TW202233705A - resin composition - Google Patents

Abstract

The present invention addresses the problem of providing a resin composition such that the minimum melt viscosity can be further reduced, the dielectric loss factor (Df) is low, and a cured article having a superior copper plating peel strength can be obtained, and provides a resin composition containing (A) a maleimide compound that has a isopropylidene group bonded to two aromatic carbon atoms in different aromatic rings, and (B) a resin having a vinyl phenyl group and/or a (meth)acryloyl group.

Description

resin composition

The present invention relates to a resin composition containing a maleimide compound. Further, it relates to a cured product, a sheet-like laminate, 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, the manufacturing method by the construction method which overlaps an insulating layer and a conductor layer alternately is known. For the manufacturing method by the construction method, generally, the insulating layer is formed by hardening the resin composition. In recent years, further improvement in dielectric properties such as the dielectric constant of the insulating layer and further improvement in copper adhesion have been demanded. However, when using a material with high peel strength by copper plating, there have been problems with the height of the minimum melt viscosity of the resin composition or the height of the dielectric loss tangent (Df) of the material.

Heretofore, maleimide compounds containing isopropylene groups have been known (Patent Document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Patent No. 6752390

[Problems solved by the invention]

The subject of this invention is to provide the resin composition which can suppress the minimum melt viscosity lower, and can obtain the hardened|cured material with low dielectric loss tangent (Df) and excellent copper plating peeling strength. [Means to solve the problem]

In order to achieve the subject of the present invention, as a result of detailed examination by the present inventors, as a component of the resin composition (A) maleic acid having an isopropylidene group bonded to two aromatic carbon atoms of different aromatic rings is used Imine compound, and (B) resin with vinylphenyl and/or (meth)acryloyl group, it was unexpectedly found that the minimum melt viscosity of the resin composition can be suppressed to a lower level, and the dielectric loss tangent can be obtained (Df) is a hardened material which is low and excellent in copper-plating peeling strength, and completed this invention.

That is, the present invention includes the following contents. [1] Maleimide compound containing (A) isopropylidene having two aromatic carbon atoms bonded to different aromatic rings, and (B) having vinylphenyl and/or (methyl) ) resin composition of acrylyl-based resin. [2] The resin composition described in the above [1] containing the maleimide compound represented by the formula (A2) as the component (A),

[In the formula, ring A and ring B each independently represent an aromatic ring which may have a substituent; a represents an integer of 1 or more]. [3] The resin composition according to the above [1] or [2] containing the maleimide compound represented by the formula (A-1) as the component (A),

[In the formula, R ¹ and R ² each independently represent an alkyl group or an aryl group; a represents an integer of 1 or more; and x and y each independently represent 0, 1, 2, or 3]. [4] The resin composition according to the above [2] or [3], wherein a is an integer of 2 to 10. [5] The resin composition according to any one of the above [1] to [4], wherein the component (B) is a thermoplastic resin having a vinylphenyl group and/or a (meth)acryloyl group. [6] Component (B) is selected from modified polyphenylene ether resins having vinylphenyl and/or (meth)acryloyl groups, and vinylphenyl and/or (meth)acryloyl groups The resin composition of any one of the above [1] to [5] of the modified polystyrene resin resin. [7] The resin composition according to any one of the above [1] to [6] in which the content of the component (A) is 5 to 30 mass % when the nonvolatile matter in the resin composition is 100 mass % . [8] The resin composition according to any one of the above [1] to [7] in which the content of the component (B) is 5 to 40 mass % when the nonvolatile content in the resin composition is 100 mass % . [9] The resin composition according to any one of the above [1] to [8] wherein the mass ratio of (A) component to (B) component ((A) component/(B) component) is 0.3 to 3 . [10] The resin composition according to any one of the above [1] to [9], which further contains (C) an inorganic filler. [11] The resin composition according to the above [10] in which the content of the component (C) is 40 mass % or more when the nonvolatile matter in the resin composition is 100 mass %. [12] The resin composition according to the above [10] or [11], wherein the mass ratio ((A) component/(C) component) of the (A) component with respect to the (C) component is 0.1 to 1. [13] The resin composition according to any one of the above [1] to [12], wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.004 or less when measured at 5.8 GHz and 23°C. [14] The resin composition according to any one of the above [1] to [13], wherein the specific conductivity (Dk) of the cured product of the resin composition is 3.5 or less when measured at 5.8 GHz and 23°C. [15] The cured product of the resin composition according to any one of the above [1] to [14]. [16] A sheet-like laminate comprising the resin composition according to any one of the above [1] to [14]. [17] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of the above [1] to [14] provided on the support. [18] A printed wiring board provided with an insulating layer formed of a cured product of the resin composition according to any one of the above [1] to [14]. [19] A semiconductor device including the printed wiring board according to the above [18]. [Effect of invention]

According to the resin composition of the present invention, the minimum melt viscosity can be suppressed to a lower level, and a cured product having a low dielectric loss tangent (Df) and excellent copper plating peeling strength can be obtained.

[Type of carrying out the invention]

Hereinafter, the present invention will be described in detail based on the preferred embodiment. However, the present invention is not limited to the following embodiments and examples, and can be implemented with arbitrary modifications without departing from the scope of the present invention and its equivalents.

<Resin composition> The resin composition of the present invention contains (A) a maleimide compound having an isopropylidene group bonded to two aromatic carbon atoms of different aromatic rings (hereinafter sometimes referred to as "specific maleimide" compound”), and (B) resins having vinylphenyl and/or (meth)acryloyl groups. By using such a resin composition, the minimum melt viscosity can be suppressed to a lower level, and a cured product having a low dielectric loss tangent (Df) and excellent copper plating peeling strength can be obtained.

The resin composition of the present invention may contain (A) a specific maleimide compound and (B) a resin having a vinylphenyl group and/or a (meth)acryloyl group, and may further contain optional components. Examples of optional components include (A') other maleimide compounds, (C) inorganic fillers, (D) radical polymerization initiators, (E) thermoplastic resins, (F) elastomers, ( G) other additives, and (H) organic solvents. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Specific maleimide compound> The resin composition of the present invention contains (A) a specific maleimide compound. (A) A specific maleimide compound may be used individually by 1 type, and may be used combining 2 or more types in arbitrary ratios.

The maleimide compound refers to a compound having at least one maleimide group (2,5-dihydro-2,5-dioxa-1H-pyrrol-1-yl) in one molecule. (A) Although the maleimide group in the specific maleimide compound may be bonded to an aromatic carbon atom or to an aliphatic carbon atom, the maleimide group that is bonded to an aromatic carbon atom is Preferably, all maleimide groups in the (A) specific maleimide compound are preferably those bonded to aromatic carbon atoms. (A) The number of maleimide groups in one molecule of the specific maleimide compound is preferably 2 or more, preferably 3 or more, preferably 3 to 11, and preferably 3 to 6 for better.

(A) The specific maleimide compound is isopropylidene (-C(CH ₃ ) ₂ -) having at least one two aromatic carbon atoms bonded to different aromatic rings in one molecule. (A) The isopropylidene group contained in the specific maleimide compound may be any of an aromatic carbon atom in an aromatic ring having a maleimide group and an aromatic ring having no maleimide group. Isopropylene bonded to two aromatic carbon atoms in combination of aromatic carbon atoms, isopropylene bonded to aromatic carbon atoms in different aromatic rings having a maleimide group, and Any of isopropylidene groups bonded to aromatic carbon atoms in different aromatic rings that do not have a maleimide group. (A) The specific maleimide compound preferably has an isopropylidene group which is an aromatic carbon atom bonded to an aromatic ring having a maleimide group and a Those on the two aromatic carbon atoms of the combination of aromatic carbon atoms in the aromatic ring of the ligimide group, particularly preferably, all isopropylidene groups contained in the (A) specific maleimide compound are, bond Isopropylidene with two aromatic carbon atoms bonded to a combination of an aromatic carbon atom in an aromatic ring having a maleimide group and an aromatic carbon atom in an aromatic ring having no maleimide group . (A) The number of isopropylidene groups in one molecule of the specific maleimide compound is preferably 2 or more, more preferably 4 or more, more preferably 4 to 20, and 4 to 10 which is excellent.

The term "aromatic ring" means that the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number) according to Hückel's rule. The aromatic ring may be an aromatic carbon ring having carbon atoms as ring constituent atoms, or an aromatic heterocyclic ring having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring constituent atoms. In one embodiment, an aromatic carbon ring is preferred. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 5- to 10-membered aromatic ring, and more preferably a 5- or 6-membered aromatic ring. Preferable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like, and a benzene ring or a naphthalene ring is preferable, and a benzene ring is particularly preferable.

(A) In one embodiment of the specific maleimide compound, it is preferable to contain a maleimide compound represented by the formula (A1),

[In the formula, ring A, ring B and ring C each independently represent an aromatic ring which may have a substituent; X each independently represents a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S- , -SO-, -SO ₂ -, -CONH- or -NHCO-; R ^x each independently represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent; a represents an integer of 1 or more; b each independently represents 0 or 1; c each independently represents 0, 1, 2 or 3]. The units a and c may be the same or different in each unit.

Ring A, ring B and ring C each independently represent an aromatic ring which may have a substituent, preferably an aromatic carbon ring which may have a substituent, preferably a benzene ring which may have a substituent, or a ring which may have a substituent. A naphthalene ring, more preferably a benzene ring that can be substituted with a group selected from an alkyl group and an aryl group, or a naphthalene ring that can be substituted with a group selected from an alkyl group and an aryl group, particularly preferably an alkyl group and an aryl group substituted benzene ring.

In the present specification, although the "substituent" is not particularly limited, for example, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl- oxy, alkyl-carbonyl, alkenyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-oxy-carbonyl, alkyl-carbonyl-oxy, Monovalent substituents such as alkenyl-carbonyl-oxy and aryl-carbonyl-oxy may also contain divalent substituents such as oxo (=O) if substitutable.

