JP2023002638A - resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition enabling obtaining a cured product excellent in laminate properties, dielectric characteristics, and adhesion.

SOLUTION: A resin composition contains (A) a maleimide compound having a biphenyl type structure, (B) a liquid or semisolid curing agent and (C) a high molecular-weight component. The (B) component is at least one kind selected from a (meth)acrylic non-solid curing agent having a cyclic structure, an allyl non-solid curing agent of a 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. (In the formula (B-1), R²⁰ and R²¹ are allyl groups, R²² is a group of q valence, q is an integral number of 1-4, p1 is an integral number of 1-4, and p2 is an integral number of 0-2.)

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

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

2. Description of the Related Art As a technique for manufacturing printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known.

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

JP 2018-053092 A

In recent years, further improvements in dielectric properties such as the dielectric constant and dielectric loss tangent of insulating layers, and further improvements in adhesiveness, including peel strength and copper foil peel strength between conductor layers formed by plating, have been sought. .

In general, when a maleimide compound is contained in a resin composition, the dielectric properties are improved. become brittle. In addition, when a resin sheet containing a resin composition containing a maleimide compound is laminated on a substrate having unevenness to form an insulating layer, the surface of the insulating layer opposite to the substrate follows the unevenness of the substrate and provides insulation. The flatness of the layer may be lowered, resulting in poor lamination properties.

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

As a result of intensive studies on the above problems, the present inventors found that the above problems can be solved by containing a predetermined maleimide compound, a liquid or semisolid curing agent, and a high molecular weight component, and have completed the present invention. Completed.

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 contents.
[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 component (A) is represented by the following formula (A-3).

In formula (A- ³ ), R ³ and R ⁸ represent a maleimide group; R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group; Each R ¹⁰ independently represents 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; n represents an integer of 1 to 100;
[3] The resin composition according to [1] or [2], wherein the content of component (A) is 10% by mass or more and 40% by mass or less when the non-volatile component in the resin composition is 100% by mass. thing.
[4] Component (B) is 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. The resin composition according to any one of [1] to [3], which is at least one selected from curing agents.
[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] Any one of [1] to [5], wherein the content of component (B) is 0.1% by mass or more and 15% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to .
[7] The resin composition according to any one of [1] to [6], wherein component (C) is a thermoplastic resin.
[8] The resin composition according to [7], wherein the thermoplastic resin is at least one selected from polyimide resins, polycarbonate resins and phenoxy resins.
[9] Any one of [1] to [8], wherein the content of component (C) is 0.5% by mass or more and 10% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to .
[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 component (D) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[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 containing the resin composition according to any one of [1] to [13] provided on the support.
[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 including the printed wiring board according to [15].

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

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

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

[Resin composition]
The resin composition of the present invention includes (A) a maleimide compound having a biphenyl type structure, (B) a liquid or semi-solid curing agent (hereinafter 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), it is possible to obtain a cured product having excellent lamination properties, dielectric properties and adhesion.

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

<(A) Maleimide compound having a biphenyl structure>
The resin composition contains (A) a maleimide compound having a biphenyl type structure as the (A) component. By including the component (A) in the resin composition, it is possible to obtain a cured product having excellent dielectric properties. (A) component may be used individually by 1 type, and may use 2 or more types together.

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。 Component (A) is a compound containing a maleimide group represented by the following formula (A-1) in the molecule. Moreover, the component (A) has a biphenyl type structure from the viewpoint of obtaining a cured product having excellent dielectric properties. A biphenyl structure is a structure represented by the following formula (A-2).

In formula (A-2), R ¹ and R ² each independently represent a substituent. a and b each independently represents an integer of 0 to 4; * represents a bond.

Examples of substituents 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, —NO ₂ and the like. Here, the term “C _xy ” (where x and y are positive integers and satisfies x<y) means that the organic group described immediately after this term has x to y carbon atoms. represents something. For example, the phrase “C _1-10 alkyl group” indicates an alkyl group having 1 to 10 carbon atoms. These substituents may combine with each other to form a ring, and the ring structure includes spiro rings and condensed rings.

The substituents described above may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As secondary substituents, unless otherwise specified, the same substituents as described above may be used.

a and b each independently represent an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1, and still more preferably 0;

From the viewpoint of obtaining a cured product having excellent dielectric properties, both ends of component (A) are preferably maleimide groups.

Component (A) preferably has either an aliphatic hydrocarbon group or an aromatic hydrocarbon group in addition to a biphenyl structure from the viewpoint of obtaining a cured product having excellent dielectric properties. It is more preferred to have both aromatic hydrocarbon groups. 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 partially contain a chain structure or an alicyclic hydrocarbon group. , heterocycle.

The aliphatic hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent saturated aliphatic hydrocarbon group, and still more preferably an alkylene group. 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 more preferable, and a methylene group is particularly preferable.

The aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group, more preferably an arylene group or an aralkylene group, and still more preferably an arylene group. 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 arylene groups include phenylene groups, naphthylene groups, anthracenylene groups, biphenylene groups and the like. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferable, an aralkylene group having 7 to 20 carbon atoms is more preferable, and an aralkylene group having 7 to 15 carbon atoms is 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 preferred, and a phenylene group is more preferred.

The number of maleimide groups per molecule in component (A) is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, from the viewpoint of obtaining a cured product having excellent dielectric properties. It is 10 or less, more preferably 6 or less, still more preferably 3 or less.

In component (A), the nitrogen atom of the maleimide group is preferably directly bonded to the aromatic hydrocarbon group from the viewpoint of significantly obtaining the desired effects of the present invention. Here, the term "directly" means that there are no other groups 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。 Component (A) preferably has a structure represented, for example, by the following formula (A-3).

In formula (A- ³ ), R ³ and R ⁸ represent a maleimide group; R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group; Each R ¹⁰ independently represents 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; 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, preferably a hydrogen atom.

The alkyl group for 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 an alkyl group having 1 to 3 carbon atoms. groups are more preferred. Alkyl groups may be straight, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and isopropyl groups.

The aryl group for 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 an aryl group having 6 to 10 carbon atoms. is more preferred. The aryl group may be monocyclic or condensed. Examples of such aryl groups include phenyl, naphthyl and anthracenyl groups.

The alkyl group and aryl group for 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 of 0 to 4 and are the same as a and b in formula (A-2).

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

n represents an integer of 1-100, preferably 1-50, more preferably 1-20, still more preferably 1-5.

R ³ and R ⁸ represent a maleimido group, and the maleimido group is directly bonded to the aromatic hydrocarbon group. The maleimido group represented by R ³ and R ⁸ is directly at the ortho-, meta-, or para-position relative to (CH ₂ ) _m1 or (CH ₂ ) _m2 bonded to the aromatic hydrocarbon group. Bonding is preferred, and direct bonding at the para-position is preferred.

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。 Component (A) preferably has a structure represented by formula (A-4).

In formula (A-4), R ¹¹ and R ¹⁶ represent a maleimido group, and 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 1-10, and n1 represents an integer of 1-100.

R ¹¹ and R ¹⁶ each 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). be.

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

n1 represents an integer of 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。 Component (A) preferably has a structure represented by formula (A-5).

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

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 of 1 to 100 and is the same as n in formula (A-3).

(A) A commercial item can be used for a component. Examples of commercially available products include "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, when the non-volatile component in the resin composition is 100% by mass. It is more preferably 25% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

<(B) Liquid or semi-solid curing agent>
The resin composition contains (B) a liquid or semi-solid curing agent as the (B) component. By including the component (B) in the resin composition, it becomes possible to improve the lamination property and to obtain a cured product having excellent adhesion. (B) component may be used individually by 1 type, and may use 2 or more types together.

Here, liquid, semi-solid, and solid judgments are made according to Attachment No. 2 "Confirmation method of liquid state" of Ministerial Ordinance Concerning Testing and Properties of Dangerous Substances (Ministry of Home Affairs Ordinance No. 1 of 1989). A specific determination method is as follows.

(1) Device constant temperature water bath:
A device equipped with a stirrer, a heater, a thermometer, and an automatic temperature controller (capable of temperature control at ±0.1° C.) and having a depth of 150 mm or more is used.
In addition, in the determination of the thermosetting resin used in the examples described later, a combination of a low temperature constant temperature water tank (model BU300) and an injection type constant temperature device Thermomate (model BF500) manufactured by Yamato Scientific Co., Ltd. was used. Put 22 liters in a low temperature constant temperature water tank (model BU300), turn on the power of Thermomate (model BF500) assembled in this, set the temperature to the set temperature (20 ° C. or 60 ° C.), and set the water temperature ± 0.1 The temperature was finely adjusted with Thermomate (Model BF500), but any device capable of similar adjustment can be used.

