Resin composition

Abstract

The present invention addresses the problem of providing a resin composition such that the minimum melt viscosity can be further reduced, the relative dielectric constant (Dk) and the dielectric loss factor (Df) are low, the glass transition temperature is high, 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, (B) an active ester compound, and (C) an epoxy resin.

Description

[Technical field]

[0001] The present invention relates to a resin composition containing a maleimide compound, and further to a cured product, a sheet-like laminate material, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. [Background technology]

[0002] A known manufacturing technique for printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked. In the build-up method, the insulating layer is generally formed by curing a resin composition. In recent years, there has been a demand for further improvement in the dielectric properties of the insulating layer, such as the dielectric constant, and further improvement in copper adhesion. On the other hand, there is also a demand for an insulating layer with a high glass transition temperature. However, up to now, when a material with high copper plating peel strength is used, there have been problems with the high minimum melt viscosity of the resin composition, the high relative dielectric constant (Dk) and dielectric dissipation factor (Df) of the material, and the low glass transition point (Tg).

[0003] So far, maleimide compounds containing an isopropylidene group have been known (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6752390 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin composition which can reduce the minimum melt viscosity, and which can give a cured product having a low dielectric constant (Dk) and dielectric dissipation factor (Df), a high glass transition point (Tg), and excellent copper plating peel strength. [Means for solving the problem]

[0006] Means for Solving the Problems of the Invention The present inventors conducted intensive research in order to achieve the objects of the present invention, and unexpectedly found that by using, as components of a resin composition, (A) a maleimide compound having an isopropylidene group bonded to two aromatic carbon atoms of different aromatic rings, (B) an active ester compound, and (C) an epoxy resin, it is possible to reduce the minimum melt viscosity of the resin composition and obtain a cured product which has a low relative dielectric constant (Dk) and dielectric dissipation factor (Df), a high glass transition point (Tg), and excellent copper plating peel strength, and thus completed the present invention.

[0007] That is, the present invention includes the following. [1] A resin composition comprising: (A) a maleimide compound having an isopropylidene group bonded to two aromatic carbon atoms of different aromatic rings; (B) an active ester compound; and (C) an epoxy resin. [2] The component (A) is represented by the formula (A2):

[0008] [ka]

[0009] [In the formula, ring A and ring B each independently represent an aromatic ring which may have a substituent; and a represents an integer of 1 or more.] The resin composition according to the above [1], comprising a maleimide compound represented by the following formula: [3] The component (A) is represented by the formula (A-1):

[0010] [ka]

[0011] [In the formula, R 1 and R 2 each independently represents 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 according to the above [1] or [2], comprising a maleimide compound represented by the following formula: [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 content of the component (A) is 3% by mass to 30% by mass, based on 100% by mass of the non-volatile components in the resin composition. [6] The resin composition according to any one of the above [1] to [5], wherein the content of the component (B) is 3% by mass to 30% by mass, based on 100% by mass of the non-volatile components in the resin composition. [7] The resin composition according to any one of the above [1] to [6], wherein a mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 0.5 to 2. [8] The resin composition according to any one of the above [1] to [7], wherein the content of the component (C) is 1% by mass to 30% by mass, relative to 100% by mass of the non-volatile components in the resin composition. [9] The resin composition according to any one of the above [1] to [8], wherein a mass ratio of the component (A) to the component (C) (component (A) / component (C)) is 0.5 to 3.

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

[11] The resin composition according to

[10] above, wherein the content of the (D) component is 40 mass% or more, based on 100 mass% of the non-volatile components in the resin composition.

[12] The resin composition according to any one of the above [1] to

[11] , wherein a dielectric loss tangent (Df) of a cured product of the resin composition is 0.0045 or less when measured at 5.8 GHz and 23°C.

[13] The resin composition according to any one of the above [1] to

[12] , wherein a cured product of the resin composition has a relative dielectric constant (Dk) of 3.5 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 glass transition temperature (Tg) of a cured product of the resin composition is 140° C. or higher.

[15] A cured product of the resin composition according to any one of [1] to

[14] above.

[16] A sheet-like laminate material comprising the resin composition according to any one of [1] to

[14] above.

[17] A resin sheet comprising: a support; and a resin composition layer formed on the support, the resin composition being formed from the resin composition according to any one of [1] to

[14] above.

[18] A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to

[14] above.

[19] A semiconductor device comprising the printed wiring board according to

[18] above. Effect of the Invention

[0012] According to the resin composition of the present invention, the minimum melt viscosity can be reduced, and a cured product can be obtained which has a low dielectric constant (Dk) and dielectric dissipation factor (Df), a high glass transition point (Tg), and excellent copper plating peel strength. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below with reference to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be modified and implemented as desired without departing from the scope of the claims of the present invention and their equivalents.

[0014] <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 a "specific maleimide compound"), (B) an active ester compound, and (C) an epoxy resin. By using such a resin composition, it is possible to further reduce the minimum melt viscosity, and to obtain a cured product having a low relative dielectric constant (Dk) and dielectric loss tangent (Df), a high glass transition point (Tg), and excellent copper plating peel strength.

[0015] The resin composition of the present invention may further contain optional components in addition to (A) the specific maleimide compound, (B) the active ester compound, and (C) the epoxy resin. Examples of the optional components include (A') other maleimide compounds, (B') other curing agents, (D) inorganic fillers, (E) curing accelerators, (F) polyimide resins, (G) other additives, and (H) organic solvents. Each component contained in the resin composition will be described in detail below.

[0016] <(A) Specific Maleimide Compound> The resin composition of the present invention contains (A) a specific maleimide compound. The (A) specific maleimide compound may be used alone or in combination of two or more kinds in any ratio.

[0017] The maleimide compound means a compound having at least one maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) in one molecule. The maleimide group in the (A) specific maleimide compound may be bonded to an aromatic carbon atom or an aliphatic carbon atom, but preferably includes one bonded to an aromatic carbon atom, and more preferably, all of the maleimide groups in the (A) specific maleimide compound are bonded to aromatic carbon atoms. The number of maleimide groups in one molecule of the (A) specific maleimide compound is preferably 2 or more, more preferably 3 or more, more preferably 3 to 11, and even more preferably 3 to 6.

[0018] (A) A specific maleimide compound has an isopropylidene group (-C(CH)) bonded to two aromatic carbon atoms of different aromatic rings. 3 ) 2-) in one molecule. The isopropylidene group contained in the (A) specific maleimide compound may be any of an isopropylidene group bonded to two aromatic carbon atoms, which is a combination of an aromatic carbon atom in an aromatic ring having a maleimide group and an aromatic carbon atom in an aromatic ring not having a maleimide group, an isopropylidene group bonded to an aromatic carbon atom in a different aromatic ring having a maleimide group, and an isopropylidene group bonded to an aromatic carbon atom in a different aromatic ring not having a maleimide group. The (A) specific maleimide compound preferably has an isopropylidene group bonded to two aromatic carbon atoms, which is a combination of an aromatic carbon atom in an aromatic ring having a maleimide group and an aromatic carbon atom in an aromatic ring not having a maleimide group, and particularly preferably, all of the isopropylidene groups contained in the (A) specific maleimide compound are isopropylidene groups bonded to two aromatic carbon atoms, which is a combination of an aromatic carbon atom in an aromatic ring having a maleimide group and an aromatic carbon atom in an aromatic ring not having a maleimide group. The number of such isopropylidene groups in one molecule of the (A) specific maleimide compound is preferably 2 or more, more preferably 4 or more, further preferably 4 to 20, and particularly preferably 4 to 10.