The alkyl group (group) refers to a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl group (group) is not particularly specified, but an alkyl group (group) having 1 to 14 carbon atoms is preferable. Examples of the alkyl group (group) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl cyclohexyl, nonyl, decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cyclopentylmethyl, cyclohexylmethyl and the like. The alkenyl group (group) means a linear, branched and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Although the alkenyl group (group) is not particularly specified, an alkenyl group having 2 to 14 carbon atoms is preferable. As an alkenyl group (group), a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a cyclohexenyl group, etc. are mentioned, for example . The aryl group (group) means a monovalent aromatic hydrocarbon group. The aryl group (group) is not particularly specified, but an aryl group (group) having 6 to 14 carbon atoms is preferable. As an aryl group (group), a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc. are mentioned, for example.

X independently represents, single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-, with single bond, -C(R ^x ) ₂ - or -O- is preferable, a single bond or -C(R ^x ) ₂ - is preferable, and a single bond is particularly preferable. R ^x each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

a represents an integer of 1 or more, preferably 2 or more, preferably an integer of 2 to 10, more preferably 2, 3, 4 or 5. (A) Specific maleimide compound In one embodiment, a maleimide compound represented by the formula (A1) in which a is 1 and a maleimide compound represented by the formula (A1) in which a is 2 or more are included. The imide compound preferably contains 1 mass % of the maleimide compound represented by the formula (A1) in which a is 2 or more, preferably contains 5 mass %, more preferably contains 8 mass %, It is especially preferable to contain 10 mass %.

b each independently represents 0 or 1, preferably 1. c each independently represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, particularly preferably 0.

(A) In one embodiment, the specific maleimide compound preferably contains a maleimide compound represented by the formula (A2),

[In the formula, each symbol is the same as above].

(A) Specific maleimide compound In another embodiment, it is preferable to contain a maleimide compound represented by any one of formulas (A-1) to (A-6),

[In the formula, R ¹ and R ² each independently represent an alkyl group or an aryl group; x and y each independently represent 0, 1, 2, or 3; other symbols are the same as above], in one embodiment, it is more preferable to contain the formula In one embodiment, the compound represented by (A-1) preferably contains a compound represented by formula (A-1a) or (A-1b),

[In the formula, each symbol is the same as the above.] In one embodiment, the compound represented by the formula (A-1a) is particularly preferably contained.

R ¹ and R ² each independently represent an alkyl group or an aryl group, preferably an alkyl group. Each of x and y independently represents 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1, particularly preferably 0.

(A) The weight average molecular weight (Mw) of the specific maleimide compound is preferably 500-5000, preferably 500-4000, more preferably 500-3000. (A) The number average molecular weight (Mn) of the specific maleimide compound is preferably 500-5000, preferably 500-4000, more preferably 500-3000. The weight-average molecular weight and the number-average molecular weight of the resin can be measured as polystyrene-equivalent values by gel permeation chromatography (GPC).

(A) The maleimide equivalent of the specific maleimide compound is preferably 100 g/eq.~1000 g/eq., more preferably 150 g/eq.~400 g/eq. The maleimide equivalent of the (A) specific maleimide compound is the mass of the (A) specific maleimide compound per 1 equivalent of the maleimide group.

As a sales item of (A) specific maleimide compound, "MIR-5000-60T" by Nippon Kayaku Co., Ltd., etc. are mentioned, for example.

The content of the (A) specific maleimide compound in the resin composition is not particularly limited, but when the nonvolatile matter in the resin composition is taken as 100% by mass, it is preferably 50% by mass or less, preferably 50% by mass or less. 40 mass % or less, more preferably 30 mass % or less, more preferably 25 mass % or less, particularly preferably 20 mass % or less. Although the lower limit of the content of the (A) specific maleimide compound in the resin composition is not particularly limited, when the nonvolatile matter in the resin composition is taken as 100% by mass, it is preferably 0.1% by mass or more. Preferably it is 1 mass % or more, More preferably, it is 5 mass % or more, More preferably, it is 8 mass % or more, Especially preferably, it is 10 mass % or more.

<(A') Other maleimide compounds> The resin composition of the present invention may further contain a (A') maleimide compound other than the (A) component as an optional component. (A') The other maleimide compound may be used alone or in any combination of two or more.

(A') The other maleimide compound is not particularly limited, and may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton , for example, "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J" manufactured by Designer Moleculars, Inc. "BMI-689", "BMI-2500" (dimer diamine structure containing maleimide compound), "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecular Co., Ltd., Japan "MIR-3000-70MT" (biphenyl aralkyl type maleimide compound) manufactured by Kayaku Co., Ltd., etc. In addition, as (A') other maleimide compounds, it can also be used in maleimide resins (maleimide resins containing an indane ring skeleton) disclosed in the Technical Bulletin No. 2020-500211 of the Invention Association. imide compounds).

(A') The maleimide equivalent of other maleimide compounds is preferably 100 g/eq.~20000 g/eq., preferably 200 g/eq.~15000 g/eq., more The optimal range is 300 g/eq.~10000 g/eq.. The maleimide equivalent of (A') other maleimide compounds is the mass of (A') other maleimide compounds per equivalent of maleimide group.

(A') The weight average molecular weight (Mw) of other maleimide compounds is preferably 500-50,000, more preferably 700-20,000. (A') The number average molecular weight (Mn) of other maleimide compounds is preferably 500 to 50,000, more preferably 700 to 20,000.

Although the content of (A') other maleimide compounds in the resin composition is not particularly limited, when the non-volatile matter in the resin composition is taken as 100% by mass, it is preferably 50% by mass or less, preferably It is 40 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 20 mass % or less, Especially preferably, it is 10 mass % or less. Although the lower limit of the content of (A') other maleimide compounds in the resin composition is not particularly limited, when the nonvolatile matter in the resin composition is taken as 100% by mass, for example, 0% by mass or more may be 0.1 mass % or more, 1 mass % or more, 2 mass % or more, and the like.

The content of the (A) specific maleimide compound in the resin composition is 100% by mass based on the total maleimide compound (the total of the (A) component and (A') component) in the resin composition At this time, it is preferably 10 mass % or more, preferably 30 mass % or more, more preferably 40 mass % or more, and particularly preferably 50 mass % or more.

<(B) Resin which has vinylphenyl group and/or (meth)acryloyl group> The resin composition of the present invention contains (B) a resin having a vinylphenyl group and/or a (meth)acryloyl group. The (meth)acryloyl group represents an acryl group or a methacryloyl group. The vinylphenyl group contains 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl, or these aromatic carbon atoms further substituted by one or more alkyl groups, and the like. The component (B) is usually a resin having two or more vinylphenyl groups and/or (meth)acryloyl groups in one molecule.

(B) component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. In one embodiment, the (B) component is obtained by reacting each molecule with the molecules of the (B) component, or with the molecules of the (A) component or (A') component.

The component (B) is preferably a thermoplastic resin having a vinylphenyl group and/or a (meth)acryloyl group. Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polystyrene resins, polyethylene resins, polypropylene resins, polybutadiene resins, polyimide resins, and polyamide imide resins. Resins, polyetherimide resins, polysiloxane resins, polyethersilk resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, etc., the (B) component can be these resins Modified resins with vinyl phenyl and/or (meth)acryloyl groups.

The component (B) is preferably selected from modified polyphenylene ether resins having vinylphenyl and/or (meth)acryloyl groups (hereinafter sometimes simply referred to as "modified polyphenylene ether resins"), and Resin of denatured polystyrene resin (henceforth abbreviated as "modified polystyrene resin") which has vinylphenyl group and/or (meth)acryloyl group.

The modified polyphenylene ether resin is preferably a resin represented by formula (B-1),

[In the formula, R ¹¹ and R ¹² each independently represent an alkyl group; R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group; R ³¹ and R ³² each independently represent, Vinylphenyl or (meth)acryloyl; Y represents a single bond, -C(R ^y ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ -; R ^y Each independently represents a hydrogen atom or an alkyl group; Z represents a single bond or an alkylene group; n and m each independently represent an integer of 1 or more; p represents 0 or 1]. Each of the n units and m units may be the same or different per unit.

R ¹¹ and R ¹² each independently represent an alkyl group, preferably a methyl group. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom. R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, more preferably a methyl group. R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, preferably one of R ²³ and R ²⁴ is a methyl group and the other is a hydrogen atom.

R ³¹ and R ³² each independently represent a vinylphenyl group or a (meth)acryloyl group, and Z represents a single bond or an alkylene group. The term "alkylene" refers to a linear, branched or cyclic divalent saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of alkylene groups include -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, and -CH ₂ -CH(CH ₃ ) -, -CH(CH ₃ )-CH ₂ -, -C(CH ₃ ) ₂ - and the like. Preferably R ³¹ and R ³² are vinylphenyl groups, and Z is an alkylene group (especially preferably -CH ₂ -), or R ³¹ and R ³² are (meth)acryloyl groups, and Z is a single bond .

Y represents a single bond, -C(R ^y ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ -, with a single bond, -C(R ^y ) ₂ - or -O - preferably, preferably a single bond. R ^y each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. n and m each independently represent an integer of 1 or more, preferably an integer of 1 to 200, more preferably an integer of 1 to 100. p represents 0 or 1, preferably 1.

Examples of commercially available modified polyphenylene ether resins include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Co., Ltd. ; "SA9000" and "SA9000-111" (methacrylic acid modified polyphenylene ether resin) manufactured by SABIC Innovative Plastics Company.

The modified polystyrene resin preferably has the formula (B-2a):

[In the formula, R ⁴¹ , R ⁴² and R ⁴³ each independently represent a hydrogen atom or an alkyl group; R ⁴⁴ each independently represents an alkyl group; s represents an integer of 0 to 3] and the repeating unit represented by the formula (B-2b):

[wherein, R ⁵¹ , R ⁵² and R ⁵³ each independently represent a hydrogen atom or an alkyl group; R ⁵⁴ each independently represents an alkyl group; t represents an integer of 0 to 3] a resin having a repeating unit represented. The repeating unit of formula (B-2a) and the repeating unit of formula (B-2b) may be the same or different in each unit.

