JP7318586B2 - resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition containing a maleimide compound. Furthermore, it relates to a cured product, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

2. Description of the Related Art As a technique for manufacturing printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition.

2. Description of the Related Art In recent years, as the frequency of signals has increased due to the miniaturization and performance enhancement of electronic devices, there has been a demand for a low dielectric constant and a low dielectric loss tangent for insulating layers of multilayer printed wiring boards. In addition, an insulating layer with a smaller surface roughness is demanded in order to improve adhesion to finer and higher-density wiring.

Patent Documents 1 and 2 disclose resin compositions using various maleimide compounds.

WO2018/212116 WO2020/045489

An object of the present invention is to provide a resin composition capable of obtaining a cured product having a small arithmetic mean roughness (Ra) and a low dielectric constant (Dk) and dielectric loss tangent (Df).

In order to achieve the object of the present invention, the present inventors conducted intensive studies and found that the use of a specific maleimide compound as a component of the resin composition unexpectedly reduces the arithmetic mean roughness (Ra), In addition, the inventors have found that a cured product having a low dielectric constant (Dk) and low dielectric loss tangent (Df) can be obtained, and have completed the present invention.

That is, the present invention includes the following contents.
[1] (A) Formula (1):

[Wherein, X ¹ is a single bond, -C(R ¹⁰ ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, - COO- or -OCO-; R ¹⁰ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group; R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ , and R ²⁴ , at least one of which is each independently an alkyl group, alkenyl group, aryl-alkyl group, or aryl group, and the others are hydrogen Atoms are indicated; and * indicates the binding site. ]
and a divalent group represented by Formula (2):

[wherein R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group or an aryl group; ]
and/or a divalent group represented by Formula (3):

[In the formula, R ⁴¹ and R ⁴² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group; and * represents a binding site. ]
A resin composition containing a maleimide compound containing a divalent group represented by in one molecule, (B) an epoxy resin, and (C) an inorganic filler,
A resin composition in which the content of the component (C) exceeds 30% by mass when the non-volatile component in the resin composition is taken as 100% by mass.
[2] X ¹ is —C(R ¹⁰ ) ₂ —; R ¹¹ , R ¹² , R ²¹ , and R ²² are each independently an alkyl group; and R ¹⁰ , R ¹³ , R ¹⁴ , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ⁴¹ and R ⁴² are hydrogen atoms, the resin composition according to [1] above.
[3] Component (A) is further represented by formula (4):

[Wherein, X ² , X ³ and X ⁴ are each independently a single bond, -C(R ⁵⁰ ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ represents -, -CONH-, -NHCO-, -COO-, or -OCO-; ^R50 , ^R51 , ^R52 , ^R53 , R54, ^R61 , ^R62 , ^R63 , ^R64 , ^{R 71} , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁸¹ , R ⁸² , R ⁸³ , and R ⁸⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group; and * indicates the binding site. ]
The resin composition according to [1] or [2] above, which contains a divalent group represented by in one molecule.
[4] X ² and X ⁴ are —O—; X ³ is —C ⁽ R ⁵⁰ ) ₂ —; R ⁵⁰ is each independently an alkyl group; R ⁵² , R ⁵³ , R ⁵⁴ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ are hydrogen atoms; The resin composition according to [3] above.
[5] Any one of [1] to [4] above, wherein the content of component (A) is 1% by mass to 40% by mass when the non-volatile component in the resin composition is 100% by mass. of the resin composition.
[6] The resin composition according to any one of [1] to [5] above, further comprising (A') a radically polymerizable compound other than component (A).
[7] The resin composition according to any one of [1] to [6] above, wherein component (B) contains (B-1) a condensed ring structure-containing epoxy resin.
[8] The resin composition according to [7] above, wherein the component (B-1) contains a naphthol aralkyl epoxy resin.
[9] Any one of the above [1] to [8], wherein the content of the component (B) is 1% by mass to 50% by mass when the non-volatile component in the resin composition is 100% by mass. of the resin composition.
[10] The mass ratio of component (A) to component (B) (component (A)/component (B)) according to any one of [1] to [9] above, wherein the mass ratio is 0.3 to 3. Resin composition.
[11] The resin composition according to any one of [1] to [10] above, wherein the content of component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. thing.
[12] Any of the above [1] to [11], wherein the mass ratio of component (A) to component (C) (component (A)/component (C)) is 0.05 to 0.5 The described resin composition.
[13] The resin composition according to any one of [1] to [12] above, further comprising (D) an active ester compound.
[14] The resin composition according to any one of [1] to [13] above, wherein the cured product of the resin composition has a dielectric loss tangent of 0.005 or less when measured at 5.8 GHz and 23°C.
[15] The resin composition according to any one of [1] to [14] above, wherein the cured product of the resin composition has a dielectric constant of 3.0 or less when measured at 5.8 GHz and 23°C. .
[16] A cured product of the resin composition according to any one of [1] to [15] above.
[17] A sheet-like laminate material containing the resin composition according to any one of [1] to [15] above.
[18] A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [15] provided on the support.
[19] A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [15] above.
[20] A semiconductor device including the printed wiring board according to [19] above.

According to the resin composition of the present invention, it is possible to obtain a cured product having a small arithmetic mean roughness (Ra) and a low dielectric constant (Dk) and dielectric loss tangent (Df).

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

<Resin composition>
The resin composition of the present invention includes (A) a divalent group represented by formula (1), a divalent group represented by formula (2), and/or 2 represented by formula (3) A maleimide compound containing a functional group in one molecule, (B) an epoxy resin, and (C) an inorganic filler, and the content of component (C) is 100% by mass of non-volatile components in the resin composition. , it exceeds 30% by mass. By using such a resin composition, it is possible to obtain a cured product having a small arithmetic average roughness (Ra) and a low dielectric constant (Dk) and dielectric loss tangent (Df).

The resin composition of the present invention includes (A) a divalent group represented by formula (1), a divalent group represented by formula (2), and/or 2 represented by formula (3) In addition to the maleimide compound containing a valence group in one molecule, (B) the epoxy resin, and (C) the inorganic filler, optional components may also be included. Examples of optional components include (A') other maleimide compounds, (D) active ester compounds, (E) curing accelerators, (F) other additives, and (G) organic solvents. Each component contained in the resin composition will be described in detail below.

<(A) Specific Maleimide Compound>
The resin composition of the present invention includes (A) a divalent group represented by formula (1), a divalent group represented by formula (2), and/or 2 represented by formula (3) It contains a maleimide compound containing a valence group in one molecule (hereinafter also referred to as "specific maleimide compound"). A maleimide compound is an organic compound containing at least one maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) in the molecule. (A) The specific maleimide compound may be used singly or in combination of two or more at any ratio.

(A) Certain maleimide compounds have the formula (1):

[In the formula, * indicates a binding site, and other symbols are as described below. ]
contains a divalent group represented by in one molecule.

In formula (1), X ¹ is a single bond, -C(R ¹⁰ ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO- , -COO-, or -OCO-. X ¹ is preferably -C(R ¹⁰ ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ -; more preferably -C(R ¹⁰ ) ₂ -, or -O-; particularly preferably -C(R ¹⁰ ) ₂ -.

In formula (1), each R ¹⁰ is independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group (an alkyl group substituted at a position that can be substituted with one aryl group), or an aryl group. indicates Each R ¹⁰ is preferably independently a hydrogen atom or an alkyl group; particularly preferably a hydrogen atom.

Alkyl (group) refers to a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl (group) preferably has 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 6 or 4 to 10 carbon atoms. Alkyl (group) includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl decyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group and the like. Alkenyl (group) refers to linear, branched and/or cyclic monovalent unsaturated aliphatic hydrocarbon groups having at least one carbon-carbon double bond. Alkenyl (groups) preferably have 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, more preferably 2 to 6 or 4 to 10 carbon atoms. Examples of alkenyl (group) include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, cyclohexenyl group and the like. Aryl (group) refers to a monovalent aromatic hydrocarbon group. Aryl (groups) preferably have 6 to 14 carbon atoms. Examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group and the like.

