % or less. When the amount of the maleimide compound (A) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the (A) maleimide compound is based on 100% by mass of the (B) epoxy resin in the resin composition, preferably 60% by mass or more, more preferably 80% by mass or more, particularly preferably 100% by mass The mass % or more is preferably 200 mass % or less, more preferably 180 mass % or less, and particularly preferably 160 mass % or less. When the amount of the maleimide compound (A) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A) The ratio of the total number of maleimide groups in the maleimide compound to the total number of epoxy groups in the (B) epoxy resin (maleimide group/epoxy group) is preferably within a specific range. The aforementioned ratio (maleimide group/epoxy group) is preferably 0.01 or more, more preferably 0.3 or more, particularly preferably 0.5 or more, and preferably 5 or less, more preferably 3 or less, and particularly preferably 2 the following. The "total number of maleimide groups in the (A) maleimide compound" means dividing the mass of the nonvolatile content of the (A) maleimide compound present in the resin composition by the number of maleimide groups in the resin composition. The value obtained by the equivalent of the imide group shall be the total value of all. When the aforementioned ratio (maleimide group/epoxy group) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the (A) maleimide compound is based on 100% by mass of the (C) active ester-based hardener in the resin composition, preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably It is 30 mass % or more, Preferably it is 160 mass % or less, More preferably, it is 130 mass % or less, Especially preferably, it is 110 mass % or less. When the amount of the maleimide compound (A) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

(A) The ratio of the total number of maleimide groups in the maleimide compound to the total number of active ester groups in the (C) active ester-based hardener (maleimide group/active ester group) Preferably, it is within a specific range. The aforementioned ratio (maleimide group/active ester group) is preferably 0.01 or more, more preferably 0.3 or more, particularly preferably 0.5 or more, and preferably 5 or less, more preferably 3 or less, particularly preferably 2 the following. When the aforementioned ratio (maleimide group/active ester group) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

[3.(B) Epoxy resin] As the epoxy resin of the (B) component contained in the resin composition, curable resins having an epoxy group, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type epoxy resins can be mentioned. Epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type Epoxy resin, tert-butylcatechol 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 novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin Epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin Epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimide type epoxy resin, phenolphthalein type epoxy resin, etc. (B) An epoxy resin may be used individually by 1 type, and may be used combining 2 or more types in arbitrary ratios.

The resin composition preferably contains, as the (B) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The ratio of the epoxy resin having two or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, relative to 100% by mass of the nonvolatile content of the epoxy resin (B), It is especially preferable that it is 70 mass % or more.

Among the epoxy resins, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter also referred to as "solid epoxy resins"). epoxy resin”). The resin composition may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin as the (B) epoxy resin. Among them, as the (B) epoxy resin, it is more preferable to use only a liquid epoxy resin.

As a liquid epoxy resin, the liquid epoxy resin which has two or more epoxy groups in 1 molecule is preferable.

As the liquid epoxy resin, 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 novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin and Epoxy resin of olefin construction.

Specific examples of liquid epoxy resins include "HP-4032", "HP-4032-D", and "HP-4032-SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; manufactured by Mitsubishi Chemical Corporation "828US", "828EL", "jER828EL", "825", "Epikote 828EL" (bisphenol A epoxy resin); "jER807", "1750" (bisphenol F epoxy resin) manufactured by Mitsubishi Chemical Corporation resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin manufactured by Mitsubishi Chemical Corporation); ADEKA "ED-523T" (glycyrrhizol type epoxy resin) manufactured by the company; "EP-3950L" and "EP-3980S" (epoxypropylamine type epoxy resin) manufactured by ADEKA; "EP-EP" manufactured by ADEKA -4088S" (dicyclopentadiene epoxy resin); "ZX1059" (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; Nagase ChemteX Corporation "EX-721" (glycidyl ester type epoxy resin) manufactured by DAICEL; "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by DAICEL; "PB-3600" manufactured by DAICEL, "JP-100", "JP-200" (epoxy resin with butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658", "ZX1658GS" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (liquid 1,4- glycidyl cyclohexane type epoxy resin) etc. These systems may be used alone or in combination of two or more.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy having three or more epoxy groups in one molecule shape epoxy resin.

The solid epoxy resin is preferably a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol novolak type epoxy resin, and a cresol novolak type epoxy resin , Dicyclopentadiene epoxy resin, triphenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A ring Oxygen resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalimide type epoxy resin, phenolphthalein type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin manufactured by DIC Corporation) resin); "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP- 7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene epoxy resin); "EXA-7311", "EXA-7311-G3" manufactured by DIC Corporation, "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Chemical Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin) manufactured by Pharma; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku ); "ESN475V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Corporation; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Corporation; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Corporation ESN375" (dihydroxynaphthalene type epoxy resin); "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" manufactured by Mitsubishi Chemical Corporation "(biphenyl type epoxy resin); "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka Gas Chemical Corporation "PG-100", "CG-500"; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (Fine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenol phthalate) manufactured by Nippon Kayaku Co., Ltd. imide epoxy resin) etc. These systems may be used alone or in combination of two or more.

(B) The epoxy equivalent of the epoxy resin is preferably 50g/eq.～5000g/eq., more preferably 50g/eq.～3000g/eq., particularly preferably 80g/eq.～2000g/eq., especially More preferably, it is 110 g/eq. to 1000 g/eq. The epoxy equivalent represents the mass of the epoxy resin per one equivalent of the epoxy group. The epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the (B) epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, particularly preferably from 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

The amount of the (B) epoxy resin in the resin composition is not particularly limited, but is preferably 1 mass % or more, more preferably 3 mass % or more with respect to 100 mass % of the nonvolatile content in the resin composition, 5 mass % or more is especially preferable, 50 mass % or less is preferable, 40 mass % or less is more preferable, and 30 mass % or less is especially preferable. (B) When the amount of the epoxy resin is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the epoxy resin (B) in the resin composition is not particularly limited, but is preferably 3% by mass or more, more preferably 10% by mass or more, based on 100% by mass of the resin component in the resin composition, and particularly 20 mass % or more is preferable, and 50 mass % or less is preferable, 40 mass % or less is more preferable, and 30 mass % or less is especially preferable. (B) When the amount of the epoxy resin is within the aforementioned range, the effect of the present invention can be remarkably obtained.

[4.(C) Active ester type hardener] The active ester hardener of (C) component contained in a resin composition is a compound which has one or more active ester groups in a molecule|numerator, and can react with (B) epoxy resin. (C) Active ester type hardening|curing agent may be used individually by 1 type, and may be used combining 2 or more types in arbitrary ratios.

(C) Active ester-based hardeners are preferably phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., which have two or more in one molecule and have high reactivity ester-based compounds. The active ester-based hardener is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred System hardener.

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

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated Alkylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolac Varnish, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing 1 molecule of dicyclopentadiene and 2 molecules of phenol.

