KR20200097645A - Resin composition - Google Patents

Abstract

The present invention provides: a resin composition capable of obtaining a cured product having excellent lamination properties, dielectric properties and adhesion; a resin sheet comprising the resin composition; and a printed wiring board and a semiconductor device including an insulating layer formed by using the resin composition. The resin composition comprises: (A) a maleimide compound having a biphenyl-type structure, (B) a liquid or semi-solid curing agent, and (C) a high molecular weight component.

Description

Resin composition {RESIN COMPOSITION}

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

As a manufacturing technique of a printed wiring board, a manufacturing method using a build-up method in which an insulating layer and a conductor layer are alternately stacked and stacked is known.

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

[Patent Document 1] Japanese Unexamined Patent Application Publication No. 2018-053092

In recent years, there is a demand for further improvement of dielectric properties such as dielectric constant and dielectric loss tangent of an insulating layer, and further improvement of adhesion, including peel strength and copper foil peel strength between a conductive layer formed by plating.

In general, when a maleimide compound is contained in a resin composition, the dielectric properties become excellent. However, since the maleimide compound usually has a high softening point, when the maleimide compound is included in the resin composition, the resin composition and its cured product become brittle. In addition, when a resin sheet containing a resin composition containing a maleimide compound is laminated on a substrate with irregularities to form an insulating layer, the surface of the insulating layer on the opposite side of the substrate follows the irregularities of the substrate and the flatness of the insulating layer This may decrease and lamination property may be inferior.

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

The present inventors, as a result of earnestly examining the above problems, found that the above problems could be solved by containing a predetermined maleimide compound, a liquid or semi-solid curing agent and a high molecular weight component, and came to complete the present invention. .

That is, the present invention includes the following contents.

[1] (A) a maleimide compound having a biphenyl-type structure,

(B) a liquid or semi-solid curing agent and

(C) A resin composition containing a high molecular weight component.

[2] The resin composition according to [1], in which the component (A) is represented by the following general formula A-3.

[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, and R ⁹ and R ¹⁰ are each Independently, it 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, and n represents an integer of 1 to 100.

[3] The resin composition according to [1] or [2], wherein the content of the component (A) is 10% by mass or more and 40% by mass or less when the nonvolatile component in the resin composition is 100% by mass.

[4] Component (B) is at least one selected from amine-based non-solid curing agents, (meth)acrylic non-solid curing agents, allyl-based non-solid curing agents, maleimide-based non-solid curing agents, and butadiene-based non-solid curing agents, [1] The resin composition according to any one of] to [3].

[5] The resin composition according to [4], in which the component (B) is at least any one of an allyl-based non-solid curing agent and a maleimide-based non-solid curing agent.

[6] The resin composition according to any one of [1] to [5], wherein the content of the component (B) is 0.1% by mass or more and 15% by mass or less when the nonvolatile component in the resin composition is 100% by mass.

[7] The resin composition according to any one of [1] to [6], wherein the component (C) is a thermoplastic resin.

[8] The resin composition according to [7], wherein the thermoplastic resin is at least one selected from polyimide resin, polycarbonate resin, and phenoxy resin.

[9] The resin composition according to any one of [1] to [8], wherein the content of the component (C) is 0.5% by mass or more and 10% by mass or less when the nonvolatile component in the resin composition is 100% by mass.

[10] (D) The resin composition according to any one of [1] to [9], further including an inorganic filler.

[11] The resin composition according to [10], wherein the content of the component (D) is 50% by mass or more when the nonvolatile 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 provided on the support and containing the resin composition according to any one of [1] to [13].

[15] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [13].

[16] A semiconductor device comprising the printed wiring board according to [15].

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 comprising the resin composition; It is possible to provide a printed wiring board and a semiconductor device including an insulating layer formed by using the resin composition.

1 is a schematic side view showing an example of two test tubes used for determination of a liquid state, a semi-solid state, and a solid state of a thermosetting resin.

Hereinafter, the present invention will be described in detail based on its preferred embodiment. However, the present invention is not limited to the following embodiments and examples, and can be carried out with arbitrary changes without departing from the claims of the present invention and their equivalent ranges.

[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, a liquid or semi-solid curing agent is appropriately referred to as a ``non-solid curing agent''), and (C) A high molecular weight component is included. In the present invention, by containing the components (A) to (C), it is possible to obtain a cured product having excellent lamination properties and excellent dielectric properties and adhesion.

The resin composition may be combined with components (A) to (C), and may further contain optional components. As an arbitrary component, (D) inorganic filler, (E) hardening agent, (F) hardening accelerator, (G) epoxy resin, (H) polymerization initiator, and (I) other additives, etc. are mentioned, for example. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Maleimide compound having a biphenyl type structure>

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

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

[Formula A-1]

[Formula A-2]

In Formula A-2, R ¹ and R ² each independently represent a substituent. a and b each independently represent an integer of 0 to 4. * Represents a bonding hand.

As a substituent represented by R ¹ and R ² , for example, a halogen atom, -OH, -OC _1-10 alkyl group, -N (C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6-10 aryl group , -NH ₂ , -CN, -C(O)OC _1-10 alkyl group, -COOH, -C(O)H, -NO ₂ , and the like. Here, the term "C _xy " (x and y are positive integers, and satisfy x<y) indicates that the number of carbon atoms in the organic group immediately following the term is x to y. For example, the expression "C _1-10 alkyl group" represents an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring or a condensed ring.

The substituent may further have a substituent (hereinafter, referred to as "secondary substituent" in some cases). As the secondary substituent, unless otherwise specified, the same as the substituent may be used.

Each of a and b independently represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1, and still more preferably 0.

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

Component (A) preferably has any one of an aliphatic hydrocarbon group and an aromatic hydrocarbon group in addition to a biphenyl-type structure from the viewpoint of obtaining a cured product having excellent dielectric properties, and has both an aliphatic hydrocarbon group and an aromatic hydrocarbon group. It is more preferable. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring. However, the aromatic hydrocarbon group does not need to be composed of only an aromatic ring, and a part thereof may contain a chain structure or an alicyclic hydrocarbon group, and the aromatic ring may be monocyclic, polycyclic or heterocyclic.

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

As the aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferable, an arylene group and an aralkylene group are more preferable, and an arylene group is still more preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is still more preferable. As such arylene group, a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, etc. are mentioned, for example. 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 still more preferable. Examples of such aralkylene groups include benzyylene groups and groups having a biphenylene-methylene structure. Among these, a phenylene group, a benzylene group, and a group having a biphenylene-methylene structure are preferable, and a phenylene group is more preferable.

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

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

It is preferable that the component (A) has, for example, a structure represented by the following formula (A-3).

[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, and R ⁹ and R ¹⁰ are each Independently, it 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, and n represents an integer of 1 to 100.

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

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 More preferable. The alkyl group may be linear, branched or cyclic. As such an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, etc. are mentioned, for example.

The aryl group in R ⁴ , R ⁵ , R ⁶ and R ⁷ is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and an aryl group having 6 to 10 carbon atoms More preferable. The aryl group may be a monocyclic ring or a condensed ring. As such aryl group, a phenyl group, a naphthyl group, an anthracenyl group, etc. are mentioned, for example.

The alkyl group and the aryl group for R ⁴ , R ⁵ , R ⁶ and R ⁷ may have a substituent. As a substituent, it 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 to 100, preferably 1 to 50, more preferably 1 to 20, and even more preferably 1 to 5.

R ³ and R ⁸ represent a maleimide group, and the maleimide group is directly bonded to an aromatic hydrocarbon group. The maleimide group represented by R ³ and R ⁸ is directly bonded to any one of the ortho position, the meta position, and the para position based on the (CH ₂ ) _m1 or (CH ₂ ) _m2 bonded to the aromatic hydrocarbon group. It is preferred, and it is preferred that it is directly bonded to the para position.

As the component (A), it is preferable to have a structure represented by the general formula (A-4).

[Formula A-4]

In Formula A-4, R ¹¹ and R ¹⁶ represent a maleimide 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 to 10, and n1 represents an integer of 1 to 100.

R ¹¹ and R ¹⁶ represent a maleimide group, and are the same as R ³ and R ⁸ in Formula A-3.

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

m3 and m4 each independently represent an integer 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.

As the component (A), it is preferable to have a structure represented by the general formula A-5.

[Formula A-5]

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

R ¹⁷ and R ¹⁸ 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.

As the component (A), a commercial item can be used. As a commercial item, "MIR-3000-70MT" by Nippon Kayaku Corporation is mentioned, for example.

The content of the component (A) is, from the viewpoint of obtaining a cured product having excellent dielectric properties, when the nonvolatile component in the resin composition is 100% by mass, preferably 10% by mass or more, more preferably 20% by mass or more, More preferably, it is 25 mass% or more, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less, More preferably, it is 30 mass% or less. In addition, in the present invention, the content of each component in the resin composition is a value when the nonvolatile 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 a component (B). By including the component (B) in the resin composition, it becomes possible to improve the lamination property, and it becomes possible to obtain a cured product having further excellent adhesion. Component (B) may be used individually by 1 type, and may use 2 or more types together.

Here, the determination of liquid, semi-solid, and solid is carried out in accordance with the second "Liquid Confirmation Method" of the Holy Spirit (Heisei 1st Year's Ordinance of Autonomy No. 1) on the test and appearance of dangerous substances. The specific determination method is as follows.

(1) device

Constant temperature water bath:

It is equipped with a stirrer, heater, thermometer, and automatic temperature controller (one that can control the temperature at ±0.1℃), and uses a depth of 150mm or more.

In addition, in the determination of the thermosetting resin used in the examples to be described later, a combination of a low-temperature constant temperature water bath (type BU300) manufactured by Yamato Chemical Co., Ltd. and an immersion thermostat thermomate (type BF500) was used, and about 22 liters of tap water were used at low temperature. Put it in a constant temperature water tank (type BU300), turn on the power of the thermomate (type BF500) assembled there, set the temperature to the set temperature (20℃ or 60℃), and set the water temperature to the set temperature ±0.1℃ thermomate (type BF500) Although it was finely adjusted to, any device that can be adjusted in the same manner can be used.

examiner:

As the test tube, as shown in Fig. 1, it is made of flat-bottom cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm, markings 11A and 12B are attached to positions at a height of 55 mm and 85 mm from the bottom of the tube, respectively, and the entrance of the test tube is a rubber stopper ( The entrance of the test tube is sealed with a rubber stopper (13b) that has the same mark on the same size as the test tube for liquid determination (10a) sealed with 13a) and has a hole in the center for inserting and supporting the thermometer. A test tube 10b for measuring temperature in which a thermometer 14 is inserted into the stopper 13b is used. Hereinafter, the mark at a height of 55 mm from the bottom of the pipe is referred to as "line A", and the mark at a height of 85 mm from the bottom of the pipe is referred to as "line B".

As the thermometer 14, a freezing point measurement (SOP-58 scale range of 0 to 100°C) specified in JIS B7410 (1982) “Glass thermometer for petroleum testing” is used, but the temperature range of 0 to 100°C can be measured. It is good if there is one.

(2) Procedure of the test

Samples left for at least 24 hours under atmospheric pressure at a temperature of 60±5°C were placed in a test tube 10a for liquid determination shown in Fig. 1(a) and a test tube 10b for temperature measurement shown in Fig. 1(b) up to line 11A, respectively. Put in. The two test tubes (10a, 10b) are set upright in a low-temperature constant temperature water bath so that the 12B line is below the water surface. The thermometer should have its lower end 30mm below line 11A.

After the sample temperature reaches the set temperature ±0.1℃, maintain it for 10 minutes. After 10 minutes, the test tube for liquid determination (10a) was taken out of the low-temperature constant temperature water bath, immediately fell horizontally on a horizontal test table, and the time the tip of the liquid level in the test tube moved from line 11A to line 12B was measured with a stopwatch and recorded. do.

Similarly, for samples left at a temperature of 20±5°C under atmospheric pressure for 24 hours or longer, the same test was performed as in the case where they were left at a temperature of 60±5°C for more than 24 hours, and the tip of the liquid level in the test tube was 12B from 11A line. Measure the time traveled to the line with a stopwatch and record it.