In ^formula (1), at least 1 ( ^preferably at ^least 2, ^{more preferably at least 4} ) each independently represent an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group; and the others represent a hydrogen atom. Preferably, at least one (more preferably at least two) of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ and at least one of R ²¹ , R ²² , R ²³ and R ²⁴ (more preferably are each independently an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group; and the others are hydrogen atoms. More preferably, R ¹¹ , R ¹² , R ²¹ and R ²² are each independently an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group; and R ¹³ , R ¹⁴ , R ²³ , and R ²⁴ is a hydrogen atom. Particularly preferably, R ¹¹ , R ¹² , R ²¹ and R ²² are each independently alkyl groups; and R ¹³ , R ¹⁴ , R ²³ and R ²⁴ are hydrogen atoms.

The divalent group represented by formula (1) is particularly preferably represented by formula (1'):

[In the formula, * indicates a binding site. ]
is a divalent group represented by

(A) The specific maleimide compound further includes, in addition to the divalent group represented by formula (1), formula (2):

[In the formula, * indicates a binding site, and other symbols are as described below. ]
and/or a divalent group represented by Formula (3):

[In the formula, * indicates a binding site, and other symbols are as described below. ]
contains a divalent group represented by in one molecule. Preferably, (A) the specific maleimide compound further contains a divalent group represented by formula (2) in one molecule in addition to the divalent group represented by formula (1).

In formula (2), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group or an aryl group. R ³¹ , R ³² and R ³³ are preferably each independently a hydrogen atom or an alkyl group; particularly preferably a hydrogen atom.

In formula (3), R ⁴¹ and R ⁴² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group. R ⁴¹ and R ⁴² are preferably each independently a hydrogen atom or an alkyl group; particularly preferably a hydrogen atom.

(A) The specific maleimide compound is preferably represented by a divalent group represented by formula (1) and a divalent group represented by formula (2) and/or represented by formula (3) In addition to the divalent group, formula (4):

[In the formula, * indicates a binding site, and other symbols are as described below. ]
contains a divalent group represented by in one molecule.

In formula (4), X ² , X ³ and X ⁴ are each independently a single bond, -C(R ⁵⁰ ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO- or -OCO-. Preferably, X ² , X ³ and X ⁴ are each independently -C(R ⁵⁰ ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ - be. More preferably, X ² , X ³ and X ⁴ are each independently -C(R ⁵⁰ ) ₂ - or -O-. Particularly preferably, X ² and X ⁴ are —O—; and X ³ is —C(R ⁵⁰ ) ₂ —.

In formula (4), each R ⁵⁰ independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group. Each R ⁵⁰ is preferably each independently a hydrogen atom or an alkyl group; particularly preferably each independently an alkyl group.

In formula (4), ^R51 , ^R52 , ^R53 , ^R54 , ^R61 , ^R62 , ^R63 , ^R64 , ^R71 , ^R72 , ^R73 , ^R74 , ^R81 , ^R82 , ^R83 , and R ⁸⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group. ^R51 , ^R52 , ^R53 , ^R54 , ^R61 , R62, ^{R63 , R64 , R71} , ^R72 , R73, ^R74 , ^R81 , ^R82 , ^R83 , and ^{R84 are} Preferably, they are each independently a hydrogen atom or an alkyl group; particularly preferably a hydrogen atom.

The divalent group represented by formula (4) is particularly preferably represented by formula (4'):

[In the formula, * indicates a binding site. ]
is a divalent group represented by

In one embodiment, (A) the specific maleimide compound comprises a divalent group represented by formula (1) and a divalent group represented by formula (2), and/or It is preferably a maleimide-terminated polyimide (hereinafter also referred to as "specific maleimide-terminated polyimide") containing a divalent group in one molecule. A maleimide-terminated polyimide is a chain polyimide having maleimide groups at both ends (a chain polymer containing an imide structure in a repeating unit). It is known that a maleimide-terminated polyimide can be obtained, for example, by imidating a component containing a diamine compound, maleic anhydride, and tetracarboxylic dianhydride.

In one embodiment, (A) certain maleimide compounds preferably have the formula (A1):

[In the formula, A ¹ is each independently two or more selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (for example, 2 to 3000, 2 to 1000, 2 to 100, 2 to 50) skeleton atoms; A ² is each independently a single bond, or one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (e.g., 1 ~ 3000, 1 to 1000, 1 to 100, 1 to 50) represents a divalent organic group consisting of skeleton atoms; n1 represents an integer of 1 or more; n2 represents an integer of 0 or more one of n1′ and n2′ represents 1 and the other represents 0; m each independently represents 0 or 1; other symbols are the same as in formula (1) . ]
is a maleimide compound represented by In formula (A1) and formulas (A2) to (A5) described below, the order and arrangement of n1 units and n2 units are not particularly limited, and alternating copolymers, block copolymers, random copolymers, etc. include. In formula (A1) and formulas (A2) to (A4) described below, n1 units and n2 units may be the same or different for each unit.

A ¹ is each independently preferably represented by the following formula (Y1):

[wherein Y ¹¹ each independently represents a single bond, an alkylene group or an alkenylene group; Y ¹² each independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO-, or -OCO-; each Z ¹ independently optionally has a substituent represents a non-aromatic ring or an optionally substituted aromatic ring; a represents 0 or an integer of 1 or more (preferably 0 or an integer of 1 to 5); * represents a binding site. ]
is a divalent group represented by In addition, the a unit may be the same or different for each unit.

In the present specification, the "substituent" is not particularly limited, but examples include alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups, alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy and aryl-carbonyl-oxy groups, and where substitutable, may also include divalent substituents such as oxo groups (=O).

An alkylene group refers to a linear or branched divalent saturated aliphatic hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms. Examples of alkylene groups include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, octamethylene, nonamethylene and decamethylene groups. Group; ethylidene group (-CH(CH ₃ )-), propylidene group (-CH(CH ₂ CH ₃ )-), isopropylidene group (-C(CH ₃ ) ₂ -), ethylmethylmethylene group (-C( CH ₃ )(CH ₂ CH ₃ )—), diethylmethylene group (—C(CH ₂ CH ₃ ) ₂ —), 2-methyltetramethylene group, 2,3-dimethyltetramethylene group, 1,3-dimethyltetramethylene group methylene group, 2-methylpentamethylene group, 2,2-dimethylpentamethylene group, 2,4-dimethylpentamethylene group, 1,3,5-methylpentamethylene group, 2-methylhexamethylene group, 2,2- Branches such as dimethylhexamethylene group, 2,4-dimethylhexamethylene group, 1,3,5-trimethylhexamethylene group, 2,2,4-trimethylhexamethylene group, and 2,4,4-trimethylhexamethylene group A chain alkylene group and the like can be mentioned. An alkenylene group refers to a straight-chain or branched-chain divalent unsaturated aliphatic hydrocarbon group having at least one carbon-carbon double bond. The alkenylene group is preferably an alkenylene group having 2 to 14 carbon atoms. Examples of alkenylene groups include groups in which any carbon-carbon single bond in the alkylene group specifically exemplified is replaced with a carbon-carbon double bond.

The aromatic ring means a ring having 4n+2 electrons (n is a natural number) contained in the π-electron system on the ring and conforming to Hückel's rule, a monocyclic aromatic ring, and two or more monocyclic It includes not only condensed aromatic rings in which aromatic rings are condensed, but also condensed aromatic rings in which one or more monocyclic aromatic rings are condensed with one or more monocyclic non-aromatic rings. The aromatic ring may be carbocyclic or heterocyclic, but in one embodiment is preferably carbocyclic. Examples of aromatic rings include monocyclic aromatic rings (preferably 5- or 6-membered) such as benzene ring and pyridine ring, condensed aromatic rings (preferably 8- to 15-membered) such as indane ring, fluorene ring and naphthalene ring. etc.

