1. A resin composition comprising the following components (A) to (C),

(A) epoxy resin containing a condensed ring structure,

(B) An alkoxy group-containing naphthol aralkyl resin, and

(C) an inorganic filler material, which is a filler,

wherein the content of the component (C) is 70% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

2. The resin composition according to claim 1, wherein the component (B) is a naphthol aralkyl resin represented by the following formula (2),

wherein R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, at least 1R is an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 20.

3. The resin composition according to claim 1, wherein the (a) component comprises:

(A-1) a monomeric epoxy resin having a condensed ring structure.

4. The resin composition according to claim 3, wherein the epoxy equivalent of the component (A-1) is 120 g/eq.or more and 200 g/eq.or less.

5. The resin composition according to claim 3, wherein the molecular weight of the component (A-1) is 500 or less.

6. The resin composition according to claim 1, wherein the (a) component comprises:

(A-2) epoxy resin containing a condensed ring structure of a repeating structure type.

7. The resin composition according to claim 6, wherein the epoxy equivalent of the component (A-2) is 250 g/eq.or more and 400 g/eq.or less.

8. The resin composition according to claim 6, wherein the component (A-2) is a naphthol aralkyl type epoxy resin.

9. The resin composition according to claim 3, wherein the component (A) contains both of (A-1) a monomeric fused ring structure-containing epoxy resin and (A-2) a repeating structure type fused ring structure-containing epoxy resin.

10. The resin composition according to claim 9, wherein the mass ratio (monomer type/repeating structure type) of the component (A-1) to the component (A-2) is 1 or more and 5 or less.

11. The resin composition according to claim 1, wherein the content of the component (A) is 90% by mass or more, based on 100% by mass of the total epoxy resin in the resin composition.

12. The resin composition according to claim 1, wherein the content of the component (A) is 50% by mass or more, based on 100% by mass of nonvolatile components other than the component (C) in the resin composition.

13. The resin composition according to claim 1, further comprising (D) an organic filler material.

14. The resin composition according to claim 13, wherein component (D) is core-shell type rubber particles.

15. The resin composition according to claim 1, wherein the content of the component (C) is 80% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

16. A cured product of the resin composition according to any one of claims 1 to 15.

17. A sheet laminate comprising the resin composition according to any one of claims 1 to 15.

18. A resin sheet having:

a support, and

a resin composition layer formed of the resin composition according to any one of claims 1 to 15 provided on the support.

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

20. A semiconductor device comprising the printed wiring board of claim 19.

Background

As a manufacturing technique of a printed wiring board, a manufacturing method based on a stack (build dup) method of alternately laminating (laminating) insulating layers and conductor layers is known. In a manufacturing method using a stack method, generally, the insulating layer is formed by curing a resin composition.

Since a printed wiring board is generally exposed to a wide range of temperature environments from a low temperature environment such as room temperature to a high temperature environment such as reflow soldering, when the linear thermal expansion coefficient is high and the dimensional stability is poor, the resin material of the insulating layer repeats expansion and contraction, and cracks are generated due to the deformation.

As a method for suppressing the linear thermal expansion coefficient to a low level, a method of filling a resin material with an inorganic filler to a high degree is known (patent document 1). However, when the resin material is highly filled with an inorganic filler, the elastic modulus during curing becomes high, and it becomes difficult to suppress warpage.

Further, the insulating layer is required to have high adhesion strength.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2016-.

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a resin composition that can suppress warpage during curing and can provide a cured product having excellent adhesion strength.

Means for solving the problems

As a result of diligent research carried out by the present inventors to achieve the object of the present invention, the present inventors have found that: even in the case of a resin composition containing 70 mass% or more of (C) an inorganic filler, by containing (a) a fused ring structure-containing epoxy resin and (B) an alkoxy group-containing naphthol aralkyl resin, warpage during curing can be suppressed and a cured product having excellent adhesion strength can be obtained, and the present invention has been completed.

That is, the present invention includes the following;

[1] a resin composition comprising:

(A) an epoxy resin having a condensed ring structure, (B) an alkoxy group-containing naphthol aralkyl resin, and (C) an inorganic filler, wherein the content of the component (C) is 70% by mass or more, assuming that 100% by mass of nonvolatile components in the resin composition are present;

[2] the resin composition according to the above [1], wherein,

(B) a naphthol aralkyl resin represented by the following formula (2),

[ chemical formula 1]

Wherein R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, at least 1R is an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 2 to 20.

[3] The resin composition according to the above [1] or [2], wherein the component (A) comprises: (A-1) a monomeric epoxy resin having a condensed ring structure;

[4] the resin composition according to the above [3], wherein the epoxy equivalent of the component (A-1) is 120 g/eq.or more and 200 g/eq.or less;

[5] the resin composition according to the above [3] or [4], wherein the molecular weight of the component (A-1) is 500 or less;

[6] the resin composition according to any one of the above [1] to [5], wherein the component (A) comprises: (A-2) epoxy resins containing a condensed ring structure of a repeating structural type;

[7] the resin composition according to the above [6], wherein the epoxy equivalent of the component (A-2) is 250 g/eq.or more and 400 g/eq.or less;

[8] the resin composition according to the above [6] or [7], wherein the component (A-2) is a naphthol aralkyl type epoxy resin;

[9] the resin composition according to any one of the above [3] to [8], wherein the component (A) comprises: both (A-1) a monomeric fused ring structure-containing epoxy resin and (A-2) a repeating structure type fused ring structure-containing epoxy resin;

[10] the resin composition according to the above [9], wherein the mass ratio (monomer type/repeating structure type) of the component (A-1) to the component (A-2) is 1 or more and 5 or less;

[11] the resin composition according to any one of the above [1] to [10], wherein the content of the component (A) is 90% by mass or more, based on 100% by mass of the total epoxy resin in the resin composition;

[12] the resin composition according to any one of the above [1] to [11], wherein the content of the component (A) is 50% by mass or more, assuming that the nonvolatile components other than the component (C) in the resin composition are 100% by mass;

[13] the resin composition according to any one of the above [1] to [12], further comprising (D) an organic filler;

[14] the resin composition according to the above [13], wherein the component (D) is core-shell type rubber particles;

[15] the resin composition according to any one of the above [1] to [14], wherein the content of the component (C) is 80% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass;

[16] a cured product of the resin composition according to any one of the above [1] to [15 ];

[17] a sheet laminate comprising the resin composition according to any one of the above [1] to [15 ];

[18] a resin sheet having:

a support, and

a resin composition layer formed of the resin composition according to any one of the above [1] to [15] and provided on the support;

[19] a printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [15 ];

[20] a semiconductor device comprising the printed wiring board according to [19 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the resin composition of the present invention, warpage during curing can be suppressed, and a cured product having excellent adhesion strength can be obtained.

Detailed Description

The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the embodiments and examples described below, and may be modified and implemented arbitrarily without departing from the scope of the claims and their equivalents.

< resin composition >

The resin composition of the present invention comprises (A) an epoxy resin having a condensed ring structure, (B) an alkoxy group-containing naphthol aralkyl resin, and (C) an inorganic filler, and the content of the component (C) is 70% by mass or more, assuming that 100% by mass of nonvolatile components in the resin composition are present. By using such a resin composition, warpage during curing can be suppressed, and a cured product having excellent adhesion strength can be obtained.

The resin composition of the present invention may further contain any component in addition to (a) the epoxy resin having a condensed ring structure, (B) the naphthol aralkyl resin having an alkoxy group, and (C) the inorganic filler. Examples of the optional components include (D) an organic filler, (E) a curing agent, (F) a curing accelerator, (G) a radical polymerizable compound, (H) a radical polymerization initiator, (I) other additives, and (J) an organic solvent. Hereinafter, each component contained in the resin composition will be described in detail.

< (A) epoxy resin having a condensed ring structure

The resin composition of the present invention comprises (a) an epoxy resin having a condensed ring structure. (A) The epoxy resin having a condensed ring structure is a resin having 1 or more condensed rings and 1 or more (preferably 2 or more) epoxy groups in 1 molecule. (A) The epoxy resin containing a condensed ring structure is an epoxy resin prepolymer crosslinkable via an epoxy group. (A) The epoxy resin having a condensed ring structure may be used alone or in combination of two or more kinds at an arbitrary ratio.

(A) The condensed ring contained in the epoxy resin having a condensed ring structure is preferably a condensed aromatic hydrocarbon ring. The fused aromatic hydrocarbon ring is an aromatic hydrocarbon ring of 2 or more ring types obtained by fusing 2 or more benzene rings, the number of carbon atoms is preferably 10 to 18, more preferably 10 to 14, and examples thereof include a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and a naphthalene ring is particularly preferable.

(A) The epoxy resin having a condensed ring structure may be any of glycidyl ether type, glycidyl amine type, glycidyl ester type and olefin oxide (alicyclic) type, and among them, glycidyl ether type is preferred.

(A) The epoxy resin having a condensed ring structure may be a monomer type or a repeating structure type. Here, the repeating structure type refers to a resin including a polymer structure having 3 or more repeating units including 1 or 2 or more condensed rings, and the monomer type refers to a resin other than these. In one embodiment, (a) the condensed ring structure-containing epoxy resin comprises (a-1) a monomeric condensed ring structure-containing epoxy resin. In one embodiment, (a) the fused ring structure-containing epoxy resin comprises (a-2) a fused ring structure-containing epoxy resin of a repeating structure type. In one embodiment, (A) the fused ring structure-containing epoxy resin is preferably both of a fused ring structure-containing epoxy resin comprising (A-1) a monomer type and a fused ring structure-containing epoxy resin comprising (A-2) a repeating structure type.

