TWI853957B - Resin composition - Google Patents

Abstract

The present invention provides a resin composition that can suppress unevenness generated in a cured substrate and obtain a cured product having excellent dielectric properties and peel strength, a resin sheet containing the resin composition, a printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device. The present invention provides a resin composition that contains (A) a compound containing an aromatic ester skeleton and an unsaturated bond, and (B) a free radical polymerizable compound, wherein the content of the component (A) is 0.1% by mass or more and 30% by mass or less, when the non-volatile components in the resin composition are 100% by mass.

Description

Resin composition

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

As a manufacturing technology for printed wiring boards, a manufacturing method using a stacking method in which insulating layers and conductive layers are alternately stacked is known.

As an insulating material for a printed wiring board having such an insulating layer, for example, a resin composition disclosed in Patent Document 1. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2019-6869

[Problems solved by the invention]

In recent years, further improvement of dielectric properties such as dielectric constant and dielectric loss tangent of the insulating layer, and further improvement of peel strength between the conductive layer formed by plating are expected. In addition, when a resin sheet is laminated on a substrate with unevenness to form an insulating layer, the surface on the opposite side of the substrate to the insulating layer will follow the unevenness of the substrate, which will reduce the flatness of the insulating layer and cause unevenness in the cured substrate (unevenness on the surface of the insulating layer). If there is unevenness on the cured substrate, the composition of the insulating layer will become uneven, which may deteriorate the wiring formability.

The subject of the present invention is to provide a resin composition that can suppress unevenness generated in a cured substrate and can obtain a cured product having excellent dielectric properties and peel strength, a resin sheet containing the resin composition, a printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device. [Means for Solving the Problem]

As a result of a detailed examination of the above-mentioned problems, the inventors found that the above-mentioned problems can be solved by making it contain a certain amount of (A) a compound containing an aromatic ester skeleton and an unsaturated bond, and (B) a radical polymerizable compound, thereby completing the present invention.

That is, the present invention comprises the following contents. [1] A resin composition comprising (A) a compound containing an aromatic ester skeleton and an unsaturated bond, and (B) a radical polymerizable compound, wherein the content of component (A) is from 0.1% by mass to 30% by mass, based on 100% by mass of the non-volatile components in the resin composition. [2] A resin composition described in [1], wherein component (A) is either a compound represented by the following general formula (A-1) or a compound represented by the following general formula (A-2). In general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of a combination thereof. n represents an integer of 0 to 10. In the general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent, and Ar ²² each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. m represents an integer of 2 or 3. ) [3] A resin composition as described in [1] or [2] which further contains (C) an inorganic filler. [4] A resin composition as described in [3] wherein the content of component (C) is 50% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. [5] A resin composition as described in any one of [1] to [4] which further contains (D) a thermoplastic resin. [6] A resin composition as described in any one of [1] to [5] which further contains (E) a thermosetting resin. [7] Component (B) is a resin composition described in any one of [1] to [6], comprising: a maleimide-based free radical polymerizable compound containing a maleimide group and a vinylphenyl-based free radical polymerizable compound containing a vinylphenyl group. [8] A resin composition described in any one of [1] to [7] for use in forming an insulating layer. [9] A resin composition described in any one of [1] to [8] for use in forming an insulating layer to be formed into a conductive layer. [10] A resin sheet comprising a support and a resin composition layer comprising the resin composition described in any one of [1] to [9] provided on the support. [11] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition described in any one of [1] to [9]. [12] A semiconductor device comprising the printed wiring board described in [11]. [Effects of the Invention]

According to the present invention, there are provided a resin composition capable of suppressing unevenness in curing a substrate and obtaining a cured product having excellent dielectric properties, peel strength and elongation at fracture, a resin sheet containing the resin composition, a printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device.

[Type of implementation of the invention]

The following is a detailed description of the preferred embodiments of the present invention. However, the present invention is not limited to the embodiments and examples described below, and any modifications within the scope of the patent application of the present invention and its equivalent scope are also possible.

[Resin composition] The resin composition of the present invention is a resin composition containing: (A) a compound containing an aromatic ester skeleton and an unsaturated bond, and (B) a free radical polymerizable compound, wherein the content of the component (A) is 0.1% by mass to 30% by mass when the non-volatile components in the resin composition are 100% by mass. In the present invention, by containing a certain amount of the component (A) and containing the component (B), the unevenness generated in the cured substrate can be suppressed, and a cured product with excellent dielectric properties and peeling strength can be obtained. In addition, a cured product with excellent elongation at the fracture point can usually be obtained.

The resin composition can be combined with (A) to (B) components and contain any component. Examples of the optional component include (C) inorganic filler, (D) thermoplastic resin, (E) thermosetting resin, (F) curing accelerator, and (G) other additives. The following is a detailed description of each component contained in the resin composition.

<(A) Compound containing an aromatic ester skeleton and an unsaturated bond> The resin composition contains a compound containing an aromatic ester skeleton and an unsaturated bond as the component (A). By including the component (A) in the resin composition, unevenness in curing the substrate can be suppressed, and a cured product with excellent dielectric properties can be obtained. The component (A) can be used alone or in combination of two or more.

The content of component (A) is 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more and 30% by mass or less, preferably 28% by mass or less, and even more preferably 25% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition, from the viewpoint of suppressing unevenness in the cured substrate and obtaining a cured product with excellent dielectric properties.

(A) component has an aromatic ester skeleton. The aromatic ester skeleton refers to a skeleton having an ester bond and an aromatic ring bonded to one or both ends of the ester bond. Among them, those having aromatic rings at both ends of the ester bond are preferred. As a group having such a skeleton, for example, there can be cited arylcarbonyloxy, aryloxycarbonyl, arylcarbonyloxyaryl, aryloxycarbonylaryl, arylcarbonyloxyaryl, aryloxycarbonylaryl, aryloxycarbonyloxyaryl, and aryloxycarbonylaryl. In addition, the number of carbon atoms of the group having such a skeleton is preferably 7 to 20, more preferably 7 to 15, and more preferably 7 to 11. Aromatic hydrocarbon groups such as aryl and aryl may have substituents.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Examples of such an aryl group include phenyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, oxazinyl, pyrazinyl, triazinyl, etc., which are obtained by removing one hydrogen atom from a monocyclic aromatic compound; naphthyl, anthracenyl, phenanthrenyl, phenanthrenyl, quinolyl, isoquinolyl, quinazolinyl, phthalazinyl, pteridinyl, coumarin, indolyl, benzimidazolyl, benzofuranyl, acridinyl, etc., which are obtained by removing one hydrogen atom from a condensed ring aromatic compound; and the like.

The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and further preferably an arylene group having 6 to 10 carbon atoms. Examples of such an arylene group include phenylene, naphthylene, anthrylene, and diphenylene (-C ₆ H ₄ -C ₆ H ₄ -).

Component (A) contains an unsaturated bond. The unsaturated bond is preferably a carbon-carbon unsaturated bond. As the unsaturated bond, it is preferred to have a substituent having at least one unsaturated bond. Examples of the unsaturated bond include unsaturated hydrocarbon groups such as alkenyl groups having 2 to 30 carbon atoms and alkynyl groups having 2 to 30 carbon atoms. The unsaturated bond is preferably present as a substituent of a terminal aromatic hydrocarbon group, and is preferably present as a substituent of aromatic hydrocarbon groups at both ends.

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

Examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl, propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, and 1,3-butadienyl.

Among them, as the unsaturated bond, an alkenyl group having 2 to 30 carbon atoms is preferred, an alkenyl group having 2 to 10 carbon atoms is more preferred, an alkenyl group having 2 to 5 carbon atoms is more preferred, an allyl group, an isopropenyl group and a 1-propenyl group is more preferred, and an allyl group is particularly preferred.

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

As the aromatic alkyl group, a divalent aromatic alkyl group is preferred, an arylene group and an arylene alkyl group are preferred, and an arylene group is more preferred. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferred, an arylene group having 6 to 20 carbon atoms is preferred, and an arylene group having 6 to 10 carbon atoms is more preferred. Examples of such an arylene group include phenylene, naphthylene, anthrylene, and diphenylene. As the arylene alkyl group, an arylene alkyl group having 7 to 30 carbon atoms is preferred, an arylene alkyl group having 7 to 20 carbon atoms is preferred, and an arylene alkyl group having 7 to 15 carbon atoms is more preferred. Among these, phenylene is also preferred.

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

The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a cycloalkyl group having 5 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, and a cycloalkyl group represented by the following formulas (a) to (d). In formulas (a) to (d), "*" represents a bond.

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

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

Examples of the alkoxy group having 1 to 10 carbon atoms include, but are not particularly limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, and nonyloxy.

As the halogen atom, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. The above substituent may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). The unsaturated hydrocarbon group is as shown above. As the secondary substituent, unless otherwise specified, the same substituent as above can be used.

The component (A) is preferably any one of a compound represented by the following general formula (A-1) and a compound represented by the following general formula (A-2). (In general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of a combination thereof. n represents an integer of 0 to 10.) (In general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent, and Ar ²² each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. m represents an integer of 2 or 3.)

In the general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic alkyl group which may have a substituent. Examples of the monovalent aromatic alkyl group include phenyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, oxazinyl, pyrazinyl, triazinyl, etc., which are obtained by removing one hydrogen atom from a monocyclic aromatic compound; naphthyl, anthracenyl, phenenyl, phenanthrenyl, quinolyl, isoquinolyl, quinazolinyl, phthalazinyl, pteridinyl, coumarin, indolyl, benzimidazolyl, benzofuranyl, acridinyl, etc., which are obtained by removing one hydrogen atom from a condensed ring aromatic compound; and the like. Among them, phenyl is preferred from the viewpoint that the effect of the present invention can be significantly obtained. The monovalent aromatic hydrocarbon group represented by Ar ¹¹ may have a substituent. The substituent may be the same as the substituent that the aromatic ester skeleton may have. Among them, the substituent of Ar ¹¹ preferably contains an unsaturated bond.

In the general formula (A-1), Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent. As the divalent aromatic hydrocarbon group, aryl groups, arylalkyl groups, etc. can be mentioned, and aryl groups are preferred. As the aryl groups, aryl groups having 6 to 30 carbon atoms are preferred, aryl groups having 6 to 20 carbon atoms are preferred, and aryl groups having 6 to 10 carbon atoms are more preferred. As such aryl groups, for example, phenylene groups, naphthylene groups, anthrylene groups, diphenylene groups, etc. can be mentioned. As arylalkyl groups, arylalkyl groups having 7 to 30 carbon atoms are preferred, arylalkyl groups having 7 to 20 carbon atoms are preferred, and arylalkyl groups having 7 to 15 carbon atoms are more preferred. Among these, phenylene groups are also preferred.

The divalent aromatic hydrocarbon group represented by ^Ar12 may have a substituent. The substituent may be the same as the substituent which the aromatic ester skeleton may have.

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

The divalent aliphatic hydrocarbon group is preferably a divalent saturated aliphatic hydrocarbon group, preferably an alkylene group or a cycloalkylene group, and preferably a cycloalkylene group.

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

The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a cycloalkyl group having 5 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, and the cycloalkyl groups represented by the above formulas (a) to (d). The cycloalkyl group represented by formula (c) is preferred.

As the divalent group formed by such a combination, a divalent aromatic hydrocarbon group which may have a substituent and a divalent group of a divalent aliphatic hydrocarbon group which may have a substituent are preferred, and a divalent group of a plurality of divalent aromatic hydrocarbon groups which may have a substituent and a plurality of divalent aliphatic hydrocarbon groups which may have a substituent are alternately combined. As specific examples of the aforementioned divalent group, the following divalent groups (A1) to (A8) can be cited. In the formula, a1 to a8 represent integers of 0 to 10, preferably integers of 0 to 5. "*" represents a bonding bond, and the wavy line represents the structure obtained by reacting an aromatic compound, an acid halogenated product of an aromatic compound, or an esterified product of an aromatic compound used in the synthesis of component (A).

The divalent aromatic alkyl group and divalent aliphatic alkyl group represented by ^Ar13 may have a substituent. The substituent may be the same as the substituent which the aromatic ester skeleton may have.

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

In general formula (A-2), Ar ²¹ represents an m-valent aromatic alkyl group which may have a substituent. As the m-valent aromatic alkyl group, an m-valent aromatic alkyl group having 6 to 30 carbon atoms is preferred, an m-valent aromatic alkyl group having 6 to 20 carbon atoms is preferred, and an m-valent aromatic alkyl group having 6 to 10 carbon atoms is further preferred. The m-valent aromatic alkyl group represented by Ar ²¹ may also have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.

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

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

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

The component (A) may be synthesized by a known method. The component (A) may be synthesized by the method described in, for example, International Publication No. 2018/235424 or International Publication No. 2018/235425.

The weight average molecular weight of the component (A) is preferably 150 or more, more preferably 200 or more, more preferably 250 or more, and preferably 3000 or less, more preferably 2000 or less, more preferably 1500 or less, from the viewpoint of significantly obtaining the effect of the present invention. The weight average molecular weight of the component (A) is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The unsaturated bond equivalent of the component (A) is preferably 50 g/eq or more, more preferably 100 g/eq or more, and more preferably 150 g/eq., and is preferably 2000 g/eq. or less, more preferably 1000 g/eq. or less, and more preferably 500 g/eq. or less, from the viewpoint of significantly obtaining the effect of the present invention. The unsaturated bond equivalent is the mass of the component (A) containing 1 equivalent of unsaturated bonds.

<(B) Radical polymerizable compound> The resin composition contains a (B) radical polymerizable compound as the (B) component. However, the (B) component is removed from the (A) component. By including the (B) component in the resin composition, unevenness in the cured substrate can be suppressed, and a cured product with excellent dielectric properties and peel strength can be obtained. The (B) component can be used alone or in combination of two or more.

As the component (B), a compound having a function of curing the component (A) by generating radicals by heat or light can be used, that is, a compound having at least one radical polymerizable unsaturated group can be used. As such a compound, at least one selected from a maleimide radical-polymerizable compound containing a maleimide group, a vinylphenyl radical-polymerizable compound containing a vinylphenyl group, a (meth)acrylic radical-polymerizable compound, an allyl radical-polymerizable compound, a butadiene radical-polymerizable compound, and a benzocyclobutene radical-polymerizable compound is preferred, at least any one of a maleimide radical-polymerizable compound, a vinylphenyl radical-polymerizable compound, a (meth)acrylic radical-polymerizable compound, and a benzocyclobutene radical-polymerizable compound is preferred, and any one of a maleimide radical-polymerizable compound, a vinylphenyl radical-polymerizable compound, and a benzocyclobutene radical-polymerizable compound is preferred.