At 20° C., it is determined that the measured time is within 90 seconds as liquid.

At 20°C, the measured time exceeds 90 seconds, and at 60°C, it is judged as a semi-solid that the measured time is within 90 seconds.

At 60° C., it is judged as a solid phase that the measured time exceeds 90 seconds.

As the component (B), a liquid or semi-solid component and having a function of curing the component (A) can be used. As such a non-solid curing agent, for example, it is preferably at least one selected from allyl-based non-solid curing agents, maleimide-based non-solid curing agents, (meth)acrylic non-solid curing agents, amine-based non-solid curing agents, and butadiene-based non-solid curing agents. And, it is more preferable that it is at least any one of an allyl type non-solid curing agent and a maleimide type non-solid curing agent.

An allyl-based non-solid curing agent is a compound that is liquid or semi-solid and has at least one allyl group in a molecule. The allyl group reacts with the maleimide group in the component (A) and has a function of curing the component (A). The allyl-based non-solid curing agent preferably has one or more allyl groups per molecule, and more preferably has two or more allyl groups. The lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

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

In the allyl-based non-solid curing agent having a benzoxazine ring, the allyl group is bonded to any one of the nitrogen atom constituting the benzoxazine ring and the carbon atom constituting the benzoxazine ring from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferable to do it, and it is more preferable to bond with a carbon atom.

The allyl-based non-solid curing agent having a benzoxazine ring is preferably an allyl-based non-solid curing agent having a benzoxazine ring represented by the following formula (B-1).

[Formula B-1]

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 any of a q-valent aromatic hydrocarbon group and a q-valent aliphatic hydrocarbon group. For example, when q is 2, R ²² is preferably a group consisting of an arylene group, an alkylene group, an oxygen atom, or a combination of two or more divalent groups, and an arylene group or a combination of two or more divalent groups It is more preferable that the group consists of, and the group which consists of a combination of 2 or more types of divalent groups is still more preferable.

As the arylene group for R ²² , an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 15 carbon atoms is more preferable, and an arylene group having 6 to 12 carbon atoms is still more preferable. As a specific example of an arylene group, a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, etc. are mentioned, and a phenylene group is preferable.

As the alkylene group for R ²² , an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is still more preferable. As a specific example of an alkylene group, a methylene group, an ethylene group, a propylene group, etc. are mentioned, for example, A methylene group is preferable.

Examples of the group consisting of a combination of two or more divalent groups for R ²² include, for example, a group in which at least one arylene group and at least one oxygen atom are bonded; For example, a group in which at least one arylene group and at least one alkylene group are bonded, such as a group having an arylene-alkylene-arylene structure; A group in which at least one alkylene group and at least one oxygen atom are bonded; A group in which at least one arylene group and at least one alkylene group and at least one oxygen atom are bonded, and the like. Do.

q represents an integer of 1 to 4, preferably an integer of 1 to 3, and 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 even more preferably 1. p2 represents an integer of 0 to 2, represents 0 or 1, and 0 is preferred.

Examples of the allyl-based non-solid curing agent having a phenol ring include a cresol resin containing an allyl group, a novolak-type phenol resin containing an allyl group, and a cresol novolak resin containing an allyl group. 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).

[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 , r represents an integer of 0 to 3.

R ²³ to R ²⁵ each independently represent an allyl group. In Formula B-2, the number of allyl groups is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 25 or less, more preferably 10 or less, More preferably, it is 5 or less.

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

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

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

It is preferable that the allyl-type non-solid curing agent having an epoxy group contains two or more epoxy groups per molecule. Further, the allyl-based non-solid curing agent having an epoxy group preferably has an aromatic structure, and when two or more allyl-based non-solid curing agents having an epoxy group are used, it is more preferable that at least one has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles. As the allyl-based non-solid curing agent having an epoxy group, it is preferable to have a bisphenol structure, and examples of the bisphenol structure include bisphenol A type, bisphenol F type, bisphenol AF type, and the like, among others, the effect of the present invention. From the viewpoint of obtaining remarkably, bisphenol A type is preferable.

As the allyl-based non-solid curing agent having a carboxylic acid derivative having a cyclic structure, allyl carboxylic acid having a cyclic structure is preferable. As the cyclic structure, any of a cyclic group including an alicyclic structure and a cyclic group including an aromatic ring structure may be used. In addition, the cyclic group may have a ring skeleton formed by a hetero atom other than a carbon atom. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, A nitrogen atom is preferable. One hetero atom may be in the ring and may have two or more. The carboxylic acid derivative having a cyclic structure improves the compatibility and dispersibility of the resin varnish by the network structure of the cyclic structure, and as a result, it becomes possible to improve the lamination property, and thus it is possible to obtain a cured product having further excellent adhesion. It becomes possible.

As a carboxylic acid having a cyclic structure, isocyanuric acid, diphenic acid, phthalic acid, cyclohexanedicarboxylic acid, etc. are mentioned, for example. As an allyl-based non-solid curing agent having a carboxylic acid derivative having a cyclic structure, for example, allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl difenate, allyl difenate, orthodiallylphthalate, meta Diallyl phthalate, paradiallyl phthalate, allyl cyclohexanedicarboxylic acid, diallyl cyclohexanedicarboxylic acid, and the like.

Allyl-based non-solid curing agents may be commercially available. As a commercial item, For example, "MEH-8000H" and "MEH-8005" manufactured by Maywa Kasei Co., Ltd. (allyl type non-solid curing agent having a phenol ring); "RE-810NM" manufactured by Nippon Kayaku Co., Ltd. (Allyl-based non-solid curing agent having an epoxy group); "ALP-d" by Shikoku Kasei Kogyo Co., Ltd. (allyl type non-solid curing agent having a benzoxazine ring); "L-DAIC" manufactured by Shikoku Kasei Kogyo Co., Ltd. (allyl-based non-solid curing agent having an isocyanuric ring); "TAIC" manufactured by Nippon Kasei Co., Ltd. (Allyl-based non-solid curing agent having an isocyanol ring (triallyl isocyanurate)); "MDAC" manufactured by Osaka Soda (Allyl-based non-solid curing agent having a cyclohexanedicarboxylic acid derivative); "DAD" (difensan diallyl) manufactured by Nisshoku Techno Fine Chemicals; "Diso dapp monomer" (ortho diallyl phthalate) manufactured by Osaka Soda Corporation, etc. are mentioned.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the allyl group equivalent of the allyl-based non-solid curing agent is preferably 20 g/eq. To 1,000 g/eq., more preferably 50 g/eq. To 500 g/eq., more preferably 100 g/eq. To 300 g/eq. The allyl group equivalent is the mass of an allyl-based non-solid curing agent containing 1 equivalent of an allyl group.

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

It is preferable that the maleimide-based non-solid curing agent contains at least any 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, and still more preferably 40 or less. These alkyl groups may be linear, branched, or cyclic, and among them, linear is preferable. As such an alkyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. are mentioned, for example. An alkyl group having 5 or more carbon atoms may have as a substituent for an alkylene group having 5 or more carbon atoms.

The number of carbon atoms of 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, and still more preferably 40 or less. These alkylene groups may be linear, branched, or cyclic, and among them, linear is preferable. Here, the cyclic alkylene group is a concept including a case consisting of only a cyclic alkylene group and a case including both a linear alkylene group and a cyclic alkylene group. As such an alkylene group, for example, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, and hexatriacone And a group having a tylene group, an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

From the viewpoint of remarkably obtaining the effect of the present invention, 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.

The alkyl group having 5 or more carbon atoms and the 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 or a condensed ring. Examples of the rings formed by bonding to each other include a cyclohexane ring.

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms preferably do not have a substituent, but may have a substituent. As a substituent, it is the same as a substituent represented by R ¹ in the above-described general formula A-2.

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

The number of maleimide groups per molecule of the maleimide-based non-solid curing agent may be 1, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less, particularly preferably 3 Below. 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.

The maleimide-based non-solid curing agent is preferably a maleimide-based non-solid curing agent represented by the following formula (B-3).

[Formula B-3]

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

M represents an alkylene group having 5 or more carbon atoms which may have a substituent. The alkylene group of M is the same as the alkylene group having 5 or more carbon atoms. The substituent of M is the same as the substituent represented by R ¹ in the 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. As a divalent linking group, 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, a carbon atom Alkyl group of number 1 to 3), oxygen atom, sulfur atom, C(=O)NR ⁰ -, divalent group derived from phthalimide, divalent group derived from pyromellitic diimide, and two or more divalent groups And a group consisting of a combination of. A group consisting of a combination of 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 combination of two or more divalent groups, has 5 carbon atoms. You may have the above alkyl group as a substituent. The divalent group derived from phthalimide refers to a divalent group derived from phthalimide, and is specifically a group represented by the general formula (A). The divalent group derived from pyromellitic diimide refers to a divalent group derived from pyromellitic diimide, and specifically is a group represented by the formula (B). In the formula, "*" represents a bonding hand.

[Formula A]

[Formula B]

The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms Do. These alkylene groups may be linear, branched or cyclic. As such an alkylene group, for example, methylethylene group, cyclohexylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, Heptadecylene group, hexatriacontylene group, group having octylene-cyclohexylene structure, group having octylene-cyclohexylene-octylene structure, group having propylene-cyclohexylene-octylene structure, etc. Can be lifted.

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

The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, and particularly preferably an alkynylene group having 2 to 10 carbon atoms Do. These alkynylene groups may be linear, branched, or cyclic. As such alkynylene group, a methylethynylene group, a cyclohexynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octinylene group, etc. are mentioned, for example.

The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, and even more preferably an arylene group having 6 to 14 carbon atoms And an arylene group having 6 to 10 carbon atoms is even more preferable. As an arylene group, a phenylene group, a naphthylene group, an anthracenylene group, etc. are mentioned, for example.

The alkylene group, alkenylene group, alkynylene group, and arylene group which are the divalent linking group in L may have a substituent. The substituent is the same as the substituent represented by R ¹ in the general formula A-2, and is 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 a phthalimide, and a divalent group consisting of a combination of an oxygen atom; A divalent group consisting of a combination of a phthalimide-derived divalent group, an oxygen atom, an arylene group, and an alkylene group; And a divalent group composed of a combination of an alkylene group and a divalent group derived from pyromellitic diimide. 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. Further, a 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, an alkylene group having 1 to 50 carbon atoms which may have a substituent, and an alkyl group having 5 or more carbon atoms. , A divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a divalent group consisting of a combination of two or more of these groups is preferable. Among them, as L, an alkylene group; A divalent group having a structure of a divalent group derived from an alkylene group-phthalimide-oxygen atom-phthalimide; A divalent group having a structure of a divalent group derived from an alkylene group-phthalimide-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-phthalimide; A divalent group having a structure of a divalent group derived from alkylene-pyromellitic diimide is more preferable.

The maleimide-based non-solid curing agent represented by the general formula (B-3) is preferably a maleimide-based non-solid curing agent represented by the general formula (B-4).

[Formula B-4]

In Formula B-4, M ¹ each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent, and A each independently has an alkylene group or a substituent having 5 or more carbon atoms which may have a substituent It represents a divalent group having an aromatic ring which may be present. t represents an integer of 1 to 10.

Each M ¹ independently represents an alkylene group having 5 or more carbon atoms which may have a substituent. M ¹ is the same as M in Formula B-3.

Each A independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent. As the alkylene group in A, any of chain, branched and cyclic may be used, and among them, cyclic, that is, a cyclic alkylene group having 5 or more carbon atoms which may have a substituent is preferable. 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, even more preferably 40 or less. Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like. have.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by A include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, and an aromatic heterocyclic ring. Benzene ring, phthalimide ring. A pyromellitic diimide ring is preferred. That is, as a divalent group having an aromatic ring, a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, and a pyromellitic diimide ring which may have a substituent A divalent group having Examples of the divalent group having an aromatic ring include a group consisting of a combination of a divalent group derived from phthalimide and an oxygen atom; A group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group and an alkylene group; A group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; Divalent groups derived from pyromellitic diimide; And a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the formula (B-3).