[0019] The aromatic ring means a ring conforming to the Huckel rule in which the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number). The aromatic ring may be an aromatic carbocycle having a carbon atom as a ring-constituting atom, or an aromatic heterocycle having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom in addition to a carbon atom as a ring-constituting atom, but in one embodiment, it is preferably an aromatic carbocycle. In one embodiment, the aromatic ring is preferably a 5-14-membered aromatic ring, more preferably a 5-10-membered aromatic ring, and even more preferably a 5- or 6-membered aromatic ring. Suitable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like, more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

[0020] (A) In one embodiment, the specific maleimide compound is preferably represented by formula (A1):

[0021] [ka]

[0022] [In the formula, ring A, ring B and ring C each independently represent an aromatic ring which may have a substituent; each X 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 which may have a substituent, or an aryl group which may have a substituent; a represents an integer of 1 or more; b represents 0 or 1; and c represents 0, 1, 2, or 3. The maleimide compound includes a maleimide compound represented by the following formula: The a units and the c units may be the same or different for each unit.

[0023] Ring A, ring B and ring C each independently represent an aromatic ring which may have a substituent, preferably an aromatic carbocycle which may have a substituent, more preferably a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, even more preferably a benzene ring which may be substituted with a group selected from an alkyl group and an aryl group, or a naphthalene ring which may be substituted with a group selected from an alkyl group and an aryl group, and particularly preferably a benzene ring which may be substituted with a group selected from an alkyl group and an aryl group.

[0024] In the present specification, the term "substituent" is not particularly limited, and examples thereof include monovalent substituents such as an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, and an aryl-carbonyl-oxy group, and may also include divalent substituents such as an oxo group (=O) if substitutable.

[0025] The alkyl group means a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl group is preferably an alkyl group having 1 to 14 carbon atoms, unless otherwise specified. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a cyclopentylmethyl group, and a cyclohexylmethyl group. The alkenyl group means a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl group is preferably an alkenyl group having 2 to 14 carbon atoms, unless otherwise specified. Examples of the alkenyl group include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and cyclohexenyl groups. The aryl group means a monovalent aromatic hydrocarbon group. Unless otherwise specified, the aryl group is preferably an aryl group having 6 to 14 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0026] Each X is independently a single bond, -C(R x ) 2-, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-, preferably a single bond, -C(R x ) 2 - or -O-, more preferably a single bond or -C(R x ) 2 R is preferably a single bond. x each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, more preferably a hydrogen atom, an alkyl group, or an aryl group, and even more preferably a hydrogen atom or an alkyl group.

[0027] a represents an integer of 1 or more, preferably 2 or more, more preferably an integer of 2 to 10, and even more preferably 2, 3, 4, or 5. In one embodiment, the (A) specific maleimide compound contains a maleimide compound represented by formula (A1) in which a is 1, and a maleimide compound represented by formula (A1) in which a is 2 or more, and preferably contains 1 mass %, more preferably 5 mass %, further preferably 8 mass %, and particularly preferably 10 mass % of the maleimide compound represented by formula (A1) in which a is 2 or more.

[0028] Each b independently represents 0 or 1, and preferably represents 1. Each c independently represents 0, 1, 2, or 3, and preferably represents 0, 1, or 2, more preferably represents 0 or 1, and particularly preferably represents 0.

[0029] In one embodiment, the specific maleimide compound (A) is more preferably represented by formula (A2):

[0030] [ka]

[0031] [In the formula, each symbol is as defined above.] The maleimide compound represented by the formula:

[0032] In another embodiment, the specific maleimide compound (A) is more preferably represented by the formulae (A-1) to (A-6):

[0033] [ka]

[0034] [In the formula, R 1 and R 2 each independently represents an alkyl group or an aryl group; x and y each independently represent 0, 1, 2, or 3; and other symbols are as defined above. In one embodiment, the maleimide compound is preferably a compound represented by formula (A-1), and in one embodiment, the maleimide compound is preferably a compound represented by formula (A-1a) or (A-1b):

[0035] [ka]

[0036] [In the formula, each symbol is the same as above.] In one embodiment, the compound represented by formula (A-1a) is particularly preferred.

[0037] R 1 and R 2 each independently represents an alkyl group or an aryl group, and is preferably an alkyl group. x and y each independently represent 0, 1, 2, or 3, and are preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0.

[0038] The weight average molecular weight (Mw) of the (A) specific maleimide compound is preferably 500 to 5000, more preferably 500 to 4000, and even more preferably 500 to 3000. The number average molecular weight (Mn) of the (A) specific maleimide compound is preferably 500 to 5000, more preferably 500 to 4000, and even more preferably 500 to 3000. The weight average molecular weight and number average molecular weight of the resin can be measured as polystyrene-equivalent values ​​by gel permeation chromatography (GPC).

[0039] The maleimide equivalent of the (A) specific maleimide compound is preferably 100 g / eq. to 1000 g / eq., more preferably 150 g / eq. to 400 g / eq. The maleimide equivalent of the (A) specific maleimide compound is the mass of the (A) specific maleimide compound per equivalent of maleimide group.

[0040] An example of a commercially available product of the (A) specific maleimide compound is "MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.

[0041] The content of the (A) specific maleimide compound in the resin composition is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. The lower limit of the content of the (A) specific maleimide compound in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

[0042] <(A') Other maleimide compounds> The resin composition of the present invention may further contain, as an optional component, (A') a maleimide compound other than the component (A). The (A') other maleimide compound may be used alone or in any combination of two or more kinds.

[0043] The (A') other maleimide compounds are not particularly limited, and may be either aliphatic maleimide compounds containing an aliphatic amine skeleton or aromatic maleimide compounds containing an aromatic amine skeleton. Commercially available products include, for example, "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", and "BMI-2500" manufactured by Designer Molecules, Inc. (maleimide compounds containing a dimer diamine structure), "BMI-6100" manufactured by Designer Molecules, Inc. (aromatic maleimide compound), "MIR-3000-70MT" (biphenylaralkyl-type maleimide compound) manufactured by Nippon Kayaku Co., Ltd., "BMI-70" and "BMI-80" manufactured by K.I. Chemical Industry Co., Ltd., and "BMI-2300" and "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd. In addition, as the (A') other maleimide compound, a maleimide resin (an indane ring skeleton-containing maleimide compound) disclosed in the Japan Institute of Invention and Innovation's Technical Journal Publication No. 2020-500211 may be used.

[0044] The maleimide equivalent of the (A') other maleimide compound is preferably 100 g / eq. to 20,000 g / eq., more preferably 200 g / eq. to 15,000 g / eq., and even more preferably 300 g / eq. to 10,000 g / eq. The maleimide equivalent of the (A') other maleimide compound is the mass of the (A') other maleimide compound per equivalent of maleimide group.

[0045] The weight average molecular weight (Mw) of the (A') other maleimide compound is preferably 500 to 50,000, more preferably 700 to 20,000. The number average molecular weight (Mn) of the (A') other maleimide compound is preferably 500 to 50,000, more preferably 700 to 20,000.

[0046] The content of the (A') other maleimide compound in the resin composition is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. The lower limit of the content of the (A') other maleimide compound in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, etc., when the non-volatile components in the resin composition are taken as 100% by mass.