The component (B) may also have a free radical polymerizable unsaturated group. Examples of the free radical polymerizable unsaturated group include a group having an ethylene double bond that is hardenable by irradiation with active energy rays. Examples of such a group include a vinyl group, an allyl group, a vinylphenyl group, an acryl group, a methacrylic group, a maleimide group, a fumaric group, and a maleic group. Preferably, the group is at least one selected from the group consisting of an allyl group, a vinylphenyl group, an acryl group, and a methacrylic group.

The component (B) preferably has one or more free radical polymerizable unsaturated groups, more preferably two or more. The upper limit is not particularly limited, but may be 10 or less.

The maleimide-based free radical polymerizable compound is a compound containing a maleimide group represented by the following formula (B-1) in the molecule. The maleimide-based free radical polymerizable compound includes a maleimide-based free radical polymerizable compound in the form of a solid component and a maleimide-based free radical polymerizable compound in the form of a liquid or semi-solid component.

The determination of liquid, semi-solid, and solid components is based on Annex 2 "Methods for Confirming Liquid State" of the Ministry's Ordinance on Testing and Properties of Hazardous Substances (Ministry of Education Autonomous Ordinance No. 1, 2001). The specific determination method is as follows.

(1) Equipment Constant temperature water tank: Use a water tank with a mixer, heater, thermometer, automatic temperature regulator (temperature control within ±0.1℃) and a depth of 150mm or more. In addition, for the determination of liquid, semi-solid, and solid components, use a combination of a low-temperature constant temperature water tank (model BU300) and a immersion constant temperature device heater (model BF500) manufactured by Yamato Scientific Co., Ltd. Place about 22 liters of tap water in the low-temperature constant temperature water tank (model BU300), input power to the heater (model BF500) installed there, set it to the set temperature (20℃ or 60℃), and fine-tune the water temperature with the heater (model BF500) to ±0.1℃. Any device that can be adjusted in the same way can be used.

Test tube: As shown in Figure 1, the test tube is a flat-bottomed cylindrical transparent glass tube with an inner diameter of 30mm and a height of 120mm. The test tube is marked with marking lines 11A and 12B at heights of 55mm and 85mm from the bottom of the tube. The test tube mouth is sealed with a rubber plug 13a. The test tube 10a for liquid determination with the same size is marked with marking lines in the same way. The test tube mouth is sealed with a rubber plug 13b with an opening in the center for inserting and supporting the thermometer. The temperature measurement test tube 10b is used with a thermometer 14 inserted in the rubber plug 13b. The marking line from the bottom of the tube to the height of 55mm is referred to as "A line" and the marking line from the bottom of the tube to the height of 85mm is referred to as "B line". As the thermometer 14, a thermometer for measuring freezing point specified in JIS B7410 (1982) "Glass thermometer for petroleum testing" (SOP-58 scale range 0 to 100°C) is used, but any thermometer capable of measuring within the temperature range of 0 to 100°C may be used.

(2) Test implementation procedure Put the sample that has been placed under atmospheric pressure at a temperature of 60±5℃ for more than 24 hours into the liquid determination test tube 10a shown in Figure 1(a) and the temperature measurement test tube 10b shown in Figure 1(b) until the 11A line is reached. Place the two test tubes 10a and 10b in a low-temperature constant-temperature water bath until the 12B line is below the water surface and they stand upright. Make the lower end of the thermometer 30mm lower than the 11A line. After the sample temperature reaches the set temperature ±0.1℃, maintain this state for 10 minutes. After 10 minutes, take the liquid state determination test tube 10a out of the low-temperature constant-temperature water tank and pour it horizontally onto a horizontal test bench. Use a stopwatch to measure and record the time it takes for the tip of the liquid surface in the test tube to move from line 11A to line 12B.

Similarly, for samples placed under atmospheric pressure at a temperature of 20±5℃ for more than 24 hours, the same test is carried out as for samples placed statically at an atmospheric pressure of 60±5℃ for more than 24 hours. The time for the tip of the liquid surface in the test tube to move from line 11A to line 12B is measured and recorded using a stopwatch.

For 20℃, the measured time is within 90 seconds and is judged as liquid. For 20℃, the measured time exceeds 90 seconds and for 60℃, the measured time is within 90 seconds and is judged as semi-solid. For 60℃, the measured time exceeds 90 seconds and is judged as solid.

The number of maleimide groups per molecule of the maleimide-based free radical polymerizable compound in the form of a solid component is preferably 1 or more, more preferably 2 or more, more preferably 3 or more, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less, 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 maleimide-based radical polymerizable compound in the form of a solid component preferably has either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably has both an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

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

As the aromatic alkyl group, monovalent and divalent aromatic alkyl groups are preferred, and aryl groups and arylene groups are more preferred. As the arylene group, arylene groups having 6 to 30 carbon atoms are preferred, arylene groups having 6 to 20 carbon atoms are preferred, and arylene groups having 6 to 10 carbon atoms are more preferred. As such arylene groups, for example, phenylene, naphthylene, anthrylene, aralkyl, diphenylene, biphenyl aralkyl, etc. can be cited, among which phenylene, aralkyl, diphenylene, biphenyl aralkyl are also preferred, and phenylene, aralkyl, and diphenylene are preferred. As the aryl group, aryl groups having 6 to 30 carbon atoms are preferred, aryl groups having 6 to 20 carbon atoms are preferred, aryl groups having 6 to 10 carbon atoms are more preferred, and phenyl is particularly preferred.

For the maleimide-based free radical polymerizable compound in the form of a solid component, it is preferred that the nitrogen atom of the maleimide group is directly bonded to a monovalent or divalent aromatic hydrocarbon group in order to significantly obtain the desired effect of the present invention. Here, "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

The maleimide compound in the form of a solid component preferably has a structure represented by the following formula (Ba), for example.

[wherein, R ^c each independently represents a substituent; X ^c each independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO-, or -OCO- (preferably a single bond or an alkylene group); Z ^c each independently represents a non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent (preferably an aromatic ring which may have a substituent, particularly preferably a benzene ring which may have a substituent); s represents an integer of 1 or more (preferably an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 20); t each independently represents an integer of 0 or more; u each independently represents an integer of 0 to 2 (preferably 0)] a maleimide compound represented by formula (Ba-1) to (Ba-4):

[wherein, R ^c1 , R ^c2 and R ^c3 each independently represent an alkyl group; X ^c1 and X ^c2 each independently represent a single bond or an alkylene group; s represents an integer greater than 1 (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and more preferably an integer of 1 to 20); t' represents an integer of 1 to 5; u1, u2 and u3 each independently represent an integer of 0 to 2 (preferably 0)] a maleimide compound represented by. Furthermore, each of the s unit, t unit, t' unit, u unit, u1 unit, u2 unit and u3 unit may be the same or different.

In another embodiment, the maleimide-based radical polymerizable compound in the form of a solid component preferably has a structure represented by the following formula (B-2). In formula (B-2), R ³¹ and R ³⁶ represent maleimide groups, R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and D each independently represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

In formula (B-2), R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.

As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred. The alkyl group may be linear, branched, or cyclic. Examples of such an alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and the like.

Among the aryl groups, an aryl group having 6 to 20 carbon atoms is preferred, an aryl group having 6 to 15 carbon atoms is more preferred, and an aryl group having 6 to 10 carbon atoms is more preferred. The aryl group may be a monocyclic ring or a condensed ring. Examples of such aryl groups include phenyl, naphthyl, anthracenyl, and the like.

Alkyl and aryl groups may also have substituents. There are no particular limitations on the substituents, and examples thereof include halogen atoms, -OH, -OC _1-6 alkyl, -N(C _1-10 alkyl) ₂ , C _1-10 alkyl, C _6-10 aryl, -NH ₂ , -CN, -C(O)OC _1-10 alkyl, -COOH, -C(O)H, -NO ₂ , etc. Among them, the term "C _pq " (p and q are positive integers, satisfying p＜q) indicates that the number of carbon atoms of the organic group recorded after the term is p~q. For example, the term "C _1-10 alkyl" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure may also contain a spiro ring or a condensed ring.

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

D in formula (B-2) represents a divalent aromatic group. Examples of the divalent aromatic group include phenylene, naphthylene, anthrylene, aralkyl, diphenylene, biphenylaralkyl, etc. Among them, diphenylene and biphenylaralkyl are preferred, and diphenylene is more preferred. The divalent aromatic group may have a substituent. The substituent may be the same as the substituent that the alkyl group represented by R ³² in formula (B-2) may have.

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

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

The maleimide-based radical polymerizable compound in the form of a solid component is preferably a resin represented by formula (B-3). In formula (B-3), R ³⁷ and R ³⁸ represent a maleimide group. a1 represents an integer of 1 to 100.

a1 is the same as a in formula (B-2), and the preferred range is also the same.

The weight average molecular weight (Mw) of the maleimide-based free radical polymerizable compound in the form of a solid component is preferably 150-5000, more preferably 300-2500.

The functional group equivalent weight of the maleimide group of the maleimide-based free radical polymerizable compound is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to 1000 g/eq., more preferably 150 g/eq. to 500 g/eq., and particularly preferably 200 g/eq. to 300 g/eq.

As the maleimide-based radical polymerizable compound in the form of a solid component, commercial products can be used. Examples of commercial products include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.; "BMI-50P" manufactured by KI Chemical Industry Co., Ltd.; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", "BMI-5100" manufactured by Yamato Chemical Industries Co., Ltd.; "BMI-4,4'-BPE", "BMI-70" manufactured by KI Chemical Industry Co., Ltd.; and "BMI-80" manufactured by KI Chemical Industry Co., Ltd.

The maleimide-based radical polymerizable compound in the form of a liquid or semi-solid component is a compound having at least one maleimide group in the molecule.

The maleimide-based radical polymerizable compound in the form of a liquid or semi-solid component preferably contains at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.

The number of carbon atoms in the alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and more preferably 40 or less. The alkyl group may be any of a straight chain, a branched chain, and a ring, and a straight chain is also preferred. Examples of such an alkyl group include pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group having 5 or more carbon atoms may have an alkylene group having 5 or more carbon atoms as a substituent.

The number of carbon atoms in the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and more preferably 40 or less. The alkylene group may be any of a linear chain, a branched chain, and a cyclic shape, with a linear chain being preferred. The so-called cyclic alkylene group includes both a case of containing only a cyclic alkylene group and a case of containing both a linear chain alkylene group and a cyclic alkylene group. As such an alkylene group, for example, a pentylene, a hexylene, a heptylene, an octylene, a nonylene, a decylene, an undecylene, a dodecanylene, a tridecanylene, a heptadecanylene, a hexadecanylene, a group having an octyl carbon-ring hexyl carbon structure, a group having an octyl carbon-ring hexyl-octyl carbon structure, a group having a propyl-ring hexyl-octyl carbon structure, and the like can be cited.

The maleimide-based radical polymerizable compound in the form of a liquid or semisolid component preferably contains both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms, from the viewpoint of significantly obtaining the effect of the present invention.

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

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms preferably have no substituent, but may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton in the component (A) may have.

For the maleimide-based free radical polymerizable compound in the form of a liquid or semi-solid component, the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms are preferably directly bonded to the nitrogen atom of the maleimide group.

The number of maleimide groups in one molecule of the maleimide radical polymerizable compound in the form of a liquid or semi-solid component may be 1, but is preferably 2 or more, more preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. By using a maleimide radical polymerizable compound in the form of a liquid or semi-solid component having 2 or more maleimide groups in one molecule, the effect of the present invention can be significantly obtained.

The maleimide-based radical polymerizable compound in liquid or semi-solid form is preferably represented by the following general formula (B-4). In the general formula (B-4), M represents an alkylene group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M represents an alkylene group having 5 or more carbon atoms which may have a substituent. The alkylene group of M is the same as the alkylene group having 5 or more carbon atoms described above. The substituent of M is the same as the substituent that the aromatic ester skeleton in the component (A) may have, and the substituent is preferably an alkylene group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR ⁰ - (R ⁰ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), an oxygen atom, a sulfur atom, C(=O)NR ⁰ -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group formed by a combination of two or more of these divalent groups. The alkylene group, the alkenylene group, the alkynylene group, the arylene group, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group formed by a combination of two or more of these divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide refers to a divalent group derived from phthalimide, specifically a group represented by the general formula (B-5). The divalent group derived from pyromellitic acid diimide refers to a divalent group derived from pyromellitic acid diimide, specifically a group represented by the general formula (B-6). In the formula, "*" represents a bonding bond.

The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. The alkylene group may be any of a linear chain, a branched chain, and a ring. Examples of such an alkylene group include a methyl ethylene group, a cyclohexylene group, 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 tridecyl group, a heptadecanyl group, a hexadecanyl group, a group having an octyl carbon-ring hexylene group structure, a group having an octyl carbon-ring hexylene group-octyl carbon structure, and a group having a propyl-ring hexylene group-octyl carbon structure.

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

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. The alkynylene group may be in any of a straight chain, a branched chain, and a ring. Examples of such an alkynylene group include methylethynylene, cyclohexynylene, pentynylene, hexynylene, heptynylene, and octynylene.

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, more preferably an arylene group having 6 to 14 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include phenylene, naphthylene, and anthrylene groups.

The divalent linking group in L, which is an alkylene group, alkenylene group, alkynylene group, and arylene group, may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton in the component (A) may have, 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 a divalent group consisting of a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; and a divalent group consisting of an alkylene group and a divalent group derived from pyromellitic acid diimide. The group consisting of a combination of two or more divalent groups may form a ring such as a condensed ring by combining the groups. The number of repeating units of the group consisting of a combination of two or more divalent groups may be 1 to 10 repeating units.

Among them, L in the general formula (B-4) is preferably an oxygen atom, an aryl group having 6 to 24 carbon atoms which may have a substituent, an alkyl group having 1 to 50 carbon atoms which may have a substituent, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or a divalent group composed of a combination of two or more of these groups. Among them, L is preferably an alkylene group; a divalent group having a structure of alkylene group-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of alkylene group-divalent group derived from phthalimide-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-divalent group derived from phthalimide; and a divalent group having a structure of alkylene group-divalent group derived from pyromellitic acid diimide.

The maleimide-based radical polymerizable compound in liquid or semi-solid form represented by the general formula (B-4) is preferably represented by the general formula (B-7). In general formula (B-7), ^M1 each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent, and Z each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group containing an aromatic ring which may have a substituent. t represents an integer of 1 to 10.

^M1 each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent. ^M1 is the same as M in the general formula (B-4).