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

The following groups are mentioned as a specific example of the group represented by A. In the formula, "*" represents a bonding hand.

The maleimide-based non-solid curing agent represented by Formula B-3 is preferably any one of the maleimide-based non-solid curing agent represented by Formula B-5 and the maleimide-based non-solid curing agent represented by Formula B-6.

[Formula B-5]

[Formula B-6]

In Formula B-5, M ² and M ³ each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, and R ³⁰ each independently represent an oxygen atom, an arylene group, an alkylene group, or these groups It represents a divalent group consisting of a combination of two or more of. t1 represents an integer of 1 to 10.

In Formula B-6, M ⁴ , M ⁶ and M ⁷ each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, and M ⁵ each independently have an aromatic ring which may have a substituent. Represents a divalent group, 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 alkylene group having 5 or more carbon atoms which may have a substituent. M ² and M ³ are the same as an alkylene group having 5 or more carbon atoms represented by M in the general formula (B-3), and a hexatriacontylene group is preferable.

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

Examples of the group consisting of a combination of two or more divalent groups for R ³⁰ include combinations of an oxygen atom, an arylene group and an alkylene group. The following groups are mentioned as a specific example of the group which consists of a combination of 2 or more types of divalent groups. In the formula, "*" represents a bonding hand.

M ⁴ , M ⁶ and M ⁷ each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent. M ⁴ , M ⁶ and M ⁷ are the same as an alkylene group having 5 or more carbon atoms which may have a substituent represented by M in the formula (B-3), and a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group It is preferable and an octylene group is more preferable.

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

As a specific example of the group represented by M ⁵ , the following groups are mentioned, for example. In the formula, "*" represents a bonding hand.

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-described alkyl group having 5 or more carbon atoms, preferably a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, and more preferably a hexyl group and an octyl group.

u1 and u2 each independently represent an integer of 1 to 15, and an integer of 1 to 10 is preferable.

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

[Formula 1]

[Formula 2]

[Chemical Formula 3]

As specific examples of the maleimide-based non-solid curing agent, ``BMI1500'' (a compound of Formula 1), ``BMI1700'' (a compound of Formula 2), and ``BMI689'' (a compound of Formula 3) manufactured by Designer Molecules Co., Ltd. are mentioned. .

From the viewpoint of remarkably obtaining the desired effect of the present invention, the maleimide group equivalent of the maleimide-based non-solid curing agent is preferably 50 g/eq. To 2,000 g/eq., more preferably 100 g/eq. To 1,000 g/eq., more preferably 150 g/eq. To 500 g/eq. The maleimide group equivalent is the mass of a maleimide-based non-solid curing agent containing 1 equivalent of a maleimide group.

The (meth)acrylic non-solid type curing agent is a liquid or semi-solid type, and is a curing agent containing an acryloyl group and a methacryloyl group, and combinations thereof. As the (meth)acrylic non-solid curing agent, it is preferable to have two or more (meth)acryloyl groups per molecule from the viewpoint of remarkably obtaining the desired effect of the present invention. The term "(meth)acryloyl group" includes an acryloyl group and a methacryloyl group, and combinations thereof.

It is preferable that the (meth)acrylic non-solid curing agent has a cyclic structure from the viewpoint of remarkably obtaining the desired effect of the present invention. As the cyclic structure, a divalent cyclic group is preferable. As the divalent cyclic group, any of a cyclic group including an alicyclic structure and a cyclic group including an aromatic ring structure may be used. Among them, it is preferable that it is a cyclic group containing an alicyclic structure from the viewpoint of remarkably obtaining the desired effect of the present invention.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the divalent cyclic group is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, preferably 20 or less, more preferably It is preferably 15-membered ring or less, more preferably 10-membered ring or less. Moreover, as a divalent cyclic group, a monocyclic structure may be sufficient and a polycyclic structure may be sufficient as it.

In the ring in the divalent cyclic group, the skeleton of the ring may be constituted by a hetero atom other than a carbon atom. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, and an oxygen atom is preferable. One hetero atom may be in the ring and may have two or more.

As a specific example of a divalent cyclic group, the following divalent groups (i) to (xi) are mentioned. Especially, as a divalent cyclic group, (x) or (xi) is preferable.

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

The (meth)acryloyl group may be directly bonded to a divalent cyclic group, or may be bonded through a divalent linking group. As a divalent linking group, for example, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O) N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like, and a group obtained by combining a plurality of these may be used. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms Rengi is more preferred. The alkylene group may be linear, branched or cyclic. As such an alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group, etc. are mentioned, for example, a methylene group, an ethylene group, 1,1 -Dimethylethylene group is preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is more preferable, and an alkenylene group having 2 to 5 carbon atoms is still more preferable. 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.

It is preferable that the (meth)acrylic non-solid curing agent is represented by the following formula (B-7).

[Formula B-7]

(In Formula B-7, R ³³ and R ³⁶ each independently represent an acryloyl group or a methacryloyl group, and R ³⁴ and R ³⁵ each independently represent a divalent linking group. Ring D is divalent. Represents a ring group)

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

R ³⁴ and R ³⁵ each independently represent a divalent linking group. As a divalent linking group, it is the same as a divalent linking group which may couple|bond with a (meth)acryloyl group.

Ring D represents a divalent cyclic group. As ring D, it is the same as the said divalent cyclic group. Ring D may have a substituent. As a substituent, it is the same as the substituent which the said 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.

As the (meth)acrylic non-solid curing agent, a commercially available product may be used. For example, "A-DOG" manufactured by Shinnakamura Kagaku Kogyo, "DCP-A" manufactured by Kyoeisha Kagaku Corporation, manufactured by Nippon Kayaku Corporation. "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA", "NK ester DCP" manufactured by Shinnakamura Kagaku Kogyo, etc. are mentioned. .

From the viewpoint of remarkably obtaining the desired effect of the present invention, the (meth)acryloyl group equivalent of the (meth)acrylic non-solid curing agent is preferably 30 g/eq. To 400 g/eq., more preferably 50 g/eq. To 300 g/eq., more preferably 75 g/eq. To 200 g/eq. The (meth)acryloyl group equivalent is the mass of the (meth)acrylic non-solid curing agent containing 1 equivalent of (meth)acryloyl group.

As the amine-based non-solid curing agent, a liquid or semi-solid amine curing agent can be used. In addition, examples of the amine-based non-solid curing agent include a curing agent having one or more amino groups per molecule, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like. From the viewpoint of showing the desired effect of the present invention, aromatic amines are preferred. The amine-based non-solid curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine.

As specific examples of the amine-based non-solid curing agent, 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-methylenedi-2,6-xylidine, m-phenylenediamine, m-c Silylenediamine, diethyltoluenediamine, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)propane, etc. Can be mentioned. Commercially available amine resins may be used. For example, "KAYABOND C-200S" manufactured by Nippon Kayaku, "KAYAHARD AA", "Kayahard AB", "Kayahard AS", and "Epi" manufactured by Mitsubishi Chemical Cure W", "jER Cure W", etc. are 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 included in the main chain or may be included in the side chain. In addition, the polybutadiene structure may be partially or entirely hydrogenated. Examples of the butadiene-based non-solid curing agent include hydrogenated polybutadiene skeleton-containing resin, hydroxy group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene. At least one resin selected from the group consisting of resins and urethane group-containing butadiene resins is more preferable.

As specific examples of the butadiene-based non-solid curing agent, Nippon Soda's "JP-100", CRAY VALLEY's "Ricon100", "Ricon150", "Ricon130MA8", "Ricon130MA13", "Ricon130MA20", "Ricon131MA5", " Ricon131MA10", "Ricon131MA17", "Ricon131MA20", "Ricon 184MA6", etc. are mentioned.

As the content of the component (B), it becomes possible to improve the lamination property, and from the viewpoint of obtaining a cured product having further excellent adhesion, when the nonvolatile component in the resin composition is 100% by mass, preferably 0.1% by mass or more, It is 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, still more preferably 5.5% by mass or less.

When the content in the case where the nonvolatile component in the resin composition of the component (B) is 100% by mass is set to b1, and the content in the case where the nonvolatile component in the resin composition of the component (A) is 100% by mass is set as a1 , a1/b1 is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, 4 or more, preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, It is 15 or less and 10 or less. By setting a1/b1 within such a range, it becomes possible to remarkably obtain the effect of the present invention.

<(C) High molecular weight component>

The resin composition contains a high molecular weight component as a component (C). By including the component (C) in the resin composition, the stress of the resin composition is relieved, and as a result, it becomes possible to obtain a cured product excellent in dielectric properties. The component (C) may be used alone or in combination of two or more.

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

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

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

Although it does not specifically limit as a diamine compound used to prepare a polyimide resin, For example, an aliphatic diamine compound and an aromatic diamine compound are mentioned.

As the aliphatic diamine compound, for example, 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1, Linear aliphatic diamine compounds such as 5-diaminopentane and 1,10-diaminodecane; Branched-chain aliphatic diamine compounds such as 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane and 2-methyl-1,5-diaminopentane; Alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4'-methylenebis(cyclohexylamine) compound; Dimer acid type diamine (hereinafter, also referred to as "dimer diamine"), and the like. The dimer acid type diamine means a diamine compound obtained by substituting two terminal carboxylic acid groups (-COOH) of a dimer acid with an aminomethyl group (-CH ₂ -NH ₂ ) or an amino group (-NH ₂ ). Dimeric 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 in the industry. have.

As an aromatic diamine compound, a phenylenediamine compound, a naphthalenediamine compound, a dianiline compound, etc. are mentioned, for example.

The phenylenediamine compound means a compound consisting of a benzene ring having two amino groups, and further, the benzene ring here may optionally have 1 to 3 substituents. The substituent here is not particularly limited. As a phenylenediamine compound, specifically, 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3 ,5-diaminobiphenyl, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, etc. are mentioned.

The naphthalenediamine compound means a compound consisting of a naphthalene ring having two amino groups, and further, the naphthalene ring here may optionally have 1 to 3 substituents. The substituent here is not particularly limited. Specific examples of the naphthalenediamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 2,3-diaminonaphthalene, and the like.

The dianiline compound means a compound containing two aniline structures in a molecule, and the two benzene rings among the two aniline structures may each optionally further have 1 to 3 substituents. The substituent here is not particularly limited. The two aniline structures in the dianiline compound may be directly bonded and/or bonded through 1 or 2 linker structures having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. . The thing in which two aniline structures are bonded by two bonds is included in a dianylene compound.

As a "linker structure" in the dianillin compound, specifically, -NHCO-, -CONH-, -OCO-, -COO-, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) _2- , -CH=CH-, -O-, -S-, -CO-, -SO ₂ -, -NH-, -Ph-, -Ph-Ph-, -C(CH ₃ ) ₂ -Ph-C( CH ₃ ) ₂ -, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph -O-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -,

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

In one embodiment, as the dianiline compound, specifically, 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether , 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4-aminophenyl4 -Aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2 -Bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)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-amino Phenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-dia Mino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4 -(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, etc. are mentioned.

As the diamine compound, a commercially available one may be used, or one synthesized by a known method may be used. The diamine compounds may be used alone or in combination of two or more.

The acid anhydride used to prepare a 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, naphthalene tetracarboxylic dianhydride, anthracene tetracarboxylic dianhydride, diphthalic dianhydride, and the like, preferably diphthalic dianhydride.

Benzenetetracarboxylic dianhydride means a benzene dianhydride having four carboxyl groups, and the benzene ring here 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 (same as the definition of the following formula 1B). Specific examples of the benzene tetracarboxylic dianhydride include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and the like.

The naphthalene tetracarboxylic dianhydride refers to a naphthalene dianhydride having four carboxyl groups, and 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 (same as the definition of the following formula 1B). Specific examples of the naphthalene tetracarboxylic dianhydride include 1,4,5,8-naphthalene tetracarboxylic dianhydride and 2,3,6,7-naphthalene tetracarboxylic dianhydride.

