JP2022088223A - Resin composition - Google Patents

Abstract

To provide a resin composition that can give a cured product capable of suppressing generation of cracks after desmear treatment, and suppressed in dielectric loss tangent (Df) low.SOLUTION: A resin composition contains (A) an epoxy resin, (B) an active ester compound and (C) an inorganic filler. The resin composition is such that: the (A) component contains a modified epoxy resin obtained by reacting (A-1) an epoxy resin having two or more epoxy groups in one molecule with an ester compound represented by the following formula (1) (in the formula (1), each symbol is as described in the specification); and a content of the (C) component is 50 mass% or more based on 100 mass% of a nonvolatile component in the resin composition.SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing an epoxy resin. Further, the present invention relates to a cured product obtained by using the resin composition, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device.

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

Printed wiring boards are generally exposed to a wide range of temperature environments, from low temperature environments such as room temperature to high temperature environments such as reflow. Therefore, if dimensional stability is poor, the resin material of the insulating layer repeatedly expands and contracts. , The distortion causes cracks. Further, in recent years, further improvement of dielectric properties such as dielectric loss tangent of an insulating layer is required.

So far, ester-modified epoxy resins have been known (Patent Document 1).

Japanese Unexamined Patent Publication No. 2020-11735

An object of the present invention is to provide a resin composition capable of suppressing the occurrence of cracks after desmear treatment and obtaining a cured product having a low dielectric loss tangent (Df).

As a result of diligent studies to achieve the object of the present invention, the present inventors have used an ester-modified epoxy resin as a component of the resin composition and set the content of the inorganic filler to 50% by mass or more. Surprisingly, they have found that it is possible to obtain a cured product in which the occurrence of cracks after the desmear treatment can be suppressed and the dielectric loss tangent (Df) is suppressed to a low level, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler.
The component (A) is an epoxy resin having two or more epoxy groups in one molecule of (A-1), and the formula (1):

[In the formula, R ¹ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² is an aryl group which may have a substituent. Is shown. ]
Contains a modified epoxy resin obtained by reacting an ester compound represented by
A resin composition in which the content of the component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[2] A resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler.
The component (A) is the formula (A-1) (2-1):

[In the formula, * indicates a binding site. ]
Group represented by and formula (2-2):

[In the formula, R ¹ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² is an aryl group which may have a substituent. , And * indicates a binding site. ]
Contains a modified epoxy resin having a group represented by
A resin composition in which the content of the component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.

[3] The component (A-1) is the formula (4-1) :.

[In the formula, R ⁴ independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and a is 0, 1, 2 or 3 Is shown. ]
Structural unit represented by, and formula (4-2) :.

[In the formula, R ¹ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² is an aryl group which may have a substituent. , R ⁴ each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and a indicates 0, 1, 2 or 3. show. ]
The resin composition according to the above [1] or [2], which is a modified epoxy resin having a structural unit represented by.
[4] Any of the above [1] to [3], wherein the content of the component (A-1) is 1% by mass to 20% by mass when the non-volatile component in the resin composition is 100% by mass. The resin composition according to.
[5] The content of the component (B) is 5% by mass to 30% by mass when the non-volatile component in the resin composition is 100% by mass, according to any one of the above [1] to [4]. Resin composition.
[6] The resin composition according to any one of the above [1] to [5], wherein the component (A) further contains (A-2) an epoxy resin liquid at 20 ° C.
[7] The resin composition according to any one of the above [1] to [6], further comprising (D) a thermoplastic resin.
[8] The resin composition according to the above [7], wherein the component (D) contains a thermoplastic resin selected from the group consisting of a polyimide resin and a phenoxy resin.
[9] The resin composition according to the above [7] or [8], wherein the weight average molecular weight (Mw) of the component (D) is 5,000 or more.
[10] The resin composition according to any one of the above [1] to [9], further comprising (E) a radically polymerizable compound.
[11] The resin composition according to the above [10], wherein the component (E) contains a (meth) acrylic radically polymerizable compound.
[12] The resin composition according to any one of the above [1] to [11], further comprising (F) an elastomer.
[13] The resin composition according to the above [12], wherein the component (F) contains core-shell type rubber particles.
[14] The resin composition according to any one of the above [1] to [13], further comprising (G) a curing accelerator.
[15] The resin according to any one of [1] to [14] above, wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0030 or less when measured at 5.8 GHz and 23 ° C. Composition.
[16] A cured product of the resin composition according to any one of the above [1] to [15].
[17] A sheet-like laminated material containing 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 from the resin composition according to any one of the above [1] to [15] provided on the support.
[19] A printed wiring board provided with an insulating layer made of a cured product of the resin composition according to any one of the above [1] to [15].
[20] A semiconductor device including the printed wiring board according to the above [19].

According to the resin composition of the present invention, it is possible to suppress the occurrence of cracks after the desmear treatment and to obtain a cured product having a low dielectric loss tangent (Df).

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

<Resin composition>
The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, and the (A) epoxy resin is described below (A-1) an ester-modified epoxy. The content of the (C) inorganic filler containing the resin is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. By using such a resin composition, it is possible to suppress the occurrence of cracks after the desmear treatment and to obtain a cured product having a low dielectric loss tangent (Df).

The resin composition of the present invention may further contain any component in addition to (A) epoxy resin, (B) active ester compound, and (C) inorganic filler. Optional components include, for example, (D) thermoplastic resin, (E) radically polymerizable compound, (F) elastomer, (G) curing accelerator, (H) other additives, and (I) organic solvent. Can be mentioned. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Epoxy resin>
The resin composition of the present invention contains (A) an epoxy resin. (A) The epoxy resin is a resin having one or more epoxy groups in one molecule. (A) The epoxy resin may be used alone or in combination of two or more at any ratio.

<(A-1) Ester-modified epoxy resin>
In the resin composition of the present invention, the (A) epoxy resin contains (A-1) an ester-modified epoxy resin.

In the first embodiment, the ester-modified epoxy resin (A-1) is an epoxy resin having two or more epoxy groups in one molecule, and the formula (1)::

[In the formula, R ¹ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² is an aryl group which may have a substituent. Is shown. ]
It is a modified epoxy resin obtained by reacting an ester compound represented by.

R ¹ indicates an alkyl group which may have a substituent or an aryl group which may have a substituent.

In the present specification, the "substituted group" in the "alkyl (group) which may have a substituent" includes, for example, a halogen atom, an aryl group, and an alkyl-aryl group (which may be substituted with an alkyl group). An aryl group), an alkyl-oxy group, an aryl-oxy group, an alkyl-carbonyl group, an aryl-carbonyl group and other monovalent substituents can be mentioned. The number of substituents in the "alkyl (group) which may have a substituent" is not particularly limited, but is preferably 0 to 5, more preferably 0, 1 or 2.

In the present specification, the "substituted group" in the "aryl (group) which may have a substituent" includes, for example, a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, and an aryl-alkyl group (aryl). An alkyl group which may be substituted with a group), a monovalent substituent such as an alkyl-oxy group, an aryl-oxy group, an alkyl-carbonyl group, an aryl-carbonyl group and the like can be mentioned. The number of substituents in the "aryl (group) which may have a substituent" is not particularly limited, but is preferably 0 to 5, more preferably 0, 1 or 2.

Alkyl (group) means a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl (group) is preferably an alkyl (group) having 1 to 14 carbon atoms, more preferably an alkyl (group) having 1 to 10 carbon atoms, and an alkyl (group) having 1 to 6 carbon atoms. Group) is particularly preferable. Examples of the alkyl (group) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. Examples thereof include a group, a decyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group and the like. Aryl (group) means a monovalent aromatic hydrocarbon group excluding one hydrogen atom of an aromatic carbocycle. Unless otherwise specified, the aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms, and particularly preferably an aryl (group) having 6 to 10 carbon atoms. Examples of the aryl (group) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like. The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

R ¹ is preferably an aryl group that may have a substituent, and more preferably a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group and an aryl. -An aryl group that may be substituted with a group selected from oxy groups, more preferably (1) a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group and From a phenyl group which may be substituted with a group selected from an aryl-oxy group, (2) a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group and an aryl-oxy group. It may be substituted with a group of choice, 1-naphthyl group, or (3) selected from halogen atom, alkyl group, aryl group, alkyl-aryl group, aryl-alkyl group, alkyl-oxy group and aryl-oxy group. It is a 2-naphthyl group which may be substituted with a group, and more preferably selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group and an aryl-oxy group. It is a phenyl group which may be substituted with a group thereof, and a phenyl group is particularly preferable.

R ² represents an aryl group which may have a substituent.

R ² is preferably an aryl group that may be substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group and an aryl-oxy group. More preferably, (1) a phenyl group which may be substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group and an aryl-oxy group. (2) A 1-naphthyl group which may be substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group and an aryl-oxy group, or (3). ) A 2-naphthyl group which may be substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group and an aryl-oxy group, more preferably. , A halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group and a 2-naphthyl group which may be substituted with a group selected from an aryl-oxy group, and is particularly preferable. , 2-naphthyl group.