Z each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group containing an aromatic ring which may have a substituent. The alkylene group in Z may be any of a chain, a branched chain, and a ring, and a ring, i.e., a cyclic alkylene group having 5 or more carbon atoms which may have a substituent is preferred. The number of carbon atoms in the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and more preferably 40 or less. Examples of such an alkylene group include a group having an octyl carbon-ring hexylene structure, a group having an octyl carbon-ring hexylene-octyl carbon structure, and a group having a propyl-ring hexylene-octyl carbon structure.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by Z include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, and an aromatic heterocyclic ring, and a benzene ring, a phthalimide ring, and a pyromellitic acid diimide ring are preferred. That is, as the divalent group having an aromatic ring, a divalent group containing a benzene ring which may have a substituent, a divalent group containing a phthalimide ring which may have a substituent, and a divalent group containing a pyromellitic acid diimide ring which may have a substituent are preferred. Examples of the divalent group having an aromatic ring include a group consisting of a divalent group derived from phthalimide and an oxygen atom; a group consisting of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group consisting of an alkylene group and a divalent group derived from pyromellitic acid diimide; a divalent group derived from pyromellitic acid diimide; a group consisting of a divalent group derived from phthalimide and an alkylene group. The above-mentioned arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in the general formula (B-4).

The divalent group having an alkylene group and an aromatic ring represented by Z may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton in the component (A) may have.

As specific examples of the group represented by Z, the following groups can be cited. In the formula, "*" represents a bonding bond.

The maleimide-based free radical polymerizable compound represented by general formula (B-4) is preferably any one of the maleimide-based free radical polymerizable compound in liquid or semi-solid form represented by general formula (B-8) and the maleimide-based free radical polymerizable compound in liquid or semi-solid form represented by general formula (B-9). In general formula (B-8), ^M2 and ^M3 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, ^R40 each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group consisting of two or more of these groups. t1 represents an integer from 1 to 10. In general formula (B-9), ^M4 , ^M6 , and ^M7 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, ^M5 each independently represents a divalent group containing an aromatic ring which may have a substituent, ^R41 and ^R42 each independently represent an alkylene group having 5 or more carbon atoms. t2 represents an integer from 0 to 10, and u1 and u2 each independently represent an integer from 0 to 4.

^M2 and ^M3 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent. ^M2 and ^M3 are the same as the alkylene group having 5 or more carbon atoms represented by M in the general formula (B-4), and are preferably hexadecylene.

R ⁴⁰ each independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more of these divalent groups. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-4). R ⁴⁰ is preferably a group consisting of a combination of two or more divalent groups or an oxygen atom.

Examples of the group consisting of two or more divalent groups in R ⁴⁰ include an oxygen atom, an arylene group, and an alkylene group. Specific examples of the group consisting of two or more divalent groups include the following groups. In the formula, "*" represents a bonding bond.

^M4 , ^M6 and ^M7 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent. ^M4 , ^M6 and ^M7 are the same as the alkylene group having 5 or more carbon atoms which may have a substituent represented by M in the general formula (B-4), preferably hexylene, heptylene, octylene, nonylene and decylene, and more preferably octylene.

^M5 each independently represents a divalent group containing an aromatic ring which may have a substituent. ^M5 is the same as the divalent group containing an aromatic ring which may have a substituent represented by Z in the general formula (B-7), and is preferably a group formed by a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; preferably, a group formed by a combination of a divalent group derived from phthalimide and an alkylene group; more preferably, a group formed by a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide. The above-mentioned arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in the general formula (B-4).

As specific examples of the group represented by M ⁵ , the following groups can be cited. In the formula, "*" represents a bonding bond.

^R41 and ^R42 each independently represent an alkyl group having at least 5 carbon atoms. ^R41 and ^R42 are the same as the above-mentioned alkyl group having at least 5 carbon atoms, preferably hexyl, heptyl, octyl, nonyl, and decyl, and more preferably hexyl and octyl.

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

As specific examples of maleimide-based free radical polymerizable compounds in liquid or semi-solid form, the following compounds (B1) to (B3) can be cited. However, maleimide-based free radical polymerizable compounds in liquid or semi-solid form are not limited to these specific examples. In the formula, v represents an integer of 1 to 10.

Specific examples of maleimide-based free radical polymerizable compounds in liquid or semisolid form include "BMI1500" (compound of formula (B1)), "BMI1700" (compound of formula (B2)), and "BMI689" (compound of formula (B3)) manufactured by Designer Moleculars.

The maleimide group equivalent of the maleimide radical polymerizable compound in the form of a liquid or semi-solid component is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to 1000 g/eq., and more preferably 150 g/eq. to 500 g/eq., from the viewpoint of significantly obtaining the desired effect of the present invention. The maleimide group equivalent is the mass of the maleimide radical polymerizable compound in the form of a liquid or semi-solid component containing 1 equivalent of maleimide groups.

The vinylphenyl radical polymerizable compound is a radical polymerizable compound having a vinylphenyl group. The vinylphenyl radical polymerizable compound is preferably in a liquid or semi-solid state. The determination of the liquid or semi-solid state is as described above. The so-called vinylphenyl group is a group having the structure shown below. (* indicates a binding key)

The vinylphenyl-based radical polymerizable compound preferably has two or more vinylphenyl groups per molecule from the viewpoint of obtaining a cured product having a low dielectric loss tangent.

The vinylphenyl-based radical polymerizable compound preferably has a cyclic structure from the viewpoint of obtaining a cured product with a low dielectric loss tangent. As the cyclic structure, a divalent cyclic group is preferred. As the divalent cyclic group, it may be any of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic cyclic structure. Furthermore, the divalent cyclic group may also be present in plural.

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

In the ring of the divalent cyclic group, the ring skeleton may be composed of heteroatoms other than carbon atoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms, and oxygen atoms are preferred. The ring may have one heteroatom or two or more heteroatoms.

Specific examples of the divalent cyclic group include the following divalent group (xii) or (xiii). (In the divalent groups (xii) and (xiii), ^R51 , ^R52 , ^R55 , ^R56 , ^R57 , ^R61 , and ^R62 each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and ^R53 , ^R54 , ^R58 , ^R59 , and ^R60 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group)

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the alkyl group having 6 or less carbon atoms include methyl, ethyl, propyl, butyl, pentyl and hexyl, preferably methyl. ^R51 , ^R52 , ^R55 , ^R56 , ^R57 , ^R61 and ^R62 preferably represent methyl. ^R53 , ^R54 , ^R58 , ^R59 and ^R60 preferably represent hydrogen or methyl.

Furthermore, the divalent cyclic group may be a combination of a plurality of divalent cyclic groups. As a specific example of a combination of divalent cyclic groups, a divalent cyclic group (divalent group (a)) represented by the following formula (B4) can be cited. (In formula (B4), R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; R ⁷³ , R ⁷⁴ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. d1 and d2 represent integers of 0 to 300. However, the case where one of d1 and d2 is 0 is excluded.)

R ⁷¹ , R ⁷² , R ⁸⁵ and R ⁸⁶ are the same as R ⁵¹ in formula (xii). R ⁷³ , R ⁷⁴ , R ⁸³ and R ⁸⁴ are the same as R ⁵³ in formula (xii). R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ and R ⁸² are the same as R ⁵⁵ in formula (xiii). R ⁷⁸ , R ⁷⁹ and R ⁸⁰ are the same as R ⁵⁸ in formula (xiii).

d1 and d2 represent integers from 0 to 300. However, the case where one of d1 and d2 is 0 is excluded. As d1 and d2, those representing integers from 1 to 100 are preferred, those representing integers from 1 to 50 are more preferred, and those representing integers from 1 to 10 are even more preferred. d1 and d2 may be the same or different.

The divalent cyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfonic acid group, a cyano group, a nitro group, a hydroxyl group, a hydroxyl group, an oxo group, and the like, with an alkyl group being preferred.

Vinylphenyl may be directly bonded to the divalent cyclic group or may be bonded via a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, arylene, heteroarylene, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., and may also be a combination of these plural groups. As the alkylene, an alkylene having 1 to 10 carbon atoms is preferred, an alkylene having 1 to 6 carbon atoms is more preferred, an alkylene having 1 to 5 carbon atoms, or an alkylene having 1 to 4 carbon atoms is more preferred. The alkylene may be any of a straight chain, a branched chain, and a ring. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene, and methylene, ethylene, and 1,1-dimethylethylene are preferred. As alkenylene, alkenylene having 2 to 10 carbon atoms is preferred, alkenylene having 2 to 6 carbon atoms is preferred, and alkenylene having 2 to 5 carbon atoms is more preferred. As arylene and heteroarylene, arylene or heteroarylene having 6 to 20 carbon atoms is preferred, and arylene or heteroarylene having 6 to 10 carbon atoms is preferred. As a divalent linking group, an alkylene group is preferred, and methylene is also preferred.

The vinylphenyl-based radical polymerizable compound is preferably one represented by the following formula (B-10). (In formula (B-10), R ⁹¹ and R ⁹² each independently represent a divalent linking group. Ring B1 represents a divalent cyclic group)

^R91 and ^R92 each independently represent a divalent linking group. The divalent linking group is the same as the above-mentioned divalent linking group.

Ring B1 represents a divalent cyclic group. Ring B is the same as the above-mentioned divalent cyclic group.

Ring B1 may have a substituent. The substituent is the same as the substituent that the above-mentioned divalent cyclic group may have.

In other embodiments, the vinylphenyl-based free radical polymerizable compound is preferably a compound having a repeating unit represented by formula (B-11) (the number of repeating units is preferably 2 to 200). The compound may also be a copolymer further having other styrene skeleton units such as styrene units and ethylstyrene units. In the case of having other styrene skeleton units, the ratio of the repeating units of formula (B-11) is preferably 5 to 70 mol% relative to the total styrene skeleton units.

[wherein, ^Re5 , ^Re6 and ^Re7 each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom)]

Although specific examples of the vinylphenyl-based radical polymerizable compound are shown below, the present invention is not limited thereto. (q1 is the same as d1 in formula (B4), q2 is the same as d2 in formula (B4))

As the vinylphenyl-based radical polymerizable compound, commercial products can be used, for example, "OPE-2St", "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl modified polyphenylene ether) manufactured by Mitsubishi Gas Chemical Co., Ltd.; "ODV-XET-X03", "ODV-XET-X04", "ODV-XET-X05" (divinylbenzene polymer) manufactured by Nippon Steel Chemical & Material Co., Ltd., etc. The vinylphenyl-based radical polymerizable compound can be used alone or in combination of two or more.

The number average molecular weight of the vinylphenyl-based free radical polymerizable compound is preferably 3000 or less, more preferably 2500 or less, more preferably 2000 or less, and 1500 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention. The lower limit is preferably 100 or more, more preferably 300 or more, more preferably 500 or more, and 1000 or more. The number average molecular weight is a polystyrene-converted number average molecular weight measured using gel permeation chromatography (GPC).

(Meth)acrylic radical polymerizable compounds are compounds containing acryl and methacrylic groups and combinations thereof. From the viewpoint of significantly obtaining the desired effect of the present invention, (meth)acrylic radical polymerizable compounds preferably have two or more (meth)acrylic groups in one molecule. The term "(meth)acrylic group" includes acryl and methacrylic groups and combinations thereof. (Meth)acrylic radical polymerizable compounds are preferably in the form of liquid or semi-solid components. The determination of liquid or semi-solid components is as described above.

The (meth)acrylic radical polymerizable compound preferably 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 preferred. As the divalent cyclic group, any of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic cyclic structure may be used. Among them, from the viewpoint of remarkably obtaining the desired effect of the present invention, a cyclic group containing an alicyclic structure is preferred.

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

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

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

The divalent cyclic group may have a substituent. Examples of such a substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfonic acid group, a cyano group, a nitro group, a hydroxyl group, a hydroxyl group, an oxo group, and the like, preferably an alkyl group.

The (meth)acryloyl group may be directly bonded to the divalent cyclic group or may be bonded via a divalent linking group. Examples of the divalent linking group include 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-, etc., and a combination of a plurality of these groups may also be used. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms is more preferred. The alkylene group may be any of a straight chain, a branched chain, and a ring. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene, and methylene, ethylene, and 1,1-dimethylethylene are preferred. As alkenylene, alkenylene having 2 to 10 carbon atoms is preferred, alkenylene having 2 to 6 carbon atoms is more preferred, and alkenylene having 2 to 5 carbon atoms is more preferred. As arylene and heteroarylene, arylene or heteroarylene having 6 to 20 carbon atoms is preferred, and arylene or heteroarylene having 6 to 10 carbon atoms is more preferred. As divalent linking groups, alkylene is preferred, and methylene and 1,1-dimethylethylene are also preferred.

The (meth)acrylic radical polymerizable compound is preferably one represented by the following formula (B-11). (In formula (B-11), ^R101 and ^R104 each independently represent an acryloyl group or a methacryloyl group, ^R102 and ^R103 each independently represent a divalent linking group. Ring B2 represents a divalent cyclic group)

^R101 and ^R104 each independently represent an acryloyl group or a methacryloyl group, and an acryloyl group is preferred.

^R102 and ^R103 each independently represent a divalent linking group. The divalent linking group is the same as the divalent linking group capable of bonding to a (meth)acryloyl group.

Ring B2 represents a divalent cyclic group. Ring B2 is the same as the above-mentioned divalent cyclic group. Ring B2 may have a substituent. The substituent is the same as the substituent that the above-mentioned divalent cyclic group may have.

Specific examples of the (meth)acrylic radical polymerizable compound include the following, but the present invention is not limited thereto.

As the (meth)acrylic free radical polymerizable compound, commercial products can be used, for example, "A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "DCP-A" manufactured by Kyoei Chemical Co., Ltd., "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" manufactured by Nippon Kayaku Co., Ltd., "NK Ester DCP" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., etc.

The (meth)acrylic acid equivalent of the (meth)acrylic acid free radical polymerizable compound is preferably 30 g/eq. to 400 g/eq., more preferably 50 g/eq. to 300 g/eq., and more preferably 75 g/eq. to 200 g/eq., from the viewpoint of significantly obtaining the desired effect of the present invention. The (meth)acrylic acid equivalent is the mass of the (meth)acrylic acid free radical polymerizable compound containing 1 equivalent of (meth)acrylic acid groups.

The so-called allyl radical polymerizable compound refers to a compound having at least one allyl group in the molecule. The allyl radical polymerizable compound is preferably in the form of a liquid or semi-solid component. The determination of the liquid or semi-solid component is as described above. The allyl radical polymerizable compound is preferably one having one or more allyl groups in one molecule, and more preferably one having two or more allyl groups. Although there is no particular lower limit, it is preferably 10 or less, and more preferably 5 or less.