Specifically, as the (C) active ester-based hardener, a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetate of a phenol novolac, Active ester compound containing benzyl phenol novolac. Among them, at least one selected from a dicyclopentadiene-type active ester compound and a naphthalene-type active ester compound is more preferred, and a dicyclopentadiene-type active ester compound is particularly preferred. As a dicyclopentadiene-type active ester compound, the active ester compound containing a dicyclopentadiene-type diphenol structure is preferable. The so-called "dicyclopentadiene-type diphenol structure" means a divalent structural unit formed of phenylene-dicyclopentylene-phenylene.

(C) Commercially available products of the active ester-based curing agent include "EXB-9451", "EXB-9460", manufactured by DIC Corporation, among active ester compounds containing a dicyclopentadiene-type diphenol structure. "EXB-9460S", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", "HPC" -8000L-65TM", "EXB-8000L-65TM"; among the active ester compounds containing a naphthalene structure, "EXB-8100L-65T", "HPC-8150-60T", "HPC-8150-62T" are exemplified , "EXB-8150-60T", "EXB-9416-70BK" (manufactured by DIC Corporation), "PC1300-02" (manufactured by Air Water Corporation); among the active ester compounds containing phosphorus, "EXB9401" ( DIC Corporation); among the active ester compounds of acetoxylated phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester compound of benzyl phenol novolak, " "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation); among the styryl group-containing active ester compounds, "PC1300-02-65MA" is exemplified (manufactured by AIR WATER) etc.

(C) The active ester group equivalent of the active ester-based hardener is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. to 400 g/eq., particularly preferably 100 g/eq. to 300 g/eq. .. The active ester group equivalent represents the mass of the active ester compound per 1 equivalent of the active ester group.

The amount of the (C) active ester-based hardener in the resin composition is not particularly limited, but is preferably 3% by mass or more, more preferably 6% by mass relative to 100% by mass of the nonvolatile content in the resin composition Above, 10 mass % or more is particularly preferable, and 80 mass % or less is preferable, 60 mass % or less is more preferable, and 50 mass % or less is also preferable. (C) When the amount of the active ester-based hardener is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the (C) active ester-based hardener in the resin composition is not particularly limited, but is preferably 6% by mass or more, more preferably 20% by mass or more with respect to 100% by mass of the resin component in the resin composition , particularly preferably 30 mass % or more, preferably 80 mass % or less, more preferably 70 mass % or less, and particularly preferably 60 mass % or less. (C) When the amount of the active ester-based hardener is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The ratio (active ester group/epoxy group) of the total number of active ester groups of the (C) active ester-based hardener to the total number of epoxy groups of the (B) epoxy resin is preferably within a specific range. The aforementioned ratio (active ester group/epoxy group) is preferably 0.1 or more, more preferably 0.5 or more, particularly preferably 0.8 or more, and preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less. When the aforementioned ratio (active ester group/epoxy group) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

[5.(D) Inorganic fillers] In addition to the above-mentioned components, the resin composition may further contain (D) an inorganic filler as an optional component. The inorganic filler of the component (D) is usually contained in the resin composition in the form of particles.

As the material of the (D) inorganic filler, an inorganic compound can be used. Examples of the material of the inorganic filler (D) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, water Bauxite, 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, particularly preferred is silicon dioxide. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. (D) Inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types in arbitrary ratios.

(D) Commercial products of inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industries, Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; ADMATECHS Corporation "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by DENKA; "UFP-30" manufactured by DENKA; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill" manufactured by TOKUYAMA NSS-5N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" made by ADMATECHS; "DAW-03", "FB-105FD" made by DENKA.

(D) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm or less, from the viewpoint of remarkably obtaining the effects of the present invention. , more preferably 2 μm or less, particularly preferably 1 μm or less. (D) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median particle size can be measured as the average particle size. For the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasound for 10 minutes. For the measurement sample, a laser diffraction particle size distribution analyzer was used, and the wavelengths of the light sources used were set to blue and red, and the volume-based particle size distribution of the inorganic filler was measured by a flow cell method. According to the particle size distribution, the average particle size was calculated as the median particle size. As a laser diffraction particle size distribution measuring apparatus, "LA-960" manufactured by Horiba Seisakusho Co., Ltd., etc. is mentioned, for example.

(D) The specific surface area of the inorganic filler is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, particularly ^{preferably 1 m 2} /g or more, from the viewpoint of remarkably obtaining the effects of the present invention. , particularly ^{preferably 3 m 2} /g or more, more preferably 100 m ² /g or less, more preferably 70 m ² /g or less, particularly ^{preferably 50 m 2} /g or less, particularly ^{preferably 40 m 2} /g or less. The specific surface area of the inorganic filler was obtained by using a BET automatic specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH) in accordance with the BET method, adsorbing nitrogen gas on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

The inorganic filler (D) is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxy silane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilicon nitrogen Alkane compounds, titanate coupling agents, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

Examples of commercially available surface treatment agents include "KBM-1003", "KBE-1003" (vinyl silane coupling agent), "KBM-303", and "KBM-402" manufactured by Shin-Etsu Chemical Co., Ltd. , "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styryl silane coupling agent) "KBM-502", "KBM- 503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", " "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amine-based silane coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (urea-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent) ; "X-12-967C" (acid anhydride silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103" ", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" ( Non-silane, non-silane coupling-alkoxysilane compound), etc.

The degree of surface treatment by the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of the (D) inorganic filler. Specifically, (D) 100% by mass of the inorganic filler is preferably surface-treated with 0.2% by mass to 5% by mass of a surface treatment agent, more preferably 0.2% by mass to 3% by mass, and particularly preferably It is surface-treated by 0.3 mass % to 2 mass %.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (D) inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and particularly preferably 0.2 mg/m m ² or more. On the other hand, from the viewpoint of preventing the increase of the melt viscosity of the resin composition or the melt viscosity of the sheet form, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and particularly preferably 0.5 mg /m ² or less.

(D) 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 (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with the surface-treating agent, and ultrasonically cleaned at 25° C. for 5 minutes. After removing the supernatant and drying the nonvolatile components, the carbon content per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.

The amount of the (D) inorganic filler in the resin composition is based on 100% by mass of the non-volatile matter in the resin composition, preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass % or more, particularly preferably 50 mass % or more, preferably 90 mass % or less, more preferably 80 mass % or less, and particularly preferably 70 mass % or less.

The amount of the (A-1) specific maleimide compound is preferably 2% by mass or more, more preferably 5% by mass or more, particularly preferably 8% by mass or more, relative to 100% by mass of the inorganic filler (D), And 40 mass % or less is preferable, 30 mass % or less is more preferable, and 20 mass % or less is especially preferable. When the (D) inorganic filler is used in an amount satisfying such a relationship, the effect of the present invention can be remarkably obtained.