Test tube:
As shown in FIG. 1, the test tube was made of flat-bottomed transparent glass with an inner diameter of 30 mm and a height of 120 mm. A rubber stopper 13b having the same size, a similarly marked line, and a hole in the center for inserting and supporting a thermometer. The opening of the test tube is sealed with , and a temperature measuring test tube 10b having a thermometer 14 inserted into a rubber plug 13b is used. Hereinafter, a marked line at a height of 55 mm from the tube bottom is referred to as "A line", and a marked line at a height of 85 mm from the tube bottom is referred to as "B line".
As the thermometer 14, the one for measuring the freezing point (SOP-58 scale range 0 to 100 ° C.) specified in JIS B7410 (1982) "Petroleum test glass thermometer" is used, but the temperature of 0 to 100 ° C. It is sufficient if the range can be measured.

(2) Test procedure A sample left at a temperature of 60 ± 5 ° C. under atmospheric pressure for 24 hours or more is subjected to a liquid determination test tube 10a shown in FIG. 1(a) and a temperature measurement test shown in FIG. The tubes 10b are each fed up to line 11A. The two test tubes 10a and 10b are placed upright in a low temperature constant temperature water bath so that the line 12B is below the surface of the water. The lower end of the thermometer should be 30 mm below the 11A line.
After the sample temperature reaches the set temperature ±0.1°C, the state is kept as it is for 10 minutes. After 10 minutes, take out the test tube 10a for judging the liquid state from the low-temperature constant temperature water bath, immediately lay it horizontally on a horizontal test table, and use a stopwatch to measure the time when the tip of the liquid surface in the test tube moves from line 11A to line 12B. Measure and record.

Similarly, the sample left at a temperature of 20 ± 5°C under atmospheric pressure for 24 hours or more was also tested in the same manner as when left at a temperature of 60 ± 5°C under atmospheric pressure for 24 hours or more. The time taken by the tip of the surface to move from line 11A to line 12B is measured with a stopwatch and recorded.

If the measured time is within 90 seconds at 20° C., it is determined to be liquid.
A semi-solid state is determined when the measured time exceeds 90 seconds at 20°C and the measured time does not exceed 90 seconds at 60°C.
If the measured time exceeds 90 seconds at 60° C., it is determined to be solid.

Component (B) may be liquid or semi-solid and has a function of curing component (A). Examples of such non-solid curing agents include allyl-based non-solid curing agents, maleimide-based non-solid curing agents, (meth)acrylic-based non-solid curing agents, amine-based non-solid curing agents, and butadiene. It is preferably at least one selected from non-solid curing agents, and more preferably at least one of allyl-based non-solid curing agents and maleimide-based non-solid curing agents.

The 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 has the function of reacting with the maleimide group in the component (A) to cure the component (A). The allyl-based non-solid curing agent preferably has one or more allyl groups per molecule, more preferably two or more allyl groups. Although the lower limit is not particularly limited, it is preferably 10 or less, more preferably 5 or less.

In addition, from the viewpoint of significantly obtaining the desired effects of the present invention, the allyl-based non-solid curing agent includes not only an allyl group but also a benzoxazine ring, a phenol ring, an epoxy group, and a carboxylic acid derivative having a cyclic structure. From the viewpoint of obtaining the desired effect of the present invention more remarkably, it is more preferable to have a benzoxazine ring.

In the allyl-based non-solid curing agent having a benzoxazine ring, the allyl group is either a nitrogen atom constituting the benzoxazine ring or a carbon atom constituting the benzoxazine ring, from the viewpoint of significantly obtaining the desired effect of the present invention. It is preferably bonded with a carbon atom, and more preferably bonded with 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。 As the allyl-based non-solid curing agent having a benzoxazine ring, for example, an allyl-based non-solid curing agent having a benzoxazine ring represented by the following formula (B-1) is preferable.

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 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, an arylene group or two or more divalent is more preferably a group consisting of a combination of groups, and 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, a biphenylene group and the like, with a phenylene group being 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, for example, a methylene group, an ethylene group, a propylene group and the like, and a methylene group is preferred.

The group consisting of a combination of two or more divalent groups for R ²² includes, for example, a group in which one or more arylene groups and one or more oxygen atoms are bonded; for example, a group having an arylene-alkylene-arylene structure, etc. A group in which one or more arylene groups and one or more alkylene groups are bonded; A group in which one or more alkylene groups and one or more oxygen atoms are bonded; One or more arylene groups, one or more alkylene groups, and one or more A group in which one or more arylene groups and one or more oxygen atoms are bonded, and a group in which one or more arylene groups and one or more alkylene groups are bonded are preferable.

q represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2;

p1 represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 1. p2 represents an integer of 0 to 2 and represents 0 or 1, with 0 being preferred.

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 allyl group-containing cresol resins, allyl group-containing novolak phenol resins, and allyl group-containing cresol novolak resins. 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 represents an integer of 0 to 4, and s2 each independently represents an integer of 0 to 3. and r represents an integer from 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, still more preferably 3 or more, preferably 25 or less, more preferably 10 or less, still more preferably 5 or less.

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

r represents an integer of 0-3, preferably an integer of 0-2, more preferably an integer of 1-2.

The allyl-based non-solid curing agent having an epoxy group preferably contains two or more epoxy groups per molecule. In addition, the allyl-based non-solid curing agent having an epoxy group preferably has an aromatic structure, and when two or more kinds of allyl-based non-solid curing agents having an epoxy group are used, at least one of them has an aromatic structure. It is more preferable to have Aromatic structures are chemical structures generally defined as aromatic and also include polycyclic aromatic and heteroaromatic rings. The allyl-based non-solid curing agent having an epoxy group preferably has a bisphenol structure. Examples of the bisphenol structure include bisphenol A type, bisphenol F type, and bisphenol AF type. Bisphenol A type is preferable from the viewpoint of obtaining a remarkable effect.

As the allyl-based non-solid curing agent having a carboxylic acid derivative having a cyclic structure, 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 ring skeleton of the cyclic group may be composed of heteroatoms other than carbon atoms. The heteroatom includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom and the like, with a nitrogen atom being preferred. The ring may have one heteroatom, or may have two or more. Carboxylic acid derivatives having a cyclic structure improve the compatibility and dispersibility of the resin varnish due to the network structure of the cyclic structure. can be obtained.

Examples of carboxylic acids having a cyclic structure include isocyanuric acid, diphenic acid, phthalic acid, cyclohexanedicarboxylic acid and the like. 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, meta diallyl phthalate, para diallyl phthalate, allyl cyclohexanedicarboxylate, diallyl cyclohexanedicarboxylate, and the like.

A commercially available product can be used as the allyl-based non-solid curing agent. Commercial products include, for example, "MEH-8000H" and "MEH-8005" manufactured by Meiwa Kasei Co., Ltd. (allylic non-solid curing agent having a phenol ring); "RE-810NM" manufactured by Nippon Kayaku Co., Ltd. (an epoxy group allyl-based non-solid curing agent); Shikoku Chemicals Co., Ltd. "ALP-d" (allyl-based non-solid curing agent having a benzoxazine ring); Shikoku Chemicals Co., Ltd. "L-DAIC" (having an isocyanuric ring Allyl-based non-solid curing agent); Nippon Kasei Co., Ltd. "TAIC" (allyl-based non-solid curing agent having an isocyanuric ring (triallyl isocyanurate)); Osaka Soda Co., Ltd. "MDAC" (having a cyclohexanedicarboxylic acid derivative allyl non-solid curing agent); "DAD" (diallyl diphenate) manufactured by NISSHOKU TECHNO FINE CHEMICAL CO., LTD.;

The allyl group equivalent of the allyl-based non-solid curing agent is preferably 20 g/eq. from the viewpoint of significantly obtaining the desired effects of the present invention. ~1000g/eq. , more preferably 50 g/eq. ~500 g/eq. , more preferably 100 g/eq. ~300 g/eq. is. An allyl group equivalent is the weight of an allyl non-solid curing agent containing one equivalent of allyl groups.

A maleimide-based non-solid curing agent is a compound that is liquid or semi-solid and has at least one maleimide group in the molecule. However, those corresponding to the (A) component are excluded.

The maleimide-based non-solid curing agent preferably 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 in the 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, still more preferably 40 or less. This alkyl group may be linear, branched, or cyclic, with linear being 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 substituted for an alkylene group having 5 or more carbon atoms.

The number of carbon atoms in the 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, still more preferably 40 or less. The alkylene group may be linear, branched, or cyclic, with linear being preferred. Here, the cyclic alkylene group is a concept that includes both a cyclic alkylene group and a linear alkylene group and a cyclic alkylene group. Examples of such alkylene groups include pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, hexatriacontylene, and octylene-cyclohexylene. a group having a structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

The maleimide-based non-solid curing agent preferably contains both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms, from the viewpoint of significantly obtaining the effects of the present invention.

An alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms may be bonded to each other to form a ring, and the ring structure includes a spiro ring and a condensed ring. Examples of the ring formed by bonding together include a cyclohexane ring and the like.