(A-1) A known epoxy resin is used as the "epoxy resin having two or more epoxy groups in one molecule" to be reacted with the ester compound represented by the formula (1) in order to obtain an ester-modified epoxy resin. It can be widely used including, but is not particularly limited, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, glycidyl ester type epoxy resin, glycidyl. Amin type epoxy resin, alicyclic epoxy resin with ester skeleton, bisphenol Z type epoxy resin, anthracene type epoxy resin, naphthalene type epoxy resin, naphthalene tetrafunctional epoxy resin, naphthol type epoxy resin, phenol novolac type epoxy resin, bisphenol A Examples include type novolak epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, and dicyclopentadiene type epoxy resin. Among them, naphthalene tetrafunctional epoxy resin, naphthol type epoxy resin, phenol novolac type epoxy resin, bisphenol A type novolak epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, bixilenol type epoxy resin. , Triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin are preferable; phenol novolac type epoxy resin, bisphenol A type novolak epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl A type epoxy resin, a bixirenol type epoxy resin, a triphenylmethane type epoxy resin, a tetraphenylethane type epoxy resin, and a dicyclopentadiene type epoxy resin are more preferable. (A-1) Only one type of "epoxy resin having two or more epoxy groups in one molecule" that reacts with the ester compound represented by the formula (1) in order to obtain an ester-modified epoxy resin is used. It may be a combination of two or more types.

(A-1) The epoxy equivalent of the "epoxy resin having two or more epoxy groups in one molecule" to react with the ester compound represented by the formula (1) in order to obtain an ester-modified epoxy resin has heat resistance. From the viewpoint of improvement, preferably 400 g / eq. Hereinafter, more preferably 350 g / eq. Hereinafter, more preferably, 300 g / eq. The following is preferable, and from the viewpoint of sufficiently ensuring the reactivity with the ester compound, 100 g / eq. As mentioned above, more preferably 120 g / eq. Above, more preferably 150 g / eq. That is all. Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

(A-1) The reaction equivalent ratio of the epoxy resin in the reaction for obtaining the ester-modified epoxy resin to the ester compound represented by the formula (1) is the number of moles of the epoxy group of the epoxy resin and the ester of the ester compound. The ratio (epoxy group / ester group) to the number of moles of the group (-CO-O-) is preferably 1.60 or more, more preferably 1.62 or more, still more preferably 1.63 or more, and particularly preferably 1. It is .65 or more, preferably 6.0 or less, more preferably 5.5 or less, still more preferably 5.0 or less, and particularly preferably 4.5 or less.

(A-1) In the reaction for obtaining an ester-modified epoxy resin, for example, tertiary amines such as 4- (dimethylamino) pyridine and 1,4-diazabicyclo [2,2,2] octane; 2- Imidazoles such as methylimidazole and 2-ethyl-4-methylimidazole; organophosphorus compounds such as tris (p-tolyl) phosphine; catalysts such as quaternary ammonium salts may be used. The amount of the catalyst used is preferably 0.001 to 1% by weight based on the reaction solid content. (A-1) In the reaction for obtaining the ester-modified epoxy resin, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene; and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Solvents; Amido solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, A solvent such as an ether alcohol solvent such as diethylene glycol monobutyl ether (butylcarbitol) may be used. (A-1) When a solvent is used in the reaction for obtaining the ester-modified epoxy resin, it is preferable to use it so that the reaction solid content concentration is 35 to 95% by mass. After completion of the reaction, the solvent may be removed or further added, if necessary. The reaction temperature in the reaction for obtaining the (A-1) ester-modified epoxy resin is preferably 50 to 200 ° C, more preferably 100 or 180 ° C, and even more preferably 120 ° C to 160 ° C. (A-1) The reaction time in the reaction for obtaining the ester-modified epoxy resin is usually 1 to 12 hours, preferably 3 to 10 hours.

The ester-modified epoxy resin (A-1) has the formula (2-1): in the second embodiment.

[In the formula, * indicates a binding site. ]
Group represented by and formula (2-2):

[In the formula, each symbol is the same as above. ]
It is a modified epoxy resin having a group represented by. In the embodiment, such a modified epoxy resin is, in addition to the group represented by the formula (2-1) and the group represented by the formula (2-2), further, the formula (2-3) :.

[In the formula, each symbol is the same as above. ]
May have a group represented by. The molar ratio of the group represented by the formula (2-2) to the group represented by the formula (2-1) in the modified epoxy resin (formula (2-2) / formula (2-1)) is 1 or less. It is preferable to have. The number of groups represented by the formula (2-1) in one molecule of the modified epoxy resin is preferably 2 or more.

In the embodiment, the group represented by the formula (2-1), the group represented by the formula (2-2), and the group represented by the formula (2-3) are aromatics in the aromatic ring, respectively. It is preferably bonded directly to the carbon atom.

The aromatic ring means a ring according to Hückel's law in which the number of electrons contained in the π-electron system on the ring is 4p + 2 (p is a natural number). The aromatic ring may be an aromatic carbocycle having a carbon atom as a ring-constituting atom, or an aromatic heterocyclic ring having a heteroatom such as an oxygen atom, a nitrogen atom, and a sulfur atom in addition to the carbon atom as the ring-constituting atom. However, in one embodiment, it is preferably an aromatic carbon ring. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 5- to 10-membered aromatic ring, and even more preferably a 5- or 6-membered aromatic ring. Preferable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

The (A-1) ester-modified epoxy resin in the embodiment is, for example, an epoxy resin having two or more groups represented by the formula (2-1) in one molecule, according to the formula (1) described above. It can be obtained by reacting the represented ester compound. The reaction conditions may be the same as the reaction conditions for obtaining the (A-1) ester-modified epoxy resin in the first embodiment. The "epoxy resin having two or more groups represented by the formula (2-1) in one molecule" is the formula of the "epoxy resin having two or more epoxy groups in one molecule" described above. Examples thereof include those having two or more groups represented by (2-1) in one molecule.

The ester-modified epoxy resin (A-1) is preferably the formula (3-1): in the second embodiment.

[In the formula, the ring Ar represents an aromatic ring which may have a substituent ^, and R3 independently has a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Indicates an aryl group that may have. ]
Structural unit represented by and formula (3-2):

[In the formula, each symbol is the same as above. ]
It is a modified epoxy resin having a structural unit represented by. In the embodiment, such a modified epoxy resin is further subjected to the formula (3-3) in addition to the structural unit represented by the formula (3-1) and the structural unit represented by the formula (3-2). ):

[In the formula, each symbol is the same as above. ]
May have a structural unit represented by. The molar ratio of the structural unit represented by the formula (3-2) to the structural unit represented by the formula (3-1) in the modified epoxy resin (formula (3-2) / formula (3-1)) is 1. The following is preferable. The number of structural units represented by the formula (3-1) in one molecule of the modified epoxy resin is preferably 2 or more.

Ring Ar represents an aromatic ring which may have a substituent.

In the present specification, the "substituent" in the "aromatic ring which may have a substituent" includes, for example, a halogen atom, an alkyl group which may have a substituent, and a substituent. A good aryl group, an alkyl-oxy group which may have a substituent, an aryl-oxy group which may have a substituent, an alkyl-carbonyl group which may have a substituent, and a substituent. Examples thereof include a monovalent substituent such as an aryl-carbonyl group which may be possessed. The number of substituents in the "aromatic ring which may have a substituent" is not particularly limited, but is preferably 0 to 5, more preferably 0, 1 or 2.

The ring Ar is preferably (1) a benzene ring which may be substituted with a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent, or (. 2) It is a naphthalene ring that may be substituted with an alkyl group that may have a substituent and an aryl group that may have a substituent, and more preferably, it may have a substituent. It is a benzene ring substituted with a group selected from a good alkyl group and an aryl group which may have a substituent, and more preferably substituted with an alkyl group which may have a substituent. It is a benzene ring which may be present, and particularly preferably, it is a benzene ring which may be substituted with an alkyl group.

R ³ independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ³ is preferably a hydrogen atom.

The (A-1) ester-modified epoxy resin in the embodiment is, for example, an epoxy resin having two or more structural units represented by the formula (3-1) in one molecule, and the formula (1) described above. It can be obtained by reacting an ester compound represented by. The reaction conditions may be the same as the reaction conditions for obtaining the (A-1) ester-modified epoxy resin in the first embodiment. The "epoxy resin having two or more groups represented by the formula (3-1) in one molecule" is the formula of the "epoxy resin having two or more epoxy groups in one molecule" described above. Examples thereof include those having two or more structural units represented by (3-1) in one molecule.

The ester-modified epoxy resin (A-1) is more preferably the formula (4-1): in the second embodiment.

[In the formula, R ⁴ independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and a is 0, 1, 2 or 3 Is shown. ]
Structural unit represented by, and formula (4-2) :.

[In the formula, each symbol is the same as above. ]
It is a modified epoxy resin having a structural unit represented by. In the embodiment, such a modified epoxy resin is further subjected to the formula (4-3) in addition to the structural unit represented by the formula (4-1) and the structural unit represented by the formula (4-2). ):

[In the formula, each symbol is the same as above. ]
May have a structural unit represented by. The molar ratio of the structural unit represented by the formula (4-2) to the structural unit represented by the formula (4-1) in the modified epoxy resin (formula (4-2) / formula (4-1)) is 1. The following is preferable. The number of structural units represented by the formula (4-1) in one molecule of the modified epoxy resin is preferably 2 or more.