Examples of the monomeric epoxy resin having a condensed ring structure of (A-1) include: epoxy resins having a condensed ring structure, such as 1, 6-bis (glycidyloxy) naphthalene, 1, 5-bis (glycidyloxy) naphthalene, 2, 7-bis (glycidyloxy) naphthalene, and 2, 6-bis (glycidyloxy) naphthalene, which are monomeric and have 1 condensed ring in 1 molecule; bis [2- (glycidyloxy) -1-naphthyl ] methane, 2-bis [2- (glycidyloxy) -1-naphthyl ] propane, bis [2, 7-bis (glycidyloxy) -1-naphthyl ] methane, and a monomer type epoxy resin having a condensed ring structure and having 2 condensed rings in 1 molecule, such as 2, 2-bis [2, 7-bis (glycidyloxy) -1-naphthyl ] propane, 2, 7-bis (glycidyloxy) -1-naphthyl ] [2- (glycidyloxy) -1-naphthyl ] methane, and 2- [2, 7-bis (glycidyloxy) -1-naphthyl ] -2- [2- (glycidyloxy) -1-naphthyl ] propane.

The monomeric epoxy resin having a condensed ring structure of (A-1) is preferably a monomeric epoxy resin having 1 condensed ring in 1 molecule, and particularly preferably 1, 6-bis (glycidyloxy) naphthalene.

The epoxy resin having a condensed ring structure of the monomer type (A-1) is preferably a difunctional to tetrafunctional epoxy resin, more preferably a difunctional or trifunctional epoxy resin, particularly preferably a difunctional epoxy resin.

The epoxy equivalent of the monomeric epoxy resin having a condensed ring structure of (A-1) is not particularly limited, but is preferably 50g/eq. or more, more preferably 80g/eq. or more, still more preferably 100g/eq. or more, still more preferably 120g/eq. or more, and particularly preferably 130g/eq. or more. The upper limit of the epoxy equivalent of the monomeric epoxy resin having a condensed ring structure of (A-1) is not particularly limited, but is preferably 1000 g/eq.or less, more preferably 500 g/eq.or less, still more preferably 300 g/eq.or less, still more preferably 200 g/eq.or less, particularly preferably 160 g/eq.or less.

The molecular weight of the monomeric epoxy resin having a condensed ring structure of (A-1) is not particularly limited, but is preferably 2000 or less, more preferably 1000 or less, further preferably 700 or less, further more preferably 600 or less, particularly preferably 500 or less.

Examples of commercially available products of the monomeric epoxy resin having a fused ring structure (A-1) include "HP-4032D" and "HP-4032 SS" (an epoxy resin having 1 naphthalene ring in 1 molecule) manufactured by DIC; "EXA-4750", "HP-4770", "HP-4700" and "HP-4710" (an epoxy resin having 2 naphthalene rings in 1 molecule) manufactured by DIC, Inc.

Examples of the epoxy resin containing a condensed ring structure of the repeating structure type (a-2) include repeating structure type epoxy resins containing a molecule having 3 or more condensed rings in 1 molecule, such as naphthol novolac type epoxy resins, naphthol-phenol co-condensation novolac type epoxy resins, naphthol-cresol co-condensation novolac type epoxy resins, naphthol aralkyl type epoxy resins, naphthalenediol aralkyl type epoxy resins, and naphthylene ether type epoxy resins. Among them, particularly preferred is a naphthol aralkyl type epoxy resin. The naphthol aralkyl type epoxy resin is an epoxy resin having a molecular structure in which a naphthylene unit and an aralkylene unit having an epoxy group are alternately repeated.

The epoxy equivalent of the epoxy resin having a condensed ring structure of the repeating structure type (A-2) is not particularly limited, but is preferably 50g/eq. or more, more preferably 100g/eq. or more, further preferably 200g/eq. or more, further preferably 250g/eq. or more, particularly preferably 300g/eq. or more. The upper limit of the epoxy equivalent of the epoxy resin having a condensed ring structure of the repeating structure type (A-2) is not particularly limited, but is preferably 2000g/eq. or less, more preferably 1000g/eq. or less, still more preferably 500g/eq. or less, and still more preferably 400g/eq. or less.

Commercially available products of the epoxy resin containing a condensed ring structure of the (a-2) repeating structure type include, for example: "ESN-155", "ESN-185V", "ESN-175", "ESN-475V", "ESN-485", "TX-1507B" (naphthol aralkyl type epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" and "HP-6000-L" (naphthylene ether type epoxy resins) manufactured by DIC corporation; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by Nippon chemical Co., Ltd.

When the (a) condensed ring structure-containing epoxy resin contains both of the (a-1) monomeric condensed ring structure-containing epoxy resin and the (a-2) repeating structure-containing epoxy resin, the mass ratio of the (a-1) monomeric condensed ring structure-containing epoxy resin to the (a-2) repeating structure-containing condensed ring structure-containing epoxy resin (monomeric/repeating structure type) is not particularly limited, and is preferably 0.1 or more, more preferably 0.5 or more, further preferably 1 or more, and particularly preferably 1.2 or more. The upper limit of the mass ratio is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

The resin composition may contain other epoxy resins in addition to the epoxy resin (a) having a condensed ring structure, and the content of the epoxy resin (a) having a condensed ring structure in the resin composition is preferably 50% by mass or more and 60% by mass or more, more preferably 70% by mass or more and 80% by mass or more, further preferably 90% by mass or more and 95% by mass or more, further preferably 98% by mass or more and 99% by mass or more, particularly preferably 100% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention, when the total amount of the epoxy resins in the resin composition is 100% by mass.

The content of the epoxy resin having a condensed ring structure (a) in the resin composition is not particularly limited, and is preferably 10 mass% or more, more preferably 30 mass% or more, further preferably 40 mass% or more, further more preferably 50 mass% or more, particularly preferably 55 mass% or more or 60 mass% or more, from the viewpoint of improving the adhesion strength, when the nonvolatile components other than the inorganic filler (C) in the resin composition are assumed to be 100 mass%. The upper limit of the content of the epoxy resin having a condensed ring structure (a) in the resin composition is not particularly limited, and the content of the epoxy resin having a condensed ring structure (a) in the resin composition is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, further preferably 70% by mass or less, particularly preferably 65% by mass or less, assuming that the nonvolatile components other than the inorganic filler (C) in the resin composition are 100% by mass.

< (B) alkoxy group-containing naphthol aralkyl resin

The resin composition of the present invention comprises (B) an alkoxy group-containing naphthol aralkyl resin. (B) The alkoxy group-containing naphthol aralkyl resin has a molecular structure in which a naphthylene unit and an aralkylene unit having a hydroxyl group and/or an alkoxy group are alternately repeated. Each unit may further have an arbitrary substituent. The alkoxy group-containing naphthol aralkyl resin (B) described below is a resin containing no epoxy group, and does not contain a component (a). (B) The alkoxy group-containing naphthol aralkyl resin may be used singly or in combination of two or more kinds at an arbitrary ratio.

In the (B) alkoxy group-containing naphthol aralkyl resin, the alkoxy group is preferably directly bonded to the naphthalene ring, particularly preferably directly bonded to the α -position of the naphthalene ring. Alkoxy means a monovalent group in which a straight, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group is bonded via an oxygen atom. (B) The alkoxy group contained in the alkoxy group-containing naphthol aralkyl resin is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy and isopropoxy, and among them, methoxy is particularly preferable.

In one embodiment, (B) the alkoxy group-containing naphthol aralkyl resin preferably further contains a hydroxyl group (preferably a phenolic hydroxyl group directly bonded to the naphthalene ring (particularly preferably directly bonded at the. alpha. -position)). Therefore, in this embodiment, the (B) alkoxy group-containing naphthol aralkyl resin may function as a curing agent for curing the epoxy resin containing the component (a). In this embodiment, the ratio of the number of equivalents of hydroxyl groups to alkoxy groups present (hydroxyl groups/alkoxy groups) is preferably 0.1 or more, more preferably 1 or more, still more preferably 2 or more, and particularly preferably 3 or more.

(B) The alkoxy group-containing naphthol aralkyl resin is not particularly limited, but a naphthol aralkyl resin represented by the following formula (1) is preferred.

[ chemical formula 2]

[ wherein R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, at least 1R is an alkyl group having 1 to 6 carbon atoms, n represents an integer of 2 to 20, X independently represents an alkylene group having 1 to 6 carbon atoms, and each of rings A, B and C independently may further have a substituent. ].

More preferred is a naphthol aralkyl resin represented by the following formula (2):

[ chemical formula 3]

[ wherein R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, at least 1R is an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 20. ].

In the formulas (1) and (2), R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and at least 1R is an alkyl group having 1 to 6 carbon atoms. Alkyl refers to a straight, branched, and/or cyclic monovalent aliphatic saturated hydrocarbon group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a sec-pentyl group, a tert-pentyl group, a cyclopentyl group, and a cyclohexyl group. R preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and at least 1R is an alkyl group having 1 to 3 carbon atoms; more preferably each independently represents a hydrogen atom or a methyl group, and at least 1R is a methyl group. In one embodiment, preferably at least 1R is a hydrogen atom. In this embodiment, the proportion of R as a hydrogen atom is preferably 50% or more, more preferably 60% or more, when all R are defined as 100%.

In the formulas (1) and (2), n represents an integer of 2 to 20. n is preferably an integer of 2 to 10, more preferably an integer of 2 to 8, further preferably an integer of 3 to 6, particularly preferably 4 or 5.