A non-aromatic ring means a ring other than an aromatic ring, and includes a monocyclic non-aromatic ring and a condensed non-aromatic ring in which two or more monocyclic non-aromatic rings are condensed. The non-aromatic ring may be carbocyclic or heterocyclic, but in one embodiment is preferably carbocyclic. A non-aromatic ring may be a saturated ring or an unsaturated ring, but in one embodiment, a saturated ring is preferred. Non-aromatic rings include, for example, monocycloalkane rings such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring and cyclooctane ring; monocycloalkene rings such as cyclopentene ring, cyclohexene ring and cycloheptene ring; ; pyrrolidine ring, tetrahydrofuran ring, dioxane ring, monocyclic non-aromatic heterocyclic ring such as tetrahydropyran ring (preferably 3-10 membered); norbornane ring, decalin ring, adamantane ring and bicyclic or higher condensed non-aromatic rings (preferably 8- to 15-membered) such as tetrahydrodicyclopentadiene ring.

Specific examples of the divalent group represented by formula (Y1) include, but are not limited to, divalent organic groups represented by the following:

[In the formula, * indicates a binding site. ].

A ² each independently preferably has the formula (Y2):

[wherein Y ² is each independently a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO- , —COO—, or —OCO—; Z ² each independently represents an optionally substituted non-aromatic ring or an optionally substituted aromatic ring; b represents an integer of 0 or 1 or more (preferably 0 or an integer of 1 to 5); * represents a binding site. ]
is a divalent group (including a single bond) represented by In addition, the b unit may be the same or different for each unit.

Specific examples of the divalent group represented by formula (Y2) are not particularly limited, but are -CH ₂ -, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -, -O-, -CO-, -S-, -SO-, and —SO ₂ — may include divalent organic groups represented by:

[In the formula, * indicates a binding site. ].

n1 preferably represents an integer of 1-100, more preferably an integer of 5-50, still more preferably an integer of 10-35, particularly preferably an integer of 15-25. n2 preferably represents an integer of 1 to 100, more preferably represents an integer of 5 to 50, still more preferably represents an integer of 10 to 35, and particularly preferably represents an integer of 15 to 25.

In the above embodiment, (A) the specific maleimide compound is more preferably represented by formula (A2):

[In the formulas, each symbol is the same as in formulas (1), (4) and (A1). ]
is a maleimide compound represented by the formula (A3):

[Wherein, X ⁵ , X ⁶ and X ⁷ are each independently a single bond, -C(R ⁹⁰ ) ₂ -, -O-, -CO-, -S-, -SO-, -SO _2- , -CONH-, -NHCO-, -COO- or -OCO- (preferably X ⁵ and X ⁷ are -O- and X ⁶ is -C(R ⁹⁰ ) ₂ -); R ⁹⁰ , R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁰¹ , R ⁰² , R ⁰³ , and R ⁰⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group (preferably represents an alkyl group for R ⁹⁰ and a hydrogen atom for the others; other symbols are the same as in formulas (1), (4) and (A1). ]
A maleimide compound represented by (the bond between the n1 unit and the n2 unit) is particularly preferably represented by the formula (A4):

[In the formulas, each symbol is the same as in formulas (4), (A1) and (A3). ]
is a maleimide compound represented by (a bond between the n1 unit and the n2 unit).

In one embodiment, the weight average molecular weight of (A) the specific maleimide compound is not particularly limited, but is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more. (A) Although the upper limit of the weight average molecular weight of the specific maleimide compound is not particularly limited, it is preferably 500,000 or less, more preferably 200,000 or less, and still more preferably 100,000 or less. The weight average molecular weight of the maleimide compound can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

In one embodiment, (A) the functional group equivalent of the maleimide group of the specific maleimide compound is not particularly limited, but is preferably 1000 g/eq. ~200000 g/eq. , more preferably 1500 g/eq. ~100000g/eq. , more preferably 2000 g/eq. ~50000 g/eq. is. The functional group equivalent weight of maleimide groups is the mass of compound per equivalent of maleimide groups.

(A) Specific examples of the specific maleimide compound include the following formula (A5):

[In the formula, each symbol is the same as in formula (A1). ]
A maleimide compound represented by (a bond is present between the n1 unit and the n2 unit).

(A) Commercially available specific maleimide compounds include, for example, "BMI-6100" manufactured by Designer Molecules.

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

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

(A') The radically polymerizable compound may be, for example, a compound having a radically polymerizable unsaturated group. The radically polymerizable unsaturated group is not particularly limited as long as it is radically polymerizable, but preferably an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or inside, specifically an allyl group. , 3-cyclohexenyl group and other unsaturated aliphatic groups; p-vinylphenyl group, m-vinylphenyl group, styryl group and other unsaturated aliphatic group-containing aromatic groups; acryloyl group, methacryloyl group, maleoyl group, fumaroyl α,β-unsaturated carbonyl groups such as groups. (A') The radically polymerizable compound preferably has one or more radically polymerizable unsaturated groups, more preferably two or more.

As the other radically polymerizable compound (A'), a wide range of known radically polymerizable compounds can be used, and is not particularly limited. For example, (A'-1) other than the component (A) Maleimide radically polymerizable compounds, (A′-2) vinylphenyl radically polymerizable compounds, (A′-3) (meth)acrylic radically polymerizable compounds, and the like.

<(A'-1) Maleimide Radical Polymerizable Compound>
(A'-1) maleimide-based radically polymerizable compound is a compound other than component (A) and is an organic compound containing one or more (preferably two or more) maleimide groups in one molecule. . (A'-1) The maleimide-based radically polymerizable compound may be used alone, or two or more of them may be used in combination at any ratio. (A'-1) Maleimide-based radically polymerizable compound includes, for example, (A'-1-1) maleimide-terminated polyimide other than component (A), (A'-1-2) aromatic maleimide compound, and (A '-1-3) It preferably contains at least one maleimide compound selected from aliphatic maleimide compounds.

<(A'-1-1) Maleimide-terminated polyimide>
(A'-1-1) Maleimide-terminated polyimide is a maleimide compound that does not correspond to component (A), and is a chain polyimide having maleimide groups at both ends. (A'-1-1) The maleimide-terminated polyimide may be a component obtained by, for example, imidating a component containing a diamine compound, maleic anhydride and tetracarboxylic dianhydride.

In one embodiment, (A'-1-1) the maleimide-terminated polyimide has, for example, the following formula (B):

[Wherein, n represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, particularly preferably an integer of 1 to 20); is similar to ]
is a maleimide compound represented by Note that n units may be the same or different for each unit.

(A'-1-1) The weight average molecular weight (Mw) of the maleimide-terminated polyimide is preferably 500 to 500,000, more preferably 1,000 to 200,000. The weight average molecular weight of the maleimide compound can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

(A'-1-1) The functional group equivalent weight of the maleimide group of the maleimide-terminated polyimide is preferably 300 g/eq. ~200000 g/eq. , more preferably 500 g/eq. ~100000 g/eq. is.

(A'-1-1) Examples of commercially available maleimide-terminated polyimides include "BMI-1500", "BMI-1700" and "BMI-3000J" manufactured by Designer Molecules.

<(A'-1-2) Aromatic maleimide compound>
(A'-1-2) Aromatic maleimide compound is a maleimide compound that does not correspond to components (A) and (A'-1-1) and contains one or more aromatic rings in one molecule. and a maleimide compound containing two or more maleimide groups. In one embodiment, (A'-2) the aromatic maleimide compound may be an addition polymerization type aromatic maleimide compound. (A'-2) The aromatic maleimide compound is a maleimide having one aromatic ring such as N,N'-1,3-phenylenedimaleimide and N,N'-1,4-phenylenedimaleimide, or polymaleimide having two or more aromatic rings, preferably maleimide having two or more aromatic rings.

In one embodiment, (A'-1-2) the aromatic maleimide compound has, for example, formula (C):

[In the formula, R ^c each independently represents a substituent; X ^c each independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO -, -SO ₂ -, -CONH-, -NHCO-, -COO- or -OCO- (preferably a single bond or an alkylene group); Z ^c each independently has a substituent an optionally non-aromatic ring or an optionally substituted aromatic ring (preferably an optionally substituted aromatic ring, particularly preferably an optionally substituted benzene ring) s is an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, more preferably an integer of 1 to 20); t is each independently 0 or 1 each u independently represents an integer of 0 to 2 (preferably 0). ] A maleimide compound represented by the formulas (C1-1) to (C1-4):

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

(A'-1-2) The weight average molecular weight (Mw) of the aromatic maleimide compound is preferably 150-5000, more preferably 300-2500.