R ⁴ independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent.

Each of ^R4 is independently and preferably substituted with (1) a halogen atom, an aryl group, an alkyl-aryl group, an alkyl-oxy group and an alkyl group which may be substituted with a group selected from an aryl-oxy group, or (2) An aryl group that may be substituted with a group selected from a halogen atom, an alkyl group, an aryl group, an alkyl-aryl group, an aryl-alkyl group, an alkyl-oxy group and an aryl-oxy group, and more preferably. , An alkyl group that may be substituted with a group selected from a halogen atom, an aryl group, an alkyl-aryl group, an alkyl-oxy group and an aryl-oxy group, more preferably an alkyl group, and particularly preferably a methyl group. Is.

a indicates 0, 1, 2 or 3, and is preferably 0 or 1.

The (A-1) ester-modified epoxy resin in the embodiment is, for example, an epoxy resin having two or more structural units represented by the formula (4-1) in one molecule, and the formula (1) described above. It can be obtained by reacting an ester compound represented by. The reaction conditions may be the same as the reaction conditions for obtaining the (A-1) ester-modified epoxy resin in the first embodiment. The "epoxy resin having two or more groups represented by the formula (4-1) in one molecule" is the formula of the "epoxy resin having two or more epoxy groups in one molecule" described above. Examples thereof include those having two or more structural units represented by (4-1) in one molecule.

(A-1) The ester-modified epoxy resin is preferably in a solid state at 20 ° C. (A-1) When the ester-modified epoxy resin is in a solid state at 20 ° C., its softening point is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably, from the viewpoint of improving the handleability of the resin. It is 70 ° C. or higher, particularly preferably 75 ° C. or higher, and from the viewpoint of sufficiently ensuring solvent solubility, it is preferably 130 ° C. or lower, more preferably 125 ° C. or lower, still more preferably 120 ° C. or lower, and particularly preferably 115 ° C. or lower. Is. The softening point can be measured according to JIS K7234.

(A-1) The weight average molecular weight (Mw) of the ester-modified epoxy resin is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, and particularly preferably 1,000, from the viewpoint of further improving the dielectric properties. From the viewpoint of improving the handleability, the amount is preferably 10,000 or less, more preferably 8,000 or less, still more preferably 7,000 or less, and particularly preferably 6,000 or less. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The epoxy equivalent of the (A-1) ester-modified epoxy resin is preferably 1,000 g / eq. From the viewpoint of improving heat resistance. Hereinafter, more preferably 900 g / eq. Hereinafter, particularly preferably 800 g / eq. The following is preferable, and from the viewpoint of further improving the dielectric property, 300 g / eq. As mentioned above, more preferably 330 g / eq. Above, more preferably 360 g / eq. That is all.

The content of the (A-1) ester-modified epoxy resin in the resin composition is not particularly limited, but is preferably 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. It is more preferably 30% by mass or less, further preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 12% by mass or less. The lower limit of the content of the (A-1) ester-modified epoxy resin in the resin composition is not particularly limited, but is preferably 0.1 when the non-volatile component in the resin composition is 100% by mass. It is by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

<(A-2) Liquid epoxy resin>
In the resin composition of the present invention, the (A) epoxy resin is a liquid epoxy resin (A-2) at 20 ° C. as an optional component in addition to the (A-1) ester-modified epoxy resin (in the present specification, " It may be abbreviated as "liquid epoxy resin"). The (A-2) liquid epoxy resin described here is an epoxy resin that does not correspond to the (A-1) ester-modified epoxy resin.

(A-2) The liquid epoxy resin preferably contains a liquid epoxy resin having one or more epoxy groups in one molecule and two or more epoxy groups in one molecule. The ratio of the liquid epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass with respect to 100% by mass of the liquid epoxy resin. That is all.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, and phenol novolac. Examples thereof include a type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure.

(A-2) As specific examples of the liquid epoxy resin, "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "828EL" manufactured by Mitsubishi Chemical Co., Ltd. jER828EL "," 825 "," Epicoat 828EL "(bisphenol A type epoxy resin);" jER807 "," 1750 "(bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .;" jER152 "(phenol novolak) manufactured by Mitsubishi Chemical Co., Ltd. Type epoxy resin); Mitsubishi Chemical's "630", "630LSD", "604" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycilol type epoxy resin); ADEKA's " "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (bisphenol) manufactured by Nittetsu Chemical & Material Chemical Co., Ltd. A mixture of A-type epoxy resin and bisphenol F-type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd .; "Selokiside 2021P" manufactured by Daicel Co., Ltd. Epoxy resin); "PB-3600" manufactured by Daisel, "JP-100", "JP-200" (epoxy resin having a butadiene structure) manufactured by Nippon Soda, "ZX1658" manufactured by Nittetsu Chemical & Materials, Examples thereof include "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin). These may be used individually by 1 type, or may be used in combination of 2 or more types.

(A-2) The epoxy equivalent of the liquid epoxy resin is preferably 50 g / eq. ~ 5,000 g / eq. , More preferably 60 g / eq. ~ 2,000 g / eq. , More preferably 70 g / eq. ~ 1,000 g / eq. , Even more preferably 80 g / eq. ~ 500 g / eq. Is. Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

(A-2) The weight average molecular weight (Mw) of the liquid epoxy resin is preferably 100 to 5,000, more preferably 150 to 3,000, and even more preferably 200 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of the (A-2) liquid epoxy resin in the resin composition is not particularly limited, but is preferably 40% by mass or less when the non-volatile component in the resin composition is 100% by mass. It is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 7% by mass or less. The lower limit of the content of the (A-2) liquid epoxy resin in the resin composition is not particularly limited, but is preferably 0.01% by mass when the non-volatile component in the resin composition is 100% by mass. % Or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 3% by mass or more.

The mass ratio of the (A-2) liquid epoxy resin to the (A-1) ester-modified epoxy resin in the resin composition ((A-2) component / (A-1) component) is not particularly limited. However, it is preferably 0.05 or more, more preferably 0.1 or more, and particularly preferably 0.3 or more. The upper limit of the mass ratio ((A-2) component / (A-1) component) of the (A-2) liquid epoxy resin to the (A-1) ester-modified epoxy resin in the resin composition is particularly limited. However, it is preferably 5 or less, more preferably 2 or less, and particularly preferably 1 or less.

<(A-3) Solid epoxy resin>
In the resin composition of the present invention, the (A) epoxy resin is a solid epoxy resin at (A-3) 20 ° C. as an optional component in addition to the (A-1) ester-modified epoxy resin (in the present specification). It may be abbreviated as "solid epoxy resin"). The (A-3) solid epoxy resin described here is an epoxy resin that does not correspond to the (A-1) ester-modified epoxy resin.

(A-3) The solid epoxy resin preferably contains a solid epoxy resin having one or more epoxy groups in one molecule and two or more epoxy groups in one molecule. The ratio of the solid epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70 with respect to 100% by mass of the solid epoxy resin. It is mass% or more.

(A-3) Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, and tris. Phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenyl ethane type epoxy Resins, phenolphthalimidine type epoxy resins, and phenolphthaline type epoxy resins are preferable.

(A-3) Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalen type tetrafunctional epoxy) manufactured by DIC. Resin); "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-" manufactured by DIC. 7200HH ”,“ HP-7200H ”,“ HP-7200L ”(dicyclopentadiene type epoxy resin);“ EXA-7311 ”,“ EXA-7311-G3 ”,“ EXA-7311-G4 ”,“ EXA-7311-G4 ”manufactured by DIC. EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin);" EPPN-502H "(trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .;" NC7000L "(naphthol novolac) manufactured by Nihon Kayaku Co., Ltd. Type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; "ESN475V", "ESN475V" manufactured by Nittetsu Chemical & Materials Co., Ltd. "ESN4100V" (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nittetsu Chemical &Materials; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nittetsu Chemical & Materials Co., Ltd .; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixilenol type epoxy resin); "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracen type) manufactured by Mitsubishi Chemical Co., Ltd. Epoxy resin); "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type) manufactured by Mitsubishi Chemical Co., Ltd. Epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. ); Examples thereof include "WHR991S" (phenol phthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used individually by 1 type, or may be used in combination of 2 or more types.

(A-3) The epoxy equivalent of the solid epoxy resin is preferably 50 g / eq. ~ 5,000 g / eq. , More preferably 60 g / eq. ~ 2,000 g / eq. , More preferably 70 g / eq. ~ 1,000 g / eq. , Even more preferably 80 g / eq. ~ 500 g / eq. Is. Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

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

The content of the (A-3) solid epoxy resin in the resin composition is not particularly limited, but is preferably 40% by mass or less when the non-volatile component in the resin composition is 100% by mass. It is more preferably 20% by mass or less, further preferably 10% by mass or less, and even more preferably 5% by mass or less.

The mass ratio of the (A-3) solid epoxy resin to the (A-1) ester-modified epoxy resin in the resin composition ((A-3) component / (A-1) component) is not particularly limited. However, it is preferably 3 or less, more preferably 2 or less, and particularly preferably 1 or less.

<(B) Active ester compound>
The resin composition of the present invention contains (B) an active ester compound. (B) The active ester compound may be used alone or in combination of two or more at any ratio. The (B) active ester compound may have a function as an epoxy resin curing agent that reacts with and cures the (A) epoxy resin.