In the formula (1), X independently represents an alkylene group having 1-6 carbon atoms. Alkylene means a straight, branched or cyclic divalent aliphatic saturated hydrocarbon group. Examples of the alkylene group include-CH₂-、-CH₂-CH₂-、-CH(CH₃)-、-CH₂-CH₂-CH₂-、-CH₂-CH(CH₃)-、-CH(CH₃)-CH₂-、-C(CH₃)₂-、-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH(CH₃)-、-CH₂-CH(CH₃)-CH₂-、-CH(CH₃)-CH₂-CH₂-、-CH₂-C(CH₃)₂-、-C(CH₃)₂-CH₂-and the like. X preferably represents an alkylene group having 1 to 3 carbon atoms, more preferably-CH₂-。

In formula (1), each of rings A, B and C independently may further have a substituent. Further substituents in the ring A, B and C are not particularly limited, and examples thereof include hydrocarbon groups such as an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 15 carbon atoms. Aryl means a monovalent aromatic hydrocarbon group. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Aralkyl means an alkyl group substituted with 1 or 2 or more aryl groups. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a 2-naphthylmethyl group. The number of further substituents of ring A, B and C is preferably 0 to 2, and ring A, B and C particularly preferably have no further substituent. Preferably, ring C is attached to 2X in para position.

(B) The number average molecular weight of the alkoxy group-containing naphthol aralkyl resin is not particularly limited, but is preferably 400 to 5000, more preferably 600 to 3000, further preferably 800 to 2000. The number average molecular weight may be a value measured as a value in terms of polystyrene by, for example, a Gel Permeation Chromatography (GPC) method.

The content of the (B) alkoxy group-containing naphthol aralkyl resin in the resin composition is not particularly limited, and the content of the (B) alkoxy group-containing naphthol aralkyl resin in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, assuming that the nonvolatile components other than the (C) inorganic filler in the resin composition are 100% by mass. The upper limit of the content of the (B) alkoxy group-containing naphthol aralkyl resin in the resin composition is not particularly limited, and the content of the (B) alkoxy group-containing naphthol aralkyl resin in the resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, further preferably 20% by mass or less, particularly preferably 15% by mass or less, assuming that the nonvolatile components other than the (C) inorganic filler in the resin composition are 100% by mass.

(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 a particulate state.

As the material of the inorganic filler (C), an inorganic compound is used. Examples of the material of the inorganic filler (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium 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, calcium zirconate titanate, zirconium phosphate, zirconium phosphotungstate and the like. Among them, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as the silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more kinds at an arbitrary ratio.

Examples of commercially available products of (C) the inorganic filler include: "UFP-30" manufactured by the electric chemical industry Co., Ltd.; "SP 60-05" and "SP 507-05" manufactured by Nissi iron-alloy materials Corp; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Admatech (Admatech); UFP-30 manufactured by DENKA corporation; "Silfil (シルフィル) NSS-3N", "Silfil NSS-4N" and "Silfil NSS-5N" manufactured by Deshan (トクヤマ); "SC 2500 SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Yadama corporation; "DAW-03" and "FB-105 FD" manufactured by DENKA corporation, and the like.

(C) The average particle size of the inorganic filler is not particularly limited, but is preferably 20 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, further preferably 3 μm or less, particularly preferably 1 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, particularly preferably 0.2 μm or more. (C) The average particle diameter of the inorganic filler can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is measured as an average particle size. As the measurement sample, a sample obtained by weighing 100mg of the inorganic filler and 10g of methyl ethyl ketone in a vial and dispersing them by ultrasonic waves for 10 minutes can be used. For the measurement sample, the volume-based particle size distribution of the inorganic filler was measured by a flow cell method using a laser diffraction type particle size distribution measuring apparatus with the wavelengths of the light source used being blue and red, and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Ltd.

(C) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1m²More than g, preferably 0.5m²More than g, preferably 1m²More than g, particularly preferably 3m²More than g. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 50m²A ratio of the total amount of the components to the total amount of the components is 30m or less²A total of 20m or less per gram²A ratio of 10m or less per gram²The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area of the inorganic filler material can be obtained as follows: according to the BET method, nitrogen gas was adsorbed onto the surface of a sample using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountech corporation), and the specific surface area was calculated by the BET multipoint method.

(C) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. The moisture resistance and dispersibility of the inorganic filler (C) can be improved by surface treatment. Examples of the surface treatment agent include: vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy silane coupling agents such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; styrene-based silane coupling agents such as p-styryltrimethoxysilane; methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; amino silane coupling agents such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris (trimethoxysilylpropyl) isocyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto 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-trimethoxysilylpropyl succinic anhydride; and the like; and non-silane-coupled alkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1, 6-bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane. The surface treatment agent may be used alone or in combination of two or more kinds at an arbitrary ratio.

Examples of commercially available surface treatment agents include: "KBM-1003" and "KBE-1003" (vinyl silane coupling agent) manufactured by shin-Etsu chemical industries, Ltd.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene-based silane coupling agent); "KBM-502", "KBM-503", "KBE-502" and "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-9103P", "KBM-573" and "KBM-575" (amino silane coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (ureido silane coupling agent); "KBM-802" and "KBM-803" (mercapto silane coupling agents); "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-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupling-alkoxysilane compound), and the like.

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

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02mg/m²Above, preferably 0.1mg/m²The above, more preferably 0.2mg/m²The above. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition or the melt viscosity in the form of a sheet from increasing, it is preferably 1.0mg/m²The concentration is preferably 0.8mg/m or less²More preferably 0.5mg/m or less²The following.

(C) The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after surface treatment is subjected to a cleaning treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, a sufficient amount of MEK was added as a solvent to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning was performed at 25 ℃ for 5 minutes. After removing the supernatant liquid and drying the solid components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd., can be used.

The content of the inorganic filler (C) in the resin composition is 70% by mass or more, preferably 75% by mass or more, more preferably 78% by mass or more, further preferably 80% by mass or more, particularly preferably 82% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass. The upper limit of the content of the (C) inorganic filler in the resin composition is not particularly limited, and the content of the (C) inorganic filler in the resin composition may be, for example, 98 mass% or less, 95 mass% or less, 90 mass% or less, or 85 mass% or less, assuming that the nonvolatile content in the resin composition is 100 mass%.

< (D) organic filling Material

The resin composition of the present invention may further contain (D) an organic filler as an optional component. (D) The organic filler may be used alone or in combination of two or more.

(D) The organic filler is present in the resin composition in the form of particles. Examples of the organic filler (D) include rubber particles, polyamide fine particles, silicone particles, and the like, and in the present invention, it is preferable to use rubber particles from the viewpoint of remarkably obtaining the effects desired by the present invention.

Examples of the rubber component contained in the rubber particles include: olefinic thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-isobutylene copolymers, acrylonitrile-butadiene copolymers, isoprene-isobutylene copolymers, isobutylene-butadiene copolymers, ethylene-propylene-diene terpolymers, and ethylene-propylene-butene terpolymers; thermoplastic elastomers such as acrylic thermoplastic elastomers such as polypropylene (meth) acrylate, polybutylene (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate, preferably olefinic thermoplastic elastomers, and more preferably styrene-butadiene copolymers. The rubber component may further contain a silicone rubber such as polyorganosiloxane rubber. The glass transition temperature of the rubber component contained in the rubber particles is, for example, 0 ℃ or lower, preferably-10 ℃ or lower, more preferably-20 ℃ or lower, further preferably-30 ℃ or lower.

From the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferable that (D) the organic filler is core-shell type rubber particles. The core-shell type rubber particles are granular organic fillers formed of core particles containing the above-mentioned rubber components and 1 or more shell portions covering the core particles. Further, the core-shell type particles are preferably core-shell type graft copolymer rubber particles formed of "core particles containing the rubber components exemplified above" and "shell portions obtained by graft-copolymerizing monomer components copolymerizable with the rubber components contained in the core particles". The core-shell type herein does not necessarily mean only those in which the core particle and the shell are clearly distinguished from each other, and includes those in which the boundary between the core particle and the shell is not clear, and the core particle may not be completely covered with the shell.

The rubber component is contained in the core-shell type rubber particles in an amount of preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. The upper limit of the content of the rubber component in the core-shell type rubber particle is not particularly limited, but is, for example, 95 mass% or less, preferably 90 mass% or less, from the viewpoint of sufficiently coating the core particle with the shell portion.

Examples of the monomer components forming the shell portion of the core-shell type rubber particle include: (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and glycidyl (meth) acrylate; (meth) acrylic acid; n-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; a maleimide; α, β -unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene and α -methylstyrene; (meth) acrylonitrile, etc., and among them, a (meth) acrylate is preferably contained, and methyl (meth) acrylate is more preferably contained.

Commercially available products of the core-shell type rubber particles include, for example: "CHT" manufactured by Chenl Industries, Inc.; "B602" manufactured by UMGABS corporation; "PARALOID EXL-2602", "PARALOID EXL-2603", "PARALOID EXL-2655", "PARALOID EXL-2311", "PARALOID EXL-2313", "PARALOID EXL-2315", "PARALOID KM-330", "PARALOID KM-336P" and "PARALOID KCZ-201" manufactured by Dow chemical Japan; "METABLEN C-223A", "METABLEN E-901", "METABLEN S-2001", "METABLEN W-450A", "METABLEN SRK-200", manufactured by Mitsubishi Rayon, Inc.; "Kane Ace M-511", "Kane Ace M-600", "Kane Ace M-400", "Kane Ace M-580", and "Kane Ace MR-01" manufactured by Kaneka corporation. These may be used alone or in combination of two or more.

(D) The average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 20nm or more, more preferably 50nm or more, further preferably 80nm or more, particularly preferably 100nm or more. (D) The upper limit of the average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 5000nm or less, more preferably 2000nm or less, further preferably 1000nm or less, particularly preferably 500nm or less. (D) The average particle diameter (average primary particle diameter) of the organic filler can be measured using a Zeta potential particle size distribution measuring instrument or the like.

The content of the organic filler (D) in the resin composition is not particularly limited, but is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, particularly preferably 15% by mass or less, based on 100% by mass of nonvolatile components other than the inorganic filler (C) in the resin composition. The lower limit of the content of the organic filler (D) in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 5% by mass or more, particularly preferably 10% by mass or more, based on 100% by mass of nonvolatile components other than the inorganic filler (C) in the resin composition.