The anthracene tetracarboxylic dianhydride refers to an anthracene dianhydride having four carboxyl groups, and the anthracene ring here 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 (same as the definition of the following formula 1B). Specific examples of the anthracene tetracarboxylic dianhydride include 2,3,6,7-anthracene tetracarboxylic dianhydride and the like.

The diphthalic acid dianhydride refers to a compound containing two phthalic anhydrides in a molecule, and the two benzene rings in the two phthalic anhydrides may each optionally have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (same as the definition of the following general formula 1B). The two phthalic anhydrides in the diphthalic dianhydride may be bonded either directly or through a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

As diphthalic acid dianhydride, for example, formula 1B:

[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 are 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 represents a single bond or a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms,

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 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. n and m are preferably 0.

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

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

As diphthalic acid dianhydride, specifically, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetra Carboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-ratio Phenyltetracarboxylic 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'-diphenyl sulfone tetracarboxylic dianhydride 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, methylene-4, 4'-diphthalic dianhydride, 1,1-ethylnylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4 ,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene- 4,4'-diphthalic acid 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 2 Anhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride, and the like.

As the acid anhydride, a commercially available one may be used, or a compound synthesized by a known method or a method similar thereto may be used. The acid anhydride may be used singly or in combination of two or more.

Commercially available products can be used for the polyimide resin. As a commercial item, "Rikacoat SN20" and "Ricacoat PN20" manufactured by Shin-Nippon Rika Corporation are mentioned.

Polycarbonate resin is a resin having a carbonate structure. Examples of such resins include carbonate resins having no reactive groups, carbonate resins containing hydroxy groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing acid anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing urethane groups, Epoxy group-containing carbonate resins, etc. are mentioned. Here, the reactor refers to a functional group capable of reacting with other components such as a hydroxyl group, a phenolic hydroxyl group, a carboxy group, an acid anhydride group, an isocyanate group, a urethane group and an epoxy group.

The carbonate resin can be commercially available. As a commercial item, "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemicals, "T6002", "T6001" (polycarbonate diol) manufactured by Asai Kasei Chemicals, and "C-1090" and "C-2090" manufactured by Kurares. ", "C-3090" (polycarbonate diol), etc. are mentioned.

As a phenoxy resin, for example, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene And phenoxy resins having at least one skeleton selected from the group consisting of skeletons, anthracene skeletons, adamantane skeletons, terpene 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.

As specific examples of the phenoxy resin, "1256" and "4250" manufactured by Mitsubishi Chemical Co., Ltd. (both bisphenol A skeleton-containing phenoxy resins); "YX8100" by Mitsubishi Chemical Co., Ltd. (bisphenol S skeleton-containing phenoxy resin); "YX6954" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenolacetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nittetsu Chemical &Materials; Mitsubishi Chemical Co., Ltd. "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482", and the like.

Polyamideimide resin is a resin having an amidimide structure. The polyamideimide resin is a polyamideimide resin having an alicyclic structure in its molecular structure from the viewpoint of compatibility with other components in the resin composition, and a polyamideimide having a siloxane structure described in Japanese Unexamined Patent Application Publication No. Hei 05-112760. It is preferable to use a resin, a polyamideimide resin having a bulky branched chain structure, a polyamideimide resin using an asymmetric monomer as a raw material, a polyamideimide resin having a multi-branched structure, and the like.

Among them, the polyamideimide resin has an isocyanuric ring structure, 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. Polyamideimide resin having an 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 (i.e., isocyanol ring structure and alicyclic structure Polyamideimide resin having a wimide skeleton or an amide skeleton), (iii) a polyamideimide resin having a repeating unit including an isocyanol ring structure and an alicyclic structure (i.e., an isocyanol ring structure and an alicyclic structure and A polyamideimide resin having a repeating unit including a de skeleton or an amide skeleton) is more preferable.

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

Specific examples of the compound (C-1) include compounds represented by the following general formula (I). In addition, the repeating unit in the compound represented by the general formula (I) is referred to as the repeating unit (I-1).

[Formula I]

(Wherein, w represents 0-15)

As the compound (C-2), a compound having structure I-2 in which GMA (glycidyl methacrylate) is added to an arbitrary part of the carboxyl group and/or terminal carboxyl group of the repeating unit (I-1) in formula (I). (II) is mentioned.

[Formula I-2]

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

The ratio of the GMA denaturation of the carboxyl group is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, and still more preferably 0.7 in the range to which GMA is added with respect to the number of moles of carboxyl groups of compound (C-1). 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.

As the compound (C-3), in the above formula (I), any part and/or terminal imide group of the repeating unit (I-1) is an isocyanate residue, and a hydroxyl group of pentaerythritol triacrylate is added thereto. The compound (III) which has 3 is mentioned.

[Formula I-3]

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

The added amount of pentaerythritol triacrylate is preferably 40 mol% or less, more preferably 38 mol% or less, still more preferably 35 mol% or less with respect to the mol number of isocyanate groups of the polyisocyanate at the time of injection. On the other hand, the addition amount of pentaerythritol triacrylate is preferably 0.3 mol% or more, more preferably, with respect to the mol number of isocyanate groups of the polyisocyanate at the time of injection, from the viewpoint of sufficiently obtaining the effect of the addition. It is 3 mol% or more, more preferably 5 mol% or more.

The polyamideimide resin can be synthesized by various known methods. As a method for synthesizing the polyamideimide resin, the description of paragraphs 0020 to 0030 of International Publication No. 2010/074197 can be taken into consideration, and the contents are incorporated herein.

As for the polyamideimide resin, a commercial item can be used. As a commercial item, for example, "Unidic V-8000" manufactured by DIC, "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo, "KS9100" and "KS9300" manufactured by Hitachi Kasei Corporation ( And modified polyamide imides such as polysiloxane skeleton-containing polyamide imide).

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

Examples of the arbitrary repeating unit include a repeating unit (conjugated diene unit) having a structure obtained by polymerizing conjugated diene, a repeating unit having a structure obtained by hydrogenating this (hydrogenated conjugated diene unit), and the like. Examples of the 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 remarkably obtaining the effect of the present invention. Conjugated diene may be used individually by 1 type, and may be used in combination of 2 or more types. Further, the polystyrene resin may be a random copolymer or a block copolymer.

Examples of the polystyrene resin include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), and 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 copolymer, Hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer, styrene-maleic anhydride copolymer, and the like. Especially, as a polystyrene resin, a styrene-maleic anhydride copolymer is preferable.

As a specific example of a polystyrene resin, "EF-40" by CRAY VALLEY company, "H1043" by Asahi Kasei, etc. are mentioned.

The polyester resin preferably has a fluorene structure in its molecular structure from the viewpoint of compatibility with other components in the resin composition, and in addition to the fluorene structure, it has a structural unit derived from diol and a structural unit derived from dicarboxylic acid. It is desirable.

As a specific example of a polyester resin, "OKP4HT" etc. made by Osaka Gas Chemicals are mentioned.

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

As polyvinyl acetal resin, polyvinyl formal resin and polyvinyl butyral resin are mentioned, for example, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include Sekisui Kagaku Kogyo Co., Ltd.'s Slec BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series. I can.

As a specific example of a polyether sulfone resin, "PES5003P" by Sumitomo Chemical Co., etc. is mentioned.

As a specific example of a polyphenylene ether resin, the oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd. is mentioned.

As the content of the component (C), from the viewpoint of obtaining a cured product having excellent dielectric properties, when the nonvolatile component in the resin composition is 100% by mass, preferably 0.5% by mass or more, more preferably 1% by mass or more, More preferably, it is 1.5 mass% or more, Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less.

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

<(D) inorganic filler>

In addition to the above-described components, the resin composition may further contain an inorganic filler as an optional component and as the component (D).

As the material of the inorganic filler, an inorganic compound is used. Examples of materials for inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, and carbonic acid. Calcium, 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, zirconate zirconate And barium oxide, calcium zirconate, zirconium phosphate, and zirconium tungsten phosphate. Among these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. (D) Inorganic fillers may be used individually by 1 type, and may be used in combination of 2 or more types.

As a commercial item of the component (D), for example, "UFP-30" manufactured by Denka Corporation; "SP60-05" and "SP507-05" manufactured by Shinnittetsu Sumikin Materials Corporation; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomex Corporation; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" and the like manufactured by Adomex Corporation are mentioned.

The specific surface area of the 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 limitation on the upper limit, it is preferably 60 m2/g or less, 50 m2/g or less, or 40 m2/g or less. The specific surface area is obtained by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mauntech Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multi-point method.

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

The average particle diameter of the component (D) can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle diameter distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle diameter distribution measuring device, and making the median diameter the average particle diameter. As a measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone were measured and put in a vial bottle, and the one obtained by dispersing for 10 minutes by ultrasound can be used. Using a laser diffraction type particle diameter distribution measuring apparatus, the measurement sample was made blue and red at the wavelength of the light source, and the particle diameter distribution based on the volume of the component (D) was measured by a flow cell method, and from the obtained particle diameter distribution The average particle diameter can be calculated as the median diameter. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba Seisakusho Corporation.

It is preferable that the component (D) is treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. As the surface treatment agent, for example, a vinylsilane coupling agent, a (meth)acrylic coupling agent, a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, An alkoxysilane, an organosilazane compound, a titanate-based coupling agent, etc. are mentioned. Among them, a vinylsilane coupling agent, a (meth)acrylic coupling agent, and an aminosilane coupling agent are preferable from the viewpoint of remarkably obtaining the effects of the present invention. Moreover, the surface treatment agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

As a commercial item of the surface treatment agent, Shin-Etsu Chemical Co., Ltd. "KBM1003" (vinyl triethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM503" (3-methacryloxypropyl triethoxysilane), Shin-Etsu "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Kagaku Kogyo, "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kogyo, "KBE903" manufactured by Shin-Etsu Kagaku Kogyo "(3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyl Disilazane), Shin-Etsu Chemical Co., Ltd. ``KBM103'' (phenyltrimethoxysilane), 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. are mentioned.

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

The degree of surface treatment with the surface treatment agent can be evaluated according to 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 still more preferably 0.2 mg/m 2 or more, from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, 1 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable.

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

The content of the component (D) is preferably 50% by mass or more, more preferably 55% by mass or more, further preferably when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of lowering the dielectric properties. Preferably it is 60 mass% or more, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.

<(E) curing agent>

In addition to the above-described components, the resin composition may further contain a curing agent as an optional component and as the component (E). However, the component (E) is excluded from the component (B). The component (E) is a curing agent that was determined to be in a solid state in a test conducted in accordance with the second "Liquid Confirmation Method" of the Holy Spirit (Heisei 1st Self-Government Ordinance No. 1) on the test and appearance of dangerous substances. Accordingly, component (E) is a solid curing agent. The test method is as described above.

As the component (E), for example, an active ester curing agent, a phenolic curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate ester curing agent, a carbodiimide curing agent, an amine curing agent, an acid anhydride curing agent, etc. Can be lifted. (E) component may be used individually by 1 type, or may use 2 or more types together.

As the active ester curing agent, a compound having one or more active ester groups per molecule can be used. Among them, as the active ester curing agent, having two or more ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, per molecule. Compounds are preferred. It is preferable that the said active ester hardening agent is obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylate compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable.

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

As a phenol compound or a naphthol compound, for example, hydroquinone, resorcin, 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, fluoroglucine, benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolac, and the like. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

Preferred 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, and phenol. And active ester-based curing agents containing benzoylates of novolac. Among them, an active ester curing agent containing a naphthalene structure and an active ester curing agent containing a dicyclopentadiene diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

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

As the phenolic curing agent and the naphthol curing agent, it is preferable to have a novolac structure from the viewpoint of heat resistance and water resistance. Further, 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 the phenolic curing agent and the naphthol curing agent include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Maywa Kasei; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Corporation; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V" and "SN375" manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and the like manufactured by DIC Corporation are mentioned.

Specific examples of the benzoxazine-based curing agent include "ODA-BOZ" manufactured by JFE Chemical, "HFB2006M" manufactured by Showa Kobunshi, and "P-d" and "F-a" manufactured by Shikoku Kasei Kogyo Corporation.