(B) As the active ester compound, generally, an ester group (ester group having high reaction activity) such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds is contained in one molecule. A compound having two or more is preferably used. The active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester compound 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, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compound, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, the (B) active ester compound includes a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing a phenol novolac acetylated product, and a phenol novolac benzoylated product. The active ester compound is preferable, and at least one selected from the dicyclopentadiene type active ester compound and the naphthalene type active ester compound is more preferable, and the dicyclopentadiene type active ester compound is further preferable. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable.

(B) Commercially available products of the active ester compound include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L" and "EXB-8000L-65M" as active ester compounds containing a dicyclopentadiene type diphenol structure. , "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM", (manufactured by DIC) ); As active ester compounds containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC); "EXB9401" (manufactured by DIC) as a phosphorus-containing active ester compound, and "DC808" (DC808) as an acetylated product of phenol novolac. Mitsubishi Chemical Co., Ltd.), "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) as active ester compounds which are benzoylated compounds of phenol novolac, and "PC1300-02" as active ester compounds containing styryl group and naphthalene structure. -65MA "(manufactured by Air Water Co., Ltd.) and the like.

(B) The active ester group equivalent of the active ester compound is preferably 50 g / eq. ~ 500 g / eq. , More preferably 50 g / eq. ~ 400 g / eq. , More preferably 100 g / eq. ~ 300 g / eq. Is. The active ester group equivalent is the mass of the active ester compound per 1 equivalent of the active ester group.

The content of the (B) active ester compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 50% by mass or less. It is 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The lower limit of the content of the (B) active ester compound in the resin composition is not particularly limited, but is preferably 0.1% by mass or more when the non-volatile component in the resin composition is 100% by mass. , More preferably 1% by mass or more, still more preferably 5% by mass or more, still more preferably 8% by mass or more, and particularly preferably 10% by mass or more.

The mass ratio of the (B) active ester compound to the (A-1) ester-modified epoxy resin in the resin composition ((B) component / (A-1) component) is not particularly limited, but is preferable. It is 0.5 or more, more preferably 1 or more, and particularly preferably 1.2 or more. The upper limit of the mass ratio ((B) component / (A-1) component) of the (B) active ester compound to the (A-1) ester-modified epoxy resin in the resin composition is not particularly limited. It is preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

<(B') Other curing agents>
The resin composition of the present invention may further contain a (B') curing agent other than the (B) component as an optional component. (B') Other curing agents may be used alone or in any combination of two or more. The (B') other curing agent may have a function as an epoxy resin curing agent that reacts with and cures the (A) epoxy resin, similarly to the (B) active ester compound.

The (B') other curing agent is not particularly limited, but for example, a phenol-based curing agent, a carbodiimide-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, a benzoxazine-based curing agent, and the like. Examples thereof include a cyanate ester-based curing agent and a thiol-based curing agent. It is particularly preferable that the (B') other curing agent contains a phenolic curing agent.

As the phenol-based curing agent, a phenol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenolic curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", and "CBN" manufactured by Nippon Kayaku Co., Ltd. GPH, "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-" manufactured by Nittetsu Chemical & Materials Co., Ltd. 375 "," SN-395 ", DIC's" LA-7052 "," LA-7054 "," LA-3018 "," LA-3018-50P "," LA-1356 "," TD2090 "," TD-2090-60M "and the like.

Examples of the carbodiimide-based curing agent include curing agents having one or more, preferably two or more carbodiimide structures in one molecule, and examples thereof include tetramethylene-bis (t-butylcarbodiimide) and cyclohexanebis (methylene-). aliphatic biscarbodiimides such as t-butylcarbodiimide; biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis (kisilylcarbodiimide); polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly (methylene). Aliphatic polycarbodiimides such as biscyclohexylene carbodiimide), poly (isophorone carbodiimide); poly (phenylene carbodiimide), poly (naphthylene carbodiimide), poly (trilen carbodiimide), poly (methyldiisopropylphenylene carbodiimide), poly (triethylphenylene) Carbodiimide), poly (diethylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), poly (diisopropylphenylene carbodiimide), poly (xylylene carbodiimide), poly (tetramethylxylylene carbodiimide), poly (methylenediphenylene carbodiimide), poly Examples thereof include polycarbodiimides such as aromatic polycarbodiimides such as [methylenebis (methylphenylene) carbodiimide].

Commercially available products of carbodiimide-based curing agents include, for example, "carbodilite V-02B", "carbodilite V-03", "carbodilite V-04K", "carbodilite V-07" and "carbodilite V-09" manufactured by Nisshinbo Chemical Co., Ltd. "; Examples thereof include" Stavaxol P "," Stavaxol P400 ", and" High Kazil 510 "manufactured by Rheinchemy.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrohydride phthalic acid, methylhexahydrohydride phthalic acid, methylnadic acid anhydride, and hydride methylnadic acid. Anhydride, Trialkyltetrahydrophthalic anhydride, Dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-franyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, Trianhydride Merit acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2-C] furan-1 , 3-Dione, ethylene glycol bis (anhydrotrimeritate), polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized, and the like. Commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nihon Rika Co., Ltd., and "OSA" manufactured by Mitsubishi Chemical Corporation. "YH-306", "YH-307", "HN-2200", "HN-5500" manufactured by Hitachi Chemical, "EF-30", "EF-40", "EF-60", "EF" manufactured by Clay Valley. -80 "and the like.

Examples of the amine-based curing agent include curing agents having one or more, preferably two or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, and alicyclic amines. Aromatic amines and the like can be mentioned, 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 amine or a secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. , M-phenylenediamine, m-xylylene diamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4' -Diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2, 2-Bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-) Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4-) (3-Aminophenoxy) phenyl) sulfone, etc. may be mentioned. Commercially available products may be used as the amine-based curing agent, for example, "SEIKACURE-S" manufactured by Seika, "KAYABOND C-200S", "KAYABOND C-100", and "Kayahard A-A" manufactured by Nippon Kayaku. , "Kayahard AB", "Kayahard AS", "Epicure W" manufactured by Mitsubishi Chemical Corporation, and the like.

Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd .; "HFB2006M" manufactured by Showa High Polymer Co., Ltd .; "Pd" manufactured by Shikoku Chemicals Corporation. Examples include "FA".

Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencianate)), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4, 4'-Etilidene diphenyl disyanate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-) Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, Examples thereof include polyfunctional cyanate resins derived from phenol novolak, cresol novolak and the like, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A dicyanate) manufactured by Ronza Japan. Alternatively, a prepolymer in which the whole is triazined to become a trimer) and the like can be mentioned.

Examples of the thiol-based curing agent include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) isocyanurate and the like.

The reaction group equivalent of the (B') other curing agent is preferably 50 g / eq. ~ 3000 g / eq. , More preferably 100 g / eq. ~ 1000 g / eq. , More preferably 100 g / eq. ~ 500 g / eq. , Particularly preferably 100 g / eq. ~ 300 g / eq. Is. The reaction group equivalent is the mass of the curing agent per reaction group equivalent.

The content of the (B') and other curing agents in the resin composition is not particularly limited, but is preferably 20% by mass or less when the non-volatile component in the resin composition is 100% by mass. It is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the (B') and other curing agents in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more. , 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, and the like.

The mass ratio of the (B') and other curing agents ((B') component / (A-1) component) to the (A-1) ester-modified epoxy resin in the resin composition is not particularly limited. It is preferably 1 or less, more preferably 0.5 or less, and particularly preferably 0.2 or less.

The content of the (B) active ester compound in the resin composition is preferably 10% by mass when the total of the (B) active ester compound and the (B') other curing agent in the resin composition is 100% by mass. % Or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more.

<(C) Inorganic filler>
The resin composition of the present invention contains (C) an inorganic filler. The content of the inorganic filler (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. (C) The inorganic filler is contained in the resin composition in the form of particles.

(C) An inorganic compound is used as the material of the inorganic filler. 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, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Of these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more at any ratio.

(C) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd .; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka Corporation; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-" manufactured by Tokuyama Corporation. 5N ”;“ SC2500SQ ”,“ SO-C4 ”,“ SO-C2 ”,“ SO-C1 ”manufactured by Admatex;“ DAW-03 ”,“ FB-105FD ”manufactured by Denka, and the like.

(C) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less, and particularly preferably 0. It is 7 μm or less. (C) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0. .2 μm or more. (C) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis by a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the light source wavelengths used were blue and red, and the volume-based particle size distribution of the inorganic filler was measured by the flow cell method. The average particle size was calculated as the median diameter. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.

(C) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² / g or more, more preferably 0.5 m ² / g or more, still more preferably 1 m ² / g or more. Particularly preferably, it is 3 m ² / g or more. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m ² / g or less, more preferably 70 m ² / g or less, still more preferably 50 m ² / g or less, and particularly preferably. Is 40 m ² / g or less. For the specific surface area of the inorganic filler, nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device (Maxorb HM-1210 manufactured by Mountech) according to the BET method, and the specific surface area is calculated using the BET multipoint method. It can be obtained by.