Furthermore, the allyl radical polymerizable compound preferably contains any one of a benzoxazine ring, a phenol ring, an isocyanuric acid ring, an epoxy group, and a carboxylic acid derivative having a cyclic structure in addition to the allyl group, from the viewpoint of remarkably obtaining the desired effect of the present invention.

The allyl radical polymerizable compound having a benzoxazine ring is preferably bonded to either the nitrogen atom of the benzoxazine ring or the benzene ring, and is more preferably bonded to the nitrogen atom.

Examples of the allyl radical polymerizable compound having a phenol ring include allyl group-containing cresol resins, allyl group-containing novolac-type phenol resins, and allyl group-containing cresol novolac resins.

The allyl radical polymerizable compound having an isocyanuric acid structure is preferably one in which the nitrogen atom of the isocyanuric acid structure is directly bonded to the allyl group. Examples of the allyl radical polymerizable compound having an isocyanuric acid structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, and the like.

The allyl radical polymerizable compound having an epoxy group is preferably one having two or more epoxy groups in one molecule. Furthermore, the allyl radical polymerizable compound having an epoxy group is preferably one having an aromatic structure. When two or more allyl radical polymerizable compounds having an epoxy group are used, it is preferred that the compound has at least one aromatic structure. The so-called aromatic structure refers to a chemical structure generally defined as an aromatic structure, and also includes polycyclic aromatics and aromatic heterocycles. The allyl radical polymerizable compound having an epoxy group is preferably one having a bisphenol structure. Examples of the bisphenol structure include bisphenol A type, bisphenol F type, bisphenol AF type, and the like.

As an allyl radical polymerizable compound containing a carboxylic acid derivative having a cyclic structure, a carboxylic acid allyl group having a cyclic structure is preferred. As a cyclic structure, it can be any one of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure. In addition, the cyclic group can also form a skeleton of the ring by heteroatoms other than carbon atoms. As heteroatoms, for example, oxygen atoms, sulfur atoms, nitrogen atoms, etc. can be cited, and nitrogen atoms are preferred. The heteroatoms in the aforementioned ring can have one or more.

Examples of the carboxylic acid having a ring structure include isocyanuric acid, phthalic acid, phthalic acid, and cyclohexanedicarboxylic acid. Examples of the allyl radical polymerizable compound containing a carboxylic acid derivative having a ring structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl phthalate, allyl phthalate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, allyl cyclohexanedicarboxylate, and diallyl cyclohexanedicarboxylate.

Allyl radical polymerizable compounds can be used as commercial products. Examples of commercial products include "MEH-8000H" and "MEH-8005" manufactured by Meiwa Chemicals (allyl radical polymerizable compounds having a phenol ring); "RE-810NM" manufactured by Nippon Kayaku Co., Ltd. (allyl radical polymerizable compound having an epoxy group); "ALP-d" manufactured by Shikoku Chemicals Co., Ltd. (allyl radical polymerizable compound having a benzoxazine ring); "L-DAIC" manufactured by Shikoku Chemicals Co., Ltd. (allyl radical polymerizable compound having an isocyanuric acid ring); "TAIC" manufactured by Nippon Chemicals Co., Ltd. (allyl radical polymerizable compound having an isocyanuric acid ring (triallyl isocyanurate)); Osaka Soda Co., Ltd. Ltd.'s "MDAC" (an allyl radical polymerizable compound having a cyclohexanedicarboxylic acid derivative); Nikko Techno Fine Chemical Co., Ltd.'s "DAD" (diallyl phthalate); Osaka Soda Co., Ltd.'s "Daiso Dup Monomer" (diallyl phthalate), etc.

The allyl equivalent of the allyl radical polymerizable compound is preferably 20 g/eq. to 1000 g/eq., more preferably 50 g/eq. to 500 g/eq., and even more preferably 100 g/eq. to 300 g/eq., from the viewpoint of significantly obtaining the desired effect of the present invention. The allyl equivalent is the mass of the allyl radical polymerizable compound containing 1 equivalent of allyl groups.

The so-called butadiene-based free radical polymerizable compound refers to a compound having at least one butadiene skeleton in the molecule. The polybutadiene structure may be contained in the main chain or in the side chain. Moreover, the polybutadiene structure may be partially or completely hydrogenated. As the butadiene-based free radical polymerizable compound, it is preferred to use at least one resin selected from the group consisting of a resin containing a hydrogenated polybutadiene skeleton, a butadiene resin containing a hydroxyl group, a butadiene resin containing a phenolic hydroxyl group, a butadiene resin containing a carboxyl group, a butadiene resin containing anhydride groups, a butadiene resin containing epoxy groups, a butadiene resin containing isocyanate groups, and a butadiene resin containing urethane groups.

Specific examples of butadiene-based free radical polymerizable compounds include "JP-100" manufactured by Nippon Soda Co., Ltd., and "Ricon 100", "Ricon 150", "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon 184MA6" manufactured by Cray Valley Co., Ltd.

The butadiene-based free radical polymerizable compound is preferably in the form of a liquid or semi-solid component. The determination of the liquid or semi-solid component state is as described above.

Benzocyclobutene-based radical polymerizable compounds are compounds having a benzocyclobutene ring. The benzocyclobutene ring may be contained in the main chain or in the side chain. Specific examples of benzocyclobutene-based radical polymerizable compounds include "CYCLOTENE 3022" manufactured by Dow Chemical.

The content of the component (B) is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 40% by mass or less, preferably 35% by mass or less, and more preferably 30% by mass or less, based on 100% by mass of the non-volatile components in the resin composition, from the viewpoint of suppressing unevenness in the cured substrate and obtaining a cured product having excellent dielectric properties, peel strength, and elongation at break.

When the content of the component (A) is 100% by mass of the nonvolatile components in the resin composition, and the content of the component (B) is b, when the content of the nonvolatile components in the resin composition is 100% by mass, a/b is preferably 0.05 or more, more preferably 0.1 or more, more preferably 0.15 or more, and preferably 3 or less, more preferably 2 or less, and more preferably 1.5 or less. When a/b is adjusted within this range, the effect of the present invention can be significantly obtained.

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

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

Examples of products sold as component (C) include "UFP-30" manufactured by Denka; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs; "SilfirNSS-3N", "SilfirNSS-4N", and "SilfirNSS-5N" manufactured by Tokuyama; and "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs.

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

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

The average particle size of component (C) can be measured by laser diffraction and scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis by using a laser diffraction and scattering particle size distribution measuring device, and the median diameter can be measured by the average particle size. The measurement sample can be 100 mg of inorganic filler and 10 g of methyl ethyl ketone weighed in a sample bottle and dispersed by ultrasound for 10 minutes. The measurement sample is measured by using a laser diffraction particle size distribution measuring device, and the wavelength of the light source used is set to blue and red. The particle size distribution of component (C) on a volume basis is measured by the flow cell method, and the average particle size as the median diameter is calculated from the obtained particle size distribution. As a laser diffraction type particle size distribution measuring apparatus, for example, "LA-960" manufactured by Horiba, Ltd. can be cited.

From the viewpoint of improving moisture resistance and dispersibility, component (C) is preferably treated with a surface treatment agent. Examples of the surface treatment agent include vinyl silane coupling agents, (meth) acrylic coupling agents, fluorine-containing silane coupling agents, amino silane coupling agents, epoxy silane coupling agents, butyl silane coupling agents, silane coupling agents, alkoxy silane, organic silazane compounds, and titanium salt coupling agents. Among them, vinyl silane coupling agents, (meth) acrylic coupling agents, and amino silane coupling agents are preferred from the viewpoint of significantly obtaining the effects of the present invention. The surface treatment agent may be used alone or in combination of two or more.

Examples of commercially available surface treatment agents include "KBM1003" (vinyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM503" (3-methacryloyloxypropyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-butyl propyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBE903" (3-amine "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment by the surface treatment agent is preferably controlled within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 0.2 to 5 parts by weight of the surface treatment agent is preferably used for surface treatment per 100 parts by weight of the inorganic filler, 0.2 to 3 parts by weight is more preferably used for surface treatment, and 0.3 to 2 parts by weight is even more preferably used for surface treatment.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/ ^m2 or more, more preferably 0.1 mg/ ^m2 or more, and more preferably 0.2 mg/ ^m2 or more. On the other hand, from the perspective of suppressing the increase in the melt viscosity of the resin coating and the melt viscosity of the flake form, it is preferably 1 mg/ ^m2 or less, more preferably 0.8 mg/ ^m2 or less, and more preferably 0.5 mg/ ^m2 or less.

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

From the viewpoint of reducing the dielectric properties, the content of the component (C) is preferably 50 mass % or more, more preferably 53 mass % or more, more preferably 55 mass % or more, and is preferably 90 mass % or less, more preferably 80 mass % or less, and more preferably 70 mass % or less, when the non-volatile components in the resin composition are taken as 100 mass %.

<(D) Thermoplastic resin> In addition to the above components, the resin composition may further contain a thermoplastic resin as a (D) component as an arbitrary component. However, the component equivalent to the (B) component is excluded. By including the (D) component in the resin composition, the stress of the resin composition can be relieved, and as a result, a cured product with excellent dielectric properties can be obtained. The (D) component may be used alone or in combination of two or more.

The weight average molecular weight (Mn) of the component (D) is preferably 5000 or more, more preferably 8000 or more, and particularly preferably 10000 or more, and preferably 100000 or less, more preferably 80000 or less, and particularly preferably 50000 or less, from the viewpoint of obtaining a cured product having excellent dielectric properties. The weight average molecular weight of the component (D) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

As the component (D), a component having a high weight average molecular weight can be used. Examples of such components include thermoplastic resins such as polyimide resins, polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyamide imide resins, polyether imide resins, polysulfide resins, polyethersulfide resins, polyetheretherketone resins, polystyrene resins, polyester resins, and bisphenol ether resins. As the component (D), at least one selected from the group consisting of polyimide resins, polycarbonate resins, phenoxy resins, and bisphenol ether resins is preferred from the viewpoint of obtaining a cured product having excellent dielectric properties.

The polyimide resin may be a resin having an imide structure. The polyimide resin generally includes a resin obtained by an imidization reaction of a diamine compound and an acid anhydride.

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

Examples of the aliphatic diamine compound include linear aliphatic diamine compounds such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5-diaminopentane, and 1,10-diaminodecane; and 1,2-diamino-2-methylpropane, 2,3-diamino-2, Branched chain aliphatic diamine compounds such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine) and the like; dimer acid type diamine (hereinafter also referred to as "dimer diamine"), etc. The so-called dimer acid type diamine refers to a diamine compound in which the two terminal carboxylic acid groups (-COOH) of the dimer acid are replaced by aminomethyl ( _-CH2 - _NH2 ) or amino ( _-NH2 ). Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those with 11 to 22 carbon atoms, particularly preferably those with 18 carbon atoms), and the industrial production process has been almost standardized in the industry.

Examples of the aromatic diamine compound include phenylenediamine compounds, naphthalenediamine compounds, and diphenylamine compounds.

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

The so-called naphthalene diamine compound refers to a compound composed of a naphthalene ring having two amino groups, and the naphthalene ring here may have 1 to 3 substituents. The substituents here are not particularly limited. Specific examples of the naphthalene diamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

The so-called diphenylamine compound refers to a compound containing two aniline structures in the molecule, and the two benzene rings in the two aniline structures may each further have 1 to 3 substituents. The substituents are not particularly limited. The two aniline structures in the diphenylamine compound are bonded via a direct bond and/or 1 or 2 connecting structures having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. The diphenylamine compound also contains two aniline structures bonded via two bonds.

Specific examples of the "linking structure" in the diphenylamine compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH2- _{, -CH2CH2- , -CH2CH2CH2- , -CH2CH2CH2CH2-} , -CH2CH2CH2CH2CH2- _, -CH ₍ CH3 ₎ -, -C(CH3)2-, -C( _CF3 ) _2- , _{-CH =} CH-, _-O- , _-S- , -CO-, _{-SO2- ,} -NH-, -Ph-, -Ph _{- Ph-} , -C( _CH3 ) ₂ -Ph-C( _CH3 ) _{2- , -O} -Ph-O-, -O-Ph-Ph-O-, -O-Ph- _SO2 -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -,

In the present specification, "Ph" represents 1,4-phenylene, 1,3-phenylene or 1,2-phenylene.

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

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

Although not particularly limited, the acid anhydride for preparing the polyimide resin may be aromatic tetracarboxylic dianhydride in a preferred embodiment. Examples of the aromatic tetracarboxylic dianhydride include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, and diphthalic dianhydride, and diphthalic dianhydride is preferred.

The so-called benzene tetracarboxylic dianhydride means benzene dianhydride having four carboxyl groups, and the naphthyl ring herein may have 1 to 3 substituents. The substituents herein are preferably selected from a halogen atom, a cyano group, and -X ³³⁰ -R ³³⁰ (same as defined in the following formula (1D)). Specific examples of benzene tetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-pyromellitic dianhydride.

Naphthalenetetracarboxylic dianhydride means naphthalene dianhydride having four carboxyl groups, and the naphthalene ring herein may have 1 to 3 substituents. The substituents are preferably selected from a halogen atom, a cyano group, and -X ³³⁰ -R ³³⁰ (same as defined in the following formula (1D)). Specific examples of naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

The so-called anthracenetetracarboxylic dianhydride means anthracene dianhydride having four carboxyl groups, and the anthracene ring herein may have 1 to 3 substituents. The substituents herein are preferably selected from a halogen atom, a cyano group, and -X ³³⁰ -R ³³⁰ (same as defined in the following formula (1D)). Specific examples of anthracenetetracarboxylic dianhydride include 2,3,6,7-anthracenetetracarboxylic dianhydride and the like.

The so-called diphthalic anhydride refers to a compound containing two phthalic anhydrides in the molecule, and further, each of the two benzene rings in the two phthalic anhydrides may have 1 to 3 substituents. The substituents are preferably selected from halogen atoms, cyano groups, and -X ³³⁰ -R ³³⁰ (same as defined in the following formula (1D)). The two phthalic anhydrides in the diphthalic anhydride are directly bonded or bonded via a connection structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

As diphthalic dianhydride, for example, the formula (1D) can be cited:

[wherein, R ²⁰¹ and R ²⁰² each independently represent a halogen atom, a cyano group, a nitro group, or -X ³³⁰ -R ³³⁰ , X ³³⁰ each independently represents a single bond, -NR ^330'- , -O-, -S-, -CO-, -SO ₂ -, -NR ^330'CO- , -CONR ^330'- , -OCO-, or -COO-, R ³³⁰ each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, R ^330' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y ¹ represents a single bond, or a connecting structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms, and n10 and n11 each independently represent an integer of 0 to 3].

^Y1 is preferably a structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. n10 and n11 are preferably 0.