(E) curing agent

The resin composition of the present invention may further contain (E) a curing agent as an optional component. (E) The curing agent has a function of curing the epoxy resin containing the component (a). The curing agent (E) is not a component of the component (B).

The curing agent (E) is not particularly limited, and examples thereof include phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, amine-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, and the like. (E) One curing agent may be used alone, or two or more curing agents may be used in combination.

As the phenol curing agent and the naphthol curing agent, a phenol curing agent having a novolak structure (novolak structure) or a naphthol curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to an adherend, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Among them, a phenol novolac resin containing a triazine skeleton is preferable from the viewpoint of satisfying heat resistance, water resistance and adhesion at a high level. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include: MEH-7700, MEH-7810, and MEH-7851 available from Ming and Cheng Co; "NHN", "CBN" and "GPH" manufactured by Nippon chemical Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", manufactured by Nissan chemical materials, Inc.; "LA-7052", "LA-7054", "LA-3018-50P", "LA-1356", "TD 2090", "TD-2090-60M" manufactured by DIC corporation, and the like.

Examples of the acid anhydride-based curing agent include a curing agent having 1 or more acid anhydride groups in 1 molecule, and preferably a curing agent having 2 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based curing agent include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic anhydride, 3,3'-4,4' -diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-C furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid, and other polymer type acid anhydrides. Commercially available acid anhydride curing agents include: "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA", manufactured by Nissan chemical and physical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi chemical corporation; HN-2200 and HN-5500 manufactured by Hitachi chemical Co.

Examples of the amine-based curing agent include those having 1 or more, preferably 2 or more, amino groups in 1 molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. The amine-based curing agent is preferably a primary or secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include: 4,4' -methylenebis (2, 6-dimethylaniline), 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethanediamine, 2-bis (4-aminophenyl) propane, 2, 4' -diaminodiphenylmethanediamine, 4-diaminodiphenylmethanediamine, and mixtures thereof, 2, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and the like. As the amine-based curing agent, commercially available products can be used, and examples thereof include "SEIKACURE-S" manufactured by SEIKA, KAYABOND C-200S "manufactured by Japan Chemicals, KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S", and "Epicure (エピキュア) W" manufactured by Mitsubishi chemical corporation.

The active ester-based curing agent is not particularly limited, and generally, a compound having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, is preferably used. The active ester-based curing agent is preferably a compound obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound 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, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac resin (phenol novolac resin), and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.

Specifically, an active ester-based curing agent containing a dicyclopentadiene diphenol structure, an active ester-based curing agent containing a naphthalene structure, an active ester-based curing agent containing an acetyl compound of a phenol novolac resin, and an active ester-based curing agent containing a benzoyl compound of a phenol novolac resin are preferable, and an active ester-based curing agent containing a naphthalene structure and an active ester-based curing agent containing a dicyclopentadiene diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" means a divalent structural unit formed from phenylene-dicyclopentylene (ジシクロペンチレン) -phenylene.

As the commercially available active ester-based curing agents, examples of the active ester-based curing agents having a dicyclopentadiene type diphenol structure include "EXB 9451", "EXB 9460S", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65 TM", "EXB-8000L-65M", "EXB-8000L-65 TM" (manufactured by DIC); examples of the active ester-based curing agent having a naphthalene structure include "EXB-9416-70 BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" and "EXB-8150-62T" (manufactured by DIC); examples of the active ester-based curing agent for the acetylated phenol novolac resin include "DC 808" (manufactured by mitsubishi chemical corporation); examples of the active ester curing agent for the benzoylate of the phenol novolak resin include "YLH 1026" (manufactured by mitsubishi chemical corporation), "YLH 1030" (manufactured by mitsubishi chemical corporation), and "YLH 1048" (manufactured by mitsubishi chemical corporation); and so on.

Specific examples of the benzoxazine-based curing agent include: "JBZ-OP 100D" and "ODA-BOZ" manufactured by JFE chemical company; "HFB 2006M" available from Showa Polymer Co; "P-d" and "F-a" manufactured by four national chemical industries, Inc.

Examples of the cyanate ester-based curing agent include: bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1, 5-phenylene cyanate), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2-bis (4-cyanate-group) phenylpropane, 1-bis (4-cyanate-group phenyl methane), bis (4-cyanate-group-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate-group-phenyl-1- (methylethylidene)) benzene, bis (4-cyanate-group-phenyl) sulfide, bis (4-cyanate-group-phenyl) ether and other difunctional cyanate resins, polyfunctional cyanate resins derived from phenol novolac resin, cresol novolac resin and the like, polyfunctional cyanate resins, and the like, Prepolymers obtained by triazinating a part of these cyanate ester resins, and the like. Specific examples of the cyanate ester-based curing agent include "PT 30" and "PT 60" (both of which are phenol novolac type polyfunctional cyanate ester resins), "BA 230" and "BA 230S 75" (prepolymers in which a part or all of bisphenol a dicyanate is triazinized to form a trimer), which are manufactured by Lonza Japan.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo chemical Co.

When the resin composition contains the curing agent (E), the amount ratio of the "epoxy resin" to the components (B) and (E) curing agent "is [ the number of epoxy groups of the epoxy resin ]: the ratio of [ (total of the number of hydroxyl groups in the component (B) and the number of reactive groups in the curing agent (E) ] is preferably 1: 0.2-1: 2, more preferably 1: 0.3-1: 1.5, more preferably 1: 0.4-1: 1.4. here, for example, if the curing agent is a phenol curing agent or a naphthol curing agent, the reactive group of the curing agent (E) is an aromatic hydroxyl group, and if the curing agent is an active ester curing agent, the reactive group of the curing agent (E) is an active ester group, and the reactive group of the curing agent (E) differs depending on the type of the curing agent.

(E) The equivalent weight of the reactive group of the curing agent is preferably 50g/eq to 3000g/eq, more preferably 100g/eq to 1000g/eq, still more preferably 100g/eq to 500g/eq, and particularly preferably 100g/eq to 300g/eq. The reactive group equivalent is the mass of the curing agent per 1 equivalent of the reactive group.

The content of the curing agent (E) in the resin composition is not particularly limited, and when the nonvolatile components other than the inorganic filler (C) in the resin composition are taken as 100 mass%, the content of the curing agent (E) in the resin composition is preferably 50 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, particularly preferably 10 mass% or less. The lower limit of the content of the (E) curing agent in the resin composition is not particularly limited, and the content of the (E) curing agent in the resin composition is, for example, 0 mass% or more, 0.01 mass% or more, 0.1 mass% or more, 1 mass% or more, 3 mass% or more, or 5 mass% or more, assuming that the nonvolatile components other than the (C) inorganic filler in the resin composition are 100 mass%.

(F) curing Accelerator

The resin composition of the present invention may contain (F) a curing accelerator as an optional component. (F) The curing accelerator has a function of accelerating curing of the epoxy resin containing the component (a).

The curing accelerator (F) is not particularly limited, and examples thereof include: phosphorus-based curing accelerators, urea-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among them, preferred are phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators, and particularly preferred are imidazole-based curing accelerators. (F) The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include: aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hexahydrophthalate hydrogen salt, tetrabutylphosphonium cresol novolak trimer salt, di-t-butylmethylphosphonium tetraphenylborate and the like; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris (3-methylphenyl) ethylphosphonium tetraphenylborate, tris (2-methoxyphenyl) ethylphosphonium tetraphenylborate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; an aromatic phosphine-quinone addition reaction product such as a triphenylphosphine-p-benzoquinone addition reaction product; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutylphenylphosphine, di-t-butylphenyl phosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-t-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2,4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, triphenylphosphine, tri (4-t-butylphenyl) phosphine, tri (4-methylphenyl) phosphine, tri (4-methoxyphenyl) phosphine, tri (4-methylphenyl) phosphine, tri (4-phenyl) phosphine, tri (4-methylphenyl) phosphine, tri (4-butyl-phenyl) phosphine, tri (4-phenyl) phosphine, tri (2-phenyl) phosphine, tri (4, tri (2-phenyl) phosphine, tri (4, tri (2-butyl-phenyl) phosphine, tri (2-butyl, tri (4, tri (2-phenyl) phosphine, tri (4, tri-phenyl) phosphine, tri (2-butyl, tri (4, tri-phenyl) phosphine, tri (2-phenyl) phosphine, tri (, And aromatic phosphines such as tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, tris (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 2-bis (diphenylphosphino) acetylene, and 2,2' -bis (diphenylphosphino) diphenyl ether.

Examples of the urea-based curing accelerator include: 1, 1-dimethylurea; aliphatic dimethylureas such as 1,1, 3-trimethylurea, 3-ethyl-1, 1-dimethylurea, 3-cyclohexyl-1, 1-dimethylurea, and 3-cyclooctyl-1, 1-dimethylurea; 3-phenyl-1, 1-dimethylurea, 3- (4-chlorophenyl) -1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea, 3- (2-methylphenyl) -1, 1-dimethylurea, 3- (4-methylphenyl) -1, 1-dimethylurea, 3- (3, 4-dimethylphenyl) -1, 1-dimethylurea, 3- (4-isopropylphenyl) -1, 1-dimethylurea, 3- (4-methoxyphenyl) -1, 1-dimethylurea, methyl-3-hydroxyurea, methyl-3-methyl-1-dimethylurea, methyl-3-methyl-4-methylphenyl-1-dimethylurea, methyl-3-methyl-1-dimethylurea, methyl-3-methyl-1-dimethylurea, methyl-3-1-methyl-1-dimethylurea, methyl-3-methyl-1-dimethylurea, methyl-1-methyl-urea, methyl-2-methyl-urea, and mixtures thereof, Aromatic dimethylureas such as 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- (1, 4-phenylene) bis (N ', N' -dimethylurea), and N, N- (4-methyl-1, 3-phenylene) bis (N ', N' -dimethylurea) [ tolylbisdimethylurea ].