(C) The inorganic filler is preferably surface-treated with an appropriate surface treatment agent. By surface treatment, (C) the moisture resistance and dispersibility of the inorganic filler can be enhanced. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epyloxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-based silane coupling agents; p-styryltrimethoxysilane and other styryl-based Silane coupling agents; methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane , 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N -Amino-based silane coupling agents such as phenyl-8-aminooctyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; tris- (trimethoxysilylpropyl) isocyanurate, etc. Isocyanurate-based silane coupling agent; ureido-based silane coupling agent such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. An isocyanate-based silane coupling agent such as 3-isopropylpropyltriethoxysilane; an acid anhydride-based silane coupling agent such as 3-trimethoxysilylpropylsuccinic anhydride; a silane coupling agent such as; methyltrimethoxysilane, Dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimeth Examples thereof include alkylalkoxysilane compounds such as xysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane. Further, the surface treatment agent may be used alone or in combination of two or more at any ratio.

Examples of commercially available surface treatment agents include "KBM-1003" and "KBE-1003" (vinyl-based silane coupling agents) manufactured by Shin-Etsu Chemical Industry Co., Ltd .; "KBM-303", "KBM-402", and "KBM-402". KBM-403 "," KBE-402 "," KBE-403 "(epoxy-based silane coupling agent);" KBM-1403 "(styryl-based silane coupling agent);" KBM-502 "," KBM-503 " , "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-" 903 ”,“ KBE-903 ”,“ KBE-9103P ”,“ KBM-573 ”,“ KBM-575 ”(amino silane coupling agent);“ KBM-9569 ”(isocyanurate-based silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X" -12-967C "(acid anhydride-based silane coupling agent);" KBM-13 "," KBM-22 "," KBM-103 "," KBE-13 "," KBE-22 "," KBE-103 " , "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" ( Alkylalkoxysilane compound) and the like.

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

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

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

The content of the (C) inorganic filler in the resin composition is 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass when the non-volatile component in the resin composition is 100% by mass. % Or more, more preferably 62% by mass or more, and particularly preferably 64% by mass or more. The upper limit of the content of the (C) inorganic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 90% by mass or less. It can be preferably 80% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass or less.

The mass ratio of the (C) inorganic filler to the (A-1) ester-modified epoxy resin in the resin composition ((C) component / (A-1) component) is not particularly limited, but is preferable. It is 2 or more, more preferably 4 or more, and particularly preferably 5 or more. The upper limit of the mass ratio ((C) component / (A-1) component) of the (C) inorganic filler to the (A-1) ester-modified epoxy resin in the resin composition is not particularly limited, but is not particularly limited. It is preferably 30 or less, more preferably 20 or less, and particularly preferably 10 or less.

<(D) Thermoplastic resin>
The resin composition of the present invention may further contain (D) a thermoplastic resin as an optional component. By containing (D) a thermoplastic resin in the resin composition of the present invention, the adhesion to copper that can be used as a conductor layer can be further improved.

Examples of the thermoplastic resin include polyimide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, and polycarbonate resin. , Polyether ether ketone resin, polyester resin and the like. (D) In one embodiment, the thermoplastic resin (D) preferably contains a thermoplastic resin selected from the group consisting of a polyimide resin and a phenoxy resin. Further, the thermoplastic resin may be used alone or in combination of two or more.

Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin-Nippon Rika Co., Ltd.

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

Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Co., Ltd. (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol S skeleton-containing phenoxy resin); "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd. Examples thereof include "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30";

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Electrified Butyral 4000-2", "Electrified Butyral 5000-A", "Electrified Butyral 6000-C", and "Electrified Butyral 6000-EP" manufactured by Sekisui Chemical Co., Ltd .; Sekisui Chemical Co., Ltd. Examples thereof include Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by the same company.

Examples of the polyolefin resin include ethylene-based copolymers such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. Resin: Polyolefin-based polymers such as polypropylene and ethylene-propylene block copolymers can be mentioned.

Examples of the polybutadiene resin include a hydride polybutadiene skeleton-containing resin, a hydroxy group-containing polybutadiene resin, a phenolic hydroxyl group-containing polybutadiene resin, a carboxy group-containing polybutadiene resin, an acid anhydride group-containing polybutadiene resin, an epoxy group-containing polybutadiene resin, and an isocyanate group. Examples thereof include polybutadiene resin, urethane group-containing polybutadiene resin, and polyphenylene ether-polybutadiene resin.

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

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

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

Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE.

Examples of the polycarbonate resin include a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, and a urethane group-containing carbonate resin. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090" and "C-2090" manufactured by Kuraray. , "C-3090" (polycarbonate diol) and the like. Specific examples of the polyetheretherketone resin include "Sumiproi K" manufactured by Sumitomo Chemical Co., Ltd.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethylterephthalate resin and the like.

(D) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 10,000 or more, from the viewpoint of remarkably obtaining the effect of the present invention. Is 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less.

The content of the (D) thermoplastic resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 20% by mass or less, more preferably 20% by mass or less. It can be 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less. The lower limit of the content of the (D) thermoplastic resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0. It may be 0.01% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.

<(E) Radical polymerizable compound>
The resin composition of the present invention may further contain (E) a radically polymerizable compound as an optional component. By containing (E) a radically polymerizable compound in the resin composition of the present invention, the smear removal property by desmear treatment can be further improved. (E) The radically polymerizable compound may be used alone or in any combination of two or more.

(E) The radically polymerizable compound is, in one embodiment, a radically polymerizable compound having an ethylenically unsaturated bond. The radically polymerizable compound (E) is not particularly limited, but is, for example, an allyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a p-vinylphenyl group, an m-vinylphenyl group and an o-vinyl. Unsaturated hydrocarbon group such as phenyl group; α, β-unsaturated carbonyl group such as acryloyl group, methacryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl group) Etc. may have a radically polymerizable group. (E) The radically polymerizable compound preferably has two or more radically polymerizable groups in one molecule.

The (E) radically polymerizable compound may be, for example, a (meth) acrylic radically polymerizable compound, a styrene radically polymerizable compound, an allyl radically polymerizable compound, a maleimide radically polymerizable compound, or the like.

The (meth) acrylic radically polymerizable compound is, for example, a compound having one or more, preferably two or more acryloyl groups and / or methacryloyl groups. Examples of the (meth) acrylic radically polymerizable compound include cyclohexane-1,4-dimethanol di (meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and neo. Pentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethanetri (meth) acrylate, glycerintri (meth) acrylate, pentaerythritol tetra (meth) acrylate And other aliphatic (meth) acrylic acid ester compounds; dioxane glycol di (meth) acrylate, 3,6-dioxa-1,8-octanediol di (meth) acrylate, 3,6,9-trioxaundecane-1, 11-diol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, ethoxylated bisphenol A di (meth) ) Acrylate, propoxylated bisphenol A Di (meth) acrylate and other ether-containing (meth) acrylic acid ester compounds; tris (3-hydroxypropyl) isocyanuratetri (meth) acrylate, tris (2-hydroxyethyl) isocyanuratetri ( Examples thereof include isocyanurate-containing (meth) acrylic acid ester compounds such as meth) acrylate and tri (meth) acrylate ethoxylated isocyanuric acid. Commercially available products of (meth) acrylic radically polymerizable compounds include, for example, "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. and "DCP-A" (tricyclode) manufactured by Kyoeisha Chemical Co., Ltd. (Candymethanol diacrylate), "DCP" (tricyclodecanedimethanol dimethacrylate), "KAYARAD R-684" (tricyclodecanedimethanol diacrylate), "KAYARAD R-604" (dioxane glycol) from Nippon Kayaku Co., Ltd. Diacrylate) and the like.

The styrene-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more vinyl groups directly bonded to an aromatic carbon atom. Examples of the styrene-based radically polymerizable compound include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, and 1,2-bis (4). -Vinylphenyl) ethane, 2,2-bis (4-vinylphenyl) propane, bis (4-vinylphenyl) ether and the like can be mentioned.

The allyl radically polymerizable compound is, for example, a compound having one or more, preferably two or more allyl groups. Examples of the allyl radically polymerizable compound include diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, diallyl 2,3-naphthalenecarboxylate, and the like. Aromatic carboxylic acid allyl ester compounds; Isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate; 2,2-bis [3-allyl-4. -(Glysidyloxy) phenyl] Epoxy-containing aromatic allyl compounds such as propane; bis [3-allyl-4- (3,4-dihydro-2H-1,3-benzoxazine-3-yl) phenyl] methane and the like Examples thereof include benzoxazine-containing aromatic allyl compounds; ether-containing aromatic allyl compounds such as 1,3,5-triallyl etherbenzene; and allylsilane compounds such as diallyldiphenylsilane. Commercially available allyl-based radically polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nihon Kasei Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nitto Technofine Chemical Co., Ltd., and Japanese products. "TRIAM-705" manufactured by Kojunyaku Kogyo Co., Ltd. (triallyl trimellitic acid), trade name "DAND" (diallyl 2,3-naphthalenecarboxylate) manufactured by Nihon Kasei Kogyo Co., Ltd., "ALP-d" manufactured by Shikoku Kasei Kogyo Co., Ltd. (Bis [3-allyl-4- (3,4-dihydro-2H-1,3-benzoxazine-3-yl) phenyl] methane), "RE-810NM" (2,2-) manufactured by Nihon Kasei Co., Ltd. Examples thereof include bis [3-allyl-4- (glycidyloxy) phenyl] propane) and "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Co., Ltd.