(A'-1-2) The functional group equivalent weight of the maleimide group of the aromatic maleimide compound is preferably 50 g/eq. ~2000 g/eq. , more preferably 100 g/eq. ~1000g/eq. More preferably 150 g/eq. ~500 g/eq. , particularly preferably 200 g/eq. ~300 g/eq. is.

(A'-1-2) Commercially available aromatic maleimide compounds include, for example, "MIR-3000-70MT" manufactured by Nippon Kayaku; "BMI-50P" manufactured by Keiai Kasei; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", "BMI-5100"; , “BMI-70”, “BMI-80” manufactured by Kei Kasei Co., Ltd., and the like.

<(A'-1-3) Aliphatic maleimide compound>
(A'-1-3) Aliphatic maleimide compound is a maleimide having a non-aromatic hydrocarbon (preferably 2 to 50 carbon atoms) as a basic skeleton and having two or more (preferably two) maleimides in one molecule. It is a compound having a group.

In one embodiment, (A'-1-3) the aliphatic maleimide compound has, for example, the following formula (D):

[Wherein, X ^d each independently represents a single bond, an alkylene group or an alkenylene group (preferably an alkylene group or alkenylene group); Z ^d is each independently selected from an alkyl group and an alkenyl group. a non-aromatic ring optionally having a group (preferably a monocycloalkane ring or monocycloalkene ring optionally having a group selected from an alkyl group and an alkenyl group); x is 0 or 1 or more is an integer (preferably an integer of 1 or more, particularly preferably 1). ] It is a maleimide compound represented by. Note that the x unit may be the same or different for each unit.

(A'-1-3) Specific examples of the aliphatic maleimide compound include linear maleimide compounds such as N,N'-ethylenedimaleimide, N,N'-tetramethylenedimaleimide, and N,N'-hexamethylenedimaleimide. 1-maleimido-3-maleimidomethyl-3,5,5-trimethylcyclohexane (IPBM), 1,1′-(cyclohexane-1,3-diylbismethylene)bis(1H-pyrrole- 2,5-dione) (CBM), 1,1′-(4,4′-methylenebis(cyclohexane-4,1-diyl))bis(1H-pyrrole-2,5-dione) (MBCM) Cyclic bismaleimide compounds; dimer acid skeleton-containing bismaleimides, and the like.

Dimer acid skeleton-containing bismaleimide refers to the two terminal carboxyl groups (-COOH) of dimer acid, maleimide group or maleimidomethyl group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-ylmethyl group ) means a bismaleimide compound replaced with Dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably having 11 to 22 carbon atoms, particularly preferably having 18 carbon atoms), and its industrial production process is almost Standardized. Among dimer acids, dimer acids having 36 carbon atoms obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, which are inexpensive and readily available, are readily available. In addition, the dimer acid may contain any amount of monomeric acid, trimeric acid, other polymerized fatty acids, etc. depending on the production method, the degree of purification, and the like. Further, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, dimer acids also include hydrogenated products obtained by further hydrogenating to lower the degree of unsaturation.

(A'-1-3) The molecular weight of the aliphatic maleimide compound is preferably 150-5000, more preferably 300-1000.

(A'-1-3) The functional group equivalent weight of the maleimide group of the aliphatic maleimide compound is preferably 50 g/eq. ~2000 g/eq. , more preferably 100 g/eq. ~1000 g/eq. More preferably 200 g/eq. ~600 g/eq. , particularly preferably 300 g/eq. ~400 g/eq. is.

(A'-1-3) Examples of commercially available products of the aliphatic maleimide compound include "BMI-689" manufactured by Designer Molecules.

<(A'-2) Vinylphenyl Radical Polymerizable Compound>
(A'-2) The vinylphenyl-based radically polymerizable compound is a radically polymerizable compound having a vinylphenyl group. The vinylphenyl-based radically polymerizable compound preferably has two or more vinylphenyl groups per molecule.

In one embodiment, (A'-2) vinylphenyl-based radically polymerizable compound is preferably a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group and a polyphenylene ether skeleton, and formula (E-1):

[In the formula, R ^e1 , R ^e2 , R ^e3 and R ^e4 each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group). ]
(The number of repeating units is preferably 2 to 300, more preferably 2 to 100) and a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group (especially the hydrogen atoms of both terminal hydroxyl groups of the polyphenylene ether are replaced by vinylbenzyl groups. It is particularly preferred that vinylbenzyl-modified polyphenylene ether at both ends is substituted with ).

In another embodiment, (A'-2) the vinylphenyl-based radically polymerizable compound has the formula (E-2):

[In the formula, R ^e5 , R ^e6 and R ^e7 each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom). ]
It is preferably a divinylbenzene polymer having a repeating unit represented by (the number of repeating units is preferably 2 to 200). The divinylbenzene polymer may further be a copolymer having other styrene skeleton units such as styrene units and ethylstyrene units. When other styrene skeleton units are present, the ratio of the repeating unit of formula (E-2) is preferably 5 to 70 mol % of the total styrene skeleton units.

(A'-2) The number average molecular weight of the vinylphenyl-based radically polymerizable compound is preferably 500 to 100,000, more preferably 700 to 80,000. (A'-2) The functional group equivalent weight of the vinyl group of the vinylphenyl-based radically polymerizable compound is preferably 200 g/eq. ~3000g/eq. , more preferably 200 g/eq. ~2000g/eq. is.

(A'-2) Examples of commercially available vinylphenyl-based radically polymerizable compounds include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether) manufactured by Mitsubishi Gas Chemical Company; "ODV-XET-X03", "ODV-XET-X04", "ODV-XET-X05" (divinylbenzene polymer) manufactured by Chemical & Material Co., Ltd., and the like can be mentioned.

<(A'-3) (Meth) acrylic radically polymerizable compound>
(A'-3) The (meth)acrylic radically polymerizable compound is a radically polymerizable compound having an acryloyl group and/or a methacryloyl group. (A'-3) The (meth)acrylic radical polymerizable compound preferably has two or more acryloyl groups and/or methacryloyl groups per molecule. (A′-3) (meth)acrylic radically polymerizable compound is preferably a (meth)acrylic-modified polyphenylene ether having an acryloyl group and/or a methacryloyl group and a polyphenylene ether skeleton, formula (F):

[In the formula, R ^f1 , R ^f2 , R ^f3 and R ^f4 each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group). ]
(The number of repeating units is preferably 2 to 300, more preferably 2 to 100) represented by (meth) acrylic modified polyphenylene ether having an acryloyl group and / or a methacryloyl group (especially both terminal hydroxyl groups of polyphenylene ether (Meth)acrylic-modified polyphenylene ether at both ends in which hydrogen atoms are replaced with acryloyl groups and/or methacryloyl groups) is particularly preferred.

(A'-3) The (meth)acrylic radically polymerizable compound preferably has a number average molecular weight of 500 to 10,000, more preferably 700 to 5,000. (A'-3) The functional group equivalent weight of the acryloyl group and the methacryloyl group of the (meth)acrylic radically polymerizable compound is preferably 200 g/eq. ~3000g/eq. , more preferably 300 g/eq. ~2000 g/eq. is.

(A'-3) Examples of commercially available (meth)acrylic radically polymerizable compounds include "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

The content of (A′) other radically polymerizable compound in the resin composition is not particularly limited, but is preferably 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. , more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of (A') other radically polymerizable compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0 mass % or more, 0.1 mass % or more, 1 mass % or more, 2 mass % or more, and the like.

The content of the specific maleimide compound (A) in the resin composition is preferably when the total amount of radically polymerizable compounds (total of components (A) and (A′)) in the resin composition is 100% by mass. is 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more.

<(B) Epoxy resin>
The resin composition of the present invention contains (B) an epoxy resin. (B) Epoxy resin means a curable resin having an epoxy group. (B) Epoxy resin preferably contains (B-1) a condensed ring structure-containing epoxy resin.

<(B-1) Condensed Ring Structure-Containing Epoxy Resin>
(B-1) Epoxy resin containing a condensed ring structure means a resin having one or more condensed rings and one or more (preferably two or more) epoxy groups in one molecule. The (B-1) condensed ring structure-containing epoxy resin may be used singly or in combination of two or more at any ratio.