As the cyanate ester curing agent, for example, bisphenol A dicyanate, 4,4'-methylenebis (2,6-dimethylphenyl cyanate), hexafluorobisphenol A dicyanate, 2,2-bis ( Bifunctional cyanate resins such as 4-cyanate)phenylpropane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, and bis(4-cyanatephenyl)thioether; Polyfunctional cyanate resins derived from phenol novolac and cresol novolac; Prepolymers in which these cyanate resins are partially triazineized, and the like can be mentioned.

As a specific example of the cyanate ester curing agent, "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", "BA230S75" manufactured by Ronza Japan (A prepolymer in which part or all of the bisphenol A dicyanate is triazineized to become a trimer), and the like.

As a specific example of a carbodiimide-based curing agent, "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd. are mentioned.

Examples of the amine-based curing agent include curing agents having one or more amino groups in one molecule, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like, among others, of the present invention. From the viewpoint of showing a desired effect, aromatic amines are preferred. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. As specific examples of the amine-based curing agent, 4,4'-diaminodiphenylmethane, diphenyldiaminosulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4' -Diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3-dimethyl-5,5 -Diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy) )Phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. A commercially available product may be used as the amine-based curing agent, and examples thereof include "KAYABOND C-100" manufactured by Nippon Kayaku Corporation.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, methyltetrahydro phthalic anhydride, methylhexahydro phthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride , Dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromelli anhydride Acid, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic 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 glycolbis (Anhydrotrimellitate), and polymeric acid anhydrides such as styrene maleic resin in which styrene and maleic acid are copolymerized.

The content of the component (E) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, with respect to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less.

<(F) hardening accelerator>

In addition to the above-described components, the resin composition may further contain a curing accelerator as an optional component and as the component (F).

Examples of the component (F) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metallic curing accelerators. (F) component may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc. are mentioned, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of amine-based 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, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a ]Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins Sieves are mentioned, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercial item may be used, and for example, "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd. may be mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1, 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc. are mentioned, dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

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

The content of the component (F) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. , More preferably, it is 0.01 mass% or more, Preferably it is 0.5 mass% or less, More preferably, it is 0.3 mass% or less, More preferably, it is 0.1 mass% or less.

<(G) Epoxy resin>

The resin composition may further contain an epoxy resin as the component (G) as an optional component other than the above component. However, the component (G) is excluded from the component (B).

As the component (G), 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, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, Glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclo A hexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, etc. are mentioned. (G) component may be used individually by 1 type, and may be used in combination of 2 or more types.

It is preferable that the resin composition contains an epoxy resin having two or more epoxy groups per molecule as the component (G). From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the nonvolatile component of the component (G) is preferably 50% by mass or more, more It is preferably 60 mass% or more, particularly preferably 70 mass% or more.

In the component (G), a liquid epoxy resin at a temperature of 20°C (hereinafter, it may be referred to as “liquid epoxy resin”), and a solid epoxy resin at a temperature of 20°C (hereinafter, referred to as a “solid epoxy resin”). Yes) there is. The resin composition, as component (G), 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, but desired effects of the present invention From the viewpoint of obtaining remarkably, it is preferable to include only a liquid epoxy resin.

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

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, glycidylamine type epoxy resin, phenol novolak type epoxy resin. , An alicyclic epoxy resin having an ester skeleton, a cyclohexane-type epoxy resin, a cyclohexanedimethanol-type epoxy resin, a glycidylamine-type epoxy resin, and an epoxy resin having a butadiene structure are preferred, and bisphenol A-type epoxy resin, bisphenol F The type epoxy resin is more preferable.

As a specific example of a liquid epoxy resin, "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "JER807" and "1750" manufactured by Mitsubishi Chemical Corporation (bisphenol F type epoxy resin); "JER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" manufactured by Mitsubishi Chemical Co., Ltd. (glycidylamine type epoxy resin); "ZX1059" by Shinnittetsu Sumikin Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase Chemtex (glycidyl ester type epoxy resin); "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel Corporation (epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Shinnittetsu Sumikin Chemical Co., Ltd. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups per molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups per molecule is more preferred.

Examples of the solid epoxy resin 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, and Phenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable.

As a specific example of a solid epoxy resin, "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200HH", "HP-7200H", and "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" by Nippon Kayaku Co., Ltd. (trisphenol type epoxy resin); "NC7000L" by the Nippon Kayaku company (naphthol novolak type epoxy resin); "NC3000H", "NC3000", "NC3000L", and "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Corporation; "ESN475V" manufactured by Shinnittetsu Sumikin Chemical Co., Ltd. (naphthol type epoxy resin); "ESN485" manufactured by Shinnittetsu Sumikin Chemical Co., Ltd. (naphthol novolak type epoxy resin); "YX4000H", "YX4000", and "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd. (bixylenol type epoxy resin); "YX8800" manufactured by Mitsubishi Chemical Co., Ltd. (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" by Mitsubishi Chemical Co., Ltd. (bisphenol AF type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (fluorene type epoxy resin); "JER1010" manufactured by Mitsubishi Chemical (solid bisphenol A type epoxy resin); "JER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (G), the amount ratio (liquid epoxy resin: solid epoxy resin) is a mass ratio, preferably 1:1 to 1:20, more preferably Is 1:1.5 to 1:15, particularly preferably 1:2 to 1:10. When the amount ratio between the liquid epoxy resin and the solid epoxy resin is in this range, the desired effect of the present invention can be remarkably obtained. In addition, usually, when used in the form of a resin sheet, moderate adhesion is caused. Further, usually, when used in the form of a resin sheet, sufficient flexibility is obtained, and handling properties are improved. In addition, in general, a cured product having sufficient breaking strength can be obtained.

The epoxy equivalent of the component (G) is preferably 50 g/eq. To 5,000 g/eq., more preferably 50 g/eq. To 3,000 g/eq., more preferably 80 g/eq. To 2,000 g/eq., even more preferably 110 g/eq. To 1,000 g/eq. By becoming such a range, the crosslinking density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be formed. Epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of an epoxy group. Such an epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the component (G) is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500 from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the component (G) can be measured by the same method as the weight average molecular weight of the component (C).

The content of the component (G) is, from the viewpoint of remarkably obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is 100% by mass, preferably 0.1% by mass or more, more preferably 0.3% 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 further contain a polymerization initiator as the component (H) as an optional component other than the above component. (H) component may be used individually by 1 type, or may use 2 or more types together.

As the component (H), for example, t-butylcumyl peroxide, t-butylperoxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butylperoxylaurate, Peroxides, such as t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy neodecanoate, and t-butyl peroxy benzoate, are mentioned.

As a commercial item of the component (H), for example, Nichiyu Corporation "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", and "Perbutyl ND. ", "perbutyl Z", "percumyl P", "percumyl D", and the like.

The content of the component (H) is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. , More preferably, it is 0.1 mass% or more, Preferably it is 1 mass% or less, More preferably, it is 0.5 mass% or less, More preferably, it is 0.3 mass% or less.

<(I) Other additives>

In addition to the above-described components, the resin composition may further contain other additives as optional components. As such an additive, resin additives, such as a thickener, a defoaming agent, a leveling agent, and an adhesive imparting agent, etc. are mentioned, for example. These additives may be used individually by 1 type, and may be used in combination of 2 or more types. Each content can be appropriately set by those skilled in the art.

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

<Physical properties and use of 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. Thereby, it is possible to obtain a cured product having excellent lamination properties and excellent dielectric properties and adhesion. Although already mentioned above, in general, when a maleimide compound is contained in a resin composition, the dielectric properties are excellent, but since the maleimide compound usually has a high softening point, the resin composition and the cured product thereof 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, the softness can be improved. In addition, (C) by containing a high molecular weight component, the stress in the cured product is alleviated, and the softness of the cured product can be improved.

The 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 between a conductor layer (plated conductor layer) formed by plating. Accordingly, the cured product forms an insulating layer having excellent peel strength between 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 can be 10 kgf/cm or less. The measurement of the peel strength of the plated conductor layer can be measured according to the method described in Examples to be described later.

The cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits a characteristic of excellent copper foil peel strength. Therefore, the hardened|cured material forms an insulating layer excellent in copper foil peeling strength. The copper foil peeling 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 peeling strength can be 10 kgf/cm or less. The copper foil peel strength can be measured according to the method described in Examples to be described later.

A cured product obtained by thermosetting the resin composition at 200° C. for 90 minutes exhibits a property of low dielectric constant. Accordingly, the cured product forms an insulating layer having a low dielectric constant. The dielectric constant is preferably 4 or less, more preferably 3.5 or less, and still more preferably 3 or less. The lower limit of the dielectric constant can be 0.001 or more. The dielectric constant can be measured according to the method described in Examples to be described later.

A cured product obtained by thermosetting the resin composition at 200° C. for 90 minutes exhibits a characteristic of low dielectric loss tangent. Accordingly, the cured product forms an insulating layer having a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.004 or less, and still more preferably 0.003 or less. The lower limit of the dielectric loss tangent can be 0.0001 or more. The measurement of the dielectric loss tangent can be measured according to the method described in Examples to be described later.

The resin composition exhibits a property of excellent lamination property. Specifically, after laminating a resin composition on a glass cloth-based epoxy resin double-sided copper-clad laminate conductor on which a comb-shaped conductor pattern having a conductor thickness of 35 μm is formed, it is thermally cured at 100°C for 30 minutes, and then at 180°C for 30 minutes to insulate. To form. The difference between the irregularities on the conductor and other parts in the insulating layer is obtained by using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Vico Instruments), using a VSI mode, a 10-fold lens, and setting the measurement range to 1.2 mm x 0.91 mm. Find by numerical value. At this time, usually, there is no generation of voids after lamination, and the difference between the irregularities on the conductor and the other portions is less than 5 μm. Details of the evaluation of the lamination property can be measured according to the method described in Examples described later.

The resin composition of the present invention is excellent in lamination properties, can lower dielectric properties, and can form an insulating layer excellent in adhesion. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating applications. Specifically, it can be suitably used as a resin composition for forming the insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. have.

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

In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is a resin composition for a redistribution forming layer as an insulating layer for forming a redistribution layer (cultivation It can be suitably used also as a resin composition for forming a line forming layer) and a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip). When a semiconductor chip package is manufactured, a redistribution layer may be further formed on the sealing layer.

(1) the process of laminating a temporary fixing film on the substrate,

(2) the process of temporarily fixing the semiconductor chip on the temporary fixing film,

(3) the step of forming a sealing layer on the semiconductor chip,

(4) the step of peeling the substrate and the temporary fixing film from the semiconductor chip,

(5) a step of forming a rewiring forming layer as an insulating layer on the surface from which the substrate and the temporary fixing film of the semiconductor chip are peeled off, and

(6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer

[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 preferably 40 μm or less, even more preferably from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulation even if the cured product of the resin composition is a thin film. Is less than 30 μm. The lower limit of the thickness of the resin composition layer is not particularly limited, but can be usually 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, the plastic material includes, for example, polyethylene terephthalate (hereinafter, sometimes abbreviated as ``PET''), polyethylene naphthalate (hereinafter, abbreviated as ``PEN'') Polyester, polycarbonate (hereinafter, sometimes abbreviated as ``PC''), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide ( PES), polyether ketone, polyimide, etc. are mentioned. 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, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and other metals (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good.

The support may be subjected to a mat treatment, a corona treatment, or an 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. As a releasing agent used for the releasing layer of the support body with a releasing layer, for example, one or more releasing agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins and silicone resins can be mentioned. As a support with a release layer, a commercial item may be used. For example, "SK-1", "AL-5", and "AL-" manufactured by Lintec, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. 7", "Lumira T60" manufactured by Tore Corporation, "Purex" manufactured by Teijin Corporation, "Uni-Feel" manufactured by Unitika Corporation, etc. are mentioned.

Although it does not specifically limit as a thickness of a support body, the range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. Moreover, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

In one embodiment, the resin sheet may further contain other layers as necessary. Examples of such other layers include a protective film conforming to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be suppressed.