The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. As a commercially available product, for example, Shin-Etsu Chemical Industry Co., Ltd. "SLK-2600" manufactured by Designer Molecule's "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide containing dimerdiamine structure) Compound), "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecule's, "MIR-5000-60T", "MIR-3000-70MT" (biphenyl aralkyl type maleimide compound) manufactured by Nippon Kayaku Co., Ltd. , "BMI-70" and "BMI-80" manufactured by KAI Kasei Co., Ltd., "BMI-2300" and "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd. and the like. Further, (as the maleimide-based radically polymerizable compound, a maleimide resin (maleimide compound containing an indane ring skeleton) disclosed in Publication No. 2020-500211 of the Japan Institute of Invention and Innovation may be used.

The ethylenically unsaturated bond equivalent of the radically polymerizable compound (E) is preferably 20 g / eq. ~ 1000 g / eq. , More preferably 50 g / eq. ~ 750 g / eq. , More preferably 70 g / eq. ~ 500 g / eq. , Particularly preferably 90 g / eq. ~ 400 g / eq. Is. The ethylenically unsaturated bond equivalent is the mass of the radically polymerizable compound per 1 equivalent of the ethylenically unsaturated bond.

The molecular weight of the radically polymerizable compound (E) is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 1,000 or less, and particularly preferably 500 or less. The lower limit is not particularly limited, but may be, for example, 150 or more.

The content of the (E) radically polymerizable compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably. Is 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the (E) radically polymerizable compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more. It is 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.

<(F) Elastomer>
The resin composition of the present invention may contain (F) an elastomer as an optional component. By containing the (F) elastomer in the resin composition of the present invention, the crack resistance after the desmear treatment can be further improved. (F) The elastomer means a resin having flexibility, and a resin exhibiting rubber elasticity or a resin exhibiting rubber elasticity by reacting with other components is preferable. Examples of the resin exhibiting rubber elasticity include a resin exhibiting an elastic modulus of 1 GPa or less when a tensile test is performed at a temperature of 25 ° C. and a humidity of 40% RH in accordance with the Japanese Industrial Standards (JIS K7161). Be done.

(F) The elastomer may be a particulate elastomer component (particulate elastomer) that maintains the morphology of particles in the resin composition, and is in the form of irregular non-particles that tend to be mixed or dissolved in the resin composition. It may be an elastomer component (non-particulate elastomer) of. (F) The elastomer preferably contains a particulate elastomer. The particulate elastomer is preferably spherical.

The particulate elastomer is, for example, a silicone-based elastomer such as polydimethylsiloxane; polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene. Olefin-based copolymers such as copolymers, acrylonitrile-butadiene copolymers, isoprene-isobutylene copolymers, isobutylene-butadiene copolymers, ethylene-propylene-diene ternary copolymers, and ethylene-propylene-butene ternary copolymers. Polymeric elastomer; rubber such as thermoplastic elastomers such as acrylic thermoplastic elastomers such as propyl poly (meth) acrylate, butyl poly (meth) acrylate, cyclohexyl poly (meth) acrylate, and octyl poly (meth) acrylate. It is preferably rubber particles contained as a component. Further, a silicone-based rubber such as polyorganosiloxane rubber may be mixed with the rubber component. The rubber component contained in the rubber particles has a glass transition temperature of, for example, 0 ° C. or lower, preferably −10 ° C. or lower, more preferably −20 ° C. or lower, still more preferably −30 ° C. or lower.

The particulate elastomer preferably contains core-shell type rubber particles from the viewpoint of remarkably obtaining the desired effect of the present invention. The core-shell type rubber particles are particulate elastomers composed of core particles containing a rubber component as described above and one or more layers of shell portions covering the core particles. Further, the core-shell type rubber particles are a core composed of a core particle containing the rubber component as described above and a shell portion obtained by graft-copolymerizing a monomer component copolymerizable with the rubber component contained in the core particle. Shell-type graft copolymer rubber particles are preferable. The core-shell type here does not necessarily mean only those in which the core particles and the shell part can be clearly distinguished, and also includes those in which the boundary between the core particles and the shell part is unclear, and the core particles are shells. It does not have to be completely covered with the part.

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

The monomer components forming the shell portion of the core-shell type rubber particles are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylic. (Meta) acrylic acid esters such as octyl acid, glycidyl (meth) acrylic acid; (meth) acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α such as maleic acid and itaconic acid. , Β-Unsaturated carboxylic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, α-methylstyrene; (meth) acrylonitrile, etc., and more preferably (meth) acrylic acid ester. ) It is more preferable to contain methyl acrylate. The "(meth) acrylic acid" is methacrylic acid or acrylic acid.

Commercially available core-shell type rubber particles include, for example, "CHT" manufactured by Chale Industries; "B602" manufactured by UMG ABS; "Paraloid EXL-2602" and "Paraloid EXL-2603" manufactured by Dow Chemical Japan. , "Paraloid EXL-2655", "Paraloid EXL-2311", "Paraloid-EXL2313", "Paraloid EXL-2315", "Paraloid KM-330", "Paraloid KM-336P", "Paraloid KCZ-201", Mitsubishi Rayon's "Metabren C-223A", "Metabren E-901", "Metabren S-2001", "Metabren W-450A", "Metabren SRK-200", Kaneka's "Kaneace M-511", Examples thereof include "Kane Ace M-600", "Kane Ace M-400", "Kane Ace M-580", and "Kane Ace MR-01".

The average particle size (average primary particle size) of the particulate elastomer is not particularly limited, but is preferably 20 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more. The upper limit of the average particle size (average primary particle size) of the particulate elastomer is not particularly limited, but is preferably 5,000 nm or less, more preferably 2,000 nm or less, and further preferably 1,000 nm or less. .. The average particle size (average primary particle size) of the particulate elastomer can be measured using a zeta potential particle size distribution measuring device or the like.

The content of the (F) elastomer in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably 20% by mass. % Or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the (F) elastomer in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0.001. It is by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more.

<(G) Curing accelerator>
The resin composition of the present invention may contain (G) a curing accelerator as an optional component. The (G) curing accelerator has a function of accelerating the curing of the (A) epoxy resin.

Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. (G) The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromeritate, and tetrabutylphosphonium hydro. Alitriphenylphosphine salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenorate, di-tert-butyldimethylphosphonium tetraphenylphosphine; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-triltriphenylphosphoniumtetra-p-trilborate, tetraphenyl Triphenylphosphinephosphine, tetraphenylphosphinetetrap-trilborate, triphenylethylphosphoniumtetraphenylborate, tris (3-methylphenyl) ethylphosphonium tetraphenylborate, tris (2-methoxyphenyl) ethylphosphonium tetraphenylborate, (4) -Arophenylphosphine salts such as triphenylphosphine thiosianate, tetraphenylphosphine thiosianate, butyl triphenyl phosphonium thiosianate; aromatic phosphine-boran complex such as triphenylphosphine / triphenylboran; triphenylphosphine / p-benzoquinone. Arophenylphosphine / quinone addition reactants such as addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-). 2-Butenyl) phosphine, tricyclophenylphosphine and other aliphatic phosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclophosphine, triphenylphosphine, tri-o -Triphenylphosphine, tri-m-triphenylphosphine, tri-p-tril Phosphine, Tris (4-ethylphenyl) phosphine, Tris (4-propylphenyl) phosphine, Tris (4-isopropylphenyl) phosphine, Tris (4-butylphenyl) phosphine, Tris (4-tert-butylphenyl) phosphine, Tris (2,4-dimethylphenyl) phosphine, tris (2,5-dimethylphenyl) phosphine, tris (2,6-dimethylphenyl) phosphine, tris (3,5-dimethylphenyl) phosphine, tris (2,4,6) -Trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, tris ( 4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1,2-bis (diphenylphosphine) ethane, 1,3-bis (diphenylphosphine) propane, 1,4-bis (diphenylphosphine) Examples thereof include aromatic phosphines such as butane, 1,2-bis (diphenylphosphino) acetylene, and 2,2'-bis (diphenylphosphino) diphenyl ether.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-. Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) ) -1,1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea, 3- (2-methylphenyl) -1,1-dimethylurea, 3- (4- (4- Methylphenyl) -1,1-dimethylurea, 3- (3,4-dimethylphenyl) -1,1-dimethylurea, 3- (4-isopropylphenyl) -1,1-dimethylurea, 3- (4-) Methoxyphenyl) -1,1-dimethylurea, 3- (4-nitrophenyl) -1,1-dimethylurea, 3- [4- (4-methoxyphenoxy) phenyl] -1,1-dimethylurea, 3- [4- (4-Chlorophenoxy) phenyl] -1,1-dimethylurea, 3- [3- (trifluoromethyl) phenyl] -1,1-dimethylurea, N, N- (1,4-phenylene) Aromatic dimethylurea such as bis (N', N'-dimethylurea), N, N- (4-methyl-1,3-phenylene) bis (N', N'-dimethylurea) [toluene bisdimethylurea] And so on.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Imidazole compounds such as phenylimidazolin and adducts of imidazole compounds and epoxy resins can be mentioned.

As the imidazole-based curing accelerator, a commercially available product may be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemicals Corporation, and "P200-H50" manufactured by Mitsubishi Chemical Corporation. And so on.

