JP7501583B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition. It also relates to a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

A known manufacturing technique for printed wiring boards is the build-up method, in which insulating layers and conductor layers are stacked alternately.

For example, Patent Document 1 discloses a resin composition as an insulating material for printed wiring boards used in such insulating layers.

JP 2018-053092 A

In recent years, there has been a demand for further improvements in the dielectric properties of the insulating layer, such as the dielectric constant and dielectric dissipation factor, as well as further improvements in adhesion, including peel strength and copper foil peel strength, between the insulating layer and the conductor layer formed by plating.

In general, when a maleimide compound is added to a resin composition, the dielectric properties become excellent. However, because maleimide compounds usually have a high softening point, when a maleimide compound is added to a resin composition, the resin composition and its cured product become brittle. In addition, when a resin sheet containing a resin composition containing a maleimide compound is laminated onto an uneven substrate to form an insulating layer, the surface of the insulating layer opposite the substrate may follow the unevenness of the substrate, reducing the flatness of the insulating layer and resulting in poor lamination properties.

The objective of the present invention is to provide a resin composition capable of producing a cured product having excellent lamination properties, dielectric properties, and adhesion; a resin sheet containing the resin composition; a printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device.

As a result of intensive research into the above-mentioned problems, the inventors discovered that the above-mentioned problems could be solved by incorporating a specific maleimide compound, a liquid or semi-solid curing agent, and a high molecular weight component, and thus completed the present invention.

式（Ａ－３）中、Ｒ^３及びＲ^８はマレイミド基を表し、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に水素原子、アルキル基、又はアリール基を表し、Ｒ^９及びＲ^１０はそれぞれ独立に置換基を表す。ａ１及びｂ１はそれぞれ独立に０～４の整数を表し、ｍ１及びｍ２はそれぞれ独立に１～１０の整数を表し、ｎは１～１００の整数を表す。
［３］ （Ａ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、１０質量％以上４０質量％以下である、［１］又は［２］に記載の樹脂組成物。
［４］ （Ｂ）成分が、アミン系非固形状硬化剤、（メタ）アクリル系非固形状硬化剤、アリル系非固形状硬化剤、マレイミド系非固形状硬化剤、及びブタジエン系非固形状硬化剤から選ばれる少なくとも１種である、［１］～［３］のいずれかに記載の樹脂組成物。
［５］ （Ｂ）成分が、アリル系非固形状硬化剤、及びマレイミド系非固形状硬化剤の少なくともいずれかである、［４］に記載の樹脂組成物。
［６］ （Ｂ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、０．１質量％以上１５質量％以下である、［１］～［５］のいずれかに記載の樹脂組成物。
［７］ （Ｃ）成分が、熱可塑性樹脂である、［１］～［６］のいずれかに記載の樹脂組成物。
［８］ 熱可塑性樹脂が、ポリイミド樹脂、ポリカーボネート樹脂及びフェノキシ樹脂から選ばれる少なくとも１種である、［７］に記載の樹脂組成物。
［９］ （Ｃ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、０．５質量％以上１０質量％以下である、［１］～［８］のいずれかに記載の樹脂組成物。
［１０］ （Ｄ）無機充填材をさらに含む、［１］～［９］のいずれかに記載の樹脂組成物。
［１１］ （Ｄ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、５０質量％以上である、［１０］に記載の樹脂組成物。
［１２］ 絶縁層形成用である、［１］～［１１］のいずれかに記載の樹脂組成物。
［１３］ 導体層を形成するための絶縁層形成用である、［１］～［１２］のいずれかに記載の樹脂組成物。
［１４］ 支持体と、該支持体上に設けられた、［１］～［１３］のいずれかに記載の樹脂組成物を含む樹脂組成物層とを含む、樹脂シート。
［１５］ ［１］～［１３］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、プリント配線板。
［１６］ ［１５］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following.
[1] (A) a maleimide compound having a biphenyl structure,
A resin composition comprising: (B) a liquid or semi-solid curing agent; and (C) a high molecular weight component.
[2] The resin composition according to [1], wherein the component (A) is represented by the following formula (A-3):

In formula (A-3), ^R3 and ^R8 represent a maleimide group, ^R4 , ^R5 , ^R6 and ^R7 each independently represent a hydrogen atom, an alkyl group or an aryl group, ^R9 and ^R10 each independently represent a substituent, a1 and b1 each independently represent an integer of 0 to 4, m1 and m2 each independently represent an integer of 1 to 10, and n represents an integer of 1 to 100.
[3] The resin composition according to [1] or [2], wherein the content of the component (A) is 10% by mass or more and 40% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass.
[4] The resin composition according to any one of [1] to [3], wherein the component (B) is at least one selected from the group consisting of an amine-based non-solid curing agent, a (meth)acrylic-based non-solid curing agent, an allyl-based non-solid curing agent, a maleimide-based non-solid curing agent, and a butadiene-based non-solid curing agent.
[5] The resin composition according to [4], wherein the component (B) is at least one of an allyl-based non-solid curing agent and a maleimide-based non-solid curing agent.
[6] The resin composition according to any one of [1] to [5], wherein the content of the component (B) is 0.1 mass% or more and 15 mass% or less, when the total amount of non-volatile components in the resin composition is 100 mass%.
[7] The resin composition according to any one of [1] to [6], wherein the component (C) is a thermoplastic resin.
[8] The resin composition according to [7], wherein the thermoplastic resin is at least one selected from a polyimide resin, a polycarbonate resin, and a phenoxy resin.
[9] The resin composition according to any one of [1] to [8], wherein the content of the component (C) is 0.5% by mass or more and 10% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass.
[10] The resin composition according to any one of [1] to [9], further comprising (D) an inorganic filler.
[11] The resin composition according to [10], wherein the content of the (D) component is 50% by mass or more, based on 100% by mass of non-volatile components in the resin composition.
[12] The resin composition according to any one of [1] to [11], which is for forming an insulating layer.
[13] The resin composition according to any one of [1] to [12], which is for forming an insulating layer for forming a conductor layer.
[14] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of [1] to [13].
[15] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [13].
[16] A semiconductor device comprising the printed wiring board according to [15].

The present invention provides a resin composition capable of producing a cured product having excellent lamination properties, dielectric properties, and adhesion; a resin sheet containing the resin composition; a printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device.

FIG. 1 is a schematic side view showing an example of two test tubes used to determine whether a thermosetting resin is in a liquid state, a semi-solid state, or a solid state.

The present invention will be described in detail below based on its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be modified as desired without departing from the scope of the claims of the present invention and their equivalents.

[Resin composition]
The resin composition of the present invention comprises (A) a maleimide compound having a biphenyl structure, (B) a liquid or semi-solid curing agent (hereinafter, the liquid or semi-solid curing agent will be referred to as a "non-solid curing agent" as appropriate), and (C) a high molecular weight component. In the present invention, by containing the components (A) to (C), a cured product having excellent lamination properties, dielectric properties, and adhesion can be obtained.

The resin composition may further contain optional components in combination with components (A) to (C). Examples of optional components include (D) inorganic filler, (E) curing agent, (F) curing accelerator, (G) epoxy resin, (H) polymerization initiator, and (I) other additives. Each component contained in the resin composition is described in detail below.

<(A) Maleimide compound having a biphenyl structure>
The resin composition contains a maleimide compound having a biphenyl structure as component (A). By including component (A) in the resin composition, it is possible to obtain a cured product having excellent dielectric properties. The component (A) may be used alone or in combination of two or more.

式（Ａ－２）中、Ｒ^１及びＲ^２はそれぞれ独立に置換基を表す。ａ及びｂはそれぞれ独立に０～４の整数を表す。＊は結合手を表す。 The component (A) is a compound containing a maleimide group represented by the following formula (A-1) in the molecule. From the viewpoint of obtaining a cured product with excellent dielectric properties, the component (A) also has a biphenyl type structure. The biphenyl type structure is a structure represented by the following formula (A-2).

In formula (A-2), ^R1 and ^R2 each independently represent a substituent. a and b each independently represent an integer of 0 to 4. * represents a bond.

Examples of the substituent represented by R ¹ and R ² include a halogen atom, -OH, -O-C _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)O-C _1-10 alkyl group, -COOH, -C(O)H, and -NO _2. Here, the term "C _x-y " (x and y are positive integers, and x<y) indicates that the number of carbon atoms in the organic group described immediately after this term is x to y. For example, the expression "C _1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a fused ring.

The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent.

a and b each independently represent an integer from 0 to 4, preferably an integer from 0 to 3, more preferably 0 or 1, and even more preferably 0.

From the viewpoint of obtaining a cured product with excellent dielectric properties, it is preferable that both ends of component (A) are maleimide groups.

From the viewpoint of obtaining a cured product with excellent dielectric properties, component (A) preferably has either an aliphatic hydrocarbon group or an aromatic hydrocarbon group in addition to the biphenyl structure, and more preferably has both an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring. However, the aromatic hydrocarbon group does not have to be composed only of aromatic rings, and may contain a chain structure or an alicyclic hydrocarbon group as part of it, and the aromatic ring may be monocyclic, polycyclic, or heterocyclic.

As the aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferable, a divalent saturated aliphatic hydrocarbon group is more preferable, and an alkylene group is even more preferable. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 3 carbon atoms is even more preferable, and a methylene group is particularly preferable.

As the aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferable, an arylene group or an aralkylene group is more preferable, and an arylene group is even more preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is even more preferable. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferable, an aralkylene group having 7 to 20 carbon atoms is more preferable, and an aralkylene group having 7 to 15 carbon atoms is even more preferable. Examples of such an aralkylene group include a benzylene group and a group having a biphenylene-methylene structure. Among these, a phenylene group, a benzylene group, and a group having a biphenylene-methylene structure are preferable, and a phenylene group is even more preferable.

From the viewpoint of obtaining a cured product with excellent dielectric properties, the number of maleimide groups per molecule in component (A) is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 10 or less, more preferably 6 or less, and even more preferably 3 or less.

In order to obtain the desired effect of the present invention more remarkably in component (A), it is preferable that the nitrogen atom of the maleimide group is directly bonded to the aromatic hydrocarbon group. Here, the term "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

式（Ａ－３）中、Ｒ^３及びＲ^８はマレイミド基を表し、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に水素原子、アルキル基、又はアリール基を表し、Ｒ^９及びＲ^１０はそれぞれ独立に置換基を表す。ａ１及びｂ１はそれぞれ独立に０～４の整数を表し、ｍ１及びｍ２はそれぞれ独立に１～１０の整数を表し、ｎは１～１００の整数を表す。 The component (A) preferably has a structure represented by the following formula (A-3), for example.

In formula (A-3), ^R3 and ^R8 represent a maleimide group, ^R4 , ^R5 , ^R6 and ^R7 each independently represent a hydrogen atom, an alkyl group or an aryl group, ^R9 and ^R10 each independently represent a substituent, a1 and b1 each independently represent an integer of 0 to 4, m1 and m2 each independently represent an integer of 1 to 10, and n represents an integer of 1 to 100.

R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group, and preferably a hydrogen atom.

The alkyl group in R ⁴ , R ⁵ , R ⁶ and R ⁷ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of such alkyl groups include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an isopropyl group.

The aryl group in R ⁴ , R ⁵ , R ⁶ and R ⁷ is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a single ring or a condensed ring. Examples of such aryl groups include a phenyl group, a naphthyl group, and an anthracenyl group.

The alkyl group and aryl group in R ⁴ , R ⁵ , R ⁶ and R ⁷ may have a substituent. The substituent is the same as R ¹ in formula (A-2).

R ⁹ and R ¹⁰ each independently represent a substituent and are the same as R ¹ and R ² in formula (A-2).

a1 and b1 each independently represent an integer from 0 to 4 and are the same as a and b in formula (A-2).

m1 and m2 each independently represent an integer from 1 to 10, preferably 1 to 6, more preferably 1 to 3, even more preferably 1 to 2, and even more preferably 1.

n represents an integer from 1 to 100, preferably from 1 to 50, more preferably from 1 to 20, and even more preferably from 1 to 5.

^R3 and ^R8 each represent a maleimide group, and the maleimide group is directly bonded to the aromatic hydrocarbon group. The maleimide group represented by ^R3 and ^R8 is preferably directly bonded to any one of the ortho-position, meta-position, and para-position, and more preferably directly bonded to the para-position, based on ( _CH2 ) _m1 or ( _CH2 ) _m2 bonded to the aromatic hydrocarbon group.

式（Ａ－４）中、Ｒ^１１及びＲ^１６はマレイミド基を表し、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は、それぞれ独立に水素原子、アルキル基、又はアリール基を表す。ｍ３及びｍ４はそれぞれ独立に１～１０の整数を表し、ｎ１は１～１００の整数を表す。 The component (A) preferably has a structure represented by formula (A-4).

