KR20210007884A - Resin composition - Google Patents

Abstract

The present invention relates to a resin composition capable of inhibiting stains generated on a cured substrate and providing a cured product having excellent dielectric properties and peel strength, a resin sheet including the resin composition, and a printed circuit board and semiconductor device provided with a dielectric layer formed by using the resin composition. The resin composition includes: (A) a compound containing an aromatic ester backbone and an unsaturated bond; and (B) a radical polymerizable compound, wherein the content of ingredient (A) is 0.1-30 wt% based on 100 wt% of the non-volatile ingredients of the resin composition.

Description

Resin composition {RESIN COMPOSITION}

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

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

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

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

In recent years, further improvement in dielectric properties such as dielectric constant and dielectric loss tangent of an insulating layer, and further improvement in peel strength between a conductive layer formed by plating are required. In addition, when an insulating layer is formed by laminating a resin sheet on a substrate with irregularities, the surface of the insulating layer on the opposite side of the substrate follows the irregularities of the substrate and the flatness of the insulating layer decreases, and the cured substrate is uneven (insulation layer surface Stains) may occur. If the cured substrate is uneven, the composition of the insulating layer becomes uneven, and thus wiring formability may be inferior.

The subject of the present invention is a resin composition capable of suppressing unevenness occurring on a cured substrate and obtaining a cured product excellent in dielectric properties and peel strength; A resin sheet containing the resin composition; It is to provide a printed wiring board provided with an insulating layer formed using the said resin composition, and a semiconductor device.

The present inventors, as a result of earnestly examining the above problem, found that the above problem can be solved by containing a predetermined amount of (A) an aromatic ester skeleton and an unsaturated bond-containing compound, and (B) a radical polymerizable compound, The present invention has been completed.

That is, the present invention includes the following contents.

[1] (A) a compound containing an aromatic ester skeleton and an unsaturated bond, and

(B) radical polymerizable compound

As a resin composition containing,

The resin composition, wherein the content of the component (A) is 0.1% by mass or more and 30% by mass or less when the nonvolatile component in the resin composition is 100% by mass.

[2] The resin composition according to [1], in which 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 the 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, Ar Each of ¹³ 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 consisting of a combination thereof. Represents an integer of 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 that may have a substituent. m is 2 or It represents an integer of 3.)

[3] The resin composition according to [1] or [2], further containing (C) an inorganic filler.

[4] The resin composition according to [3], wherein the content of the component (C) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

[5] The resin composition according to any one of [1] to [4], further containing (D) a thermoplastic resin.

[6] The resin composition according to any one of [1] to [5], further containing (E) a thermosetting resin.

[7] In [1] to [6], in which the component (B) contains any one of a maleimide radical polymerizable compound containing a maleimide group and a vinylphenyl radical polymerizable compound containing a vinylphenyl group The resin composition according to any one.

[8] The resin composition according to any one of [1] to [7], which is for forming an insulating layer.

[9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer for forming a conductor layer.

[10] A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of [1] to [9], provided on the support.

[11] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [9].

[12] A semiconductor device comprising the printed wiring board according to [11].

According to the present invention, a resin composition capable of suppressing unevenness occurring on a cured substrate and capable of obtaining a cured product excellent in dielectric properties, peel strength, and elongation at break point; A resin sheet containing the resin composition; A printed wiring board provided with an insulating layer formed using the resin composition, and a semiconductor device can be provided.

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

Hereinafter, the present invention will be described in detail based on its preferred embodiment. However, the present invention is not limited to the following embodiments and examples, and can be carried out with arbitrary changes within the scope of the claims of the present invention and the scope of their equivalents.

[Resin composition]

The resin composition of the present invention is a resin composition containing (A) an aromatic ester skeleton and an unsaturated bond-containing compound, and (B) a radically polymerizable compound, wherein the content of the component (A) is a nonvolatile component in the resin composition. When it is set as 100 mass %, it is 0.1 mass% or more and 30 mass% or less. In the present invention, by containing a predetermined amount of the component (A) and further containing the component (B), unevenness occurring on the cured substrate can be suppressed, and a cured product having excellent dielectric properties and peel strength can be obtained. . In addition, usually, a cured product excellent in elongation at break can be obtained.

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

<(A) Aromatic ester skeleton and unsaturated bond-containing compound>

The resin composition contains (A) an aromatic ester skeleton and an unsaturated bond-containing compound as component (A). By including the component (A) in the resin composition, unevenness occurring in the cured substrate can be suppressed, and a cured product having excellent dielectric properties can be obtained. (A) component may be used individually by 1 type, and may use 2 or more types together.

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

The component (A) has an aromatic ester skeleton. The aromatic ester skeleton represents a skeleton having an ester bond and an aromatic ring bonded to one or both ends of the ester bond. Especially, it is preferable to have an aromatic ring at both ends of an ester bond. As a group having such a skeleton, for example, arylcarbonyloxy group, aryloxycarbonyl group, arylenecarbonyloxy group, aryleneoxycarbonyl group, arylcarbonyloxyarylene group, aryloxycarbonylarylene group, arylenecarbon Nyloxyarylene group, aryleneoxycarbonylarylene group, etc. are mentioned. In addition, the number of carbon atoms in the group having such a skeleton is preferably 7 to 20, more preferably 7 to 15, and still more preferably 7 to 11. Aromatic hydrocarbon groups, such as an aryl group and an arylene group, may have a substituent.

As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is still more preferable. Examples of such aryl groups include phenyl group, furanyl group, pyrrolyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyridine One hydrogen atom removed from a monocyclic aromatic compound such as a nil group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, and a triazinyl group; Naphthyl group, anthracenyl group, phenalenyl group, phenanthrenyl group, quinolinyl group, isoquinolinyl group, quinazolyl group, phthalazinyl group, pteridinyl group, cuminyl group, indole group, benzoimidazolyl group, One hydrogen atom removed from a condensed ring aromatic compound such as a benzofuranyl group and an acridinyl group; And the like.

As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is still more preferable. As such arylene group, a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group (-C ₆ H ₄ -C ₆ H ₄ -), etc. are mentioned, for example.

The component (A) contains an unsaturated bond. This unsaturated bond is preferably a carbon-carbon unsaturated bond. As an unsaturated bond, it is preferable to have it as a substituent which has at least one unsaturated bond. Examples of the unsaturated bond include an unsaturated hydrocarbon group such as an alkenyl group having 2 to 30 carbon atoms and an alkynyl group having 2 to 30 carbon atoms. It is preferable to have an unsaturated bond as a substituent of the aromatic hydrocarbon group at the terminal, and it is more preferable to have it as a substituent of the aromatic hydrocarbon group at both ends.

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

Examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1,3 -Butadiinyl group, etc. are mentioned.

Among these, the unsaturated bond is preferably an alkenyl group having 2 to 30 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, and still more preferably an alkenyl group having 2 to 5 carbon atoms. , An allyl group, an isopropenyl group, and a 1-propenyl group are more preferable, and an allyl group is particularly preferable.

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

As the aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferable, an arylene group and an aralkylene group are more preferable, and an arylene group is still more preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is still more preferable. As such arylene group, a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, etc. are mentioned, for example. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferable, an aralkylene group having 7 to 20 carbon atoms is more preferable, and an aralkylene group having 7 to 15 carbon atoms is still more preferable. Among these, a phenylene group is preferable.

As the aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferable, a divalent saturated aliphatic hydrocarbon group is more preferable, and an alkylene group and a cycloalkylene group are still more preferable. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is still more preferable. As the alkylene group, for example, methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1-dimethylethylene group, 1,2-dimethyl Ethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, etc. are mentioned.

As the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferred, a cycloalkylene group having 3 to 15 carbon atoms is more preferred, and a cycloalkylene group having 5 to 10 is still more preferred. As the cycloalkylene group, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, a cycloalkylene group represented by the following formulas (a) to (d), etc. Can be mentioned. In formulas (a) to (d), "*" represents a bonded hand.

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

As an alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso Pentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, Cycloheptyl group, cyclooctyl group, and cyclononyl group are mentioned.

The alkoxy group having 1 to 10 carbon atoms is not particularly limited, but a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, oxy group A yloxy group, a nonyloxy group, etc. are mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The above-described substituent may further have a substituent (hereinafter, referred to as "secondary substituent" in some cases). The unsaturated hydrocarbon group is as described above. As the secondary substituent, unless otherwise specified, the same as the substituent described above may be used.

It is preferable that 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 the 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, Ar Each of ¹³ 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 consisting of a combination thereof. Represents an integer of 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 that may have a substituent. m is 2 or It represents an integer of 3.)

In General Formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. As a monovalent aromatic hydrocarbon group, for example, a phenyl group, a furanyl group, a pyrrolyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, One hydrogen atom removed from a monocyclic aromatic compound such as a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, and a triazinyl group; Naphthyl group, anthracenyl group, phenalenyl group, phenanthrenyl group, quinolinyl group, isoquinolinyl group, quinazolyl group, phthalazinyl group, pteridinyl group, cuminyl group, indole group, benzoimidazolyl group, One hydrogen atom has been removed from a condensed ring aromatic compound such as a benzofuranyl group and an acridinyl group; Etc. are mentioned, Among them, a phenyl group is preferable from the viewpoint of obtaining remarkably the effect of this invention. The monovalent aromatic hydrocarbon group represented by Ar ¹¹ may have a substituent. As a substituent, it is the same as a substituent which the aromatic ester skeleton may have. Especially, it is preferable that the substituent of Ar ¹¹ contains an unsaturated bond.

In General Formula (A-1), Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent. Examples of the divalent aromatic hydrocarbon group include an arylene group and an aralkylene group, and an arylene group is preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is still more preferable. As such arylene group, a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, etc. are mentioned, for example. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferable, an aralkylene group having 7 to 20 carbon atoms is more preferable, and an aralkylene group having 7 to 15 carbon atoms is still more preferable. Among these, a phenylene group is preferable.

The divalent aromatic hydrocarbon group represented by Ar ¹² may have a substituent. As a substituent, it is the same as a substituent which the aromatic ester skeleton may have.

In the general formula (A-1), Ar ¹³ is each independently 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 combination thereof. It represents a divalent group composed of, and a divalent group composed of a combination thereof is preferable. The divalent aromatic hydrocarbon group is the same as the divalent aromatic hydrocarbon group represented by Ar ¹² .

As the divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is more preferable, an alkylene group and a cycloalkylene group are preferable, and a cycloalkylene group is more preferable.