(B-1) The condensed ring contained in the epoxy resin containing a condensed ring structure is preferably a condensed aromatic carbocyclic ring. The condensed aromatic carbocyclic ring is a bicyclic or higher aromatic carbocyclic ring obtained by condensing two or more benzene rings, and preferably has 10 to 18 carbon atoms, preferably 10 to 14 carbon atoms. More preferred examples include naphthalene ring, anthracene ring, phenanthrene ring, and the like, with naphthalene ring being particularly preferred.

(B-1) The epoxy resin containing a condensed ring structure may be any of a glycidyl ether type, a glycidyl amine type, a glycidyl ester type, and an olefin oxidation (alicyclic) type. is preferred.

(B-1) The epoxy resin containing a condensed ring structure may be of a monomer type or a repeating structure type. Here, the repeating structure type refers to a polymer structure having an average of 3 or more repeating units containing one or more condensed rings. A molecular structure having two repeating units containing one or more condensed rings. (B-1) condensed ring structure-containing epoxy resin is composed of (B-1-1) monomeric condensed ring structure-containing epoxy resin and (B-1-2) repeating structure-type condensed ring structure-containing epoxy resin The selected epoxy resin preferably contains (B-1-2) a repeating structure-type condensed ring structure-containing epoxy resin.

Examples of (B-1-1) monomeric epoxy resins containing condensed ring structures include 1,6-bis(glycidyloxy)naphthalene, 1,5-bis(glycidyloxy)naphthalene, 2,7-bis( monomeric condensed ring structure-containing epoxy resins having one condensed ring per molecule such as glycidyloxy)naphthalene, 2,6-bis(glycidyloxy)naphthalene; bis[2-(glycidyloxy)-1- naphthyl]methane, 2,2-bis[2-(glycidyloxy)-1-naphthyl]propane, bis[2,7-bis(glycidyloxy)-1-naphthyl]methane, 2,2-bis[2,7 -bis(glycidyloxy)-1-naphthyl]propane, [2,7-bis(glycidyloxy)-1-naphthyl][2-(glycidyloxy)-1-naphthyl]methane, 2-[2,7-bis (Glycidyloxy)-1-naphthyl]-2-[2-(glycidyloxy)-1-naphthyl]propane and other monomeric condensed ring structure-containing epoxy resins having two condensed rings per molecule. be done.

(B-1-1) The monomeric condensed ring structure-containing epoxy resin is, in one embodiment, preferably a bifunctional to tetrafunctional epoxy resin, and may be a bifunctional or trifunctional epoxy resin. More preferably, it is particularly preferably a bifunctional epoxy resin.

(B-1-1) The epoxy equivalent of the monomeric condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 50 g/eq. above, more preferably 80 g/eq. above, more preferably 100 g/eq. above, and more preferably 120 g/eq. above, particularly preferably 130 g/eq. That's it. (B-1-1) The upper limit of the epoxy equivalent of the monomeric condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 1000 g/eq. Below, more preferably 500 g/eq. Below, more preferably 300 g/eq. Below, even more preferably 200 g/eq. Below, particularly preferably 160 g/eq. It is below. Epoxy equivalent weight is the mass of resin per equivalent of epoxy groups. Epoxy equivalent can be measured according to JIS K7236.

(B-1-1) The molecular weight of the monomeric condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 2000 or less, more preferably 1000 or less, still more preferably 700 or less, and even more preferably. is 600 or less, particularly preferably 500 or less.

(B-1-1) Commercial products of the monomeric condensed ring structure-containing epoxy resin include, for example, DIC's "HP-4032D" and "HP-4032SS" (one naphthalene ring per molecule epoxy resin); DIC's "EXA-4750", "HP-4770", "HP-4700", "HP-4710" (an epoxy resin having two naphthalene rings in one molecule), etc. mentioned.

(B-1-2) Repeating structure-type condensed ring structure-containing epoxy resins include, for example, naphthol novolak type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolak type epoxy resins, and naphthol aralkyls. repeating structure-type condensed ring structure-containing epoxy resins having three or more condensed rings in one molecule, such as a type epoxy resin, a naphthalenediol aralkyl-type epoxy resin, and a naphthylene ether-type epoxy resin. In one embodiment, (B-1-2) the repeating structure-type condensed ring structure-containing epoxy resin preferably includes a naphthol aralkyl-type epoxy resin.

(B-1-2) The epoxy equivalent of the repeating structure-type condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 50 g/eq. above, more preferably 100 g/eq. above, more preferably 200 g/eq. above, and more preferably 250 g/eq. above, particularly preferably 300 g/eq. That's it. (B-1-2) The upper limit of the epoxy equivalent of the repeating structure-type condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 2000 g/eq. Below, more preferably 1000 g/eq. Below, more preferably 500 g/eq. Below, even more preferably 400 g/eq. It is below.

(B-1-2) Examples of commercially available epoxy resins containing repeating structure-type condensed ring structures include “ESN-155”, “ESN-185V”, and “ESN-175” manufactured by Nippon Steel Chemical & Materials Co., Ltd. , “ESN-475V”, “ESN-485”, “TX-1507B” (naphthol aralkyl type epoxy resin); DIC “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4” ”, “EXA-7311-G4S”, “HP-6000”, “HP-6000-L” (naphthylene ether type epoxy resin); “NC7000L” (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. mentioned.

In one embodiment, (B-1) the condensed ring structure-containing epoxy resin preferably contains a naphthol aralkyl type epoxy resin.

The resin composition may contain (B-2) other epoxy resins in addition to (B-1) the fused ring structure-containing epoxy resin, but (B-1) the fused ring structure in the resin composition When the total epoxy resin in the resin composition is 100% by mass, the content of the contained epoxy resin is preferably 50% by mass or more, 60% by mass or more, or more, from the viewpoint of significantly obtaining the desired effects of the present invention. It is preferably 70% by mass or more and 80% by mass or more, more preferably 90% by mass or more and 95% by mass or more, still more preferably 98% by mass or more and 99% by mass or more, and particularly preferably 100% by mass.

<(B-2) Other epoxy resins>
(B-2) Other epoxy resins include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin. , trisphenol type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin , 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, cyclohexanedimethanol-type epoxy resins, trimethylol-type epoxy resins , tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, phenolphthalein type epoxy resin, and the like. (B-2) Other epoxy resins may be used singly or in combination of two or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (B-2) other epoxy resin. (B-2) The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass, relative to 100% by mass of the non-volatile components of other epoxy resins. above, and particularly preferably at least 70% by mass.

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). The resin composition of the present invention may contain only a liquid epoxy resin as (B-2) other epoxy resin, or may contain only a solid epoxy resin, or may contain a liquid epoxy resin and a solid epoxy resin. It may be included in combination with an epoxy resin.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, and alicyclic epoxy resin having an ester skeleton. Resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferred.

Specific examples of liquid epoxy resins include "828US", "828EL", "jER828EL", "825" and "Epicoat 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" manufactured by Mitsubishi Chemical Corporation. , "1750" (bisphenol F type epoxy resin); "jER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical; "630", "630LSD", "604" manufactured by Mitsubishi Chemical (glycidylamine type epoxy resin ); ADEKA "ED-523T" (glycirrol type epoxy resin); ADEKA "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); ADEKA "EP-4088S" (Dicyclopentadiene type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin); "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (Epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol Aralkyl-type epoxy resins, tetraphenylethane-type epoxy resins, phenolphthalimidine-type epoxy resins, and phenolphthalein-type epoxy resins are preferred.

Specific examples of solid epoxy resins include "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP -7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); Nippon Kayaku "EPPN-502H" (trisphenol type epoxy resin); Japan "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Kayaku; "YX4000H", "YX4000", "YX4000HK", "YL7890" manufactured by Mitsubishi Chemical "(Bixylenol type epoxy resin); "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" manufactured by Osaka Gas Chemical Co., Ltd. ”, “CG-500”; Mitsubishi Chemical “YL7760” (bisphenol AF type epoxy resin); Mitsubishi Chemical “YL7800” (fluorene type epoxy resin); Mitsubishi Chemical “jER1010” (bisphenol A type epoxy resin); "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; These may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ~5,000g/eq. , more preferably 60 g/eq. ~2,000 g/eq. , more preferably 70 g/eq. ~1,000g/eq. , even more preferably 80 g/eq. ~500 g/eq. is.