R ⁴¹ , R ⁴² , R ⁴³ , R ⁵¹ , R ⁵² and R ⁵³ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. R ⁴⁴ and R ⁵⁴ each independently represent an alkyl group, preferably an ethyl group or a methyl group. s represents an integer of 0 to 3, preferably 0 or 1, and preferably 0. t represents an integer of 0 to 3, preferably 0 or 1.

The molar content of the repeating unit of the formula (B-2a) is 8 mol% when the sum of the repeating unit of the formula (B-2a) and the repeating unit of the formula (B-2b) is taken as 100 mol% ~54 mol% is preferred.

Examples of commercially available modified polystyrene resins include "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" manufactured by Nippon Steel Chemical & Materials Co., Ltd. ( styrene-divinylbenzene copolymer) etc.

The functional group equivalent of component (B) is preferably 250 g/eq.~2500 g/eq., preferably 300 g/eq.~1500 g/eq. The functional group equivalent of the component (B) represents the mass of the resin per 1 equivalent of vinylphenyl group or (meth)acryloyl group.

The weight average molecular weight (Mw) of the component (B) is preferably 1,000 to 40,000, preferably 1,000 to 10,000, and particularly preferably 1,000 to 5,000. The number-average molecular weight (Mn) of the component (B) is preferably 1,000 to 40,000, preferably 1,000 to 10,000, and particularly preferably 1,000 to 5,000. The weight-average molecular weight and the number-average molecular weight of the resin can be measured as polystyrene-equivalent values by gel permeation chromatography (GPC).

Although the content of component (B) in the resin composition is not particularly limited, when the nonvolatile matter in the resin composition is taken as 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, and more 40 mass % or less is preferable, 30 mass % or less is more preferable, and 25 mass % or less is especially preferable. Although the lower limit of the content of the component (B) in the resin composition is not particularly limited, it is preferably 0.1% by mass or more, preferably 1% by mass or more, taking the nonvolatile matter in the resin composition as 100% by mass , more preferably 5 mass % or more, more preferably 10 mass % or more, and particularly preferably 15 mass % or more.

The mass ratio ((A) component/(B) component) of the (A) specific maleimide compound with respect to the (B) component in the resin composition is preferably 0.1 or more, preferably 0.3 or more, particularly preferably is 0.5 or more. The upper limit of the mass ratio ((A) component/(B) component) of the (A) specific maleimide compound with respect to the (B) component in the resin composition is preferably 5 or less, more preferably 3 or less, Particularly preferred is 1.5 or less.

<(C) Inorganic fillers> The resin composition of the present invention may contain (C) an inorganic filler as an optional component. (C) The inorganic filler is contained in the resin composition in a particle state.

As the material of the (C) inorganic filler, an inorganic compound is used. As a material of (C) inorganic filler, for example, silica, alumina, aluminosilicate, glass, cordierite, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide can be mentioned. , hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate , magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Of these, silica or aluminosilicates are also preferred, and silica is particularly preferred. As silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. are mentioned, for example. In addition, spherical silica is preferable as silica. (C) Inorganic filler may be used individually by 1 type, and may be used combining 2 or more types in arbitrary ratios.

Examples of the (C) inorganic filler sold include "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Materials Co., Ltd.; Admatechs Co., Ltd. "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Denka Corporation; "UFP-30" manufactured by Denka Corporation; "SilfirNSS-3N", "SilfirNSS-4N", "SilfirNSS-5N manufactured by Tokuyama Corporation" "; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs; "DAW-03", "FB-105FD" manufactured by Denka; The "BA-S" of the Pacific Cement Company; the "MG-005" manufactured by the Pacific Cement Company, etc.

Although the average particle size of the inorganic filler (C) is not particularly limited, it is preferably 10 μm or less, preferably 5 μm or less, more preferably 2 μm or less, more preferably 1 μm or less, and particularly preferably 0.7 μm or less. Although the lower limit of the average particle diameter of the (C) inorganic filler is not particularly limited, it is preferably 0.01 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. (C) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median diameter can be measured as an average particle size. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone were weighed into a sample bottle, and those that were dispersed by ultrasonic waves for 10 minutes were used. A laser diffraction particle size distribution analyzer was used for the measurement sample, the wavelengths of the light sources used were set to blue and red, and the volume-based particle size distribution of the inorganic filler was measured by a flow cell method, and calculated from the obtained particle size distribution. The average particle size as the median diameter. As a laser diffraction particle size distribution measuring apparatus, "LA-960" manufactured by Horiba, Ltd., etc. is mentioned, for example.

(C) Although the specific surface area of the inorganic filler is not particularly limited, it is preferably 0.1 m ² /g or more, preferably 0.5 m ² /g or more, more preferably 1 m ² /g or more, particularly preferably 3 m ² /g or more g or more. (C) Although the upper limit of the specific surface area of the inorganic filler is not particularly limited, it is preferably 100 m ² /g or less, preferably 70 m ² /g or less, more preferably 50 m ² /g or less, particularly preferably 40 m ² /g g or less. The specific surface area of the inorganic filler is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mounttech) according to the BET method, and calculating the specific surface area using the BET multi-point method.

(C) The inorganic filler can be a non-hollow inorganic filler with a porosity of 0 vol% (preferably non-hollow silica and non-hollow aluminosilicate), or a hollow with a porosity exceeding 0 vol% Inorganic fillers (preferably hollow silica and hollow aluminosilicate) may also contain both. (C) Inorganic fillers may contain only hollow inorganic fillers (preferably hollow silica and hollow aluminosilicate), or may contain non-hollow inorganic fillers from the viewpoint of suppressing the dielectric constant to a lower level Materials (preferably non-hollow silica, non-hollow aluminosilicate) and hollow inorganic fillers (preferably hollow silica, hollow aluminosilicate) are preferred. The porosity of the hollow inorganic filler is preferably less than 90% by volume, preferably less than 85% by volume. (C) Although the lower limit of the porosity of the inorganic filler is not particularly limited, it may be, for example, more than 0 vol%, 1 vol% or more, 5 vol% or more, 10 vol% or more, 20 vol% or more, 30 vol% or more Wait. The porosity P (volume %) of the inorganic filler is defined as the volume reference ratio of the total volume of one or two or more pores inside the particle with respect to the overall volume of the particle on the outside of the particle (voids). The total volume/particle volume), such as the measured value D _M (g/cm ³ ) of the actual density of the inorganic filler and the theoretical value D _T (g/cm ³ ) of the material density of the material forming the inorganic filler, It is calculated by the following formula (I).

[Number 1]

The actual density of the inorganic filler can be measured, for example, using a true density measuring device. As a true density measuring apparatus, the ULTRAPYCNOMETER1000 by QUANTACHROME company etc. are mentioned, for example. As the measurement gas, for example, nitrogen is used.

(C) The inorganic filler is preferably surface-treated with an appropriate surface-treating agent. By performing surface treatment, the moisture resistance and dispersibility of the (C) inorganic filler can be improved. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Epoxy silane coupling agents such as glycidoxypropyl triethoxy silane; styrene silane coupling agents such as p-styrene trimethoxy silane; 3-methacryloyloxypropyl methyl dimethyl dimethyl oxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane Methacrylic silane coupling agents such as methacrylic silane; acrylic silane coupling agents such as 3-acryloyloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldicarbonate Methoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-Triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-amine Amino silane coupling agents such as octyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; ginseng-(trimethoxysilane) isocyanurate-based silane coupling agents such as propyl) isocyanurate; urea-based silane coupling agents such as 3-ureapropyl trialkoxysilane; Mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropyl succinic anhydride ; Silane coupling agents such as; methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethyl Oxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane , 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane and other alkyl alkoxysilane compounds, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types in arbitrary ratios.

Examples of surface treatment agents sold include "KBM-1003", "KBE-1003" (vinyl silane coupling agent), "KBM-303", and "KBM-402" manufactured by Shin-Etsu Chemical Co., Ltd. , "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene silane coupling agent); "KBM-502", "KBM- 503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", " "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amine-based silane coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (urea-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); " X-12-967C" (acid anhydride silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (alkyl alkoxysilane compounds), etc.

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

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, preferably 0.1 mg/m ² or more, and 0.2 mg/m 2 ² or more is better. On the other hand, from the viewpoint of preventing an increase in the minimum melt viscosity of the resin composition or the minimum melt viscosity in the form of a sheet, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, More preferably, it is 0.5 mg/m ² or less.

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

Although the content of the inorganic filler (C) in the resin composition is not particularly limited, when the nonvolatile matter in the resin composition is taken as 100% by mass, it is preferably 90% by mass or less, more preferably 80% by mass or less , more preferably 75 mass % or less, particularly preferably 70 mass % or less. Although the lower limit of the content of the inorganic filler (C) in the resin composition is not particularly limited, when the nonvolatile content in the resin composition is taken as 100% by mass, for example, it can be 0% by mass or more, 1% by mass or more, etc. 10 mass % or more is preferable, 30 mass % or more is preferable, 40 mass % or more is more preferable, 50 mass % or more is more preferable, and 60 mass % or more is especially preferable.

The mass ratio ((A) component/(C) component) of the (A) specific maleimide compound in the (C) inorganic filler in the resin composition is preferably 0.05 or more, more preferably 0.1 or more, Particularly preferred is 0.2 or more. The upper limit of the mass ratio ((A) component/(C) component) of the (A) specific maleimide compound with respect to the (C) inorganic filler in the resin composition is preferably 2 or less, more preferably 1 or less, particularly preferably 0.5 or less.

<(D) Radical Polymerization Initiator> The resin composition of the present invention may further contain (D) a radical polymerization initiator as an optional component. (D) The radical polymerization initiator may be, for example, a thermal polymerization initiator that generates radicals when heated. (D) A radical polymerization initiator may be the polymerization initiator containing the radically polymerizable component of (A) component - (B) component demonstrated above. (D) A radical polymerization initiator may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

(D) As a radical polymerization initiator, a peroxide type radical polymerization initiator, an azo type radical polymerization initiator, etc. are mentioned, for example. Among them, peroxide-based radical polymerization initiators are also preferred.