As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is still more preferable. As the alkylene group, for example, methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1-dimethylethylene group, 1,2-dimethyl Ethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, etc. are mentioned.

As the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferred, a cycloalkylene group having 3 to 15 carbon atoms is more preferred, and a cycloalkylene group having 5 to 10 is still more preferred. As the cycloalkylene group, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, a cycloalkylene group represented by the above formulas (a) to (d), etc. May be mentioned, and a cycloalkylene group represented by formula (c) is preferable.

The divalent group composed of these combinations is preferably a divalent aromatic hydrocarbon group which may have a substituent and a divalent group combining a divalent aliphatic hydrocarbon group which may have a substituent, and a plurality of divalent groups which may have a substituent A divalent group obtained by alternately combining an aromatic hydrocarbon group and a plurality of divalent aliphatic hydrocarbon groups which may have a substituent is more preferable. Specific examples of the above divalent groups include the following divalent groups (A1) to (A8). In the formula, a1 to a8 represents an integer of 0 to 10, preferably an integer of 0 to 5. "*" represents a bonding hand, and a broken line represents a structure obtained by reacting an aromatic compound used when synthesizing the component (A), an acid halide of an aromatic compound, or an esterified product of an aromatic compound.

The divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group represented by Ar ¹³ may have a substituent. As a substituent, it is the same as a 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. In addition, 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 hydrocarbon group which may have a substituent. The m-valent aromatic hydrocarbon group is preferably an m-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an m-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and an m-valent aromatic hydrocarbon group having 6 to 10 carbon atoms More preferable. The m-valent aromatic hydrocarbon group represented by Ar ²¹ may have a substituent. As a substituent, it is the same as a substituent which 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 have a substituent. As a substituent, it is the same as a substituent which the aromatic ester skeleton may have.

In General Formula (A-2), m represents the integer of 2 or 3, and 2 is preferable.

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

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

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

From the viewpoint of remarkably obtaining the effect of the present invention, the unsaturated bond equivalent of the component (A) is preferably 50 g/eq. Or more, more preferably 100g/eq. Above, more preferably 150 g/eq., preferably 2000 g/eq. Below, more preferably 1000 g/eq. Hereinafter, more preferably 500 g/eq. Below. The unsaturated bond equivalent is the mass of the component (A) containing 1 equivalent of an unsaturated bond.

<(B) radical polymerizable compound>

The resin composition contains (B) a radical polymerizable compound as a component (B). However, in (B) component, the thing corresponding to (A) component is excluded. By including the component (B) in the resin composition, unevenness occurring on the cured substrate can be suppressed, and a cured product excellent in dielectric properties and peel strength can be obtained. Component (B) may be used individually by 1 type, and may use 2 or more types together.

As the component (B), a compound having a function of generating a radical by heat or light and curing the component (A), that is, a compound having at least any one of radically polymerizable unsaturated groups can be used. Examples of such compounds include maleimide radical polymerizable compounds containing a maleimide group, vinylphenyl radical polymerizable compounds containing vinylphenyl groups, (meth)acrylic radical polymerizable compounds, allyl radical polymerizable compounds, butadiene radical polymerization It is preferable that it is 1 type selected from a sexual compound and a benzocyclobutene-based radical polymerizable compound, and a maleimide-based radical polymerizable compound, a vinylphenyl-based radical polymerizable compound, a (meth)acrylic radical polymerizable compound, and a benzocyclo moiety It is more preferable that it is at least any one of ten radical polymerizable compounds, and it is more preferable that it is any one of a maleimide radical polymerizable compound, a vinylphenyl radical polymerizable compound, and a benzocyclobutene radical polymerizable compound.

The component (B) may have a radically polymerizable unsaturated group. Examples of the radically polymerizable unsaturated group include a group having an ethylenic double bond exhibiting curability by irradiation with an active energy ray. Examples of such groups include vinyl group, allyl group, vinylphenyl group, acryloyl group, and methacryloyl group, maleimide group, fumaroyl group, maleoyl group, and allyl group, vinylphenyl group, acrylic It is preferable that it is at least 1 type selected from a royl group and a methacryloyl group.

As the component (B), it is preferable to have one or more radically polymerizable unsaturated groups, more preferably two or more. Although there is no restriction|limiting in particular about an upper limit, It can be set as 10 or less etc.

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

Here, the determination of liquid, semi-solid, and solid is carried out in accordance with the second "Liquid Confirmation Method" of the Holy Spirit (Self-Governmental Spirit No. 1 in 1989) on the test and appearance of dangerous substances. The specific determination method is as follows.

(1) device

Constant temperature water bath:

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

In addition, in the determination of liquid, semi-solid, and solid, a combination of a low-temperature constant temperature water bath (type BU300) manufactured by Yamato Chemical Co., Ltd. and an immersion thermostat thermomate (model name BF500) is used, and approximately 22 liters of tap water are used at low temperature. Put it in a constant temperature water tank (type BU300), turn on the power of the thermomate (type BF500) assembled in it, set it to the set temperature (20℃ or 60℃), and set the water temperature to the set temperature ±0.1℃ (type BF500) It can be finely adjusted with, but any device capable of the same adjustment can be used.

examiner:

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

As the thermometer 14, one for measuring the freezing point specified in JIS B7410 (1982) "glass thermometer for testing petroleum" (SOP-58 scale range 0 to 100°C) is used, but the temperature range of 0 to 100°C can be measured. It's good if you can.

(2) Procedure of the test

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

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

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

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

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

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

The number of maleimide groups per molecule of the solid maleimide radical polymerizable compound is preferably 1 or more, more preferably 2 or more, further from the viewpoint of remarkably obtaining the desired effect of the present invention. It is 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, the solid maleimide radical polymerizable compound preferably has either an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and more preferably has an aliphatic hydrocarbon group and an aromatic hydrocarbon group. desirable.

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

As the aromatic hydrocarbon group, monovalent and divalent aromatic hydrocarbon groups are preferable, and an aryl group and an arylene group are more preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is still more preferable. Examples of such arylene group include phenylene group, naphthylene group, anthracenylene group, aralkyl group, biphenylene group, biphenylaralkyl group, and the like, and among them, phenylene group, aralkyl group, biphenylene group, A biphenylaralkyl group is preferable, and a phenylene group, an aralkyl group, and a biphenylene group are more preferable. As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, an aryl group having 6 to 10 carbon atoms is still more preferable, and a phenyl group is particularly preferable.

In the solid maleimide-based radical polymerizable compound, from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferable that the nitrogen atom of the maleimide group is directly bonded to a monovalent or divalent aromatic hydrocarbon group. Here, "direct" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

It is preferable that the solid maleimide compound has a structure represented by the following formula (B-a), for example.

[In the formula, R ^c each independently represents a substituent; X ^c is each independently 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); Each of Z ^c independently represents a non-aromatic ring which may have a substituent, or an aromatic ring that may have a substituent (preferably an aromatic ring which may have a substituent, particularly preferably a benzene ring which may have a substituent). Indicate; s represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, still more preferably an integer of 1 to 20); each t independently represents 0 or an integer of 1 or more; u are each independently a maleimide compound represented by an integer of 0 to 2 (preferably 0), and particularly preferably formulas (Ba-1) to (Ba-4):

[In the formula, 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 of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, still more preferably an integer of 1 to 20); t'represents an integer of 1 to 5; u1, u2 and u3 are each independently a maleimide compound represented by an integer of 0 to 2 (preferably 0). Further, the s unit, t unit, t'unit, u unit, u1 unit, u2 unit, and u3 unit may be the same or different for each unit, respectively.

In addition, as another embodiment, the solid maleimide radical polymerizable compound is preferably a structure represented by, for example, the following formula (B-2).

In formula (B-2), R ³¹ and R ³⁶ represent a maleimide group, R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and D is each independently It 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.

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

As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is still more preferable. The alkyl group may be linear, branched or cyclic. As such an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, etc. are mentioned, for example.

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

The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and for example, a halogen atom, -OH, -OC _1-6 alkyl group, -N (C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6-10 aryl group,- NH ₂ , -CN, -C(O)OC _1-10 alkyl group, -COOH, -C(O)H, -NO ₂ , and the like. Here, the term "C _pq " (p and q are positive integers and satisfies p<q) indicates that the number of carbon atoms in the organic group immediately following the term is p to q. For example, the expression "C _1-10 alkyl group" represents an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring or a condensed ring.

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

D in formula (B-2) represents a divalent aromatic group. Examples of the divalent aromatic group include a phenylene group, a naphthylene group, an anthracenylene group, an aralkyl group, a biphenylene group, and a phenylaralkyl group, and among them, a biphenylene group and a phenylaralkyl group are preferable. And a biphenylene group is more preferable. The divalent aromatic group may have a substituent. As a substituent, it is the same as a substituent which may have the alkyl group represented by R ³² in Formula (B-2).

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

a represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, and still more preferably 1 to 5.

As the solid maleimide radical polymerizable compound, resin represented by formula (B-3) is preferable.

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 a preferred range is also the same.

The weight average molecular weight (Mw) of the solid maleimide radical polymerizable compound is preferably 150 to 5000, more preferably 300 to 2500.

The functional group equivalent of the maleimide group of the maleimide 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., particularly preferably 200 g/eq. To 300 g/eq.

As for the solid maleimide-based radical polymerizable compound, a commercial item can be used. As a commercial item, for example, "MIR-3000-70MT" manufactured by Nippon Kayaku Corporation; "BMI-50P" by K-I Kasei Co., Ltd.; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", "BMI-5100" manufactured by Yamato Kasei Kogyo; "BMI-4,4'-BPE", "BMI-70" manufactured by K-I Kasei, and "BMI-80" manufactured by K-I Kasei, etc. are mentioned.

A liquid or semi-solid maleimide radical polymerizable compound is a compound having at least one maleimide group in a molecule.

It is preferable that the liquid or semi-solid maleimide radical polymerizable compound 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 still more preferably 40 or less. This alkyl group may be linear, branched, or cyclic, and linear is preferable among them. As such an alkyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. are mentioned, for example. An alkyl group having 5 or more carbon atoms may have as a substituent for an alkylene group having 5 or more carbon atoms.

The number of carbon atoms of the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and still more preferably 40 or less. This alkylene group may be linear, branched, or cyclic, and among them, linear is preferable. Here, the cyclic alkylene group is a concept including a case consisting of only a cyclic alkylene group and a case including both a linear alkylene group and a cyclic alkylene group. As such an alkylene group, for example, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, and hexatriacone A group having a tylene group, an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like may be mentioned.