[0047] The content of the specific maleimide compound (A) in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, when the total amount of the maleimide compounds in the resin composition (the sum of the components (A) and (A')) is taken as 100% by mass.

[0048] <(B) Active ester compound> The resin composition of the present invention contains an active ester compound (B). The active ester compound (B) may be used alone or in combination of two or more at any ratio. The active ester compound (B) may function as an epoxy resin curing agent that reacts with the epoxy resin (C) to cure the epoxy resin.

[0049] As the (B) active ester compound, generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. The active ester compound is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0050] Specifically, the (B) active ester compound is preferably a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, or an active ester compound containing a benzoylated product of phenol novolac, and more preferably at least one selected from a dicyclopentadiene type active ester compound and a naphthalene type active ester compound, and even more preferably a dicyclopentadiene type active ester compound. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferred.

[0051] (B) Commercially available active ester compounds include, as active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as active ester compounds containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", Examples of the active ester compound containing phosphorus include "EXB9401" (manufactured by DIC Corporation), "DC808" (manufactured by Mitsubishi Chemical Corporation) which is an active ester compound that is an acetylated product of phenol novolac, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) which are active ester compounds that are benzoylated products of phenol novolac, and "PC1300-02-65MA" (manufactured by Air Water Corporation) which is an active ester compound containing a styryl group and a naphthalene structure.

[0052] The active ester group equivalent of the (B) active ester compound is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and further preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester compound per equivalent of the active ester group.

[0053] The content of the (B) active ester compound in the resin composition is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. The lower limit of the content of the (B) active ester compound in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

[0054] The mass ratio of the specific maleimide compound (A) to the active ester compound (B) in the resin composition (component (A) / component (B)) is preferably 0.1 or more, more preferably 0.3 or more, and particularly preferably 0.5 or more. The upper limit of the mass ratio of the specific maleimide compound (A) to the active ester compound (B) in the resin composition (component (A) / component (B)) is preferably 5 or less, more preferably 2 or less, and particularly preferably 1 or less.

[0055] <(B') Other hardeners> The resin composition of the present invention may further contain a (B') curing agent other than the (B) component as an optional component. The (B') other curing agent may be used alone or in any combination of two or more. The (B') other curing agent may function as an epoxy resin curing agent that reacts with the (C) epoxy resin to cure it, similar to the (B) active ester compound.

[0056] (B') Other curing agents are not particularly limited, but examples thereof include phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents. (B') Other curing agents particularly preferably include a phenol-based curing agent.

[0057] As the phenol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferable. Also, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a triazine skeleton-containing phenol novolac resin is preferable. Specific examples of phenol-based curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", and "TD-2090-60M" manufactured by DIC Corporation.

[0058] Examples of the carbodiimide-based curing agent include curing agents having one or more, preferably two or more, carbodiimide structures in one molecule, such as aliphatic biscarbodiimides, such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides, such as phenylene-bis(xylylcarbodiimide); and aliphatic polycarbodiimides, such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide). ; polycarbodiimides such as aromatic polycarbodiimides such as poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide].

[0059] Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P", "Stavaxol P400", and "Hi-Kasil 510" manufactured by Rhein Chemie.

[0060] Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and the like. Examples of acid anhydrides include anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. Commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Japan Chemical Co., Ltd., "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation, "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd., and "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Clay Valley.

[0061] The amine-based curing agent may be a curing agent having one or more, preferably two or more, amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. As the amine-based curing agent, commercially available products may be used, and examples thereof include "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0062] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0063] Examples of the cyanate ester curing agent include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both of which are phenol novolac-type multifunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been converted to triazine to form a trimer), all of which are manufactured by Lonza Japan.

[0064] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0065] The reactive group equivalent of the (B') other curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive group equivalent is the mass of the curing agent per equivalent of the reactive group.

[0066] The content of the (B') other curing agent in the resin composition is not particularly limited, but is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, when the non-volatile components in the resin composition are 100% by mass. The lower limit of the content of the (B') other curing agent in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, when the non-volatile components in the resin composition are 100% by mass.

[0067] The content of the (B) active ester compound in the resin composition is preferably 10 mass% or more, more preferably 30 mass% or more, even more preferably 40 mass% or more, and particularly preferably 50 mass% or more, when the total of the (B) active ester compound and the (B') other curing agents in the resin composition is 100 mass%.

[0068] <(C) Epoxy resin> The resin composition of the present invention contains an epoxy resin (C). The epoxy resin (C) is a curable resin having an epoxy group.

[0069] (C) Examples of epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, and glycidyl ester type epoxy resins. Examples of the epoxy resins include cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, isocyanurate type epoxy resins, phenolphthalimidine type epoxy resins, phenolphthalein type epoxy resins, etc. (C) The epoxy resins may be used alone or in combination of two or more.

[0070] The resin composition preferably contains, as the epoxy resin (C), an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile components of the epoxy resin (C) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0071] Epoxy resins include epoxy resins that are liquid at a temperature of 20° C. (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20° C. (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present invention may contain only liquid epoxy resins as the epoxy resin, or may contain only solid epoxy resins, or may contain a combination of liquid epoxy resins and solid epoxy resins. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin or a combination of a liquid epoxy resin and a solid epoxy resin, and is more preferably a liquid epoxy resin.

[0072] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0073] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferred.

[0074] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "Epikote 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", and "604" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L" and "EP-3980S" ( glycidylamine type epoxy resin); ADEKA's "EP-4088S" (dicyclopentadiene type epoxy resin); Nippon Steel Chemical & Material Chemical's "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase Chemtex's "EX-721" (glycidyl ester type epoxy resin); Daicel's "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton); Daicel's "PB-3600", Nippon Soda's "JP-100" and "JP-200" (epoxy resin having a butadiene structure); Nippon Steel Chemical & Material's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin), etc. These may be used alone or in combination of two or more types.

[0075] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0076] Preferred solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, phenolphthalimidine type epoxy resins, and phenolphthalein type epoxy resins.

[0077] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC Corporation; and "EXA-7311" manufactured by DIC Corporation. , "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN475V", "ESN4 100V" (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "Y Examples of epoxy resins include "X7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical; and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.These may be used alone or in combination of two or more.

[0078] When a solid epoxy resin and a liquid epoxy resin are used in combination as the (C) epoxy resin, the mass ratio of the solid epoxy resin to the liquid epoxy resin (solid epoxy resin / liquid epoxy resin) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, still more preferably 0.5 or less, and particularly preferably 0.1 or less.

[0079] The epoxy equivalent of the (C) epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., even more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

[0080] The weight average molecular weight (Mw) of the epoxy resin (C) is preferably from 100 to 5,000, more preferably from 250 to 3,000, and further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0081] The content of the epoxy resin (C) in the resin composition is not particularly limited, but is preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. The lower limit of the content of the epoxy resin (C) in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

[0082] The mass ratio of the specific maleimide compound (A) to the epoxy resin (C) in the resin composition (component (A) / component (C)) is preferably 0.1 or more, more preferably 0.5 or more, and particularly preferably 0.8 or more. The upper limit of the mass ratio of the specific maleimide compound (A) to the epoxy resin (C) in the resin composition (component (A) / component (C)) is preferably 10 or less, more preferably 3 or less, and particularly preferably 1.5 or less.