Examples of the amine-based curing accelerator include: trialkylamines such as triethylamine and tributylamine, 4-Dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5.4.0) undecene, and the like, with 4-dimethylaminopyridine being preferred.

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

As the imidazole-based curing accelerator, commercially available products such as "P200-H50" manufactured by Mitsubishi chemical company can be used.

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

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

The content of the curing accelerator (F) in the resin composition is not particularly limited, and when the nonvolatile components other than the inorganic filler (C) in the resin composition are taken as 100 mass%, the content of the curing accelerator (F) in the resin composition is preferably 5 mass% or less, more preferably 2 mass% or less, further preferably 1 mass% or less, further preferably 0.5 mass% or less, particularly preferably 0.2 mass% or less. The lower limit of the content of the (F) curing accelerator in the resin composition is not particularly limited, and the content of the (F) curing accelerator in the resin composition may be, for example, 0 mass% or more, 0.0001 mass% or more, 0.001 mass% or more, 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, or the like, when the nonvolatile component other than the (C) inorganic filler in the resin composition is 100 mass%.

< G radical polymerizable Compound

The resin composition of the present invention may further contain (G) a radical polymerizable compound as an optional component. (G) The radical polymerizable compound may be used alone or in any combination of two or more.

(G) The radical polymerizable compound may be, for example, a compound having a radical polymerizable unsaturated group. The radical polymerizable unsaturated group is not particularly limited as long as it is radical polymerizable, and may be any ethylenically unsaturated group having a carbon-carbon double bond at the end or inside thereof, and specifically may be an unsaturated aliphatic group such as allyl group or 3-cyclohexenyl group; aromatic groups containing unsaturated aliphatic groups such as p-vinylphenyl group, m-vinylphenyl group, and styryl group; and α, β -unsaturated carbonyl groups such as acryloyl, methacryloyl, maleoyl, and fumaroyl groups. (G) The radical polymerizable compound preferably has 1 or more radical polymerizable unsaturated groups, more preferably 2 or more radical polymerizable unsaturated groups.

Examples of the compound having a radical polymerizable unsaturated group include: a maleimide-based radical polymerizable compound having a maleimide group; a vinyl phenyl radical polymerizable compound having a vinyl phenyl group such as a p-vinyl phenyl group or a m-vinyl phenyl group; a (meth) acrylic radical polymerizable compound having an acryloyl group and/or a methacryloyl group (hereinafter collectively referred to as a "(meth) acryloyl group"); an allyl radical polymerizable compound having an allyl group; the polybutadiene-based radical polymerizable compound having a polybutadiene skeleton is preferably any of a maleimide-based radical polymerizable compound and a vinylphenyl-based radical polymerizable compound.

The maleimide-based radical polymerizable compound is a compound having a maleimide group in the molecule. The number of maleimide groups per 1 molecule of the maleimide-based radical polymerizable compound is preferably 2 or more.

In the first embodiment, the maleimide-based radical polymerizable compound is preferably a polymaleimide compound having a repeating unit, more preferably an aromatic polymaleimide compound having a repeating unit, and particularly preferably an aromatic polymaleimide compound represented by the following formula (3).

[ chemical formula 4]

[ in the formula, X¹And X²Independently represents a single bond, an alkylene group having 1 to 6 carbon atoms, -O-, -CO-, -S-, -SO-, or-SO₂- (preferably an alkylene group having 1 to 6 carbon atoms, more preferably-CH)₂-, Ar represents an arylene group having 6 to 14 carbon atoms (preferably 4,4' -biphenyl group) which may have an alkyl group having 1 to 6 carbon atoms, n1 independently represents 0 or 1, and n2 represents an integer of 1 to 100 (preferably 1 to 50, more preferably 1 to 20, further preferably 1 to 5).]。

Arylene refers to a divalent aromatic hydrocarbon group, which may be multiple aromatic rings fused or directly connected. Examples of the arylene group include a1, 3-phenylene group, a1, 4-phenylene group, a1, 5-naphthylene group, a1, 8-naphthylene group, a2, 6-naphthylene group, a 4,4 '-biphenyl group, and a 3,4' -biphenyl group.

In the second embodiment, the maleimide-based radical polymerizable compound is preferably a bismaleimide compound obtained by imidizing a polyamine compound (particularly, a diamine compound), maleic anhydride, and, if necessary, a polycarboxylic anhydride (particularly, tetracarboxylic dianhydride), and particularly preferably a bismaleimide compound represented by the following formula (4).

[ chemical formula 5]

[ in the formula, Y¹And Y³Each independently represents the removal of 2-NH groups from the diamine compound₂The divalent group may be, for example, a divalent organic group formed of 2 or more (for example, 2 to 3000, 2 to 1000, 2 to 100, 2 to 50) skeleton atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Y is²The tetravalent group obtained by removing 2-CO-O-CO-atoms from tetracarboxylic dianhydride may be, for example, a tetravalent organic group formed by 2 or more (for example, 2 to 3000, 2 to 1000, 2 to 100, 2 to 50) skeleton atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. m represents 0 or an integer of 1 or more.]。

The diamine compound used for producing the maleimide-based radical polymerizable compound is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

Examples of the aliphatic diamine compound include: linear aliphatic diamine compounds such as 1, 2-ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, and 1, 10-diaminodecane; branched aliphatic diamine compounds such as 1, 2-diamino-2-methylpropane, 2, 3-diamino-2, 3-butane and 2-methyl-1, 5-diaminopentane; alicyclic diamine compounds such as 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, and 4,4' -methylenebis (cyclohexylamine); dimer acid type diamines, and the like.

Dimer acid type diamine refers to dimer acid with two terminal carboxyl groups (-COOH) being substituted by aminomethyl (-CH)₂-NH₂) Or amino (-NH)₂) And a diamine compound obtained by substitution. The dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably, an unsaturated fatty acid having 11 to 22 carbon atoms, particularly preferably, an unsaturated fatty acid having 18 carbon atoms), and its industrial production process is generally standardized in the industry. The dimer acid is easily obtained, in particular, from a dimer acid containing 36 carbon atoms, which is obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid or linoleic acid, which is inexpensive and easily available, as a main component. Further, the dimer acid may contain a monomer acid, a trimer acid, other polymerized fatty acid, and the like in an arbitrary amount depending on the production method, the degree of purification, and the like. In addition, although a double bond remains after the polymerization reaction of the unsaturated fatty acid, in the present specification, a hydride which is further hydrogenated to reduce the degree of unsaturation is also included in the dimer acid. Commercially available dimer-type diamines are available, and examples thereof include "PRIAMINE 1073", "PRIAMINE 1074", "PRIAMINE 1075" manufactured by Croda Japan, and "Versamine 551" and "Versamine 552" manufactured by Cognis Japan.

Examples of the aromatic diamine compound include: phenylenediamine compounds such as 1, 4-phenylenediamine, 1, 2-phenylenediamine, 1, 3-phenylenediamine, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 3, 5-diaminobiphenyl, and 2,4,5, 6-tetrafluoro-1, 3-phenylenediamine; naphthalene diamine compounds such as 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, 2, 6-diaminonaphthalene and 2, 3-diaminonaphthalene; 4,4 '-diamino-2, 2' -bis (trifluoromethyl) -1,1 '-biphenyl, 3,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 2-bis (4-aminophenyl) propane, 4' - (hexafluoroisopropylidene) diphenylamine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis (4-aminophenoxy) phenyl ] propane, 4-aminobenzoic acid, phenylformic acid, or a salt thereof, 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, α -bis [4- (4-aminophenoxy) phenyl ] -1, 3-diisopropylbenzene, α -bis [4- (4-aminophenoxy) phenyl ] -1, 4-diisopropylbenzene, 4'- (9-fluorenylidene)) diphenylamine, 2-bis (3-methyl-4-aminophenyl) propane, 2-bis (3-methyl-4-aminophenyl) benzene, 4' -diamino-3, 3 '-dimethyl-1, 1' -biphenyl, 4 '-diamino-2, 2' -dimethyl-1, diphenylamine compounds such as 1' -biphenyl, 9' -bis (3-methyl-4-aminophenyl) fluorene, 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl ] -1,1, 3-trimethylindane, and 5-amino-1, 1' -biphenyl-2-yl 4-aminobenzoate.

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

The tetracarboxylic anhydride used for producing the maleimide-based radical polymerizable compound is not particularly limited, and examples thereof include aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride.

Specific examples of the aliphatic tetracarboxylic acid dianhydride include 1,2,3, 4-cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, cyclohexane-1, 2,3, 4-tetracarboxylic acid dianhydride, cyclohexane-1, 2,4, 5-tetracarboxylic acid dianhydride, 3',4,4' -dicyclohexyltetracarboxylic acid dianhydride, carbonyl-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, methylene-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 1, 2-ethylene-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, oxy-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, thio-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, sulfonyl-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, and the like.