The amount of the maleimide compound containing the structure represented by the formula (A1) is preferably 2% by mass or more, more preferably 5% by mass or more, and particularly preferably 8% by mass relative to 100% by mass of the inorganic filler (D) The mass % or more is preferably 40 mass % or less, more preferably 30 mass % or less, and particularly preferably 20 mass % or less. When the (D) inorganic filler is used in an amount satisfying such a relationship, the effect of the present invention can be remarkably obtained.

The amount of the (A) maleimide compound is preferably 2% by mass or more, more preferably 5% by mass or more, particularly preferably 10% by mass or more, relative to 100% by mass of the (D) inorganic filler, and more preferably It is 40 mass % or less, More preferably, it is 30 mass % or less, Especially preferably, it is 20 mass % or less. When the (D) inorganic filler is used in an amount satisfying such a relationship, the effect of the present invention can be remarkably obtained.

[6.(E) Optional hardener] In addition to the above-mentioned components, the resin composition may further contain (E) an arbitrary curing agent as an arbitrary component. However, in (E) arbitrary hardener, (C) active ester type hardener is not included. Examples of the optional curing agent of the component (E) include phenol-based curing agents, naphthol-based curing agents, benzodiazepine-based curing agents, cyanate-based curing agents, carbodiimide-based curing agents, and acid anhydrides. Hardener, etc. Among them, from the viewpoint of remarkably obtaining the effects of the present invention, the optional curing agent (E) is preferably any of a phenol-based curing agent, a naphthol-based curing agent, a cyanate-based curing agent, and a carbodiimide-based curing agent Any one or more types, more preferably any one type or more of a phenol-based curing agent and a naphthol-based curing agent, and particularly preferably a phenol-based curing agent. (E) Arbitrary hardener may be used individually by 1 type, or may be used in combination of 2 or more types in arbitrary ratios.

As the phenol-based hardener and the naphthol-based hardener, from the viewpoint of heat resistance and water resistance, a phenol-based hardener having a novolak structure or a naphthol-based hardener having a novolak structure is preferred. In addition, from the viewpoint of the adhesiveness with the conductor layer, a nitrogen-containing phenol-based curing agent is preferred, and a phenol-based curing agent containing a tris-skeleton is more preferred.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. ", "CBN", "GPH", "SN170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. ", "SN-495V", "SN-375", "SN-395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA3018" manufactured by DIC Corporation -50P", "EXB-9500", etc.

Specific examples of benzo-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; "HFB2006M" manufactured by Shikoku Chemical Industry Co., Ltd. Pd", "Fa", etc.

Examples of cyanate-based curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4' - Methylene bis(2,6-dimethylphenylcyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,1 3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) sulfide and bis(4-cyanate phenyl) ether, etc. Bifunctional cyanate resins, polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, etc., and prepolymers of these cyanate resins partially trimmed. Specific examples of cyanate-based hardeners include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate resin) and "ULL-950S" (polyfunctional cyanate resin manufactured by LONZA Japan). ), "BA230", "BA230S75" (a prepolymer of bisphenol A dicyanate partially or completely trimmed into trimer), etc.

As a specific example of a carbodiimide type hardening|curing agent, "V-03", "V-07" by Nisshinbo Chemical Co., Ltd., etc. are mentioned.

As an acid anhydride type hardening|curing agent, the hardening agent which has 1 or more of acid anhydride groups in 1 molecule is mentioned, Preferably it is a hardening agent which has 2 or more acid anhydride groups in 1 molecule. Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Dicarboxylic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenylketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene Tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyltetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro -5-(Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene and Styrene and maleic acid resins copolymerized with maleic acid are polymer-type acid anhydrides, etc. As a commercial item of an acid anhydride type hardening|curing agent, "HNA-100", "MH-700" by Nippon Chemical Co., Ltd., etc. are mentioned, for example.

The amount of the (E) optional hardener in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more with respect to 100% by mass of the nonvolatile matter in the resin composition , 0.3 mass % or more is particularly preferable, and 8 mass % or less is preferable, 5 mass % or less is more preferable, and 3 mass % or less is particularly preferable. (E) When the amount of the arbitrary hardener is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the optional hardener (E) in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to 100% by mass of the resin component in the resin composition, 1 mass % or more is especially preferable, 10 mass % or less is preferable, 8 mass % or less is more preferable, and 6 mass % or less is especially preferable. (E) When the amount of the arbitrary hardener is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The ratio (active group/epoxy group) of the total number of active groups of the (E) arbitrary hardener to the total number of epoxy groups of the (B) epoxy resin is preferably within a specific range. The aforementioned ratio (active group/epoxy group) is preferably 0.01 or more, more preferably 0.05 or more, particularly preferably 0.1 or more, and preferably 3 or less, more preferably 1 or less, and particularly preferably 0.5 or less. "(E) The total number of active groups of the optional hardener" is the value obtained by dividing the mass of the nonvolatile content of the (E) optional hardener present in the resin composition by the equivalent of the active group, and adding the total total value. When the aforementioned ratio (active group/epoxy group) is within the aforementioned range, the effect of the present invention can be remarkably obtained.

[7.(F) Hardening accelerator] In addition to the above-mentioned components, the resin composition may further contain (F) a curing accelerator as an optional component. Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. (F) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types in arbitrary ratios.

Examples of phosphorus-based curing accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium caprate, tetrabutylphosphonium laurate, bis (Tetrabutylphosphonium) pyromellitic acid ester, Tetrabutylphosphonium hydrogen hexahydrophthalate, Tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl Aliphatic phosphonium salts such as ]-4-methylphenol ester, di-tert-butylmethylphosphonium tetraphenyl borate, etc.; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenyl Phosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenylborate, gins (3-methylphenyl) ethyl phosphonium tetraphenyl borate, gins (2-methoxyl) phenyl) ethyl phosphonium tetraphenyl borate, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. Aromatic phosphonium salts; Aromatic phosphine-borane complexes such as triphenylphosphine and triphenylborane; Aromatic phosphine and quinone addition reactants such as triphenylphosphine and p-benzoquinone addition reactants ; tributyl phosphine, tri-tert-butyl phosphine, tri-octyl phosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine Aliphatic phosphines such as tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, Cyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, sine (4-ethylphenyl) phosphine, sine (4-propylphenyl) phosphine, sine (4-Isopropylphenyl)phosphine, Ps(4-butylphenyl)phosphine, Ps(4-tert-butylphenyl)phosphine, Ps(2,4-dimethylphenyl)phosphine, Ps(2,4-dimethylphenyl)phosphine (2,5-Dimethylphenyl)phosphine, Ps(2,6-dimethylphenyl)phosphine, Ps(3,5-dimethylphenyl)phosphine, Ps(2,4,6-tris) Methylphenyl) phosphine, sine (2,6-dimethyl-4-ethoxyphenyl) phosphine, sine (2-methoxyphenyl) phosphine, sine (4-methoxyphenyl) phosphine , ginseng (4-ethoxyphenyl) phosphine, sine (4-tertiary butoxyphenyl) phosphine, diphenyl-2-pyridyl phosphine, 1,2-bis (diphenylphosphino) ethyl Alkane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'- Aromatic phosphines such as bis(diphenylphosphino)diphenyl ether and the like.