In formula (A-4), R ¹¹ and R ¹⁶ represent a maleimide group, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group, m3 and m4 each independently represent an integer of 1 to 10, and n1 represents an integer of 1 to 100.

R ¹¹ and R ¹⁶ represent a maleimide group and are the same as R ³ and R ⁸ in formula (A-3).

R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group, and are the same as R ⁴ , R ⁵ , R ⁶ and R ⁷ in formula (A-3).

m3 and m4 each independently represent an integer from 1 to 10 and are the same as m1 and m2 in formula (A-3).

n1 represents an integer from 1 to 100 and is the same as n in formula (A-3).

式（Ａ－５）中、Ｒ^１７及びＲ^１８はマレイミド基を表す。ｎ２は１～１００の整数を表す。 The component (A) preferably has a structure represented by formula (A-5).

In formula (A-5), R ¹⁷ and R ¹⁸ each represent a maleimide group, and n2 represents an integer of 1 to 100.

R ¹⁷ and R ¹⁸ each represent a maleimide group and are the same as R ³ and R ⁸ in formula (A-3).

n2 represents an integer from 1 to 100 and is the same as n in formula (A-3).

Component (A) can be a commercially available product. An example of a commercially available product is "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.

From the viewpoint of obtaining a cured product with excellent dielectric properties, the content of component (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. In the present invention, the content of each component in the resin composition is the value when the non-volatile components in the resin composition are taken as 100% by mass, unless otherwise specified.

<(B) Liquid or Semi-Solid Curing Agent>
The resin composition contains a liquid or semi-solid curing agent (B) as the component (B). By including the component (B) in the resin composition, it is possible to improve lamination properties and obtain a cured product with excellent adhesion. The component (B) may be used alone or in combination of two or more.

Here, the determination of whether a substance is liquid, semi-solid, or solid is made in accordance with the "Method of Confirming Liquid State" in Appendix 2 of the Ministerial Ordinance on the Testing and Properties of Hazardous Materials (Ministry of Home Affairs Ordinance No. 1 of 1989). The specific determination method is as follows:

(1) Thermostatic water bath:
Use a vessel equipped with a stirrer, heater, thermometer, and automatic temperature regulator (capable of controlling temperature to within ±0.1°C) and with a depth of 150 mm or more.
In assessing the thermosetting resins used in the examples described below, a combination of a low-temperature constant temperature water bath (model BU300) and an input type thermostat Thermomate (model BF500), all manufactured by Yamato Scientific Co., Ltd., was used. Approximately 22 liters of tap water was placed in the low-temperature constant temperature water bath (model BU300), the Thermomate (model BF500) attached to it was turned on and set to the set temperature (20°C or 60°C), and the water temperature was fine-tuned using the Thermomate (model BF500) to within ±0.1°C of the set temperature; however, any device capable of similar adjustments can be used.

Test tube:
The test tubes used are cylindrical, flat-bottomed transparent glass tubes with an inner diameter of 30 mm and a height of 120 mm, with marked lines 11A and 12B at heights of 55 mm and 85 mm from the bottom of the tube, respectively, and a liquid determination test tube 10a with its mouth sealed with a rubber stopper 13a, as shown in Fig. 1, and a temperature measurement test tube 10b with the same size and marked lines, its mouth sealed with a rubber stopper 13b with a hole in the center for inserting and supporting a thermometer, and a thermometer 14 inserted into the rubber stopper 13b. Hereinafter, the marked line at the height of 55 mm from the bottom of the tube will be referred to as "line A" and the marked line at the height of 85 mm from the bottom of the tube will be referred to as "line B".
As the thermometer 14, a thermometer for measuring the freezing point (SOP-58 scale range 0 to 100°C) as specified in JIS B7410 (1982) "Glass thermometer for testing petroleum products" is used, but any thermometer that can measure temperatures in the range of 0 to 100°C will do.

(2) Test Procedures Samples that have been left for 24 hours or more under atmospheric pressure at a temperature of 60±5°C are placed in a test tube for liquid determination 10a shown in Fig. 1(a) and a test tube for temperature measurement 10b shown in Fig. 1(b) up to the 11A line. The two test tubes 10a and 10b are placed upright in a low-temperature constant temperature water bath so that the 12B line is below the water surface. The thermometer is placed so that its bottom end is 30 mm below the 11A line.
After the sample temperature reaches the set temperature ±0.1° C., maintain this state for 10 minutes. After 10 minutes, remove the liquid state determination test tube 10a from the low-temperature constant temperature water bath and immediately lay it horizontally on a horizontal test table. Use a stopwatch to measure and record the time it takes for the tip of the liquid level in the test tube to move from line 11A to line 12B.

Similarly, for samples that have been left at atmospheric pressure at a temperature of 20±5°C for 24 hours or more, the test is carried out in the same manner as for samples that have been left at atmospheric pressure at a temperature of 60±5°C for 24 hours or more, and the time it takes for the tip of the liquid level in the test tube to move from line 11A to line 12B is measured and recorded with a stopwatch.

At 20°C, a sample is judged to be in a liquid state if the measured time is within 90 seconds.
A sample whose measured time exceeds 90 seconds at 20° C. and whose measured time is within 90 seconds at 60° C. is judged to be semi-solid.
At 60° C., a sample that lasts for more than 90 seconds is considered to be solid.

The (B) component can be liquid or semi-solid and has the function of curing the (A) component. Such a non-solid curing agent is preferably at least one selected from, for example, an allyl-based non-solid curing agent, a maleimide-based non-solid curing agent, a (meth)acrylic-based non-solid curing agent, an amine-based non-solid curing agent, and a butadiene-based non-solid curing agent, and more preferably at least one of an allyl-based non-solid curing agent and a maleimide-based non-solid curing agent.

An allyl-based non-solid curing agent is a liquid or semi-solid compound having at least one allyl group in the molecule. The allyl group reacts with the maleimide group in component (A) and has the function of curing component (A). An allyl-based non-solid curing agent preferably has one or more allyl groups per molecule, and more preferably has two or more allyl groups. There is no particular lower limit, but it is preferably 10 or less, more preferably 5 or less.

In addition, from the viewpoint of obtaining the desired effect of the present invention more significantly, the allyl-based non-solid curing agent preferably has, in addition to the allyl group, any of a benzoxazine ring, a phenol ring, an epoxy group, and a carboxylic acid derivative having a ring structure, and from the viewpoint of obtaining the desired effect of the present invention more significantly, it is more preferable that the allyl-based non-solid curing agent has a benzoxazine ring.

In an allyl-based non-solid curing agent having a benzoxazine ring, from the viewpoint of significantly obtaining the desired effect of the present invention, the allyl group is preferably bonded to either a nitrogen atom constituting the benzoxazine ring or a carbon atom constituting the benzoxazine ring, and more preferably bonded to a carbon atom.

式（Ｂ－１）中、Ｒ^２０、及びＲ^２１はアリル基を表し、Ｒ^２２はｑ価の基を表す。ｑは１～４の整数を表し、ｐ１は０～４の整数を表し、ｐ２は０～２の整数を表す。 The allyl-based non-solid curing agent having a benzoxazine ring is preferably, for example, an allyl-based non-solid curing agent having a benzoxazine ring represented by the following formula (B-1).

In formula (B-1), R ²⁰ and R ²¹ represent an allyl group, and R ²² represents a q-valent group, in which q represents an integer of 1 to 4, p1 represents an integer of 0 to 4, and p2 represents an integer of 0 to 2.

The q-valent group represented by R ²² is preferably an allyl group, a q-valent aromatic hydrocarbon group, a q-valent aliphatic hydrocarbon group, an oxygen atom, or a q-valent group consisting of a combination thereof. When R ²² has an allyl group, the allyl group may be a substituent of either a q-valent aromatic hydrocarbon group or a q-valent aliphatic hydrocarbon group. For example, when q is 2, R ²² is preferably an arylene group, an alkylene group, an oxygen atom, or a group consisting of a combination of two or more of these divalent groups, more preferably an arylene group or a group consisting of a combination of two or more divalent groups, and even more preferably a group consisting of a combination of two or more divalent groups.

The arylene group for R ²² is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and even more preferably an arylene group having 6 to 12 carbon atoms. Specific examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group, and the phenylene group is preferred.

The alkylene group for R ²² is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples of the alkylene group include a methylene group, an ethylene group, and a propylene group, and a methylene group is preferred.

Examples of the group consisting of a combination of two or more divalent groups in R ²² include a group in which one or more arylene groups are bonded to one or more oxygen atoms; a group in which one or more arylene groups are bonded to one or more alkylene groups, such as a group having an arylene-alkylene-arylene structure; a group in which one or more alkylene groups are bonded to one or more oxygen atoms; a group in which one or more arylene groups, one or more alkylene groups, and one or more oxygen atoms are bonded to one or more oxygen atoms, and the like. A group in which one or more arylene groups are bonded to one or more oxygen atoms, and a group in which one or more arylene groups are bonded to one or more alkylene groups are preferred.

q represents an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 1 or 2.

p1 represents an integer from 0 to 4, preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 1. p2 represents an integer from 0 to 2, preferably 0 or 1, and even more preferably 0.

式（Ｂ－２）中、Ｒ^２３、Ｒ^２４、及びＲ^２５はそれぞれ独立にアリル基を表し、ｓ１はそれぞれ独立に０～４の整数を表し、ｓ２はそれぞれ独立に０～３の整数を表し、ｒは０～３の整数を表す。 Examples of the allyl-based non-solid curing agent having a phenol ring include a cresol resin containing an allyl group, a novolac-type phenol resin containing an allyl group, a cresol novolac resin containing an allyl group, etc. Among them, the allyl-based non-solid curing agent having a phenol ring is preferably an allyl-based non-solid curing agent having a phenol ring represented by the following formula (B-2).

In formula (B-2), R ²³ , R ²⁴ , and R ²⁵ each independently represent an allyl group; s1 each independently represent an integer of 0 to 4; s2 each independently represent an integer of 0 to 3; and r represents an integer of 0 to 3.

R ²³ to R ²⁵ each independently represent an allyl group. In formula (B-2), the number of allyl groups is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 25 or less, more preferably 10 or less, and even more preferably 5 or less.

s1 each independently represents an integer of 0 to 4, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

Each s2 independently represents an integer of 0 to 3, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

r represents an integer from 0 to 3, preferably an integer from 0 to 2, and more preferably an integer from 1 to 2.

The allyl-based non-solid curing agent having an epoxy group preferably contains two or more epoxy groups in one molecule. In addition, the allyl-based non-solid curing agent having an epoxy group preferably has an aromatic structure, and when two or more allyl-based non-solid curing agents having an epoxy group are used, it is more preferable that at least one of them has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. The allyl-based non-solid curing agent having an epoxy group preferably has a bisphenol structure, and examples of the bisphenol structure include bisphenol A type, bisphenol F type, bisphenol AF type, etc., and among them, bisphenol A type is preferable from the viewpoint of obtaining the effect of the present invention remarkably.

As an allyl-based non-solid curing agent having a carboxylic acid derivative having a cyclic structure, an allyl carboxylate having a cyclic structure is preferred. The cyclic structure may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. In addition, the cyclic group may have a ring skeleton formed by heteroatoms other than carbon atoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms, and nitrogen atoms are preferred. The ring may have one heteroatom or two or more heteroatoms. The carboxylic acid derivative having a cyclic structure has a network structure due to the cyclic structure, which improves the compatibility and dispersibility of the resin varnish, and as a result, it is possible to improve lamination properties and obtain a cured product with excellent adhesion.

Examples of carboxylic acids having a cyclic structure include isocyanuric acid, diphenic acid, phthalic acid, cyclohexanedicarboxylic acid, etc. Examples of allyl-based non-solid curing agents having a carboxylic acid derivative having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl diphenate, allyl diphenate, ortho-diallyl phthalate, meth-diallyl phthalate, para-diallyl phthalate, allyl cyclohexanedicarboxylate, diallyl cyclohexanedicarboxylate, etc.

Allyl-based non-solid hardeners can be commercially available products. Commercially available products include, for example, Meiwa Kasei's "MEH-8000H" and "MEH-8005" (allylic non-solid curing agent having a phenol ring); Nippon Kayaku's "RE-810NM" (allylic non-solid curing agent having an epoxy group); Shikoku Kasei Kogyo's "ALP-d" (allylic non-solid curing agent having a benzoxazine ring); Shikoku Kasei Kogyo's "L-DAIC" (allylic non-solid curing agent having an isocyanuric ring); Nippon Kasei's "TAIC" (allylic non-solid curing agent having an isocyanuric ring (triallyl isocyanurate)); Osaka Soda's "MDAC" (allylic non-solid curing agent having a cyclohexanedicarboxylic acid derivative); Nisshoku Techno Fine Chemical's "DAD" (diallyl diphenate); Osaka Soda's "Daiso DAP Monomer" (ortho-diallyl phthalate), etc.