From the viewpoint of remarkably obtaining the effects of the present invention, the liquid or semi-solid maleimide radical polymerizable compound preferably contains both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.

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

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms preferably do not have a substituent, but may have a substituent. As a substituent, it is the same as a substituent which the aromatic ester skeleton in (A) component may have.

In the liquid or semi-solid maleimide radical polymerizable compound, it is preferable that an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms are directly bonded to the nitrogen atom of the maleimide group.

The number of maleimide groups per molecule of the liquid or semi-solid maleimide radical polymerizable compound may be 1, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less , Particularly preferably 3 or less. By using a liquid or semi-solid maleimide radical polymerizable compound having two or more maleimide groups per molecule, the effects of the present invention can be remarkably obtained.

It is preferable that a liquid or semi-solid maleimide radical polymerizable compound is represented by the following general formula (B-4).

In 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 connecting 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 above-described alkylene group having 5 or more carbon atoms. The substituent of M is the same as the substituent which may be present in the aromatic ester skeleton in the component (A), and the substituent is preferably an alkyl group having 5 or more carbon atoms.

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

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

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

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

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

The alkylene group, alkenylene group, alkynylene group, and arylene group as the divalent linking group in L may have a substituent. As a substituent, it is the same as the substituent which the aromatic ester skeleton in (A) component may have, Preferably it is a C5 or more alkyl group.

Examples of the group consisting of a combination of two or more divalent groups in L include, for example, an alkylene group, a phthalimide-derived divalent group, and a divalent group consisting of a bond with an oxygen atom; A divalent group consisting of a combination of a phthalimide-derived divalent group, an oxygen atom, an arylene group, and an alkylene group; A divalent group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; And the like. A group consisting of a combination of two or more divalent groups may form a ring such as a condensed ring by combining the respective groups. Further, a group consisting of a combination of two or more divalent groups may be a repeating unit having 1 to 10 repeating units.

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

The liquid or semi-solid maleimide radical polymerizable compound represented by the general formula (B-4) is preferably represented by the general formula (B-7).

In general formula (B-7), M ¹ 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 or a substituent having 5 or more carbon atoms which may have a substituent It represents a divalent group which has an aromatic ring which may have it. t represents an integer of 1 to 10.

M ¹ each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent. M ¹ is the same as M in General Formula (B-4).

Each of Z independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent. As the alkylene group in Z, any of chain, branched, and cyclic may be used, and among them, cyclic, that is, a cyclic alkylene group having 5 or more carbon atoms which may have a substituent is preferable. The number of carbon atoms in the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, even more preferably 40 or less. Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like. have.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by Z include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, and an aromatic heterocyclic ring. A benzene ring, a phthalimide ring, and a pyromellitic diimide ring are preferable. That is, as a divalent group having an aromatic ring, a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, and a pyromellitic diimide ring which may have a substituent A divalent group having Examples of the divalent group having an aromatic ring include a group consisting of a combination of a divalent group derived from phthalimide and an oxygen atom; A group consisting of a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group and an alkylene group; A group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; Divalent groups derived from pyromellitic diimide; A group consisting of a combination of a divalent group derived from phthalimide and an alkylene group; And the like. 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).

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

As a specific example of the group represented by Z, the following groups are mentioned. In the formula, "*" represents a bond hand.

The maleimide radical polymerizable compound represented by the general formula (B-4) is a liquid or semi-solid maleimide radical polymerizable compound represented by the general formula (B-8), and the general formula (B-9) It is preferable that it is either a liquid or semi-solid maleimide radical polymerizable compound represented by.

In General Formula (B-8), M ² and M ³ each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, and R ⁴⁰ each independently represent an oxygen atom, an arylene group, an alkylene group, or It represents a divalent group consisting of a combination of two or more of these groups. t1 represents an integer of 1 to 10.

In the general formula (B-9), M ⁴ , M ⁶ and M ⁷ each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, and M ⁵ each independently represents an aromatic ring which may have a substituent. Represents a divalent group having, and R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

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

Each of R ⁴⁰ independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more divalent groups. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in General Formula (B-4). It is preferable that R ⁴⁰ is a group consisting of a combination of two or more divalent groups or an oxygen atom.

Examples of the group consisting of a combination of two or more divalent groups for R ⁴⁰ include combinations of an oxygen atom, an arylene group, and an alkylene group. The following groups are mentioned as a specific example of the group which consists of a combination of 2 or more types of divalent groups. In the formula, "*" represents a bond hand.

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

M ⁵ each independently represents a divalent group having an aromatic ring which may have a substituent. M ⁵ is the same as a divalent group having an aromatic ring which may have a substituent represented by Z in the general formula (B-7), and is a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; A group consisting of a combination of a phthalimide-derived divalent group and an alkylene group is preferable, and a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide is more preferable. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-4).

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

R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. R ⁴¹ and R ⁴² are the same as the above-described alkyl group having 5 or more carbon atoms, preferably a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, and more preferably a hexyl group and an octyl group.

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

As a specific example of a liquid or semi-solid maleimide radical polymerizable compound, the following compounds (B1) to (B3) are mentioned. However, the liquid or semi-solid maleimide radical polymerizable compound is not limited to these specific examples. In the formula, v represents an integer of 1 to 10.

As specific examples of the liquid or semi-solid maleimide radical polymerizable compound, "BMI1500" (compound of formula (B1)), "BMI1700" (compound of formula (B2)), "BMI689" ( The compound of formula (B3)), etc. are mentioned.

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

The vinylphenyl radical polymerizable compound is a radical polymerizable compound having a vinylphenyl group. It is preferable that the vinylphenyl-based radical polymerizable compound is liquid or semi-solid. The determination of the liquid or semi-solid is as described above. The vinylphenyl group is a group having a structure shown below.

(* indicates a bonded hand.)

The vinylphenyl 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.

It is preferable that the vinylphenyl-based radical polymerizable compound has a cyclic structure from the viewpoint of obtaining a cured product having a low dielectric loss tangent. As the cyclic structure, a divalent cyclic group is preferable. As the divalent cyclic group, any one of a cyclic group including an alicyclic structure and a cyclic group including an aromatic ring structure may be used. Moreover, you may have a plurality of divalent cyclic groups.

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

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

As a specific example of a divalent cyclic group, the following divalent group (xii) or (xiii) is mentioned.

(In divalent groups (xii) and (xiii), R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁶¹ , and R ⁶² are each independently a halogen atom, an alkyl group having 6 or less carbon atoms, Or a phenyl group, and R ⁵³ , R ⁵⁴ , R ⁵⁸ , R ⁵⁹ , and R ⁶⁰ 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 a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like, and a methyl group is preferable. As R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁶¹ , and R ⁶² , it is preferable to represent a methyl group. R ⁵³ , R ⁵⁴ , R ⁵⁸ , R ⁵⁹ , and R ⁶⁰ are preferably a hydrogen atom or a methyl group.

Further, the divalent cyclic group may be combined with a plurality of divalent cyclic groups. As a specific example when a divalent cyclic group is combined, a divalent cyclic group (divalent group (a) represented by the following formula (B4)) is mentioned.

(In formula (B4), R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ are each independently a halogen atom, an alkyl group having 6 or less carbon atoms, or Represents a phenyl group, and 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. d2 represents an integer 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 an integer of 0 to 300. However, the case where one of d1 and d2 is 0 is excluded. As d1 and d2, it is preferable to represent an integer of 1-100, it is more preferable to represent an integer of 1-50, and it is still more preferable to represent an integer of 1-10. d1 and d2 may be the same or different.

The divalent cyclic group may have a substituent. As a substituent, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, And an oxo group, and an alkyl group is preferable.

The vinylphenyl group may be directly bonded to a divalent cyclic group, or may be bonded through a divalent linking group. As a divalent linking group, for example, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O) N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like, and a group obtained by combining a plurality of these may be used. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms Rengi is more preferred. The alkylene group may be linear, branched or cyclic. As such an alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group, etc. are mentioned, for example, a methylene group, an ethylene group, 1,1 -Dimethylethylene group is preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is more preferable, and an alkenylene group having 2 to 5 carbon atoms is still more preferable. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and a methylene group is particularly preferable.

It is preferable that the vinylphenyl-based radical polymerizable compound is 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.)

R ⁹¹ and R ⁹² each independently represent a divalent linking group. As a divalent connecting group, it is the same as the said divalent connecting group.

Ring B1 represents a divalent cyclic group. As ring B, it is the same as the said divalent cyclic group.

Ring B1 may have a substituent. As a substituent, it is the same as the substituent which the said divalent cyclic group may have.

In another embodiment, it is preferable that the vinylphenyl-based radically polymerizable compound is 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 having other styrene skeleton units such as styrene units and ethylstyrene units. In the case of having other styrene skeleton units, it is preferable that the ratio of the repeating units of formula (B-11) is 5 to 70 mol% with respect to all styrene skeleton units.

[In the formula, R ^e5 , R ^e6 and R ^e7 each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom).]

Hereinafter, a specific example of the vinylphenyl-based radical polymerizable compound is shown, but the present invention is not limited thereto.

(q1 is the same as d1 in formula (B4), and q2 is the same as d2 in formula (B4).)

As the vinylphenyl radical polymerizable compound, a commercial item may be used. For example, "OPE-2St", "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl-modified polyphenyl) manufactured by Mitsubishi Gas Chemical Co., Ltd. Ren ether); "ODV-XET-X03", "ODV-XET-X04", "ODV-XET-X05" (divinylbenzene polymer) manufactured by Nittetsu Chemical & Materials Co., Ltd. are mentioned. The vinylphenyl radical polymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more types.

The number average molecular weight of the vinylphenyl radically polymerizable compound is preferably 3000 or less, more preferably 2500 or less, still 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, still more preferably 500 or more, and 1000 or more. The number average molecular weight is a number average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC).

The (meth)acrylic radical polymerizable compound is a compound containing an acryloyl group and a methacryloyl group, and combinations thereof. As the (meth)acrylic radical polymerizable compound, it is preferable to have two or more (meth)acryloyl groups per molecule from the viewpoint of remarkably obtaining the desired effect of the present invention. The term "(meth)acryloyl group" includes an acryloyl group and a methacryloyl group, and combinations thereof. It is preferable that the (meth)acrylic radical polymerizable compound is liquid or semi-solid. The determination of the liquid or semi-solid is as described above.