[0083] <(D) Inorganic filler> The resin composition of the present invention may contain an inorganic filler (D) as an optional component. The inorganic filler (D) is contained in the resin composition in the form of particles.

[0084] (D) An inorganic compound is used as the material of the inorganic filler. (D) Examples of the material of the inorganic filler include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica or aluminosilicate is preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferred as the silica. The (D) inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0085] (D) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Company; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "DAW-03" and "FB-105FD" manufactured by Denka Company; "BA-S" manufactured by JGC Catalysts and Chemicals Co., Ltd.; and "MG-005" manufactured by Taiheiyo Cement Corporation.

[0086] The average particle size of the (D) inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less. The lower limit of the average particle size of the (D) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the (D) 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 is created on a volume basis using a laser diffraction / scattering type particle size distribution measuring device, and the median diameter is taken as the average particle size. The measurement sample can be prepared by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device with blue and red light source wavelengths, and the particle size distribution of the inorganic filler on a volume basis was measured using a flow cell method, and the average particle size was calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction type particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

[0087] The specific surface area of ​​the (D) inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 The upper limit of the specific surface area of ​​the inorganic filler (D) is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 40m 2 The specific surface area of ​​the inorganic filler is obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0088] The (D) inorganic filler may be a non-hollow inorganic filler with a porosity of 0 volume % (preferably non-hollow silica, non-hollow aluminosilicate), may be a hollow inorganic filler with a porosity of more than 0 volume % (preferably hollow silica, hollow aluminosilicate), or may contain both. From the viewpoint of lowering the dielectric constant, the (D) inorganic filler preferably contains only a hollow inorganic filler (preferably hollow silica, hollow aluminosilicate), or contains both a non-hollow inorganic filler (preferably non-hollow silica, non-hollow aluminosilicate) and a hollow inorganic filler (preferably hollow silica, hollow aluminosilicate). The porosity of the hollow inorganic filler is preferably 90 volume % or less, more preferably 85 volume % or less. (D) The lower limit of the porosity of the inorganic filler is not particularly limited, but may be, for example, more than 0 volume %, 1 volume % or more, 5 volume % or more, 10 volume % or more, 20 volume % or more, 30 volume % or more, etc. The porosity P (volume %) of the inorganic filler is defined as the volume-based ratio of the total volume of one or more voids present inside the particle to the total volume of the particle based on the outer surface of the particle (total volume of voids / volume of particle), and is, for example, the measured value D of the actual density of the inorganic filler. M (g / cm 3 ), and the theoretical value of the material density of the material forming the inorganic filler D T (g / cm 3 ) is used to calculate according to the following formula (I).

[0089]

number

[0090] The actual density of the inorganic filler can be measured, for example, by using a true density measuring device. Examples of the true density measuring device include ULTRAPYCNOMETER 1000 manufactured by QUANTACHROME Co., Ltd. As the measurement gas, for example, nitrogen is used.

[0091] The inorganic filler (D) is preferably surface-treated with an appropriate surface treatment agent, which can enhance the moisture resistance and dispersibility of the inorganic filler (D). Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; methacryl-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, and N-2-(aminoethyl)-3-aminopropyltriethoxysilane; Amino-based silane coupling agents such as trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris-(trimethoxysilylpropyl)isocyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; and other silane coupling agents;Examples of the surface treatment agent include alkylalkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and trifluoropropyltrimethoxysilane. The surface treatment agent may be used alone or in combination of two or more in any ratio.

[0092] Commercially available surface treatment agents include, for example, "KBM-1003" and "KBE-1003" (vinyl-based silane coupling agents), "KBM-303", "KBM-402", "KBM-403", "KBE-402", and "KBE-403" (epoxy-based silane coupling agents), "KBM-1403" (styryl-based silane coupling agents), "KBM-502", "KBM-503", "KBE-502", and "KBE-503" (methacrylic-based silane coupling agents), "KBM-5103" (acrylic-based silane coupling agents), "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", and "KBM-575" (amino-based silane coupling agents), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (ureido-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-based 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" (alkylalkoxysilane compound), and the like.

[0093] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably 0.2% to 3% by mass, and even more preferably 0.3% to 2% by mass.

[0094] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 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 more preferable that the content is 1.0 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0095] (D) 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 (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant 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 the carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0096] The content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100 mass%, it may be preferably 90 mass% or less, more preferably 85 mass% or less, even more preferably 80 mass% or less, and particularly preferably 75 mass% or less. The lower limit of the content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100 mass%, it may be, for example, 0 mass% or more, 1 mass% or more, etc., preferably 10 mass% or more, more preferably 20 mass% or more, even more preferably 30 mass% or more, even more preferably 40 mass% or more, and particularly preferably 50 mass% or more.

[0097] The mass ratio of the specific maleimide compound (A) to the inorganic filler (D) in the resin composition (component (A) / component (D)) is preferably 0.01 or more, more preferably 0.05 or more, and particularly preferably 0.1 or more. The upper limit of the mass ratio of the specific maleimide compound (A) to the inorganic filler (D) in the resin composition (component (A) / component (D)) is preferably 1 or less, more preferably 0.5 or less, and particularly preferably 0.3 or less.

[0098] <(E) Curing accelerator> The resin composition of the present invention may contain an optional curing accelerator (E). The curing accelerator (E) has the function of accelerating the curing of the epoxy resin (C).

[0099] Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among them, imidazole-based curing accelerators are preferred from the viewpoint of improving crosslinking properties. (E) The curing accelerator may be used alone or in combination of two or more.

[0100] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium acetate, tetrabutyl phosphonium decanoate, tetrabutyl phosphonium laurate, bis(tetrabutyl phosphonium)pyromellitate, tetrabutyl phosphonium hydrogenhexahydrophthalate, tetrabutyl phosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butyldimethylphosphonium tetraphenylborate; methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, tetraphenyl phosphonium bromide, p-tolyl triphenyl phosphonium tetra-p-tolylborate, tetraphenyl phosphonium bromide, and the like. aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine Examples of aromatic phosphines include tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0101] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as butylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0102] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0103] Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-methylimidazole. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct imidazole compounds such as 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds and epoxy resins.

[0104] As the imidazole-based curing accelerator, commercially available products may be used, for example, "1B2PZ", "2MZA-PW", and "2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0105] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0106] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0107] As the amine-based curing accelerator, a commercially available product may be used, for example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0108] The content of the (E) curing accelerator in the resin composition is not particularly limited, but is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 1% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. The lower limit of the content of the (E) curing accelerator in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

[0109] <(F) Polyimide resin> The resin composition of the present invention may contain a polyimide resin (F) as an optional component. The polyimide resin (F) is a resin having an imide bond in a repeating unit. The polyimide resin (F) also includes modified polyimide resins such as siloxane-modified polyimide resins.

[0110] In one embodiment, the (F) polyimide resin preferably includes an aromatic polyimide resin that does not have an aliphatic chain in the main chain.

[0111] In one embodiment, the (F) polyimide resin is more preferably represented by the formula (F1):

[0112] [ka]

[0113] [In the formula, X 1 , Y 1 and Y 2 are each independently a single bond, -CR 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-; R each independently represents a hydrogen atom or an alkyl group; Ring X a , Ring X b , and ring Y a each independently represents an aromatic ring which may have a substituent; R y1 each independently represents a substituent; Each y1 independently represents 0, 1, 2, or 3; xa and ya each independently represent 0, 1, 2, 3, 4, or 5; yb represents 0 or 1. The xa units may be the same or different for each unit. The ya units may be the same or different for each unit.