The resin sheet can be produced, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support body using a die coater, etc., and drying to form a resin composition layer. have.

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

Drying may be performed by a known method such as heating and hot air spraying. Although drying conditions are not particularly limited, drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin varnish, for example, in the case of using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, the resin composition is dried at 50°C to 150°C for 3 minutes to 10 minutes. Layers can be formed.

The resin sheet can be wound up and stored in a roll shape. When a resin sheet has a protective film, it becomes usable by peeling off a protective film.

[Printed wiring board]

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

The printed wiring board can be manufactured by a method including the following steps (I) and (II) using, for example, the resin sheet described above.

(I) Step of laminating on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate

(II) Process of forming an insulating layer by thermosetting the resin composition layer

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

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. As a member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as "heat-pressing member"), for example, a heated metal plate (SUS hard plate, etc.) or a metal roll (SUS roll) may be mentioned. Further, it is preferable not to press the heat-compressed member directly onto the resin sheet, but to press the heat-resistant rubber or the like with an elastic material therebetween so that the resin sheet sufficiently follows the surface irregularities 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 heating compression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the heating compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably Is in the range of 0.29 MPa to 1.47 MPa, and the heating and compression time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less of pressure.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurized laminator.

After lamination, the laminated resin sheet may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing the heat-pressed member from the support side. The press conditions of the smoothing treatment can be set to the same conditions as the heat-pressing conditions of the lamination. The smoothing treatment can be performed by a commercially available laminator. In addition, lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator.

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

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

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

Before thermosetting the resin composition layer, you may preheat the resin composition layer at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 115°C or less, more preferably 70°C or more and 110°C or less), the resin composition layer is You may preheat 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 the printed wiring board, (III) the step of drilling the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art used for manufacturing a printed wiring board. In addition, when the support is removed after the step (II), the removal of the support may be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). ) May be carried out. Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

Step (III) is a step of drilling 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 according to the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear is also removed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid used for roughening treatment, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As a commercially available swelling liquid, ``Swelling Deep Securigans P'', ``Swelling Deep Securigans SBU'', ``Swelling Deep Securiganth P'' manufactured by Atotech Japan, etc. are mentioned, for example. . The swelling treatment with the swelling liquid is not particularly limited, but can be performed by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution of 40°C to 80°C for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent used for roughening treatment, For example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment with an oxidizing agent, such as an alkaline permanganic acid solution, is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Further, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan. In addition, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial item, "Reduction Solution Securigant P" by Atotech Japan is mentioned, for example. Treatment with the neutralizing liquid can be performed by immersing the treated surface on which the roughening treatment with an oxidizing agent has been performed in the neutralizing liquid at 30°C to 80°C for 1 minute to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object subjected to the roughening treatment with an oxidizing agent in a neutralizing solution of 40°C to 70°C for 5 minutes to 20 minutes is preferable.

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

Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Include. 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 (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy. ) Formed by. Among them, from the viewpoint of versatility, cost, and ease of patterning for forming a conductor layer, a monometallic layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, or a copper-nickel alloy , A copper-titanium alloy alloy layer is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper This is more preferable.

The conductor layer may have a single-layer structure, or a multilayer structure in which two or more layers of a single metal layer or an alloy layer made of different types of metals or alloys are stacked. 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 a nickel-chromium alloy.

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

In one embodiment, the conductor layer may be formed by plating. For example, it is possible to form a conductor layer having a desired wiring pattern by plating on the surface of the insulating layer by conventionally known techniques such as a semi-positive method and a full-positive method. It is preferable to form by the additive method. Hereinafter, an example of forming a conductor layer by a semi-positive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, so that a conductor layer having a desired wiring pattern can be formed.

[Semiconductor device]

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

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

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) in a conductive portion of a printed wiring board. The "conducting point" is "a place that transmits an electric signal from a printed wiring board", and the place may be a surface, a buried place, or any place. In addition, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

A method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer (BBUL) A mounting method by, a mounting method by an anisotropic conductive film (ACF), a mounting method by a non-conductive film (NCF), etc. are mentioned. Here, the "mounting method using a bumpless build-up layer (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a recessed portion of a printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board".

[Example]

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

<(B) Determination of liquid and semi-solid form of liquid or semi-solid hardener>

(B) Determination of liquid, semi-solid, and solid state of liquid or semi-solid hardeners is the second ``Method of Confirmation of Liquid Matter'' of the Holy Spirit (Heisei First Ordinance No. 1) on the examination and properties of dangerous substances. I did it according to. The "liquid phase confirmation method" was performed as described above. The results are shown below.

"JER Cure W" manufactured by Mitsubishi Chemical: liquid

「KAYAHARD A-A」 manufactured by Nippon Kayaku: Liquid

「MEH-8000H」 Made by Meiwa Kasei: Liquid

「NK Ester DCP」 manufactured by Shinnakamura Kagaku Kogyo: Liquid

「NK Ester A-DOG」 manufactured by Shinnakamura Kagaku Kogyo: Liquid

「RE-810NM」 manufactured by Nippon Kayaku: Liquid

"BMI689" Designer Molecules Corporation: Liquid

"Ricon100" manufactured by CRAY VALLEY: liquid

"Ricon130MA13" manufactured by CRAY VALLEY: liquid

"Ricon150" manufactured by CRAY VALLEY: liquid

「JP-100」 manufactured by Nippon Soda: Liquid

``ALP-d'' manufactured by Shikoku Kasei Kogyo: Liquid

「L-DAIC」 manufactured by Shikoku Kasei Kogyo: Liquid

「TAIC」 manufactured by Nippon Kasei: Liquid

"Daiso Dapp Monomer" manufactured by Osaka Soda: Liquid

「MDAC」 manufactured by Osaka Soda: Liquid

「DAD」 manufactured by Nisshoku Techno Fine Chemicals: Liquid

[Synthesis Example: Synthesis of polyimide resin]

A 500 mL separable flask equipped with a water meter connected to a reflux condenser, a nitrogen introduction tube, and a stirrer was prepared. In this flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy) Si) phenyl]-1,1,3-trimethylindane 29.6 g was added, and the mixture was stirred at 45° C. for 2 hours under a nitrogen stream to react. Subsequently, the temperature of this reaction solution was raised and the condensed water was azeotropically removed with toluene under a nitrogen stream while maintaining at about 160°C. It was confirmed that a predetermined amount of water was accumulated in the water metering device and that water outflow was not visible. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. Then, it cooled and obtained the polyimide solution (non-volatile content 20 mass %) containing the polyimide resin which has 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 said polyimide resin was 12,000.

[Formula X1]

[Formula X2]

[Example 1. Preparation of resin composition 1]

Biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution of 70% non-volatile content) 180 parts, polycarbonate resin (Mitsubishi Gas Kaga 10 parts of "FPC2136" manufactured by Kusa, a weight average molecular weight of 30,000) were heated and dissolved while stirring in 30 parts of toluene and 30 parts of MEK. After cooling the obtained solution to room temperature, 18 parts of an amine-based non-solid curing agent ("jER Cure W" manufactured by Mitsubishi Chemical), an inorganic filler (vinyl-based coupling agent ("KBM1003" manufactured by Shin-Etsu Chemical Co., Ltd.)) 300 parts of spherical silica ("SO-C2" manufactured by Adomex Co., Ltd., average particle diameter of 0.5 μm)) was mixed and uniformly dispersed with a high-speed rotary mixer to obtain a resin composition 1.

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

[Example 2. Preparation of resin composition 2]

In Example 1,

1) 18 parts of an amine-based non-solid curing agent ("jER Cure W" manufactured by Mitsubishi Chemical Corporation) was changed to 25 parts of an amine-based non-solid curing agent (“KAYAHARD A-A” manufactured by Nippon Kayaku Corporation),

2) 10 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., weight average molecular weight 30,000) was changed to 50 parts of varnish containing 20 mass% of the polyimide resin obtained in the synthesis example.

Except for the above matters, it carried out similarly to Example 1, and obtained the resin composition 2.

[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), an allyl group-containing phenol resin (allyl-based non-solid curing agent having a phenol ring, "MEH-8000H" manufactured by Maywa Kasei Corporation, phenol equivalent) 240) change to 20 copies,

2) 10 parts of a polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., a weight average molecular weight of 30,000), a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corp., a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass), Weight average molecular weight 35,000) 33.3 parts,

3) Further, 0.5 part of a polymerization initiator ("Perbutyl C" manufactured by Nichiyu) was used.

Except for the above matters, it carried out similarly to Example 1, and obtained the resin composition 3.

[Example 4. Preparation of resin composition 4]

In Example 3,

1) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical, a 1:1 solution of 30% by mass solid content of MEK and cyclohexanone, a weight average molecular weight of 35,000), containing 20% by mass of the polyimide resin obtained in Synthesis Example Change it to 50 parts of varnish,

2) Further, 10 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., an active group equivalent of about 216, a toluene solution having a solid content of 50% by mass) was used.

Except the above matters, it carried out similarly to Example 3, and obtained the resin composition 4.

[Example 5. Preparation of resin composition 5]

In Example 3,

1) Allyl group-containing phenol resin (Allyl-based non-solid curing agent having a phenol ring, Maywa Kasei Co., Ltd. ``MEH-8000H,'' phenol equivalent of 240) 20 parts, bifunctional methacrylate ((meth)acrylic non-solid curing agent, Shin Nakamura Kagaku Kogyo Co., Ltd. ``NK ester DCP'', molecular weight 332) changed to 13 parts,

2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical, a 1:1 solution of 30 mass% solid content of MEK and cyclohexanone, a weight average molecular weight of 35,000), a polyamideimide resin ("Unidic V-" manufactured by DIC) 8000", weight average molecular weight 11,000, ethyldiglycol acetate solution of 40 mass% of non-volatile component) changed to 25 parts,

3) 300 parts of inorganic fillers (vinyl-based coupling agent ("KBM1003" manufactured by Shin-Etsu Chemical Co., Ltd.)) 300 parts of spherical silica ("SO-C2" manufactured by Adomex Corporation, average particle diameter 0.5 μm)), an inorganic filler (Spherical silica surface-treated with a methacrylic coupling agent ("KBM503" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C2" manufactured by Adomex Corporation, average particle diameter 0.5 μm)) was changed to 300 parts.

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 5.

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

[Example 6. Preparation of resin composition 6]

In Example 5,

1) 13 parts of bifunctional methacrylate ((meth)acrylic non-solid curing agent, Shinnakamura Kagaku Co., Ltd. ``NK ester DCP'', molecular weight 332) 13 parts, bifunctional acrylate ((meth)acrylic non-solid curing agent, Shinnakamura Changed to 13 parts of "NK ester A-DOG" manufactured by Kagaku Kogyo, molecular weight 326),

2) 25 parts of polyamideimide resin ("Unidic V-8000" manufactured by DIC, a weight average molecular weight of 11,000, an ethyldiglycol acetate solution of 40% by mass of a nonvolatile component) is an acid anhydride group-containing vinyl resin (polystyrene resin, CRAY VALLEY company make "EF-40", weight average molecular weight 11,000) It changed to 10 parts.

Except the above matters, it carried out similarly to Example 5, and obtained the resin composition 6.

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

[Example 7. Preparation of resin composition 7]

In Example 3,

1) Allyl group-containing phenol resin (Allyl-based non-solid curing agent having a phenol ring, ``MEH-8000H'' manufactured by Maywa Kasei, phenol equivalent 240) 20 parts, an allyl-based non-solid curing agent having an epoxy group (manufactured by Nippon Kayaku Corporation `` RE-810NM'', epoxy equivalent 220) changed to 13 parts,

2) Further, 2 parts of a curing accelerator (2P4MZ (2-phenyl-4-methylimidazole) solid content 2.5% MEK solution) was used.

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 7.