Examples of peroxide-based radical polymerization initiators include sheet-form compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; tert-butyl cumyl peroxide, di- tert-butyl peroxide, di-tert-hexyl peroxide, cumene diperoxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, 2, Dialkyl peroxide compounds such as 5-dimethyl-2,5-bis(tert-butylperoxy)hexane; dilauryl peroxide, didecyl peroxide, dicyclohexyl peroxide Diacyl peroxide compounds such as oxydicarbonate and bis(4-tert-butylcyclohexyl)peroxydicarbonate; tert-butylperoxyacetate, tert-butylperoxybenzoate , tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyisopropyl monocarbonate Esters, tert-butylperoxylaurate, (1,1-dimethylpropyl)ethyl 2-perhexanoate, tert-butyl ethyl 2-perhexanoate, tert-butyl 3,5 , 5-trimethyl percaproate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxymaleic acid and other peroxyester compounds.

As an azo radical polymerization initiator, for example, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis( 2,4-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclo Hexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 2-phenylazo-4-methoxy-2,4-di Nitrilation compounds such as methyl-valeronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl] Propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-azobis[2 -Methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide] ], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], Azoamines such as 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide) Compounds; 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane) and other alkyl azo compounds, etc.

Examples of commercially available products of the (D) radical polymerization initiator include "perbutyl C", "perbutyl A", "perbutyl P", and "perbutyl L" manufactured by NOF Corporation. ", "Perbutyl O", "Perbutyl ND", "Perbutyl Z", "Perbutyl I", "Percumene P", "Percumene D", "Perhexyl D" ”, “Hexyl A”, “Passexyl I”, “Passexyl Z”, “Passexyl ND”, “Passexyl O”, “Passexyl PV”, “Passexyl O”, etc.

Although the content of the (D) radical polymerization initiator in the resin composition is not particularly limited, when the nonvolatile matter in the resin composition is taken as 100% by mass, it is preferably 5% by mass or less, more preferably 3% by mass. The mass % or less is preferably 2 mass % or less, more preferably 1 mass % or less, and particularly preferably 0.8 mass % or less. Although the lower limit of the content of the (D) radical polymerization initiator in the resin composition is not particularly limited, when the nonvolatile content in the resin composition is taken as 100% by mass, for example, it is 0% by mass or more and 0.0001% by mass The above content is preferably 0.001 mass % or more, preferably 0.01 mass % or more, more preferably 0.05 mass % or more, more preferably 0.1 mass % or more, particularly preferably 0.3 mass % or more.

<(E) Thermoplastic resin> The resin composition of the present invention may further contain (E) thermoplastic resin as an optional component. The thermoplastic resin (E) described here is a component corresponding to the components other than the components (A) to (B) described above.

Examples of thermoplastic resins of the component (E) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, and polyethers. Imide resins, polyether resins, polyether resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, polyester resins, etc. Among them, the thermoplastic resin (E) is preferably one containing a resin selected from the group consisting of a phenoxy resin and a polyimide resin from the viewpoint that the effects of the present invention can be remarkably obtained. Moreover, a thermoplastic resin can be used individually by 1 type, or in combination of 2 or more types.

Examples of phenoxy resins include those having a structure selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, and dicyclopentane. A phenoxy resin of one or more skeletons consisting of a diene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group.

Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (containing bisphenol A skeleton) Phenoxy resin with phenol S skeleton); "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation; Mitsubishi "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891T30" manufactured by Chemical Corporation.

As the polyvinyl acetal resin, for example, polyvinyl acetal resin and polyvinyl butyral resin can be mentioned, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Electrobutyral 4000-2", "Electrical butyral 5000-A", "Electrobutyral 6000-C", "Electrobutyral 6000-C", manufactured by Denki Chemical Industry Co., Ltd. Electrochemical Butyral 6000-EP"; S-LECBH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. made by Sekisui Chemical Industry Co., Ltd.

Examples of polyolefin resins include ethylene such as low density polyethylene, ultra-low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. Copolymer resins; Polyolefin-based polymers such as polypropylene, ethylene-propylene block copolymers, etc.

Specific examples of the polyamide imide resin include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide imide resins include modified polyamide imide resins such as "KS9100" and "KS9300" (polyamide imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. amine.

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

As a specific example of a polymer resin, "P1700", "P3500" etc. are mentioned by Solvay Advanced Polymers company.

As polyester resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polybutylene terephthalate resin, trimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexane dimethyl terephthalate resin, and the like.

Modified polyimide resins such as siloxane-modified polyimide resins may also be contained in the polyimide resins. In one embodiment, the polyimide resin is preferably an aromatic polyimide resin that does not have an aliphatic chain in the main chain.

The polyimide resin is preferably one of the embodiments, preferably containing the formula (E1):

[wherein, X ¹ , Y ¹ and Y ² each independently represent a single bond, -CR ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO -; R each independently represents a hydrogen atom and an alkyl group; each of ring X ^a , ring X ^b and ring Y ^a independently represents an aromatic ring which may have a substituent; R ^y1 each independently represents a substituent; y1 each independently represents 0, 1, 2 or 3; xa and ya each independently represent 0, 1, 2, 3, 4 or 5; yb represents the resin of the repeating unit represented by 0 or 1]. The xa units may be the same or different in each unit. The ya units may be the same or different in each unit.

X ¹ , Y ¹ and Y ² each independently represent a single bond, -CR ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-; with - CR ₂ -, -O- or -CO- is preferred; preferably -CR ₂ - or -O-.

R each independently represents a hydrogen atom and an alkyl group; preferably a hydrogen atom and a methyl group; more preferably a methyl group.

Ring X ^a , ring X ^b and ring Y ^a each independently represent an aromatic ring which may have a substituent; a benzene ring which may be substituted by a group selected from an alkyl group, an alkenyl group and an aryl group; A naphthalene ring substituted with a base of an alkyl group and an aryl group; preferably a benzene ring substituted with a base selected from an alkyl group, an alkenyl group and an aryl group; more preferably a benzene ring substituted with an alkyl group; particularly preferably ( unsubstituted) benzene ring.

R ^y1 each independently represents a substituent; preferably an alkyl group, an alkenyl group or an aryl group; preferably an alkyl group.

y1 independently represents 0, 1, 2 or 3; preferably 0, 1 or 2; preferably 0 or 1; particularly preferably 0. xa represents 0, 1, 2, 3, 4 or 5; preferably 1, 2, 3, 4 or 5; preferably 2, 3, 4 or 5; more preferably 3, 4 or 5; 4. ya represents 0, 1, 2, 3, 4 or 5; preferably 0, 1, 2, 3 or 4; preferably 0, 1, 2 or 3; more preferably 1, 2 or 3; 2. yb represents 0 or 1; 1 is preferred.

As the formula (Ex) contained in the structural unit represented by the formula (E1):

[In the formula, * represents the bonding position; its symbol is as shown above] Specific examples of the partial structures shown in the formulas (Ex-1) to (Ex-24) can be cited:

[In the formula, * is the same as the above-mentioned partial structure shown in any one.

As the formula (Ey) contained in the structural unit represented by the formula (E1):

[In the formula, * represents the bonding position; other symbols are as shown above] Specific examples of the partial structures shown in the formulas (Ey-1) to (Ey-25) can be cited:

[In the formula, * is the same as the above-mentioned partial structure shown in any one.

For one embodiment, the polyimide resin preferably contains formulas (E2-1) to (E2-4):

[wherein, X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , Y ¹¹ , Y ¹² and Y ² are each independently represented, single bond, -CR ₂ -, -O-, -CO-, -S-, -SO -, -SO ₂ -, -CONH- or -NHCO-; Ring X ^a1 , Ring X ^a2 , Ring X ^a3 , Ring X ^a4 , Ring X ^b , Ring Y ^a1 and Ring Y ^a2 each independently represent an optionally substituted Aromatic ring; Resins having repeating units represented by other symbols as above], among which resins having repeating units represented by formula (E2-1) are particularly preferred.

X ¹¹ , X ¹² , X ¹³ and X ¹⁴ each independently represent a single bond, -CR ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO- ; preferably -CR ₂ -, -O- or -CO-; preferably -CR ₂ - or -O-; more preferably X ¹¹ and X ¹⁴ are -O- and X ¹² and X ¹³ are -CR _2- . Y ¹¹ , Y ¹² and Y ² each independently represent a single bond, -CR ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-; with - CR ₂ -, -O- or -CO- is preferred; preferably -CR ₂ - or -O-; more preferably Y ¹¹ and Y ² are -O-, and Y ¹² is -CR ₂ -.

Ring X ^a1 , ring X ^a2 , ring X ^a3 , ring X ^a4 , ring X ^b , ring Y ^a1 and ring Y ^a2 each independently represent an aromatic ring which may have a substituent; and may be selected from an alkyl group, an alkenyl group and an aryl group A benzene ring substituted with a group selected from an alkyl group, an alkenyl group and a naphthalene ring substituted with a aryl group; preferably a benzene ring substituted with a group selected from an alkyl group, an alkenyl group and an aryl group; more Preferred is a benzene ring which may be substituted with an alkyl group; particularly preferred is an (unsubstituted) benzene ring.

In one embodiment, the polyimide resin preferably contains the formula (E3):

[In the formula, R ^x1 and R ^y2 each independently represent a substituent; x1 and y2 each independently represent 0, 1, 2, 3 or 4; other symbols are as shown above] The resin of the repeating unit.

R ^x1 and R ^y2 each independently represent a substituent; preferably an alkyl group, an alkenyl group or an aryl group; more preferably an alkyl group.

Each of x1 and y2 independently represents 0, 1, 2, 3 or 4; preferably 0, 1, 2 or 3; preferably 0, 1 or 2; more preferably 0 or 1;

Although the polyimide resin is not particularly limited, for example, it can be obtained by known synthesis methods such as imidization reaction of a diamine compound and tetracarboxylic anhydride, and imidization reaction of a diisocyanate compound and tetracarboxylic anhydride. As the polyimide resin, commercially available products can be used, and examples of the polyimide resin products include "RIKACOATSN20" and "RIKACOATPN20" manufactured by Nippon Chemical Corporation.