[0114] X 1, Y 1 and Y 2 are each independently a single bond, -CR 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-; preferably -CR 2 -, -O-, or -CO-; more preferably -CR 2 -, or -O-.

[0115] R each independently represents a hydrogen atom or an alkyl group; preferably a hydrogen atom or a methyl group; and more preferably a methyl group.

[0116] Ring X a , Ring X b , and ring Y a each independently represents an aromatic ring which may have a substituent; preferably a benzene ring which may be substituted with a group selected from an alkyl group, an alkenyl group, and an aryl group, or a naphthalene ring which may be substituted with a group selected from an alkyl group, an alkenyl group, and an aryl group; more preferably a benzene ring which may be substituted with a group selected from an alkyl group, an alkenyl group, and an aryl group; even more preferably a benzene ring which may be substituted with an alkyl group; and particularly preferably an (unsubstituted) benzene ring.

[0117] R y1 each independently represents a substituent; preferably an alkyl group, an alkenyl group, or an aryl group; more preferably an alkyl group.

[0118] Each y1 independently represents 0, 1, 2 or 3; preferably 0, 1 or 2; more preferably 0 or 1; particularly preferably 0. xa represents 0, 1, 2, 3, 4 or 5; preferably 1, 2, 3, 4 or 5; more preferably 2, 3, 4 or 5; even more preferably 3, 4 or 5; particularly preferably 4. ya represents 0, 1, 2, 3, 4 or 5; preferably 0, 1, 2, 3 or 4; more preferably 0, 1, 2 or 3; even more preferably 1, 2 or 3; particularly preferably 2. yb represents 0 or 1; preferably 1.

[0119] The structural unit represented by formula (F1) contains the formula (Fx):

[0120] [ka]

[0121] [wherein * indicates a binding site; other symbols are as defined above.] Specific examples of the partial structure represented by the formulae (Fx-1) to (Fx-24):

[0122] [ka]

[0123] [In the formula, * is the same as above.] Examples of the partial structure include those represented by any one of the following:

[0124] The structural unit represented by formula (F1) contains the formula (Fy):

[0125] [ka]

[0126] [wherein * indicates a binding site; other symbols are as defined above.] Specific examples of the partial structure represented by the formulae (Fy-1) to (Fy-25):

[0127] [ka]

[0128] [In the formula, * is the same as above.] Examples of the partial structure include those represented by any one of the following:

[0129] In one embodiment, the polyimide resin (F) is more preferably represented by the formulas (F2-1) to (F2-4):

[0130] [ka]

[0131] [In the formula, X 11 , X 12 , X 13 , X 14 , Y 11 , Y 12 and Y 2 are each independently a 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 represents an aromatic ring which may have a substituent; Other symbols are as above.] In particular, it is preferable that the resin contains a repeating unit represented by formula (F2-1).

[0132] X 11 , X 12 , X 13 and X14 are each independently a single bond, -CR 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-; preferably -CR 2 -, -O-, or -CO-; more preferably -CR 2 - or -O-; more preferably, X 11 and X 14 is -O- and X 12 and X 13 -CR 2 -It is. Y 11 , Y 12 and Y 2 are each independently a single bond, -CR 2 -, -O-, -CO-, -S-, -SO-, -SO 2 -, -CONH-, or -NHCO-; preferably -CR 2 -, -O-, or -CO-; more preferably -CR 2 - or -O-; more preferably, Y 11 and Y 2 is -O- and Y 12 -CR 2 -It is.

[0133] Ring X a1 , Ring X a2 , Ring X a3 , Ring X a4 , Ring X b , ring Y a1 and ring Y a2 each independently represents an aromatic ring which may have a substituent; preferably a benzene ring which may be substituted with a group selected from an alkyl group, an alkenyl group, and an aryl group, or a naphthalene ring which may be substituted with a group selected from an alkyl group, an alkenyl group, and an aryl group; more preferably a benzene ring which may be substituted with a group selected from an alkyl group, an alkenyl group, and an aryl group; even more preferably a benzene ring which may be substituted with an alkyl group; and particularly preferably an (unsubstituted) benzene ring.

[0134] In one embodiment, the (F) polyimide resin is more preferably represented by the formula (F3):

[0135] [ka]

[0136] [In the formula, R x1 and R y2 each independently represents a substituent; x1 and y2 each independently represent 0, 1, 2, 3, or 4; Other symbols are as above.] The resin includes a resin having a repeating unit represented by the formula:

[0137] R x1 and R y2 each independently represents a substituent; preferably an alkyl group, an alkenyl group, or an aryl group; more preferably an alkyl group.

[0138] x1 and y2 each independently represent 0, 1, 2, 3, or 4; preferably represent 0, 1, 2, or 3; more preferably represent 0, 1, or 2; further preferably represent 0 or 1; and particularly preferably represent 0.

[0139] The polyimide resin (F) is not particularly limited, and can be obtained by a known synthesis method such as an imidization reaction between a diamine compound and a tetracarboxylic anhydride, an imidization reaction between a diisocyanate compound and a tetracarboxylic anhydride, etc. Commercially available polyimide resins (F) may be used, and examples of commercially available polyimide resins (F) include "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

[0140] The weight average molecular weight of the polyimide resin (F) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, even more preferably 3000 or more, and particularly preferably 4000 or more. The upper limit of the weight average molecular weight of the polyimide resin (F) is not particularly limited, but is preferably 200000 or less, more preferably 150000 or less, particularly preferably 100000 or less, and particularly preferably 75000 or less. The weight average molecular weight here may be a value measured by gel permeation chromatography (GPC) method (polystyrene equivalent).

[0141] The glass transition temperature of the (F) polyimide resin is not particularly limited, but is preferably 50°C to 400°C, more preferably 75°C to 350°C, further preferably 100°C to 300°C, and particularly preferably 125°C to 250°C.

[0142] The content of the polyimide resin (F) in the resin composition is not particularly limited, but is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 1% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass. The lower limit of the content of the polyimide resin (F) in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0143] <(G) Other Additives> The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; and benzotriazole-based ultraviolet absorbing agents. antioxidants such as hindered phenol antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. The (G) other additives may be used alone or in any combination of two or more kinds at any ratio. The content of the (G) other additives can be appropriately determined by a person skilled in the art.

[0144] <(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 non-volatile components described above. As the (H) organic solvent, a known one can be appropriately used, and the type is not particularly limited. As the (H) organic solvent, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole, etc.; alcohol-based solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methoxypropionic acid, etc. Examples of suitable organic solvents include ether ester solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butylcarbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (H) The organic solvent may be used alone or in combination of two or more in any ratio.

[0145] In one embodiment, the content of the (H) organic solvent is not particularly limited, but when all components in the resin composition are taken as 100 mass%, it can be, for example, 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, etc.

[0146] <Method of producing resin composition> The resin composition of the present invention can be produced, for example, by adding (A) a specific maleimide compound, (B) an active ester compound, (C) an epoxy resin, if necessary (A') other maleimide compounds, if necessary (B') other curing agents, if necessary (D) an inorganic filler, if necessary (E) a curing accelerator, if necessary (F) a polyimide resin, if necessary (G) other additives, and if necessary (H) an organic solvent in any order and / or all at once and mixing them in any preparation vessel. In addition, the temperature can be appropriately set during the process of adding and mixing each component, and heating and / or cooling may be performed temporarily or throughout. In addition, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to disperse uniformly. In addition, degassing may be performed under low pressure conditions such as under vacuum at the same time as stirring or shaking.