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

[Example 8. Preparation of resin composition 8]

In Example 7,

1) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical, a 1:1 solution of 30 mass% solid content of MEK and cyclohexanone, a weight average molecular weight of 35,000), a hydrogenated styrene-based thermoplastic elastomer ("H1043" manufactured by Asahi Kasei) , The weight average molecular weight of 35,000) was changed to 10 parts,

2) In addition, 10 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, an active group equivalent of 223, a toluene solution having a solid content of 65% by mass) was used,

3) 2 parts of a curing accelerator (MeK solution of 2.5% solid content of 2P4MZ) was changed to 2 parts of a curing accelerator (MEK solution of 2.5% solid content of 1B2PZ (1-benzyl-2-phenylimidazole)),

4) 300 parts of inorganic fillers (vinyl-based coupling agent ("KBM1003" manufactured by Shin-Etsu Chemical Co., Ltd.)) 300 parts of spherical silica ("SO-C2" manufactured by Adomex Corporation, average particle diameter 0.5 μm)), inorganic filler (Phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573") surface-treated spherical silica (Adomatex company "SO-C2", average particle diameter 0.5 μm)) 300 parts.

Except for the above matters, it carried out similarly to Example 7 and obtained the resin composition 8.

[Example 9. Preparation of resin composition 9]

In Example 5,

1) 13 parts of bifunctional methacrylate ((meth)acrylic non-solid curing agent, Shinnakamura Kagaku Kogyo ``NK ester DCP'', molecular weight 332) 13 parts, liquid bismaleimide (maleimide non-solid curing agent, designer Molecule Changed to 13 parts of "BMI689" manufactured by Zu Corporation, maleimide group equivalent 345),

2) 25 parts of polyamideimide resin ("Unidic V-8000" manufactured by DIC, a weight average molecular weight of 11,000, an ethyldiglycol acetate solution of 40% by mass of a nonvolatile component), a polyester resin ("OKP4HT" manufactured by Osaka Gas Chemical) ", the weight average molecular weight of 50,000) was changed to 10 parts.

Except the above matters, it carried out similarly to Example 5, and obtained the resin composition 9.

BMI689 is a compound represented by the following structural formula.

[Example 10. Preparation of resin composition 10]

In Example 3,

1) Allyl-containing phenol resin (Allyl-based non-solid curing agent having a phenol ring, Maywa Kasei Co., Ltd. ``MEH-8000H,'' phenol equivalent weight 240) 20 parts, liquid styrene butadiene polymer (butadiene-based non-solid curing agent, CRAY VALLEY) ``Ricon100'', styrene content of 25%, Mn about 4,500) changed to 13 parts,

2) 33.3 parts of a phenoxy resin (``YX7553BH30'' manufactured by Mitsubishi Chemical, a 1:1 solution of MEK and cyclohexanone having a weight average molecular weight of 35,000 and a solid content of 30% by mass) is a hydrogenated styrene-based thermoplastic elastomer ("H1043" manufactured by Asahi Kasei , The weight average molecular weight 35,000) was changed to 10 parts.

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 10.

[Example 11. Preparation of resin composition 11]

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 Maywa Kasei, 240 phenol equivalent), an acid anhydride group-containing liquid butadiene polymer (butadiene-based non-solid curing agent, "Ricon130MA13" manufactured by CRAY VALLEY, acid anhydride equivalent 732, Mn about 2,900) 13 parts,

2) 33.3 parts of a phenoxy resin (``YX7553BH30'' manufactured by Mitsubishi Chemical, a 1:1 solution of MEK and cyclohexanone having a weight average molecular weight of 35,000 and a solid content of 30% by mass), an acid anhydride group-containing vinyl resin (manufactured by CRAY VALLEY) EF-40", weight average molecular weight 11,000) was changed to 10 parts.

Except the above matters, it carried out similarly to Example 3, and obtained the resin composition 11.

[Example 12. Preparation of resin composition 12]

In Example 3,

1) Allyl group-containing phenol resin (Allyl-based non-solid curing agent having a phenol ring, Maywa Kasei Co., Ltd. ``MEH-8000H,'' phenol equivalent 240) 20 parts, liquid butadiene polymer (butadiene-based non-solid curing agent, CRAY VALLEY) 「Ricon150」, Mn about 3,900) changed to 13 copies,

2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical, a weight average molecular weight of 35,000, a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass), containing 20% by mass of the polyimide resin obtained in Synthesis Example Changed to 50 pieces of varnish.

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 12.

[Example 13. Preparation of resin composition 13]

In Example 3,

1) Allyl group-containing phenol resin (Allyl-based non-solid curing agent having a phenol ring, Maywa Kasei Co., Ltd. ``MEH-8000H,'' phenol equivalent 240) 20 parts, epoxidized polybutadiene (butadiene-based non-solid curing agent, Nippon Soda Corporation Manufacturing ``JP-100'', epoxy equivalent 210, Mn about 1,300) changed to 13 parts,

2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemicals, a weight average molecular weight of 35,000, a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass) 33.3 parts of a polyamideimide resin ("Unidic V-" manufactured by DIC) 8000", weight average molecular weight 11,000, ethyldiglycol acetate solution of 40 mass% of non-volatile component) changed to 25 parts,

3) Further, 2 parts of a hardening accelerator (a MEK solution of 2.5% solid content of 1B2PZ) was used.

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 13.

[Example 14. Preparation of resin composition 14]

In Example 7,

1) 13 parts of an allyl-based non-solid curing agent having an epoxy group ("RE-810NM" manufactured by Nippon Kayaku, 220 epoxy equivalent), epoxidized polybutadiene (butadiene-based non-solid curing agent, "JP-100" manufactured by Nippon Soda Corporation, epoxy Equivalent 210, Mn about 1,300) change to 13 parts,

2) In addition, 3 parts of a benzoxazine-based curing agent ("ODA-BOZ" manufactured by JFE Chemical) was used,

3) 300 parts of inorganic fillers (vinyl-based coupling agent ("KBM1003" manufactured by Shin-Etsu Chemical Co., Ltd.)) 300 parts of spherical silica ("SO-C2" manufactured by Adomex Corporation, average particle diameter 0.5 μm)), an inorganic filler (Phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573") surface-treated spherical silica (Adomatex company "SO-C2", average particle diameter 0.5 μm)) 300 parts.

Except for the above matters, it carried out similarly to Example 7 and obtained the resin composition 14.

[Example 15. Preparation of resin composition 15]

In Example 3,

1) Allyl group-containing phenol resin (Allyl-based non-solid curing agent having a phenol ring, Maywa Kasei Co., Ltd. ``MEH-8000H,'' phenol equivalent 240) 20 parts, bifunctional acrylate ((meth)acrylic non-solid curing agent, new Changed to 5 parts of "NK ester A-DOG" manufactured by Nakamura Kagaku Kogyo, molecular weight 326),

2) 33.3 parts of a phenoxy resin (``YX7553BH30'' manufactured by Mitsubishi Chemical, a 1:1 solution of MEK and cyclohexanone having a weight average molecular weight of 35,000 and a solid content of 30% by mass), a polycarbonate resin (``FPC2136'' manufactured by Mitsubishi Gas Chemicals, Inc., Weight average molecular weight of 30,000) 10 parts,

3) In addition, 20 parts of a 50% solid content MEK solution of 4,4-Diaminodiphenylmethane was used.

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 15.

[Example 16. Preparation of resin composition 16]

In Example 3,

1) Allyl group-containing phenol resin (Allyl-based non-solid curing agent having a phenol ring, Meiwa Kasei Co., Ltd. ``MEH-8000H,'' phenol equivalent 240) 20 parts, allyl-based non-solid curing agent having a benzoxazine ring (Shikoku Kasei Co., Ltd. ``ALP-d'' manufactured by the teacher, MEK solution of 65% solid content) changed to 20 parts,

2) 33.3 parts of a phenoxy resin (``YX7553BH30'' manufactured by Mitsubishi Chemical, a 1:1 solution of MEK and cyclohexanone having a weight average molecular weight of 35,000 and a solid content of 30% by mass), a polyester resin ("OKP4HT" manufactured by Osaka Gas Chemicals), It changed to 10 parts of weight average molecular weight 50,000).

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 16.

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., an epoxy equivalent 220), an allyl-based non-solid curing agent having a benzoxazine ring (“ALP-d” manufactured by Shikoku Kasei Kogyo Co., Ltd., MEK solution of 65% solid content) to 20 parts,

2) Hydrogenated styrenic thermoplastic elastomer ("H1043" manufactured by Asahi Kasei, weight average molecular weight 35,000) 10 parts, polyamideimide resin ("Unidic V-8000" manufactured by DIC Corporation), weight average molecular weight 11,000, non-volatile component 40 mass % Ethyldiglycol acetate solution) to 25 parts,

3) 10 parts of active ester curing agent ("HPC-8000-65T" manufactured by DIC, active group equivalent 223, solid content 65 mass% of toluene solution) 10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical, epoxy equivalent 180 ) Changed to part 5.

Except the above matters, it carried out similarly to Example 8, and obtained the resin composition 17.

[Example 18. Preparation of resin composition 18]

In Example 3,

1) Allyl group-containing phenol resin (Allyl-based non-solid curing agent having a phenol ring, Meiwa Kasei Co., Ltd. ``MEH-8000H,'' phenol equivalent weight 240) 20 parts, allyl-based non-solid curing agent having an isocyanol ring (Shikoku Kasei Co., Ltd. Teacher Manufacturing 「L-DAIC」) changed to 13 copies,

2) 33.3 parts of a phenoxy resin (``YX7553BH30'' manufactured by Mitsubishi Chemical, a 1:1 solution of MEK and cyclohexanone having a weight average molecular weight of 35,000 and a solid content of 30% by mass), a polyester resin ("OKP4HT" manufactured by Osaka Gas Chemicals), It changed to 10 parts of weight average molecular weight 50,000).

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 18.

[Example 19. Preparation of resin composition 19]

In Example 3,

1) Allyl group-containing phenolic resin (Allyl-based non-solid curing agent having a phenol ring, Meiwa Kasei Co., Ltd. ``MEH-8000H,'' phenol equivalent is 240) 20 parts, an allyl-based non-solid curing agent (triallyl is Socyanurate, Nippon Kasei Co., Ltd. ``TAIC'', molecular weight 249) changed to 13 parts,

2) 33.3 parts of a phenoxy resin (``YX7553BH30'' manufactured by Mitsubishi Chemical, a 1:1 solution of MEK and cyclohexanone having a weight average molecular weight of 35,000 and a solid content of 30% by mass), a polycarbonate resin (``FPC2136'' manufactured by Mitsubishi Gas Chemicals, Inc., It changed to 10 parts of weight average molecular weight 30,000).

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 19.

[Example 20. Preparation of resin composition 20]

In Example 3,

1) Allyl group-containing phenol resin (Allyl-based non-solid curing agent having a phenol ring, Meiwa Kasei Co., Ltd. ``MEH-8000H,'' phenol equivalent 240) 20 parts, allyl-based non-solid curing agent (orthodiallylphthalate, Osaka Soda Corporation Manufacturing ``Diso Dapp Monomer'', molecular weight 246) was changed to 13 parts,

2) 33.3 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical, a weight average molecular weight of 35,000, a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass), containing 20% by mass of the polyimide resin obtained in Synthesis Example Changed to 50 pieces of varnish.

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 20.

[Example 21. Preparation of resin composition 21]

In Example 3,

1) Allyl group-containing phenol resin (Allyl-based non-solid curing agent having a phenol ring, Meiwa Kasei Co., Ltd. ``MEH-8000H,'' phenol equivalent 240) 20 parts, cyclohexanedicarboxylic acid diallyl (allyl-based non-solid curing agent, Osaka Changed to 13 parts of "MDAC" manufactured by Soda Corporation, molecular weight 252),

2) 33.3 parts of a phenoxy resin (``YX7553BH30'' manufactured by Mitsubishi Chemical, a 1:1 solution of MEK and cyclohexanone having a weight average molecular weight of 35,000 and a solid content of 30% by mass), a polyester resin ("OKP4HT" manufactured by Osaka Gas Chemicals), It changed to 10 parts by weight molecular weight 50,000).

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 21.