The "connecting structure" in ^Y1 represents a structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. The "connecting structure" is preferably a divalent group represented by -[A1-Ph] _a10 -A1-[Ph-A1] _b10 - [wherein A1 each independently represents a single bond, -(substituted or unsubstituted alkylene)-, -O-, -S-, -CO-, -SO ₂ -, -CONH-, -NHCO-, -COO-, or -OCO-, and a10 and b10 each independently represent an integer of 0 to 2 (preferably 0 or 1)].

Specific examples of the "connecting structure" in ^Y1 include _-CH2- , _{-CH2CH2- , -CH2CH2CH2- ,} -CH2CH2CH2CH2- _, -CH2CH2CH2CH2CH2- _, -CH(CH3) _- , -C(CH3)2-, _{-O- , -CO-} , -SO2- _{, -Ph- , -O} -Ph-O-, -O _- Ph _{- SO2} -Ph-O-, -O-Ph-C( _CH3 ) ₂ -Ph-O-, and the like. In the present specification, "Ph" represents 1,4-phenylene, _1,3 -phenylene or _1,2 -phenylene.

Specific examples of diphthalic acid dianhydride include 4,4'-oxydiphthalic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4 '-Biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonium tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfonium dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethidium-4,4'-diphthalic acid dianhydride, 2,2- Propyriden-4,4'-diphthalic acid anhydride, 1,2-ethylidene-4,4'-diphthalic acid anhydride, 1,3-trimethylene-4,4'-diphthalic acid anhydride, 1,4-tetramethylene-4,4'-diphthalic acid anhydride, 1,5-pentamethylene-4,4'-diphthalic acid anhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene Dianhydride, 1,4-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylenediphenoxy)bisphthalic anhydride, and the like.

Acid anhydrides may be commercially available ones or those synthesized by a known method or a method based thereon. Acid anhydrides may be used alone or in combination of two or more.

As the polyimide resin, a commercial product can be used. Examples of commercial products include "RIKACOATSN20" and "RIKACOATPN20" manufactured by Shin Nippon Rika Co., Ltd.

Polycarbonate resin is a resin having a carbonate structure. Examples of such resins include carbonate resins without reactive groups, carbonate resins containing hydroxyl 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, and carbonate resins containing epoxy groups. The reactive group refers to a functional group obtained by reacting with other components such as hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, acid anhydride groups, isocyanate groups, urethane groups, and epoxy groups.

As the carbonate resin, commercial products can be used. Examples of commercial products include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemicals, "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kuraray.

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

As specific examples of phenoxy resins, we can cite "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol acetophenone skeleton); and "Phenoxy 1256" and "Phenoxy 1250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton). "FX280" and "FX293" manufactured by Rial; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation.

The polyamide imide resin is a resin having an amide imide structure. From the viewpoint of compatibility with other components in the resin composition, the polyamide imide resin having an alicyclic structure in the molecular structure, the polyamide imide resin having a siloxane structure described in Japanese Patent Application Laid-Open No. 05-112760, the polyamide imide resin having a bulky high-branched chain structure, the polyamide imide resin using an asymmetric monomer as a raw material, the polyamide imide resin having a multi-branched structure, etc. are preferably used.

Among them, polyamide imide resins are classified into (i) polyamide imide resins having an isocyanuric acid ring structure in their molecular structure (i.e., polyamide imide resins having an isocyanuric acid ring structure and an imide skeleton or an amide skeleton) and (ii) polyamide imide resins having an isocyanuric acid ring structure and an alicyclic structure in their molecular structure. Preferred are (i) a polyamide imide resin (i.e., a polyamide imide resin having an isocyanuric acid ring structure, an alicyclic structure and an imide skeleton or an amide skeleton), and (ii) a polyamide imide resin having a repeating unit containing an isocyanuric acid ring structure and an alicyclic structure (i.e., a polyamide imide resin having a repeating unit containing an isocyanuric acid ring structure and an alicyclic structure and an imide skeleton or an amide skeleton).

As a preferred embodiment of the polyamide imide resin of (i) to (iii), there can be cited (1) a polyisocyanate compound containing an isocyanuric acid ring derived from an alicyclic diisocyanate and an acid anhydride of a polycarboxylic acid having three or more carboxyl groups, wherein the carboxylic acid group of the compound obtained by reacting the polyisocyanate compound containing an isocyanuric acid ring and the anhydride of a polycarboxylic acid having three or more carboxyl groups (hereinafter, the compound may be referred to as "(Compound D-1)"), (2) compound (D-1) and a polyisocyanate having one epoxy group and one or more free (3) a branched polymerizable polyamide imide containing a carboxylic acid group which is a compound obtained by reacting a residual isocyanate group with a compound having one hydroxyl group and one or more free radical polymerizable unsaturated groups in the synthesis process of compound (D-1) (hereinafter sometimes referred to as "compound (D-3)").

Specific examples of compound (D-1) include compounds represented by the following general formula (I). The repeating unit in the compound represented by general formula (I) is referred to as repeating unit (I-1). (Wherein, w represents 0~15)

Examples of the compound (D-2) include a compound (II) having a structure (I-2) in which GMA (glycidyl methacrylate) is added to the carboxyl group and/or the terminal carboxyl group of any part of the repeating unit (I-1) in the general formula (I). (wherein R ⁴⁰ represents a residual group in formula (I))

The ratio of GMA denaturation of carboxyl groups is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, more preferably 0.7 mol% or more, or 0.9 mol% or more, based on the molar number of carboxyl groups in compound (D-1), and the upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, more preferably 30 mol% or less, or 20 mol% or less.

The compound (D-3) is a compound (III) having a structure (I-3) in which any part of the repeating units (I-1) and/or the terminal imide group in the above formula (I) is an isocyanate residue and a hydroxyl group of pentaerythritol triacrylate is added thereto. (wherein R' represents a residue in formula (I))

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

The polyamide imide resin can be synthesized by various known methods. For the synthesis method of the polyamide imide resin, for example, reference can be made to paragraphs 0020 to 0030 of International Publication No. 2010/074197, the contents of which are incorporated herein by reference.

The polyamide imide resin can be a commercial product. Examples of commercial products include "Unidic V-8000" manufactured by DIC Corporation, "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd., and "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd. (polyamide imide containing a polysiloxane skeleton).

As the polystyrene resin, any elastomer containing repeating units (styrene units) having a structure obtained by polymerizing styrene can be used. In addition, the polystyrene resin can be a copolymer or a hydrogenated polystyrene resin containing any repeating units different from the above-mentioned styrene units in which styrene units are combined.

As the arbitrary repeating unit, for example, there can be mentioned a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), a repeating unit having a structure obtained by hydrogenating the same (hydrogenated conjugated diene unit), etc. As the conjugated diene, for example, there can be mentioned aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, etc.; and halogenated aliphatic conjugated dienes such as chloroprene, etc. As the conjugated diene, from the viewpoint of significantly obtaining the effect of the present invention, an aliphatic conjugated diene is preferred, and butadiene is more preferred. The conjugated diene may be used alone or in combination of two or more. Furthermore, 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), 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, etc. Among them, styrene-maleic anhydride copolymer is preferred as the polystyrene resin.

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

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

As a specific example of polyester resin, "OKP4HT" manufactured by Osaka Gas Chemical Co., Ltd. can be cited.

As specific examples of polyol resins, polyols "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd. can be cited.

Examples of the polyvinyl acetal resin include polyvinyl formaldehyde resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include S-LECBH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Industries, Ltd.

As a specific example of the polyether sulfide resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. can be cited.

The bisphenol ether resin is a resin having a bisphenol ether structure. From the viewpoint of significantly obtaining the effects of the present invention, the bisphenol ether resin preferably contains repeating units represented by the following formula (Da).

[In the formula, Ring A represents a nitrogen-containing aromatic ring which may have a substituent; Ring B and Ring C each independently represent an aromatic ring which may have a substituent; and X represents a single bond or a divalent non-aromatic hydrocarbon group]

Ring A represents a nitrogen-containing aromatic ring which may have a substituent. The so-called aromatic ring refers to a ring in which the number of electrons contained in the π-electron system on the ring is 4n+2 (n is a natural number) according to Hückel's rule. The nitrogen-containing aromatic ring represented by ring A has, in addition to carbon atoms, one or more (preferably two or more, particularly preferably two) nitrogen atoms as ring-constituting atoms, and may have miscellaneous atoms other than nitrogen atoms such as oxygen atoms and sulfur atoms. The nitrogen-containing aromatic ring represented by ring A is preferably a 5-14-membered nitrogen-containing aromatic ring, more preferably a 5-10-membered nitrogen-containing aromatic ring, more preferably a 5- or 6-membered nitrogen-containing aromatic ring, and particularly preferably a 6-membered nitrogen-containing aromatic ring. The nitrogen-containing aromatic ring represented by Ring A may include not only a monocyclic aromatic ring and a condensed ring in which two or more monocyclic aromatic rings are condensed, but also a condensed ring in which one or more monocyclic non-aromatic rings are condensed in one or more monocyclic aromatic rings.

Preferred specific examples of the nitrogen-containing aromatic ring represented by ring A include a pyrrole ring, an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a tetrazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a oxazine ring, a 1,2,3-triazine ring, a 1,2,4-triazine ...ridine ring, a pyridine ring, a pyridine ring, a 1,2,3-triazine ring, a 1,2,4-triazine ring, a tetrazole ring, a pyridine ring, a pyridine ring, Monocyclic nitrogen-containing aromatic rings such as 4-triazine ring and 1,3,5-triazine ring; condensed rings of monocyclic nitrogen-containing aromatic rings such as indole ring, isoindole ring, benzimidazole ring, indazole ring, benzotriazole ring, quinoxaline ring, cinnoline ring, quinazoline ring, phthalazine ring and benzene ring; pteridine ring, purine ring The ring may be a condensed ring of a monocyclic nitrogen-containing aromatic ring such as a 4-azaindole ring, a 5-azaindole ring, a 6-azaindole ring, a 7-azaindole ring, a 7-azaindole ring, a pyrazolo[1,5-a]pyrimidine ring, a 1,8-naphthyridine ring, a pyrido[3,2-d]pyrimidine ring, a pyrido[4,3-d]pyrimidine ring, a pyrido[3,4-b]pyrazine ring, a pyrido[2,3-b]pyrazine ring, etc. The monocyclic nitrogen-containing aromatic ring is preferred, and a 6-membered monocyclic nitrogen-containing aromatic ring is preferred, a pyrimidine ring or a oxazine ring is more preferred, and a pyrimidine ring is particularly preferred.

The nitrogen-containing aromatic ring may have a substituent. Examples of the substituent include, but are not particularly limited to, alkyl, alkenyl, aryl, alkyl-aryl (aryl substituted with one or more alkyl groups), aryl-aryl (aryl substituted with one or more aryl groups), aryl-alkyl (alkyl substituted with one or more aryl groups), alkyl-oxy, alkenyl-oxy, aryl-oxy, alkyl-carbonyl, alkenyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-oxy-carbonyl, alkyl-carbonyl-oxy, alkenyl-carbonyl-oxy, aryl-carbonyl-oxy and the like, and, if substitutable, may include a divalent substituent such as an oxo group (=O).

The so-called alkyl group refers to a straight chain, branched chain and/or cyclic monovalent aliphatic saturated alkyl group. The alkyl group preferably has 1 to 14 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 or 4 to 10 carbon atoms. The so-called alkenyl group refers to a straight chain, branched chain and/or cyclic monovalent aliphatic unsaturated alkyl group having at least one carbon-carbon double bond. The alkenyl group preferably has 2 to 14 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 or 4 to 10 carbon atoms. The so-called aryl group refers to a monovalent aromatic alkyl group. The aryl group is preferably an aryl group having 6 to 14 carbon atoms.

Ring B and Ring C each independently represent an aromatic ring which may have a substituent. The aromatic ring represented by Ring B or Ring C is a carbocyclic ring having carbon atoms as ring constituent atoms, or a heterocyclic ring having, in addition to carbon atoms, heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms. In one embodiment, a carbocyclic ring is preferred. The aromatic ring represented by Ring B or Ring C is preferably an aromatic ring having 5 to 14 members, more preferably an aromatic ring having 5 to 10 members, more preferably an aromatic ring having 5 or 6 members, and particularly preferably an aromatic ring having 6 members. The aromatic ring represented by Ring B or Ring C includes not only a monocyclic aromatic ring and a condensed ring of two or more monocyclic aromatic rings, but also a condensed ring of one or more monocyclic aromatic rings and one or more monocyclic non-aromatic rings.

Preferred specific examples of the aromatic ring represented by ring B or ring C include a monocyclic aromatic ring such as a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, an oxazine ring, a pyrimidine ring, and a pyrazine ring; a naphthalene ring, an anthracene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a benzoxazole ring, a benzene ring; a condensed ring in which two or more monocyclic aromatic rings such as isoxazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, acridine ring, quinazoline ring, cinnoline ring, phthalazine ring are condensed; a condensed ring in which one or more monocyclic aromatic rings such as indane ring, fluorene ring, tetrahydronaphthalene ring are condensed with one or more monocyclic non-aromatic rings, etc., preferably a monocyclic aromatic ring, more preferably a 6-membered monocyclic aromatic ring, and particularly preferably a benzene ring.

X is a single bond or a divalent non-aromatic hydrocarbon group. The divalent non-aromatic hydrocarbon group represented by X is a saturated or unsaturated straight chain, branched chain and/or cyclic divalent non-aromatic hydrocarbon group. The divalent non-aromatic hydrocarbon group represented by X is, for example, a divalent non-aromatic hydrocarbon group having 1 to 100 carbon atoms, preferably 1 to 50, more preferably 1 to 30, and more preferably 1 to 20 carbon atoms.

X is preferably a divalent non-aromatic hydrocarbon group, preferably a formula (X1):

[wherein, ^R1 and ^R2 each independently represent a hydrogen atom, an alkyl group or an alkenyl group, or represent that ^R1 and ^R2 can be bonded together to form a cycloalkane ring having a group selected from an alkyl group and an alkenyl group, or a cycloalkene ring having a group selected from an alkyl group and an alkenyl group; * represents a bonding site], preferably a divalent group represented by formula (X2-1) to (X2-3):

[wherein, R ³ , R ⁴ , and R ⁵ each independently represent an alkyl group; x represents an integer of 0 to 5 (preferably 1 to 5, more preferably 2 to 4); and * represents a bonding site] is any divalent group, particularly preferably a divalent group represented by formula (X2-1).