Examples of the aromatic tetracarboxylic dianhydride include: pyromellitic dianhydride, such as 1,2,3, 4-pyromellitic dianhydride; naphthalene tetracarboxylic acid dianhydrides such as 1,4,5, 8-naphthalene tetracarboxylic acid dianhydride and 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride; anthracene tetracarboxylic acid dianhydrides such as 2,3,6, 7-anthracene tetracarboxylic acid dianhydride; 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 3,3',4,4' -diphenylethertetracarboxylic dianhydride, 3,3',4,4' -diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -benzophenonetetracarboxylic dianhydride, 2,3,3',4' -diphenylethertetracarboxylic dianhydride, 2,3,3',4' -diphenylsulfonetetracarboxylic dianhydride, 2 '-bis (3, 4-dicarboxyphenoxyphenyl) sulfone dianhydride, methylene-4, 4' -biphthalic dianhydride, 1-ethynylene (ethylidene4), 4 '-Bisphthalic dianhydride, 2-propylene (propylidene) -4,4' -Bisphthalic dianhydride, 1, 2-ethylene-4, 4 '-Bisphthalic dianhydride, 1, 3-trimethylene-4, 4' -Bisphthalic dianhydride, 1, 4-tetramethylene-4, 4 '-Bisphthalic dianhydride, 1, 5-pentamethylene-4, 4' -Bisphthalic dianhydride, 1, 3-bis (3, 4-dicarboxyphenyl) benzene dianhydride, 1, 4-bis (3, 4-dicarboxyphenyl) benzene dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, And biphthalic dianhydrides such as 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, and 4,4'- (4,4' -isopropylidenediphenoxy) biphthalic dianhydride.

The maleimide-based radical polymerizable compound may include both the maleimide-based radical polymerizable compound of the first embodiment and the maleimide-based radical polymerizable compound of the second embodiment.

Examples of commercially available products of maleimide-based radical polymerizable compounds include: "MIR-3000-70 MT" manufactured by Nippon chemical company; "BMI 689", "BMI 1500", "BMI 1700", and "BMI 3000", manufactured by DESIGNER MOLECULES corporation, and the like.

The vinyl phenyl radical polymerizable compound is a radical polymerizable compound having a vinyl phenyl group. The vinyl phenyl radical polymerizable compound preferably has 2 or more vinyl phenyl groups per 1 molecule.

The vinyl phenyl radical polymerizable compound is preferably a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group and a polyphenylene ether skeleton, and particularly preferably a resin represented by the following formula (5).

[ chemical formula 6]

[ in the formula, R¹And R²Each independently represents an alkyl group having 1 to 6 carbon atoms (preferably methyl group), Z¹、Z²And Z³Independently represents a single bond, an alkylene group having 1 to 6 carbon atoms, -O-, -CO-, -S-, -SO-, or-SO₂-(Z¹And Z³preferably-O-, Z²Preferably a single bond), a1 and a2 each independently represent an integer of 1 to 300 (preferably 1 to 100, more preferably 1 to 50), and b1 and b2 each independently represent an integer of 0 to 4.]。

Examples of commercially available products of the vinylphenyl radical polymerizable compound include "OPE-2 St" (vinylbenzyl-modified polyphenylene ether) manufactured by Mitsubishi gas chemical company.

The (meth) acrylic radical polymerizable compound is a compound having a (meth) acryloyl group. The (meth) acrylic radical polymerizable compound preferably has 2 or more (meth) acryloyl groups per 1 molecule. As THE (meth) acrylic radically polymerizable compound, commercially available products can be used, and examples thereof include "A-DOG" manufactured by Newzhou chemical industry, and "DCP-A" manufactured by Cogrong chemical, and "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA", and "NK ester DCP" manufactured by Newzhou chemical industry.

The allyl radical polymerizable compound having an allyl group means a compound having an allyl group in the molecule. The allyl radical polymerizable compound preferably has 2 or more allyl groups. Commercially available allyl radical polymerizable compounds can be used. Examples of commercially available products include: MEH-8000H and MEH-8005 (allyl radical polymerizable compound having a phenol structure) manufactured by MINGHE CHEMICAL CORPORATION; "RE-810 NM" (an allyl radical polymerizable compound having an epoxy group) manufactured by Nippon Chemicals Co., Ltd; ALP-d (an allyl radical polymerizable compound having a benzoxazine ring) manufactured by four national chemical industry Co., Ltd; L-DAIC (an allyl radical polymerizable compound having an isocyanuric ring (a ring イソシアヌル hooked thereon), manufactured by four national chemical industry Co.); "TAIC" (an allyl radical polymerizable compound having an isocyanuric ring) manufactured by japan chemical company; MDAC (allyl radical polymerizable compound having cyclohexanedicarboxylic acid derivative) manufactured by Osaka SODA (OSAKA SODA); DAD (diallyl bibenzoate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., (Nisshoku Techno Fine Chemical Co., Ltd.); DAISO DAP Monomer (diallyl phthalate) manufactured by Osaka Co.

The polybutadiene-based radical polymerizable compound is a compound having a polybutadiene skeleton. It should be noted that the polybutadiene skeleton may be partially hydrogenated. The polybutadiene-based radical polymerizable compound is more preferably at least one resin selected from the group consisting of a hydroxyl group-containing butadiene resin, a phenolic hydroxyl group-containing butadiene resin, a carboxyl group-containing butadiene resin, an anhydride group-containing butadiene resin, an epoxy group-containing butadiene resin, an isocyanate group-containing butadiene resin and a urethane group-containing butadiene resin. Specific examples of the polybutadiene-based radical polymerizable compound include: JP-100 (manufactured by Nippon Kagaku Co., Ltd.), "Ricon 100 (manufactured by CRAY VALLEY Co., Ltd.)," Ricon150 "," Ricon130MA8 "," Ricon130MA13 "," Ricon130MA20 "," Ricon131MA5 "," Ricon131MA10 "," Ricon131MA17 "," Ricon131MA20 "," Ricon 184MA6 ", and the like.

The content of the radical polymerizable compound (G) in the resin composition is not particularly limited, and when the nonvolatile components other than the inorganic filler (C) in the resin composition are taken as 100% by mass, the content of the radical polymerizable compound (G) in the resin composition is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of the radical polymerizable compound (G) in the resin composition is not particularly limited, and when the nonvolatile component other than the inorganic filler (C) in the resin composition is 100 mass%, it may be, for example, 0 mass% or more, 0.001 mass% or more, 0.01 mass% or more, 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, or the like.

(H) radical polymerization initiator

The resin composition of the present invention may further contain (H) a radical polymerization initiator as an optional component. (H) The radical polymerization initiator may be, for example, a thermal polymerization initiator which generates free radicals (free radials) upon heating. (H) One kind of radical polymerization initiator may be used alone, or two or more kinds may be used in any combination.

Examples of the radical polymerization initiator (H) include peroxide-based radical polymerization initiators and azo-based radical polymerization initiators. Among them, peroxide-based radical polymerization initiators are preferred.

Examples of the peroxide-based radical polymerization initiator include: hydrogen peroxide compounds such as 1,1,3, 3-tetramethylbutylhydroperoxide; dialkyl peroxide compounds such as t-butylcumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, dicumyl peroxide, 1, 4-bis (1-t-butylperoxy-1-methylethyl) benzene, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane; diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis (4-t-butylcyclohexyl) peroxydicarbonate; peroxy ester compounds such as t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxylaurate, 1-dimethylpropyl 2-ethylperoxyhexanoate, t-butyl 3,5, 5-trimethylperoxyhexanoate, t-butyl peroxy-2-ethylhexyl monocarbonate, and t-butyl peroxymaleate; and so on.

Examples of the azo radical polymerization initiator include: azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), 2' -azobisisobutyronitrile, 2 '-azobis (2-methylbutyronitrile), 1' -azobis (cyclohexane-1-carbonitrile), 1- [ (1-cyano-1-methylethyl) azo ] formamide, 2-phenylazo-4-methoxy-2, 4-dimethyl-valeronitrile and the like; 2,2 '-azobis [ 2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide ], 2' -azobis [ 2-methyl-N- [1, 1-bis (hydroxymethyl) ethyl ] propionamide ], 2 '-azobis [ 2-methyl-N- [2- (1-hydroxybutyl) ] -propionamide ], 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) -propionamide ], 2 '-azobis (2-methylpropionamide) dihydrate, 2' -azobis [ N- (2-propenyl) -2-methylpropionamide ], 2, azoamide compounds such as 2 '-azobis (N-butyl-2-methylpropionamide) and 2,2' -azobis (N-cyclohexyl-2-methylpropionamide); alkyl azo compounds such as 2,2 '-azobis (2,4, 4-trimethylpentane) and 2,2' -azobis (2-methylpropane); and so on.

Examples of commercially available products of the radical polymerization initiator (H) include: "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", "PERBUTYL O", "PERBUTYL ND", "PERBUTYL Z", "PERBUTYL I", "PERCUTYL P", "PERCUTYL D", "PERHEXYL A", "PERHEXYL I", "PERHEXYL Z", "PERHEXYL ND", "PERHEXYL O", "PERHEXYL PV", "PERHEXYL O", etc., manufactured by Nichigan oil Co.

The content of the radical polymerization initiator (H) in the resin composition is not particularly limited, and when the nonvolatile components other than the inorganic filler (C) in the resin composition are taken as 100% by mass, the content of the radical polymerization initiator (H) in the resin composition is preferably 5% by mass or less, more preferably 1% by mass or less, further preferably 0.5% by mass or less, further preferably 0.3% by mass or less, particularly preferably 0.2% by mass or less. The lower limit of the content of the radical polymerization initiator (H) in the resin composition is not particularly limited, and the content of the radical polymerization initiator (H) in the resin composition may be, for example, 0 mass% or more, 0.001 mass% or more, 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, or the like, when the nonvolatile components other than the inorganic filler (C) in the resin composition are 100 mass%.

Other additives

The resin composition of the present invention may further contain any additive as a nonvolatile component. Examples of such additives include: epoxy resins other than the component (A), such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, phenol novolac type epoxy resins, biphenyl type epoxy resins, and linear aliphatic epoxy resins; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, and the like; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentonite (Benton) and montmorillonite; defoaming agents such as silicone defoaming agents, acrylic defoaming agents, fluorine defoaming agents, and vinyl resin defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improving agents such as urea silane; an adhesion-imparting agent such as a triazole-based adhesion-imparting agent, a tetrazole-based adhesion-imparting agent, or a triazine-based adhesion-imparting agent; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus flame retardants (e.g., phosphoric acid ester compounds, phosphazene compounds, phosphinic acid (phosphinic acid) compounds, red phosphorus), nitrogen flame retardants (e.g., melamine sulfate), halogen flame retardants, inorganic flame retardants (e.g., antimony trioxide), and the like. One kind of the additive may be used alone, or two or more kinds may be used in combination at an arbitrary ratio. The content of the other additives (I) can be appropriately set by those skilled in the art.