(F) Although the glass transition temperature of the polyimide resin is not particularly limited, it is preferably 50°C to 400°C, preferably 75°C to 350°C, more preferably 100°C to 300°C, and particularly preferably 125°C ~250℃.

(E) The weight-average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, preferably 10,000 or more, particularly preferably 20,000 or more, more preferably 70,000 or less, from the viewpoint that the effects of the present invention can be remarkably obtained. Preferably it is 60,000 or less, and particularly preferably 50,000 or less.

Although the content of the thermoplastic resin (E) in the resin composition is not particularly limited, when the non-volatile matter in the resin composition is taken as 100% by mass, the desired effect of the present invention can be remarkably obtained from the viewpoint of 20%. The mass % or less is preferable, preferably 15 mass % or less, more preferably 10 mass % or less, more preferably 7 mass % or less, and particularly preferably 5 mass % or less. Although the lower limit of the content of the thermoplastic resin (E) in the resin composition is not particularly limited, it is, for example, 0 mass % or more, 0.01 mass % or more, and 0.05 mass % when the nonvolatile content in the resin composition is taken as 100 mass %. % or more, preferably 0.1 mass % or more, preferably 0.5 mass % or more, more preferably 1 mass % or more, more preferably 2 mass % or more, particularly preferably 3 mass % or more.

<(F) Elastomer> The resin composition of the present invention may further contain (F) an elastomer as an optional component. The (F) elastomer described here is a component other than those corresponding to the components (A) to (B) described above.

The elastomer as the component (F) is a resin having flexibility, preferably a resin having rubber elasticity or other resins that exhibit rubber elasticity by being polymerized. Examples of rubber elasticity include resins showing an elastic modulus of 1 GPa or less when subjected to a tensile test at a temperature of 25° C. and a humidity of 40% RH in accordance with Japanese Industrial Standards (JIS K7161).

In one embodiment, the (F) elastomer has a structure selected from the group consisting of polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkylene oxide structure in the molecule. The resin with one or more types of structure, polyisoprene structure, polyisobutylene structure, polycarbonate structure, and polystyrene structure is preferable. "(meth)acrylate" means methacrylate and acrylate.

Moreover, in another embodiment, the (F) elastomer is preferably one or more selected from resins having a glass transition temperature (Tg) of 25° C. or lower and resins that are liquid at 25° C. or lower. The glass transition temperature (Tg) of the resin having a glass transition temperature (Tg) of 25°C or lower is preferably 20°C or lower, more preferably 15°C or lower. The lower limit of the glass transition temperature is not particularly limited, but is usually -15°C or higher. Moreover, as resin which is liquid at 25 degreeC, the resin which is liquid at 20 degreeC or less is preferable, and the resin which is liquid at 15 degreeC or less is preferable. The glass transition temperature can be determined by DSC (differential scanning calorimetry).

(F) The elastomer is usually an amorphous resin component soluble in an organic solvent. The (F) elastomer may be used alone or in combination of two or more types in an arbitrary ratio.

As (F) elastomer, the resin containing a polybutadiene structure is mentioned, for example. The polybutadiene structure may be contained in the main chain or in the side chain. Also, a part or all of the polybutadiene structure may be hydrogenated. A resin containing a polybutadiene structure is sometimes referred to as a "polybutadiene resin". Specific examples of polybutadiene resins include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", and "Ricon 131MA17" manufactured by Clay Valley Corporation. 131MA20", "Ricon 184MA6" (polybutadiene containing acid anhydride group), "GQ-1000" (polybutadiene introduced with hydroxyl and carboxyl groups) manufactured by Nippon Soda Co., Ltd., "G-1000", "G-2000" ", "G-3000" (two-terminal hydroxyl polybutadiene), "GI-1000", "GI-2000", "GI-3000" (two-terminal hydroxyl hydrogenated polybutadiene), manufactured by Nagase Chemtex "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin), etc. Further, specific examples of the polybutadiene resin include linear polyimide using hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials (JP-A No. 2006-37083, International Polyimide described in Publication No. 2008/153208), phenolic hydroxyl group-containing butadiene, and the like. The content of the butadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For the details of the polyimide resin, reference can be made to the descriptions of Japanese Patent Laid-Open No. 2006-37083 and International Publication No. 2008/153208, and the contents are described in this specification.

As (F) elastomer, the resin containing a poly(meth)acrylate structure is mentioned, for example. A resin containing a poly(meth)acrylate structure is sometimes referred to as a "poly(meth)acrylic resin". Specific examples of poly(meth)acrylic resins include Teisan resin manufactured by Nagase Chemtex, "ME-2000", "W-116.3", and "W-197C" manufactured by Negami Kogyo Co., Ltd. , "KG-25", "KG-3000", etc.

As (F) elastomer, the resin containing a polycarbonate structure is mentioned, for example. A resin containing a polycarbonate structure is sometimes referred to as a "polycarbonate resin". As a specific example of polycarbonate resin, "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., "C-1090", "C-2090", "C-2090" manufactured by Kuraray Co., Ltd. -3090" (polycarbonate diol), etc. Moreover, the linear polyimide of a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a tetrabasic acid anhydride can be used as a raw material. The content rate of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, reference can be made to the description of International Publication No. 2016/129541, and the content is described in this specification.

As (F) elastomer, the resin containing a polysiloxane structure is mentioned, for example. Resins containing polysiloxane structures are sometimes referred to as "siloxane resins". Specific examples of siloxane resins include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA", amino-terminated polysiloxanes and tetrabasic acid anhydrides manufactured by Shin-Etsu Silicone Co., Ltd. as raw materials The linear polyimide (International Publication No. 2010/053185, Japanese Patent Laid-Open No. 2002-12667, Japanese Patent Laid-Open No. 2000-319386, etc.) and the like.

As (F) elastomer, the resin containing a polyalkylene structure or a polyalkoxy structure is mentioned, for example. Resins containing polyalkylene structures are sometimes referred to as "alkylene resins". Moreover, the resin containing a polyalkoxy structure may be called "alkoxy resin". The polyalkoxy structure is preferably a polyalkoxy structure with 2 to 15 carbon atoms, preferably a polyalkoxy structure with 3 to 10 carbon atoms, and a polyalkoxy structure with 5 to 6 carbon atoms. Alkyleneoxy structures are particularly preferred. As a specific example of an alkylene resin and an alkylene oxide resin, "PTXG-1000", "PTXG-1800" by Asahi Kasei Fiber Co., Ltd., etc. are mentioned.

As (F) elastomer, the resin containing a polyisoprene structure is mentioned, for example. Resins containing a polyisoprene structure are sometimes referred to as "isoprene resins". Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray Corporation.

As (F) elastomer, the resin containing a polyisobutylene structure is mentioned, for example. A resin containing a polyisobutylene structure is sometimes referred to as "isobutylene resin". Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation. Wait.

As (F) elastomer, the resin containing a polystyrene structure is mentioned, for example. Resins containing a polystyrene structure are sometimes referred to as "styrene resins". Examples of styrene resins include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene Styrene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), Styrene-butadiene-butene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoamyl Diene block copolymer, hydrogenated styrene-butadiene random copolymer, etc. Specific examples of styrene resins include hydrogenated styrene thermoplastic elastomers "H1041", "Tuff TechH1043", "Tuff TechP2000", "Tuff TechMP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene Thermoplastic elastomer "EpofriendAT501", "CT310" (manufactured by Daicel Chemical Industries, Ltd.); modified styrene-based elastomer with hydroxyl group "SeptonHG252" (manufactured by Kuraray); modified styrene-based elastomer with carboxyl group "Tuff TechN503M" ”, modified styrene-based elastomer with amine group “Tuff TechN501”, modified styrene-based elastomer with acid anhydride group “Tuff TechM1913” (manufactured by Asahi Kasei Chemical Co., Ltd.); unmodified styrene-based elastomer “SeptonS8104” (Kuraray Co., Ltd.); styrene-ethylene/butylene-styrene block copolymer "FG1924" (manufactured by Kraton Co., Ltd.).

(F) The number average molecular weight (Mn) of the elastomer is preferably 1,000 or more, preferably 1,500 or more, more preferably 3,000 or more, particularly preferably 5,000 or more, preferably 1,000,000 or less, preferably 900,000 or less. The number average molecular weight (Mn) can be measured in terms of polystyrene using GPC (gel permeation chromatography).

Although the content of the (F) elastomer in the resin composition is not particularly limited, when the non-volatile matter in the resin composition is taken as 100% by mass, the desired effect of the present invention can be remarkably obtained from the viewpoint of 20%. The mass % or less is preferable, preferably 15 mass % or less, more preferably 10 mass % or less, more preferably 7 mass % or less, and particularly preferably 5 mass % or less. Although the lower limit of the content of the (F) elastomer in the resin composition is not particularly limited, when the nonvolatile content in the resin composition is taken as 100% by mass, for example, 0% by mass or more, 0.01% by mass or more, 0.05% by mass The above content is preferably 0.1 mass % or more, preferably 0.5 mass % or more, more preferably 1 mass % or more, more preferably 2 mass % or more, particularly preferably 3 mass % or more.