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

In the maleimide-based non-solid curing agent, the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms are preferably 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 1, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. is. 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 remarkably 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 general formula (B-3), M represents an optionally substituted alkylene group having 5 or more carbon atoms, and L represents a single bond or a divalent linking group.

M represents an optionally substituted alkylene group having 5 or more carbon atoms. The alkylene group for M is the same as the above-described alkylene group having 5 or more carbon atoms. The substituent for 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. The divalent linking group includes 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, carbon an alkyl group having 1 to 3 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 two or more of these Examples thereof include a group consisting of a combination of divalent groups. An alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group consisting of a combination of two or more divalent groups have a number of carbon atoms. may have an alkyl group having 5 or more as a substituent. A divalent group derived from phthalimide represents a divalent group derived from phthalimide, specifically a group represented by general formula (A). The bivalent group derived from pyromellitic diimide means 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 for 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 an alkylene group having 1 to 40 carbon atoms. preferable. 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, hexatriene, Examples thereof include a contylene 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.

The alkenylene group as the divalent linking group for 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 for 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 methylethynylene, cyclohexynylene, pentynylene, hexynylene, heptynylene and octinylene groups.

The arylene group as the divalent linking group for L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, and even more preferably an arylene group having 6 to 14 carbon atoms. , and arylene groups having 6 to 10 carbon atoms are even more preferred. The arylene group includes, for example, a phenylene group, a naphthylene group, an anthracenylene group and the like.

The alkylene group, alkenylene group, alkynylene group, and arylene group, which are 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), preferably an alkyl group having 5 or more carbon atoms.

Examples of the group consisting of a combination of two or more divalent groups in L include, for example, an alkylene group, a divalent group derived from phthalimide and a divalent group consisting of a combination with an oxygen atom; a divalent group derived from phthalimide , a divalent group consisting of a combination of 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 combining the respective groups. Moreover, the group consisting of a combination of two or more divalent groups may be a repeating unit having 1 to 10 repeating units.

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

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 general formula (B-4), M ¹ represents an alkylene group having 5 or more carbon atoms each independently optionally having a substituent, and A each independently optionally having a substituent It represents an alkylene group having 5 or more carbon atoms or a divalent group having an optionally substituted aromatic ring. t represents an integer of 1-10.

Each M ¹ independently represents an optionally substituted alkylene group having 5 or more carbon atoms. M ¹ is the same as M in general formula (B-3).

Each A independently represents an optionally substituted alkylene group having 5 or more carbon atoms or an optionally substituted divalent group having an aromatic ring. The alkylene group for A may be chain, branched, or cyclic, and is preferably cyclic, that is, an optionally substituted alkylene group having 5 or more carbon atoms. 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, still more preferably 40 or less. Examples of such an alkylene group include groups having an octylene-cyclohexylene structure, groups having an octylene-cyclohexylene-octylene structure, groups having a propylene-cyclohexylene-octylene structure, and the like.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by A include benzene ring, naphthalene ring, anthracene ring, phthalimide ring, pyromellitic acid diimide ring, aromatic heterocycle, etc., and benzene ring, phthalimide A ring, a pyromellitic diimide ring, is preferred. That is, the divalent group having an aromatic ring includes a divalent group having an optionally substituted benzene ring, a divalent group having an optionally substituted phthalimide ring, a substituted A divalent group having a pyromellitic diimide ring which may have a group is preferred. The divalent group having an aromatic ring includes, for example, a group consisting of a combination of a divalent group derived from phthalimide and an oxygen atom; 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; mentioned. 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).

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

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 the general formula (B-3), the maleimide-based non-solid curing agent represented by the general formula (B-5), and the maleimide-based non-solid curing agent represented by the general formula (B-6) It is preferably any maleimide-based non-solid curing agent.

In general formula (B-5), M ² and M ³ each independently represent an optionally substituted alkylene group having 5 or more carbon atoms, and R ³⁰ each independently represent an oxygen atom, arylene group, an alkylene group, or a divalent group consisting of a combination of two or more of these groups. t1 represents an integer of 1-10.
In general formula (B-6), M ⁴ , M ⁶ and M ⁷ each independently represent an optionally substituted alkylene group having 5 or more carbon atoms, and M ⁵ each independently represents a substituent and 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.

M ² and M ³ each independently represent an optionally substituted alkylene group having 5 or more carbon atoms. M ² and M ³ are the same as the alkylene group having 5 or more carbon atoms represented by M in general formula (B-3), 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 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). R ³⁰ is preferably a group consisting of a combination of two or more divalent groups or an oxygen atom.

The group consisting of a combination of two or more divalent groups for R ³⁰ includes 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.

M ⁴ , M ⁶ and M ⁷ each independently represent an optionally substituted alkylene group having 5 or more carbon atoms. M ⁴ , M ⁶ and M ⁷ are the same as the optionally substituted alkylene group having 5 or more carbon atoms represented by M in general formula (B-3), a hexylene group and a heptylene group. , an octylene group, a nonylene group and a decylene group are preferred, and an octylene group is more preferred.

^M5 each independently represents a divalent group having an optionally substituted aromatic ring. M ⁵ is the same as the divalent group having an optionally substituted aromatic ring represented by A in general formula (B-4), and is an alkylene group and a divalent divalent group derived from pyromellitic diimide. A group consisting of a combination of groups; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group is preferred, and a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide is more preferred. 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).

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 above alkyl groups having 5 or more carbon atoms, preferably hexyl group, heptyl group, octyl group, nonyl group and decyl group, more preferably hexyl group and octyl group.

u1 and u2 each independently represent an integer of 1-15, preferably an integer of 1-10.

Specific examples of maleimide-based non-solid curing agents 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 1-10.

Specific examples of maleimide-based non-solid curing agents include "BMI1500" (compound of formula (1)), "BMI1700" (compound of formula (2)), "BMI689" (formula ( 3) compound), and the like.

The maleimide group equivalent of the maleimide-based non-solid curing agent is preferably 50 g/eq. from the viewpoint of significantly obtaining the desired effects of the present invention. ~2000g/eq. , more preferably 100 g/eq. ~1000 g/eq. , more preferably 150 g/eq. ~500 g/eq. is. A maleimide group equivalent is the weight of a maleimide-based non-solid curing agent containing one equivalent of maleimide groups.

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

The (meth)acrylic non-solid curing agent preferably has a cyclic structure from the viewpoint of significantly obtaining the desired effects of the present invention. As the cyclic structure, a divalent cyclic group is preferred. The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Among them, a cyclic group containing an alicyclic structure is preferable from the viewpoint of significantly obtaining the desired effects of the present invention.

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, still more preferably a 5-membered ring or more, and preferably a 20-membered ring. Below, it is more preferably a 15-membered ring or less, still more preferably a 10-membered ring or less. Moreover, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

The ring in the divalent cyclic group may have a ring skeleton composed of heteroatoms other than carbon atoms. The heteroatom includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc., and an oxygen atom is preferred. The ring may have one heteroatom, or may have two or more.

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

The bivalent cyclic group may have a substituent. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, A mercapto group, an oxo group and the like can be mentioned, and 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 divalent linking groups include alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, -C(=O)O-, -O-, -NHC(=O)-, and -NC(=O). Examples include N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, and -NH-, and may be a group combining a plurality of these. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. is more preferred. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, 1,1-dimethylethylene group and the like. - dimethylethylene group is preferred. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 2 to 5 carbon atoms. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and a methylene group and a 1,1-dimethylethylene group are particularly preferable.

（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. Ring D is a divalent represents a cyclic group.)

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

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

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 may have.

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

The (meth)acrylic non-solid curing agent may be a commercially available product, for example, "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., Nippon Kayaku Co., Ltd. "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" manufactured by Shin-Nakamura Chemical Co., Ltd., "NK Ester DCP" manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

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

As the amine-based non-solid curing agent, a liquid or semi-solid amine-based curing agent can be used. In addition, the amine-based non-solid curing agent includes curing agents having one or more amino groups in one molecule. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. Amine-based non-solid curing agents are preferably primary amines or secondary amines, more preferably primary amines.

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-xylylene amine, diethyltoluenediamine, 3,3′-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)propane and the like. Commercially available amine-based resins may be used. "Epicure W" and "jER Cure W" manufactured by Chemical Co., Ltd. may be mentioned.

A butadiene-based non-solid curing agent is a compound that is liquid or semi-solid and has at least one butadiene skeleton in its molecule. The polybutadiene structure may be contained in the main chain or in side chains. Part or all of the polybutadiene structure may be hydrogenated. Examples of butadiene-based non-solid curing agents include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing butadiene resins, phenolic hydroxyl group-containing butadiene resins, carboxy group-containing butadiene resins, acid anhydride group-containing butadiene resins, epoxy group-containing butadiene resins, One or more resins selected from the group consisting of isocyanate group-containing butadiene resins and urethane group-containing butadiene resins are more preferred.