(J) organic solvent

The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the nonvolatile component. As the organic solvent (J), a known solvent can be suitably used, and the kind thereof is not particularly limited. Examples of the organic solvent (J) include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ -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, carbitol acetate (ethylene glycol acetate), γ -butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (J) One kind of the organic solvent may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

In one embodiment, the (J) organic solvent may be, for example, 60 mass% or less, 40 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, or the like, when the total components in the resin composition are 100 mass%.

< method for producing resin composition >

The resin composition of the present invention can be produced, for example, by: the epoxy resin having a condensed ring structure (a), the naphthol aralkyl resin having an alkoxy group (B), the inorganic filler (C), the organic filler (D) if necessary, the curing agent (E) if necessary, the curing accelerator (F) if necessary, the radical polymerizable compound (G) if necessary, the radical polymerization initiator (H) if necessary, the other additives (I) if necessary, and the organic solvent (J) if necessary are added to an arbitrary reaction vessel and mixed in an arbitrary order and/or partially or entirely at the same time. In addition, the temperature may be appropriately set during the addition and mixing of the components, and heating and/or cooling may be performed temporarily or throughout. In addition, the components may be added and mixed while stirring or shaking. In addition, when or after the addition and mixing, the resin composition can be stirred and uniformly dispersed by using a stirring device such as a mixer.

< Property of resin composition >

The resin composition of the present invention comprises (a) an epoxy resin having a condensed ring structure, (B) an alkoxy group-containing naphthol aralkyl resin, and (C) an inorganic filler, and when the nonvolatile content in the resin composition is 100% by mass, the content of the component (C) is 70% by mass or more, whereby warpage during curing can be suppressed and a cured product having excellent adhesion strength can be obtained. In one embodiment, a cured product of the resin composition of the present invention can have excellent electrical characteristics.

In one embodiment, the resin composition of the present invention can suppress warpage during curing, and therefore, for example, as in test example 1 described below, when warpage is measured according to JEITA EDX-7311-24, which is a standard of the Japan society for electronics and information technology industries, the warpage amount is preferably less than 10mm, more preferably less than 5mm, still more preferably less than 3mm, and particularly preferably less than 2 mm.

In one embodiment, the resin composition of the present invention can give a cured product having excellent adhesion strength, and therefore, as in test example 2 described below, when the peel strength (adhesion strength) is measured by a bolt Pull (Stud Pull) peel strength test, the peel strength (adhesion strength) is preferably 100kgf/cm³Above, more preferably 200kgf/cm³Above, more preferably 230kgf/cm³Above, particularly preferably 250kgf/cm³The above.

In one embodiment, since the cured product of the resin composition of the present invention can also have excellent electrical characteristics, the dielectric loss tangent of the cured product of the resin composition as measured under the conditions of 5.8GHz and 23 ℃ as in test example 3 described below is preferably 0.030 or less and 0.020 or less, more preferably 0.015 or less and 0.012 or less, still more preferably 0.010 or less and 0.009 or less, and particularly preferably 0.008 or less and 0.007 or less.

< use of resin composition >

The resin composition of the present invention can be suitably used as a resin composition for insulation applications, particularly a resin composition for forming an insulation layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (insulating layer forming resin composition for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer(s). In addition, the resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board) can be suitably used in a printed wiring board described later. The resin composition of the present invention can be widely used in applications requiring a resin composition, such as a resin sheet, a sheet-like laminate material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, and a component embedding resin.

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as: a resin composition for forming a rewiring layer 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 sealing a semiconductor chip). In manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer;

(1) a step of laminating a temporary fixing film on a base material,

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

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

(4) a step of peeling the base material and the temporary fixing film from the semiconductor chip,

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

(6) and forming a rewiring layer as a conductor layer on the rewiring-forming layer.

Further, the resin composition of the present invention can be suitably used also in the case where a printed wiring board is a component-embedded circuit board, since it forms an insulating layer having good component embeddability.

< sheet-like laminated Material >

The resin composition of the present invention can also be used by applying it in the form of varnish, but it is generally preferable to use it in the form of a sheet-like laminate containing the resin composition industrially.

As the sheet-like laminate, a resin sheet or a prepreg as shown below is preferred.

In one embodiment, the resin sheet comprises a support and a resin composition layer provided on the support, the resin composition layer being formed from the resin composition of the present invention.

From the viewpoint of making the printed wiring board thin and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 5 μm or more and 10 μm or more.

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

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

When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferred. As the copper foil, a foil formed of a single metal of copper may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.

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

Further, as the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include at least one selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having a release layer, commercially available products can be used, and examples thereof include a PET film having a release layer containing an alkyd resin-based release agent as a main component, "SK-1", "AL-5" and "AL-7" manufactured by Lindedaceae, "Lumiror T60" manufactured by Toray, and "Purex" manufactured by Ditika, and "Unipel" manufactured by Unitika.

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

In one embodiment, the resin sheet may further include an arbitrary layer, as necessary. Examples of the optional layer include a protective film provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support) and selected for the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust or the like to the surface of the resin composition layer or generation of damage on the surface of the resin composition layer.

The resin sheet can be produced, for example, by: the resin composition layer is formed by directly applying a liquid resin composition onto a support using a die coater or the like, or by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish onto a support using a die coater or the like, and drying the resin varnish.

Examples of the organic solvent include the same organic solvents as those described as components of the resin composition. One kind of the organic solvent may be used alone, or two or more kinds may be used in combination.

The drying can be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, and drying is performed so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. Although the boiling point of the organic solvent in the resin composition or the resin varnish varies, for example, when a resin composition or a resin varnish containing 30 to 60 mass% of the organic solvent is used, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.

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

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

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

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

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

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

< printed wiring board >

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

The printed wiring board can be produced, for example, by a method including the steps (I) and (II) below using the above resin sheet;

(I) a step of laminating the resin sheet on the inner substrate in such a manner that the resin composition layer of the resin sheet is bonded to the inner substrate,

(II) a step of forming an insulating layer by curing (for example, thermosetting) the resin composition layer.

The "inner layer substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. The substrate may have a conductive layer on one surface or both surfaces thereof, and the conductive layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one surface or both surfaces of a substrate is sometimes referred to as an "inner layer circuit substrate". Further, an intermediate manufactured article in which an insulating layer and/or a conductor layer is to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate in which components are embedded may be used.

The lamination of the inner substrate and the resin sheet can be performed, for example, by heating and pressure-bonding the resin sheet to the inner substrate from the support side. Examples of the member for heat-pressure bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "heat-pressure bonding member") include a heated metal plate (SUS end plate or the like) and a metal roll (SUS roll). It is preferable that the heating and pressure-bonding member is not directly pressed against the resin sheet, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

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

The lamination can be carried out by means of a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Nikko Co., Ltd, a vacuum applicator (vacuum applicator) manufactured by Nikko-Materials, and a batch vacuum pressure laminator.

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

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

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

For example, the heat curing conditions of the resin composition layer may vary depending on the kind of the resin composition, but the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and still more preferably 170 to 210 ℃. The curing time is preferably from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, and still more preferably from 15 minutes to 100 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer is preheated at a temperature of 50 to 120 ℃, preferably 60 to 115 ℃, more preferably 70 to 110 ℃ for 5 minutes or more, preferably 5 to 150 minutes, more preferably 15 to 120 minutes, further preferably 15 to 100 minutes before the resin composition layer is thermally cured.

In the production of the printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) can be carried out by various methods known to those skilled in the art, which can be used for manufacturing a printed wiring board. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). If necessary, the insulating layer and the conductor layer may be formed by repeating the steps (II) to (V) 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 the case of using the resin sheet.

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

The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), stain (scum) is also removed. The step and conditions of the roughening treatment are not particularly limited, and known steps and conditions generally used for forming an insulating layer of a printed wiring board can be used. For example, the roughening treatment may be performed on the insulating layer by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid.

The swelling solution used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred, and a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available Swelling liquids include "spinning Dip securigant P" and "spinning Dip securigant SBU" manufactured by amanit (ato ech) japan. The swelling treatment with the swelling solution is not particularly limited, and for example, the swelling treatment can be performed by immersing the insulating layer in the swelling solution at 30 to 90 ℃ 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 solution at 40 to 80 ℃ for 5 to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution securigant P" manufactured by amett japan.

The neutralizing Solution used for the roughening treatment is preferably an acidic aqueous Solution, and examples of commercially available products include "Reduction Solution securigant P" manufactured by amatt japan.

The treatment with the neutralizing solution can be performed by immersing the treated surface having been subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of handling and the like, it is preferable to immerse the object subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.

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

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

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, and is preferably formed by the semi-additive method from the viewpoint of ease of manufacturing. 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, on the formed plating seed layer, a mask pattern is formed to expose a part of the plating seed layer corresponding to a desired wiring pattern. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, 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 another embodiment, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, the step (V) is preferably performed between the steps (I) and (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The conditions for lamination may be the same as those described for the step (I). Next, step (II) is performed to form an insulating layer. Then, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method.

The metal foil can be produced by a known method such as an electrolytic method or a rolling method. As commercially available products of the metal foil, for example, HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil, etc., available from JX Nikki Stone Metal Co., Ltd.

< semiconductor device >

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

Examples of the semiconductor device include various semiconductor devices used in electric products (for example, a computer, a mobile phone, a digital camera, a television, and the like) and vehicles (for example, a motorcycle, an automobile, a train, a ship, an aircraft, and the like).

