TW202346444A - Resin composition capable of obtaining a cured product that is excellent in both crack resistance and desmear resistance - Google Patents

Abstract

An object of the present invention is to provide a resin composition capable of obtaining a cured product that is excellent in both crack resistance and desmear resistance. The solution of the present invention is a resin composition in which a combination of (A) a specific phenolic hardener containing a long-chain aliphatic hydrocarbon group, (B) an epoxy resin, and (C) an active ester compound, can be included.

Description

resin composition

The present invention relates to a resin composition. In addition, the present invention relates to cured products, sheet-like laminated materials, resin sheets, circuit boards, semiconductor chip packages and semiconductor devices using the resin composition.

Insulating layers are usually provided in circuit substrates and semiconductor chip packages. For example, an interlayer insulating layer as an insulating layer may be provided in a printed wiring board which is a type of circuit board. In addition, for example, a rewiring forming layer as an insulating layer may be provided in a semiconductor wafer package. These insulating layers are usually formed from a cured product obtained by curing a resin composition. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2020-23714 [Patent Document 2] Japanese Patent Application Publication No. 2020-136542 [Patent Document 3] Japanese Patent Application Publication No. 2019-48952.

[Problem to be solved by the invention]

In recent years, as the wiring density of circuit boards and semiconductor chip packages has increased, there has been a demand to improve the crack resistance of the insulating layer. In order to improve the crack resistance, the present inventors tried to use a component capable of relaxing stress in the hardened material (hereinafter sometimes referred to as a "stress relaxation component"). However, it was found that when conventional stress relaxation components are used, although crack resistance may be improved, stain removal resistance tends to decrease. When the decontamination resistance is low, the surface roughness of the insulating layer after the decontamination treatment becomes larger, which may cause the transmission loss to increase due to the skin effect. In addition, it becomes difficult to stably form thin wiring on the insulating layer, which may become an obstacle to high-density wiring.

The present invention was proposed to the inventors in view of the above-mentioned problems, and its object is to provide: a resin composition capable of obtaining a cured product that is excellent in both crack resistance and desmear resistance; and a cured product of the resin composition; A sheet-like laminated material and a resin sheet containing the resin composition; a circuit board, a semiconductor chip package and a semiconductor device containing a cured product of the resin composition. [Means used to solve problems]

The present inventors conducted intensive research in order to solve the above-mentioned problems. As a result, the present inventors found that the above problems can be solved by a resin composition containing a specific phenolic hardener containing a long-chain aliphatic hydrocarbon group, an epoxy resin, and an active ester compound in combination, and completed the present invention. . That is, the present invention includes the following.

[1] A resin composition containing (A) a resin represented by the following formula (A-1), (B) an epoxy resin, and (C) an active ester compound; [Chemical 1] (In formula (A-1), R ¹ represents a chain aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent, R ² represents a hydrocarbon group which may have a substituent, n represents a number of 1 or more, and m represents 0 or more number; wherein, R ¹ includes a chain unsaturated aliphatic hydrocarbon group with 7 or more carbon atoms that may have a substituent.) [2] The resin composition of [1], wherein the component (A) has 1,000 or less The weight average molecular weight of Or its combination: [Chemification 2] (In the formulas (a-1) to (a-4), R ¹ represents a chain aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent. Wherein, R ¹ includes a chain aliphatic hydrocarbon group having 7 carbon atoms which may have a substituent. The above chain unsaturated aliphatic hydrocarbon group.) [4] The resin composition according to any one of [1] to [3], wherein relative to 100% by mass of the non-volatile components in the resin composition, (A) The amount of the component is 0.01 mass% or more and 10 mass% or less; [5] The resin composition according to any one of [1] to [4], which contains (D) inorganic filler; [6] As [1] The resin composition according to any one of [5], which contains (E) hardener in addition to component (A) and (C); [7] The resin according to any one of [1] to [6] Composition, which contains (F) hardening accelerator; [8] The resin composition according to any one of [1] to [7], which contains (G) thermoplastic resin; [9] Such as [1] to [8] ] A resin composition according to any one of [1] to [9], which is used to form an insulating layer of a printed wiring board; [10] A hardened product of a resin composition according to any one of [1] to [9]; [11] A sheet -like laminated material, which includes a resin composition according to any one of [1] to [9]; [12] a resin sheet having a support and a resin composition layer formed on the support, and the resin The composition layer includes a resin composition according to any one of [1] to [9]; [13] A circuit substrate having a cured product including a resin composition according to any one of [1] to [9] an insulating layer; [14] a semiconductor chip package, which includes a cured product of the resin composition as described in any one of [1] to [9]; [15] a semiconductor device, which is provided with the resin composition as described in [13] Circuit substrate; [16] A semiconductor device having a semiconductor chip package as in [14]. [Effects of the invention]