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

The content of the component (B) is preferably 0 when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of improving lamination properties and obtaining a cured product with excellent adhesion. .1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5.5% by mass or less is.

The content when the nonvolatile component in the resin composition of component (B) is 100% by mass is b1, and the content when the nonvolatile component in the resin composition of component (A) is 100% by mass is a1 , a1/b1 is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, 4 or more, preferably 30 or less, more preferably 25 or less, further preferably 20 or less, 15 or less , 10 or less. By setting a1/b1 within such a range, it becomes possible to obtain the effects of the present invention remarkably.

<(C) High molecular weight component>
The resin composition contains a high molecular weight component as the (C) component. By including the component (C) in the resin composition, the stress of the resin composition is relaxed, and as a result, it becomes possible to obtain a cured product having excellent dielectric properties. (C) component may be used individually by 1 type, and may use 2 or more types together.

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

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

A resin having an imide structure can be used as the polyimide resin. Polyimide resins generally include those obtained by the imidization reaction between a diamine compound and an acid anhydride.

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

Examples of aliphatic diamine compounds include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, and 1,5-diaminopentane. , 1,10-diaminodecane and other linear aliphatic diamine compounds; 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5- Branched aliphatic diamine compounds such as diaminopentane; 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis(cyclohexyl) alicyclic diamine compounds such as amines); dimer acid-type diamines (hereinafter also referred to as "dimer diamines"), and the like. A dimer acid-type diamine is a diamine compound obtained by substituting _two terminal carboxylic acid groups (--COOH) of a dimer _acid with an aminomethyl group (--CH.sub.2--NH.sub.2) or an amino group ( _--NH.sub.2 ). means. Dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably having 11 to 22 carbon atoms, particularly preferably having 18 carbon atoms), and its industrial production process is almost Standardized.

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

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

A naphthalenediamine compound means a compound consisting of a naphthalene ring having two amino groups, and the naphthalene ring herein may optionally have 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.

A dianiline compound means a compound containing two aniline structures in the molecule, and two benzene rings in the two aniline structures each further optionally have 1 to 3 substituents. can. The substituents here are not particularly limited. Two aniline structures in a dianiline compound are directly bonded and/or bonded via 1 or 2 linker structures having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. can. Dianiline compounds also include those in which two aniline structures are bound by two bonds.

Specific examples of the "linker structure" in the dianiline compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH ₂ -, -CH ₂ CH ₂ -, and -CH ₂ CH ₂ CH ₂ -. , -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - , -CH=CH-, -O-, -S-, -CO-, -SO ₂ -, -NH-, -Ph-, -Ph-Ph-, -C(CH ₃ ) ₂ -Ph-C( CH ₃ ) ₂ -, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph —O—, —C(CH ₃ ) ₂ —Ph—C(CH ₃ ) ₂ —,

etc. As used herein, "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'-(hexafluoroisopropyl lidene)dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4- (4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4′-(9-fluorenylidene) Dianiline, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl- 1,1′-biphenyl, 4,4′-diamino-2,2′-dimethyl-1,1′-biphenyl, 9,9′-bis(3-methyl-4-aminophenyl)fluorene, 5-(4 -aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane and the like.

A commercially available diamine compound may be used, or one synthesized by a known method may be used. A diamine compound may be used individually by 1 type, and may be used in combination of 2 or more type.

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 the aromatic tetracarboxylic dianhydride include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, diphthalic dianhydride and the like, preferably It is diphthalic dianhydride.

Benzenetetracarboxylic dianhydride means the dianhydride of benzene having 4 carboxy groups, and further, the benzene ring herein may optionally have 1-3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and —X ³³ —R ³³ (as defined 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 4 carboxy groups, and furthermore, the naphthalene ring herein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and —X ³³ —R ³³ (as defined in formula (1B) below). Specific examples of the naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

Anthracenetetracarboxylic dianhydride means an anthracene dianhydride having four carboxy groups, and the anthracene ring herein may optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and —X ³³ —R ³³ (as defined in formula (1B) below). Specific examples of anthracenetetracarboxylic dianhydride include 2,3,6,7-anthracenetetracarboxylic dianhydride and the like.

Diphthalic dianhydride means a compound containing two phthalic anhydrides in the molecule, and two benzene rings in each of the two phthalic anhydrides are optionally 1 to 3 It can have substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and —X ³³ —R ³³ (as defined in formula (1B) below). Two phthalic anhydrides in diphthalic dianhydride can be linked directly or via a linker structure having 1 to 100 backbone atoms selected from carbon, oxygen, sulfur and nitrogen atoms.

Examples of diphthalic dianhydride include formula (1B):

[In the formula,
R ³¹ and R ³² each independently represent a halogen atom, a cyano group, a nitro group, or -X ³³ -R ³³ ,
X ³³ is each independently 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 is a single bond or a linker structure having 1 to 100 skeleton atoms selected from carbon, oxygen, sulfur and nitrogen atoms;
n10 and m10 each independently represent an integer of 0 to 3; ]
The compound represented by is mentioned.

Y is preferably a linker structure having 1-100 backbone atoms selected from carbon, oxygen, sulfur and nitrogen atoms. n and m are preferably zero.

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

The "linker structure" for Y is specifically -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -O-, -CO-, -SO ₂ -, -Ph-, -O-Ph-O-, - O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O- and the like can be mentioned. As used herein, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group or a 1,2-phenylene group.

Specific examples of diphthalic dianhydride include 4,4′-oxydiphthalic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′- diphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 2 ,3,3′,4′-diphenyl ether tetracarboxylic dianhydride, 2,3,3′,4′-diphenylsulfone 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 anhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3, 4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2 ,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4′-(4,4′-isopropyl dendiphenoxy)bisphthalic dianhydride and the like.

A commercially available acid anhydride may be used, or an acid anhydride synthesized by a known method or a method analogous thereto may be used. An acid anhydride may be used individually by 1 type, and may be used in combination of 2 or more type.

A commercially available polyimide resin can be used. Commercially available products include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika.

A polycarbonate resin is a resin having a carbonate structure. Examples of such resins include carbonate resins having no reactive groups, hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, containing carbonate resins, epoxy group-containing carbonate resins, and the like. Here, the reactive group means a functional group capable of reacting with other components such as a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, a urethane group and an epoxy group.

A commercially available product can be used as the carbonate resin. Commercially available products include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090" and "C-2090" manufactured by Kuraray Co., Ltd. ”, “C-3090” (polycarbonate diol), and the like.

Examples of phenoxy resins include 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, and terpene. Examples include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. 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 the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel Chemical &Materials; "FX280" and "FX293" manufactured by Nippon Steel Chemical &Materials; ", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482";

A polyamideimide resin is a resin having an amideimide structure. Polyamideimide resin, from the viewpoint of compatibility with other components in the resin composition, a polyamideimide resin having an alicyclic structure in the molecular structure, a polyamide having a siloxane structure described in JP-A-05-112760 It is preferable to use an imide resin, a polyamide-imide resin having a bulky branched chain structure, a polyamide-imide resin made from an asymmetric monomer, a polyamide-imide resin having a multi-branched structure, or the like.

Among them, the polyamideimide resin has an isocyanuric ring structure, and from the viewpoint of improving the compatibility and dispersibility of the resin varnish, (i) a polyamideimide resin having an isocyanuric ring structure in the molecular structure (i.e., isocyanuric ring structure and an imide skeleton or an amide skeleton) (ii) a polyamideimide resin having an isocyanuric ring structure and an alicyclic structure in the molecular structure (that is, an isocyanuric ring structure, an alicyclic structure and an imide skeleton or (iii) a polyamideimide resin having a repeating unit containing an isocyanuric ring structure and an alicyclic structure (that is, an isocyanuric ring structure, an alicyclic structure, an imide skeleton or an amide skeleton, and Polyamide-imide resins having repeating units containing polyimide) are more preferred.

As a preferred embodiment of the polyamideimide resins (i) to (iii), (1) an isocyanuric ring-containing polyisocyanate compound derived from an alicyclic structure diisocyanate and a polycarboxylic acid having 3 or more carboxyl groups A carboxylic acid group-containing branched polyamideimide which is a compound obtained by reacting an acid anhydride (hereinafter, the compound may be referred to as "(compound C-1)".), (2) Compound (C -1) is a compound obtained by reacting a compound having one epoxy group and one or more radically polymerizable unsaturated groups with a carboxylic acid group-containing branched polymerizable polyamideimide (hereinafter referred to as "compound (C- 2)”), or (3) reacting the residual isocyanate group with a compound having one hydroxyl group and one or more radically polymerizable unsaturated groups in the process of synthesizing the compound (C-1). carboxylic acid group-containing branched polymerizable polyamideimide (hereinafter sometimes referred to as "compound (C-3)"), which is a compound obtained by the above.

（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 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。） As the compound (C-2), a structure (I- 2) is exemplified by compound (II).