The allyl group equivalent of the allyl-based non-solid curing agent is preferably 20 g/eq. to 1000 g/eq., more preferably 50 g/eq. to 500 g/eq., and even more preferably 100 g/eq. to 300 g/eq., from the viewpoint of significantly obtaining the desired effect of the present invention. The allyl group equivalent is the mass of the allyl-based non-solid curing agent containing one equivalent of an allyl group.

A maleimide-based non-solid curing agent is a liquid or semi-solid compound that has at least one maleimide group in the molecule. However, this does not include those that fall under component (A).

It is preferable that the maleimide-based non-solid curing agent contains at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.

The number of carbon atoms of an alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This alkyl group may be linear, branched, or cyclic, and linear is preferred. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. An alkyl group having 5 or more carbon atoms may be present as a substituent of an alkylene group having 5 or more carbon atoms.

The number of carbon atoms in an alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This alkylene group may be linear, branched, or cyclic, and linear is preferred. Here, the concept of a cyclic alkylene group includes a case in which the alkylene group is composed only of a cyclic alkylene group, and a case in which the alkylene group contains both a linear alkylene group and a cyclic alkylene group. Examples of such alkylene groups include a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexatriacontylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

From the viewpoint of obtaining a significant effect of the present invention, it is preferable that the maleimide-based non-solid curing agent contains both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.

Alkyl groups having 5 or more carbon atoms and alkylene groups having 5 or more carbon atoms may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. Examples of rings formed by bonding to each other include a cyclohexane ring.

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms preferably have no substituent, but may have a substituent. The substituent is the same as the substituent represented by R ¹ in the above formula (A-2).

In maleimide-based non-solid curing agents, it is preferable that the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms are directly bonded to the nitrogen atom of the maleimide group.

The number of maleimide groups per molecule of the maleimide-based non-solid curing agent may be one, but is preferably two or more, and is preferably ten or less, more preferably six or less, and particularly preferably three or less. By using a maleimide-based non-solid curing agent having two or more maleimide groups per molecule, the effects of the present invention can be significantly obtained.

一般式（Ｂ－３）中、Ｍは置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｌは単結合又は２価の連結基を表す。 The maleimide-based non-solid curing agent is preferably a maleimide-based non-solid curing agent represented by the following general formula (B-3).

In formula (B-3), M represents an alkylene group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M represents an alkylene group having 5 or more carbon atoms which may have a substituent. The alkylene group of M is the same as the alkylene group having 5 or more carbon atoms described above. The substituent of M is the same as the substituent represented by R ¹ in general formula (A-2), and the substituent is preferably an alkyl group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR ⁰ - (R ⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms), an oxygen atom, a sulfur atom, C(=O)NR ⁰ -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, and a group consisting of a combination of two or more of these divalent groups. The alkylene group, the alkenylene group, the alkynylene group, the arylene group, the divalent group derived from phthalimide, the divalent group derived from pyromellitic diimide, and a group consisting of a combination of two or more of these divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide represents a divalent group derived from phthalimide, and specifically, is a group represented by the general formula (A). The divalent group derived from pyromellitic diimide refers to a divalent group derived from pyromellitic diimide, specifically, a group represented by general formula (B): In the formula, "*" represents a bond.

The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. This alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include methylethylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, hexatriacontylene, groups having an octylene-cyclohexylene structure, groups having an octylene-cyclohexylene-octylene structure, and groups having a propylene-cyclohexylene-octylene structure.

The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, and particularly preferably an alkenylene group having 2 to 10 carbon atoms. This alkenylene group may be linear, branched, or cyclic. Examples of such alkenylene groups include a methylethylenylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, and an octenylene group.

The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, and particularly preferably an alkynylene group having 2 to 10 carbon atoms. This alkynylene group may be linear, branched, or cyclic. Examples of such alkynylene groups include a methylethynylene group, a cyclohexynylene group, a pentynylene group, a hexynylene group, a heptynylene group, and an octynylene group.

The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, even more preferably an arylene group having 6 to 14 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

The alkylene group, alkenylene group, alkynylene group, and arylene group which are the divalent linking groups in L may have a substituent. The substituent is the same as the substituent represented by R ¹ in general formula (A-2), and is preferably an alkyl group having 5 or more carbon atoms.

Examples of groups consisting of a combination of two or more divalent groups in L include a divalent group consisting of a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; and the like. A group consisting of a combination of two or more divalent groups may form a ring such as a condensed ring by the combination of the respective groups. In addition, a group consisting of a combination of two or more divalent groups may have a repeating unit number of 1 to 10.

Among these, L in the general formula (B-3) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, an alkylene group having 1 to 50 carbon atoms which may have a substituent, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a divalent group consisting of a combination of two or more of these groups. Among these, L is more preferably an alkylene group; a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-a divalent group derived from phthalimide; or a divalent group having a structure of an alkylene-a divalent group derived from pyromellitic diimide.

一般式（Ｂ－４）中、Ｍ^１はそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ａはそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基又は置換基を有していてもよい芳香環を有する２価の基を表す。ｔは１～１０の整数を表す。 The maleimide-based non-solid curing agent represented by general formula (B-3) is preferably a maleimide-based non-solid curing agent represented by general formula (B-4).

In formula (B-4), M ¹ 's each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, A's each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent, and t represents an integer from 1 to 10.

Each ^M1 independently represents an alkylene group having 5 or more carbon atoms which may have a substituent. ^M1 is the same as M in formula (B-3).

Each A independently represents an alkylene group having 5 or more carbon atoms which may have a substituent, or a divalent group having an aromatic ring which may have a substituent. The alkylene group in A may be linear, branched, or cyclic, and is preferably cyclic, i.e., a cyclic alkylene group having 5 or more carbon atoms which may have a substituent. The number of carbon atoms in the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. Examples of such alkylene groups include groups having an octylene-cyclohexylene structure, groups having an octylene-cyclohexylene-octylene structure, and groups having a propylene-cyclohexylene-octylene structure.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by A include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic diimide ring, and an aromatic heterocycle, and the like are mentioned, with a benzene ring, a phthalimide ring, and a pyromellitic diimide ring being preferred. That is, examples of the divalent group having an aromatic ring include a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, and a divalent group having a pyromellitic diimide ring which may have a substituent. Examples of the divalent group having an aromatic ring include a group consisting of a combination of a divalent group derived from phthalimide and an oxygen atom; a group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; a divalent group derived from pyromellitic diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group; and the like. The above arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in general formula (B-3).

The alkylene group and the divalent group having an aromatic ring represented by A may have a substituent. The substituent is the same as the substituent represented by R ¹ in the above formula (A-2).

Specific examples of the group represented by A include the following groups: In the formula, "*" represents a bond.

一般式（Ｂ－５）中、Ｍ^２及びＭ^３はそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｒ^３０はそれぞれ独立に、酸素原子、アリーレン基、アルキレン基、又はこれらの基の２以上の組み合わせからなる２価の基を表す。ｔ１は１～１０の整数を表す。
一般式（Ｂ－６）中、Ｍ^４、Ｍ^６及びＭ^７はそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｍ^５はそれぞれ独立に置換基を有していてもよい芳香環を有する２価の基を表し、Ｒ^３１及びＲ^３２はそれぞれ独立に炭素原子数が５以上のアルキル基を表す。ｔ２は０～１０の整数を表し、ｕ１及びｕ２はそれぞれ独立に０～４の整数を表す。 The maleimide-based non-solid curing agent represented by general formula (B-3) is preferably any one of a maleimide-based non-solid curing agent represented by general formula (B-5) and a maleimide-based non-solid curing agent represented by general formula (B-6).

In formula (B-5), ^M2 and ^M3 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, ^R30 each independently represent an oxygen atom, an arylene group, an alkylene group, or a divalent group consisting of a combination of two or more of these groups, and t1 represents an integer from 1 to 10.
In formula (B-6), ^M4 , ^M6 , and ^M7 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, ^M5 each independently represent a divalent group having an aromatic ring which may have a substituent, ^R31 and ^R32 each independently represent an alkyl group having 5 or more carbon atoms, t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

^M2 and ^M3 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent. ^M2 and ^M3 are the same as the alkylene group having 5 or more carbon atoms represented by M in general formula (B-3), and are preferably a hexatriacontylene group.

Each R ³⁰ independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more of these divalent groups. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-3). R ³⁰ is preferably a group consisting of a combination of two or more of the divalent groups or an oxygen atom.

Examples of the group consisting of a combination of two or more divalent groups in R ³⁰ include a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of the group consisting of a combination of two or more divalent groups include the following groups. In the formula, "*" represents a bond.

^M4 , ^M6 , and ^M7 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent. ^M4 , ^M6 , and ^M7 are the same as the alkylene group having 5 or more carbon atoms which may have a substituent represented by M in formula (B-3), and are preferably a hexylene group, a heptylene group, an octylene group, a nonylene group, or a decylene group, and more preferably an octylene group.

M ⁵ each independently represents a divalent group having an aromatic ring which may have a substituent. M ⁵ is the same as the divalent group having an aromatic ring which may have a substituent represented by A in the general formula (B-4), and is preferably a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group, and more preferably a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide. The arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in the general formula (B-3).

Specific examples of the group represented by ^M5 include the following groups: In the formula, "*" represents a bond.

R ³¹ and R ³² each independently represent an alkyl group having 5 or more carbon atoms. R ³¹ and R ³² are the same as the alkyl group having 5 or more carbon atoms described above, and are preferably a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group, and more preferably a hexyl group or an octyl group.

u1 and u2 each independently represent an integer from 1 to 15, preferably an integer from 1 to 10.

Specific examples of the maleimide-based non-solid curing agent include the following compounds (1) to (3). However, the maleimide-based non-solid curing agent is not limited to these specific examples. In the formula, v represents an integer of 1 to 10.

Specific examples of maleimide-based non-solid curing agents include "BMI1500" (compound of formula (1)), "BMI1700" (compound of formula (2)), and "BMI689" (compound of formula (3)), all manufactured by Designer Molecules.

From the viewpoint of significantly obtaining the desired effect of the present invention, the maleimide group equivalent of the maleimide-based non-solid curing agent is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to 1000 g/eq., and even more preferably 150 g/eq. to 500 g/eq. The maleimide group equivalent is the mass of the maleimide-based non-solid curing agent containing one equivalent of maleimide group.

A (meth)acrylic non-solid curing agent is a curing agent that is liquid or semi-solid and includes acryloyl groups, methacryloyl groups, and combinations thereof. From the viewpoint of significantly obtaining the desired effects of the present invention, it is preferable that the (meth)acrylic non-solid curing agent has two or more (meth)acryloyl groups per molecule. The term "(meth)acryloyl group" includes acryloyl groups, methacryloyl groups, and combinations thereof.

From the viewpoint of significantly obtaining the desired effect of the present invention, it is preferable that the (meth)acrylic non-solid curing agent has a cyclic structure. The cyclic structure is preferably a divalent cyclic group. The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Of these, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferable that the cyclic group is a cyclic group containing an alicyclic structure.

From the viewpoint of significantly obtaining the desired effect of the present invention, the divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, and even more preferably a 5-membered ring or more, and is preferably a 20-membered ring or less, more preferably a 15-membered ring or less, and even more preferably a 10-membered ring or less. In addition, the divalent cyclic group may be a monocyclic structure or a polycyclic structure.

The ring in the divalent cyclic group may have a ring skeleton formed by heteroatoms in addition to carbon atoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms, with oxygen atoms being preferred. The ring may have one heteroatom or two or more heteroatoms.

Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Among them, the divalent cyclic group is preferably (x) or (xi).

The divalent cyclic group may have a substituent. Examples of such a substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group. An alkyl group is preferred.

The (meth)acryloyl group may be directly bonded to the divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like, and may be groups combining a plurality of these. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms is even more preferable. The alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene groups, with methylene, ethylene, and 1,1-dimethylethylene being preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is even more preferred. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferred, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferred. As the divalent linking group, an alkylene group is preferred, with a methylene group and a 1,1-dimethylethylene group being particularly preferred.