The so-called cycloalkane ring is a cyclic aliphatic saturated hydrocarbon ring. The cycloalkane ring is preferably a cycloalkane ring having 3 to 8 carbon atoms, and more preferably a cycloalkane ring having 5 or 6 carbon atoms. Examples of the cycloalkane ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. The so-called cycloalkene ring refers to a cyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond. The cycloalkene ring is preferably a cycloalkene ring having 4 to 8 carbon atoms, more preferably a cycloalkene ring having 5 or 6 carbon atoms. Examples of the cycloalkene ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, and a cyclohexadiene ring.

The compound containing the repeating unit represented by formula (D-a) contains formula (1A) or (1B):

[wherein, X ¹ , X ² , X ³ and X ⁴ each independently represent N, CH or CR ^a (preferably N or CH), and at least one (preferably at least two, particularly preferably two) of X ¹ , X ² , X ³ and X ⁴ is N; ^Ra , R ^b and R ^c each independently represent a substituent (preferably an alkyl group, an alkenyl group, an aryl group, an alkyl-aryl group, an aryl-aryl group, or an aryl-alkyl group, preferably an alkyl group, an alkenyl group, or an aryl group, particularly preferably an aryl group); b and c each independently represent an integer of 0 to 3 (preferably 0); other symbols are the same as those in formula (X1)], preferably a compound having a repeating unit as shown in formula (1A-1) to (1B-3):

[wherein a represents an integer of 0 to 2 (preferably 0); other symbols are the same as those of formula (1A), formula (1B) and formula (X2-1) to (X2-3)], and a compound containing the repeating unit represented by any of formula (1A-1) is particularly preferred.

The compound containing the repeating unit represented by formula (D-a) may have a reactive group such as a phenolic hydroxyl group, a thiol group, an amine group, a carboxyl group, a sulfonic acid group, etc. in one embodiment, preferably having a phenolic hydroxyl group. In one embodiment, the reactive group preferably has two or more in one molecule.

For compounds containing repeating units represented by formula (D-a), the number of repeating units is preferably 5 or more, more preferably 10 or more, more preferably 30 or more, and particularly preferably 50 or more. The upper limit of the number of repeating units is not particularly limited, and is, for example, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, etc.

The glass transition temperature (Tg) of the compound containing the repeating unit represented by formula (D-a) is not particularly limited, but is preferably 100 to 300°C, more preferably 150 to 250°C.

The compound containing the repeating unit represented by formula (D-a) can be synthesized using, for example, the method described in WO2019/054335 or WO2020/021827 or a method according thereto.

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

<(E) Thermosetting resin> The resin composition may contain a thermosetting resin as an optional component (E) in addition to the above-mentioned components. However, components corresponding to components (A) and (B) are excluded. Examples of the thermosetting resin (E) include epoxy resins, phenolic resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins. Component (E) may be used alone or in combination of two or more types at any ratio. The following resins such as phenol resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins, and resins that react with epoxy resins to harden the resin composition are collectively referred to as "hardeners".

Examples of the epoxy resin as the component (E) include bis(xylenol) type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-ophthalic acid type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, Glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, oxalicyclic epoxy resin, oxalicyclic methanol type epoxy resin, naphthylene ether type epoxy resin, trihydroxymethyl type epoxy resin, tetraphenylethane type epoxy resin, etc. The epoxy resin may be used alone or in combination of two or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as component (E). From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on 100% by mass of the nonvolatile component of component (E).

Epoxy resins include those that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and those that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin as the component (E), may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin.

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

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure are preferred, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "EPICOAT828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "jER808", "HP4032SS" (naphthalene-type epoxy resins) manufactured by Mitsubishi Chemical Corporation. "1750" (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; Nagase "EX-721" manufactured by Chemtex (glycidyl ester type epoxy resin); "CELLOXIDE2021P" manufactured by Daicel Chemical Industries, Ltd. (lipidic epoxy resin with ester skeleton); "PB-3600" manufactured by Daicel Chemical Industries, Ltd. (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical & Material Co., Ltd. (liquid 1,4-glycidyl cyclohexane type epoxy resin), etc. These can be used alone or in combination of two or more.

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

As the solid epoxy resin, bis(xylenol) type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and naphthalene type epoxy resin is more preferred.

As the solid epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, tetraphenylethane-type epoxy resin are preferred, and naphthalene-type tetrafunctional epoxy resin, naphthol-type epoxy resin, and biphenyl-type epoxy resin are more preferred. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-based epoxy resin), "HP-4700", "HP-4710" (naphthalene-based tetrafunctional epoxy resin), "N-690" (cresol novolac-based epoxy resin), "N-695" (cresol novolac-based epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" manufactured by DIC Corporation. (dicyclopentadiene epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. 3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" manufactured by Mitsubishi Chemical Corporation (bis(xylenol) epoxy resin), "YX8800" (anthracene) epoxy resin; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF) epoxy resin, "YL7800" (fluorene) epoxy resin, "jER1010" (solid bisphenol A) epoxy resin, "jER1031S" (tetraphenylethane) epoxy resin, etc. These may be used alone or in combination of two or more.

When the liquid epoxy resin and the solid epoxy resin as the component (E) are used in combination, the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.3 to 1:15, and particularly preferably 1:0.5 to 1:10. By making the mass ratio of the liquid epoxy resin to the solid epoxy resin within this range, the desired effect of the present invention can be significantly obtained. And when it is usually used in the form of a film, moderate adhesion can be obtained. In addition, when it is usually used in the form of a film, sufficient flexibility can be obtained and the handling property is improved. Furthermore, a cured product with sufficient breaking strength can usually be obtained.

The epoxy equivalent of the epoxy resin as the component (E) is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., more preferably 80 g/eq. to 2000 g/eq., and even more preferably 110 g/eq. to 1000 g/eq. Within this range, the crosslinking density of the cured product of the resin composition can be obtained to be a sufficient cured product. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

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

The content of the epoxy resin as the component (E) is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition, from the viewpoint of obtaining a cured product having good mechanical strength and insulation reliability. The upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of significantly obtaining the desired effect of the present invention.

As the active ester resin of component (E), resins having one or more active ester groups in one molecule can be used. Among them, preferred active ester resins are phenol esters, thiophenol esters, N-hydroxylamine esters, heterocyclic hydroxyl compound esters, etc., which have two or more highly reactive ester groups in one molecule. The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.

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.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalazine, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, o-cresol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. The so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Preferred specific examples of active ester resins include active ester resins containing a dicyclopentadiene diphenol structure, active ester resins containing a naphthalene structure, active ester resins containing acetylated products of phenol novolacs, and active ester resins containing benzoylated products of phenol novolacs. Among them, active ester resins containing a naphthalene structure and active ester resins containing a dicyclopentadiene diphenol structure are preferred. The so-called "dicyclopentadiene diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

As the active ester resins for sale, as active ester resins containing a dicyclopentadiene-type diphenol structure, there are "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation); as active ester resins containing a naphthalene structure, there are "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", "HPC-8150-62T" "(manufactured by DIC Corporation); as an active ester resin containing an acetylated phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester resin containing a benzoylated phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation); as an active ester resin of an acetylated phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester resin of a benzoylated phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "EXB-8500-65T" (manufactured by DIC Corporation), etc.

The phenolic resin and naphthol resin as component (E) preferably have a novolac structure from the viewpoint of heat resistance and water resistance. Also, from the viewpoint of adhesion to the conductive layer, a nitrogen-containing phenolic hardener is preferred, and a phenolic resin containing a triazine skeleton is more preferred.

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

Specific examples of the benzoxazine resin as the component (b) include "JBZ-OD100" (benzoxazine ring equivalent: 218), "JBZ-OP100D" (benzoxazine ring equivalent: 218), and "ODA-BOZ" (benzoxazine ring equivalent: 218) manufactured by JFE Chemicals; "P-d" (benzoxazine ring equivalent: 217), and "F-a" (benzoxazine ring equivalent: 217) manufactured by Shikoku Chemical Industries; and "HFB2006M" (benzoxazine ring equivalent: 432) manufactured by Showa High Molecular Co., Ltd.

Examples of the cyanate ester resin as the component (E) include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylpropane), Bifunctional cyanate resins such as bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers of these cyanate resins partially triazine-modified, etc. Specific examples of cyanate ester resins include "PT30", "PT30S" and "PT60" manufactured by Lonza Japan (phenol novolac type multifunctional cyanate ester resins), "ULL-950S" (multifunctional cyanate ester resin), "BA230", "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazine-treated to become a trimer), etc.

Specific examples of the carbodiimide resin as the component (E) include Carbonite (registered trademark) V-03 (carbodiimide equivalent: 216, V-05 (carbodiimide equivalent: 216), V-07 (carbodiimide equivalent: 200), and V-09 (carbodiimide equivalent: 200) manufactured by Nisshinbo Chemical Co., Ltd.; and Stavaxol (registered trademark) P (carbodiimide equivalent: 302) manufactured by Line Chemie.

The amine resin as component (E) includes resins having one or more amine groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effect of the present invention. The amine resin is preferably a primary amine or a secondary amine, and a primary amine is more preferred. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfonate, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfonate, 3,3'-diaminodiphenylsulfonate, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino 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. As the amine resin, commercial products can be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kaya hard A-A", "Kaya hard A-B", "Kaya hard A-S" manufactured by Nippon Kayaku Co., Ltd., "Epicure W" manufactured by Mitsubishi Chemical Corporation, etc.

As the acid anhydride resin of the component (E), there can be mentioned resins having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenylmethanediol, and the like. Ketonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonatetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrous trimellitate), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, and other polymer anhydrides.

When the component (E) contains an epoxy resin and a hardener, the ratio of the amount of the epoxy resin to the total hardener is [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the hardener], preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and even more preferably 1:0.5 to 1:2. The "number of epoxy groups of the epoxy resin" refers to the total value of the mass of the non-volatile components of the epoxy resin present in the resin composition divided by the value of the epoxy equivalent. In addition, the "number of active groups of the hardener" refers to the total value of the mass of the non-volatile components of the hardener present in the resin composition divided by the value of the active group equivalent. By setting the amount ratio of the epoxy resin to the hardener as the component (E) within the above range, a hardened body having excellent flexibility can be obtained.

The content of the hardener as the component (E) is preferably 1 mass % or more, more preferably 3 mass % or more, more preferably 5 mass % or more, and preferably 20 mass % or less, preferably 15 mass % or less, and more preferably 10 mass % or less, based on 100 mass % of the nonvolatile components in the resin composition, from the viewpoint of obtaining a hardened body having excellent flexibility.

From the viewpoint of obtaining a cured product having excellent flexibility, the content of the component (E) is preferably 5 mass % or more, more preferably 10 mass % or more, more preferably 15 mass % or more, and preferably 25 mass % or less, more preferably 20 mass % or less, and more preferably 15 mass % or less, based on 100 mass % of the non-volatile components in the resin composition.

<(F) Curing accelerator> In addition to the above components, the resin composition may further contain a curing accelerator as a component (F) as an optional component. By containing the component (F), polymerization by heat can be further accelerated.

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

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

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

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino 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-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxy Imidazole compounds such as methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, a commercial product can be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation can be cited.

Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazacyclo[4.4.0]dec-5-enyl, 7-methyl-1,5,7-triazacyclo[4.4.0] Dec-5-enyl, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc., preferably dicyandiamide and 1,5,7-triazacyclo[4.4.0]dec-5-enyl.

Examples of metal hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organic metal complexes include organic cobalt complexes such as cobalt (II) acetylacetone and cobalt (III) acetylacetone, organic copper complexes such as copper (II) acetylacetone, organic zinc complexes such as zinc (II) acetylacetone, organic iron complexes such as iron (III) acetylacetone, organic nickel complexes such as nickel (II) acetylacetone, and organic manganese complexes such as manganese (II) acetylacetone. Examples of the organic metal salt include zinc octylate, tin octylate, zinc cycloalkane, cobalt cycloalkane, tin stearate, zinc stearate, and the like.

Examples of the peroxide-based curing accelerator include di-t-butyl peroxide, t-butyl cumyl peroxide, t-butyl peroxyacetate, α,α′-di(t-butylperoxy)diisopropylbenzene, t-butyl peroxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butylperoxybenzoate.

Examples of the peroxide-based curing accelerators available for sale include "Perhexyl D," "Perbutyl C," "Perbutyl A," "Perbutyl P," "Perbutyl L," "Perbutyl O," "Perbutyl ND," "Perbutyl Z," "Percomil P," and "Percomil D," all of which are manufactured by NOF Corporation.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the component (F) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and is preferably 1% by mass or less, more preferably 0.8% by mass or less, and more preferably 0.5% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

<(G) Other additives> In addition to the above-mentioned components, the resin composition may further contain other additives as arbitrary components. Examples of such additives include resin additives such as thickeners, defoamers, leveling agents, and adhesion-imparting agents. These additives may be used alone or in combination of two or more. The amount of each additive may be appropriately set by the industry.

The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a solvent is added to the ingredients as required, and the mixture is mixed and dispersed using a rotary mixer or the like.

<Physical properties and uses of resin composition> The resin composition contains a certain amount of (A) component and (B) component. This can suppress unevenness in the cured substrate and obtain a cured product with excellent dielectric properties, peel strength, and fracture elongation. Usually, if the content of inorganic filler is large, there is a tendency for unevenness in the cured substrate. However, by containing a certain amount of (A) component and (B) component, even if the content of inorganic filler is large, unevenness in the cured substrate can be suppressed. Further, a cured product with excellent dielectric properties, peel strength, and fracture elongation can be obtained.

The resin composition is a property that can suppress unevenness generated in the cured substrate. Specifically, after the resin composition layer of the resin sheet was laminated on the glass cloth substrate epoxy resin double-sided copper sheet laminate with a copper foil thickness of 18μm, it was heat-cured at 130℃ for 30 minutes and then at 170℃ for 30 minutes to form an insulating layer. The insulating layer of the portion laminated with the resin sheet was visually observed, and the surface uniformity of the surface on the opposite side of the glass cloth substrate epoxy resin double-sided copper sheet laminate was observed. At this time, the inner portion was more uniform in surface compared to the portion 1cm from the outer periphery of the portion where the resin sheet was usually laminated. It is preferred that the entire surface of the laminate opposite to the insulating layer be a uniform surface. The details of the uneven evaluation of the cured substrate can be measured according to the method described in the examples described below.

A cured product obtained by heating a resin composition at 130°C for 30 minutes and then heating it at 170°C for 30 minutes can exhibit excellent peel strength characteristics with a conductive layer (plated conductive layer) formed by coating. Thus, the cured product can form an insulating layer with excellent peel strength with the coated conductive layer. The peel strength is preferably 0.3kgf/cm or more, more preferably 0.35kgf/cm or more, and even more preferably 0.4kgf/cm or more. The upper limit of the peel strength can be 10kgf/cm or less. The peel strength of the coated conductive layer can be measured according to the method described in the embodiments described below.