<(G) Other additives> The resin composition of the present invention may further contain optional additives as nonvolatile components. Examples of such additives include epoxy resins, epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate ester resins, polyimide resins, and benzoxazine resins. , unsaturated polyester resin, phenol resin, melamine resin, silicone resin and other thermosetting resins; imidazole-based curing accelerator, phosphorus-based curing accelerator, urea-based curing accelerator, guanidine-based curing accelerator, metal-based curing accelerator curing accelerators such as amine-based curing accelerators; phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, mercaptan-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, Carbodiimide-based hardeners, imidazole-based hardeners, active ester compounds and other hardeners; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green , iodine green, diazo yellow, crystal violet, titanium oxide, carbon black and other colorants; hydroquinone, catechol, pyrogallol, phenothiazine and other polymerization inhibitors; silicone-based leveling agent, acrylic polymerization Material-based coating and leveling agents; tackifiers such as bentonite and montmorillonite; silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, vinyl resin-based defoaming agents, and other defoaming agents ; UV absorbers such as benzotriazole-based UV absorbents; Adhesion-up agents such as urea silanes; Adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent whitening agents such as stilbene derivatives; fluorine-based surfactants, silicone-based surfactants and other surfactants; phosphorus-based surfactants Flame retardants (such as phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic flame retardants (such as antimony trioxide) Burning agents; dispersants such as phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, negative ionic dispersants, cationic dispersants; borate stabilizers, titanate dispersants Stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic acid anhydride stabilizers, and other stabilizers. (G) Other additive may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. (G) The content of other additives can be appropriately set by the manufacturer.

<(H) Organic solvent> The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the above-mentioned nonvolatile component. As (H) an organic solvent, a well-known thing can be used suitably, and this kind is not specifically limited. Examples of (H) organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate. , isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone and other ester solvents; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl Ether, dibutyl ether, diphenyl ether, anisole and other ether solvents; methanol, ethanol, propanol, butanol, ethylene glycol and other alcohol solvents; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diethylene glycol acetate, γ-butyrolactone, methyl methoxypropionate and other ether ester solvents; methyl lactate, Ethyl lactate, methyl 2-hydroxyisobutyrate and other ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol Monobutyl ether (butyl carbitol) and other ether alcohol solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. amide-based solvents; sulfite-based solvents such as dimethyl sulfoxide; nitrile-based solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; benzene, Aromatic hydrocarbon-based solvents such as toluene, xylene, ethylbenzene, and trimethylbenzene, etc. (H) An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

In one embodiment, the content of the organic solvent (H) is not particularly limited, but when the total components in the resin composition are taken as 100% by mass, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20 mass % or less, 15 mass % or less, 10 mass % or less, etc.

<Manufacturing method of resin composition> For example, the resin composition of the present invention can be prepared by mixing (A) a specific maleimide compound, (B) a resin having a vinylphenyl group and/or a (meth)acryloyl group, and optionally ( A') other maleimide compounds, optional (C) inorganic filler, optional (D) radical polymerization initiator, optional (E) thermoplastic resin, optional (F) elastomer, optional (G) Other additives and optionally (H) an organic solvent are added in an arbitrary order and/or a part or all of them are simultaneously added and mixed to manufacture. Moreover, in the process of adding and mixing each component, the temperature can be set suitably, and heating and/or cooling can be performed temporarily or all the time. In addition, in the process of adding and mixing or after that, the resin composition can be uniformly dispersed by stirring or shaking the resin composition using, for example, a stirring device such as a mixer or a shaking device. In addition, defoaming may be performed under low pressure conditions such as under vacuum simultaneously with stirring or shaking.

<Characteristics of resin composition> The resin composition of the present invention contains (A) a specific maleimide compound and (B) a resin having a vinylphenyl group and/or a (meth)acryloyl group. By using these resin compositions, the minimum melt viscosity can be suppressed lower, and a cured product having a low dielectric loss tangent (Df) and excellent copper plating peeling strength can be obtained.

The cured product of the resin composition of the present invention is characterized by excellent copper plating peel strength. Therefore, for one of the embodiments, the copper plating peeling strength calculated from the load when the copper plating conductor layer was formed on the cured product as described in the following Test Example 2 and the copper plating conductor layer was pulled apart in the vertical direction was 0.1 kgf /cm or more is preferable, preferably 0.2 kgf/cm or more, more preferably 0.25 kgf/cm or more, particularly preferably 0.3 kgf/cm or more, and 0.35 kgf/cm or more. Although the upper limit is not particularly limited, for example, it may be 10 kgf/cm or less.

The cured product of the resin composition of the present invention is characterized by a low dielectric loss tangent (Df). Therefore, in one of the embodiments, as described in Test Example 1 below, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. is preferably 0.020 or less and 0.010 or less. Preferably it is 0.009 or less, 0.008 or less, more preferably 0.007 or less, 0.006 or less, 0.005 or less, particularly preferably 0.004 or less, 0.0035 or less, and 0.003 or less.

The resin composition of the present invention has the characteristic that the minimum melt viscosity is low. Therefore, for one of the embodiments, as described in Test Example 4 below, a dynamic viscoelasticity measuring device was used, and the measurement was performed at a frequency of 1 Hz, a deformation of 5 degrees, a load of 100 g, a temperature increase rate of 5°C/min, and a temperature range of 60°C to 180°C. The minimum melt viscosity at that time is preferably 2500 poise or less, preferably 2000 poise or less, more preferably 1800 poise or less.

In one of the embodiments, the cured product of the resin composition of the present invention has the characteristic of being lower than the electrical conductivity (Dk). Therefore, in one of the embodiments, as described in Test Example 1 below, the specific conductivity (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. is preferably 5.0 or less, more preferably 4.0 or less. , more preferably 3.5 or less, particularly preferably 3.2 or less, and 3.0 or less.

In one embodiment, the cured product of the resin composition of the present invention has a characteristic that the surface after roughening treatment has a low arithmetic mean roughness (Ra). Therefore, in one of the embodiments, the arithmetic mean roughness (Ra) of the surface of the cured product after the roughening treatment, measured as described in Test Example 3 below, is preferably 300 nm or less, preferably 200 nm or less, and more preferably 150 nm. Hereinafter, it is more preferably 130 nm or less, and particularly preferably 110 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, and the like.

<Application of resin composition> The resin composition of the present invention is preferably used as a resin composition for insulating purposes, particularly as a resin composition for forming an insulating layer. Specifically, it is preferably used as a resin composition for forming a conductor layer (including a rewiring layer) formed on the insulating layer (resin composition for forming an insulating layer for forming a conductor layer). Moreover, it is preferable to use it as a resin composition (resin composition for insulating layer formation of a printed wiring board) which is going to form the insulating layer of a printed wiring board about the printed wiring board mentioned later. The resin composition of the present invention can also be used for sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, mold bonding materials, semiconductor sealing materials, hole filling resins, and parts embedding resins, etc. , Resin composition as a wide range of essential uses.

Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be used as a resin composition for a rewiring forming layer of an insulating layer to be formed as a rewiring layer (rewiring). It is preferable to use it as a resin composition for forming a layer formation), and as a resin composition for sealing a semiconductor wafer (a resin composition for sealing a semiconductor wafer). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the sealing layer. (1) The step of laminating the temporary fixing film on the substrate, (2) the step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) the step of forming a sealing layer on the semiconductor wafer, (4) the step of peeling off the base material and the temporary fixing film from the semiconductor wafer, (5) a step of forming a rewiring forming layer as an insulating layer on the substrate of the semiconductor wafer and the surface of the peeling temporary fixing film, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

In addition, the resin composition of the present invention can be applied even when the printed wiring board is a component-embedded circuit board from the viewpoint of obtaining an insulating layer with good component-embedding properties.

<Laminated sheet material> The resin composition of the present invention can be used for coating in a painted state, but industrially, it is generally preferable to use it in the form of a sheet-like laminate containing the resin composition.

As the sheet-like laminate, resin sheets and prepregs shown below are preferable.

In one embodiment, the resin sheet includes a support, and a resin composition layer is formed on the support, and the resin composition layer is formed of the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoints of thinning the printed wiring board and the fact that the cured product of the resin composition can provide a cured product with excellent insulating properties even if it is a thin film. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it is usually 5 μm or more, 10 μm or more, or the like.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate ( Polyester such as "PEN" may be abbreviated hereinafter), polycarbonate (hereinafter may be abbreviated as "PC"), acrylic acid such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose ( TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are also preferred, and convenient polyethylene terephthalate is particularly preferred.

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

Matting treatment, corona treatment, and antistatic treatment may be applied to the bonding surface of the support and the resin composition layer.

Moreover, as a support, it can be used for the support with a mold release layer which has a mold release layer on the resin composition layer bonding surface. As a mold release agent used for the mold release layer of the support with a mold release layer, for example, one selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins can be used The above release agent. As the support with a release layer, commercially available products can be used, for example, a PET film having a release layer containing an alkyd resin-based release agent as a main component, "SK-1", "AL" manufactured by Lintec -5", "AL-7", "Le Miller T60" manufactured by Toray Corporation, "Purex" manufactured by Teijin Corporation, "Unipeel" manufactured by Unitika Corporation, etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when the support with a mold release layer is used, the thickness of the entire support with a mold release layer is preferably within the above-mentioned range.

In one of the embodiments, an arbitrary layer may be further contained in the resin sheet as necessary. As this optional layer, for example, a protective film based on a support provided on the surface not joined to the support of the resin composition layer (that is, on the side opposite to the support) can be mentioned. Although the thickness of a protective film is not specifically limited, For example, it is 1 micrometer - 40 micrometers. By laminating the protective film, adhesion or damage to the surface of the resin composition layer such as dust can be suppressed.

For the resin sheet, for example, a liquid resin composition is directly prepared, or a resin composition is prepared by dissolving the resin composition in an organic solvent, and this is coated on a support using a die coater or the like, and further dried to form a resin composition. layers are manufactured.

As an organic solvent, what was demonstrated as a component of a resin composition and the same as an organic solvent is mentioned. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

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

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

In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-like fibrous base material used for the prepreg is not particularly limited, and those commonly used as base materials for prepregs such as glass cloth, aramid-based nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, preferably 40 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually 10 μm or more.

The prepreg can be produced by a known method such as a hot melt method and a solvent method.

The thickness of the prepreg may be in the same range as the resin composition layer in the above-mentioned resin sheet.

The sheet-like laminate of the present invention can preferably be used to form an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be used to form an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board) ) is better.

＜Printed wiring board＞ The printed wiring board of the present invention includes an insulating layer formed of a cured product obtained by curing the resin composition of the present invention.