(Wherein R represents a residue in formula (I).)

The ratio of GMA modification of the carboxyl group is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, still more preferably 0.5 mol% or more, with respect to the number of moles of carboxyl groups of the compound (C-1), in which GMA is added. It is 0.7 mol % or more, or 0.9 mol % or more. The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, or 20 mol% or less.

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

(Wherein, 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, still more preferably 35 mol % or less, relative to the number of moles of isocyanate groups in the polyisocyanate at the time of preparation. On the other hand, the amount of pentaerythritol triacrylate added is preferably 0.3 mol% or more, more preferably 0.3 mol% or more, based on the number of moles of isocyanate groups in the polyisocyanate at the time of preparation, from the viewpoint of sufficiently obtaining the effect of addition. It is 3 mol % or more, more preferably 5 mol % or more.

Polyamideimide resins can be synthesized by various known methods. As a method for synthesizing a polyamideimide resin, for example, paragraphs 0020 to 0030 of International Publication No. WO 2010/074197 can be referred to, the contents of which are incorporated herein.

A commercially available product can be used as the polyamide-imide resin. Commercially available products include, for example, "Unidic V-8000" manufactured by DIC, "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo, "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd. (polysiloxane skeleton-containing polyamideimide) and other modified polyamideimides.

Any elastomer containing repeating units (styrene units) having a structure obtained by polymerizing styrene can be used as the polystyrene resin. Moreover, 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.

Examples of the optional repeating unit include a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), a repeating unit having a structure obtained by hydrogenating it (hydrogenated conjugated diene unit), and the like. be done. Examples of conjugated dienes include aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene and 1,3-hexadiene; and halogenated aliphatic conjugated dienes such as chloroprene. As the conjugated diene, an aliphatic conjugated diene is preferable, and butadiene is more preferable, from the viewpoint of significantly obtaining the effects of the present invention. Conjugated dienes may be used singly or in combination of two or more. Moreover, the polystyrene resin may be a random copolymer or a block copolymer.

Examples of polystyrene resins include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene- Ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, styrene-maleic anhydride copolymers, and the like. Among them, a styrene-maleic anhydride copolymer is preferable as the polystyrene resin.

Specific examples of the polystyrene resin include "EF-40" manufactured by CRAY VALLEY and "H1043" manufactured by Asahi Kasei.

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

Specific examples of the polyester resin include "OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd., and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

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

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

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

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

The content when the nonvolatile component in the resin composition of component (C) is 100% by mass is c1, and the content when the nonvolatile component in the resin composition of component (A) is 100% by mass is a1 , a1/c1 is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more and 12 or more, preferably 50 or less, more preferably 30 or less, still more preferably 20 or less and 15 or less is. By setting a1/c1 within such a range, it becomes possible to obtain the effects of the present invention remarkably.

<(D) Inorganic filler>
In addition to the components described above, the resin composition may optionally contain an inorganic filler as component (D).

An inorganic compound is used as the material of the inorganic filler. Examples of inorganic filler materials 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. Moreover, as silica, spherical silica is preferable. (D) The inorganic filler may be used singly or in combination of two or more.

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

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. Although there is no particular upper limit, 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 by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area using the BET multipoint method. .

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

The average particle size of component (D) can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. The particle size distribution obtained by measuring the volume-based particle size distribution of the component (D) by the flow cell method, using a laser diffraction particle size distribution analyzer, using blue and red wavelengths as the light source for the measurement sample. The average particle diameter can be calculated as the median diameter from Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

Component (D) is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of surface treatment agents include vinylsilane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, Examples include silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, and the like. Among them, vinylsilane-based coupling agents, (meth)acrylic-based coupling agents, and aminosilane-based coupling agents are preferred from the viewpoint of obtaining the effects of the present invention remarkably. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in combination.

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

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

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. 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 more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of suppressing 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 further preferably 0.5 mg/m ² or less. preferable.

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

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

<(E) Curing agent>
In addition to the components described above, the resin composition may optionally contain a curing agent as component (E). However, the (E) component excludes those corresponding to the (B) component. The component (E) is a hardening determined to be solid in a test conducted in accordance with the "liquid confirmation method" attached to the Ministerial Ordinance on the Test and Properties of Dangerous Goods (Ministry of Home Affairs Ordinance No. 1 of 1989). is an agent. Therefore, the (E) component is a solid curing agent. The test method is as described above.

Examples of component (E) include active ester curing agents, phenolic curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, amine curing agents, and acid anhydrides. system curing agents and the like. (E) component may be used individually by 1 type, or may use 2 or more types together.

A compound having one or more active ester groups in one molecule can be used as the active ester curing agent. Among them, active ester curing agents include phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, and the like, and have two or more ester groups per molecule with high reaction activity. Preferred are compounds having The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. .

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, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Preferred specific examples of the active ester curing agent include an active ester curing agent containing a dicyclopentadiene type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated phenol novolac, Examples include active ester curing agents containing benzoylated phenol novolacs. Among them, an active ester curing agent containing a naphthalene structure and an active ester curing agent containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

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

From the viewpoint of heat resistance and water resistance, the phenol-based curing agent and naphthol-based curing agent preferably have a novolak structure. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable.

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

Specific examples of benzoxazine-based curing agents include "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd. mentioned.

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

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

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 them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine curing agents include 4,4'-diaminodiphenylmethane, diphenyldiaminosulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 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-amino phenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone and the like. Commercially available amine-based curing agents may be used, such as "KAYABOND C-100" manufactured by Nippon Kayaku Co., Ltd., and the like.

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, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 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), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid.

The content of component (E) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, based on 100% by mass of non-volatile components in the resin composition, from the viewpoint of significantly obtaining the desired effects of the present invention. It is 3% by mass or more, more preferably 0.5% by mass or more, 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 components described above, the resin composition may optionally contain a curing accelerator as component (F).

Component (F) includes, for example, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. (F) component may be used individually by 1 type, and may be used in combination of 2 or more types.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

Examples of imidazole 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'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

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

Guanidine curing accelerators include, for example, 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, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being 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, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

From the viewpoint of significantly obtaining the desired effects of the present invention, the content of component (F) is preferably 0.001% by mass or more, more preferably 0%, when the non-volatile component in the resin composition is 100% by mass. 005% by mass or more, more preferably 0.01% by mass or more, 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.

<(G) Epoxy resin>
The resin composition may contain an epoxy resin as an optional component (G) in addition to the components described above. However, the (G) component excludes those corresponding to the (B) component.

Component (G) includes, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin. resins, naphthol novolak-type epoxy resins, phenol novolak-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 novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedioxy Examples include methanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin and the like. (G) Component may be used individually by 1 type, and may be used in combination of 2 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 remarkably, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass with respect to 100% by mass of the non-volatile components of the component (G). Above, more preferably 60% by mass or more, 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 a "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter referred to as a "solid epoxy resin"). There is.) As the component (G), the resin composition may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. However, from the viewpoint of significantly obtaining the desired effects of the present invention, it is preferable that only the liquid epoxy resin is included.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

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

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

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, and more preferably naphthalene type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200HH", "HP-7200H", "HP -7200" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; YX8800" (anthracene type epoxy resin); Osaka Gas Chemicals Co., Ltd. "PG-100", "CG-500"; Mitsubishi Chemical Co., Ltd. "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Co., Ltd. "YL7800 (fluorene type epoxy resin); Mitsubishi Chemical Corp.'s "jER1010" (solid bisphenol A type epoxy resin); Mitsubishi Chemical Corp.'s "jER1031S" (tetraphenylethane type epoxy resin). These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a combination of a liquid epoxy resin and a solid epoxy resin is used 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, particularly preferably 1:2 to 1:10. The desired effect of the present invention can be remarkably obtained by setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range. In addition, it usually provides moderate tackiness when used in the form of a resin sheet. In addition, when used in the form of a resin sheet, sufficient flexibility is usually obtained, and handleability is improved. Furthermore, usually, a cured product having sufficient breaking strength can be obtained.

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

The weight average molecular weight (Mw) of component (G) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500 from the viewpoint of significantly obtaining the desired effects of the present invention. The weight average molecular weight of component (G) can be measured by the same method as for 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%, when the non-volatile component in the resin composition is 100% by mass. 3% by mass or more, more preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less.

<(H) polymerization initiator>
The resin composition may contain a polymerization initiator as an optional component (H) in addition to the components described above. (H) component may be used individually by 1 type, or may use 2 or more types together.

Component (H) includes, for example, t-butylcumyl peroxide, t-butylperoxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butylperoxylaurate, t-butyl Peroxides such as peroxy-2-ethylhexanoate, t-butylperoxyneodecanoate and t-butylperoxybenzoate can be mentioned.

Commercially available products of component (H) include, for example, NOF Corporation's "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", "PERBUTYL O", "PERBUTYL ND", and "PERBUTYL Z". ”, “Percumyl P”, “Percumyl D” and the like.