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

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

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

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

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

The (meth)acryloyl group may be directly bonded to a divalent cyclic group, or may be bonded through a divalent linking group. As a divalent linking group, for example, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O) N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like, and a group obtained by combining a plurality of these may be used. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms Rengi is more preferred. The alkylene group may be linear, branched or cyclic. As such an alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group, etc. are mentioned, for example, a methylene group, an ethylene group, 1,1 -Dimethylethylene group is preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is more preferable, and an alkenylene group having 2 to 5 carbon atoms is still more preferable. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and a methylene group and a 1,1-dimethylethylene group are particularly preferable.

It is preferable that the (meth)acrylic radical polymerizable compound is represented by the following formula (B-11).

(In formula (B-11), R ¹⁰¹ and R ¹⁰⁴ each independently represent an acryloyl group or a methacryloyl group, and R ¹⁰² and R ¹⁰³ each independently represent a divalent linking group. Ring B2 is divalent. It represents an illusion.)

R ¹⁰¹ and R ¹⁰⁴ each independently represent an acryloyl group or a methacryloyl group, and an acryloyl group is preferable.

R ¹⁰² and R ¹⁰³ each independently represent a divalent linking group. As a divalent linking group, it is the same as a divalent linking group which may have a (meth)acryloyl group bonded.

Ring B2 represents a divalent cyclic group. As ring B2, it is the same as the said divalent cyclic group. Ring B2 may have a substituent. As a substituent, it is the same as the substituent which the said divalent cyclic group may have.

Although the following are mentioned as a specific example of a (meth)acrylic-type radical polymerizable compound, this invention is not limited to this.

As the (meth)acrylic radical polymerizable compound, a commercial item may be used, for example, "A-DOG" manufactured by Shin-Nakamura Kagaku Kogyo, "DCP-A" manufactured by Kyoeisha Kagaku Corporation, and Nippon Kayaku Corporation. Manufacturing "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA", and "NK ester DCP" manufactured by Shinnakamura Kagaku Kogyo. have.

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

The allyl radical polymerizable compound is a compound having at least one allyl group in a molecule. It is preferable that the allyl-based radical polymerizable compound is liquid or semi-solid. The determination of the liquid or semi-solid is as described above. The allyl radical polymerizable compound preferably has one or more allyl groups per molecule, and more preferably has two or more allyl groups. The lower limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

Further, from the viewpoint of remarkably obtaining the desired effect of the present invention, the allyl radical polymerizable compound is, in addition to the allyl group, any one of a benzoxazine ring, a phenol ring, an isocyanur ring, an epoxy group, and a carboxylic acid derivative having a cyclic structure. It is preferable to have.

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

Examples of the allyl radical polymerizable compound having a phenol ring include a cresol resin containing an allyl group, a novolak type phenol resin containing an allyl group, and a cresol novolak resin containing an allyl group.

The allyl radical polymerizable compound having an isocyanur structure preferably has an isocyanur structure nitrogen atom and an allyl group directly bonded thereto. Examples of the allyl radical polymerizable compound having an isocyanuric structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, and the like.

It is preferable that the allyl-based radical polymerizable compound having an epoxy group contains two or more epoxy groups per molecule. Further, the allyl radical polymerizable compound having an epoxy group preferably has an aromatic structure, and when two or more allyl radical polymerizable compounds having an epoxy group are used, it is more preferable that at least one has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles. The allyl radical polymerizable compound having an epoxy group preferably has a bisphenol structure, and examples of the bisphenol structure include bisphenol A type, bisphenol F type, and bisphenol AF type.

As the allyl-based radically polymerizable compound having a carboxylic acid derivative having a cyclic structure, allyl carboxylic acid having a cyclic structure is preferable. As the cyclic structure, either of a cyclic group including an alicyclic structure and a cyclic group including an aromatic ring structure may be used. In addition, the cyclic group may have a ring skeleton formed by a hetero atom other than a carbon atom. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, A nitrogen atom is preferable. One hetero atom may be in the ring, and may have two or more.

As a carboxylic acid having a cyclic structure, isocyanuric acid, diphenic acid, phthalic acid, cyclohexanedicarboxylic acid, etc. are mentioned, for example. Examples of the allyl radical polymerizable compound having a carboxylic acid derivative having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl difenate, allyl difenate, orthodiallyl And phthalate, metadiallyl phthalate, paradiallyl phthalate, allyl cyclohexanedicarboxylic acid, diallyl cyclohexanedicarboxylic acid, and the like.

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

From the viewpoint of remarkably obtaining the desired effect of the present invention, the allyl group equivalent of the allyl radical polymerizable compound is preferably 20 g/eq. To 1000 g/eq., more preferably 50 g/eq. To 500 g/eq., more preferably 100 g/eq. To 300 g/eq. The allyl group equivalent is the mass of the allyl-based radical polymerizable compound containing 1 equivalent of an allyl group.

The butadiene-based radical polymerizable compound is a compound having at least one butadiene skeleton in a molecule. The polybutadiene structure may be included in the main chain or may be included in the side chain. In addition, the polybutadiene structure may be partially or entirely hydrogenated. Examples of the butadiene radical polymerizable compound include hydrogenated polybutadiene skeleton-containing resin, hydroxy group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing At least one resin selected from the group consisting of butadiene resins and urethane group-containing butadiene resins is more preferable.

As specific examples of the butadiene-based radical polymerizable compound, ``JP-100'' manufactured by Japan Soda Corporation, ``Ricon100'', ``Ricon150'', ``Ricon130MA8'', ``Ricon130MA13'', ``Ricon130MA20'', ``Ricon131MA5'' manufactured by CRAY VALLEY, "Ricon131MA10", "Ricon131MA17", "Ricon131MA20", "Ricon 184MA6", etc. are mentioned.

It is preferable that the butadiene-based radical polymerizable compound is in a liquid or semi-solid form. The determination of the liquid or semi-solid is as described above.

The benzocyclobutene-based radical polymerizable compound is a compound having a benzocyclobutene ring. The benzocyclobutene ring may be included in the main chain or may be included in the side chain. As a specific example of a benzocyclobutene-based radical polymerizable compound, "CYCLOTENE 3022" by Dow Chemical Co., Ltd. is mentioned.

As the content of the component (B), unevenness occurring in the cured substrate can be suppressed, and from the viewpoint of obtaining a cured product having excellent dielectric properties, peel strength, and elongation at break, the nonvolatile component in the resin composition is 100% by mass. In the case, it is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably It is 30 mass% or less.

When the content of the component (A) when the nonvolatile component in the resin composition is 100% by mass is set to a, and the content of the component (B) when the nonvolatile component in the resin composition is 100% by mass is set to b , a/b is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.15 or more, preferably 3 or less, more preferably 2 or less, even more preferably 1.5 or less. By adjusting a/b to fall within such a range, it becomes possible to remarkably obtain the effect of the present invention.

<(C) inorganic filler>

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

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

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

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. Although there is no particular limitation on the upper limit, it is preferably 60 m2/g or less, 50 m2/g or less, or 40 m2/g or less. The specific surface area is obtained by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mauntech Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multi-point method.

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

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

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

As a commercial item of the surface treatment agent, Shin-Etsu Chemical Co., Ltd. "KBM1003" (vinyl triethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM503" (3-methacryloxypropyl triethoxysilane), Shin-Etsu "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Kagaku Kogyo, "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kogyo, "KBE903" manufactured by Shin-Etsu Kagaku Kogyo "(3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyl Disilazane), Shin-Etsu Chemical Co., Ltd. ``KBM103'' (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. ``KBM-4803'' (long-chain epoxy-type silane coupling agent), Shin-Etsu Chemical Co., Ltd. ``KBM -7103" (3,3,3-trifluoropropyltrimethoxysilane), etc. are mentioned.

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

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more, from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, 1 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable.

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

The content of the component (C) is preferably 50% by mass or more, more preferably 53% by mass or more, further preferably when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of lowering the dielectric properties. Preferably it is 55 mass% or more, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.

<(D) Thermoplastic resin>

In addition to the above-described components, the resin composition may further contain a thermoplastic resin as an optional component and as the component (D). However, those corresponding to component (B) are excluded. By including the component (D) in the resin composition, the stress of the resin composition is relieved, and as a result, it becomes possible to obtain a cured product excellent in dielectric properties. (D) component may be used individually by 1 type, and may use 2 or more types together.

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

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

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

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

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

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

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

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

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

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

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

In one embodiment, as the dianiline compound, specifically, 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl Ether, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4-amino Phenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2 ,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 -Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α- Bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorenylidene)dianiline, 2,2-bis(3-methyl-4 -Aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4' -Diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3- [4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan, and the like.

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

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

Benzenetetracarboxylic dianhydride means a benzene dianhydride having four carboxyl groups, and the benzene ring here may optionally have 1 to 3 substituents. Here, as a substituent, it is preferable that it is selected from a halogen atom, a cyano group, and -X ³³⁰ -R ³³⁰ (same as the definition of the following formula (1D)). Specific examples of the benzene tetracarboxylic dianhydride include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and the like.

The naphthalene tetracarboxylic dianhydride refers to a naphthalene dianhydride having four carboxyl groups, and the naphthalene ring herein may optionally have 1 to 3 substituents. Here, as a substituent, it is preferable that it is selected from a halogen atom, a cyano group, and -X ³³⁰ -R ³³⁰ (same as the definition of the following formula (1D)). Specific examples of the naphthalene tetracarboxylic dianhydride include 1,4,5,8-naphthalene tetracarboxylic dianhydride and 2,3,6,7-naphthalene tetracarboxylic dianhydride.

The anthracene tetracarboxylic dianhydride refers to an anthracene dianhydride having four carboxyl groups, and the anthracene ring here may optionally have 1 to 3 substituents. Here, as a substituent, it is preferable that it is selected from a halogen atom, a cyano group, and -X ³³⁰ -R ³³⁰ (same as the definition of the following formula (1D)). Specific examples of the anthracene tetracarboxylic dianhydride include 2,3,6,7-anthracene tetracarboxylic dianhydride and the like.

The diphthalic acid dianhydride refers to a compound containing two phthalic anhydrides in a molecule, and the two benzene rings in the two phthalic anhydrides may each optionally have 1 to 3 substituents. Here, as a substituent, it is preferable that it is selected from a halogen atom, a cyano group, and -X ³³⁰ -R ³³⁰ (same as the definition of the following formula (1D)). The two phthalic anhydrides in the diphthalic acid dianhydride may be bonded directly or via a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

As diphthalic acid dianhydride, for example, formula (1D):

[In the formula,

R ²⁰¹ and R ²⁰² each independently represent a halogen atom, a cyano group, a nitro group, or -X ³³⁰ -R ³³⁰ ,

X ³³⁰ is, each independently, 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 linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms,

Each of n10 and n11 independently represents an integer of 0 to 3.]