The resin composition is heat-cured at 200°C for 90 minutes, and the cured product shows the characteristics of low dielectric constant. Thus, the cured product can achieve an insulating layer with low dielectric constant. The dielectric constant is preferably 4 or less, preferably 3.5 or less, and more preferably 3 or less. The lower limit of the dielectric constant can reach 0.001 or more. The dielectric constant can be measured according to the method described in the following embodiments.

The resin composition is heat-cured at 200°C for 90 minutes, and the cured product shows the characteristics of low dielectric loss tangent. Thus, the cured product can achieve an insulating layer with low dielectric loss tangent. The dielectric loss tangent is preferably less than 0.005, more preferably less than 0.004, and more preferably less than 0.003. The lower limit of the dielectric loss tangent can be greater than 0.0001. The dielectric loss tangent can be measured according to the method described in the embodiments described below.

The resin composition is heat-cured at 200°C for 90 minutes, and the cured product shows the characteristic of large elongation at the fracture point due to its high toughness. Thus, the cured product can achieve an insulating layer with large elongation at the fracture point. The elongation at the fracture point is preferably 0.5% or more, more preferably 0.8% or more, and more preferably 1% or more. On the other hand, although the upper limit of the elongation at the fracture point is not particularly limited, it can be 10% or less. The evaluation of the elongation at the fracture point can be measured according to the method described in the embodiment described below.

The resin composition of the present invention can suppress the unevenness generated in the cured substrate, and can obtain an insulating layer with excellent dielectric properties, peel strength, and elongation at the fracture point. Therefore, the resin composition of the present invention can be used as a resin composition for insulating purposes. Specifically, it can be used as the following resin composition (resin composition for forming an insulating layer used to form a conductive layer), the resin composition is used to form the insulating layer, the insulating layer is used to form a conductive layer (including a redistribution layer), and the conductive layer is formed on the insulating layer.

Furthermore, for the multilayer printed wiring board described later, it can be suitably used as the following resin composition, which is a resin composition used to form an insulating layer of the multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board) and a resin composition used to form an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board).

Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as the following resin composition, which is a resin composition for a redistribution forming layer as an insulating layer to be formed as a redistribution layer (resin composition for forming a redistribution forming layer), and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When manufacturing a semiconductor chip package, a redistribution layer can also be further formed on the sealing layer. (1) laminating a temporary fixing film on a substrate, (2) temporarily fixing a semiconductor chip on the temporary fixing film, (3) forming a sealing layer on the semiconductor chip, (4) peeling the substrate and the temporary fixing film from the semiconductor chip, (5) forming a redistribution layer as an insulating layer on the surface of the substrate and the temporary fixing film from which the semiconductor chip is peeled, and (6) forming a redistribution layer as a conductive layer on the redistribution layer

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

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and more preferably 30 μm or less, from the viewpoint of thinning the printed wiring board and improving the good insulation of the cured product when the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, and can usually be 5 μm or more.

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

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

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

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

In addition, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent used for the release layer of the support with a release layer, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins can be cited. The support with a release layer can be a commercial product, for example, PET film having a release layer with an alkyd resin release agent as a main component, such as "SK-1", "AL-5", "AL-7" manufactured by Lintec, "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipeel" manufactured by Unitika, etc.

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

In one embodiment, the resin sheet may further contain other layers as necessary. Examples of such other layers include a protective film based on the support and disposed on the surface of the resin composition layer that is not bonded to the support (i.e., the opposite side 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, it is possible to suppress the adhesion or scratching of dirt on the surface of the resin composition layer.

The resin sheet is produced, for example, by preparing a resin paint by dissolving a resin composition in an organic solvent, applying the resin paint on a support using a die coating or the like, and further drying the resin composition layer.

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

Drying can be carried out by known methods such as heating and hot air blowing. Although the drying conditions are not particularly limited, the content of the organic solvent in the resin composition layer is 10% by mass or less, and it is preferably dried to 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin coating, for example, when a resin coating containing 30% to 60% by mass of an organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

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

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

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

The so-called "inner layer substrate" used in step (I) refers to a component that becomes the substrate of the printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Furthermore, the substrate may have a conductive layer on one or both sides, and the conductive layer may also be patterned. An inner layer substrate having a conductive layer (loop) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate." Furthermore, when manufacturing a printed wiring board, an intermediate product that further requires the formation of an insulating layer and/or a conductive layer is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components can be used.

The inner substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet on the inner substrate from the support body side. As a member for heat-pressing the resin sheet on the inner substrate (hereinafter also referred to as "heat-pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller) can be cited. Moreover, the heat-pressing member is not directly pressed on the resin sheet, but it is preferably pressed through an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface unevenness of the inner substrate.

The lamination of the inner substrate and the resin sheet can be performed by vacuum lamination. For vacuum lamination, the heating and pressing temperature is preferably 60°C to 160°C, preferably 80°C to 140°C, the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, preferably 0.29MPa to 1.47MPa, and the heating and pressing time is preferably 20 seconds to 400 seconds, preferably 30 seconds to 300 seconds. Lamination is performed under reduced pressure conditions with a pressure of less than 26.7hPa.

Lamination can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Material Co., Ltd., and a batch vacuum pressurized laminator.

After lamination, the laminated resin sheet can be smoothed by, for example, applying pressure to the support side of the heat-pressing member under normal pressure (atmospheric pressure). The pressurizing conditions for the smoothing treatment can be the same as the heat-pressing conditions for the lamination described above. The smoothing treatment can be performed using a commercially available laminate. Furthermore, the lamination and smoothing treatment can be performed continuously using the commercially available vacuum laminator described above.

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

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

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

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

When manufacturing a printed wiring board, a step (III) of opening a hole in the insulating layer, a step (IV) of roughening the insulating layer, and a step (V) of forming a conductive layer may be further performed. These steps (III) to (V) are performed according to various methods known to those skilled in the art for manufacturing printed wiring boards. Furthermore, when the support is removed after step (II), the removal of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Furthermore, if necessary, the formation of the insulating layer and the conductive layer in steps (II) to (V) may be repeated to form a multi-layer wiring board.

Step (III) is a step of drilling holes in the insulating layer, thereby forming through holes, through holes, etc. in the insulating layer. Step (III) is carried out in accordance with the composition of the resin composition used to form the insulating layer, for example, by using a drill, laser, plasma, etc. The size or shape of the hole can be appropriately determined in accordance with the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, stains are also removed in step (IV). The procedure and conditions for the roughening treatment are not particularly limited, and the known procedures and conditions generally used when forming the insulating layer of the printed wiring board can be used. For example, the insulating layer can be roughened by swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. Although there is no particular limitation on the swelling liquid used for the roughening treatment, alkaline solutions, surfactant solutions, etc. can be cited, and alkaline solutions are preferred. As the alkaline solution, sodium hydroxide solutions and potassium hydroxide solutions are preferred. Examples of the swelling liquid sold include "Swelling Dip Security P", "Swelling Dip Security SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed by, for example, immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes. As an oxidizing agent used for the roughening treatment, although not particularly limited, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be cited. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated at 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, for example, alkaline permanganic acid solutions such as "Concentrate compactCP" and "Dosing Solution SecurityP" manufactured by Atotech Japan can be cited. In addition, as a neutralizing solution used in the roughening treatment, an acidic aqueous solution is preferred, and as a commercial product, for example, "Reduction Solution Security P" manufactured by Atotech Japan Co., Ltd. can be cited. The treatment with the neutralizing solution can be performed by immersing the surface treated by the roughening treatment with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 1 minute to 30 minutes. From the perspective of workability, etc., it is preferred to immerse the object treated by the roughening treatment with the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes.

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

Step (V) is a step of forming a conductive layer, and a conductive layer is formed on the insulating layer. The conductive material used for the conductive layer is not particularly limited. In a preferred embodiment, the conductive layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductive layer can be a single metal layer or an alloy layer. As an example of the alloy layer, there can be cited a layer formed by an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, from the viewpoint of versatility, cost, and ease of patterning of the conductive layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred; a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred; and a single metal layer of copper is even more preferred.

The conductive layer may be a single layer structure or a composite structure including two or more single metal layers or alloy layers composed of different types of metals or alloys. When the conductive layer is a composite structure, the layer connected to the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

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

In one embodiment, the conductive layer can be formed by plating. For example, by plating on the surface of the insulating layer using a semi-additive method, a fully additive method, or other conventionally known techniques, a conductive layer having a desired wiring pattern can be formed. From the perspective of manufacturing simplicity, it is preferred to form the conductive layer by a semi-additive method. The following is an example of forming the conductive layer by a semi-additive method.

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

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

As semiconductor devices, there can be cited various semiconductor devices provided in electrical appliances (such as computers, mobile phones, digital cameras, and televisions) and transportation vehicles (such as motorcycles, cars, trains, ships, and airplanes).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The so-called "conductive portion" means "a place in a printed wiring board where electrical information is transmitted", and the place can be a surface or an embedded portion. In addition, the semiconductor chip is not particularly limited as long as it is an electric circuit element using semiconductor as a material.

The semiconductor chip mounting method when manufacturing semiconductor devices is not particularly limited as long as it can effectively exert the function of the semiconductor chip, but specifically includes a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc. Among them, the so-called "mounting method using a bumpless build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board." [Example]

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

[Synthesis Example 1: Synthesis of Compound A containing an Aromatic Ester Skeleton and an Unsaturated Bond (Compound A)] 89 parts by mass of o-allylphenol, 110 parts by mass of dicyclopentadiene-phenol copolymer resin (softening point 85°C, hydroxyl equivalent of about 165 g/eq.), and 1000 parts by mass of toluene were placed in a reaction container, and the pressure in the container was reduced and replaced with nitrogen while dissolving. Next, 135 parts by mass of isophthalic acid chloride was placed and dissolved. Next, 0.5 g of tetrabutylammonium bromide was added, and 309 g of a 20% aqueous sodium hydroxide solution was dripped into the container over 3 hours while nitrogen was blown into the container. At this time, the temperature in the system was controlled below 60°C. Thereafter, the reaction was stirred for 1 hour. After the reaction is completed, the reactants are separated and the aqueous layer is removed. This operation is repeated until the pH of the aqueous layer reaches 7, and toluene and the like are distilled off under heating and reduced pressure conditions to obtain a compound A containing an aromatic ester skeleton and unsaturated bonds. The unsaturated bond equivalent of the obtained compound A containing an aromatic ester skeleton and unsaturated bonds is calculated from the charge ratio to be 428 g/eq. Compound A is represented by the following formula, s represents an integer greater than 0 or 1, and the average value of r calculated from the charge ratio is 1. In addition, the wavy line represents the structure obtained by reacting isophthalic acid chloride with a polyaddition reaction resin of phenol and/or o-allylphenol.

[Synthesis Example 2: Synthesis of Compound B (Compound B) Containing an Aromatic Ester Skeleton and an Unsaturated Bond] Place 201 parts by mass of o-allylphenol and 1000 parts by mass of toluene in a reaction vessel, and dissolve while reducing the pressure in the vessel and replacing it with nitrogen. Continue to add 152 parts by mass of isophthalic acid chloride and dissolve it. While filling the container with nitrogen, drip 309 g of a 20% aqueous sodium hydroxide solution over 3 hours. At this time, the temperature in the system is controlled below 60°C. Thereafter, stir the reaction for 1 hour. After the reaction is completed, separate the reactants and remove the water layer. This operation is repeated until the pH of the aqueous layer reaches 7, and toluene and the like are distilled off under heating and reduced pressure to obtain a compound B containing an aromatic ester skeleton and unsaturated bonds. The unsaturated bond equivalent of the obtained compound B containing an aromatic ester skeleton and unsaturated bonds is calculated from the charge ratio to be 199 g/eq. Compound B has a structure shown in the following formula.

[Synthesis Example 3: Synthesis of polyimide resin] Prepare a 500 mL separable flask with a water dosing receiver connected to a reflux cooler, a nitrogen inlet tube, and a stirrer. In the flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were placed, and stirred and reacted at 45°C for 2 hours under a nitrogen flow. Next, the reaction solution was heated and maintained at about 160°C, and condensed water and toluene were azeotropically removed simultaneously under a nitrogen flow. Confirm that the determined amount of water is retained in the water dosing receiver and that no water is seen to flow out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. After cooling, a polyimide solution (non-volatile matter 20% by mass) containing a polyimide resin having a 1,1,3-trimethylindane skeleton was obtained. The obtained polyimide resin has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). In addition, the weight average molecular weight of the aforementioned polyimide resin is 12,000.

[Synthesis Example 4: Synthesis of Bisphenol Ether Resin] 894.96 mmol of dichloropyrimidine, 900.00 mmol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1.2 mol of potassium carbonate, and N-methyl-2-pyrrolidone (450 g) were placed in a 4-necked flask. After replacing the atmosphere in the flask with nitrogen, the contents of the flask were heated at 130°C for 6 hours. The water generated during heating was removed from time to time using a Dean-Stark tube. After the contents of the flask were cooled to room temperature, the precipitated solid components were separated by filtration, methanol was added to the filtrate, the precipitated solid components were washed with methanol, and the solid components were dried to obtain a bisphenol ether resin (weight average molecular weight (Mw); 87000 (polystyrene conversion value)). The obtained bisphenol ether resin was measured by ¹³ C-NMR to confirm the product. The bisphenol ether resin has a structure shown in the following formula.

[Synthesis Example 5: Synthesis of Maleimide Resin] A MEK solution (non-volatile component 70% by mass) of a maleimide compound synthesized by the method described in Synthesis Example 1 described in the Japan Patent Publication No. 2020-500211 was prepared. The maleimide compound has a structure represented by the following formula.

The FD-MS spectrum of the maleimide compound was measured and the absorption peaks of M ⁺ = 560, 718 and 876 were confirmed. These absorption peaks correspond to the cases where n1 is 0, 1 and 2, respectively. In addition, the maleimide compound was analyzed by GPC, and the value of the repeating unit n1 of the indane skeleton portion was obtained based on the number average molecular weight, and n1 = 1.47, and the molecular weight distribution (Mw/Mn) = 1.81. And the content ratio of the maleimide compound with an average repeating unit n1 of 0 in the total amount of 100 area % of the maleimide compound was 26.5 area %.

[Example 1. Preparation of resin composition 1] 10 parts of compound A obtained in Synthesis Example 1 were dissolved in 10 parts of toluene and 10 parts of MEK while being stirred and heated. After the obtained solution was cooled to room temperature, 80 parts of biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., MEK/toluene mixed solution with 70% non-volatile matter), 15 parts of paint containing 20% by mass of the polyimide resin obtained in Synthesis Example 3, 1 part of a curing accelerator ("perhexyl D" manufactured by NOF Corporation), and 130 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5 μm) surface-treated with an inorganic filler (amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) were mixed and uniformly dispersed with a high-speed rotary mixer to obtain a resin composition 1.