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%, when the non-volatile component in the resin composition is 100% by mass. 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less.

<(I) Other Additives>
The resin composition may further contain other additives as optional components in addition to the components described above. Examples of such additives include resin additives such as thickeners, antifoaming agents, leveling agents, and adhesiveness imparting agents. These additives may be used singly or in combination of two or more. Each content can be appropriately set by those skilled in the art.

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

<Physical properties and applications of the resin composition>
The resin composition contains (A) a maleimide compound having a biphenyl type structure, (B) a liquid or semi-solid curing agent, and (C) a high molecular weight component. This makes it possible to obtain a cured product that is excellent in lamination properties, dielectric properties and adhesion. As already mentioned above, in general, if a maleimide compound is contained in a resin composition, the dielectric properties are improved, but since the softening point of the maleimide compound is generally high, 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 increases, and as a result, brittleness can be improved. Furthermore, the inclusion of (C) the high-molecular-weight component relaxes the stress in the cured product, making it possible to improve the brittleness of the cured product.

A cured product obtained by thermally curing the resin composition at 100° C. for 30 minutes and then at 180° C. for 30 minutes exhibits excellent peel strength to a conductor layer formed by plating (plated conductor layer). Therefore, the cured product provides an insulating layer with excellent peel strength between itself 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 still 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 Examples below.

A cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits excellent copper foil peeling strength. Therefore, the cured product provides an insulating layer having excellent copper foil peeling strength. The copper foil peel strength is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm or more, and still more preferably 0.5 kgf/cm or more. The upper limit of the copper foil peel strength can be set to 10 kgf/cm or less. The copper foil peel strength can be measured according to the method described in Examples below.

A cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits a low dielectric constant. The cured product thus provides an insulating layer with a low dielectric constant. The dielectric constant is preferably 4 or less, more preferably 3.5 or less, 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 Examples below.

A cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits a characteristic of low dielectric loss tangent. Thus, the cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.004 or less, still more preferably 0.003 or less. The lower limit value of the dielectric loss tangent may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in Examples below.

The resin composition exhibits excellent lamination properties. Specifically, after laminating the resin composition on a glass cloth-based epoxy resin double-sided copper-clad laminate conductor on which a comb-shaped conductor pattern with a conductor thickness of 35 μm is formed, the resin composition is laminated at 100° C. for 30 minutes, and then at 180° C. for 30 minutes. The insulating layer is formed by heat curing for 1 minute. A non-contact surface roughness meter (WYKO NT3300 manufactured by Beecoinstruments Co.) was used to measure the unevenness of the insulating layer between the conductor and the rest of the insulating layer using a VSI mode and a 10-fold lens with a measurement range of 1.2 mm x 0.2 mm. Determined by the numerical value obtained as 91 mm. At this time, voids are not normally generated after lamination, and the unevenness difference between the conductor and other portions is less than 5 μm. The details of evaluation of lamination properties can be measured according to the method described in Examples below.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can provide an insulating layer having excellent lamination properties, low dielectric properties, and excellent adhesion. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition).

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

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

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer formed of 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 It is preferably 40 μm or less, more preferably 30 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can usually be 5 μm or more.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

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

Further, 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. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain other layers as necessary. Such other layers include, for example, a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

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

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol; carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it 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 the organic solvent, drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes The resin composition layer can be formed.

The resin sheet can be wound into a roll and stored. When 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.

A printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) Step of laminating the resin composition layer of the resin sheet on the inner layer substrate such that the resin composition layer is bonded to the inner layer substrate (II) 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 serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

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

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned 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 thermosetting conditions for the resin composition layer are not particularly limited, and conditions that are commonly used for forming insulating layers of printed wiring boards may be used.

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

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

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

Step (III) is a step of making holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, 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 according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Smear is usually 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 commonly used in forming insulating layers of printed wiring boards can be employed. 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 neutralizing treatment with a neutralizing liquid in this order. The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P", "Swelling Dip Securigans SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. be done. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. 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 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 1 minute to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. Although the lower limit is not particularly limited, it is preferably 30 nm or more, more preferably 40 nm or more, and still 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, in which 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 selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

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 a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[Semiconductor device]
A 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.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, "a mounting method using a build-up layer without bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

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

<(B) Judgment of Liquid or Semi-Solid Curing Agent>
(B) Judgment of liquid, semi-solid, and solid state of liquid or semi-solid curing agent shall be made in Attachment 2 of Ministerial Ordinance Concerning Testing and Properties of Dangerous Goods (Ministry of Home Affairs Ordinance No. 1 of 1989). confirmation method”. "Confirmation method of liquid state" was carried out as described above. The results are shown below.
"JER Cure W" Mitsubishi Chemical Co., Ltd.: liquid "KAYAHARD AA" Nippon Kayaku Co., Ltd.: liquid "MEH-8000H" Meiwa Kasei Co., Ltd.: liquid "NK Ester DCP" Shin-Nakamura Chemical Co., Ltd.: liquid "NK Ester A-DOG” Shin-Nakamura Chemical Co., Ltd.: liquid “RE-810NM” Nippon Kayaku: liquid “BMI689” Designer Molecules: liquid “Ricon 100” CRAY VALLEY: liquid “Ricon 130MA13” CRAY VALLEY Company: liquid "Ricon 150" Cray Valley: liquid "JP-100" Nippon Soda: liquid "ALP-d" Shikoku Chemicals: liquid "L-DAIC" Shikoku Chemicals: liquid "TAIC Nippon Kasei Co., Ltd.: liquid "Daiso Dup Monomer" Osaka Soda Co., Ltd.: liquid "MDAC" Osaka Soda Co., Ltd.: liquid "DAD" Nissho Techno Fine Chemical Co., Ltd.: 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. The flask was charged with 20.3 g 4,4′-oxydiphthalic anhydride (ODPA), 200 g γ-butyrolactone, 20 g toluene, and 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy). Phenyl]-1,1,3-trimethylindane (29.6 g) was added, and the reaction was carried out by stirring at 45° C. for 2 hours under a nitrogen stream. Then, the temperature of this reaction solution was raised, and the condensed water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160°C. It was confirmed that a predetermined amount of water was accumulated in the water content receiver, and that water was no longer seen to flow out. After confirmation, the reaction solution was further heated and stirred at 200° C. for 1 hour. Thereafter, the mixture was cooled to obtain a polyimide solution (non-volatile content: 20% by mass) containing a polyimide resin having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). Moreover, the weight average molecular weight of the polyimide resin was 12,000.

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

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

[Example 2. Preparation of resin composition 2]
In Example 1,
1) 18 parts of amine-based non-solid curing agent (Mitsubishi Chemical Co., Ltd. "jER Cure W") is replaced with 25 parts of amine-based non-solid curing agent (Nippon Kayaku Co., Ltd. "KAYAHARD AA"),
2) 10 parts of a polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., weight average molecular weight of 30000) was replaced with 50 parts of a varnish containing 20% by mass of the polyimide resin obtained in Synthesis Example.
A resin composition 2 was obtained in the same manner as in Example 1 except for the above matters.

[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 Co., Ltd.) is added to 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) changed to 20 parts,
2) Polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., weight average molecular weight 30000) 10 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass, weight Average molecular weight 35000) changed to 33.3 parts,
3) Furthermore, 0.5 part of a polymerization initiator ("Perbutyl C" manufactured by NOF Corporation) was used.
A resin composition 3 was obtained in the same manner as in Example 1 except for the above matters.

[Example 4. Preparation of resin composition 4]
In Example 3,
1) 33.3 parts of phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7553BH30", 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass, weight average molecular weight of 35000), 20% by mass of polyimide resin obtained in Synthesis Example Change to 50 parts of varnish containing,
2) Further, 10 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent weight: about 216, solid content: 50% by mass, toluene solution) was used.
A resin composition 4 was obtained in the same manner as in Example 3 except for the above matters.

[Example 5. Preparation of resin composition 5]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240), bifunctional methacrylate ((meth)acrylic non-solid Curing agent, Shin Nakamura Chemical Co., Ltd. "NK Ester DCP", molecular weight 332) changed to 13 parts,
2) 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK with a solid content of 30% by mass and cyclohexanone, weight average molecular weight of 35000), polyamideimide resin (manufactured by DIC "Unidic V -8000", weight average molecular weight 11000, ethyl diglycol acetate solution with 40% by mass of non-volatile components) changed to 25 parts,
3) 300 parts of an inorganic filler (spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) surface-treated with a vinyl coupling agent (“KBM1003” manufactured by Shin-Etsu Chemical Co., Ltd.)) , Inorganic filler (spherical silica surface-treated with a methacrylic coupling agent (“KBM503” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm))) 300 parts rice field.
A resin composition 5 was obtained in the same manner as in Example 3 except for the above matters.