The compound represented by is mentioned.

Y ¹ is preferably a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. n10 and n11 are preferably 0.

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

The "linker structure" in Y ¹ is specifically, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -O-, -CO-, -SO ₂ -, -Ph-, -O-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, and the like. In this specification, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group.

As diphthalic acid dianhydride, specifically, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetra Carboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-ratio Phenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2.3,3',4'-diphenyl Ethertetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4 '-Diphthalic dianhydride, 1,1-ethynylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4, 4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4 ,4'-diphthalic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride , 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic acid dianhydride, and the like.

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

Commercially available products can be used for the polyimide resin. As a commercial item, "Licacoat SN20" and "Licacoat PN20" manufactured by the Shinnipon Rica company can be mentioned.

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

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

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

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

Polyamideimide resin is a resin having an amidimide structure. From the viewpoint of compatibility with other components in the resin composition, the polyamideimide resin is a polyamideimide resin having an alicyclic structure in its molecular structure, and a polyamide having a siloxane structure described in JP-A05-112760A It is preferable to use a mid resin, a polyamideimide resin having a bulky branched chain structure, a polyamideimide resin using an asymmetric monomer as a raw material, a polyamideimide resin having a multi-branched structure, and the like.

Among them, the polyamideimide resin has an isocyanuric ring structure, from the viewpoint of improving the compatibility and dispersibility of the resin varnish, (i) a polyamideimide resin having an isocyanuric ring structure in the molecular structure (I.e., a polyamideimide resin having an isocyanuric ring structure and an imide skeleton or an amide skeleton) (ii) a polyamideimide resin having an isocyanuric ring structure and an alicyclic structure in the molecular structure (i.e., isocyanuric ring A polyamideimide resin having a structure and an alicyclic structure and an imide skeleton or an amide skeleton), (iii) a polyamideimide resin having a repeating unit including an isocyanuric structure and an alicyclic structure (i.e., isocyanuric ring A polyamideimide resin having a structure, an alicyclic structure, and a repeating unit including an imide skeleton or an amide skeleton) is more preferable.

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

As the compound (D-1), a compound specifically represented by the following general formula (I) can be mentioned. In addition, the repeating unit in the compound represented by the general formula (I) is referred to as the repeating unit (I-1).

(Wherein, w represents 0-15.)

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

(In the formula, R ⁴⁰ represents a residue in formula (I).)

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

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

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

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

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

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

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

As an arbitrary repeating unit, a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), a repeating unit having a structure obtained by hydrogenating it (hydrogenated conjugated diene unit), etc. are mentioned, for example. Examples of the conjugated dienes include aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and 1,3-hexadiene; And halogenated aliphatic conjugated dienes such as chloroprene. As the conjugated diene, an aliphatic conjugated diene is preferable and butadiene is more preferable from the viewpoint of remarkably obtaining the effect of the present invention. Conjugated diene may be used individually by 1 type, and may be used in combination of 2 or more types. Further, the polystyrene resin may be a random copolymer or a block copolymer.

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

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

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

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

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

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

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

Bisphenol ether resin is a resin having a bisphenol ether structure. From the viewpoint of remarkably obtaining the effect of the present invention, the bisphenol ether resin preferably contains a repeating unit represented by the following formula (D-a).

[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; 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 aromatic ring refers to a ring according to the Huckel rule in which the number of electrons in the π electron system on the ring is 4n+2 (n is a natural number). The nitrogen-containing aromatic ring represented by ring A has one or more (preferably two or more, particularly preferably two) nitrogen atoms as ring constituent atoms, in addition to carbon atoms, and further, an oxygen atom, You may have a hetero atom other than a nitrogen atom, such as a sulfur atom. The nitrogen-containing aromatic ring represented by ring A is preferably a 5 to 14 membered nitrogen-containing aromatic ring, more preferably a 5 to 10 membered nitrogen-containing aromatic ring, more preferably a 5 or 6 membered nitrogen-containing aromatic ring, and 6 membered A nitrogen-containing aromatic ring is particularly preferred. In the nitrogen-containing aromatic ring represented by ring A, not only a monocyclic aromatic ring and a condensed ring in which two or more monocyclic aromatic rings are condensed, but also one or more monocyclic non-aromatic rings are included in one or more monocyclic aromatic rings. Condensed condensed rings are also included.

As suitable specific examples of the nitrogen-containing aromatic ring represented by ring A, for example, 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, Monocyclic nitrogen-containing aromatic rings such as a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring; A condensed ring of a monocyclic nitrogen-containing aromatic ring such as an indole ring, an isoindole ring, a benzoimidazole ring, an indazole ring, a benzotriazole ring, a quinoxaline ring, a cinnoline ring, a quinazoline ring, and a phthalazine ring, and a benzene ring; Pteridine ring, purine ring, 4-azaindole ring, 5-aza indole ring, 6-aza indole ring, 7-aza indole ring, 7-azaindole ring, pyrazolo[1,5-a]pyrimidine ring, 1,8-naphthyridine ring, pyrid[3,2-d]pyrimidine ring, pyrid[4,3-d]pyrimidine ring, pyrid[3,4-b]pyrazine ring, pyrid[2] And a condensed ring between monocyclic nitrogen-containing aromatic rings such as ,3-b]pyrazine ring, and the like. Preferably, it is a monocyclic nitrogen-containing aromatic ring, and more preferably, a six-membered monocyclic It is a nitrogen-containing aromatic ring, more preferably a pyrimidine ring or a pyridazine ring, and particularly preferably a pyrimidine ring.

The nitrogen-containing aromatic ring may have a substituent. The substituent is not particularly limited, but for example, an alkyl group, an alkenyl group, an aryl group, an alkyl-aryl group (an aryl group substituted with one or more alkyl groups), an aryl-aryl group (an aryl substituted with one or more aryl groups) Group), aryl-alkyl group (alkyl group substituted with one or more aryl groups), alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl -Monovalent substituents such as oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group, etc. And divalent substituents such as an oxo group (=O) may also be included if substitution is possible.

An alkyl (group) refers to a linear, branched and/or cyclic monovalent saturated aliphatic hydrocarbon group. The alkyl (group) preferably has 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 or 4 to 10 carbon atoms. Alkenyl (group) refers to a linear, branched and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl (group) preferably has 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 2 to 6 or 4 to 10 carbon atoms. The aryl (group) refers to a monovalent aromatic hydrocarbon 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 may be a carbocyclic ring having a carbon atom as a ring constituent atom, or a heterocycle having a hetero atom such as an oxygen atom, a nitrogen atom, and a sulfur atom in addition to a carbon atom as a ring constituent atom, In one embodiment, it is preferable that it is a carbocyclic ring. As for the aromatic ring represented by ring B or ring C, a 5 to 14 membered aromatic ring is preferable, a 5 to 10 membered aromatic ring is more preferable, a 5 or 6 membered aromatic ring is more preferable, and a 6 membered aromatic ring is particularly preferable. . In the aromatic ring represented by ring B or ring C, not only a monocyclic aromatic ring and a condensed ring in which two or more monocyclic aromatic rings are condensed, but also one or more monocyclic non-directions in one or more monocyclic aromatic rings. Condensed rings in which the rings are condensed are also included.

As suitable specific examples of the aromatic ring represented by ring B or ring C, 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, a pyridazine ring, Monocyclic aromatic rings such as pyrimidine ring and pyrazine ring; Naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzoimidazole ring, indazole ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring, quinoline ring , A condensed ring in which two or more monocyclic aromatic rings such as an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, and a phthalazine ring are condensed; Condensed rings in which one or more monocyclic non-aromatic rings are condensed with one or more monocyclic aromatic rings such as an indan ring, a fluorene ring, and a tetralin ring, and the like, preferably a monocyclic aromatic ring. , More preferably, it is a 6-membered monocyclic aromatic ring, Most preferably, it is 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 linear, branched 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, preferably 1 to 50, more preferably 1 to 30, and still more preferably 1 to 20 carbon atoms. to be.

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

[In the formula, R ¹ and R ² may each independently represent a hydrogen atom, an alkyl group, or an alkenyl group, or R ¹ and R ² become one and bond to each other and have a group selected from an alkyl group and an alkenyl group. Forming a good cycloalkane ring or a cycloalkene ring which may have a group selected from an alkyl group and an alkenyl group; * Represents a binding site.] is a divalent group, more preferably, formulas (X2-1) to (X2-3):

[In the formula, 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); * Represents a binding site.]

It is a divalent group represented by any of, and particularly preferably, it is a divalent group represented by formula (X2-1).

The cycloalkane ring means a cyclic aliphatic saturated hydrocarbon ring. The cycloalkane ring is preferably a cycloalkane ring having 3 to 8 carbon atoms, and a cycloalkane ring having 5 or 6 carbon atoms is more preferable. As a cycloalkane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, etc. are mentioned, for example. The 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, and a cycloalkene ring having 5 or 6 carbon atoms is more preferable. As a cycloalkene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, a cyclohexadiene ring, etc. are mentioned, for example.

The compound containing a repeating unit represented by formula (D-a) is preferably, formula (1A) or (1B):

[In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent N, CH or CR ^a (preferably N or CH), and among X ¹ , X ² , X ³ and X ⁴ , At least one (preferably at least two, particularly preferably two) is N; R ^a , R ^b and R ^c are each independently 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, more preferably an alkyl group, alke Represents an aryl 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 formula (X1).]

It is a compound containing a repeating unit represented by, More preferably, formulas (1A-1) to (1B-3):

[In the formula, a represents an integer of 0 to 2 (preferably 0); Other symbols are the same as those of formulas (1A), (1B), and formulas (X2-1) to (X2-3).]

It is a compound containing a repeating unit represented by any of, and particularly preferably, a compound containing a repeating unit represented by formula (1A-1).

The compound containing the repeating unit represented by the formula (Da) may, in one embodiment, have a reactive group such as a phenolic hydroxyl group, a thiol group, an amino group, a carboxy group, and a sulfo group, and preferably, a phenolic hydroxyl group. Can have In one embodiment, it is preferable to have two or more reactive groups per molecule.

In the compound containing a repeating unit represented by formula (D-a), the number of repeating units is preferably 5 or more, more preferably 10 or more, still more preferably 30 or more, and particularly preferably 50 or more. The upper limit of the number of repeating units is not particularly limited, but may be, for example, 10000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less.

The glass transition temperature (Tg) of the compound containing the repeating unit represented by the formula (D-a) is not particularly limited, but may be 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, a method described in WO2019/054335 or WO2020/021827 or a method similar thereto.