Examples of urea-based curing accelerators include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl- Aliphatic dimethyl urea such as 1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4 -Chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl )-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea , 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- Methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy ) phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl) )phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methylurea) Aromatic dimethyl urea such as -1,3-phenylene)bis(N',N'-dimethylurea)[toluene bisdimethylurea] and the like.

Examples of guanidine-based curing accelerators include cyanoguanidine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dimethylguanidine. Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1, 5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1- Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide and the like.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole , 1,2-dimethylimidazole, 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 trimellitate, 1-cyanoethyl-2-phenylimidazole Onium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-trisyllium, 2,4-diamino-6- [2'-Undecylimidazolyl-(1')]-ethyl-s-tris(2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-( 1')]-ethyl-s-tris-tris-cyanuric acid, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tris-cyanuric 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 -Imidazole compounds such as phenylimidazoline and adducts of imidazole compounds and epoxy resins. As the imidazole-based hardening accelerator, commercially available products can be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemical Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation Wait.

As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and tin, are mentioned, for example. Specific examples of the organometallic complex include organocobalt complexes such as cobalt acetylacetonate (II), cobalt acetylacetonate (III), and the like, and organocopper complexes such as copper acetylacetonate (II). , Organo-zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organo-nickel complexes such as nickel (II) acetylacetonate, manganese acetylacetonate (II) Organic manganese complexes and the like. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,- See (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. As an amine type hardening accelerator, a commercial item can be used, for example, "MY-25" by Ajinomoto Precision Technology Co., Ltd., etc. are mentioned.

The amount of the (F) hardening accelerator in the resin composition is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, relative to 100% by mass of the nonvolatile content in the resin composition, 0.05 mass % or more is especially preferable, 15 mass % or less is preferable, 10 mass % or less is more preferable, and 5 mass % or less is especially preferable. (F) When the amount of the hardening accelerator is within the aforementioned range, the effect of the present invention can be remarkably obtained.

The amount of the (F) hardening accelerator in the resin composition is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, based on 100% by mass of the resin component in the resin composition. 0.1 mass % or more is preferable, 15 mass % or less is preferable, 10 mass % or less is more preferable, and 5 mass % or less is especially preferable. (F) When the amount of the hardening accelerator is within the aforementioned range, the effect of the present invention can be remarkably obtained.

[8. (G) Solvent] In addition to the above-mentioned components, the resin composition may further contain the (G) solvent as an optional component. The solvent is usually a volatile component, and an organic solvent can be used. Examples of the solvent (G) include ketone-based solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, celoxel acetate, and propylene glycol monomethyl ether. Acetate-based solvents such as acetate and carbitol acetate; carbitol-based solvents such as celoxol and butyl carbitol; aromatic hydrocarbon-based solvents such as toluene and xylene; dimethyl Amide-based solvents such as carboxamide, dimethylacetamide (DMAc), and N-methylpyrrolidone, etc. The (G) solvent may be used alone or in combination of two or more at an arbitrary ratio.

The amount of the (G) solvent is not particularly limited. (G) The amount of the solvent is based on 100 mass % of the total components in the resin composition, and may be, for example, 60 mass % or less, 40 mass % or less, 30 mass % or less, 20 mass % or less, 15 mass % or less, and 10 mass % or less. % or less, etc.

[9. Other ingredients] In addition to the above-mentioned components, the resin composition may further contain optional additives as optional components. As such an additive, a thermosetting resin, an organic filler, a tackifier, an antifoamer, a leveling agent, an adhesiveness imparting agent, a flame retardant, etc. are mentioned, for example. These may be used individually by 1 type, and may be used in combination of 2 or more types in arbitrary ratios.

[10. Manufacturing method of resin composition] The resin composition can be produced, for example, by mixing the above-mentioned components in an arbitrary order. Moreover, in the process of mixing each component, heating and/or cooling can be performed by adjusting temperature suitably. In addition, during or after the mixing of each component, a stirring device such as a mixer may be used for stirring to uniformly disperse each component. In addition, a defoaming process can be performed with respect to a resin composition as needed.

[11. Characteristics of resin composition] The above-mentioned resin composition can obtain a cured product with a low dielectric tangent and a high glass transition temperature.

For example, the dielectric tangent Df of the cured product obtained by curing the resin composition under the conditions described in the examples below is preferably 0.010 or less, more preferably 0.005 or less, and particularly preferably 0.004 or less. The lower limit value of the dielectric tangent Df of the cured product is not particularly limited, but may be 0.001 or more. The dielectric tangent of the cured product can be measured by the method described in the examples.

For example, the glass transition temperature Tg of the cured product obtained by curing the resin composition under the conditions described in the examples below is preferably 130°C or higher, more preferably 140°C or higher, and particularly preferably 150°C or higher. The upper limit of the glass transition temperature Tg of the above-mentioned cured product is not particularly limited, but may be 260° C. or lower.

The hardened product of the resin composition can generally have a small dielectric constant. For example, the dielectric constant Dk of the cured product obtained by curing the resin composition under the conditions described in the Examples below is preferably 3.5 or less, more preferably 3.2 or less, and particularly preferably 3.0 or less. The lower limit value of the dielectric constant of the cured product is not particularly limited, but may be, for example, 2.0 or more. The dielectric constant of the cured product can be measured by the method described in the examples.

When an insulating layer is formed from a cured product of a resin composition, the surface roughness of the insulating layer after roughening treatment can generally be reduced. For example, when the insulating layer is formed and roughened by the method described in the following examples, the arithmetic mean roughness Ra of the surface of the insulating layer is preferably 200 nm or less, more preferably 100 nm or less, and particularly preferably 70 nm or less. The lower limit value of the arithmetic mean roughness Ra is not particularly limited, but may be, for example, 10 nm or more. The arithmetic mean roughness Ra of the surface of the insulating layer can be measured by the method described in the examples.

Furthermore, when the insulating layer is formed from the cured product of the resin composition and the conductor layer is formed on the insulating layer by plating, the plating peeling strength, which is the adhesion strength between the insulating layer and the conductor layer, can be improved. For example, when the insulating layer and the conductor layer are formed by the method described in the following examples, the plating peel strength between the insulating layer and the conductor layer is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm More preferably, it may be 0.5 kgf/cm or more. The upper limit value of the plating peel strength is not particularly limited, but may be, for example, 2.0 kgf/cm or less. The plating peel strength between the insulating layer and the conductor layer can be measured by the method described in the examples.