(B) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of the (B) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass. % by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The lower limit of the content of the (B) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.01% by mass or more, It is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more.

The mass ratio of the specific maleimide compound (A) to the epoxy resin (B) in the resin composition (component (A)/component (B)) is preferably 0.1 or more, more preferably 0.3 or more, and particularly Preferably it is 0.5 or more. The upper limit of the mass ratio ((A) component/(B) component) of the specific maleimide compound (A) to the epoxy resin (B) in the resin composition is preferably 10 or less, more preferably 3 or less, and particularly preferably 1 or less.

<(C) Inorganic filler>
The resin composition of the present invention contains (C) an inorganic filler. (C) The inorganic filler is contained in the resin composition in the form of particles.

(C) An inorganic compound is used as the material of the inorganic filler. (C) Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, 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 is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. (C) Inorganic fillers may be used singly or in combination of two or more at any ratio.

(C) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; 5N”; “SC2500SQ”, “SO-C4”, “SO-C2” and “SO-C1” manufactured by Admatechs; “DAW-03” and “FB-105FD” manufactured by Denka.

The average particle size of the inorganic filler (C) 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 0.001 μm or less. 7 μm or less. (C) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0 .2 μm or more. (C) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(C) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, still more preferably 1 m ² /g or more, Particularly preferably, it is 3 m ² /g or more. Although the upper limit of the specific surface area of the inorganic filler (C) is not particularly limited, it is preferably 100 m ² /g or less, more preferably 70 m ² /g or less, even more preferably 50 m ² /g or less, and particularly preferably is 30 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. obtained by

(C) The inorganic filler is preferably surface-treated with an appropriate surface-treating agent. The surface treatment can enhance the moisture resistance and dispersibility of (C) the inorganic filler. Examples of surface treatment agents include vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-based silane coupling agents; p-styryltrimethoxysilane and other styryl-based Silane coupling agents; Methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N - Amino silane coupling agents such as phenyl-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; tris-(trimethoxysilylpropyl) isocyanurate, etc. isocyanurate-based silane coupling agents; 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-isocyanatopropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; silane coupling agents such as; methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltri Non-silane coupling-alkoxysilane compounds such as ethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, and the like are included. The surface treatment agents may be used singly or in combination of two or more at any ratio.

Examples of commercially available surface treatment agents include "KBM-1003" and "KBE-1003" (vinyl silane coupling agents) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", " KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styryl silane coupling agent); "KBM-502", "KBM-503" , "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM- 903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amino-based silane 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” ( non-silane coupling-alkoxysilane compounds) and the like.

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 a surface treatment agent of 0.2% to 5% by mass, and is surface-treated with 0.2% to 3% by mass. more preferably 0.3 mass % to 2 mass % of the surface treatment.

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

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

The content of the inorganic filler (C) in the resin composition exceeds 30% by mass when the non-volatile component in the resin composition is 100% by mass, and from the viewpoint of further suppressing the coefficient of thermal expansion, it is preferably 40%. % by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and particularly preferably 55% by mass or more. The upper limit of the content of the inorganic filler (C) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, preferably 90% by mass or less, more It is preferably 80% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass or less.

The mass ratio of the specific maleimide compound (A) to the inorganic filler (C) in the resin composition ((A) component/(C) component) is preferably 0.01 or more, more preferably 0.05 or more, Especially preferably, it is 0.1 or more. The upper limit of the mass ratio ((A) component/(C) component) of the specific maleimide compound (A) to the inorganic filler (C) in the resin composition is preferably 1 or less, more preferably 0.5 or less, Especially preferably, it is 0.3 or less.

<(D) Active ester compound>
The resin composition of the present invention may contain (D) an active ester compound as an optional component. (D) The active ester compound may be used singly or in combination of two or more at any ratio. In one embodiment, (D) the active ester compound may have the function of reacting with (B) the epoxy resin to cure the resin composition.

(D) Active ester compounds generally have two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. is preferably used. The active ester compound is preferably 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 carboxylic acid compounds 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, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, component (D) includes a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolac, and an active ester containing a benzoylated phenol novolac. Among them, at least one compound selected from a dicyclopentadiene-type active ester compound and a naphthalene-type active ester compound is more preferable, and a dicyclopentadiene-type active ester compound is even more preferable. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

(D) Commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", and "EXB-8000L-65M" as active ester compounds containing a dicyclopentadiene type diphenol structure. ”, “EXB-8000L-65TM”, “HPC-8000L-65TM”, “HPC-8000”, “HPC-8000-65T”, “HPC-8000H”, “HPC-8000H-65TM”, (manufactured by DIC ); "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T" as active ester compounds containing a naphthalene structure, "HPC-8150-62T" (manufactured by DIC Corporation), "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester compound, and "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is an acetylated product of phenol novolac. , "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds that are benzoylated phenol novolacs, and "PC1300-02-65MA" (air・Water Co., Ltd.) and the like.

(D) The active ester group equivalent of the active ester compound is preferably 50 g/eq. ~500 g/eq. , more preferably 50 g/eq. ~400g/eq. , more preferably 100 g/eq. ~300 g/eq. is. The active ester group equivalent is the mass of active ester compound per equivalent of active ester group.

The content of (D) the active ester compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably It is 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less. The lower limit of the content of (D) the active ester compound in the resin composition is not particularly limited. 01% by mass or more, 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. is.

The mass ratio of the specific maleimide compound (A) to the active ester compound (D) in the resin composition ((A) component/(D) component) is preferably 0.1 or more, more preferably 0.5 or more, Especially preferably, it is 0.8 or more. The upper limit of the mass ratio ((A) component/(D) component) of the specific maleimide compound (A) to the active ester compound (D) in the resin composition is preferably 10 or less, more preferably 3 or less, and particularly preferably is 1.5 or less.

<(E) Curing accelerator>
The resin composition of the present invention may contain (E) a curing accelerator as an optional component.

Examples of curing accelerators 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. (E) The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 -methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; 2-butenyl)phosphine, aliphatic phosphines such as tricyclohexylphosphine; -tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, 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, 2,2′-bis(diphenylphosphino)diphenyl ether, and other aromatic phosphines. be done.

Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as 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, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 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) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] etc.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]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, 1-(o-tolyl)biguanide and the like.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 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 , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins.

As the imidazole-based curing accelerator, a commercially available product may be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Kasei Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation. etc.

Metal-based curing accelerators include, for example, 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, and zinc (II) acetylacetonate. and the like, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

As the amine-based curing accelerator, a commercially available product may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.

The content of (E) the curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably It is 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of (E) the curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0 0.001% by weight or more, 0.01% by weight or more, 0.1% by weight or more, 0.5% by weight or more, and the like.

<(F) Other additives>
The resin composition of the present invention may further contain optional additives as non-volatile components. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, and thiols. Epoxy curing agents other than active ester compounds such as curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, imidazole curing agents; phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, poly Thermoplastic resins such as ether sulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; 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, carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine; silicone leveling agents, acrylic polymer leveling agents, etc. leveling agents; thickeners such as bentone and montmorillonite; defoaming agents such as silicone defoaming agents, acrylic defoaming agents, fluorine defoaming agents, and vinyl resin defoaming agents; UV absorber; Adhesion improver such as urea silane; Adhesion improver such as triazole adhesion imparting agent, tetrazole adhesion imparting agent, triazine adhesion imparting agent; Antioxidants such as antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g. melamine sulfate), halogen flame retardants, inorganic flame retardants (e.g. antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants agent, acetylene dispersant, silicone dispersant, anionic dispersant, cationic dispersant; borate stabilizer, titanate stabilizer, aluminate stabilizer, zirconate stabilizer, isocyanate stabilizer stabilizers, carboxylic acid-based stabilizers, carboxylic anhydride-based stabilizers, and the like. (F) Other additives may be used singly or in combination of two or more at any ratio. (F) The content of other additives can be appropriately set by those skilled in the art.