（式（Ｂ－７）中、Ｒ^３３及びＲ^３６はそれぞれ独立にアクリロイル基又はメタクリロイル基を表し、Ｒ^３４及びＲ^３５はそれぞれ独立に２価の連結基を表す。環Ｄは、２価の環状基を表す。） The (meth)acrylic non-solid curing agent is preferably represented by the following formula (B-7).

(In formula (B-7), R ³³ and R ³⁶ each independently represent an acryloyl group or a methacryloyl group, R ³⁴ and R ³⁵ each independently represent a divalent linking group, and ring D represents a divalent cyclic group.)

R ³³ and R ³⁶ each independently represent an acryloyl group or a methacryloyl group, and an acryloyl group is preferable.

R ³⁴ and R ³⁵ each independently represent a divalent linking group. The divalent linking group is the same as the divalent linking group which may have a (meth)acryloyl group bonded thereto.

Ring D represents a divalent cyclic group. Ring D is the same as the divalent cyclic group described above. Ring D may have a substituent. The substituent is the same as the substituent that the divalent cyclic group described above may have.

Specific examples of the (meth)acrylic non-solid curing agent include the following, but the present invention is not limited thereto.

As the (meth)acrylic non-solid curing agent, commercially available products may be used, such as "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", and "DPHA" manufactured by Nippon Kayaku Co., Ltd., and "NK Ester DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.

The (meth)acryloyl group equivalent of the (meth)acrylic non-solid curing agent is preferably 30 g/eq. to 400 g/eq., more preferably 50 g/eq. to 300 g/eq., and even more preferably 75 g/eq. to 200 g/eq., from the viewpoint of significantly obtaining the desired effects of the present invention. The (meth)acryloyl group equivalent is the mass of the (meth)acrylic non-solid curing agent containing one equivalent of (meth)acryloyl groups.

As the amine-based non-solid curing agent, a liquid or semi-solid amine-based curing agent can be used. In addition, as the amine-based non-solid curing agent, a curing agent having one or more amino groups in one molecule can be used, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. As the amine-based non-solid curing agent, a primary amine or a secondary amine is preferred, and a primary amine is more preferred.

Specific examples of amine-based non-solid curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-methylenedi-2,6-xylidine, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)propane, etc. Commercially available amine-based resins may be used, such as "KAYABOND C-200S", "KAYAHARD A-A", "KAYAHARD A-B", and "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" and "jER Cure W" manufactured by Mitsubishi Chemical Corporation.

A butadiene-based non-solid curing agent is a liquid or semi-solid compound having at least one butadiene skeleton in the molecule. The polybutadiene structure may be contained in the main chain or in the side chain. The polybutadiene structure may be partially or entirely hydrogenated. As the butadiene-based non-solid curing agent, one or more resins selected from the group consisting of hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxyl group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin are more preferable.

Specific examples of butadiene-based non-solid curing agents include "JP-100" manufactured by Nippon Soda Co., Ltd., and "Ricon 100," "Ricon 150," "Ricon 130MA8," "Ricon 130MA13," "Ricon 130MA20," "Ricon 131MA5," "Ricon 131MA10," "Ricon 131MA17," "Ricon 131MA20," and "Ricon 184MA6" manufactured by CRAY VALLEY.

The content of component (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5.5% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass, from the viewpoint of improving lamination properties and obtaining a cured product with excellent adhesion.

If the content of the non-volatile components in the resin composition of component (B) is taken as 100% by mass as b1, and the content of the non-volatile components in the resin composition of component (A) is taken as 100% by mass as a1, then a1/b1 is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, 4 or more, and preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, 15 or less, 10 or less. By keeping a1/b1 within this range, it is possible to obtain the effects of the present invention significantly.

<(C) High Molecular Weight Component>
The resin composition contains a high molecular weight component as component (C). By including component (C) in the resin composition, the stress of the resin composition is alleviated, and as a result, it is possible to obtain a cured product having excellent dielectric properties. The component (C) may be used alone or in combination of two or more types.

From the viewpoint of obtaining a cured product with excellent dielectric properties, the weight average molecular weight (Mn) of component (C) is preferably 5,000 or more, more preferably 8,000 or more, and particularly preferably 10,000 or more, and is preferably 100,000 or less, more preferably 80,000 or less, and particularly preferably 50,000 or less. The weight average molecular weight of component (C) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

As the (C) component, those having a high weight average molecular weight can be used. Examples of such components include thermoplastic resins such as polyimide resins, polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, polystyrene resins, and polyester resins. Among these, from the viewpoint of obtaining a cured product with excellent dielectric properties, it is preferable that the (C) component is at least one selected from polyimide resins, polycarbonate resins, and phenoxy resins.

The polyimide resin may be a resin having an imide structure. Polyimide resins generally include those obtained by the imidization reaction of a diamine compound with an acid anhydride.

The diamine compound for preparing the polyimide resin is not particularly limited, but examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

Examples of the aliphatic diamine compound include linear aliphatic diamine compounds such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5-diaminopentane, and 1,10-diaminodecane; branched aliphatic diamine compounds such as 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5-diaminopentane; alicyclic diamine compounds such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4'-methylenebis(cyclohexylamine); and dimer acid type diamines (hereinafter also referred to as "dimer diamines"). The dimer acid diamine refers to a diamine compound obtained by substituting two terminal carboxylic acid groups (-COOH) of a dimer acid with an aminomethyl group (-CH ₂ -NH ₂ ) or an amino group (-NH ₂ ). Dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably one having 11 to 22 carbon atoms, particularly preferably one having 18 carbon atoms), and its industrial production process is almost standardized in the industry.

Examples of aromatic diamine compounds include phenylenediamine compounds, naphthalenediamine compounds, and dianiline compounds.

The phenylenediamine compound means a compound consisting of a benzene ring having two amino groups, and further, the benzene ring here may have any of 1 to 3 substituents. The substituents here are not particularly limited. Specific examples of the phenylenediamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobiphenyl, and 2,4,5,6-tetrafluoro-1,3-phenylenediamine.

Naphthalenediamine compounds refer to compounds consisting of a naphthalene ring having two amino groups, and further, the naphthalene ring here may have any of 1 to 3 substituents. The substituents here are not particularly limited. Specific examples of naphthalenediamine compounds include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

The dianiline compound means a compound containing two aniline structures in the molecule, and further, each of the two benzene rings in the two aniline structures may further have 1 to 3 optional substituents. The substituents here are not particularly limited. The two aniline structures in the dianiline compound may be bonded via a direct bond and/or one or two linker structures having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The dianiline compound also includes those in which two aniline structures are bonded by two bonds.

Specific examples of the "linker structure" in the dianiline compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH 2 -, -CH 2 CH _{2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 - , -CH 2 CH 2 CH 2 CH 2 CH 2} -, -CH(CH ₃ )-, -C( _{CH 3 ) 2} -, -C(CF ₃ ) ₂ -, -CH═CH-, -O-, -S-, -CO-, -SO ₂ -, -NH-, -Ph-, -Ph-Ph-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -, -O-Ph-O-, -O-Ph-Ph-O-, and -O-Ph-SO ₂ -Ph-O-, -O-Ph-C( _CH3 ) ₂ -Ph-O-, -C( _CH3 ) ₂ -Ph-C( _CH3 ) _2- ,

In this specification, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group.

In one embodiment, the dianiline compound specifically includes 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4- 4,4'-(9-fluorenylidene)dianiline, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, etc.

The diamine compound may be a commercially available product or may be synthesized by a known method. The diamine compound may be used alone or in combination of two or more types.

The acid anhydride for preparing the polyimide resin is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. Examples of aromatic tetracarboxylic dianhydrides include benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, anthracene tetracarboxylic dianhydride, diphthalic dianhydride, etc., and preferably diphthalic dianhydride.

Benzenetetracarboxylic dianhydride means a dianhydride of benzene having four carboxy groups, and further, the benzene ring here may have any of 1 to 3 substituents. Here, the substituents are preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (same definition as in formula (1B) below). Specific examples of benzenetetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

Naphthalenetetracarboxylic dianhydride means a dianhydride of naphthalene having four carboxy groups, and further, the naphthalene ring here may have any of 1 to 3 substituents. Here, the substituents are preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (same definition as in formula (1B) below). Specific examples of naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

Anthracene tetracarboxylic dianhydride means a dianhydride of anthracene having four carboxy groups, and further, the anthracene ring here may have any of 1 to 3 substituents. Here, the substituents are preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (same definition as in formula (1B) below). Specific examples of anthracene tetracarboxylic dianhydride include 2,3,6,7-anthracene tetracarboxylic dianhydride.

Diphthalic dianhydride means a compound containing two phthalic anhydrides in the molecule, and further, each of the two benzene rings in the two phthalic anhydrides may have 1 to 3 optional substituents. Here, the substituents are preferably selected from a halogen atom, a cyano group, and ^-X33 - ^R33 (same definition as in formula (1B) below). The two phthalic anhydrides in diphthalic dianhydride may be bonded directly or via a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

Diphthalic dianhydride is, for example, represented by formula (1B):

[Wherein,
R ³¹ and R ³² each independently represent a halogen atom, a cyano group, a nitro group, or -X ³³ -R ³³ ;
Each X ³³ independently represents a single bond, —NR ^33′ —, —O—, —S—, —CO—, —SO ₂ —, —NR 33 ^′ CO—, —CONR ^33′ —, —OCO— or —COO—;
R ³³ each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group;
R ^33′ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group;
Y represents a single bond or a linker structure having 1 to 100 skeletal atoms selected from a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom;
n10 and m10 each independently represent an integer of 0 to 3.
Examples of the compound include compounds represented by the following formula:

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

The "linker structure" in Y has 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The "linker structure" is preferably a divalent group represented by -[A1-Ph] _a10 -A1-[Ph-A1] _b10 - (wherein A1 each independently represents a single bond, -(substituted or unsubstituted alkylene group)-, -O-, -S-, -CO-, -SO ₂ -, -CONH-, -NHCO-, -COO-, or -OCO-, and a10 and b10 each independently represent an integer of 0 to 2 (preferably 0 or 1).).

Specific examples of the "linker structure" for Y include _-CH2- , _{-CH2CH2- , -CH2CH2CH2- , -CH2CH2CH2CH2- ,} -CH2CH2CH2CH2CH2- _, -CH2CH2CH2CH2CH2-, -CH( _CH3 ) _- , -C(CH3) _{2- ,} -O-, _{-CO- , -SO2- , -Ph-} , -O-Ph-O-, -O-Ph _- SO2-Ph-O-, _-O -Ph-C( _CH3 ) ₂ -Ph-O-, etc. In this specification, "Ph _" represents a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group.

Specific examples of diphthalic dianhydrides include 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethynylidene-4 ,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride Examples include 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride.

The acid anhydride may be commercially available or may be synthesized by a known method or a method similar thereto. The acid anhydride may be used alone or in combination of two or more kinds.

Commercially available polyimide resins can be used. Examples of commercially available products include "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

Polycarbonate resin is a resin having a carbonate structure. Examples of such resins include carbonate resins without reactive groups, hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, and epoxy group-containing carbonate resins. Here, reactive groups refer to functional groups that can react with other components, such as hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, acid anhydride groups, isocyanate groups, urethane groups, and epoxy groups.

Commercially available carbonate resins can be used. Examples of commercially available products include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090", "C-2090", and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd.

Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin is preferably a phenoxy resin having a weight average molecular weight of 30,000 or more.

Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation; and the like.

The polyamide-imide resin is a resin having an amide-imide structure. From the viewpoint of compatibility with other components in the resin composition, it is preferable to use polyamide-imide resins having an alicyclic structure in the molecular structure, polyamide-imide resins having a siloxane structure as described in JP-A-05-112760, polyamide-imide resins having a bulky branched chain structure, polyamide-imide resins made from asymmetric monomers, polyamide-imide resins having a multi-branched structure, etc.

Among them, from the viewpoint that the polyamide-imide resin has an isocyanuric ring structure, which improves compatibility and dispersibility of the resin varnish, (i) a polyamide-imide resin having an isocyanuric ring structure in the molecular structure (i.e., a polyamide-imide resin having an isocyanuric ring structure and an imide skeleton or an amide skeleton), (ii) a polyamide-imide resin having an isocyanuric ring structure and an alicyclic structure in the molecular structure (i.e., a polyamide-imide resin having an isocyanuric ring structure, an alicyclic structure, and an imide skeleton or an amide skeleton), and (iii) a polyamide-imide resin having a repeating unit containing an isocyanuric ring structure and an alicyclic structure (i.e., a polyamide-imide resin having a repeating unit containing an isocyanuric ring structure, an alicyclic structure, and an imide skeleton or an amide skeleton) are more preferable.