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

<(E) Thermosetting resin>

In addition to the above-described components, the resin composition may further contain a thermosetting resin as the component (E) as an optional component. However, those corresponding to the component (A) and component (B) are excluded. (E) As the thermosetting resin, for example, epoxy resin, phenol resin, naphthol resin, benzoxazine resin, active ester resin, cyanate ester resin, carbodiimide resin, amine resin, acid anhydride Resin, etc. are mentioned. (E) component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Hereinafter, a resin composition by reacting with an epoxy resin, such as a phenol resin, a naphthol resin, a benzoxazine resin, an active ester resin, a cyanate ester resin, a carbodiimide resin, an amine resin, and an acid anhydride resin. A resin capable of curing is sometimes referred to as a "curing agent" generically.

Examples of the epoxy resin as the component (E) include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin. , Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type Epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy Resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and the like. Epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

It is preferable that the resin composition contains an epoxy resin having two or more epoxy groups per molecule as the component (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 to 100% by mass of the nonvolatile component of the component (E) is preferably 50% by mass or more, more It is preferably 60 mass% or more, particularly preferably 70 mass% or more.

Epoxy resins include a liquid epoxy resin at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resin”), and a solid epoxy resin at a temperature of 20°C (hereinafter referred to as “solid epoxy resin” in some cases). There is. As the component (E), the resin composition may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin.

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

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

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

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

Examples of the solid epoxy resin include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and Phenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable.

As the solid epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin , Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. As a specific example of a solid epoxy resin, "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation, and "N-690" (cresol novolac Type epoxy resin), ``N-695'' (cresol novolac type epoxy resin), ``HP-7200'', ``HP-7200HH'', ``HP-7200H'' (dicyclopentadiene type epoxy resin), manufactured by DIC "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); Nippon Kayaku's "EPPN-502H" (trisphenol-type epoxy resin), "NC7000L" (naphthol novolac-type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy resin) Suzy); "ESN475V" (naphthalene-type epoxy resin), "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nittetsu Chemical & Materials Co., Ltd.; "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bicylenol-type epoxy resin), "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals, "YL7760" manufactured by Mitsubishi Chemicals (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), and "jER1010" (solid phase) Bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (E), their quantity ratio (liquid epoxy resin: solid epoxy resin) is by mass ratio, preferably 1:0.1 to 1:20, more preferably 1:0.3 to 1:15, particularly preferably 1:0.5 to 1:10. When the amount ratio between the liquid epoxy resin and the solid epoxy resin is in this range, the desired effect of the present invention can be remarkably obtained. Further, usually, when used in the form of an adhesive film, suitable adhesiveness is formed. In addition, usually, when used in the form of an adhesive film, sufficient flexibility is obtained and handling properties are improved. Further, usually, a cured product having sufficient breaking strength can 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., even more preferably 110 g/eq. To 1000 g/eq. By being in this range, a cured product having a sufficient crosslink density of the cured product of the resin composition can be formed. Epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to 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, still more preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention. to be. The weight average molecular weight of an epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

The content of the epoxy resin as the component (E) is, from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, when the nonvolatile component in the resin composition is 100% by mass, preferably 5% by mass or more, and more preferably Is 10 mass% or more, more preferably 15 mass% or more. 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 remarkably obtaining the desired effect of the present invention.

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

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

As a phenol compound or a naphthol compound, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolac, and the like. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

Preferred examples of the active ester resin include an active ester resin containing a dicyclopentadiene-type diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated phenol novolac, and phenol. And active ester resins containing the benzoylates of novolac. Among them, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available active ester resins are active ester resins containing dicyclopentadiene-type diphenol structures, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H- 65TM", "EXB-8000L-65TM" (manufactured by DIC); As an active ester resin containing a naphthalene structure, "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", "HPC -8150-62T" (manufactured by DIC); "DC808" (manufactured by Mitsubishi Chemical) as an active ester resin containing an acetylated product of phenol novolak; "YLH1026" (manufactured by Mitsubishi Chemical) as an active ester resin containing a benzoylated phenol novolac; "DC808" (manufactured by Mitsubishi Chemical) as an active ester resin which is an acetylated product of phenol novolac; As an active ester resin that is a benzoylated phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical), "YLH1030" (manufactured by Mitsubishi Chemical), and "YLH1048" (manufactured by Mitsubishi Chemical); "EXB-8500-65T" (manufactured by DIC); And the like.

As the phenolic resin and naphthol resin as the component (E), it is preferable to have a novolac structure from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic resin is more preferable.

As specific examples of the phenolic resin and the naphthol resin, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Maywa Kasei, "NHN", "CBN" manufactured by Nippon Kayaku ", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "manufactured by Nittetsu Chemical & Materials. SN395", "TD-2090" manufactured by DIC Corporation, "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and the like are mentioned.

(b) As a specific example of the benzoxazine-based resin as a component, "JBZ-OD100" (benzoxazine ring equivalent 218), "JBZ-OP100D" (benzoxazine ring equivalent 218), "ODA-BOZ" ( Benzoxazine ring equivalent weight 218); "P-d" (benzoxazine ring equivalent 217) and "F-a" (benzoxazine ring equivalent 217) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "HFB2006M" (benzoxazine ring equivalent 432) manufactured by Showa Kobunshi Corporation, etc. are mentioned.

As a cyanate ester resin as a component (E), for example, bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1 -Bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, Bifunctional cyanate resins such as bis(4-cyanatephenyl)thioether and bis(4-cyanatephenyl)ether; Polyfunctional cyanate resins derived from phenol novolac and cresol novolac; These cyanate resins are partially triazineized prepolymers; And the like. As a specific example of a cyanate ester resin, "PT30", "PT30S" and "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin) manufactured by Ronza Japan ), "BA230", "BA230S75" (a prepolymer in which part or all of the bisphenol A dicyanate is triazineized to form a trimer), and the like.

As a specific example of the carbodiimide resin as the component (E), Nisshinbo Chemical Co., Ltd. carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216, V-05 (carbodiimide group equivalent: 216) ), V-07 (carbodiimide group equivalent: 200); V-09 (carbodiimide group equivalent: 200); Line Chemie's Starboxol (registered trademark) P (carbodiimide group equivalent: 302) Can be lifted.

Examples of the amine resin as the component (E) include resins having one or more amino groups per molecule, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like. , From the viewpoint of showing the desired effect of the present invention, aromatic amines are preferable. The amine-based resin is preferably a primary amine or a secondary amine, and more preferably a primary amine. As specific examples of the amine resin, 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone , 3,3'-diaminodiphenylsulfone, 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-4-hydroxyphenyl) )Propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-amino Phenoxy)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. . Commercially available amine resins may be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard AA", "Kayahard AB", "Kayahard AS" manufactured by Nippon Kayaku Corporation. And "Epicure W" manufactured by Mitsubishi Chemical Corporation.

Examples of the acid anhydride resin as the component (E) include resins having at least one acid anhydride group in one molecule. Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydro phthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride , Dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride , Benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a ,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycolbis( Anhydrotrimellitate), and polymeric acid anhydrides such as styrene maleic resin in which styrene and maleic acid are copolymerized.

In the case of containing an epoxy resin and a curing agent as the component (E), the amount ratio of the epoxy resin and all curing agents is a ratio of [the total number of epoxy groups of the epoxy resin]: [the total number of reactors of the curing agent], from 1:0.01 to The range of 1:5 is preferable, 1:0.3 to 1:3 are more preferable, and 1:0.5 to 1:2 are more preferable. Here, "the number of epoxy groups of the epoxy resin" is a value obtained by dividing the mass of the nonvolatile component of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, the "number of active groups of the curing agent" is a value obtained by dividing the mass of the nonvolatile component of the curing agent present in the resin composition by the active group equivalent. As the component (E), a cured product excellent in flexibility can be obtained by making the amount ratio of the epoxy resin and the curing agent within this range.

The content of the curing agent as the component (E) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably based on 100% by mass of the nonvolatile component in the resin composition from the viewpoint of obtaining a cured product having excellent flexibility. Preferably it is 5 mass% or more, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

The content of the component (E) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably based on 100% by mass of the nonvolatile component in the resin composition from the viewpoint of obtaining a cured product having excellent flexibility. It is 15 mass% or more, Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.

<(F) hardening accelerator>

In addition to the above-described components, the resin composition may further contain a curing accelerator as the component (F) as an optional component. By containing the component (F), it becomes possible to further promote polymerization by heat.

Examples of the component (F) include epoxy resin curing accelerators such as phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, and metal curing accelerators; Thermal polymerization hardening accelerators, such as a peroxide-type hardening accelerator, etc. are mentioned. (F) component may be used individually by 1 type, and may be used in combination of 2 or more types.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid addition Water, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2 -a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, imidazole compounds, and epoxy resins And the adduct body of, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

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

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

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

Examples of the peroxide-based curing accelerator include dit-butyl peroxide, t-butyl cumyl peroxide, t-butyl peroxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t Peroxides, such as -butyl peroxy laurate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy neodecanoate, and t-butyl peroxy benzoate, are mentioned.

As a commercial product of a peroxide-based curing accelerator, for example, "Perhexyl D", "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O" manufactured by Nichiyu Corporation. ", "perbutyl ND", "perbutyl Z", "percumyl P", "percumyl D", and the like.

The content of the component (F) is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. , More preferably, it is 0.3 mass% or more, Preferably it is 1 mass% or less, More preferably, it is 0.8 mass% or less, More preferably, it is 0.5 mass% or less.

<(G) Other additives>

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

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

<Physical properties and use of resin composition>

The resin composition contains a predetermined amount of component (A) and component (B). Thereby, unevenness occurring on a cured substrate can be suppressed, and a cured product excellent in dielectric properties, peel strength, and elongation at break can be obtained. Usually, when the content of the inorganic filler is increased, there is a tendency that unevenness occurring in the cured substrate tends to occur. However, by combining and containing a predetermined amount of the component (A) and the component (B), even if the content of the inorganic filler is large, it becomes possible to suppress the occurrence of unevenness occurring in the cured substrate. Further, it becomes possible to obtain a cured product excellent in dielectric properties, peel strength, and elongation at break.