[0147] <Characteristics of resin composition> The resin composition of the present invention contains (A) a specific maleimide compound, (B) an active ester compound, and (C) an epoxy resin. By using such a resin composition, it is possible to further reduce the minimum melt viscosity, and to obtain a cured product having a low relative dielectric constant (Dk) and dielectric loss tangent (Df), a high glass transition point (Tg), and excellent copper plating peel strength.

[0148] The cured product of the resin composition of the present invention may be characterized by a high glass transition temperature (Tg). Thus, in one embodiment, the glass transition temperature (Tg) measured as in Test Example 4 below may be preferably 110° C. or higher, more preferably 130° C. or higher, even more preferably 140° C. or higher, and particularly preferably 150° C. or higher.

[0149] The cured product of the resin composition of the present invention may be characterized by excellent copper plating peel strength. Thus, in one embodiment, as in the following Test Example 2, a copper plating conductor layer is formed on the cured product, and the copper plating peel strength calculated from the load when the copper plating conductor layer is peeled off in the vertical direction may be preferably 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, even more preferably 0.4 kgf / cm or more, particularly preferably 0.45 kgf / cm or more, 0.5 kgf / cm or more. The upper limit is not particularly limited, but may be, for example, 10 kgf / cm or less.

[0150] The cured product of the resin composition of the present invention may be characterized by a low dielectric loss tangent (Df). Thus, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition, as measured at 5.8 GHz and 23° C. as in Test Example 1 below, may be preferably 0.020 or less, 0.010 or less, more preferably 0.009 or less, 0.008 or less, even more preferably 0.007 or less, 0.006 or less, and particularly preferably 0.005 or less, 0.0045 or less, 0.004 or less.

[0151] The cured product of the resin composition of the present invention may be characterized by a low dielectric constant (Dk). Thus, in one embodiment, the dielectric constant (Dk) of the cured product of the resin composition, as measured at 5.8 GHz and 23° C. as in the following Test Example 1, is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.5 or less, particularly preferably 3.2 or less, and may be 3.0 or less.

[0152] The resin composition of the present invention may be characterized by a low minimum melt viscosity. Thus, in one embodiment, the minimum melt viscosity measured using a dynamic viscoelasticity measuring device at a frequency of 1 Hz, a strain of 5 degrees, a load of 100 g, a heating rate of 5°C / min, and a temperature range of 60°C to 180°C as in Test Example 5 below may be preferably 4000 poise or less, 3000 poise or less, more preferably 2000 poise or less, 1700 poise or less, further preferably 1500 poise or less, 1300 poise or less, and particularly preferably 1100 poise or less.

[0153] In one embodiment, the cured product of the resin composition of the present invention may be characterized by a low arithmetic mean roughness (Ra) of the surface after roughening treatment. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the cured product surface after roughening treatment measured as in the following Test Example 3 may be preferably 300 nm or less, more preferably 200 nm or less, even more preferably 150 nm or less, even more preferably 100 nm or less, and particularly preferably 70 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, etc.

[0154] <Applications of resin composition> The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on an insulating layer. In addition, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can also be used in a wide range of applications requiring a resin composition, such as a resin sheet, a sheet-like laminate material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin.

[0155] In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer (resin composition for forming a rewiring formation layer) as an insulating layer for forming a rewiring layer, and as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer. (1) A step of laminating a temporary fixing film onto a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A process of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0156] Furthermore, the resin composition of the present invention provides an insulating layer with good component embedding properties, and therefore can be suitably used when the printed wiring board is a circuit board with built-in components.

[0157] <Sheet-type laminated material> The resin composition of the present invention can be used by coating in the form of a varnish, but from an industrial perspective, it is generally preferred to use the resin composition in the form of a sheet-like laminate material containing the resin composition.

[0158] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0159] In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

[0160] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of making the printed wiring board thinner and being able to provide a cured product with excellent insulation even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

[0161] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0162] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0163] When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0164] The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0165] In addition, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by Unitika Limited, which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0166] 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. When a support with a release layer is used, it is preferable that the total thickness of the support with a release layer is in the above range.

[0167] In one embodiment, the resin sheet may further include an optional layer as necessary. For example, such an optional layer may be a protective film equivalent to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dirt and the like to the surface of the resin composition layer and scratches can be suppressed.

[0168] The resin sheet can be produced, for example, by preparing a liquid resin composition as is or a resin varnish by dissolving the resin composition in an organic solvent, applying this onto a support using a die coater or the like, and then drying to form a resin composition layer.

[0169] The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of two or more kinds.

[0170] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0171] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0172] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0173] The sheet-like fiber substrate used for the prepreg is not particularly limited, and can be a substrate commonly used for prepreg, such as glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, etc. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited. It is usually 10 μm or more.

[0174] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0175] The thickness of the prepreg may be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

[0176] The sheet-like laminate material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

[0177] <Printed wiring board> The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

[0178] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate such that a resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., heat curing) the resin composition layer to form an insulating layer.

[0179] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be called an "inner layer circuit substrate". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be formed during the manufacture of a printed wiring board is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0180] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). It is preferable to press the thermocompression member not directly onto the resin sheet, but via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

[0181] The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination may be performed under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0182] The lamination can be performed by a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch type vacuum pressure laminator.

[0183] After lamination, the laminated resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. The lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0184] The support may be removed between step (I) and step (II) or after step (II).

[0185] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions that are usually adopted when forming an insulating layer for a printed wiring board may be used.

[0186] For example, the thermal curing conditions for 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., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0187] Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50° C. to 120° C., preferably 60° C. to 115° C., more preferably 70° C. to 110° C. for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0188] In manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0189] In another embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when a resin sheet is used.

[0190] Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined depending on the design of the printed wiring board.

[0191] Step (IV) is a step of roughening the insulating layer. Usually, smears are also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by carrying out a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0192] The swelling liquid used in the roughening treatment is not particularly limited, but includes an alkaline solution, a surfactant solution, etc., and is preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes, for example. 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 to 15 minutes.

[0193] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate 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. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan.

[0194] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be mentioned.

[0195] The treatment with the neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0196] In one embodiment, the root mean square roughness (Rq) of the insulating layer surface after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, etc. The root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0197] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals 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, and examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0198] The conductor layer may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a 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 a nickel-chromium alloy.

[0199] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

[0200] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of ease of production, it is preferable to form the conductor layer by the semi-additive method. An example of forming the conductor layer by the semi-additive method will be described below.

[0201] First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0202] In another embodiment, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, it is preferable to carry out step (V) between steps (I) and (II). For example, after step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method, using the metal foil on the insulating layer.

[0203] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0204] <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 by using the printed wiring board of the present invention.

[0205] Examples of the semiconductor device include various semiconductor devices used in electric appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). EXAMPLES

[0206] The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Unless otherwise specified, the temperature and pressure conditions are room temperature (23°C) and atmospheric pressure (1 atm).