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

[Example 6. Preparation of resin composition 6]
In Example 5,
1) 13 parts of a bifunctional methacrylate ((meth)acrylic non-solid curing agent, "NK Ester DCP" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 332) is added to a bifunctional acrylate ((meth)acrylic non-solid curing agent , "NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326) changed to 13 parts,
2) 25 parts of polyamideimide resin ("Unidic V-8000" manufactured by DIC, weight average molecular weight 11000, ethyl diglycol acetate solution of 40% by mass of non-volatile components), an acid anhydride group-containing vinyl resin (polystyrene resin, "EF-40" manufactured by CRAY VALLEY, weight average molecular weight 11000) was changed to 10 parts.
A resin composition 6 was obtained in the same manner as in Example 5 except for the above matters.

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

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

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 a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK with a solid content of 30% by mass and cyclohexanone, a weight average molecular weight of 35000) is added to a hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Corporation "H1043", weight average molecular weight 35000) changed to 10 parts,
2) In addition, using 10 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC, an active group equivalent of 223, a toluene solution with a solid content of 65% by mass),
3) 2 parts curing accelerator (2P4MZ 2.5% solids MEK solution), 2 parts curing accelerator (1B2PZ (1-benzyl-2-phenylimidazole) 2.5% solids MEK solution) to
4) 300 parts of an inorganic filler (spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) surface-treated with a vinyl coupling agent (“KBM1003” manufactured by Shin-Etsu Chemical Co., Ltd.)) , Inorganic filler (spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5 μm) surface-treated with a phenylaminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) to 300 parts changed.
A resin composition 8 was obtained in the same manner as in Example 7 except for the above matters.

[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), liquid bismaleimide (maleimide non-solid curing agent, Designer More "BMI689" manufactured by Kühl's, maleimide group equivalent 345) 13 parts,
2) 25 parts of polyamideimide resin ("Unidic V-8000" manufactured by DIC, weight average molecular weight 11000, ethyl diglycol acetate solution with 40% by mass of non-volatile components), polyester resin ("OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd., weight average molecular weight 50000) was changed to 10 parts.
A resin composition 9 was obtained in the same manner as in Example 5 except for the above matters.

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 (allyl-based non-solid curing agent having a phenol ring, Meiwa Kasei Co., Ltd. "MEH-8000H", phenol equivalent 240), liquid styrene-butadiene polymer (butadiene-based non-solid curing agent , "Ricon 100" manufactured by CRAY VALLEY, styrene content 25%, Mn about 4500) 13 parts,
2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a weight average molecular weight of 35,000, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), a hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Corporation "H1043", weight average molecular weight 35000) was changed to 10 parts.
A resin composition 10 was obtained in the same manner as in Example 3 except for the above matters.

[Example 11. Preparation of resin composition 11]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (allylic non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240), an acid anhydride group-containing liquid butadiene polymer (butadiene non- Solid curing agent, "Ricon 130MA13" manufactured by CRAY VALLEY, acid anhydride equivalent 732, Mn about 2900) 13 parts,
2) 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight of 35000, 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass), an acid anhydride group-containing vinyl resin (CRAY VALLEY "EF-40" manufactured by Co., Ltd., weight average molecular weight 11000) 10 parts.
A resin composition 11 was obtained in the same manner as in Example 3 except for the above matters.

[Example 12. Preparation of resin composition 12]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240), a liquid butadiene polymer (butadiene-based non-solid curing agent, "Ricon 150" manufactured by CRAY VALLEY, Mn about 3900) 13 parts,
2) 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight of 35000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), 20 mass of the polyimide resin obtained in Synthesis Example % of the varnish was changed to 50 parts.
A resin composition 12 was obtained in the same manner as in Example 3 except for the above matters.

[Example 13. Preparation of resin composition 13]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240), epoxidized polybutadiene (butadiene-based non-solid curing agent, "JP-100" manufactured by Nippon Soda Co., Ltd., epoxy equivalent 210, Mn about 1300) Change to 13 parts,
2) 33.3 parts of phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35000, 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass), polyamideimide resin (manufactured by DIC "Unidic V -8000", weight average molecular weight 11000, ethyl diglycol acetate solution with 40% by mass of non-volatile components) changed to 25 parts,
3) In addition, 2 parts of curing accelerator (2.5% solids MEK solution of 1B2PZ) was used.
A resin composition 13 was obtained in the same manner as in Example 3 except for the above matters.

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

[Example 15. Preparation of resin composition 15]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (allylic non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240), bifunctional acrylate ((meth)acrylic non-solid Curing agent, "NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326) changed to 5 parts,
2) 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., weight average molecular weight 35000, 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass), polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd.) , weight average molecular weight 30000) changed to 10 parts,
3) In addition, 20 parts of a 50% solids MEK solution of 4,4-Diaminodiphenylmethane was used.
A resin composition 15 was obtained in the same manner as in Example 3 except for the above matters.

[Example 16. Preparation of resin composition 16]
In Example 3,
1) 20 parts of an allyl group-containing phenol resin (allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240) is added to an allyl-based non-solid curing agent having a benzoxazine ring ("ALP-d" manufactured by Shikoku Kasei Kogyo Co., Ltd., MEK solution with a solid content of 65%) Change to 20 parts,
2) 33.3 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., weight average molecular weight 35000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), polyester resin (“OKP4HT” manufactured by Osaka Gas Chemicals Co., Ltd.) , weight average molecular weight 50000) was changed to 10 parts.
A resin composition 16 was obtained in the same manner as in Example 3 except for the above matters.

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 added to an allyl-based non-solid curing agent having a benzoxazine ring (Shikoku Kasei Kogyo Co., Ltd. "ALP-d", MEK solution with a solid content of 65%) changed to 20 parts,
2) 10 parts of a hydrogenated styrene thermoplastic elastomer (“H1043” manufactured by Asahi Kasei Co., Ltd., weight average molecular weight 35000), polyamideimide resin (“Unidic V-8000” manufactured by DIC Corporation, weight average molecular weight 11000, non-volatile component 40 mass % ethyl diglycol acetate solution) changed to 25 parts,
3) 10 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC, a toluene solution with an active group equivalent of 223 and a solid content of 65% by mass) was added to a bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical). , an epoxy equivalent of about 180) to 5 parts.
A resin composition 17 was obtained in the same manner as in Example 8 except for the above matters.

[Example 18. Preparation of resin composition 18]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240), an allyl-based non-solid curing agent having an isocyanuric ring ( "L-DAIC" manufactured by Shikoku Kasei Co., Ltd.) Changed to 13 parts,
2) 33.3 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., weight average molecular weight 35000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), polyester resin (“OKP4HT” manufactured by Osaka Gas Chemicals Co., Ltd.) , weight average molecular weight 50000) was changed to 10 parts.
A resin composition 18 was obtained in the same manner as in Example 3 except for the above matters.

[Example 19. Preparation of resin composition 19]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240), an allyl-based non-solid curing agent having an isocyanuric ring ( Triallyl isocyanurate, "TAIC" manufactured by Nippon Kasei Co., Ltd., molecular weight 249) changed to 13 parts,
2) 33.3 parts of phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35000, 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass), polycarbonate resin (manufactured by Mitsubishi Gas Chemical Company "FPC2136" , weight average molecular weight 30000) was changed to 10 parts.
A resin composition 19 was obtained in the same manner as in Example 3 except for the above matters.

[Example 20. Preparation of resin composition 20]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (allylic non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240), an allyl non-solid curing agent (ortho diallyl phthalate, "Daiso Dap Monomer" manufactured by Osaka Soda Co., Ltd., molecular weight 246) changed to 13 parts,
2) 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight of 35000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), 20 mass of the polyimide resin obtained in Synthesis Example % of the varnish was changed to 50 parts.
A resin composition 20 was obtained in the same manner as in Example 3 except for the above matters.

[Example 21. Preparation of resin composition 21]
In Example 3,
1) 20 parts of an allyl group-containing phenolic resin (allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenol equivalent 240), diallyl cyclohexanedicarboxylate (allyl-based non-solid curing agent , "MDAC" manufactured by Osaka Soda Co., Ltd., molecular weight 252) changed to 13 parts,
2) 33.3 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., weight average molecular weight 35000, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), polyester resin ("OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd.) , weight molecular weight 50000) was changed to 10 parts.
A resin composition 21 was obtained in the same manner as in Example 3 except for the above matters.