Examples

The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. In the following description, "part" and "%" representing amounts are "part by mass" and "% by mass", respectively, unless otherwise stated.

< example 1 >

30 parts of a naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1, 6-bis (glycidyloxy) naphthalene having an epoxy equivalent of about 145g/eq.)30 parts, 20 parts of a naphthol aralkyl-type epoxy resin ("ESN-475V" manufactured by Nippon iron chemical Co., epoxy equivalent of about 332g/eq.), 20 parts of a naphthol aralkyl resin ("SN-4110V" manufactured by Nippon iron chemical Co., Ltd., containing a part of methoxy groups), and 20 parts of a spherical silica ("SO-C2" manufactured by Yatoma, having an average particle diameter of 0.5 μm and a specific surface area of 5.8m were mixed by a mixer²(g) 400 parts, 12 parts of core-shell type graft copolymer rubber particles (EXL-2655, manufactured by Takara chemical Japan Co., Ltd.), and 0.1 part of an imidazole-based curing accelerator (1B 2PZ, manufactured by Sikko chemical industries Co., Ltd.; 1-benzyl-2-phenylimidazole) were uniformly dispersed to prepare a resin composition.

< example 2 >

A resin composition was prepared in the same manner as in example 1, except that the amount of the naphthol aralkyl resin ("SN-4110V" manufactured by Nippon iron chemical Co., Ltd., containing a part of methoxy groups) was changed from 20 parts to 15 parts, and 10 parts of the triazine-containing cresol novolac resin ("LA-3018-50P" manufactured by DIC Co., Ltd., propylene glycol monomethyl ether solution with a solid content of 50% by mass) was further used.

< example 3 >

Except that spherical silica (SO-C2, product of Yatoma corporation, average particle diameter 0.5 μm, specific surface area 5.8 m)²The amount of the catalyst used is changed from 400 parts by weightA resin composition was prepared in the same manner as in example 2 except that the amount of 430 parts was changed to 430 parts, and 5 parts of a vinyl phenyl radical polymerizable compound ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation) and 0.1 part of a radical polymerization initiator ("PERBUTYL C" manufactured by Nikkiso Co., Ltd.) were used.

< example 4 >

Except that spherical silica (product of Yadmama corporation, "SO-C2", average particle diameter 0.5 μm, specific surface area 5.8 m)²A resin composition was prepared in the same manner as in example 3, except that the amount of the maleimide-based radical polymerizable compound (BMI-689, manufactured by Designer polymers) was changed from 430 parts to 410 parts and 2 parts of the maleimide-based radical polymerizable compound was used instead of 5 parts of the vinylphenyl-based radical polymerizable compound (OPE-2 St, manufactured by mitsubishi gas chemical corporation).

< example 5 >

A resin composition was prepared in the same manner as in example 3, except that 7.1 parts of a maleimide-based radically polymerizable compound ("MIR-3000-70 MT" manufactured by Nippon Chemicals, 70% solid content MEK/toluene mixed solution) was used in place of 5 parts of a vinylbenzene-based radically polymerizable compound ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation).

< example 6 >

Except that spherical silica (product of Yadmama corporation, "SO-C2", average particle diameter 0.5 μm, specific surface area 5.8 m)²A resin composition was prepared in the same manner as in example 2, except that the amount of the curing agent used was changed from 400 parts to 430 parts, and 8.1 parts of an active ester curing agent ("EXB-8150-62T" manufactured by DIC corporation, having an active group equivalent of about 230g/eq., and a toluene solution having a solid content of 62 mass%) was further used.

< comparative example 1 >

A resin composition was prepared in the same manner as in example 1, except that 20 parts of a naphthol aralkyl resin ("SN-485" manufactured by Nippon iron chemical Co., Ltd., containing no methoxy group) was used in place of 20 parts of the naphthol aralkyl resin ("SN-4110V" manufactured by Nippon iron chemical Co., Ltd., containing a part of the methoxy group).

< comparative example 2 >

A resin composition was prepared in the same manner as in example 1 except that 50 parts of a bisphenol type epoxy resin ("ZX-1059" manufactured by Nippon iron chemical Co., Ltd., epoxy equivalent of about 165 g/eq) was used in place of 30 parts of a naphthalene type epoxy resin ("HP-4032-SS" manufactured by DIC Co., Ltd., 1, 6-bis (glycidyloxy) naphthalene, epoxy equivalent of about 145 g/eq) and 20 parts of a naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon iron chemical Co., Ltd., epoxy equivalent of about 332 g/eq) to prepare a resin composition.

< production example 1: resin sheet having a thickness of 165 μm for resin composition layer

As a support, a polyethylene terephthalate film (AL 5, manufactured by Linekekaceae) having a release layer was prepared (thickness: 38 μm). The resin compositions obtained in examples and comparative examples were uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer was 165 μm. Then, the resin composition was dried at 80 to 120 ℃ (average 100 ℃) for 10 minutes to obtain a resin sheet including a support and a resin composition layer.

< production example 2: resin sheet having a resin composition layer with a thickness of 70 μm

As a support, a polyethylene terephthalate film (AL 5, manufactured by Linekekaceae) having a release layer was prepared (thickness: 38 μm). The resin compositions obtained in examples and comparative examples were uniformly applied to the release layer of the support so that the thickness of the resin composition layer after drying was 70 μm. Then, the resin composition was dried at 80 to 100 ℃ (average 90 ℃) for 5 minutes to obtain a resin sheet including a support and a resin composition layer.

< test example 1: measurement and evaluation of warpage amount

On a 12-inch silicon wafer, the resin sheet produced in production example 1 was laminated on one surface of an inner layer substrate so that the resin composition layer was in contact with the inner layer substrate using a batch vacuum press Laminator (2-Stage build up Laminator (CVP 700), manufactured by Nikko-Materials) in which the protective film was peeled off from the resin sheet to expose the resin composition layer. The lamination was carried out by: the pressure was reduced for 30 seconds to a pressure of 13hPa or less, and then the pressure was bonded at 100 ℃ for 30 seconds at a pressure of 0.74 MPa. Next, hot pressing was performed at 100 ℃ for 60 seconds under a pressure of 0.5 MPa.

Then, the support was peeled off, and the wafer laminated with the resin sheet was put into an oven at 130 ℃ and heated for 30 minutes, and then transferred to an oven at 200 ℃ and heated for 90 minutes to thermally cure the resin composition layer, thereby forming an insulating layer.

The warpage amount of the sample substrate at 25 ℃ was measured using a shadow moire (shadow moir) measuring apparatus ("thermoureaxp" manufactured by Akorometrix corporation). The measurement was carried out according to JEITA EDX-7311-24, a standard of the Japan electronic information technology industry Association. Specifically, a fitting plane obtained by the least square method for all data on the substrate surface of the measurement region is used as a reference plane, and the difference between the minimum value and the maximum value in the vertical direction from the reference plane is obtained as the warping amount. A case where the warpage amount is less than 2mm is judged as "O", and a case where the warpage amount is 2mm or more is judged as "X".

< test example 2: evaluation of adhesion Strength Using bolt Pull test

(1) Preparation of inner layer substrate

The both surfaces of the glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.4mm thick, "R1515A" manufactured by panasonic corporation) on which the inner layer circuit was formed were etched by a microetching agent ("CZ 8101" manufactured by meige corporation) for 1 μm to roughen the copper surface.

(2) Lamination of resin sheets

The protective film was peeled from the resin sheet produced in production example 2 to expose the resin composition layer. The resin composition layer was laminated on both surfaces of the inner substrate using a batch vacuum press laminator (2-stage stack laminator "CVP 700" manufactured by Nikko-Materials) so as to contact the inner substrate. The lamination was carried out by: the pressure was reduced for 30 seconds to a pressure of 13hPa or less, and then the pressure was bonded at 100 ℃ for 30 seconds at a pressure of 0.74 MPa. Next, hot pressing was performed at 100 ℃ for 60 seconds under a pressure of 0.5 MPa.

(3) Thermal curing of resin composition layers

Then, the support was peeled off, and the inner layer substrate on which the resin sheet was laminated was put in an oven at 130 ℃ and heated for 30 minutes, and then transferred to an oven at 200 ℃ and heated for 90 minutes to thermally cure the resin composition layer, thereby forming an insulating layer. A cured substrate A having an insulating layer, an inner substrate and an insulating layer in this order was obtained.

(4) Bolt pull peel strength test

The cured substrate A was cut into a 1cm square, and then bolts having a diameter of 2.7mm and provided with an epoxy adhesive were attached to each other, and cured at 150 ℃ for 1 hour to attach the substrates. The tensile strength of the bolt was measured by a ROMULUS film adhesion strength tester manufactured by the Quad Group company. The peel strength was set to 250kgf/cm³The above condition is judged to be "good", and the peel strength is less than 250kgf/cm³Is determined as "x".

< test example 3: measurement of dielectric loss tangent (Df) >

The resin sheet produced in production example 2 was cured in an oven at 190 ℃ for 90 minutes, and further peeled from the support to obtain a cured product. The cured product was cut into a length of 80mm and a width of 2mm to obtain an evaluation sample. For the evaluation sample, the dielectric loss tangent was measured by the resonance cavity perturbation method using a HP8362B apparatus manufactured by Agilent Technologies, Inc. under the conditions of a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃. The measurement was performed for 2 test pieces, and the average value was calculated.

The amounts of nonvolatile components used in the resin compositions of examples and comparative examples, and the evaluation results of test examples are shown in table 1 below.

[ Table 1]

It was found that by using the following resin composition, a cured product having excellent adhesion strength can be obtained while suppressing warpage during curing; the resin composition comprises (A) an epoxy resin having a condensed ring structure, (B) an alkoxy group-containing naphthol aralkyl resin, and (C) an inorganic filler, and the content of the component (C) is 70% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.