<(G) 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 (G) organic solvent, a known one can be used as appropriate, and the type thereof is not particularly limited. (G) Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate ester alcohol solvents such as; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) and other ether alcohol solvents; N,N-dimethylformamide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide solvents; dimethyl sulfoxide and other sulfoxide solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane and other fats aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene; (G) The organic solvent may be used singly or in combination of two or more at any ratio.

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

<Method for producing resin composition>
The resin composition of the present invention can be, for example, placed in any preparation vessel (A) a specific maleimide compound, (B) an epoxy resin, (C) an inorganic filler, optionally (A') other maleimide compounds, (D) an active ester compound, optionally (E) a curing accelerator, optionally (F) other additives, and optionally (G) an organic solvent, in any order and / Or by adding and mixing partly or wholly at the same time. Also, during the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or over time. In addition, during or after the addition and mixing, the resin composition may be stirred or shaken using a stirring or shaking device such as a mixer to uniformly disperse. Moreover, simultaneously with stirring or shaking, defoaming may be performed under low pressure conditions such as vacuum.

<Characteristics of resin composition>
The resin composition of the present invention contains (A) a specific maleimide compound, (B) an epoxy resin, and (C) an inorganic filler, and the content of component (C) is such that the non-volatile components in the resin composition are When 100% by mass, it exceeds 30% by mass. By using such a resin composition, it is possible to obtain a cured product having a small arithmetic average roughness (Ra) and a low dielectric constant (Dk) and dielectric loss tangent (Df).

A cured product of the resin composition of the present invention may have a feature of low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 0.020 or less and 0.010 or less. , more preferably 0.009 or less and 0.008 or less, still more preferably 0.007 or less and 0.006 or less, and particularly preferably 0.005 or less and 0.004 or less.

A cured product of the resin composition of the present invention may have a feature of a low dielectric constant (Dk). Therefore, in one embodiment, the dielectric constant (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 5.0 or less, more preferably It can be 4.0 or less, more preferably 3.5 or less, and particularly preferably 3.0 or less.

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 surface of the cured product after roughening treatment measured as in Test Example 2 below is preferably 300 nm or less, more preferably 200 nm or less, and still more preferably 150 nm. Below, more preferably 100 nm or less, particularly preferably 80 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more.

In one embodiment, the cured product of the resin composition of the present invention is calculated from the load when a copper-plated conductor layer is formed on the cured product as in Test Example 2 below and the copper-plated conductor layer is peeled off in the vertical direction. The resulting copper plating peel strength is preferably 0.2 kgf/cm or more, more preferably 0.3 kgf/cm or more, still more preferably 0.35 kgf/cm or more, and particularly preferably 0.4 kgf/cm or more. Although the upper limit is not particularly limited, it can be, for example, 10 kgf/cm or less.

<Application of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulation, particularly as a resin composition for forming an insulation layer. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition). Moreover, in the 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 also includes resin sheets, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, and the like. It can be used in a wide range of applications.

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

Moreover, since the resin composition of the present invention provides an insulating layer having good component embedding properties, it can be suitably used when the printed wiring board is a component built-in circuit board.

<Sheet-like laminated material>
Although the resin composition of the present invention can be applied in the form of a varnish, it is industrially preferably used in the form of a sheet-like laminated material containing the resin composition.

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

In one embodiment, the resin sheet comprises 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.

The thickness of the resin composition layer is preferably 50 μm or less, more It is preferably 40 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 5 μm or more, 10 μm or more, or the like.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

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

In one embodiment, the resin sheet may further contain any layer as necessary. Examples of such an optional layer include a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

The resin sheet is produced by, for example, using a liquid resin composition as it is or preparing a resin varnish by dissolving the resin composition in an organic solvent, coating it on a support using a die coater or the like, and drying it. It can be produced by forming a resin composition layer.

Examples of the organic solvent include the same organic solvents as those described as components of the resin composition. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of the organic solvent, the temperature is 50° C. to 150° C. for 3 minutes to 10 minutes. A resin composition layer can be formed by drying for minutes.

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

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

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

A prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.

The sheet-like laminated 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 for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for interlayer insulating layers of wiring boards).

<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.

A printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate (II) Curing (for example, thermosetting) the resin composition layer to form an insulating layer process

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer board" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, 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 "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination can be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch-type vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. Pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

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

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

For example, the thermosetting 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 150° C. to 220° C. is between 170°C and 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured 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, It may be preheated for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes.

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of 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 that are used in the manufacture of 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 step ( It may be carried out between IV) and step (V). If necessary, the steps (II) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.

In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as in the case of using a resin sheet.

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

Step (IV) is a step of roughening the insulating layer. Smear is usually 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 commonly used in forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.

The swelling liquid used for the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

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 with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes. Further, the permanganate concentration 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 Security P" manufactured by Atotech Japan.

Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned.

The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and still 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. The root mean square roughness (Rq) of the surface of the insulating layer after 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. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, in which 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 selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

The conductor layer may have 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 multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

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

In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably performed between step (I) and step (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. 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). Then, step (II) is performed to form an insulating layer. After that, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.

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

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. The 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 condition is room temperature (25° C.).

<Example 1>
Maleimide-terminated polyimide (“BMI-6100” manufactured by Designer Molecules) 10 parts, naphthol aralkyl epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical & Materials) 18 parts, phenylaminosilane “KBM” manufactured by Shin-Etsu Chemical Co., Ltd. -573” surface-treated spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm, specific surface area 5.8 m ² /g) 60 parts, active ester compound (“HPC- 8150-60T", a toluene solution with a solid content of 60% by mass) 18.3 parts, an imidazole curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part), mixed at high speed A resin composition was prepared by uniformly dispersing with a rotating mixer.

<Example 2>
The amount of naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd.) was changed from 18 parts to 15 parts, and an active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, solid content 60 mass% toluene solution) was changed from 18.3 parts to 16.7 parts, and an aromatic maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution with a solid content of 70% ) to prepare a resin composition in the same manner as in Example 1, except that 5.7 parts of

<Example 3>
Maleimide compound A (Mw/Mn=1.81, t″=1 .47 (mainly 1, 2 or 3)) MEK solutions (70 wt% non-volatiles) were prepared.

The amount of naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd.) was changed from 18 parts to 15 parts, and an active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, solid content 60 mass% toluene solution) was changed from 18.3 parts to 16.7 parts, and 5.7 parts of aromatic maleimide (maleimide compound A, MEK solution with a solid content of 70%) was further used. A resin composition was prepared in the same manner as in Example 1.

<Example 4>
The amount of naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd.) was changed from 18 parts to 15 parts, and an active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, solid content 60 mass% toluene solution) was changed from 18.3 parts to 16.7 parts, and divinylbenzene / styrene copolymer ("ODV-XET-X04" manufactured by Nippon Steel Chemical & Materials Co., Ltd., solid content 65% A resin composition was prepared in the same manner as in Example 1, except that 6.2 parts of a toluene solution of ) was further used.

<Example 5>
The amount of naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd.) was changed from 18 parts to 15 parts, and an active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, solid content 60 mass % toluene solution) was changed from 18.3 parts to 16.7 parts, and vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., solid content 65% toluene solution) 6 A resin composition was prepared in the same manner as in Example 1, except that an additional .2 part was used.

<Example 6>
The amount of naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd.) was changed from 18 parts to 15 parts, and an active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, solid content 60 mass% toluene solution) was changed from 18.3 parts to 16.7 parts, and methacrylic-modified polyphenylene ether ("SA9000-111" manufactured by Subic Innovative Plastics Co., Ltd. was used as a toluene solution with a solid content of 50%. A resin composition was prepared in the same manner as in Example 1, except that 8 parts of the compound was further used.

<Comparative Example 1>
Instead of 10 parts of maleimide-terminated polyimide ("BMI-6100" manufactured by Designer Molecules), an aromatic maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixed solution with a solid content of 70%) A resin composition was prepared in the same manner as in Example 1, except that 14.3 parts were used.