[12. Use of resin composition] The resin composition according to one embodiment of the present invention is suitable as a resin composition for insulating purposes, and is particularly suitable as a resin composition for forming an insulating layer. Therefore, for example, the resin composition is suitable as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). In addition, the resin composition is suitable as the resin composition for forming the insulating layer (the resin composition for forming the insulating layer for forming the conductor layer) for forming the conductor layer (including the rewiring layer) formed on the insulating layer. ). In addition, the resin composition can be widely used in sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die-bonding materials, semiconductor sealing materials, buried-hole resins, and parts-embedded resins. Use of resin compositions.

Further, for example, when a semiconductor chip package is produced through the following steps (1) to (6), the resin composition of the present embodiment can also be suitably used as a resin composition for a rewiring forming layer of an insulating layer for forming a rewiring layer (resin composition for rewiring formation layer formation) and resin composition for sealing semiconductor wafers (resin composition for semiconductor wafer sealing). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the sealing layer. (1) the step of laminating the temporary fixing film on the substrate, (2) the step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) the step of forming a sealing layer on the semiconductor wafer, (4) the step of peeling off the base material and the temporary fixing film from the semiconductor wafer, (5) a step of forming a rewiring formation layer as an insulating layer on the surface after peeling off the base material of the semiconductor wafer and temporarily fixing the thin film, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

The above-mentioned resin composition can also be used in the case where the printed wiring board is a circuit board with built-in parts.

[13. Sheet-like laminated material] The resin composition of one embodiment of the present invention may be applied in a varnish state and used, but it is industrially preferably used in the form of a sheet-like laminate containing the resin composition. As a sheet-like laminate material, resin sheets and prepregs shown below are preferable.

The resin sheet includes a support and a resin composition layer formed of the above-mentioned resin composition on the support.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulating properties even if the cured product of the resin composition is a thin film Below, it is especially preferable that it is 30 micrometers or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be, for example, 3 μm or more, 5 μm or more, or the like.

As the support, for example, a film made of a plastic material, a metal foil, and a release paper can be mentioned, and a film and a metal foil made of a plastic material are preferable.

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter also referred to as "PET"), polyethylene naphthalate (hereinafter also referred to as ""PET"). Polyester such as PEN”), polycarbonate (hereinafter also referred to as “PC”), acrylic acid such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether vulcanized (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using a metal foil as a support body, as a metal foil, a copper foil, an aluminum foil, etc. are mentioned, for example, Preferably it is a copper foil. As the copper foil, a foil made of a single metal of copper can be used, and a foil made of an alloy of copper and other metals (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

The support system may be subjected to surface treatments such as matte treatment, corona treatment, antistatic treatment, etc., to the surface bonded to the resin composition layer.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined to a resin composition layer can also be used. As a mold release agent used for the mold release layer of the mold release layer-attached support, for example, one selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a polysiloxane resin can be used. of 1 or more release agents. As the support with a release layer, commercially available products can be used, for example, "SK-1", "AL- 5", "AL-7", "Lumirror T60" manufactured by Toray Corporation, "Purex" manufactured by Teijin Corporation, "Unipeel" manufactured by UNITIKA Corporation, etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Moreover, when the support body with a mold release layer is used, the thickness of the whole support body with a mold release layer is preferably within the above-mentioned range.

In one embodiment, the resin sheet may further include an arbitrary layer as needed. As this arbitrary layer, the protective film etc. which correspond to a support provided on the surface (that is, the surface on the opposite side to a support) of the resin composition layer which are not joined to a support are mentioned, for example. Although the thickness of a protective film is not specifically limited, For example, it is 1 micrometer - 40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from adhering to or damaging the surface of the resin composition layer.

The resin sheet can be formed by, for example, preparing a resin varnish in which the resin composition is dissolved in a solvent, applying the resin varnish on a support using a coating apparatus such as a die coater, and drying it to form a resin composition layer. to manufacture. As a solvent, the thing similar to what demonstrated as (G) component which can be contained as a resin composition is mentioned, for example. One type of solvent may be used alone, or two or more types may be used in combination in an arbitrary ratio.

Drying can be implemented by methods such as heating and hot air blowing. The drying conditions are not particularly limited, but are dried so that the content of the organic solvent in the resin composition layer is 10 mass % or less, preferably 5 mass % or less. Although it also depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing an organic solvent of 30 to 60 mass % is used, it can be dried at 50 to 150° C. for 1 to 10 minutes. , to form a resin composition layer.

The resin sheet can be wound into a roll shape and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

In one embodiment, the prepreg system is formed by impregnating a sheet-like fiber base material with a resin composition.

The sheet-like fibrous base material used for the prepreg is not particularly limited, and examples thereof include glass cloth, polyaramide nonwoven fabric, and liquid crystal polymer nonwoven fabric. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, particularly preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited, but is usually 10 μm or more.

The prepreg can be produced by a well-known method such as a hot melt method and a solvent method.

The thickness of the prepreg can be set in the same range as the resin composition layer in the above-mentioned resin sheet.

[14. Printed wiring board] A printed wiring board according to an embodiment of the present invention includes an insulating layer formed of a cured product obtained by curing the above-mentioned resin composition.

A printed wiring board can be manufactured by the method including the steps of the following (I) and (II) using, for example, the above-mentioned resin sheet. (1) on the inner layer substrate, the step of laminating the resin sheet in a manner that the resin composition layer of the resin sheet is bonded to the inner layer substrate, (II) The step of hardening the resin composition layer to form an insulating layer.

The "inner layer substrate" used in the step (I) is a member that becomes the substrate of the printed wiring board, for example, glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting type Polyphenylene ether substrates, etc. Also, 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 is formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, when manufacturing a printed wiring board, an intermediate product in which an insulating layer and/or a conductor layer should be further formed 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 substrate with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding of the resin sheet to the inner layer substrate from the support side. As a member for thermocompression bonding of the resin sheet to the inner layer substrate (hereinafter, also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS end plate or the like) or a metal roll ( SUS roll) etc. Furthermore, it is preferable that the thermocompression bonding member is not directly pressurized on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate.

The lamination of the inner layer substrate and the resin sheet can be carried out by vacuum lamination. In the vacuum lamination method, the heating and crimping temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and crimping pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47 In the range of MPa, the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination can preferably be carried out under reduced pressure with a pressure below 26.7 hPa.

Lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurization laminator manufactured by Ming Machinery Co., Ltd., a vacuum applicator by Nikko Materials Co., Ltd., a batch vacuum pressurization laminator, etc. are mentioned.

After lamination, under atmospheric pressure, for example, by pressing the thermocompression-bonding member from the support side, smoothing treatment of the laminated resin sheet can be performed. The pressing conditions of the smoothing process can be made into the same conditions as the thermocompression bonding conditions of the lamination mentioned above. The smoothing process can be performed by a commercially available laminator. In addition, the lamination and smoothing process can also be performed continuously using the above-mentioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions employed when forming the insulating layer of the printed wiring board can be used. In general, the curing of the resin composition layer can be performed by thermosetting.