[0207] <Synthesis Example 1: Polyimide resin 1> A monomer composition was obtained by mixing 49.6g of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 50.4g of 4,4'-[1,4-phenylenebis[(1-methylethylidene)-4,1-phenyleneoxy]]bisbenzenamine (BPPAN), and 40g of toluene as a solvent in 400g of N,N-dimethylacetamide, and the mixture was stirred and reacted at room temperature and atmospheric pressure for 3 hours. As a result, a polyamic acid solution was obtained.

[0208] Subsequently, the polyamic acid solution was heated, and the temperature was kept at about 160°C, and the condensed water was removed azeotropically with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the water content receiver, and that no water was flowing out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. Then, it was cooled. As a result, a varnish containing 20% ​​by mass of polyimide resin 1 (a polyimide resin having a repeating unit represented by the following formula (F)) as a non-volatile component was obtained. The glass transition temperature Tg of polyimide resin 1 was measured according to the above-mentioned method, and was found to be 210°C.

[0209] [ka]

[0210] <Example 1> The mixture consisted of 23 parts of an isopropylidene group-containing maleimide compound ("MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd., a toluene solution containing 60% by mass of non-volatile components, main component (non-volatile component): a maleimide compound represented by the following formula (A)), 10 parts of a liquid naphthalene skeleton-containing epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, epoxy equivalent 144 g / eq.), 30 parts of an active ester curing agent containing a dicyclopentadiene-type diphenol structure ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution containing 65% by mass of non-volatile components, active ester group equivalent 223 g / eq.), and 10 parts of an inorganic filler (spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). 2 80 parts of the hydroxyethyl ether (1 / g)) and 0.5 parts of a curing accelerator (imidazole compound "1B2PZ" manufactured by Shikoku Kasei Corporation) were mixed and uniformly dispersed using a high-speed rotating mixer to obtain a resin composition (resin varnish).

[0211] [ka]

[0212] <Example 2> A resin composition (resin varnish) was obtained in the same manner as in Example 1, except that 30 parts of an active ester compound containing a naphthalene structure ("HPC-8150-62T" manufactured by DIC Corporation, a toluene solution containing 62% by mass of non-volatile components, active ester group equivalent weight of 229 g / eq.) was used instead of an active ester curing agent containing a dicyclopentadiene-type diphenol structure ("HPC-8000-65T" manufactured by DIC Corporation).

[0213] <Example 3> A resin composition (resin varnish) was obtained in the same manner as in Example 1, except that the amount of the isopropylidene group-containing maleimide compound ("MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.) was changed from 23 parts to 18 parts, and 30 parts of an active ester compound containing a naphthalene structure ("HPC-8150-62T" manufactured by DIC Corporation, a toluene solution with a non-volatile content of 62% by mass, active ester group equivalent of 229 g / eq.) was used in place of an active ester curing agent containing a dicyclopentadiene type diphenol structure ("HPC-8000-65T" manufactured by DIC Corporation), and 5 parts of a biphenylaralkyl type maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution with a non-volatile content of 70%) was used.

[0214] <Example 4> A resin composition (resin varnish) was obtained in the same manner as in Example 1, except that the amount of the isopropylidene group-containing maleimide compound ("MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.) was changed from 23 parts to 21 parts, and 30 parts of an active ester compound containing a naphthalene structure ("HPC-8150-62T" manufactured by DIC Corporation, a toluene solution containing 62% by mass of non-volatile components, active ester group equivalent of 229 g / eq.) was used in place of an active ester curing agent containing a dicyclopentadiene-type diphenol structure ("HPC-8000-65T" manufactured by DIC Corporation), and 2 parts of a liquid aliphatic maleimide compound ("BMI-1500" manufactured by Designer Molecules, Inc.) were used.

[0215] <Example 5> A resin composition (resin varnish) was obtained in the same manner as in Example 1, except that 25 parts of an active ester compound containing a naphthalene structure (DIC Corporation's "HPC-8150-62T", a toluene solution containing 62% by mass of non-volatile components, active ester group equivalent of 229 g / eq.) was used instead of an active ester curing agent containing a dicyclopentadiene type diphenol structure (DIC Corporation's "HPC-8000-65T"), the amount of the curing accelerator (Shikoku Kasei Corporation's imidazole compound "1B2PZ") was changed from 0.5 parts to 0.1 parts, and 5 parts of a triazine skeleton-containing cresol novolac-based curing agent (DIC Corporation's "LA-3018-50P", hydroxyl group equivalent: about 151, 2-methoxypropanol solution containing 50% non-volatile components) was used.

[0216] <Example 6> A resin composition (resin varnish) was obtained in the same manner as in Example 5, except that 2 parts of the polyimide resin 1 obtained in Synthesis Example 1 was added.

[0217] <Example 7> A resin composition (resin varnish) was obtained in the same manner as in Example 5, except that the amount of "SO-C2" manufactured by Admatechs was changed from 80 parts to 60 parts, and 20 parts of an inorganic filler having hollow portions (spherical silica having hollow portions ("BA-S" manufactured by JGC Catalysts and Chemicals, average particle size 2.6 μm) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) were used instead.

[0218] <Comparative Example 1> A resin composition (resin varnish) was obtained in the same manner as in Example 1, except that no isopropylidene group-containing maleimide compound ("MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.) was used, and instead of an active ester curing agent containing a dicyclopentadiene-type diphenol structure ("HPC-8000-65T" manufactured by DIC Corporation), 30 parts of an active ester compound containing a naphthalene structure ("HPC-8150-62T" manufactured by DIC Corporation, a toluene solution containing 62% by mass of non-volatile components, active ester group equivalent of 229 g / eq.) was used, and the amount of inorganic filler used was changed from 80 parts to 55 parts.

[0219] <Comparative Example 2> A resin composition (resin varnish) was obtained in the same manner as in Example 1, except that 20 parts of a biphenylaralkyl-type maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq., MEK / toluene mixed solution with 70% non-volatile content) was used instead of an isopropylidene-type maleimide compound ("MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.), and 30 parts of an active ester compound containing a naphthalene structure ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with 62% non-volatile content by mass, active ester group equivalent 229 g / eq.) was used instead of an active ester curing agent containing a dicyclopentadiene-type diphenol structure ("HPC-8000-65T" manufactured by DIC Corporation).

[0220] <Comparative Example 3> A resin composition (resin varnish) was obtained in the same manner as in Example 1, except that 14 parts of a liquid aliphatic maleimide compound (Designer Molecules' "BMI-1500", maleimide group equivalent 750 g / eq.) was used instead of an isopropylidene group-containing maleimide compound (Nippon Kayaku's "MIR-5000-60T"), and 30 parts of an active ester compound containing a naphthalene structure (DIC's "HPC-8150-62T", toluene solution with 62% by mass of non-volatile components, active ester group equivalent 229 g / eq.) was used instead of an active ester curing agent containing a dicyclopentadiene type diphenol structure (DIC's "HPC-8000-65T").

[0221] <Test Example 1: Measurement of relative dielectric constant (Dk) and dielectric loss tangent (Df)> A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. On the release layer of this support, the resin compositions (resin varnishes) obtained in the examples and comparative examples were uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin compositions were dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet including a support and a resin composition layer.

[0222] The obtained resin sheet was heated at 190°C for 90 minutes to heat-cure the resin composition layer. The support was then peeled off to obtain a cured product of the resin composition. This cured product was cut into a test piece having a width of 2 mm and a length of 80 mm. The relative dielectric constant (Dk) and dielectric loss tangent (Df) of the test piece were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by a cavity resonance perturbation method using an Agilent Technologies "HP8362B". Measurements were performed on three test pieces, and the average values ​​are shown in Table 1 below.