[Example 22. Preparation of resin composition 22]
Biphenyl aralkyl type maleimide resin (manufactured by Nippon Kayaku Co., Ltd. "MIR-3000-70MT", maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution with 70% non-volatile content) 180 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30"", weight average molecular weight 35000, 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass) 33.3 parts, 20 parts of toluene, 20 parts of MEK, diallyl cyclohexanedicarboxylate ("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 of about 180) 5 parts, triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, a solid with a hydroxyl equivalent of about 151 50% 2-methoxypropanol solution) 3 parts, active ester curing agent (manufactured by DIC "HPC-8000-65T", active group equivalent 223, solid content 65 wt% toluene solution) 5 parts, polymerization initiator ("Perbutyl C" manufactured by NOF Corporation) 0.5 parts, curing accelerator (1B2PZ solid content 2.5% MEK solution) 2 parts, inorganic filler (vinyl coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. " 150 parts of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm)) surface-treated with “KBM1003”), an inorganic filler (phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. “KBM573 ”) surface-treated spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm)) was uniformly dispersed in a high-speed rotating mixer to obtain a resin composition 22.

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

[Comparative Example 1. Preparation of comparative resin composition 1]
In Example 3, 20 parts of allyl group-containing phenolic resin (“MEH-8000H” manufactured by Meiwa Kasei Co., Ltd., phenol equivalent: 240) was not used.
Comparative resin composition 1 was obtained in the same manner as in Example 3 except for the above matters.

[Comparative Example 2. Preparation of comparative resin composition 2]
In Example 11, 10 parts of the acid anhydride group-containing vinyl resin ("EF-40" manufactured by CRAY VALLEY, weight average molecular weight 11000) was not used.
Comparative resin composition 2 was obtained in the same manner as in Example 11 except for the above matters.

[Comparative Example 3. Preparation of comparative resin composition 3]
In Example 2, 180 parts of a biphenyl aralkyl-type maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution with a non-volatile content of 70%) was added to polyphenylmethane. It was changed to 126 parts of 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 matters.

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

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

Resin Compositions 1 to 23 and Comparative Resin Compositions 1 to 3 were each uniformly coated on a support with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and the temperature was adjusted from 70° C. to 95° C. C. for 4 minutes to form a resin composition layer on the support. Next, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) was attached as a protective film to the surface of the resin composition layer not bonded to the support. As a result, a resin sheet A having a support, a resin composition layer, and a protective film in this order was obtained.

[Measurement of Peel Strength of Plated Conductor Layer]
(1) Preparation of inner layer substrate Glass cloth-based epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic “R1515A”) on which the inner layer circuit is formed. The copper surface was roughened by etching by 1 μm with an etchant (“CZ8101” manufactured by MEC).

(2) Lamination of resin sheet The protective film was peeled off from the resin sheet A to expose the resin composition layer. Both surfaces of the inner layer substrate were laminated so that the resin composition layer was in contact with the inner layer substrate using a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"). Lamination was carried out by pressure bonding for 30 seconds at 120° C. and pressure of 0.74 MPa after reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

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

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

(5) Formation of Conductor Layer A conductor layer was formed on the roughened surface of the insulating layer according to the semi-additive method. That is, the roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Then, after annealing by heating at 150° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm, and 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 conductor layer was measured according to Japanese Industrial Standards (JIS C6481). Specifically, the conductor layer of evaluation board B was cut into a portion having a width of 10 mm and a length of 100 mm. The load (kgf/cm) was measured when 35 mm was peeled off to obtain the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[Measurement of Copper Foil Peeling Strength]
(1) Surface treatment of copper foil The glossy surface of “3EC-III” (Electrolytic copper foil, 35 μm) manufactured by Mitsui Kinzoku Mining Co., Ltd. was etched by 1 μm with a micro-etching agent (“CZ8101” manufactured by MEC Co., Ltd.) to form a copper surface. It was roughened, then rust-proofed (CL8300), and heat-treated for 30 minutes in an oven at 130° C. This copper foil is called a CZ copper foil.

(2) Preparation of inner layer substrate Both sides of a glass cloth-based epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) on which an inner layer circuit is formed are micro-coated. The copper surface was roughened by etching by 1 μm with an etchant (“CZ8101” manufactured by MEC).

(3) Lamination of Copper Foil and Formation of Insulating Layer The protective film was removed from the resin sheet A to expose the resin composition layer. Both surfaces of the inner layer substrate were laminated so that the resin composition layer was in contact with the inner layer substrate using a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"). Lamination was carried out by pressure bonding for 30 seconds at 120° C. and pressure of 0.74 MPa after reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less. Then, hot pressing 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, a sample A was produced by curing the resin composition layer under curing conditions of 200° C. for 90 minutes to form an insulating layer.

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

[Measurement of dielectric properties (dielectric constant, dielectric loss tangent)]
The protective film was peeled off from the resin sheet A produced in 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 resulting cured product is referred to as “evaluation cured product C”. The cured product C for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm. Using HP8362B manufactured by Agilent Technologies, the permittivity 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 cavity resonance perturbation method. Three test pieces were measured, and the average value was calculated.
In addition, the cured product C for evaluation of Comparative Example 2, which did not use the component (C), had a weak strength and was difficult to handle. Therefore, the dielectric properties of Comparative Example 2 could not be measured.

[Evaluation of laminating property]
(1) Preparation of inner layer substrate Glass cloth-based epoxy resin double-sided copper-clad lamination with a conductor thickness of 35 μm and a comb-like conductor pattern of L (line: wiring width) / S (space: interval width) = 160 μm / 160 μm. Both sides of the plate (substrate thickness 0.8 mm, Panasonic's "R1515A") were etched by 1 μm with a micro-etching agent (Mec's "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 (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), a glass cloth was applied so that the resin composition layer was in contact with the glass cloth-based epoxy resin double-sided copper-clad laminate. Both sides of the substrate epoxy resin double-sided copper-clad laminate were laminated. Lamination was carried out by pressure bonding for 30 seconds at 120° C. and pressure of 0.74 MPa after reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

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

(4) Lamination property evaluation The value of the unevenness difference (Rt: maximum peak-to-valley) between the conductor and the other part in the insulating layer of the cured substrate D is a non-contact surface roughness meter (WYKO NT3300) in VSI mode with a 10-fold lens with a measurement range of 1.2 mm×0.91 mm. If no voids were generated after lamination and the difference in unevenness between the conductor and other areas was less than 5 µm, the result was marked as "○". A case where the difference was 5 μm or more was evaluated as “Δ”, and a case where voids occurred after lamination was evaluated as “×”.

In Examples 1 to 23, even if the components (D) to (H) are not contained, it has been confirmed that results similar to those of the above Examples are obtained, albeit to varying degrees.

Claims (17)

(A) a maleimide compound having a biphenyl-type structure;
(B) a liquid or semi-solid curing agent, and (C) a high molecular weight component, a resin composition comprising
Component (B) is 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), or a carboxylic acid having a cyclic structure. A resin composition comprising at least one selected from an allyl-based non-solid curing agent having an acid derivative and a maleimide-based non-solid curing agent represented by the following general formula (B-6).

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

(In general formula (B-6), M ⁴ , M ⁶ and M ⁷ each independently represent an optionally substituted alkylene group having 5 or more carbon atoms, and M ⁵ is each independently substituted represents a divalent group having an aromatic ring which may have a group, R ³¹ and R ³² each independently represents an alkyl group having 5 or more carbon atoms, t2 represents an integer of 0 to 10, u1 and u2 each independently represent an integer of 0 to 4.) The resin composition according to claim 1, wherein component (A) is represented by the following formula (A-3).

In formula (A- ³ ), R ³ and R ⁸ represent a maleimide group; R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group; Each R ¹⁰ independently represents 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; n represents an integer of 1 to 100; 3. 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 when the non-volatile component in the resin composition is 100% by mass. (B) component 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 any one of claims 1 to 3, wherein the atoms constituting the ring skeleton in the cyclic group containing an alicyclic structure contain or do not contain heteroatoms. 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,
The resin composition according to any one of claims 1 to 3, wherein the carboxylic acid having a cyclic structure is at least one selected from isocyanuric acid, diphenic acid, phthalic acid, and cyclohexanedicarboxylic acid. (B) component contains the maleimide-based non-solid curing agent,
The resin composition according to any one of claims 1 to 3, wherein the maleimide-based non-solid curing agent contains a compound represented by the following formula (3).

The content of component (B) is 0.1% by mass or more and 15% by mass or less when the non-volatile component in the resin composition is 100% by mass, according to any one of claims 1 to 6. Resin composition. The resin composition according to any one of claims 1 to 7, wherein component (C) is a thermoplastic resin. The resin composition according to claim 8, wherein the thermoplastic resin is at least one selected from polyimide resins, polycarbonate resins and phenoxy resins. The content of component (C) is 0.5% by mass or more and 10% by mass or less when the non-volatile component in the resin composition is 100% by mass, according to any one of claims 1 to 9. Resin composition. (D) The resin composition according to any one of claims 1 to 10, further comprising an inorganic filler. 12. The resin composition according to claim 11, wherein the content of 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 12, which is used for forming an insulating layer. The resin composition according to any one of claims 1 to 13, which is used for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of claims 1 to 14 provided on the support. 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 14. A semiconductor device comprising the printed wiring board according to claim 16 .

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