For example, although the thermal curing conditions of the resin composition layer vary with the type of the resin composition, in one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, especially It is preferably 170°C to 210°C. The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and particularly preferably 15 minutes to 100 minutes.

Before thermally curing the resin composition layer, the resin composition layer may be preliminarily heated at a temperature lower than the curing temperature. For example, before thermally curing the resin composition layer, the resin composition layer may be preliminarily heated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes Above, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, particularly preferably 15 minutes to 100 minutes.

When manufacturing a printed wiring board, (III) the step of opening a hole in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer can be further carried out. When the support is removed after step (II), the support can be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step ( V) between implementations. Moreover, as needed, the formation of the insulating layer and the conductor layer of step (I) - step (V) can be repeated, and a multilayer wiring board can be formed.

In other embodiment, a printed wiring board can be manufactured using the said prepreg. The manufacturing method is basically the same as the case of using the resin sheet.

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

Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear removal is also performed. The order and conditions of the roughening treatment are not particularly limited. For example, the insulating layer can be roughened by performing the swelling treatment of the swelling liquid, the roughening treatment of the oxidizing agent, and the neutralization treatment of the neutralizing liquid in this order.

Examples of the swelling liquid used for the roughening treatment include an alkaline solution, a surfactant solution, and the like, and an alkaline solution is preferred, and a sodium hydroxide solution and a potassium hydroxide solution are more preferred as the alkaline solution. As a commercially available swelling liquid, "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU" by ATOTECH Japan Co., Ltd., etc. are mentioned, for example. Although the swelling treatment system of the swelling liquid is not particularly limited, for example, it can be performed 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, the insulating layer is preferably immersed in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

As an oxidizing agent used for a roughening process, the alkaline permanganic acid solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned, for example. The roughening treatment of an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 minutes to 30 minutes. Moreover, it is preferable that the density|concentration of the permanganate in an alkaline permanganic acid solution is 5 mass % - 10 mass %. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by ATOTECH Japan.

As a neutralization liquid for roughening process, an acidic aqueous solution is preferable, and as a commercial item, "Reduction Solution Securigant P" by ATOTECH Japan Co., Ltd. is mentioned, for example. The treatment of the neutralization liquid can be performed by immersing the treated surface of the roughening treatment to which the oxidizing agent was applied in the neutralization liquid at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, the method of immersing the object of the roughening treatment to which the oxidizing agent is applied is preferably immersed in a neutralization liquid at 40° C. to 70° C. for 5 minutes to 20 minutes.

In one embodiment, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, or the like. In addition, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, or the like. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

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

The conductor layer may be a single-layer structure, or may be a single-layer structure formed of different kinds 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 nickel-chromium alloy.

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

The conductor layer is preferably formed by plating. For example, the surface of the insulating layer can be plated by a semi-additive method, a full-additive method, or the like to form a conductor layer having a desired wiring pattern. From the viewpoint of easiness of manufacture, the preferred Formed by the semi-additive method. Hereinafter, an example in which the conductor layer is formed by the semi-additive method is shown.

On the surface of the insulating layer, a plating seed layer is formed by electroless plating. Next, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer is formed in accordance with a desired wiring pattern. On the exposed plating seed layer, after forming a metal layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[15. Semiconductor device] A semiconductor device according to an embodiment of the present invention includes the above-mentioned printed wiring board. This semiconductor device can be manufactured using the above-mentioned printed wiring board.

Examples of semiconductor devices include various semiconductor devices used in electrical products (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, locomotives, automobiles, trains, ships, aircraft, etc.). [Example]

Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited by the following Example. In the following description, unless otherwise specified, "parts" and "%" indicating amounts mean "parts by mass" and "% by mass", respectively. In addition, unless otherwise indicated, the operation demonstrated below was performed in the environment of normal temperature and normal pressure.

_{[Preparation of maleimide compound] The MEK solution of maleimide compound A 1} (non-volatile) synthesized by the method described in Synthesis Example 1 of the Japan Institute of Inventions Kokai Publication No. 2020-500211 was prepared. ingredient 70% by mass). This maleimide compound A ₁ has a structure represented by the following formula.

Maleic measurement acyl imine compound A FD-MS spectrum of _1, it was confirmed M + = 560,718 and a peak of 876. These peaks correspond to _{the cases where n 1} is 0, 1 and 2, respectively. Further, when the maleimide compound A _{1 was} analyzed by GPC, and the value of the _{number of repeating units n 1} of the indenane skeleton moiety was determined from the number average molecular weight _{, n 1} =1.47 and molecular weight distribution (Mw/Mn)=1.81. In addition, the content ratio of the maleimide compound _{in which the average repeating unit number n 1} is 0 is 26.5 area % in 100 area % of the total amount of the _{maleimide compound A 1 .}

(PEI) the maleic A FD-MS spectrum of compound ₁ represented by the following measurement of the measurement apparatus and measurement conditions are. (Measuring device and measuring conditions of FD-MS spectrum) Measuring device: JMS-T100GC AccuTOF Measuring conditions Measuring range: m/z=4.00～2000.00 Change rate: 51.2mA/min Final current value: 45mA Cathode voltage: -10kV Recording interval : 0.07sec

The maleic A GPC ₁ acyl imine compound represented by the following measurement of the measurement apparatus and measurement conditions are. Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation Column: "HXL-L" manufactured by Tosoh Corporation, "TSK-GEL G2000HXL" manufactured by Tosoh Corporation, "TSK-GEL G2000HXL" manufactured by Tosoh Corporation , Tosoh Corporation "TSK-GEL G3000HXL" and Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation "GPC workstation EcoSEC-WorkStation" Measurement conditions: tube Column temperature 40°C Developing solvent Tetrahydrofuran flow rate 1.0ml/min Standard: According to the measurement manual of the aforementioned "GPC Workstation EcoSEC-WorkStation", the molecular weight is a known monodisperse polystyrene. Sample: A tetrahydrofuran solution (50 μl) of 1.0 mass % in terms of the nonvolatile content of the maleimide compound was filtered with a microfilter.

Maleic acyl imine compound ₁ A molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)), and the contribution of average repeating unit backbone of maleic hydrindane compound (PEI) "n _1", Department of Indicates that calculated from the GPC chart obtained by the aforementioned GPC measurement. In addition, the average number of repeating units “n ₁ ” represents one calculated from the number average molecular weight (Mn). Specifically, about _{the compound in which n 1} is 0 to 4, the theoretical molecular weight and the molecular weight measured by GPC are plotted on a scatter diagram, and an approximate straight line is drawn. Then, from the point indicated by the measured value Mn(1) on the straight line, the number-average molecular weight (Mn) was obtained, and “n ₁ ” of the average repeating unit was further calculated. Furthermore, based on the result of GPC measurement, the content ratio (area %) of the maleimide compound in which the _{average repeating unit number n 1} is 0 is calculated in 100 area % of the total amount of the _{maleimide compound A 1 .} For details, please refer to the Public Technical Report No. 2020-500211 of the Japan Invention Association.