[Example 22. Preparation of resin composition 22]

Biphenyl aralkyl maleimide resin (manufactured by Nippon Kayaku, 「MIR-3000-70MT」, maleimide group equivalent: 275 g/eq, MEK/toluene mixed solution of 70% non-volatile content) 180 parts, phenoxy resin (Mitsubishi Chemical ``YX7553BH30'' manufactured by Co., Ltd., a 1:1 solution of MEK and cyclohexanone having a weight average molecular weight of 35,000 and a solid content of 30% by mass) 33.3 parts, toluene 20 parts, MEK 20 parts, cyclohexanedicarboxylic acid diallyl (manufactured by Osaka Soda Corporation ``MDAC '', molecular weight 252) 13 parts, bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "828US", epoxy equivalent 180) 5 parts, triazine skeleton-containing phenolic curing agent (DIC Co., Ltd. "LA-3018-50P", hydroxyl group equivalent About 151 of a solid content of 50% 2-methoxypropanol solution) 3 parts, an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, an active group equivalent of 223, a solid content of 65 mass% of toluene solution) 5 parts, polymerization initiator (Nichiyu Co., Ltd. ``Perbutyl C'') 0.5 parts, curing accelerator (1B2PZ solid content 2.5% MEK solution) 2 parts, inorganic filler (vinyl-based coupling agent (Shin-Etsu Chemical Co., Ltd. ``KBM1003'') surface-treated) Spherical silica ("SO-C2" manufactured by Adomatex, average particle diameter 0.5 μm)) 150 parts, spherical silica surface-treated with inorganic filler (phenylaminosilane coupling agent (``KBM573'' manufactured by Shin-Etsu Chemical Co., Ltd.)) ("SO-C2" manufactured by Adomex Corporation, average particle diameter 0.5 μm)) 150 parts were uniformly dispersed with a high-speed rotary mixer to obtain a resin composition 22.

[Example 23. Preparation of resin composition 23]

In Example 9,

1) 13 parts of liquid bismaleimide (maleimide non-solid curing agent, ``BMI689'' manufactured by Designer Molecules, maleimide group equivalent 345), diallyl difensan (allyl non-solid curing agent, manufactured by Nisshoku Techno Fine Chemicals `` DAD'', molecular weight 322) changed to 13 parts,

2) 10 parts of polyester resin ("OKP4HT" manufactured by Osaka Gas Chemical, weight average molecular weight 50,000) was changed to 10 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Corporation, weight average molecular weight 30,000).

Except for the above matters, it carried out similarly to Example 9, and obtained the resin composition 23.

[Comparative Example 1. Preparation of Comparative Resin Composition 1]

In Example 3, 20 parts of an allyl group-containing phenol resin (Meiwa Kasei Co., Ltd. "MEH-8000H", phenol equivalent weight 240) was not used.

Except for the above matters, it carried out similarly to Example 3, and obtained the resin composition 1 for comparison.

[Comparative Example 2. Preparation of Comparative Resin Composition 2]

In Example 11, 10 parts of an acid anhydride group-containing vinyl resin ("EF-40" manufactured by CRAY VALLEY, weight average molecular weight 11,000) was not used.

Except for the above matters, it carried out similarly to Example 11, and obtained the resin composition 2 for comparison.

[Comparative Example 3. Preparation of Comparative Resin Composition 3]

In Example 2, 180 parts of a biphenylaralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq, a MEK/toluene mixed solution of 70% nonvolatile content), poly It was changed to 126 parts of phenylmethane maleimide ("BMI2300" manufactured by Yamato Kaseiko).

Except for the above matters, it carried out similarly to Example 2, and obtained the resin composition 3 for comparison.

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

[Production of resin sheet]

As a support, a polyethylene terephthalate film ("Lumira R80" manufactured by Tore Corporation, a thickness of 38 μm, a softening point of 130° C.) subjected to a release treatment with an alkyd resin type releasing 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 the support with a die coater so that the thickness of the dried resin composition layer became 40 μm, and dried at 70°C to 95°C for 4 minutes, on the support. A resin composition layer was formed. Next, a rough surface of a polypropylene film ("Alpan MA-411" manufactured by Oji Ftex Co., Ltd., 15 μm in thickness) was bonded to the surface not bonded to the support of the resin composition layer as a protective film. Thereby, the resin sheet A which has a support body, a resin composition layer, and a protective film in this order was obtained.

[Measurement of peel strength of plated conductor layer]

(1) Preparation of the inner layer substrate

Copper coated on both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic Corporation ``R1515A'') with a micro-etchant ("CZ8101" manufactured by MEC) by 1 μm etching The surface was roughened.

(2) Lamination of resin sheet

The protective film was peeled off from the resin sheet A, and the resin composition layer was exposed. Using a batch-type vacuum pressurized laminator (manufactured by Nikko Materials, a two-stage build-up laminator "CVP700"), the resin composition layer was laminated on both sides of the inner layer substrate so that it may contact the inner layer substrate. After the lamination was decompressed for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, it was carried out by pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, 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

Thereafter, the inner-layer substrate on which the resin sheet was laminated was put in an oven at 100°C and heated for 30 minutes, and then transferred to an oven at 180°C and heated for 30 minutes to heat-cure the resin composition layer to form an insulating 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) Harmonization 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 was immersed in a swelling liquid ("Swelling Deep Securigant P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60° C. for 5 minutes, and then an oxidizing agent solution (Ato It is immersed in "Concentrate Compact CP" manufactured by Tec Japan, an aqueous solution having a potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80°C for 15 minutes, and then a neutralizing solution ("Reduction Solution Securie manufactured by Atotech Japan") Gantt P", sulfuric acid aqueous solution) was immersed at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(5) Formation of conductor layer

According to the semi-positive method, a conductor layer was formed on the roughened surface of the insulating layer. That is, the substrate after the roughening treatment was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Subsequently, after performing an annealing treatment by heating at 150° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Thereafter, copper sulfate electroplating 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 referred to as "evaluation substrate B".

<Measurement of the peel strength of the plated conductor layer>

The measurement of the peel strength of the insulating layer and the conductor layer was performed in accordance with the Japanese Industrial Standard (JIS C6481). Specifically, a sheath having a width of 10 mm and a length of 100 mm is put in the conductor layer of the evaluation substrate B, this end is peeled off and picked up with a picker, and 35 mm is peeled off in the vertical direction at a rate of 50 mm/min at room temperature. The load (kgf/cm) was measured to determine the peel strength. For the measurement, a tensile tester ("AC-50C-SL" manufactured by TSE) was used.

[Measurement of copper foil peel strength]

(1) Copper foil treatment

The polished surface of ``3EC-III'' (electric field copper foil, 35 μm) manufactured by Mitsui Kinzoku Co., Ltd. is etched 1 μm with a micro-etchant ("CZ8101" manufactured by MEC) to perform roughening treatment on the copper surface, followed by rust prevention treatment (CL8300) Further, it heat-treated for 30 minutes in an oven at 130° C. This copper foil is referred to as CZ copper foil.

(2) Preparation of the inner layer substrate

Copper coated on both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic Corporation ``R1515A'') with a micro-etchant ("CZ8101" manufactured by MEC) by 1 μm etching The surface was roughened.

(3) Lamination of copper foil and formation of insulating layer

The protective film was peeled off from the resin sheet A, and the resin composition layer was exposed. Using a batch-type vacuum pressurized laminator (manufactured by Nikko Materials, a two-stage build-up laminator "CVP700"), the resin composition layer was laminated on both sides of the inner layer substrate so that it contacts the inner layer substrate. After the lamination was decompressed for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, it was carried out by pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds. On this resin composition layer, the treated surface of CZ copper foil was laminated under the same conditions as above. Then, sample A was produced by curing the resin composition layer under curing conditions at 200°C for 90 minutes to form an insulating layer.

<Measurement of copper foil peel strength (copper foil adhesion)>

The produced sample A was cut into 150 x 30 mm small pieces. Using a cutter, insert a sheath with a width of 10 mm and a length of 100 mm in the copper foil part of the small piece, peel off one end of the copper foil, and pick it up with a picker, and the load when peeling off 35 mm in the vertical direction at a speed of 50 mm/min at room temperature ( kgf/cm) was measured to determine the peel strength. For the measurement, a tensile tester ("AC-50C-SL" manufactured by TSE) was used. Measurement was performed in accordance with the Japanese Industrial Standard (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, heated at 200° C. for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The obtained cured product is referred to as "cured product C for evaluation". The cured product C for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm. With respect to the test piece, the dielectric constant and dielectric loss tangent were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by a cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies. Measurement was performed on three test pieces, and an average value was calculated.

In addition, the cured product C for evaluation of Comparative Example 2 in which the component (C) was not used was poor in strength and difficult to handle. For this reason, the dielectric properties of Comparative Example 2 could not be measured.

[Evaluation of lamination property]

(1) Preparation of the inner layer substrate

A glass cloth-based epoxy resin double-sided copper clad laminate (substrate thickness of 0.8 mm, manufactured by Panasonic) with a conductor thickness of 35 μm and a comb-shaped conductor pattern of L (line: wiring width)/S (space: gap width) = 160 μm/160 μm Both surfaces of "R1515A") were etched 1 μm with a micro-etchant ("CZ8101" manufactured by MEC) to perform roughening treatment on 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 pressurized laminator (manufactured by Nikko Materials, a two-stage build-up laminator ``CVP700''), the resin composition layer is in contact with the glass cloth-based epoxy resin double-sided copper clad laminate, so that both sides of the glass cloth-based epoxy resin double-sided copper clad laminated plate Laminated on. After the lamination was decompressed for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, it was carried out by pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, 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

Thereafter, the glass cloth-based epoxy resin double-sided copper-clad laminate on which the resin sheet was laminated was put into an oven at 100°C and heated for 30 minutes, and then transferred to an oven at 180°C and heated for 30 minutes to heat-cure the resin composition layer to insulate. Formed a layer. Thereafter, the support was peeled 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) on the conductor in the insulating layer of the cured substrate D was determined using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Vico Instruments), in VSI mode, It was calculated|required by the numerical value obtained by making the measurement range 1.2 mm x 0.91 mm with a 10-fold lens. In addition, when there is no occurrence of voids after lamination, and the difference between the irregularities on the conductor and other parts is less than 5 μm, ``○'' is used, and there is no generation of voids after lamination, but when the difference between the irregularities on the conductor and other parts is 5 μm or more Was evaluated as "Δ" and a case in which voids occurred after lamination was evaluated as "x".

In Examples 1 to 23, even when the components (D) to (H) are not contained, there is a difference in degree, but it is confirmed that the results are the same as in the above examples.

Claims (16)

(A) a maleimide compound having a biphenyl-type structure,
(B) a liquid or semi-solid curing agent and
(C) A resin composition containing a high molecular weight component. The resin composition according to claim 1, wherein the component (A) is represented by the following formula (A-3).
[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, and R ⁹ and R ¹⁰ are Each 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, and n represents an integer of 1 to 100. The resin composition according to claim 1, wherein the content of the component (A) is 10% by mass or more and 40% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The method according to claim 1, wherein the component (B) is at least one selected from amine-based non-solid curing agents, (meth)acrylic non-solid curing agents, allyl-based non-solid curing agents, maleimide-based non-solid curing agents, and butadiene-based non-solid curing agents. , Resin composition. The resin composition according to claim 4, wherein the component (B) is at least any one of an allyl-based non-solid curing agent and a maleimide-based non-solid curing agent. The resin composition according to claim 1, wherein the content of the component (B) is 0.1% by mass or more and 15% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein the component (C) is a thermoplastic resin. The resin composition according to claim 7, wherein the thermoplastic resin is at least one selected from polyimide resin, polycarbonate resin, and phenoxy resin. The resin composition according to claim 1, wherein the content of the component (C) is 0.5% by mass or more and 10% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, further comprising (D) an inorganic filler. The resin composition according to claim 10, wherein the content of the component (D) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, which is for forming an insulating layer. The resin composition according to claim 1, which is for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 13 provided on the support. A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 13. A semiconductor device comprising the printed wiring board according to claim 15.

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