According to the present invention, it is possible to provide: a resin composition capable of obtaining a cured product that is excellent in both crack resistance and stain removal resistance; a cured product of the resin composition; a sheet-like laminated material and a resin sheet containing the resin composition; Circuit boards, semiconductor chip packages, and semiconductor devices containing a cured product of the resin composition.

Hereinafter, embodiments and examples will be shown to explain the present invention. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified and implemented within the scope of the patent application and its equivalent range.

In the following description, the term “which may have a substituent” with respect to a compound or group refers to the case where the hydrogen atom of the compound or group is not substituted by a substituent, and a part or portion of the hydrogen atom of the compound or group. Both sides when all are substituted by substituents.

In the following description, the term "(meth)acrylic acid" means including acrylic acid, methacrylic acid and combinations thereof. In addition, the term "(meth)acrylate" is meant to include acrylate, methacrylate, and combinations thereof.

In the following description, unless otherwise stated, the term "dielectric constant" means the relative dielectric constant.

[Outline of resin composition] A resin composition according to one embodiment of the present invention contains (A) a resin represented by the following formula (A-1), (B) an epoxy resin, and (C) an active ester compound. Hereinafter, "(A) the resin represented by formula (A-1)" may be referred to as "(A) long-chain aliphatic phenol resin".

[Chemical 3] (In formula (A-1), R ¹ represents a chain aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent, R ² represents a hydrocarbon group which may have a substituent, n represents a number of 1 or more, and m represents 0 or more The number; wherein, R ¹ includes a chain unsaturated aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent.).

(A) The long-chain aliphatic phenol resin may contain not only a compound having a single structure, but may also contain a composition containing one or more compounds selected from the group of compounds represented by formula (A-1) . Therefore, in the formula (A-1) representing the long-chain aliphatic phenol resin (A), within the scope of the definition stipulated by the formula (A-1), the chain aliphatic hydrocarbon group R ¹ may include a plurality of different structures. The base. The chain aliphatic hydrocarbon group R ¹ includes a chain unsaturated aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent. That is, (A) among the compounds contained in the long-chain aliphatic phenol resin, R ¹ of at least a part of the compounds is a chain unsaturated aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent. Therefore, for example, when (A) the long-chain aliphatic phenol resin contains only a compound having a single structure, the R ¹ group of the compound represents a chain unsaturated aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent. For example, when (A) the long-chain aliphatic phenol resin is a composition containing a plurality of compounds having different structures, the R ¹ group of one or more compounds contained in the composition represents the number of carbon atoms that may have a substituent. Chain unsaturated aliphatic hydrocarbon groups of 7 or more.

According to the resin composition according to one embodiment of the present invention, a cured product excellent in both crack resistance and stain removal resistance can be obtained. The present inventors speculate as follows on the mechanism by which the above-mentioned excellent effects can be obtained. However, the scope of the present invention is not limited by the mechanism described below.

For the resin composition according to one embodiment of the present invention, since (A) the phenolic hydroxyl group of the long-chain aliphatic phenol resin, (B) the epoxy group of the epoxy resin, and (C) the active ester group of the active ester compound It can react and combine to form a cross-linked structure, so it can be hardened. The cured product obtained by the above-mentioned curing contains the long-chain aliphatic hydrocarbon group contained in the long-chain aliphatic phenol resin (A) as represented by the R ¹ group in the formula (A-1). Since this long-chain aliphatic hydrocarbon group has a soft carbon skeleton, it functions as a stress relaxation component capable of absorbing stress in the cured product. Therefore, even if stress is generated in the hardened material, damage to the hardened material caused by the stress can be suppressed, and therefore the crack resistance can be improved.