As a preferred embodiment of the polyamide-imide resins (i) to (iii), there may be mentioned (1) a carboxylic acid group-containing branched polyamide-imide obtained by reacting an isocyanuric ring-containing polyisocyanate compound derived from an alicyclic diisocyanate with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups (hereinafter, this compound may be referred to as "(compound C-1)"); (2) a carboxylic acid group-containing branched polymerizable polyamide-imide obtained by reacting a compound having one epoxy group and one or more radically polymerizable unsaturated groups with compound (C-1) (hereinafter, this may be referred to as "compound (C-2)"); or (3) a carboxylic acid group-containing branched polymerizable polyamide-imide obtained by reacting a compound having one hydroxyl group and one or more radically polymerizable unsaturated groups with the remaining isocyanate groups in the synthesis process of compound (C-1) (hereinafter, this may be referred to as "compound (C-3)").

（式中、ｗは０～１５を表す。） Specific examples of the compound (C-1) include compounds represented by the following general formula (I): The repeating unit in the compound represented by the general formula (I) is referred to as repeating unit (I-1).

(In the formula, w represents 0 to 15.)

（式中、Ｒは式（Ｉ）中の残基を表す。） An example of the compound (C-2) is a compound (II) having a structure (I-2) in which GMA (glycidyl methacrylate) is added to any part of the carboxyl groups and/or terminal carboxyl groups of the repeating unit (I-1) in the general formula (I).

(In the formula, R represents a residue in formula (I).)

The proportion of GMA modification of carboxyl groups is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.7 mol% or more, or 0.9 mol% or more, relative to the number of moles of carboxyl groups in compound (C-1). The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, or 20 mol% or less.

（式中、Ｒ’は式（Ｉ）中の残基を表す。） Examples of the compound (C-3) include a compound (III) having a structure (I-3) in which any part of the repeating unit (I-1) and/or the terminal imide group in the above formula (I) is an isocyanate residue to which a hydroxyl group of pentaerythritol triacrylate is added.

(In the formula, R′ represents a residue in formula (I).)

The amount of pentaerythritol triacrylate added is preferably 40 mol% or less, more preferably 38 mol% or less, and even more preferably 35 mol% or less, based on the number of moles of isocyanate groups in the polyisocyanate at the time of charging. On the other hand, from the viewpoint of fully obtaining the effect of the addition, the amount of pentaerythritol triacrylate added is preferably 0.3 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, based on the number of moles of isocyanate groups in the polyisocyanate at the time of charging.

Polyamide-imide resins can be synthesized by various known methods. For a method of synthesizing polyamide-imide resins, see, for example, paragraphs 0020 to 0030 of International Publication No. 2010/074197, the contents of which are incorporated herein by reference.

Commercially available polyamide-imide resins can be used. Examples of commercially available products include modified polyamide-imides such as "Unidic V-8000" manufactured by DIC Corporation, "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd., and "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

As the polystyrene resin, any elastomer containing a repeating unit (styrene unit) having a structure obtained by polymerizing styrene can be used. In addition, the polystyrene resin may be a copolymer containing any repeating unit different from the styrene unit in combination with the styrene unit, or may be a hydrogenated polystyrene resin.

The optional repeating unit may be, for example, a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), or a repeating unit having a structure obtained by hydrogenating the conjugated diene (hydrogenated conjugated diene unit). The conjugated diene may be, for example, an aliphatic conjugated diene such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, or 1,3-hexadiene; or a halogenated aliphatic conjugated diene such as chloroprene. The conjugated diene is preferably an aliphatic conjugated diene, and more preferably butadiene, from the viewpoint of obtaining the effects of the present invention significantly. The conjugated diene may be used alone or in combination of two or more types. The polystyrene resin may be a random copolymer or a block copolymer.

Examples of polystyrene resins include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS), styrene-butadiene-butylene-styrene block copolymers (SBBS), styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, and styrene-maleic anhydride copolymers. Of these, styrene-maleic anhydride copolymers are preferred as polystyrene resins.

Specific examples of polystyrene resins include "EF-40" manufactured by Cray Valley and "H1043" manufactured by Asahi Kasei Corporation.

From the viewpoint of compatibility with other components in the resin composition, the polyester resin preferably has a fluorene structure in its molecular structure, and preferably has a diol-derived structural unit and a dicarboxylic acid-derived structural unit in addition to the fluorene structure.

A specific example of a polyester resin is "OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd.

Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include S-LEC BH series, BX series (e.g. BX-5Z), KS series (e.g. KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

An example of a polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

Specific examples of polyphenylene ether resins include the oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc.

From the viewpoint of obtaining a cured product with excellent dielectric properties, the content of component (C) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more, based on 100% by mass of non-volatile components in the resin composition, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

If the content of the non-volatile components in the resin composition of component (C) is taken as 100% by mass, c1, and the content of the non-volatile components in the resin composition of component (A) is taken as 100% by mass, a1/c1 is preferably 2 or more, more preferably 5 or more, even more preferably 10 or more, 12 or more, and preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, 15 or less. By setting a1/c1 within this range, it is possible to obtain the effects of the present invention significantly.

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

As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferable as the silica. (D) The inorganic filler may be used alone or in combination of two or more types.

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

The specific surface area of component (D) is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly preferably 3 m ² /g or more. There is no particular upper limit, but it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is obtained according to the BET method by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

From the viewpoint of significantly obtaining the desired effects of the present invention, the average particle size of component (D) is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more, and is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

The average particle size of component (D) can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, a particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction/scattering particle size distribution measuring device, and the median diameter is taken as the average particle size. The measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture ultrasonically for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution measuring device with blue and red light wavelengths as the light source, and the volume-based particle size distribution of component (D) is measured using a flow cell method, and the average particle size can be calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

From the viewpoint of improving moisture resistance and dispersibility, it is preferable that the (D) component is treated with a surface treatment agent. Examples of the surface treatment agent include vinylsilane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Among them, vinylsilane coupling agents, (meth)acrylic coupling agents, and aminosilane coupling agents are preferred from the viewpoint of obtaining the effects of the present invention significantly. Moreover, the surface treatment agent may be used alone or in any combination of two or more types.

Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd.'s "KBM1003" (vinyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM503" (3-methacryloxypropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), and Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxy silane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc.

From the viewpoint of improving the dispersibility of the inorganic filler, it is preferable that the degree of surface treatment with the surface treatment agent falls within a specified range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of the surface treatment agent, more preferably with 0.2 parts by mass to 3 parts by mass, and more preferably with 0.3 parts by mass to 2 parts by 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 inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon 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 even more preferably 0.2 mg/m ² or more. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and even more preferably 0.5 mg/m ² or less.

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 (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. An example of a carbon analyzer that can be used is the "EMIA-320V" manufactured by Horiba, Ltd.

From the viewpoint of reducing the dielectric properties, the content of component (D) is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

<(E) Curing Agent>
The resin composition may further contain a curing agent as an optional component (E) in addition to the above-mentioned components. However, component (E) does not include those that fall under component (B). Component (E) is a curing agent that has been determined to be solid in a test conducted in accordance with the "Method of Confirming Liquid State" in Appendix 2 of the Ministerial Ordinance on the Testing and Properties of Hazardous Materials (Ministry of Home Affairs Ordinance No. 1 of 1989). Therefore, component (E) is a solid curing agent. The test method is as described above.

Examples of the (E) component include active ester-based curing agents, phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, amine-based curing agents, and acid anhydride-based curing agents. One type of (E) component may be used alone, or two or more types may be used in combination.

As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester curing agent, a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, is preferable. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable.

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

Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specific examples of preferred active ester-based hardeners include active ester-based hardeners containing a dicyclopentadiene-type diphenol structure, active ester-based hardeners containing a naphthalene structure, active ester-based hardeners containing an acetylated product of phenol novolac, and active ester-based hardeners containing a benzoylated product of phenol novolac. Among these, active ester-based hardeners containing a naphthalene structure and active ester-based hardeners containing a dicyclopentadiene-type diphenol structure are more preferred. The term "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC8000-65T", "HPC8000H-65TM", "EXB8000L-65TM", and "EXB8150-65T" (manufactured by DIC Corporation) as active ester curing agents containing a dicyclopentadiene-type diphenol structure; "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester curing agent containing a naphthalene structure; and an active ester curing agent containing an acetylated product of phenol novolac. Examples of such active ester curing agents include "DC808" (manufactured by Mitsubishi Chemical Corporation); "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing a benzoyl derivative of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent which is an acetylated derivative of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester curing agents which are benzoyl derivatives of phenol novolac; and the like.

From the viewpoint of heat resistance and water resistance, phenol-based and naphthol-based curing agents having a novolac structure are preferred. From the viewpoint of adhesion to the conductor layer, nitrogen-containing phenol-based curing agents are preferred, and triazine skeleton-containing phenol-based curing agents are more preferred.

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

Specific examples of benzoxazine-based curing agents include "ODA-BOZ" manufactured by JFE Chemical Corporation, "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industries Co., Ltd.

Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, 4,4'-methylenebis(2,6-dimethylphenylcyanate), hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, and bis(4-cyanatephenyl)thioether; polyfunctional cyanate resins derived from phenol novolac, cresol novolac, and the like; and prepolymers in which these cyanate resins are partially converted to triazine.
Specific examples of cyanate ester-based curing agents include "PT60" (phenol novolac type multifunctional cyanate ester resin), "ULL-950S" (multifunctional cyanate ester resin), "BA230" and "BA230S75" (prepolymer in which a part or all of bisphenol A dicyanate is converted to a triazine trimer), all of which are manufactured by Lonza Japan.

Specific examples of carbodiimide-based curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

Amine-based curing agents include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among these, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-diaminodiphenylmethane, diphenyldiaminosulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, and bis(4-(3-aminophenoxy)phenyl)sulfone. Commercially available amine-based curing agents may be used, such as "KAYABOND C-100" manufactured by Nippon Kayaku Co., Ltd.

Examples of acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Examples of such anhydrides include polymeric acid anhydrides such as biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and styrene-maleic acid resin, which is a copolymer of styrene and maleic acid.

From the viewpoint of significantly obtaining the desired effect of the present invention, the content of component (E) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on 100% by mass of non-volatile components in the resin composition, and is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

<(F) Curing Accelerator>
In addition to the above-mentioned components, the resin composition may further contain, as an optional component, a curing accelerator as component (F).

Examples of the (F) component include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. The (F) component may be used alone or in combination of two or more types.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 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-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4 -diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl Examples of the imidazole compounds include 1-dodecyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

Commercially available imidazole curing accelerators may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, 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, Examples include o[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide, and dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, organozinc complexes such as zinc (II) acetylacetonate, organoiron complexes such as iron (III) acetylacetonate, organonickel complexes such as nickel (II) acetylacetonate, and organomanganese complexes such as manganese (II) acetylacetonate. Organometallic salts include, for example, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

From the viewpoint of significantly achieving the desired effect of the present invention, the content of component (F) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, and is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0.1% by mass or less, based on 100% by mass of non-volatile components in the resin composition.

<(G) Epoxy Resin>
In addition to the above-mentioned components, the resin composition may further contain an optional component (G) which is an epoxy resin, provided that component (G) does not include those which fall under component (B).

Examples of the (G) component include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, etc. The (G) component may be used alone or in combination of two or more types.

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

Component (G) includes an epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resin"). The resin composition may contain only liquid epoxy resin as component (G), only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin, but from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferable to contain only liquid epoxy resin.

Preferably, the liquid epoxy resin has two or more epoxy groups in one molecule.

Preferred liquid epoxy resins are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure, with bisphenol A type epoxy resins and bisphenol F type epoxy resins being more preferable.

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

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

As solid epoxy resins, bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins are preferred, with naphthalene type epoxy resins being more preferred.

Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin); DIC's "N-690" (cresol novolac type epoxy resin); DIC's "N-695" (cresol novolac type epoxy resin); DIC's "HP-7200HH", "HP-7200H", and "HP-7200" (dicyclopentadiene type epoxy resins). DIC Corporation's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthylene ether type epoxy resins); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H", "NC3000", and "NC "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8" manufactured by Mitsubishi Chemical Corporation 800" (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical. These may be used alone or in combination of two or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as component (G), the ratio by mass (liquid epoxy resin:solid epoxy resin) is preferably 1:1 to 1:20, more preferably 1:1.5 to 1:15, and particularly preferably 1:2 to 1:10. When the ratio by mass of the liquid epoxy resin and the solid epoxy resin is within this range, the desired effects of the present invention can be significantly obtained. Furthermore, when used in the form of a resin sheet, appropriate adhesion is usually achieved. Furthermore, when used in the form of a resin sheet, sufficient flexibility is usually obtained, improving handling. Furthermore, a cured product having sufficient breaking strength can usually be obtained.