The resin composition exhibits a property of being able to suppress unevenness occurring on a cured substrate. Specifically, after laminating a resin composition layer of a resin sheet on a glass cloth-based epoxy resin double-sided copper clad laminate having a copper foil thickness of 18 μm, heat curing at 130°C for 30 minutes and then at 170°C for 30 minutes to form an insulating layer . The surface uniformity of the surface on the opposite side of the glass cloth-based epoxy resin double-sided copper clad laminate was observed with the naked eye of the insulating layer in the portion where the resin sheet was laminated. At this time, in general, the portion inside the resin sheet is a uniform surface than the portion 1 cm from the outer circumference of the laminated portion. Preferably, the entire surface of the insulating layer opposite to the laminated plate is a uniform surface. Details of the evaluation of the unevenness of the cured substrate can be measured according to the method described in Examples to be described later.

The cured product obtained by thermally curing the resin composition at 130° C. for 30 minutes and then at 170° C. for 30 minutes exhibits excellent peel strength between a conductor layer (plated conductor layer) formed by plating. Accordingly, the cured product forms an insulating layer having excellent peel strength between the plated conductor layer and the plated conductor layer. The peel strength is preferably 0.3 kgf/cm or more, more preferably 0.35 kgf/cm or more, and still more preferably 0.4 kgf/cm or more. The upper limit of the peel strength can be 10 kgf/cm or less. The measurement of the peel strength of the plated conductor layer can be measured according to the method described in Examples to be described later.

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

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

A cured product obtained by thermosetting the resin composition at 200° C. for 90 minutes exhibits a property of high elongation at break because of its high toughness. Therefore, the hardened|cured material mentioned above forms an insulating layer with high elongation at break. The breaking point elongation is preferably 0.5% or more, more preferably 0.8% or more, and still more preferably 1% or more. On the other hand, the upper limit of elongation at break is not particularly limited, but may be 10% or less. The evaluation of the above breaking point elongation can be measured according to the method described in Examples to be described later.

The resin composition of the present invention can suppress unevenness occurring on a cured substrate, and can form an insulating layer excellent in dielectric properties, peel strength, and elongation at break. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating applications. Specifically, it can be suitably used as a resin composition for forming the insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. have.

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

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

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

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

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

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

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

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

[Resin sheet]

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

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, even more preferably from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulating properties even if the cured product of the resin composition is a thin film. It is less than 30 μm. The lower limit of the thickness of the resin composition layer is not particularly limited, but can be usually 5 μm or more.

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

When a film made of a plastic material is used as the support, as the plastic material, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”) Yes.) polyester, polycarbonate (hereinafter sometimes abbreviated as ``PC''), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), polyether sulfide ( PES), polyether ketone, polyimide, etc. are mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

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

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

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

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

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

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

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

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

[Printed wiring board]

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

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

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

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

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

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. As a member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as "heat-pressing member"), a heated metal plate (SUS hard plate, etc.) or a metal roll (SUS roll) may be mentioned. Further, it is preferable not to press the heat-compressed member directly onto the resin sheet, but to press the heat-resistant rubber or the like with an elastic material therebetween so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

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

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

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

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

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

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

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

In manufacturing the printed wiring board, (III) the step of drilling the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art used for manufacturing a printed wiring board. In addition, when the support is removed after the step (II), the removal of the support is between the step (II) and the step (III), between the step (III) and the step (IV), or the step (IV). You may implement it between and process (V). Further, if necessary, the insulating layer and the conductor layer in the steps (II) to (V) may be repeatedly formed to form a multilayer wiring board.

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

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

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

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

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

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

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

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

[Semiconductor device]

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

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

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

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

[Example]

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

[Synthesis Example 1: Synthesis of Aromatic Ester Skeleton and Unsaturated Bond-Containing Compound A (Compound A)]

89 parts by mass of orthoallylphenol, 110 parts by mass of dicyclopentadiene-phenol copolymer resin (softening point of 85° C., about 165 g/eq. of hydroxyl group equivalent), and 1000 parts by mass of toluene were poured into the reaction vessel, and the inside of the container was dissolved while substituting under reduced pressure with nitrogen. Made it. Subsequently, 135 parts by mass of isophthalic acid chloride was poured and dissolved. Next, 0.5 g of tetrabutylammonium bromide was added, and 309 g of a 20% aqueous sodium hydroxide solution was dripped over 3 hours while purging the inside of the container with nitrogen. At that time, the temperature in the system was controlled to 60°C or less. Then, it was stirred for 1 hour and made to react. After completion of the reaction, the reaction product was separated to remove an aqueous layer. This operation was repeated until the pH of the aqueous layer became 7, and toluene and the like were distilled under heating and reduced pressure conditions to obtain an aromatic ester skeleton and an unsaturated bond-containing compound A. The unsaturated bond equivalent of the obtained aromatic ester skeleton and the unsaturated bond-containing compound A was 428 g/eq. calculated from the injection ratio. Compound A is represented by the following formula, s represents an integer of 0 or 1 or more, and the average value of r calculated from the injection ratio is 1. In addition, a broken line is a structure obtained by reaction of isophthalic acid chloride, and polyaddition reaction resin of phenol, and/or orthoallylphenol.

[Synthesis Example 2: Synthesis of Aromatic Ester Skeleton and Unsaturated Bond-Containing Compound B (Compound B)]

201 parts by mass of orthoallylphenol and 1000 parts by mass of toluene were poured into the reaction container, and the inside of the container was dissolved under reduced pressure with nitrogen. Then, 152 parts by mass of isophthalic acid chloride was poured and dissolved. While purging the inside of the container with nitrogen, 309 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. At that time, the temperature in the system was controlled to 60°C or less. Then, it was stirred for 1 hour and made to react. After completion of the reaction, the reaction product was separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer became 7, and toluene and the like were distilled off under heating and reduced pressure conditions to obtain an aromatic ester skeleton and an unsaturated bond-containing compound B. The unsaturated bond equivalent of the obtained aromatic ester skeleton and the unsaturated bond-containing compound B was 199 g/eq. calculated from the injection ratio. Compound B is a structure represented by the following formula.

[Synthesis Example 3: Synthesis of polyimide resin]

A 500 mL separable flask equipped with a water meter connected to a reflux condenser, a nitrogen introduction tube, and a stirrer was prepared. In this flask, 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5-(4-aminophenoxy)-3-[4-(4-amino 29.6 g of phenoxy)phenyl]-1,1,3-trimethylindane was added, and the mixture was stirred at 45°C for 2 hours under a nitrogen stream to react. Subsequently, the temperature of this reaction solution was raised and the condensed water was azeotropically removed with toluene under a nitrogen stream while maintaining at about 160°C. It was confirmed that a predetermined amount of water was accumulated in the water metering device and that water outflow was not seen. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. Then, it cooled and obtained the polyimide solution (non-volatile content 20 mass %) containing the polyimide resin which has a 1,1,3-trimethylindane skeleton. The obtained polyimide resin had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). Moreover, the weight average molecular weight of the said polyimide resin was 12,000.

[Synthesis Example 4: Synthesis of bisphenol ether resin]

In a four-necked flask, 894.96 mmol of dichloropyrimidine, 900.00 mmol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1.2 mol of potassium carbonate, N-methyl-2- Pyrrolidone (450g) was added. After the inside of the flask was purged with nitrogen, the contents of the flask were heated at 130° C. for 6 hours, and water generated during heating was removed from the Dean-Stark tube from time to time. After cooling the contents of the flask to room temperature, the precipitated solid was filtered, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried, and a bisphenol ether resin (weight average molecular weight (Mw); 87000 (polystyrene conversion value)) was obtained. The obtained bisphenol ether resin was measured by ¹³ C-NMR, and the product was confirmed. The bisphenol ether resin has a structure represented by 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 Technical Report Air No. 2020-500211 was prepared. This maleimide compound has a structure represented by the following formula.

When the FD-MS spectrum of the maleimide compound was measured, peaks of M ⁺ = 560, 718 and 876 were confirmed. These peaks correspond when n1 is 0, 1, and 2, respectively. Further, when the maleimide compound is analyzed by GPC and the value of the number of repeating units n1 of the indan skeleton moiety is obtained based on the number average molecular weight, n1 is 1.47 and molecular weight distribution (Mw/Mn) is 1.81. In addition, in 100 area% of the total amount of the maleimide compound, the content ratio of the maleimide compound in which the average number of repeat units n1 is 0 was 26.5 area%.

[Example 1. Preparation of resin composition 1]

10 parts of Compound A obtained in Synthesis Example 1 were heated and dissolved in 10 parts of toluene and 10 parts of MEK while stirring. After cooling the obtained solution to room temperature, a biphenylaralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., and a mixed solution of MEK/toluene having 70% non-volatile content) ) 80 parts, 15 parts of varnish containing 20% by mass of the polyimide resin obtained in Synthesis Example 3, 1 part of curing accelerator ("Perhexyl D" manufactured by Nichiyu), inorganic filler (amine-based silane coupling agent (Shin-Etsu Chemical Co., Ltd.) (Manufactured "KBM573") surface-treated spherical silica ("SO-C2" manufactured by Adomex Co., Ltd., an average particle diameter of 0.5 μm)) 130 parts were mixed and uniformly dispersed with a high-speed rotary mixer to obtain a resin composition 1.

[Example 2. Preparation of resin composition 2]

In Example 1,

1) change the amount of compound A from 10 parts to 50 parts,

2) The amount of biphenylaralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., MEK/toluene mixed solution of 70% non-volatile content) from 80 parts to 70 Change to wealth,

3) Using 7 parts of liquid bismaleimide ("BMI689" manufactured by Designer Molecules, maleimide group equivalent 345 g/eq.),

4) 15 parts of the varnish containing 20% by mass of the polyimide resin obtained in Synthesis Example 3, a polyamideimide resin ("Unidic V-8000" manufactured by DIC, a weight average molecular weight of 11000, a nonvolatile component of 40% by mass ethyldiglycol Acetate solution) was changed to 12.5 parts.

A resin composition 2 was prepared in the same manner as in Example 1 except for the above matters.

[Example 3. Preparation of resin composition 3]

In Example 1,

1) change the amount of compound A from 10 parts to 20 parts,

2) 80 parts of biphenylaralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., mixed solution of MEK/toluene of 70% non-volatile content), Mitsubishi Gas Chemical Co., Ltd. Production of oligophenylene ether styrene resin "OPE-2St 1200", a toluene solution of 65% non-volatile content) was changed to 60 parts,

3) Using 5 parts of a bifunctional acrylate ((meth)acrylic radical polymerizable compound, ``NK ester A-DOG'' manufactured by Shinnakamura Kagaku Kogyo, molecular weight 326),

4) 15 parts of the varnish containing 20 mass% of the polyimide resin obtained in Synthesis Example 3 was changed to 5 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., weight average molecular weight 30000).