<Comparative Example 2>
Without using 10 parts of maleimide-terminated polyimide ("BMI-6100" manufactured by Designer Molecules), the amount of naphthol aralkyl epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials) used was reduced from 18 parts to 23. parts, except that the amount of active ester compound ("HPC-8150-60T" manufactured by DIC, a toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 26.7 parts. A resin composition was prepared in the same manner as in 1.

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

The obtained resin sheet A was cured in an oven at 190° C. for 90 minutes. By removing the support from the resin sheet A taken out of the oven, a cured product of the resin composition layer was obtained. The cured product was cut into a piece having a length of 80 mm and a width of 2 mm to obtain a cured product B for evaluation.

For the cured product B for evaluation, using "HP8362B" manufactured by Agilent Technologies, the dielectric constant value (Dk value) and the dielectric loss tangent were measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. (Df value) was measured. Two test pieces were measured, and the average was calculated.

<Test Example 2: Measurement of peel strength and arithmetic mean roughness (Ra)>
(1) Preparation of inner layer substrate Glass cloth-based epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic “R1515A”) on which the inner layer circuit is formed. The copper surface was roughened by etching by 1 μm with an etchant (“CZ8101” manufactured by MEC).

(2) Lamination of resin sheet A Using a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"), Test Example 1 so that the resin composition layer is in contact with the inner layer substrate. The resin sheet A obtained in 1. was laminated on both sides of the inner layer substrate. Lamination was carried out by pressure bonding for 30 seconds at 120° C. and pressure of 0.74 MPa after reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

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

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

(Wet desmear treatment)
The cured substrate A is immersed in a swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, and then an oxidizing agent solution (Atotech Japan "Concentrate Compact CP" manufactured by Co., Ltd., an aqueous solution with a potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80° C. for 20 minutes. Then, it was immersed in a neutralizing solution ("Reduction Solution Securigant P" manufactured by Atotech Japan, sulfuric acid aqueous solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(5) Measurement of arithmetic mean roughness (Ra) of insulating layer surface after roughening treatment The arithmetic mean roughness (Ra) of the insulating layer surface of the cured substrate A after roughening treatment was (Bruker WYKO NT3300), VSI mode, 50x lens, measurement range 121 μm×92 μm. Each was measured by calculating the average value of 10 points.

(6) Formation of Conductor Layer A conductor layer was formed on the roughened surface of the insulating layer of the cured substrate A according to the semi-additive method. That is, the roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Then, after annealing by heating at 150° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Thereafter, copper sulfate electroplating was performed to form a conductor layer having a thickness of 25 μm, and annealing treatment was performed at 190° C. for 60 minutes. The obtained substrate is called "evaluation substrate B".

(7) Measurement of Peel Strength of Plated Conductor Layer The peel strength of the insulating layer and the conductor layer was measured according to Japanese Industrial Standards (JIS C6481). Specifically, the conductor layer of evaluation board B was cut into a portion having a width of 10 mm and a length of 100 mm. The load (kgf/cm) was measured when 35 mm was peeled off to obtain the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

Table 1 below shows the amounts of non-volatile components used in the resin compositions of Examples and Comparative Examples and the measurement results of Test Examples.

As described above, (A) the divalent group represented by the formula (1), the divalent group represented by the formula (2), and/or the divalent group represented by the formula (3) A resin composition containing a maleimide compound contained in the molecule, (B) an epoxy resin, and (C) an inorganic filler, wherein the content of component (C) is 100% by mass of non-volatile components in the resin composition. When using a resin composition exceeding 30% by mass, a cured product having a small arithmetic average roughness (Ra) and a low dielectric constant (Dk) and dielectric loss tangent (Df) can be obtained. I found out.

Claims (19)

(A) Formula (1):

[In the formula,
X ¹ is a single bond, -C(R ¹⁰ ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO-, or showing -OCO-;
each R ¹⁰ independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group;
At least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represents an alkyl group, an alkenyl group, an aryl-alkyl group, or denotes an aryl group, and the other denotes a hydrogen atom; and * denotes a bonding site. ]
and a divalent group represented by Formula (2):

[In the formula,
R ³¹ , R ³² , and R ³³ denote hydrogen atoms ; and * denotes a binding site. ]
and/or a divalent group represented by Formula (3):

[In the formula,
R ⁴¹ and R ⁴² indicate hydrogen atoms ; and * indicates the binding site. ]
A resin composition containing a maleimide compound containing a divalent group represented by in one molecule, (A') a radically polymerizable compound other than component (A), (B) an epoxy resin, and (C) an inorganic filler. being a thing,
The component (A) has the formula (A1):

[In the formula,
A ¹ each independently represents a divalent organic group consisting of two or more skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms;
A ² each independently represents a single bond or a divalent organic group consisting of one or more skeletal atoms selected from carbon, oxygen, nitrogen and sulfur atoms;
n1 represents an integer of 1 or more;
n2 represents an integer of 0 or more;
one of n1′ and n2′ represents 1 and the other represents 0;
m each independently represents 0 or 1;
Other symbols are the same as in formula (1),
The order and arrangement of n1 units and n2 units are not particularly limited,
The n1 unit and the n2 unit may be the same or different for each unit. ]
Including a maleimide compound represented by
A resin composition in which the content of the component (C) exceeds 30% by mass when the non-volatile component in the resin composition is taken as 100% by mass. X ¹ is —C(R ¹⁰ ) ₂ —; R ¹¹ , R ¹² , R ²¹ and R ²² are each independently an alkyl group; and R ¹⁰ , R ¹³ , R ¹⁴ , R ^23. The resin composition according to claim 1, wherein R24 and ^R24 are hydrogen atoms. The component (A) further has the formula (4):

[Wherein, X ² , X ³ and X ⁴ are each independently a single bond, -C(R ⁵⁰ ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ represents -, -CONH-, -NHCO-, -COO-, or -OCO-; ^R50 , ^R51 , ^R52 , ^R53 , R54, ^R61 , ^R62 , ^R63 , ^R64 , ^{R 71} , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁸¹ , R ⁸² , R ⁸³ , and R ⁸⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl-alkyl group, or an aryl group; and * indicates the binding site. ]
3. The resin composition according to claim 1, which contains a divalent group represented by in one molecule. X ² and X ⁴ are —O—; X ³ is —C(R ⁵⁰ ) ₂ —; R ⁵⁰ is each independently an alkyl group; and R ⁵¹ , R ⁵² , ^{wherein R53} , ^R54 , ^{R61 , R62} , R63, ^R64 , ^R71 , ^R72 , R73, ^R74 , ^R81 , ^{R82 , R83} , and ^R84 are hydrogen atoms Item 4. The resin composition according to item 3. The resin composition according to any one of claims 1 to 4, wherein the content of component (A) is 1% by mass to 40% by mass when the non-volatile component in the resin composition is 100% by mass. . The resin composition according to any one of claims 1 to 5 , wherein component (B) comprises (B-1) a condensed ring structure-containing epoxy resin. 7. The resin composition according to claim 6 , wherein the component (B-1) contains a naphthol aralkyl type epoxy resin. The resin composition according to any one of claims 1 to 7 , wherein the content of component (B) is 1% by mass to 50% by mass when the non-volatile component in the resin composition is 100% by mass. . The resin composition according to any one of claims 1 to 8 , wherein the mass ratio of component (A) to component (B) (component (A)/component (B)) is 0.3-3. The resin composition according to any one of claims 1 to 9 , wherein the content of component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 10 , wherein the mass ratio of component (A) to component (C) (component (A)/component (C)) is 0.05 to 0.5. thing. The resin composition according to any one of claims 1 to 11 , further comprising (D) an active ester compound. The resin composition according to any one of claims 1 to 12 , wherein the cured resin composition has a dielectric loss tangent of 0.005 or less when measured at 5.8 GHz and 23°C. The resin composition according to any one of claims 1 to 13 , wherein a cured product of the resin composition has a dielectric constant of 3.0 or less when measured at 5.8 GHz and 23°C. A cured product of the resin composition according to any one of claims 1 to 14 . A sheet-like laminate material containing the resin composition according to any one of claims 1 to 14 . A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 14 provided on the support. A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 14 . A semiconductor device comprising the printed wiring board according to claim 18 .