The epoxy equivalent of component (G) is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., even more preferably 80 g/eq. to 2000 g/eq., and even more preferably 110 g/eq. to 1000 g/eq. Within this range, the crosslink density of the cured product of the resin composition is sufficient, and an insulating layer with small surface roughness can be obtained. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

From the viewpoint of significantly obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of component (G) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight average molecular weight of component (G) can be measured in the same manner as the weight average molecular weight of component (C).

From the viewpoint of significantly obtaining the desired effect of the present invention, the content of component (G) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on 100% by mass of non-volatile components in the resin composition, and is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less.

<(H) Polymerization initiator>
In addition to the above-mentioned components, the resin composition may further contain a polymerization initiator as an optional component (H). The component (H) may be used alone or in combination of two or more kinds.

Examples of component (H) include peroxides such as t-butylcumyl peroxide, t-butyl peroxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butyl peroxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butyl peroxybenzoate.

Commercially available products of component (H) include, for example, NOF Corp.'s "Perbutyl C," "Perbutyl A," "Perbutyl P," "Perbutyl L," "Perbutyl O," "Perbutyl ND," "Perbutyl Z," "Percumyl P," and "Percumyl D."

From the viewpoint of significantly obtaining the desired effect of the present invention, the content of component (H) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less, based on 100% by mass of non-volatile components in the resin composition.

<(I) Other Additives>
The resin composition may further contain other additives as optional components in addition to the above-mentioned components. Examples of such additives include resin additives such as thickeners, defoamers, leveling agents, and adhesion-imparting agents. These additives may be used alone or in combination of two or more. The content of each additive can be appropriately set by a person skilled in the art.

The method for preparing the resin composition of the present invention is not particularly limited, and examples include a method in which the blending components are mixed and dispersed using a rotary mixer, etc., with the addition of a solvent, etc., as necessary.

<Physical properties and applications of resin composition>
The resin composition contains (A) a maleimide compound having a biphenyl structure, (B) a liquid or semi-solid curing agent, and (C) a high molecular weight component. This allows a cured product with excellent lamination properties, dielectric properties, and adhesion to be obtained. As already mentioned above, in general, when a maleimide compound is contained in a resin composition, the resin composition has excellent dielectric properties, but since the maleimide compound usually has a high softening point, the resin composition and its cured product become brittle. However, by containing (B) a liquid or semi-solid curing agent, the viscosity of the resin composition before curing is increased, and as a result, the brittleness can be improved. Furthermore, by containing (C) a high molecular weight component, the stress in the cured product is relaxed, and the brittleness of the cured product can also be improved.

The resin composition is thermally cured at 100°C for 30 minutes and then at 180°C for 30 minutes to produce a cured product that exhibits excellent peel strength between the resin composition and the conductor layer (plated conductor layer) formed by plating. Thus, the cured product produces an insulating layer that exhibits excellent peel strength between the resin composition and the plated conductor layer. The peel strength is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm or more, and even more preferably 0.45 kgf/cm or more. The upper limit of the peel strength may be 10 kgf/cm or less. The peel strength of the plated conductor layer can be measured according to the method described in the examples below.

The resin composition is thermally cured at 200°C for 90 minutes to produce a cured product that exhibits excellent copper foil peel strength. Thus, the cured product produces an insulating layer that has excellent copper foil peel strength. The copper foil peel strength is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm or more, and even more preferably 0.5 kgf/cm or more. The upper limit of the copper foil peel strength may be 10 kgf/cm or less. The copper foil peel strength can be measured according to the method described in the examples below.

The cured product obtained by thermally curing the resin composition at 200°C for 90 minutes exhibits the characteristic of a low dielectric constant. Thus, the cured product provides an insulating layer with a low dielectric constant. The dielectric constant is preferably 4 or less, more preferably 3.5 or less, and even more preferably 3 or less. The lower limit of the dielectric constant may be 0.001 or more. The dielectric constant can be measured according to the method described in the examples below.

The resin composition is thermally cured at 200°C for 90 minutes to produce a cured product with a low dielectric tangent. Thus, the cured product produces an insulating layer with a low dielectric tangent. The dielectric tangent is preferably 0.005 or less, more preferably 0.004 or less, and even more preferably 0.003 or less. The lower limit of the dielectric tangent may be 0.0001 or more. The dielectric tangent can be measured according to the method described in the examples below.

The resin composition exhibits excellent lamination properties. Specifically, the resin composition is laminated on a glass cloth-based epoxy resin double-sided copper-clad laminate conductor having a comb-tooth conductor pattern with a conductor thickness of 35 μm, and then heat-cured at 100°C for 30 minutes and then at 180°C for 30 minutes to form an insulating layer. The unevenness difference between the conductor and other parts of the insulating layer is determined using a non-contact surface roughness meter (WYKO NT3300 manufactured by B-CO Instruments) in VSI mode with a 10x lens, with a measurement range of 1.2 mm x 0.91 mm. At this time, usually, no voids are generated after lamination, and the unevenness difference between the conductor and other parts is less than 5 μm. Details of the evaluation of lamination properties can be measured according to the method described in the examples below.

The resin composition of the present invention has excellent lamination properties, can reduce dielectric properties, and can provide an insulating layer with excellent adhesion. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating purposes. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductor layer) to form a conductor layer (including a rewiring layer) formed on the insulating layer.

In addition, in the multilayer printed wiring board described below, the resin composition can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board) and as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board).

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

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

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less, from the viewpoint of making the printed wiring board thinner and being able to provide a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

Examples of the support include films made of plastic materials, metal foils, and release paper, with films made of plastic materials and metal foils being preferred.

When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

The support may be subjected to a matte treatment, corona treatment, or antistatic treatment on the surface that is to be bonded to the resin composition layer.

As the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product, such as "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by Unitika Limited, which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

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

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

The resin sheet can be produced, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying this resin varnish onto a support using a die coater or the like, and then drying it to form a resin composition layer.

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

Drying may be performed by known methods such as heating or blowing hot air. There are no particular limitations on the drying conditions, but drying is performed so that the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

The resin sheet can be stored in a roll. If the resin sheet has a protective film, it can be used by peeling off the protective film.

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

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

The "inner layer substrate" used in step (I) is a member that will be the substrate of the printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be called an "inner layer circuit substrate." In addition, intermediate products on which an insulating layer and/or a conductor layer is to be formed during the manufacture of a printed wiring board are also included in the "inner layer substrate" of the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate with a component embedded therein may be used.

The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet to the inner layer substrate (hereinafter also referred to as the "heat-pressing member") include a heated metal plate (such as a SUS panel) or a metal roll (SUS roll). Note that rather than pressing the heat-pressing member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heat-pressure bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat-pressure bonding pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heat-pressure bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably performed under reduced pressure conditions of a pressure of 26.7hPa or less.

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

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example by pressing a heat-pressure bonding member from the support side. The pressing conditions for the smoothing treatment may be the same as the heat-pressure bonding conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

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

In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions for the resin composition layer are not particularly limited, and conditions that are typically used when forming an insulating layer for a printed wiring board may be used.

For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes) at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 115°C or less, and more preferably 70°C or more and 110°C or less).

When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. When the support is removed after step (II), the removal of the support may be carried out between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated as necessary to form a multilayer wiring board.

Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined depending on the design of the printed wiring board.

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

In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. There is no particular lower limit, but it is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

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

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of ease of production, it is preferable to form the conductor layer by a semi-additive method. Below, an example of forming the conductor layer by a semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and the mask pattern is then removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, and a conductor layer having the desired wiring pattern can be formed.

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conductive portion" is a portion of a printed wiring board that transmits an electrical signal, and the portion may be either on the surface or embedded. There are no particular limitations on the semiconductor chip, so long as it is an electrical circuit element made of semiconductor material.

The method of mounting semiconductor chips when manufacturing semiconductor devices is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include wire bonding mounting, flip chip mounting, bumpless buildup layer (BBUL) mounting, anisotropic conductive film (ACF) mounting, non-conductive film (NCF) mounting, etc. Here, "bumpless buildup layer (BBUL) mounting" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess in a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board."

The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

<(B) Determination of Liquid and Semi-Solid State of Liquid or Semi-Solid Curing Agent>
(B) The liquid, semi-solid, and solid forms of the liquid or semi-solid hardener were determined in accordance with the "Method of Confirming Liquid Form" in Appendix 2 of the Ministerial Ordinance on the Testing and Properties of Hazardous Materials (Ministry of Home Affairs Ordinance No. 1 of 1989). The "Method of Confirming Liquid Form" was performed as described above. The results are shown below.
"jER Cure W" manufactured by Mitsubishi Chemical Corporation: liquid "KAYAHARD AA" manufactured by Nippon Kayaku Co., Ltd.: liquid "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.: liquid "NK Ester DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.: liquid "NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.: liquid "RE-810NM" manufactured by Nippon Kayaku Co., Ltd.: liquid "BMI689" manufactured by Designer Molecules, Inc.: liquid "Ricon100" manufactured by CRAY VALLEY Co., Ltd.: liquid "Ricon130MA13" manufactured by CRAY VALLEY Co., Ltd.: liquid "Ricon150" CRAY VALLEY: Liquid "JP-100" Nippon Soda: Liquid "ALP-d" Shikoku Kasei Kogyo: Liquid "L-DAIC" Shikoku Kasei Kogyo: Liquid "TAIC" Nippon Kasei: Liquid "DAISO DAP Monomer" Osaka Soda: Liquid "MDAC" Osaka Soda: Liquid "DAD" Nisshoku Techno Fine Chemical: Liquid

[Synthesis example: synthesis of polyimide resin]
A 500 mL separable flask equipped with a water content receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to the flask, and the mixture was stirred at 45°C for 2 hours under a nitrogen stream to carry out a reaction. Next, the reaction solution was heated and maintained at about 160°C, while condensed water was azeotropically removed together with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the water content receiver, and that no water was flowing out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. The mixture was then cooled to obtain a polyimide solution (non-volatile content 20% by mass) containing a polyimide resin having a 1,1,3-trimethylindane skeleton. The polyimide resin thus obtained had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2): The weight average molecular weight of the polyimide resin was 12,000.

[Example 1. Preparation of resin composition 1]
180 parts of biphenylaralkyl-type maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution with 70% nonvolatile content) and 10 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., weight average molecular weight 30,000) were dissolved in 30 parts of toluene and 30 parts of MEK while stirring and heating. After the obtained solution was cooled to room temperature, 18 parts of an amine-based non-solid curing agent ("jER Cure W" manufactured by Mitsubishi Chemical Co., Ltd.) and 300 parts of an inorganic filler (spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with a vinyl-based coupling agent ("KBM1003" manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed into the solution and uniformly dispersed in a high-speed rotating mixer to obtain a resin composition 1.

MIR-3000-70MT is a compound represented by the following structural formula: In the formula, e1 represents an integer of 1 to 100.

[Example 2. Preparation of resin composition 2]
In Example 1,
1) 18 parts of an amine-based non-solid curing agent ("jER Cure W" manufactured by Mitsubishi Chemical Corporation) was changed to 25 parts of an amine-based non-solid curing agent ("KAYAHARD AA" manufactured by Nippon Kayaku Co., Ltd.),
2) 10 parts of polycarbonate resin (Mitsubishi Gas Chemical Company, Inc., "FPC2136", weight average molecular weight 30,000) was replaced with 50 parts of varnish containing 20% by weight of the polyimide resin obtained in Synthesis Example.
Resin composition 2 was obtained in the same manner as in Example 1 except for the above points.

[Example 3. Preparation of resin composition 3]
In Example 1,
1) 18 parts of an amine-based non-solid curing agent ("jER Cure W" manufactured by Mitsubishi Chemical Corporation) was replaced with 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent 240);
2) 10 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., weight average molecular weight 30,000) was replaced with 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass, weight average molecular weight 35,000);
3) Furthermore, 0.5 parts of a polymerization initiator ("Perbutyl C" manufactured by NOF Corporation) was used.
Resin composition 3 was obtained in the same manner as in Example 1 except for the above points.

[Example 4. Preparation of resin composition 4]
In Example 3,
1) 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass, weight average molecular weight of 35,000) was replaced with 50 parts of the varnish containing 20% by mass of the polyimide resin obtained in Synthesis Example.
2) Furthermore, 10 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216, toluene solution with solid content of 50% by mass) was used.
Resin composition 4 was obtained in the same manner as in Example 3 except for the above points.