A printed wiring board can be manufactured by the method including the steps of the following (I) and (II) using the above-mentioned resin sheet, for example. (1) Step of laminating a resin sheet on the inner layer substrate to form the resin composition layer of the resin sheet and bonding the inner layer substrate (II) Step of hardening (for example, thermosetting) the resin composition layer to form an insulating layer

The so-called "inner layer substrate" in step (I) is a member that becomes a substrate of a printed wiring board, for example, glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting type polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one side or both sides, and the conductor layer may also 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 substrate". In addition, when manufacturing a printed wiring board, it is further necessary to form an intermediate product of an insulating layer and/or a conductor layer, which is also included in the "inner layer substrate" of the present invention. If the printed wiring board is a circuit board with built-in components, the inner-layer substrate with built-in components can also be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-bonding the resin sheet to the inner layer substrate from the support side. As a member for heat-bonding a resin sheet as an inner-layer substrate (hereinafter also referred to as a "heat-bonding member"), for example, a heated metal plate (SUS mirror plate, etc.), a metal roller (SUS roller), etc. can be mentioned. . Furthermore, instead of pressing the thermocompression member directly onto the resin sheet, it is preferable that the resin sheet can sufficiently follow the surface unevenness of the inner layer substrate and is pressed through an elastic material such as heat-resistant rubber.

The lamination of the inner layer substrate and the resin sheet can be carried out by a vacuum lamination method. For the vacuum lamination method, the heating and pressing temperature is preferably 60°C~160°C, preferably 80°C~140°C, and the heating and pressing pressure is preferably 0.098MPa~1.77MPa, preferably 0.29MPa~1.47MPa The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, preferably in the range of 30 seconds to 300 seconds. Lamination can be carried out under reduced pressure at a pressure of 26.7 hPa or less.

Lamination can be carried out by means of a commercially available vacuum laminate. Examples of the commercially available vacuum laminates include vacuum pressurized laminates manufactured by Famous Machinery Co., Ltd., vacuum applicators by Nikko Materials Co., Ltd., and batch-type vacuum pressurized laminates.

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

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

For step (II), the resin composition layer is hardened (eg, thermally hardened) to form an insulating layer made of a hardened product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally employed when forming an insulating layer of a printed wiring board can be used.

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

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

When manufacturing a printed wiring board, (III) the step of opening a hole in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer can be further carried out. These steps (III) to (V) can be used in the manufacture of printed wiring boards, and can be implemented according to various methods known to those skilled in the art. And, when the support is removed after step (II), the removal of the support can be between step (II) and step (III), between step (III) and step (IV), or between step (IV) between step (V). In addition, the formation of the insulating layer and the conductor layer in steps (II) to (V) can be repeated as necessary to form a multilayer wiring board.

In other embodiment, the printed wiring board of this invention can be manufactured using the said prepreg. The manufacturing method is basically the same as the case of using the resin sheet.

Step (III) is a step of opening holes in the insulating layer, whereby holes such as through holes and through holes can be formed in the insulating layer. The step (III) can be carried out using, for example, a drill, a laser, a plasma, etc., in order to match the composition of the resin composition used for the formation of the insulating layer. The size or shape of the holes can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually for this step (IV), the removal of stains can also be carried out. The procedures and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions generally used when forming an insulating layer of a printed wiring board can be employed. For example, the roughening treatment of the insulating layer can be carried out in the order of swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid.

The swelling liquid used for the roughening treatment is not particularly limited, but an alkaline solution, a surfactant solution, etc. are exemplified, and an alkaline solution is preferred, and a sodium hydroxide solution and a potassium hydroxide solution are preferred as the alkaline solution. . Examples of commercially available swelling liquids include "Swering Dip Securigant P" and "Swering Dip Security SBU" manufactured by Atotech Japan. Although the swelling treatment by the swelling liquid is not particularly limited, for example, it can be performed by immersing the insulating layer in the swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganic acid solution of potassium permanganate or sodium permanganate dissolved in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment by 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. In addition, the concentration of the 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 "Dozing Solution Security P" manufactured by Atotech Japan.

Moreover, as a neutralization liquid used for a roughening process, an acidic aqueous solution is preferable, and "Reduction Solution Security Gant P" by Atotech Japan is mentioned as a commercial item, for example.

The treatment by the neutralizing solution can be performed by immersing the treated surface roughened by the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, the method of immersing the object to be roughened by the oxidizing agent in the neutralization solution at 40° C. to 70° C. for 5 minutes to 20 minutes is preferable.

In one embodiment, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, preferably 400 nm or less, and more preferably 300 nm or less. The lower limit is not particularly limited, but may be, for example, 1 nm or more, 2 nm or more, or the like. The root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact 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 preferred embodiment, the conductor layer contains 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. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). alloy) layers. Among them, from the viewpoints of the versatility, cost, and ease of drawing of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a nickel-chromium alloy , copper-nickel alloy, copper-titanium alloy alloy layer is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is preferred , a single metal layer of copper is better.

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

Although the thickness of the conductor layer varies according to the design of the desired printed wiring board, it is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one of the embodiments, the conductor layer can be formed by plating. For example, by plating on the surface of the insulating layer by conventional techniques such as the semi-additive method and the full-additive method, a conductor layer having a desired wiring pattern can be formed. The creator is better. An example in which the conductor layer is formed by the semi-additive method is shown below.

First, on the surface of the insulating layer, a plating seed layer is formed by electroless plating. Next, on the formed plating seed layer, a part of the plating seed layer is exposed corresponding to the desired wiring pattern to form a mask pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, by removing the unnecessary plating seed layer by etching or the like, a conductor layer having a desired wiring pattern can be formed.

In other embodiments, the conductor layer can be formed using metal foil. When the conductor layer is formed using the metal foil, it is preferable that the step (V) is performed between the step (I) and the step (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be carried out by a vacuum lamination method. The conditions for lamination may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventionally known techniques such as a subtractive method and a modified semi-additive method.

The metal foil can be produced by known methods such as an electrolytic method and a rolling method, for example. As a sale item of metal foil, HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil by Mitsui Metal Mining Co., Ltd. made by JX Nippon Mining Co., Ltd., etc. are mentioned, for example.

<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 electrical products (eg, computers, mobile phones, digital cameras, televisions, etc.) and passenger vehicles (eg, locomotives, automobiles, trains, ships, aircraft, etc.). [Example]

Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to these embodiments. In addition, "parts" and "%" indicating the amounts in the following mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In particular, when the temperature and pressure are not specified, the temperature conditions and pressure conditions indicate room temperature (23° C.) and atmospheric pressure (1 atm).

<Synthesis example 1: Polyimide resin 1> 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) 49.6g, 4,4' was mixed with N,N-dimethylacetamide 400g Monomer obtained from -[1,4-phenylene bis[(1-methylethylidene)-4,1-phenyleneoxy]]bisaniline (BPPAN) 50.4 g and 40 g of toluene as a solvent The composition was stirred and reacted at normal temperature and atmospheric pressure for 3 hours. Thereby, a solution of polyamic acid was obtained.

Next, after raising the temperature of the polyamic acid solution, the water of condensation and toluene were azeotropically removed under nitrogen flow while maintaining the temperature at about 160°C. It was confirmed that the water had accumulated to the specified amount in the moisture quantitative receiver, and no water outflow was seen. After the confirmation, the temperature of the reaction solution was further increased, and stirring was performed at 200° C. for 1 hour. It is then allowed to cool. Thereby, the paint containing the polyimide resin 1 (polyimide resin having a repeating unit represented by the following formula (E)) as a nonvolatile content of 20% by mass was obtained. The glass transition temperature Tg of the polyimide resin 1 was measured according to the above-mentioned method, and was 210°C.

<Example 1> A maleimide compound containing isopropylidene (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd., a toluene solution with a non-volatile content of 60% by mass) was mixed, and the main components (non-volatile content): Maleimide compound represented by the following formula (A)) 23 parts, vinylbenzyl modified polyphenylene ether resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1200, non-volatile 65 mass % toluene solution) 20 parts, polymerization initiator (peroxide "peroxybutyl (registered trademark) C" manufactured by NOF Corporation) 0.5 part, inorganic filler (using amine-based alkoxysilane compound) ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 50 parts of spherical silica ("SO-C2" manufactured by Admatechs Corporation, average particle size 0.5 μm, specific surface area 5.8 m ² /g)), and ester-type benzene 10 parts of oxygen-based resin ("YL7891T30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was uniformly dispersed using a high-speed rotary mixer to obtain a resin composition (resin paint ).

<Example 2> 20 parts of substituted vinylbenzyl modified polyphenylene ether resin (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Ltd.), using styrene-divinylbenzene copolymer (“ODV- XET (X04)", weight average molecular weight 3110, vinyl equivalent 380 g/eq., 65 mass % solution) except 20 parts, it carried out similarly to Example 1, and obtained the resin composition (resin paint).

<Example 3> Substituted vinylbenzyl modified polyphenylene ether resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd.) 20 parts, using methacrylic acid modified polyphenylene ether resin ("SA9000-111" manufactured by SABIC Corporation, A resin composition (resin paint) was obtained in the same manner as in Example 1 except that the number average molecular weight was 1850 to 1950) 20 parts.

<Example 4> The usage amount of the isopropylidene-containing maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.) was changed from 23 parts to 18 parts, and biphenyl aralkyl type maleimide was used A resin composition (resin paint) was obtained in the same manner as in Example 1 except for 5 parts of an imine compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., a MEK/toluene mixed solution of 70% nonvolatile content).

<Example 5> The usage amount of the isopropylidene-containing maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.) was changed from 23 parts to 21 parts, and the liquid aliphatic maleimide compound was used A resin composition (resin paint) was obtained in the same manner as in Example 1 except for 2 parts (“BMI-1500” manufactured by Designer Molecular Co., Ltd.).

<Example 6> 10 parts of substituted ester phenoxy resin ("YL7891T30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), and an elastomer (styrene-ethylene/butyl manufactured by Kraton Corporation) was used A resin composition (resin paint) was obtained in the same manner as in Example 1 except that the olefin-styrene block copolymer "FG1924") was 3 parts.