[Example 1] (PEI) mixing maleic Compound A ₁ (non-volatile content of 70% by mass solution) 20 parts of the above, a liquid epoxy resin containing naphthalene skeleton (DIC Corporation, "HP-4032-SS" Epoxy equivalent 144 g/eq.) 10 parts, active ester hardener containing dicyclopentadiene-type diphenol structure (“HPC-8000-65T” manufactured by DIC Corporation, toluene solution of 65% by mass of nonvolatile content, active ester 30 parts of spherical silica ("SO-C2" manufactured by ADMATECHS Co., Ltd.), surface-treated with an inorganic filler (amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). Average particle size 0.5 μm, specific surface area 5.8 m ² /g) 80 parts and a hardening accelerator (imidazole compound “1B2PZ” manufactured by Shikoku Chemical Co., Ltd.) 0.5 part, which were uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish .

As a support, a polyethylene terephthalate film (“AL5” manufactured by LINTEC, thickness 38 μm) provided with a mold release layer was used. On the mold release layer of this support, the resin varnish was uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Then, the resin varnish was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet containing a support and a resin composition layer.

[Example 2] In place of the active ester hardener containing a dicyclopentadiene-type diphenol structure (“HPC-8000-65T” manufactured by DIC Corporation), an active ester compound containing a naphthalene structure (“HPC-8150-62T” manufactured by DIC Corporation) was used. 30 parts of toluene solution of 62 mass % of volatile components, active ester group equivalent 229 g/eq. A resin sheet was produced in the same manner as in Example 1 except for the above matters.

[Example 3] The amount of the maleimide compound A ₁ (70 mass % nonvolatile content solution) was changed from 20 parts to 15 parts. In addition, instead of the active ester hardener containing a dicyclopentadiene-type diphenol structure (“HPC-8000-65T” manufactured by DIC Corporation), an active ester compound containing a naphthalene structure (“HPC-8150-62T” manufactured by DIC Corporation) was used , 62 mass % toluene solution of non-volatile content, active ester group equivalent 229 g/eq.) 30 parts. Furthermore, in the resin composition, a biphenyl aralkyl type maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., 70% nonvolatile MEK/toluene mixed solution) 5 parts. A resin sheet was produced in the same manner as in Example 1 except for the above matters.

[Example 4] The amount of the maleimide compound A ₁ (70 mass % nonvolatile content solution) was changed from 20 parts to 18 parts. In addition, instead of the active ester hardener containing a dicyclopentadiene-type diphenol structure (“HPC-8000-65T” manufactured by DIC Corporation), an active ester compound containing a naphthalene structure (“HPC-8150-62T” manufactured by DIC Corporation) was used , a toluene solution with a non-volatile content of 62% by mass, an active ester group equivalent of 229g/eq.) 30 parts. Furthermore, 2 parts of a liquid aliphatic maleimide compound ("BMI-1500" manufactured by Designer Molecules, maleimide group equivalent 750 g/eq.) was added to the resin composition. A resin sheet was produced in the same manner as in Example 1 except for the above matters.

[Example 5] In place of the active ester hardener containing a dicyclopentadiene-type diphenol structure (“HPC-8000-65T” manufactured by DIC Corporation), an active ester compound containing a naphthalene structure (“HPC-8150-62T” manufactured by DIC Corporation) was used. The toluene solution of 62 mass % of volatile components, active ester group equivalent 229 g/eq.) 25 parts. Moreover, the quantity of the hardening accelerator (the imidazole compound "1B2PZ" by Shikoku Chemical Co., Ltd.) was changed from 0.5 part to 0.1 part. Furthermore, to the resin composition, a cresol novolak-based hardener ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl equivalent: about 151, 50% non-volatile content of 2-methoxyl group) containing a tri-skeleton skeleton was added. propyl alcohol solution) 5 parts. A resin sheet was produced in the same manner as in Example 1 except for the above matters.

[Comparative Example 1] Maleimide compound A _{1 was} not used. In addition, instead of the active ester hardener containing a dicyclopentadiene-type diphenol structure (“HPC-8000-65T” manufactured by DIC Corporation), an active ester compound containing a naphthalene structure (“HPC-8150-62T” manufactured by DIC Corporation) was used , a toluene solution with a non-volatile content of 62% by mass, an active ester group equivalent of 229g/eq.) 30 parts. Furthermore, the amount of the inorganic filler was changed from 80 parts to 55 parts. A resin sheet was produced in the same manner as in Example 1 except for the above matters.

[Comparative Example 2] was used instead of maleic acyl imine compound A ₁ (non-volatile content of 70% by mass solution) 20 parts of a biphenyl aralkyl type using maleic acyl imine compound (manufactured by Nippon Kayaku Co., "MIR- 3000-70MT", maleimide group equivalent: 275g/eq., 70% nonvolatile MEK/toluene mixed solution) 20 parts. In addition, instead of the active ester hardener containing a dicyclopentadiene-type diphenol structure (“HPC-8000-65T” manufactured by DIC Corporation), an active ester compound containing a naphthalene structure (“HPC-8150-62T” manufactured by DIC Corporation) was used , a toluene solution with a non-volatile content of 62% by mass, an active ester group equivalent of 229g/eq.) 30 parts. A resin sheet was produced in the same manner as in Example 1 except for the above matters.

[Comparative Example 3] instead of 20 parts of maleic acyl imine compound A ₁ (non-volatile content of 70% by mass solution), using liquid aliphatic acyl maleic imide compound (Designer Molecules Corporation "BMI-1500" Maleimide group equivalent 750g/eq.) 14 parts. In addition, instead of the active ester hardener containing a dicyclopentadiene-type diphenol structure (“HPC-8000-65T” manufactured by DIC Corporation), an active ester compound containing a naphthalene structure (“HPC-8150-62T” manufactured by DIC Corporation) was used , a toluene solution with a non-volatile content of 62% by mass, an active ester group equivalent of 229g/eq.) 30 parts. A resin sheet was produced in the same manner as in Example 1 except for the above matters.

[Measurement of Dielectric Properties] The resin sheets produced in Examples and Comparative Examples were heated at 200° C. for 90 minutes to thermoset the resin composition layer. Then, the support was peeled off to obtain a cured product of the resin composition. This cured product was cut into test pieces having a width of 2 mm and a length of 80 mm. For this test piece, the dielectric constant Dk and the dielectric tangent Df were measured by the cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies, at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Three test pieces were measured, and the average value is shown in the following table.