[Example 5. Preparation of resin composition 5]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent 240) was replaced with 13 parts of a bifunctional methacrylate (a (meth)acrylic non-solid curing agent, "NK Ester DCP" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 332);
2) 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass, weight average molecular weight of 35,000) was replaced with 25 parts of polyamideimide resin ("Unidic V-8000" manufactured by DIC Corporation, weight average molecular weight of 11,000, ethyl diglycol acetate solution with a non-volatile content of 40% by mass);
3) 300 parts of an inorganic filler (spherical silica (Admatechs'"SO-C2", average particle size 0.5 μm) surface-treated with a vinyl coupling agent (Shin-Etsu Chemical's "KBM1003")) was changed to 300 parts of an inorganic filler (spherical silica (Admatechs'"SO-C2", average particle size 0.5 μm) surface-treated with a methacrylic coupling agent (Shin-Etsu Chemical's "KBM503")).
Resin composition 5 was obtained in the same manner as in Example 3 except for the above points.

Unidic V-8000 is a compound represented by the following structural formula: In the formula, e2 represents an integer of 0 to 15.

[Example 6. Preparation of resin composition 6]
In Example 5,
1) 13 parts of a bifunctional methacrylate ((meth)acrylic non-solid curing agent, Shin-Nakamura Chemical Co., Ltd.'s "NK Ester DCP", molecular weight 332) was replaced with 13 parts of a bifunctional acrylate ((meth)acrylic non-solid curing agent, Shin-Nakamura Chemical Co., Ltd.'s "NK Ester A-DOG", molecular weight 326);
2) 25 parts of polyamideimide resin (DIC Corporation's "UNIDIC V-8000", weight average molecular weight 11,000, 40% by mass of non-volatile components in an ethyl diglycol acetate solution) was changed to 10 parts of an acid anhydride group-containing vinyl resin (polystyrene resin, Cray Valley Corporation's "EF-40", weight average molecular weight 11,000).
Resin composition 6 was obtained in the same manner as in Example 5 except for the above.

EF-40 is a compound represented by the following structural formula: In the formula, e3 represents an integer of 8 to 12, and e4 represents an integer of 1 to 8.

[Example 7. Preparation of resin composition 7]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240) was replaced with 13 parts of an allyl-based non-solid curing agent having an epoxy group ("RE-810NM" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 220);
2) In addition, 2 parts of a curing accelerator (2.5% solids solution of 2P4MZ (2-phenyl-4-methylimidazole) in MEK) was used.
Resin composition 7 was obtained in the same manner as in Example 3 except for the above points.

RE-810NM is a compound represented by the following structural formula: e5 represents an integer of 0 to 5.

[Example 8. Preparation of resin composition 8]
In Example 7,
1) 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass, weight average molecular weight of 35,000) was replaced with 10 parts of hydrogenated styrene-based thermoplastic elastomer ("H1043" manufactured by Asahi Kasei Corporation, weight average molecular weight of 35,000);
2) Further, 10 parts of an active ester curing agent (DIC Corporation's "HPC-8000-65T", active group equivalent 223, toluene solution with solid content of 65% by mass) was used,
3) 2 parts of the hardening accelerator (2.5% solids solution of 2P4MZ in MEK) was replaced with 2 parts of the hardening accelerator (2.5% solids solution of 1B2PZ (1-benzyl-2-phenylimidazole) in MEK);
4) 300 parts of inorganic filler (spherical silica (Admatechs'"SO-C2", average particle size 0.5 μm) surface-treated with a vinyl coupling agent (Shin-Etsu Chemical's "KBM1003")) was changed to 300 parts of inorganic filler (spherical silica (Admatechs'"SO-C2", average particle size 0.5 μm) surface-treated with a phenylaminosilane coupling agent (Shin-Etsu Chemical's "KBM573")).
Resin composition 8 was obtained in the same manner as in Example 7 except for the above points.

[Example 9. Preparation of resin composition 9]
In Example 5,
1) 13 parts of bifunctional methacrylate ((meth)acrylic non-solid curing agent, "NK Ester DCP" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 332) was replaced with 13 parts of liquid bismaleimide (maleimide non-solid curing agent, "BMI689" manufactured by Designer Molecules, maleimide group equivalent 345),
2) 25 parts of polyamideimide resin (DIC Corporation's "Unidic V-8000", weight average molecular weight 11,000, 40% by mass of non-volatile components in ethyl diglycol acetate solution) was changed to 10 parts of polyester resin (Osaka Gas Chemicals Co., Ltd.'s "OKP4HT", weight average molecular weight 50,000).
Resin composition 9 was obtained in the same manner as in Example 5 except for the above points.

BMI689 is a compound represented by the following structural formula:

[Example 10. Preparation of resin composition 10]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent 240) was replaced with 13 parts of a liquid styrene-butadiene polymer (a butadiene-based non-solid curing agent, "Ricon 100" manufactured by Cray Valley, styrene content 25%, Mn about 4500);
2) 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, 1:1 solution of MEK and cyclohexanone with solid content of 30% by mass) was changed to 10 parts of hydrogenated styrene-based thermoplastic elastomer ("H1043" manufactured by Asahi Kasei Corporation, weight average molecular weight 35,000).
Resin composition 10 was obtained in the same manner as in Example 3 except for the above points.

[Example 11. Preparation of resin composition 11]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl type non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent 240) was replaced with 13 parts of an acid anhydride group-containing liquid butadiene polymer (a butadiene type non-solid curing agent, "Ricon130MA13" manufactured by CRAY VALLEY, acid anhydride equivalent 732, Mn about 2900);
2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was changed to 10 parts of an acid anhydride group-containing vinyl resin ("EF-40" manufactured by CRAY VALLEY Corporation, weight average molecular weight 11,000).
Resin composition 11 was obtained in the same manner as in Example 3 except for the above points.

[Example 12. Preparation of resin composition 12]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, MEH-8000H manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent 240) was replaced with 13 parts of a liquid butadiene polymer (a butadiene-based non-solid curing agent, Ricon 150 manufactured by Cray Valley, Mn approx. 3900);
2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was replaced with 50 parts of a varnish containing 20% by mass of the polyimide resin obtained in Synthesis Example.
Resin composition 12 was obtained in the same manner as in Example 3 except for the above points.

[Example 13. Preparation of resin composition 13]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent 240) was replaced with 13 parts of an epoxidized polybutadiene (a butadiene-based non-solid curing agent, "JP-100" manufactured by Nippon Soda Co., Ltd., epoxy equivalent 210, Mn approx. 1300);
2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was replaced with 25 parts of a polyamideimide resin ("Unidic V-8000" manufactured by DIC Corporation, weight average molecular weight 11,000, ethyl diglycol acetate solution with a non-volatile content of 40% by mass);
3) In addition, 2 parts of a hardening accelerator (a MEK solution containing 2.5% solids of 1B2PZ) was used.
Resin composition 13 was obtained in the same manner as in Example 3 except for the above points.

[Example 14. Preparation of resin composition 14]
In Example 7,
1) 13 parts of an allyl-based non-solid curing agent having an epoxy group ("RE-810NM" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 220) was replaced with 13 parts of epoxidized polybutadiene (butadiene-based non-solid curing agent, "JP-100" manufactured by Nippon Soda Co., Ltd., epoxy equivalent 210, Mn about 1300);
2) Furthermore, 3 parts of a benzoxazine-based curing agent ("ODA-BOZ" manufactured by JFE Chemical Corporation) was used.
3) 300 parts of inorganic filler (spherical silica (Admatechs'"SO-C2", average particle size 0.5 μm) surface-treated with a vinyl coupling agent (Shin-Etsu Chemical's "KBM1003")) was changed to 300 parts of inorganic filler (spherical silica (Admatechs'"SO-C2", average particle size 0.5 μm) surface-treated with a phenylaminosilane coupling agent (Shin-Etsu Chemical's "KBM573")).
Resin composition 14 was obtained in the same manner as in Example 7 except for the above points.

[Example 15. Preparation of resin composition 15]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent 240) was replaced with 5 parts of a bifunctional acrylate (a (meth)acrylic non-solid curing agent, "NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326),
2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was replaced with 10 parts of a polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Company, weight average molecular weight 30,000);
3) Furthermore, 20 parts of an MEK solution containing 50% solids of 4,4-Diaminodiphenylmethane was used.
Resin composition 15 was obtained in the same manner as in Example 3 except for the above points.

[Example 16. Preparation of resin composition 16]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent 240) was replaced with 20 parts of an allyl-based non-solid curing agent having a benzoxazine ring ("ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd., MEK solution with a solid content of 65%),
2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was changed to 10 parts of a polyester resin ("OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd., weight average molecular weight 50,000).
Resin composition 16 was obtained in the same manner as in Example 3 except for the above points.

ALP-d is a compound represented by the following structural formula:

[Example 17. Preparation of resin composition 17]
In Example 8,
1) 13 parts of an allyl-based non-solid curing agent having an epoxy group ("RE-810NM" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 220) was replaced with 20 parts of an allyl-based non-solid curing agent having a benzoxazine ring ("ALP-d" manufactured by Shikoku Kasei Corporation, MEK solution with a solid content of 65%),
2) 10 parts of hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation's "H1043", weight average molecular weight 35,000) was replaced with 25 parts of polyamide-imide resin (DIC Corporation's "Unidic V-8000", weight average molecular weight 11,000, ethyl diglycol acetate solution with 40% by mass of non-volatile components);
3) 10 parts of an active ester curing agent (DIC Corporation's "HPC-8000-65T", active group equivalent 223, toluene solution with solid content of 65% by mass) was changed to 5 parts of a bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828US", epoxy equivalent approximately 180).
Resin composition 17 was obtained in the same manner as in Example 8 except for the above points.

[Example 18. Preparation of resin composition 18]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent 240) was replaced with 13 parts of an allyl-based non-solid curing agent having an isocyanuric ring ("L-DAIC" manufactured by Shikoku Chemical Industry Co., Ltd.),
2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was changed to 10 parts of a polyester resin ("OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd., weight average molecular weight 50,000).
Resin composition 18 was obtained in the same manner as in Example 3 except for the above points.

[Example 19. Preparation of resin composition 19]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240) was replaced with 13 parts of an allyl-based non-solid curing agent having an isocyanuric ring (triallyl isocyanurate, "TAIC" manufactured by Nippon Kasei Co., Ltd., molecular weight 249),
2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, a 1:1 solution of MEK and cyclohexanone with a solid content of 30 mass %) was changed to 10 parts of a polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Company, Inc., weight average molecular weight 30,000).
Resin composition 19 was obtained in the same manner as in Example 3 except for the above points.

[Example 20. Preparation of resin composition 20]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240) was replaced with 13 parts of an allyl-based non-solid curing agent (ortho-diallyl phthalate, "Daiso DAP Monomer" manufactured by Osaka Soda Co., Ltd., molecular weight 246),
2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was replaced with 50 parts of a varnish containing 20% by mass of the polyimide resin obtained in Synthesis Example.
A resin composition 20 was obtained in the same manner as in Example 3 except for the above points.

[Example 21. Preparation of resin composition 21]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (an allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent 240) was replaced with 13 parts of diallyl cyclohexanedicarboxylate (an allyl-based non-solid curing agent, "MDAC" manufactured by Osaka Soda Co., Ltd., molecular weight 252);
2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35,000, 1:1 solution of MEK and cyclohexanone with a solid content of 30 mass %) was changed to 10 parts of a polyester resin ("OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd., weight average molecular weight 50,000).
Resin composition 21 was obtained in the same manner as in Example 3 except for the above points.

[Example 22. Preparation of resin composition 22]
Biphenylaralkyl-type maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution with 70% non-volatile content) 180 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35000, 1:1 solution of MEK and cyclohexanone with 30% solid content by mass) 33.3 parts, toluene 20 parts, MEK 20 parts, cyclohexanedicarboxylate diallyl ("MDAC" manufactured by Osaka Soda Co., Ltd., molecular weight 252) 13 parts, bisphenol A-type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 180) 5 parts, triazine skeleton-containing phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation, 2-methoxy 2-methyl-2-propanediol with hydroxyl group equivalent of about 151 and 50% solid content) A resin composition 22 was obtained by uniformly dispersing 3 parts of a cyclopropanol solution, 5 parts of an active ester curing agent (DIC Corporation's "HPC-8000-65T", active group equivalent 223, toluene solution with a solid content of 65% by mass), 0.5 parts of a polymerization initiator (NOF Corporation's "Perbutyl C"), 2 parts of a curing accelerator (1B2PZ solid content 2.5% MEK solution), 150 parts of an inorganic filler (spherical silica (Admatechs Co., Ltd.'s "SO-C2", average particle size 0.5 μm) surface-treated with a vinyl coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM1003"), and 150 parts of an inorganic filler (spherical silica (Admatechs Co., Ltd.'s "SO-C2", average particle size 0.5 μm) surface-treated with a phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM573")).