<Example 7> The usage amount of the ester-type phenoxy resin (“YL7891T30” manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was changed from 10 parts to 5 parts, obtained in Synthesis Example 1 A resin composition (resin paint) was obtained in the same manner as in Example 1 except that 7 parts of the polyimide resin 1 was added.

<Example 8> The use amount of "SO-C2" manufactured by Admatechs was changed from 50 parts to 40 parts, and an inorganic filler with a hollow part (an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was used for the surface treatment. A resin composition (resin paint) was obtained in the same manner as in Example 6, except for 10 parts of spherical silica having a hollow portion (“BA-S” manufactured by Nikko Kasei Co., Ltd., average particle size: 2.6 μm)).

<Comparative Example 1> A vinylbenzyl-modified polyphenylene ether resin (“OPE” manufactured by Mitsubishi Gas Chemical Co., Ltd. A resin composition (resin paint) was obtained in the same manner as in Example 1 except that the usage amount of -2St 1200") was changed from 20 parts to 40 parts.

<Comparative Example 2> No isopropylidene-containing maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.), substituted vinylbenzyl modified polyphenylene ether resin (“OPE” manufactured by Mitsubishi Gas Chemical Corporation) A resin composition ( resin paint).

<Comparative Example 3> No isopropylidene-containing maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.), substituted vinylbenzyl modified polyphenylene ether resin (“OPE” manufactured by Mitsubishi Gas Chemical Corporation) A resin composition was obtained in the same manner as in Example 1, except that 20 parts of methacrylic acid modified polyphenylene ether resin (“SA9000-111” manufactured by SABIC Corporation, number average molecular weight 1850-1950) was used in 20 parts of -2St 1200”). (resin painted).

<Comparative Example 4> In place of the isopropylidene-containing maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.), a biphenyl aralkyl-type maleimide compound (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd.) was used. A resin composition (resin paint) was obtained in the same manner as in Example 1, except for 20 parts of MEK/toluene mixed solution of 70% non-volatile content: -3000-70MT".

<Test Example 1: Measurement of Specific Conductivity (Dk) and Dielectric Loss Tangent (Df)> As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm) provided with a mold release layer was prepared. On the mold release layer of the support, the resin compositions (resin paints) obtained in Examples and Comparative Examples were uniformly applied until the thickness of the dried resin composition layer was 40 μm. Then, after drying the resin composition for 4 minutes at 80 degreeC - 100 degreeC (average 90 degreeC), the resin sheet containing a support body and a resin composition layer was obtained.

The obtained resin sheet was heated at 190° C. for 90 minutes to thermoset the resin composition layer. After that, the support was peeled off to obtain a cured product of the resin composition. This cured product was cut into test pieces of 2 mm in width and 80 mm in length. For this test piece, the specific conductivity (Dk) and the dielectric loss tangent (Df) were measured by the cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Three test pieces were measured, and the average value is shown in Table 1 below.

<Test Example 2: Measurement of Copper Plating Peeling Strength> (1) Basic treatment of inner layer circuit board As an inner-layer circuit board, a glass cloth-based epoxy resin double-sided copper sheet laminate with inner-layer circuit (copper foil) on both sides was prepared (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) . Both sides of this inner-layer circuit board were etched at 1 μm with “CZ8101” manufactured by MEC Corporation, and the copper surface was roughened.

(2) Lamination of resin sheets The resin sheet obtained in Test Example 1 was laminated on both sides of the inner-layer circuit board using a batch-type vacuum press laminate (manufactured by Nikko Materials Co., Ltd., two-stage build-up laminate, CVP700). The lamination is carried out by connecting the resin composition layer of the resin sheet to the inner layer circuit board. In addition, this lamination was implemented by performing pressure reduction for 30 seconds and setting the air pressure to 13 hPa or less, and performing pressing at 130° C. and a pressure of 0.74 MPa for 45 seconds. Next, hot pressing was performed at 120° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Hardening of resin composition The laminated resin sheet and inner-layer circuit board were heated at 130° C. for 30 minutes, and then heated at 170° C. for 30 minutes to harden the resin composition to form an insulating layer. Then, the support body was peeled off, and the laminated board provided in this order of an insulating layer, an inner-layer circuit board, and an insulating layer was obtained.

(4) Roughening treatment The above-mentioned laminated substrate was immersed in a swelling solution (Swering Dip Securigant P (aqueous solution of glycol ethers and sodium hydroxide) containing diethylene glycol monobutyl ether, manufactured by Atotech Japan Co., Ltd.). 10 minutes at 60°C. Next, the laminated substrate was immersed at 80° C. for 20 minutes in a roughening solution (Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) manufactured by Atotech Japan). The laminated substrate was immersed in a neutralizing solution (Reduction Shorusin Securigant P (aqueous solution of sulfuric acid) manufactured by Atotech Japan) at 40°C for 5 minutes. After that, the laminated substrate was dried at 80°C for 30 minutes to obtain an "evaluation substrate". A".

(5) Plating by semi-additive method: The evaluation substrate A was immersed in a solution for electroless plating containing PdCl ₂ at 40° C. for 5 minutes, followed by immersion in an electroless copper plating solution at 25° C. 20 minutes. Then, it heated at 150 degreeC for 30 minutes, and performed the annealing process. After that, an etching resist is formed, and patterning is performed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 μm. Next, after performing annealing treatment at 190° C. for 60 minutes, an “evaluation substrate B” was obtained.

(6) Determination of peel strength of copper plating For the conductor layer of the evaluation substrate B, a peripheral cutout of a rectangular portion having a width of 10 mm and a length of 100 mm was formed. One end of the rectangular part was peeled off and clamped with a jig (TSE Co., Ltd., automatic communication type testing machine "AC-50C-SL"). With a jig, at room temperature, the rectangular portion was pulled vertically at a speed of 50 mm/min, and the load (kgf/cm) when pulled apart by 35 mm was measured as the copper plating peeling strength, as shown in the following Table 1. Show.

<Test Example 3: Measurement of Surface Roughness Ra> The arithmetic mean roughness Ra of the surface of the insulating layer of the evaluation board|substrate A produced in Test Example 2 (4) was measured. The measurement was performed using a non-contact surface roughness meter (WYKO NT3300, manufactured by VICO INSTRUMENTS) with a 50-fold lens in the VSI mode, and the measurement range was set to 121 μm×92 μm. This measurement was performed at 10 measurement points, and the average value is shown in Table 1 below.

<Test Example 4: Measurement of Minimum Melt Viscosity> The resin sheet obtained in Test Example 1 was peeled off from the self-supporting film, and a dynamic viscoelasticity measuring device G-3000 manufactured by UBM was used at a frequency of 1 Hz, a deformation of 5 degrees, a load of 100 g, a heating rate of 5 °C/min, and a temperature range of 60 °C. Measured at ℃~180℃.

The amount of raw materials used, the content of non-volatile components, and the measurement results of the test examples of the resin compositions of Examples and Comparative Examples are shown in Tables 1 and 2 below.

Referring to Table 1, it was found that in Comparative Examples 1 to 3 in which the maleimide compound was not used, the copper plating peeling strength was low. In Comparative Example 4 in which an aromatic polymaleimide compound without isopropylidene was used as the maleimide compound, the minimum melt viscosity was high and the dielectric loss tangent (Df) was also high. . On the other hand, when the resin composition of the present invention containing (A) a specific maleimide compound and (B) a resin having a vinylphenyl group and/or a (meth)acryloyl group is used, these problems can be overcome. subject.

This case is based on Japanese Patent Application No. 2020-189016 (filed on November 12, 2020) filed with the Japan Patent Office, and the contents are all incorporated herein by reference.

Claims (19)

A resin composition comprising (A) a maleimide compound having an isopropylidene group bonded to 2 aromatic carbon atoms of different aromatic rings, and (B) having a vinylphenyl group and/or (Meth)acryloyl resin. The resin composition of claim 1, wherein component (A) contains a maleimide compound represented by formula (A2),

[In the formula, ring A and ring B each independently represent an aromatic ring which may have a substituent; a represents an integer of 1 or more]. The resin composition according to claim 1, wherein component (A) contains a maleimide compound represented by formula (A-1),

[In the formula, R ¹ and R ² each independently represent an alkyl group or an aryl group; a represents an integer of 1 or more; and x and y each independently represent 0, 1, 2, or 3]. The resin composition of claim 3, wherein a is an integer from 2 to 10. The resin composition according to claim 1, wherein the component (B) has a vinylphenyl group and/or a (meth)acryloyl group. The resin composition according to claim 1, wherein component (B) is selected from modified polyphenylene ether resins having vinylphenyl and/or (meth)acryloyl groups, and vinylphenyl and/or (Meth)acryloyl-based modified polystyrene resin. The resin composition of claim 1, wherein the content of component (A) is 5 to 30 mass % when the non-volatile matter in the resin composition is taken as 100 mass %. The resin composition of claim 1, wherein the content of component (B) is 5 to 40 mass % when the non-volatile matter in the resin composition is taken as 100 mass %. The resin composition according to claim 1, wherein the mass ratio of (A) component ((A) component/(B) component) to (B) component is 0.3 to 3. The resin composition according to claim 1, further comprising (C) an inorganic filler. The resin composition according to claim 10, wherein the content of the component (C) is 40% by mass or more when the nonvolatile matter in the resin composition is taken as 100% by mass. The resin composition of claim 10, wherein the mass ratio of (A) component ((A) component/(C) component) to (C) component is 0.1 to 1. The resin composition according to claim 1, wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.004 or less when measured at 5.8 GHz and 23°C. The resin composition according to claim 1, wherein the specific conductivity (Dk) of the cured product of the resin composition is 3.5 or less when measured at 5.8 GHz and 23°C. A hardened product of the resin composition according to any one of claims 1 to 14. A sheet-like laminate containing the resin composition according to any one of claims 1 to 14. A resin sheet comprising a support, and a resin composition layer formed of the resin composition according to any one of claims 1 to 14 provided on the support. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 14. A semiconductor device comprising the printed wiring board as claimed in claim 18.