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

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. (5, 4, 0) -Undesen and the like can be mentioned.

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

The content of the (G) curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably. It is 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less. The lower limit of the content of the (G) curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0. It can be 001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, and the like.

<(H) Other additives>
The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; epoxy acrylate resins, urethane acrylate resins, urethane resins, surfactant resins, and thermosetting polyimides. Thermocurable resins other than epoxy resins such as resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, silicone resins; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, Coloring agents such as phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black; polymerization prohibiting agents such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents. Thickeners such as Benton and montmorillonite; Defoamers such as silicone defoamers, acrylic defoamers, fluorine defoamers, vinyl resin defoamers; UV absorption such as benzotriazole UV absorbers Agents; Adhesive improvers such as ureasilane; Adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, Triazine-based adhesion-imparting agents; Antioxidants such as hindered phenol-based antioxidants Fluorescent whitening agents such as stylben derivatives; Surfactants such as fluorine-based surfactants and silicone-based surfactants; Phosphorus-based flame retardants (eg, phosphoric acid ester compounds, phosphazenic compounds, phosphinic acid compounds, red phosphorus), nitrogen Flame-retardant agents such as flame-retardants (eg, melamine sulfate), halogen-based flame retardants, inorganic flame-retardants (eg, antimony trioxide); phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based Dispersants such as dispersants, anionic dispersants, cationic dispersants; borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, carboxylics. Examples thereof include stabilizers such as acid anhydride-based stabilizers. (H) As the other additives, one type may be used alone, or two or more types may be used in combination at any ratio. (H) The content of other additives can be appropriately set by those skilled in the art.

<(I) Organic solvent>
The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the above-mentioned non-volatile component. (I) As the organic solvent, a known one can be appropriately used, and the type thereof is not particularly limited. (I) Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate and γ-. Ester-based solvents such as butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether and anisol; alcohol-based solvents such as methanol, ethanol, propanol, butanol and ethylene glycol Solvents: Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, 2-hydroxyiso Ester alcohol solvent such as methyl butyrate; ether alcohol solvent such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N, N-dimethylformamide , N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide solvents; dimethylsulfoxide and other sulfoxide solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane and the like. The above-mentioned aliphatic hydrocarbon-based solvent; aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene can be mentioned. (I) The organic solvent may be used alone or in combination of two or more at any ratio.

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

<Manufacturing method of resin composition>
The resin composition of the present invention can be, for example, in any preparation container (A) epoxy resin, (B) active ester compound, (C) inorganic filler, if necessary (D) thermoplastic resin, if necessary. (E) Radical polymerizable compounds, (F) elastomers as needed, (G) cure accelerators as needed, (H) other additives as needed, and (I) organic solvents as needed. Can be produced by adding and / or partially or all at the same time in any order and mixing. Further, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or from beginning to end. Further, the resin composition may be uniformly dispersed by stirring or shaking using, for example, a stirring device such as a mixer or a shaking device in the process of adding and mixing, or thereafter. Further, at the same time as stirring or shaking, defoaming may be performed under low pressure conditions such as under vacuum.

<Characteristics of resin composition>
The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, and (A) an epoxy resin contains (A-1) an ester-modified epoxy resin. The content of the inorganic filler (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. By using such a resin composition, it is possible to suppress the occurrence of cracks after the desmear treatment and to obtain a cured product having a low dielectric loss tangent (Df).

The cured product of the resin composition of the present invention can suppress the occurrence of cracks after the desmear treatment. Therefore, in one embodiment, after the circuit board is manufactured and desmear-treated as in Test Example 2 below, when 100 copper pad portions of the circuit board are observed, the number of cracks may be preferably 10 or less.

The cured product of the resin composition of the present invention may have a feature of low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric positive contact (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23 ° C. as in Test Example 1 below is preferably 0.0200 or less and 0.0100 or less. , More preferably 0.0090 or less, 0.0080 or less, 0.0070 or less, still more preferably 0.0060 or less, 0.0050 or less, 0.0040 or less, particularly preferably 0.0035 or less, 0.0030 or less, It can be 0.0027 or less.

<Use of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulating use, particularly as a resin composition for forming an insulating layer. Specifically, a resin composition for forming the insulating layer for forming the conductor layer (including the rewiring layer) formed on the insulating layer (resin for forming the insulating layer for forming the conductor layer). It can be suitably used as a composition). Further, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention also requires a resin composition such as a resin sheet, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin. Can be used in a wide range of applications.

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

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

<Sheet-like laminated material>
The resin composition of the present invention can be applied and used in a varnished state, but industrially, it is generally preferable to use the resin composition in the form of a sheet-like laminated material containing the resin composition.

As the sheet-shaped laminated material, the following resin sheets and prepregs are preferable.

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

The thickness of the resin composition layer is preferably 50 μm or less from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulating properties even if the cured product of the resin composition is a thin film. It is preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 5 μm or more, 10 μm or more, or the like.

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

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyimides. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The support may be matted, corona-treated, or antistatic-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumilar T60" manufactured by Toray Industries, "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

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

In one embodiment, the resin sheet may further contain any layer, if desired. Examples of such an arbitrary layer include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion and scratches of dust and the like on the surface of the resin composition layer.

For the resin sheet, for example, a resin varnish prepared by dissolving the resin composition as it is in a liquid resin composition or in an organic solvent is applied onto a support using a die coater or the like, and further dried. It can be produced by forming a resin composition layer.

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

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

The resin sheet can be rolled up and stored. If the resin sheet has a protective film, it can be used by peeling off the protective film.

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

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as a prepreg base material such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-shaped fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited. Usually, it is 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 above-mentioned resin sheet.

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

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

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

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

The inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

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

Lamination can be performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

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

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

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

For example, the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but in one embodiment, the curing temperature is preferably 120 ° C. to 240 ° C., more preferably 150 ° C. to 220 ° C., still more preferable. Is 170 ° C to 210 ° C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

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

In manufacturing the printed wiring board, (III) a step of drilling 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 carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after the step (II), the support may be removed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

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

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

Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear removal is also performed. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions usually used for forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

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

The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. to 100 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dozing Solution Security P" manufactured by Atotech Japan.

The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Security Gant P" manufactured by Atotech Japan.

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

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

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

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

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

In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern, and the semi-additive can be manufactured from the viewpoint of ease of manufacture. It is preferably formed by the method. Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown.

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

In other embodiments, the conductor layer may be formed using metal leaf. When the conductor layer is formed using the metal foil, it is preferable that the step (V) is carried out between the steps (I) and the step (II). For example, after step (I), the support is removed and a metal leaf is laminated on the surface of the exposed resin composition layer. The laminating of the resin composition layer and the metal foil may be carried out by a vacuum laminating method. The laminating conditions may be the same as the conditions described for step (I). Then, step (II) is carried out to form an insulating layer. After that, the metal foil on the insulating layer can be used to form a conductor layer having a desired wiring pattern 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 electrolysis method or a rolling method. Examples of commercially available metal foils include HLP foils and JXUT-III foils manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foils and TP-III foils manufactured by Mitsui Mining & Smelting 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 by using the printed wiring board of the present invention.

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

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

<Example 1>
Epoxy resin A (modified epoxy resin having a structure represented by the following formula (A) synthesized by the method described in Example 1 of Japanese Patent Application Laid-Open No. 2020-11735 (from FD / MS measurement results 1 ≦ x ≦ 5) , 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, maximum peak is m / z = 588.3 (x = z = 1, y = 0)), epoxy equivalent about 455 g / eq.) Contains 10 parts and naphthalene skeleton. Five parts of an epoxy resin (“HP-4032-D” manufactured by DIC, epoxy equivalent of about 140 g / eq.) Were dissolved in 15 parts of MEK. There, 65 parts of spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by Admatex) surface-treated with an amino-based silane coupling agent (“KBM-573” manufactured by Shinetsu Chemical Industry Co., Ltd.), core shell rubber. 1 part of particles (“EXL-2655” manufactured by Dow), 24 parts of active ester curing agent (“HPC-8000-65T” manufactured by DIC, active ester equivalent 223, toluene solution with solid content of 65% by mass), acrylate compound ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.), 5 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., MEK / cyclohexanone mixed solution with a solid content of 30% by mass), curing accelerator (Wako Pure Chemical Industries, Ltd.) The resin composition was prepared by adding 0.1 part of "4-dimethylaminopyridine") manufactured by Mf. Co., Ltd. and uniformly dispersing the mixture with a high-speed rotary mixer.

<Example 2>
Active ester curing agent ("HPC-8150-62T" manufactured by DIC, active ester equivalent) instead of 24 parts of active ester curing agent ("HPC-8000-65T" manufactured by DIC, toluene solution having a solid content of 65% by mass) A resin composition was prepared in the same manner as in Example 1 except that 25 parts (234, a toluene solution having a solid content of 62%) was used.