[0223] <Test Example 2: Measurement of copper plating peel strength> (1) Surface preparation for inner layer circuit boards A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, board thickness 0.4 mm, Panasonic "R1515A") with inner layer circuits (copper foil) on both sides was prepared as an inner layer circuit board. Both sides of this inner layer circuit board were etched by 1 μm using MEC's ​​"CZ8101" to roughen the copper surface.

[0224] (2) Lamination of resin sheet The resin sheet obtained in Test Example 1 was laminated on both sides of the inner layer circuit board using a batch type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator, CVP700). This lamination was performed so that the resin composition layer of the resin sheet was in contact with the inner layer circuit board. This lamination was also performed by reducing the pressure for 30 seconds to 13 hPa or less, and pressing at 130°C and a pressure of 0.74 MPa for 45 seconds. Next, a heat press was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

[0225] (3) Curing of the resin composition The laminated resin sheet and the 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 and form an insulating layer. The support was then peeled off to obtain a laminated substrate having an insulating layer, an inner layer circuit board, and an insulating layer in this order.

[0226] (4) Roughening treatment The laminated substrate was immersed in a swelling solution (a swelling dip containing diethylene glycol monobutyl ether, Securigant P (aqueous solution of glycol ethers and sodium hydroxide), manufactured by Atotech Japan) at 60°C for 10 minutes. Next, the laminated substrate was immersed in a roughening solution (Concentrate Compact P (KMnO 4 The laminated substrate was then immersed in a neutralizing solution (Reduction Shoreucin Securigant P (aqueous sulfuric acid solution) manufactured by Atotech Japan) at 40°C for 5 minutes. The laminated substrate was then dried at 80°C for 30 minutes to obtain "Evaluation Substrate A."

[0227] (5) Semi-additive plating: Evaluation substrate A was prepared by 2 The substrate was immersed in an electroless plating solution containing the compound at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. After that, the substrate was heated at 150°C for 30 minutes and annealed. After that, an etching resist was formed, and a pattern was formed by etching. After that, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 μm. Next, an annealing treatment was performed at 190°C for 60 minutes, and "Evaluation Substrate B" was obtained.

[0228] (6) Measurement of copper plating peel strength A cut was made in the conductor layer of evaluation board B to surround a rectangular portion 10 mm wide and 100 mm long. One end of the rectangular portion was peeled off and held with a gripper (Autocom type testing machine "AC-50C-SL" manufactured by TSE Corporation). The rectangular portion was peeled off vertically at room temperature with the gripper at a speed of 50 mm / min, and the load (kgf / cm) when 35 mm had been peeled off was measured as the copper plating peel strength, and is shown in Table 1 below.

[0229] <Test Example 3: Measurement of surface roughness Ra> The arithmetic mean roughness Ra of the surface of the insulating layer of the evaluation 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 B-CO Instruments) in VSI mode with a 50x lens, with a measurement range of 121 μm × 92 μm. This measurement was performed at 10 measurement points, and the average values ​​are shown in Table 1 below.

[0230] <Test Example 4: Measurement of glass transition temperature Tg> The resin sheet obtained in Test Example 1 was heated in an oven at 190° C. for 90 minutes to cure the resin composition layer. The support was then peeled off to obtain a cured product of the resin composition layer. This cured product was cut into a length of 20 mm and a width of 6 mm to obtain a cured product for evaluation.

[0231] A first TMA curve was obtained for this cured product for evaluation using a Rigaku thermomechanical analyzer (TMA) at a temperature rise rate of 5°C / min from 25°C to 250°C using the tensile load method. The same measurements were then performed on the same cured product for evaluation to obtain a second TMA curve. The glass transition temperature Tg (°C) was calculated from the second TMA curve and is shown in Table 1 below.

[0232] <Test Example 5: Measurement of minimum melt viscosity> The resin sheet obtained in Test Example 1 was peeled off from the support film and measured using a dynamic viscoelasticity measuring device G-3000 manufactured by UBM at a frequency of 1 Hz, a strain of 5 degrees, a load of 100 g, a heating rate of 5°C / min, and a temperature range of 60°C to 180°C.

[0233] The amounts of raw materials used and the non-volatile component contents of the resin compositions of the Examples and Comparative Examples, as well as the measurement results of the Test Examples, are shown in Table 1 below.

[0234] [Table 1]

[0235] Referring to Table 1, in Comparative Example 1 in which no maleimide compound was used, the relative dielectric constant (Dk) was high and the copper plating peel strength was low. In Comparative Example 3 in which a maleimide compound containing a dimer diamine skeleton was used as the maleimide compound, the glass transition temperature (Tg) was low. In Comparative Example 2 in which an aromatic polymaleimide compound having no isopropylidene group was used as the maleimide compound, the minimum melt viscosity and the dielectric loss tangent (Df) were high. In contrast, it can be seen that these problems can be overcome when the resin composition of the present invention containing (A) a specific maleimide compound, (B) an active ester compound, and (C) an epoxy resin is used.

[0236] This application is based on patent application No. 2020-189015 (filed on November 12, 2020) filed with the Japan Patent Office, the contents of which are incorporated in their entirety herein.

Claims

1. (A) a maleimide compound having an isopropylidene group bonded to two aromatic carbon atoms of different aromatic rings, (B) an active ester compound, (C) an epoxy resin, and (D) an inorganic filler, The content of the (D) component is 30% by mass or more, based on 100% by mass of the non-volatile components in the resin composition; The component (A) is represented by the formula (A-1): 【Chemistry 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; x represents 0, and y each independently represents 0, 1, 2, or 3.] A resin composition comprising a maleimide compound represented by the formula:

2. The resin composition according to claim 1, wherein a is an integer from 2 to 10.

3. 3. The resin composition according to claim 1, wherein the content of the component (A) is 3% by mass to 30% by mass, based on 100% by mass of non-volatile components in the resin composition.

4. The resin composition according to any one of claims 1 to 3, wherein the content of the component (B) is 3% by mass to 30% by mass, based on 100% by mass of non-volatile components in the resin composition.

5. The resin composition according to any one of claims 1 to 4, wherein a mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 0.5 to 2.

6. The resin composition according to any one of claims 1 to 5, wherein the content of the component (C) is 1% by mass to 30% by mass, based on 100% by mass of non-volatile components in the resin composition.

7. The resin composition according to any one of claims 1 to 6, wherein a mass ratio of the component (A) to the component (C) (component (A) / component (C)) is 0.5 to 3.

8. The resin composition according to any one of claims 1 to 7, wherein the content of the component (D) is 40 mass% or more, based on 100 mass% of non-volatile components in the resin composition.

9. The resin composition according to any one of claims 1 to 8, wherein the dielectric loss tangent (Df) of a cured product of the resin composition is 0.0045 or less when measured at 5.8 GHz and 23°C.

10. The resin composition according to any one of claims 1 to 9, wherein the cured product of the resin composition has a dielectric constant (Dk) of 3.5 or less when measured at 5.8 GHz and 23°C.

11. The resin composition according to any one of claims 1 to 10, wherein the glass transition temperature (Tg) of a cured product of the resin composition is 140°C or higher.

12. A cured product of the resin composition according to any one of claims 1 to 11.

13. A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 11.

14. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 11 provided on the support.

15. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 11.

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

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