[Measurement of Plating Peeling Strength] (1) Base treatment of inner circuit substrate: As an inner-layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate with inner-layer circuits (copper foils) on both sides was prepared (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by PANASONIC). Both sides of the inner layer circuit board having a thickness of 1 μm were etched with “CZ8101” manufactured by MEC, and the copper surface was roughened.

(2) Lamination of resin sheets: Using a batch vacuum press laminator (manufactured by NIKKO Materials Co., Ltd., a second-stage build-up laminator, CVP700), the resin sheets were laminated on both sides of the inner-layer circuit board. This lamination is carried out so that the resin composition layer of the resin sheet is in contact with the inner layer circuit board. In addition, this lamination system was decompressed for 30 seconds so that the air pressure was 13 hPa or less, and was carried out by pressure bonding at 130° C. and a pressure of 0.74 MPa for 45 seconds. Next, hot pressing was performed at 120° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Hardening of resin composition: The laminated resin sheet and inner-layer circuit board were heated at 130° C. for 30 minutes, and then heated at 170° C. for 30 minutes to harden the resin composition to form an insulating layer. Then, the support body is peeled off to obtain a laminate substrate including an insulating layer, an inner-layer circuit board, and an insulating layer in this order.

(4) Roughening treatment: The above-mentioned laminated substrate was heated at 60°C in a swelling solution (Swelling Dip Securigant P (glycol ethers, aqueous solution of sodium hydroxide containing diethylene glycol monobutyl ether, manufactured by ATOTECH Japan Co., Ltd.) )) for 10 minutes. Next, the laminated substrate was immersed in a roughening solution (Concentrate Compact P ( _{aqueous solution of KMnO 4} : 60 g/L, NaOH: 40 g/L) manufactured by ATOTECH Japan Co., Ltd.) at 80° C. for 20 minutes. Then, the laminated substrate was immersed in a 40 It was immersed in a neutralizing solution (Reduction Solution Securigant P (aqueous solution of sulfuric acid), manufactured by ATOTECH Japan Co., Ltd.) for 5 minutes. Then, the laminate substrate was dried at 80°C for 30 minutes to obtain an "evaluation substrate A".

(5) Plating by semi-additive method: The evaluation substrate A was immersed in _{a solution for electroless plating containing PdCl 2} at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes . Then, annealing treatment was performed by heating at 150° C. for 30 minutes. Then, an etching resist is formed, and patterning by etching is performed. Then, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 μm. Next, an annealing process was performed at 200 degreeC for 60 minutes, and "evaluation board|substrate B" was obtained.

(6) Determination of plating peel strength: Into the conductor layer of the evaluation board B, an incision was introduced to surround a rectangular portion with a width of 10 mm and a length of 100 mm. At room temperature, the load (kgf/cm) when the aforementioned rectangular portion of 35 mm was peeled off in the vertical direction at a speed of 50 mm/min was measured as the plating peel strength.

[Measurement of surface roughness Ra] The arithmetic mean roughness Ra of the surface of the insulating layer of the evaluation board|substrate A produced by the said [measurement of plating peeling strength] was measured. The measurement was performed using a non-contact surface roughness meter (WYKO NT3300, manufactured by VEECO Instrument Co., Ltd.) with a VSI mode and a 50-fold lens, and the measurement range was set to 121 μm×92 μm. This measurement was carried out at 10 measurement points, and the average value thereof is shown in the table below.

[Measurement of glass transition temperature Tg] The resin sheet was heated in an oven at 190° C. for 90 minutes to harden the resin composition layer. Then, the support was peeled off to obtain a cured product of the resin composition layer. From this cured product, a length of 20 mm and a width of 6 mm were cut out to obtain a cured product for evaluation. The first TMA curve of the cured product for evaluation was obtained from 25°C to 250°C by a tensile weighting method at a temperature increase rate of 5°C/min using a thermomechanical analyzer (TMA) manufactured by Rigaku Corporation. Then, the same measurement was performed on the same cured product for evaluation, and the TMA curve of the second time was obtained. From the TMA curve obtained the second time, the value of the glass transition temperature Tg (°C) was determined.

[result] The results of Examples and Comparative Examples are shown in Table 1 below.

Claims (13)

A resin composition comprising (A) a maleimide compound, (B) an epoxy resin and (C) an active ester-based hardener, (A) Maleimide Compound Contains (A-1) a trimethylindan skeleton-containing maleimide compound. The resin composition of claim 1, wherein the component (A-1) comprises a structure represented by the following formula (A4);

(In formula (A4), Ar ^a1 represents a divalent aromatic hydrocarbon group which may have a substituent; R ^a1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carbon atom Alkylthio group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, arylthio group having 6 to 10 carbon atoms, cycloalkane having 3 to 10 carbon atoms group, halogen atom, nitro group, hydroxyl group or mercapto group; R ^a2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, aryl group with 6-10 carbon atoms, aryloxy group with 6-10 carbon atoms, arylthio group with 6-10 carbon atoms, cycloalkyl group with 3-10 carbon atoms, halogen atom, hydroxyl or mercapto group; R ^a3 each independently represents a divalent aliphatic hydrocarbon group; n _a1 represents a positive whole number; n _a2 each independently represent an integer of 0 to 4 of; n _a3 each independently represent an integer of 0 to 3, of; R ^a1 is an alkyl group, an alkoxy Hydrogen atoms of radicals, alkylthio groups, aryl groups, aryloxy groups, arylthio groups and cycloalkyl groups may be substituted by halogen atoms; the alkyl, alkoxy, alkylthio, aryl, aryloxy groups of ^{R a2} , arylthio and cycloalkyl hydrogen atoms can be substituted by halogen atoms; when n _a2 is 2-4, R ^a1 can be the same or different in the same ring; when n _a3 is 2-3, R ^a2 is can be the same or different within the same ring). The resin composition of claim 1, wherein the amount of the component (A-1) is 0.5 mass % or more and 70 mass % or less with respect to 100 mass % of the resin component in the resin composition. The resin composition of claim 1, wherein the amount of (A) component is 0.5 mass % or more and 70 mass % or less with respect to 100 mass % of the resin component in the resin composition. The resin composition of claim 1, wherein the amount of the (B) component is 3 mass % or more and 50 mass % or less with respect to 100 mass % of the resin component in the resin composition. The resin composition of claim 1, wherein the amount of (C) component is 6 mass % or more and 80 mass % or less with respect to 100 mass % of the resin component in the resin composition. The resin composition according to claim 1, further comprising (D) an inorganic filler. The resin composition of claim 7, wherein the amount of (D) component is 20 mass % or more and 90 mass % or less with respect to 100 mass % of the non-volatile matter in the resin composition. The resin composition according to claim 1 is for forming an insulating layer. A hardened product of the resin composition according to any one of claims 1 to 9. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 9 on the support. A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor device comprising the printed wiring board of claim 12.