<Example 3>
Active ester curing agent ("HPC-8150-62T" manufactured by DIC, active ester equivalent) instead of 24 parts of active ester curing agent ("HPC-8000-65T" manufactured by DIC, toluene solution having a solid content of 65% by mass) Using 25 parts of 234, a toluene solution with a solid content of 62%, and 5 parts of a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., a MEK / cyclohexanone mixed solution with a solid content of 30% by mass), a polyimide resin (Shinetsu Chemical Industry Co., Ltd.) A resin composition was prepared in the same manner as in Example 1 except that 6 parts of "SLK-6100" manufactured by Anisol (anisole solution having a solid content of 25%) was used.

<Example 4>
Active ester curing agent ("HPC-8150-62T" manufactured by DIC, active ester equivalent) instead of 24 parts of active ester curing agent ("HPC-8000-65T" manufactured by DIC, toluene solution having a solid content of 65% by mass) Using 24 parts of a toluene solution having a solid content of 234 and a solid content of 62%, a triazine-containing cresol novolak resin (“LA-3018-50P” manufactured by DIC, a propylene glycol monomethyl ether solution having a nitrogen content of 18% and a solid content of 50% by mass). A resin composition was prepared in the same manner as in Example 1 except that two parts were further added.

<Example 5>
Active ester curing agent ("HPC-8150-62T" manufactured by DIC, active ester equivalent) instead of 24 parts of active ester curing agent ("HPC-8000-65T" manufactured by DIC, toluene solution having a solid content of 65% by mass) Spherical silica (average particle size 0.5 μm, Admatex) surface-treated with an amino-based silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) using 24 parts of a toluene solution (234, solid content 62%). The amount of "SO-C2" manufactured by the company was changed from 65 parts to 82 parts, and the triazine-containing cresol novolak resin ("LA-3018-50P" manufactured by DIC, nitrogen content 18%, solid content 50% by mass) was changed. A resin composition was prepared in the same manner as in Example 1 except that 2 parts (propylene glycol monomethyl ether solution) was further added.

<Comparative Example 1>
Instead of epoxy resin A, 9 parts of naphthalene type epoxy resin (“ESN-475V” manufactured by Nittetsu Chemical & Materials Co., Ltd., epoxy equivalent 330) is used, and an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Co., Ltd.), Instead of 24 parts of a toluene solution having a solid content of 65% by mass, 26 parts of an active ester curing agent (“HPC-8150-62T” manufactured by DIC, an active ester equivalent of 234, a toluene solution having a solid content of 62%) was used and contained triazine. The resin composition is the same as in Example 1 except that 2 parts of cresol novolak resin (“LA-3018-50P” manufactured by DIC, a propylene glycol monomethyl ether solution having a nitrogen content of 18% and a solid content of 50% by mass) is further added. Was prepared.

<Comparative Example 2>
Active ester curing agent ("HPC-8150-62T" manufactured by DIC, active ester equivalent) instead of 24 parts of active ester curing agent ("HPC-8000-65T" manufactured by DIC, toluene solution having a solid content of 65% by mass) Spherical silica (average particle size 0.5 μm, Admatex) surface-treated with an amino-based silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) using 25 parts (234, toluene solution with a solid content of 62%). The amount of "SO-C2" manufactured by the company was changed from 65 parts to 35 parts, and the triazine-containing cresol novolak resin ("LA-3018-50P" manufactured by DIC), nitrogen content 18%, solid content 50% by mass. A resin composition was prepared in the same manner as in Example 1 except that 2 parts (propylene glycol monomethyl ether solution) was further added.

<Production Example 1: Resin sheet with a resin composition layer thickness of 40 μm>
As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. The resin compositions obtained in Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying was 40 μm. Then, the resin composition was dried at 80 ° C. to 100 ° C. (average 90 ° C.) for 4 minutes to obtain a resin sheet containing a support and a resin composition layer.

<Production Example 2: Resin sheet with a resin composition layer thickness of 25 μm>
Similar to Production Example 1, the resin compositions obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 25 μm, and the temperature was 70 ° C to 80 ° C (average 75 ° C). The mixture was dried for 2.5 minutes to obtain a resin sheet containing a support and a resin composition layer.

<Test Example 1: Measurement of dielectric loss tangent>
The resin sheet produced in Production Example 1 was heated at 190 ° C. for 90 minutes to thermally cure the resin composition layer. Then, the support was peeled off to obtain a cured product of the resin composition. This cured product was cut into test pieces having a width of 2 mm and a length of 80 mm. Dissipation factor (Df) was measured for the test piece by a cavity resonance perturbation method using "HP8632B" manufactured by Agilent Technologies, Inc. at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. Measurements were made on three test pieces, and the average values are shown in Table 1 below.

<Test Example 2: Evaluation of crack resistance after desmear treatment>
A core material (Hitachi Kasei Kogyo Co., Ltd.) in which a circular copper pad (copper thickness 35 μm) having a diameter of 350 μm is formed in a lattice pattern at intervals of 400 μm so that the resin sheet having a thickness of 25 μm obtained in Production Example 2 has a residual copper ratio of 60%. The resin composition layer is bonded to the inner layer substrate by using a batch type vacuum pressurizing laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) on both sides of "E705GR" manufactured by Japan, with a thickness of 400 μm). As described above, it was laminated on both sides of the inner layer substrate. This laminating was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at a temperature of 100 ° C. and a pressure of 0.74 MPa for 30 seconds. This was placed in an oven at 130 ° C. and heated for 30 minutes, then transferred to an oven at 170 ° C. and heated for 30 minutes. Further, the support layer was peeled off, and the obtained circuit board was immersed in a swollen liquid, Swelling Dip Securigant P of Atotech Japan Co., Ltd., at 60 ° C. for 10 minutes. Next, it was immersed in Concentrate Compact P (Aqueous solution of KMnO ₄ : 60 g / L, NaOH: 40 g / L) of Atotech Japan Co., Ltd., which is a roughening liquid, at 80 ° C. for 30 minutes. Finally, it was immersed in the neutralizing solution, Reduction Solution Securigant P of Atotech Japan Co., Ltd., at 40 ° C. for 5 minutes. 100 copper pads of the circuit board after the roughening treatment were observed, and the presence or absence of cracks in the resin composition layer was confirmed. If the number of cracks is 10 or less, it is evaluated as "○", and if it is more than 10, it is evaluated as "×".

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

Referring to Table 1, in Comparative Example 1 in which the ester-modified epoxy resin was not used, the evaluation of crack resistance was poor, and in Comparative Example 2 in which the amount of the inorganic filler used was less than 50% by mass, the evaluation of crack resistance was poor. In addition to being bad, the dielectric loss tangent is high. On the other hand, it contains (A) epoxy resin, (B) active ester compound, and (C) inorganic filler, (A) epoxy resin contains ester-modified epoxy resin, and (C) content of inorganic filler. However, it can be seen that these problems can be overcome when a resin composition having a content of 50% by mass or more is used.

Claims (20)

A resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler.
The component (A) is an epoxy resin having two or more epoxy groups in one molecule of (A-1), and the formula (1):

[In the formula, R ¹ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² is an aryl group which may have a substituent. Is shown. ]
Contains a modified epoxy resin obtained by reacting an ester compound represented by
A resin composition in which the content of the component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. A resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler.
The component (A) is the formula (A-1) (2-1):

[In the formula, * indicates a binding site. ]
Group represented by and formula (2-2):

[In the formula, R ¹ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² is an aryl group which may have a substituent. , And * indicates a binding site. ]
Contains a modified epoxy resin having a group represented by
A resin composition in which the content of the component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. The component (A-1) is the formula (4-1) :.

[In the formula, R ⁴ independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and a is 0, 1, 2 or 3 Is shown. ]
Structural unit represented by, and formula (4-2) :.

[In the formula, R ¹ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ² is an aryl group which may have a substituent. , R ⁴ each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and a indicates 0, 1, 2 or 3. show. ]
The resin composition according to claim 1 or 2, which is a modified epoxy resin having a structural unit represented by. The resin according to any one of claims 1 to 3, wherein the content of the component (A-1) is 1% by mass to 20% by mass when the non-volatile component in the resin composition is 100% by mass. Composition. The resin composition according to any one of claims 1 to 4, wherein the content of the component (B) is 5% by mass to 30% by mass when the non-volatile component in the resin composition is 100% by mass. .. The resin composition according to any one of claims 1 to 5, wherein the component (A) further contains (A-2) an epoxy resin liquid at 20 ° C. The resin composition according to any one of claims 1 to 6, further comprising (D) a thermoplastic resin. The resin composition according to claim 7, wherein the component (D) contains a thermoplastic resin selected from the group consisting of a polyimide resin and a phenoxy resin. (D) The resin composition according to claim 7 or 8, wherein the weight average molecular weight (Mw) of the component is 5,000 or more. The resin composition according to any one of claims 1 to 9, further comprising (E) a radically polymerizable compound. The resin composition according to claim 10, wherein the component (E) contains a (meth) acrylic radically polymerizable compound. The resin composition according to any one of claims 1 to 11, further comprising (F) an elastomer. The resin composition according to claim 12, wherein the component (F) contains core-shell type rubber particles. The resin composition according to any one of claims 1 to 13, further comprising (G) a curing accelerator. The resin composition according to any one of claims 1 to 14, wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0030 or less when measured at 5.8 GHz and 23 ° C. The cured product of the resin composition according to any one of claims 1 to 15. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 15. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 15 provided on the support. A printed wiring board provided with an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 15. A semiconductor device comprising the printed wiring board according to claim 19.