[Example 23. Preparation of resin composition 23]
In Example 9,
1) 13 parts of liquid bismaleimide (maleimide-based non-solid curing agent, Designer Molecules'"BMI689", maleimide group equivalent 345) was replaced with 13 parts of diallyl diphenate (allyl-based non-solid curing agent, Nisshoku Techno Fine Chemical's "DAD", molecular weight 322);
2) 10 parts of polyester resin ("OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd., weight average molecular weight 50,000) was changed to 10 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., weight average molecular weight 30,000).
Resin composition 23 was obtained in the same manner as in Example 9 except for the above points.

[Comparative Example 1. Preparation of Comparative Resin Composition 1]
In Example 3, 20 parts of the allyl group-containing phenolic resin ("MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd., phenol equivalent weight 240) was not used.
Comparative resin composition 1 was obtained in the same manner as in Example 3 except for the above.

[Comparative Example 2. Preparation of Comparative Resin Composition 2]
In Example 11, 10 parts of the acid anhydride group-containing vinyl resin (CRAY VALLEY's "EF-40", weight average molecular weight 11,000) was not used.
Comparative resin composition 2 was obtained in the same manner as in Example 11 except for the above.

[Comparative Example 3. Preparation of Comparative Resin Composition 3]
In Example 2, 180 parts of the biphenylaralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution with 70% nonvolatile content) was changed to 126 parts of polyphenylmethane maleimide ("BMI2300" manufactured by Daiwa Kasei Kogyo Co., Ltd.).
Comparative resin composition 3 was obtained in the same manner as in Example 2 except for the above.

BMI2300 is a compound represented by the following structural formula: where n10 represents an integer of 1 to 10.

[Preparation of resin sheet]
As a support, a polyethylene terephthalate film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130° C.) that had been subjected to a release treatment with an alkyd resin-based release agent ("AL-5" manufactured by Lintec Corporation) was prepared.

Resin compositions 1 to 23 and comparative resin compositions 1 to 3 were each uniformly applied to a support using a die coater so that the thickness of the resin composition layer after drying was 40 μm, and then dried at 70°C to 95°C for 4 minutes to form a resin composition layer on the support. Next, the rough surface of a polypropylene film (Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) was attached as a protective film to the surface of the resin composition layer that was not joined to the support. This resulted in a resin sheet A having a support, a resin composition layer, and a protective film in this order.

[Measurement of peel strength of plated conductor layer]
(1) Preparation of Inner Layer Board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, board thickness 0.4 mm, Panasonic Corporation "R1515A") on which an inner layer circuit was formed was etched by 1 μm with a microetching agent (Mec Corporation "CZ8101") to roughen the copper surface.

(2) Lamination of resin sheet The protective film was peeled off from the resin sheet A to expose the resin composition layer. Using a batch type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), the resin composition layer was laminated on both sides of the inner layer substrate so that it was in contact with the inner layer substrate. The lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

(3) Thermal curing of resin composition layer The inner layer substrate with the resin sheet laminated thereon was placed in an oven at 100° C. and heated for 30 minutes, and then transferred to an oven at 180° C. and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. The support was then peeled off to obtain a cured substrate A having the insulating layer, the inner layer substrate, and the insulating layer in this order.

(4) Roughening Treatment A desmear treatment was carried out as a roughening treatment on the cured substrate A. As the desmear treatment, the following wet desmear treatment was carried out.
(Wet desmear treatment)
The cured substrate A was immersed in a swelling liquid (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, then immersed in an oxidizing agent solution (Atotech Japan's "Concentrate Compact CP", an aqueous solution of potassium permanganate at about 6% and sodium hydroxide at about 4%) at 80°C for 15 minutes, and then immersed in a neutralizing liquid (Atotech Japan's "Reduction Solution Securigant P", an aqueous sulfuric acid solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(5) Formation of Conductive Layer According to the semi-additive method, a conductive layer was formed on the roughened surface of the insulating layer. That is, the substrate after the roughening treatment was immersed in an electroless plating solution containing _PdCl2 at 40 ° C for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes. Next, after heating at 150 ° C for 30 minutes and performing an annealing treatment, an etching resist was formed, and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed to form a conductive layer having a thickness of 30 μm, and an annealing treatment was performed at 200 ° C for 60 minutes. The obtained substrate is called "evaluation substrate B".

<Measurement of peel strength of plated conductor layer>
The peel strength of the insulating layer and the conductor layer was measured in accordance with the Japanese Industrial Standards (JIS C6481). Specifically, a cut was made in the conductor layer of the evaluation board B, measuring 10 mm in width and 100 mm in length, and one end of the cut was peeled off and held with a gripper. The load (kgf/cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm/min at room temperature was measured to determine the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[Measurement of copper foil peel strength]
(1) Copper foil undercoat treatment The shiny side of "3EC-III" (electrolytic copper foil, 35 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. was etched to a depth of 1 μm with a microetching agent ("CZ8101" manufactured by MEC Co., Ltd.) to roughen the copper surface, and then an anti-rust treatment (CL8300) was applied. Furthermore, the foil was heated in an oven at 130° C. for 30 minutes. This copper foil is called CZ copper foil.

(2) Preparation of Inner Layer Board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, board thickness 0.4 mm, Panasonic Corporation "R1515A") on which an inner layer circuit was formed was etched by 1 μm with a microetching agent (Mech Corporation "CZ8101") to roughen the copper surface.

(3) Lamination of copper foil and formation of insulating layer The protective film was peeled off from the resin sheet A to expose the resin composition layer. Using a batch type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), the resin composition layer was laminated on both sides of the inner layer substrate so that it was in contact with the inner layer substrate. The lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing at 120 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, a heat press was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds. The treated surface of the CZ copper foil was laminated on the resin composition layer under the same conditions as above. Then, the resin composition layer was cured under a curing condition of 200 ° C. and 90 minutes to form an insulating layer, thereby producing sample A.

<Measurement of copper foil peel strength (copper foil adhesion)>
The prepared sample A was cut into small pieces of 150 x 30 mm. A cutter was used to make a 10 mm wide and 100 mm long cut in the copper foil portion of the small piece, and one end of the copper foil was peeled off and gripped with a gripper. The load (kgf/cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm/min at room temperature was measured to determine the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement. The measurement was performed in accordance with the Japanese Industrial Standards (JIS C6481).

[Measurement of dielectric properties (dielectric constant, dielectric dissipation factor)]
The protective film was peeled off from the resin sheet A produced in the examples and comparative examples, and the resin composition layer was thermally cured by heating at 200°C for 90 minutes, and then the support was peeled off. The obtained cured product is referred to as "evaluation cured product C". The evaluation cured product C was cut into a test piece having a width of 2 mm and a length of 80 mm. The dielectric constant and dielectric loss tangent of the test piece were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by a cavity resonance perturbation method using an Agilent Technologies "HP8362B". Measurements were performed on three test pieces, and the average value was calculated.
The cured product C for evaluation of Comparative Example 2, which did not use the component (C), was weak and difficult to handle. Therefore, the dielectric properties of Comparative Example 2 could not be measured.

[Evaluation of Lamination]
(1) Preparation of inner layer substrate A glass cloth-based epoxy resin double-sided copper-clad laminate (substrate thickness 0.8 mm, Panasonic Corporation "R1515A") having a comb-shaped conductor pattern with a conductor thickness of 35 μm and L (line: wiring width)/S (space: spacing width)=160 μm/160 μm was etched on both sides by 1 μm with a microetching agent (Mec Corporation "CZ8101") to roughen the copper surface.

(2) Lamination of resin sheet The protective film was peeled off from the resin sheet A to expose the resin composition layer. Using a batch type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), the resin composition layer was laminated on both sides of the glass cloth substrate epoxy resin double-sided copper-clad laminate so that it was in contact with the glass cloth substrate epoxy resin double-sided copper-clad laminate. The lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing at 120 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Thermal curing of resin composition layer The glass cloth-based epoxy resin double-sided copper-clad laminate with the resin sheet laminated thereon was placed in an oven at 100° C. and heated for 30 minutes, and then transferred to an oven at 180° C. and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. The support was then peeled off to obtain a cured substrate D having the insulating layer, the glass cloth-based epoxy resin double-sided copper-clad laminate, and the insulating layer in this order.

(4) Lamination property evaluation The value of the unevenness difference (Rt: maximum peak-to-valley) between the conductor and other parts in the insulating layer of the cured substrate D was obtained using a non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments) in VSI mode with a 10x lens to obtain a measurement range of 1.2 mm x 0.91 mm. Note that the evaluation was made as follows: "○" indicates that no voids were generated after lamination and the unevenness difference between the conductor and other parts was less than 5 μm; "△" indicates that no voids were generated after lamination but the unevenness difference between the conductor and other parts was 5 μm or more; and "×" indicates that voids were generated after lamination.

In Examples 1 to 23, it has been confirmed that even when components (D) to (H) are not contained, the results are similar to those of the above examples, although to a different extent.

Claims (15)

(A) a maleimide compound having a biphenyl structure,
(B) a liquid or semi-solid curing agent ;
( C) a high molecular weight component, and
(H) A resin composition comprising a polymerization initiator ,
The component (A) is represented by the following formula (A-3):
the component (B) is at least one selected from the group consisting of a (meth)acrylic non-solid curing agent having a cyclic structure, an allyl non-solid curing agent having a benzoxazine ring represented by the following formula (B-1), an allyl non-solid curing agent having a carboxylic acid derivative having a cyclic structure, and a maleimide non-solid curing agent represented by the following general formula (B-6),
A resin composition, wherein the component (C) comprises at least one selected from the group consisting of a polyimide resin, a polycarbonate resin, a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polyamideimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polyetheretherketone resin, a polystyrene resin, and a polyester resin.

(In formula (A-3), ^R3 and ^R8 represent a maleimide group, ^R4 , ^R5 , ^R6 and ^R7 each independently represent a hydrogen atom, an alkyl group or an aryl group, ^R9 and ^R10 each independently represent a substituent, a1 and b1 each independently represent an integer of 0 to 4, m1 and m2 each independently represent an integer of 1 to 10, and n represents an integer of 1 to 100.)

(In formula (B-1), R ²⁰ and R ²¹ represent an allyl group, and R ²² represents a q-valent group. q represents an integer of 1 to 4, p1 represents an integer of 1 to 4, and p2 represents an integer of 0 to 2.)

(In general formula (B-6), M ⁴ , M ⁶ and M ⁷ each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, M ⁵ each independently represent a divalent group having an aromatic ring which may have a substituent, R ³¹ and R ³² each independently represent an alkyl group having 5 or more carbon atoms, t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.) The resin composition according to claim 1, wherein the content of component (A) is 10% by mass or more and 40% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass. The component (B) contains the (meth)acrylic non-solid curing agent,
the cyclic structure of the (meth)acrylic non-solid curing agent is a cyclic group containing an alicyclic structure,
The resin composition according to claim 1 or 2, wherein atoms constituting the ring skeleton of the cyclic group containing an alicyclic structure contain or do not contain heteroatoms. the component (B) contains an allyl-based non-solid curing agent having a carboxylic acid derivative having a cyclic structure,
the allyl-based non-solid curing agent is an allyl carboxylate having a cyclic structure,
3. The resin composition according to claim 1, wherein the carboxylic acid having a cyclic structure is at least one selected from the group consisting of isocyanuric acid, diphenic acid, phthalic acid, and cyclohexanedicarboxylic acid. The component (B) contains the maleimide-based non-solid curing agent,
The resin composition according to claim 1 or 2, wherein the maleimide-based non-solid curing agent comprises a compound represented by the following formula (3):

The resin composition according to any one of claims 1 to 5, wherein the content of component (B) is 0.1% by mass or more and 15% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass. The resin composition according to any one of claims 1 to 6 , wherein the component (C) is at least one selected from the group consisting of polyimide resins, polycarbonate resins, and phenoxy resins. The resin composition according to any one of claims 1 to 7 , wherein the content of the component (C) is 0.5% by mass or more and 10% by mass or less, based on 100% by mass of non-volatile components in the resin composition. The resin composition according to any one of claims 1 to 8 , further comprising (D) an inorganic filler. The resin composition according to claim 9 , wherein the content of the component (D) is 50% by mass or more, based on 100% by mass of non-volatile components in the resin composition. The resin composition according to any one of claims 1 to 10 , which is used for forming an insulating layer. The resin composition according to any one of claims 1 to 11 , which is for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of claims 1 to 12 . A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 12 . A semiconductor device comprising the printed wiring board according to claim 14 .

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