[Example 2. Preparation of Resin Composition 2] For Example 1; 1) Change the amount of compound A from 10 parts to 50 parts, 2) Change the amount of biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide equivalent: 275g/eq., MEK/toluene mixed solution with 70% non-volatile matter) from 80 parts to 70 parts, 3) Use liquid bismaleimide (Designer 7 parts of "BMI689" manufactured by DIC Corporation, maleimide equivalent 345 g/eq.), 4) 15 parts of the paint containing 20% by weight of the polyimide resin obtained in Synthesis Example 3 were replaced with 12.5 parts of polyimide imide resin ("Unidic V-8000" manufactured by DIC Corporation, weight average molecular weight 11000, 40% by weight of ethyl diglycol acetate solution of non-volatile components). Other than the above matters, resin composition 2 was prepared in the same manner as in Example 1.

[Example 3. Preparation of Resin Composition 3] For Example 1; 1) Change the amount of compound A from 10 parts to 20 parts, 2) Change 80 parts of biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide equivalent: 275 g/eq., MEK/toluene mixed solution with 70% non-volatile matter) to oligophenylene ether styrene resin "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd. 1200", 60 parts of toluene solution with 65% non-volatile matter), 3) 5 parts of functional acrylate ((meth) acrylic acid free radical polymerizable compound, "NK ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326), 4) 15 parts of paint containing 20% by weight of polyimide resin obtained in Synthesis Example 3 were replaced with 5 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., weight average molecular weight 30000). Resin composition 3 was prepared in the same manner as in Example 1 except for the above matters.

[Example 4. Preparation of Resin Composition 4] For Example 1; 1) The amount of biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide equivalent: 275g/eq., MEK/toluene mixed solution with 70% non-volatile matter) was changed from 80 parts to 40 parts, 2) 15 parts of the paint containing 20% by mass of the polyimide resin obtained in Synthesis Example 3 was changed to a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., weight average molecular weight 35,000, solid content 30% by mass) 3) Use 10 parts of naphthalene epoxy resin (made by DIC Corporation, "HP4032SS"), 10 parts of carbodiimide resin (made by Nisshinbo Chemical Co., Ltd., "V-03", active group equivalent of about 216, toluene solution with a solid content of 50% by mass), 20 parts of active ester resin (made by DIC Corporation, "HPC-8000-65T", active group equivalent of 223, toluene solution with a solid content of 65% by mass), and 1 part of curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 10% by mass). Other than the above matters, resin composition 4 was prepared in the same manner as in Example 1.

[Example 5. Preparation of Resin Composition 5] For Example 1; 10 parts of Compound A obtained in Synthesis Example 1 were replaced with 10 parts of Compound B obtained in Synthesis Example 2. Resin Composition 5 was prepared in the same manner as in Example 1 except for the above matters.

[Example 6. Preparation of Resin Composition 6] For Example 3, 20 parts of Compound A obtained in Synthesis Example 1 were replaced with 20 parts of Compound B obtained in Synthesis Example 2. Resin Composition 6 was prepared in the same manner as in Example 3 except for the above matters.

[Example 7. Preparation of Resin Composition 7] For Example 3, 20 parts of Compound A obtained in Synthesis Example 1 were replaced with 50 parts of Compound B obtained in Synthesis Example 2. Resin Composition 7 was prepared in the same manner as in Example 3 except for the above matters.

[Example 8. Preparation of Resin Composition 8] For Example 4; 1) 10 parts of Compound A obtained in Synthesis Example 1 were replaced with 20 parts of Compound B obtained in Synthesis Example 2, 2) 40 parts of biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide equivalent: 275 g/eq., MEK/toluene mixed solution with 70% non-volatile matter) were replaced with 30 parts of oligophenylene ether styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with 65% non-volatile matter). Resin composition 8 was prepared in the same manner as in Example 4 except for the above matters.

[Comparative Example 1. Preparation of Comparative Resin Composition 1] For Example 1; 10 parts of Compound A obtained in Synthesis Example 1 were not used. Comparative Resin Composition 1 was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 2. Preparation of Comparative Resin Composition 2] For Example 1; The amount of compound A obtained in Synthesis Example 1 was changed from 10 parts to 85 parts. Other than the above matters, Comparative Resin Composition 2 was prepared in the same manner as Example 1.

[Comparative Example 3. Preparation of Comparative Resin Composition 3] For Example 6; The amount of compound B obtained in Synthesis Example 2 was changed from 20 parts to 85 parts. Other than the above matters, Comparative Resin Composition 3 was prepared in the same manner as Example 6.

[Example 9. Preparation of Resin Composition 9] For Example 1; Replace 15 parts of the polyimide resin in Synthesis Example 3 with 15 parts of a cyclohexanone solution containing 20% non-volatile matter of the bisphenol ether resin in Synthesis Example 4. Resin composition 9 was prepared in the same manner as in Example 1 except for the above matters.

[Example 10. Preparation of Resin Composition 10] For Example 1; 80 parts of biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide equivalent: 275 g/eq., MEK/toluene mixed solution with 70% non-volatile content) were replaced with 80 parts of the maleimide resin of Synthesis Example 5 (MEK solution with 70% non-volatile content by mass). Resin composition 10 was prepared in the same manner as in Example 1 except for the above matters.

[Example 11. Preparation of Resin Composition 11] For Example 3; The amount of compound A obtained in Synthesis Example 1 was changed from 20 parts to 50 parts, and 60 parts of oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd. (65% non-volatile toluene solution) was changed to 67.7 parts of "ODV-XET-X04" (weight average molecular weight 3110, 65% solution) manufactured by Nippon Steel Chemical & Material Co., Ltd., and no bifunctional acrylate ((meth) acrylic acid-based free radical polymerizable compound, "NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326) was used. Resin composition 11 was prepared in the same manner as in Example 3 except for the above matters.

[Example 12. Preparation of resin composition 12] For Example 3; 60 parts of oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd. (a toluene solution with a non-volatile content of 65%) were replaced with 44 parts of benzocyclobutene resin ("CYCLOTENE 3022" manufactured by Dow Chemical Co., Ltd.), and 5 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., with a weight average molecular weight of 30,000) were replaced with 16.7 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., with a weight average molecular weight of 35,000, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass). Resin composition 12 was prepared in the same manner as in Example 3 except for the above matters.

[Example 13. Preparation of Resin Composition 13] For Example 9; 10 parts of Compound A obtained in Synthesis Example 1 were replaced with 10 parts of Compound B obtained in Synthesis Example 2. Resin Composition 13 was prepared in the same manner as in Example 9 except for the above matters.

[Example 14. Preparation of Resin Composition 14] For Example 10; 10 parts of Compound A obtained in Synthesis Example 1 were replaced with 10 parts of Compound B obtained in Synthesis Example 2. Resin Composition 14 was prepared in the same manner as in Example 10 except for the above items.

[Example 15. Preparation of Resin Composition 15] For Example 11, 50 parts of Compound A obtained in Synthesis Example 1 were replaced with 20 parts of Compound B obtained in Synthesis Example 2. Resin Composition 15 was prepared in the same manner as in Example 11 except for the above matters.

[Example 16. Preparation of Resin Composition 16] For Example 12, 20 parts of Compound A obtained in Synthesis Example 1 were replaced with 50 parts of Compound B obtained in Synthesis Example 2. Resin Composition 16 was prepared in the same manner as in Example 12 except for the above matters.

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

Resin compositions 1 to 16 and comparative resin compositions 1 to 3 were uniformly applied on the support by die coating until the thickness of the dried resin composition layer was 40 μm, and then dried at a temperature of 70°C to 95°C for 4 minutes to form the resin composition layer on the support. Next, the rough surface of a polypropylene film ("AlfanMA-411" manufactured by Oji F-Tex, thickness 15 μm) was attached as a protective film to the surface not bonded to the support of the resin composition layer. Thus, a resin sheet having a support, a resin composition layer, and a protective film in this order was obtained.

[Evaluation of unevenness of hardened substrate, determination of peel strength of plated conductor layer] (1) Preparation of inner substrate The copper surface of a glass cloth-based epoxy-resin double-sided copper sheet laminate (copper foil thickness 18μm, substrate thickness 0.4mm, "R1515A" manufactured by Panasonic) with an inner circuit was roughened by etching with a micro-etchant ("CZ8101" manufactured by MEC) for 1μm on both sides.

(2) Lamination of resin sheets The protective film is peeled off from the resin sheet to expose the resin composition layer. The resin composition layer is laminated to both sides of the inner substrate using a batch vacuum pressure laminator (2-stage accumulation laminator "CVP700" manufactured by Nikko Material Co., Ltd.) to bond the resin composition layer to the inner substrate. Lamination is performed by adjusting the air pressure to below 13hPa under decompression for 30 seconds, and then pressing at 120°C and a pressure of 0.74MPa for 30 seconds. Next, hot pressing is performed at 100°C and a pressure of 0.5MPa for 60 seconds.

(3) Thermal curing of the resin composition layer The inner substrate layered with the resin sheet is then placed in an oven at 130°C for 30 minutes and then moved to an oven at 170°C for 30 minutes to thermally cure the resin composition layer and form an insulating layer. The support is then peeled off to obtain a cured substrate A having an insulating layer, an inner substrate, and an insulating layer in this order.

<Evaluation of unevenness of cured substrate> For both sides of the cured substrate A, the surface uniformity of the portion where the resin sheet was laminated (the surface on the opposite side to the laminate) was visually observed and evaluated as follows. ◎: The surface was completely uneven and completely uniform. ○: Unevenness was observed in a portion only 1 cm from the outer periphery of the portion where the resin sheet was laminated, while the inner portion was a completely uniform surface. ×: Unevenness was observed in a portion further inward than 1 cm from the outer periphery of the portion where the resin sheet was laminated.

(4) Roughening treatment The cured substrate A was subjected to a desmearing treatment as a roughening treatment. The desmearing treatment was the wet desmearing treatment described below. (Wet desmearing treatment) The cured substrate A was immersed in a swelling solution ("Swering Dip Security GanttP" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, then immersed in an oxidizing solution ("Concentrate compactCP" manufactured by Atotech Japan, an aqueous solution of potassium permanganate with a concentration of about 6% and sodium hydroxide with a concentration of about 4%) at 80°C for 15 minutes, then immersed in a neutralizing solution ("Reduction Solution SecurityP" manufactured by Atotech Japan, an aqueous solution of sulfuric acid) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

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

<Determination of the peel strength of the coated conductive layer> The peel strength of the insulating layer and the conductive layer was measured in accordance with the Japanese Industrial Standard (JIS C6481). Specifically, for the conductive layer of the evaluation substrate B, a portion of 10 mm wide and 100 mm long was cut out, one end was peeled off and clamped with a clamp, and the load (kgf/cm) when it was pulled vertically by 35 mm at a speed of 50 mm/min at room temperature was measured to obtain the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[Measurement of dielectric properties (dielectric constant, dielectric loss tangent)] The protective film was peeled off from the resin sheet prepared in the embodiment and the comparative example, and the resin composition layer was heat-cured at 200°C for 90 minutes and then peeled off the support. The obtained cured product is called "Evaluation Cured Product C". The Evaluation Cured Product C was cut into test pieces with a width of 2mm and a length of 80mm. For the test piece, the dielectric constant and dielectric loss tangent were measured by the cavity resonance propagation method at a measurement frequency of 5.8GHz and a measurement temperature of 23°C using "HP8362B" manufactured by Agilent Technologies. The measurement was performed on 3 test pieces and the average value was calculated.

[Determination of elongation at break] For the evaluation hardened material C, a tensile test was performed in accordance with Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orient Tech) to determine the elongation at break (%).

* In the table, "content of component (A)" indicates the content of component (A) when the non-volatile components in the resin composition are assumed to be 100% by mass, and "content of component (C)" indicates the content of component (A) when the non-volatile components in the resin composition are assumed to be 100% by mass.

In Examples 1 to 16, even when the components (C) to (F) were not contained, it was confirmed that the same results as those of the above examples were obtained, although there was a certain degree of difference.

10a: Test tube 10b: Test tube 11A: Marking line 12B: Marking line 13a: Rubber plug 13b: Rubber plug

[Figure 1] Figure 1 is a schematic side view of an example of two test tubes used to determine the liquid, semi-solid, and solid components of a thermosetting resin.

Claims (12)

A resin composition comprising (A) a compound having an aromatic ester skeleton and an unsaturated bond, and (B) a radical polymerizable compound (but excluding components equivalent to component (A)), wherein the content of component (A) is 0.1% by mass or more and 30% by mass or less based on 100% by mass of nonvolatile components in the resin composition, and the content of component (B) is 0.1% by mass or more and 30% by mass or less based on 100% by mass of nonvolatile components in the resin composition. The content is 1 mass % or more and 30 mass % or less, and the component (B) is at least any one of a maleimide radical polymerizable compound containing a maleimide group, a vinylphenyl radical polymerizable compound containing a vinylphenyl group, a (meth)acrylic radical polymerizable compound, and a benzocyclobutene radical polymerizable compound, wherein the (meth)acrylic radical polymerizable compound has a divalent cyclic group represented by the following formula (x),

The resin composition as described in claim 1, wherein the component (A) is any one of a compound represented by the following general formula (A-1) and a compound represented by the following general formula (A-2);

In general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of these groups; n represents an integer of 0 to 10;

In the general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent, and Ar ²² each independently represents a monovalent aromatic hydrocarbon group which may have a substituent; and m represents an integer of 2 or 3. The resin composition of claim 1 further contains (C) an inorganic filler. The resin composition described in claim 3, wherein when the non-volatile components in the resin composition are taken as 100% by mass, the content of component (C) is 50% by mass or more. The resin composition of claim 1 further contains (D) a thermoplastic resin. The resin composition of claim 1 further contains (E) a thermosetting resin. The resin composition of claim 1, wherein the component (B) contains: any one of a maleimide-based free radical polymerizable compound containing a maleimide group and a vinylphenyl-based free radical polymerizable compound containing a vinylphenyl group. The resin composition of claim 1 is used for forming an insulating layer. The resin composition of claim 1 is used to form an insulating layer for forming a conductive layer. A resin sheet comprising a support and a resin composition layer disposed on the support and comprising a resin composition as described in any one of claims 1 to 9. A printed wiring board comprising an insulating layer formed by a cured product of a resin composition as described in any one of claims 1 to 9. A semiconductor device comprising a printed wiring board as claimed in claim 11.

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