A 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]

In Example 1,

1) The amount of biphenylaralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., MEK/toluene mixed solution of 70% non-volatile content) from 80 parts to 40 Change to wealth,

2) 15 parts of the varnish containing 20 mass% of the polyimide resin obtained in Synthesis Example 3, a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical, a weight average molecular weight of 35000, a solid content of 30 mass%, a 1:1 solution of MEK and cyclohexanone) ) Change to 10 copies,

3) Naphthalene type epoxy resin (manufactured by DIC, "HP4032SS") 10 parts, carbodiimide resin (manufactured by Nisshinbo Chemical, "V-03", active group equivalent of about 216, solid content 50 mass% toluene solution) 10 parts , 20 parts of active ester resin ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of 223, solid content 65% by mass), and curing accelerator (4-dimethylaminopyridine (DMAP), 10% by mass solid content) MEK solution) 1 part was used.

A resin composition 4 was prepared in the same manner as in Example 1 except for the above matters.

[Example 5. Preparation of resin composition 5]

In Example 1, 10 parts of Compound A obtained in Synthesis Example 1 were changed to 10 parts of Compound B obtained in Synthesis Example 2. A 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]

In Example 3, 20 parts of Compound A obtained in Synthesis Example 1 were changed to 20 parts of Compound B obtained in Synthesis Example 2. A 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]

In Example 3, 20 parts of Compound A obtained in Synthesis Example 1 were changed to 50 parts of Compound B obtained in Synthesis Example 2. A 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]

In Example 4,

1) 10 parts of Compound A obtained in Synthesis Example 1 were changed to 20 parts of Compound B obtained in Synthesis Example 2,

2) 40 parts of biphenylaralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., mixed solution of MEK/toluene with 70% non-volatile content) 40 parts, oligophenylene ether -It was changed to 30 parts of styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution of 65% of non-volatile content).

Except for the above matters, it carried out similarly to Example 4, and prepared the resin composition 8.

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

In Example 1, 10 parts of Compound A obtained in Synthesis Example 1 were not used. Except for the above matters, it carried out similarly to Example 1, and prepared the resin composition 1 for comparison.

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

In Example 1, the amount of Compound A obtained in Synthesis Example 1 was changed from 10 parts to 85 parts. Except for the above matters, it carried out similarly to Example 1, and prepared the resin composition 2 for comparison.

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

In Example 6, the amount of Compound B obtained in Synthesis Example 2 was changed from 20 parts to 85 parts. Except for the above matters, it carried out similarly to Example 6, and prepared the resin composition 3 for comparison.

[Example 9. Preparation of resin composition 9]

In Example 1, 15 parts of the polyimide resin of Synthesis Example 3 was changed to 15 parts of a cyclohexanone solution containing 20% of the nonvolatile content of the bisphenol ether resin of Synthesis Example 4. A 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]

In Example 1, 80 parts of a biphenylaralkyl-type maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., a MEK/toluene mixed solution of 70% non-volatile content), It was changed to 80 parts of maleimide resin of Synthesis Example 5 (MEK solution of 70 mass% of non-volatile component). Except for the above matters, it carried out similarly to Example 1, and prepared the resin composition 10.

[Example 11. Preparation of resin composition 11]

In Example 3, the amount of Compound A obtained in Synthesis Example 1 was changed from 20 parts to 50 parts, and oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., and toluene having a non-volatile content of 65% Solution) 60 parts is changed to 67.7 parts of "ODV-XET-X04" (weight average molecular weight 3110, 65 mass% solution) manufactured by Nittetsu Chemical & Materials, and bifunctional acrylate ((meth)acrylic radical polymerizable compound , Shinnakamura Kagaku Kogyo Co., Ltd. "NK ester A-DOG", molecular weight 326) was not used. Except the above matters, it carried out similarly to Example 3, and prepared the resin composition 11.

[Example 12. Preparation of resin composition 12]

In Example 3, 60 parts of a benzocyclobutene resin ("CYCLOTENE 3022" manufactured by Dow Chemical) of an oligophenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Corporation, a toluene solution of 65% non-volatile content). '') to 44 parts, and polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Corporation, weight average molecular weight 30000) 5 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 35000, solid content 30 mass%) A 1:1 solution of MEK and cyclohexanone) was changed to 16.7 parts. Except the above matters, it carried out similarly to Example 3, and prepared the resin composition 12.

[Example 13. Preparation of resin composition 13]

In Example 9, 10 parts of Compound A obtained in Synthesis Example 1 were changed to 10 parts of Compound B obtained in Synthesis Example 2. A 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]

In Example 10, 10 parts of Compound A obtained in Synthesis Example 1 were changed to 10 parts of Compound B obtained in Synthesis Example 2. Except for the above matters, it carried out similarly to Example 10, and prepared the resin composition 14.

[Example 15. Preparation of resin composition 15]

In Example 11, 50 parts of the compound A obtained in Synthesis Example 1 was changed to 20 parts of the compound B obtained in Synthesis Example 2. A 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]

In Example 12, 20 parts of Compound A obtained in Synthesis Example 1 were changed to 50 parts of Compound B obtained in Synthesis Example 2. A resin composition 16 was prepared in the same manner as in Example 12 except for the above matters.

[Production of resin sheet]

As a support, a polyethylene terephthalate film ("Lumira R80" manufactured by Tore Corporation, a thickness of 38 μm, a softening point of 130° C.) subjected to a release treatment with an alkyd resin type releasing agent (“AL-5” manufactured by Lintec) was prepared.

Resin compositions 1 to 16 and comparative resin compositions 1 to 3 were applied uniformly with a die coater so that the thickness of the resin composition layer after drying was 40 μm on the support, and dried at 70°C to 95°C for 4 minutes. A resin composition layer was formed on it. Next, a rough surface of a polypropylene film ("Alpan MA-411" manufactured by Oji Ftex Co., Ltd., thickness 15 μm) was bonded to the surface of the resin composition layer not bonded to the support body as a protective film. Thereby, the resin sheet which has a support body, a resin composition layer, and a protective film in this order was obtained.

[Evaluation of unevenness on cured substrate, measurement of peel strength of plated conductor layer]

(1) Preparation of the inner layer substrate

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

(2) Lamination of resin sheet

The protective film was peeled off from the resin sheet, and the resin composition layer was exposed. Using a batch-type vacuum pressurized laminator (manufactured by Nikko Materials, a two-stage build-up laminator "CVP700"), the resin composition layer was laminated on both sides of the inner layer substrate so that it contacts the inner layer substrate. After the lamination was decompressed for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, it was carried out by pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

(3) Thermal curing of the resin composition layer

Thereafter, the inner-layer substrate on which the resin sheet was laminated was put into an oven at 130° C. and heated for 30 minutes, and then transferred to an oven at 170° C. and heated for 30 minutes, thereby thermally curing the resin composition layer to form an insulating layer. After that, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner layer substrate, and an insulating layer in this order.

<Evaluation of unevenness on the cured substrate>

With respect to both surfaces of the cured substrate A, observation of the surface uniformity of the portion on which the resin sheet was laminated (the surface on the opposite side to the laminated plate) was visually evaluated, and evaluated as follows.

(Double-circle): No unevenness is observed, and it is a completely uniform surface.

○: Unevenness was observed only in a portion 1 cm from the outer periphery of the portion on which the resin sheet was laminated, and the portion inside the resin sheet was a completely uniform surface.

X: A non-uniform part is observed in a part inside than 1 cm from the outer circumference of the part where the resin sheet was laminated.

(4) Harmonization treatment

The cured substrate A was subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.

(Wet desmear treatment)

The cured substrate A was immersed in a swelling liquid ("Swelling Deep Securigant P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, and then an oxidizing agent solution (Ato It is immersed in "Concentrate Compact CP" manufactured by Tec Japan, an aqueous solution having a potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) for 15 minutes at 80°C, followed by a neutralization solution ("Reduction Solution Securie manufactured by Atotech Japan"). Gantt P", sulfuric acid aqueous solution) was immersed at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(5) Formation of conductor layer

According to the semi-positive method, a conductor layer was formed on the roughened surface of the insulating layer. That is, the substrate after the roughening treatment was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Subsequently, after performing an annealing treatment by heating at 150° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Thereafter, copper sulfate electroplating was performed to form a conductor layer having a thickness of 30 μm, and annealing treatment was performed at 200°C for 60 minutes. The obtained substrate is referred to as "evaluation substrate B".

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

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

[Measurement of dielectric properties (dielectric constant, dielectric loss tangent)]

The protective film was peeled off from the resin sheet produced in Examples and Comparative Examples, heated at 200° C. for 90 minutes to heat cure the resin composition layer, and then the support was peeled off. The obtained cured product is referred to as "cured product for evaluation C". The cured product C for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm. With respect to this test piece, the dielectric constant and dielectric loss tangent were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by a cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies. Measurement was performed on three test pieces, and an average value was calculated.

[Measurement of elongation at break]

The cured product C for evaluation was subjected to a tensile test with a Tenshiro universal testing machine (“RTC-1250A” manufactured by Orientec Co., Ltd.) in accordance with Japanese Industrial Standard (JIS K7127), and the elongation at break (%) was measured. .

* In the table, "the content of the component (A)" represents the content of the component (A) when the nonvolatile component in the resin composition is 100% by mass, and the "content of the component (C)" is in the resin composition. The content of the component (C) when the nonvolatile component is 100% by mass is shown.

In Examples 1 to 16, even when the components (C) to (F) are not contained, there is a difference in degree, but it has been confirmed that results are the same as those of the above examples.

Claims (12)

(A) an aromatic ester skeleton and an unsaturated bond-containing compound, and
(B) radical polymerizable compound
As a resin composition containing,
The resin composition, wherein the content of the component (A) is 0.1% by mass or more and 30% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein the component (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 the 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, Ar Each of ¹³ 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 consisting of a combination thereof. Represents an integer of 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 that may have a substituent. m is 2 or It represents an integer of 3.) The resin composition according to claim 1, further comprising (C) an inorganic filler. The resin composition according to claim 3, wherein the content of the component (C) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, further comprising (D) a thermoplastic resin. The resin composition according to claim 1, further comprising (E) a thermosetting resin. The resin composition according to claim 1, wherein the component (B) contains either a maleimide radical polymerizable compound containing a maleimide group and a vinylphenyl radical polymerizable compound containing a vinylphenyl group. The resin composition according to claim 1, which is for forming an insulating layer. The resin composition according to claim 1, which is for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 9 provided on the support. A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor device comprising the printed wiring board according to claim 11.

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