In addition, in the decontamination treatment, an oxidizing agent is usually brought into contact with the hardened material. When an oxidizing agent comes into contact with a hardened product, if a large number of bonds generated by the reaction of phenolic hydroxyl groups, epoxy groups and active ester groups are cut off due to oxidation, the cross-linked structure will be excessively destroyed and the surface roughness may become larger. However, if the cured product of the resin composition according to one embodiment of the present invention is brought into contact with an oxidizing agent, the unsaturated bond of the long-chain aliphatic hydrocarbon group of the long-chain aliphatic phenol resin (A) is preferentially oxidized, thereby inhibiting Oxidation of bonds produced by the reaction of phenolic hydroxyl groups, epoxy groups and active ester groups. Therefore, since the destruction of the cross-linked structure can be suppressed, excellent stain removal resistance can be achieved.

The resin composition according to one embodiment of the present invention can generally have a low minimum melt viscosity. In addition, the cured product of the resin composition according to one embodiment of the present invention can generally reduce dielectric properties such as dielectric constant and dielectric loss tangent. In addition, when a conductive layer is generally formed on the cured product of the resin composition according to one embodiment of the present invention, the adhesion to the conductive layer can be improved.

[(A) Long-chain aliphatic phenol resin] The resin composition according to one embodiment of the present invention contains (A) long-chain aliphatic phenol resin as (A) component. (A) The long-chain aliphatic phenol resin is any one represented by the following formula (A-1) or a combination thereof.

[Chemical 4] (In formula (A-1), R ¹ represents a chain aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent, R ² represents a hydrocarbon group which may have a substituent, n represents a number of 1 or more, and m represents 0 or more The number; wherein R ¹ includes a chain unsaturated aliphatic hydrocarbon group with 7 or more carbon atoms which may have a substituent.).

In formula (A-1), R ¹ represents a chain aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent. The chain aliphatic hydrocarbon group represents a group obtained by removing one hydrogen atom from a chain aliphatic hydrocarbon compound. Examples of the aliphatic hydrocarbon group include chain saturated aliphatic hydrocarbon groups such as alkyl groups; chain unsaturated aliphatic hydrocarbon groups such as alkenyl groups and polyalkenyl groups (alkapolyenyl), and the like. The chain aliphatic hydrocarbon group may be straight chain or branched, but straight chain is preferred.

The chain aliphatic hydrocarbon group in ^R1 has a specific range of carbon number. Specifically, the number of carbon atoms of the chain aliphatic hydrocarbon group in ^R1 is usually 7 or more, preferably 9 or more, more preferably 12 or more, particularly preferably 14 or more, preferably 50 or less, preferably 40. below, preferably below 30, and particularly preferably below 20. Here, the number of carbon atoms does not include the number of carbon atoms of the substituent.

Examples of the alkyl group include heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl. , Heptadecyl, octadecyl, nonadecyl, eicosyl, etc.

Examples of the alkenyl group include: heptenyl, octenyl, nonenyl, decenel, undecenyl, dodecenyl, tridecenyl, tetradecenyl, decenyl, etc. Five carbon alkenyl, hexadecyl alkenyl, heptadecenyl alkenyl, octadecyl alkenyl, nonadecenyl alkenyl, eicosyl alkenyl, etc.

The number of double bonds in the polyalkenyl group is usually 2 or more, and may be 3 or more. In addition, it is preferably 10 or less, more preferably 6 or less, and particularly preferably 4 or less. Examples of the polyalkenyl group include heptadienyl, octadienyl, nonadienyl, decadienyl, undecadienyl, dodecadienyl, and tridecadienyl. , Tetradecadienyl, pentadecadienyl, hexadecadienyl, heptadecadienyl, octadecadienyl, nonadecadienyl, eicosadienyl, etc. Alkadienyl; heptatrienyl, octatrienyl, nonatrienyl, decatrienyl, undecatrienyl, dodecatrienyl, tridecatrienyl, tetradecaneyl Trienyl groups such as carbotrienyl, pentadecatrienyl, hexadecatrienyl, heptadecatrienyl, octadecatrienyl, nonadecatrienyl, and eicosactrienyl (alkatrienyl) etc.

The chain aliphatic hydrocarbon group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkoxy group, and a monovalent heterocyclic group. , alkylidene group, amine group, silicon group, acyl group, acyloxy group, carboxyl group, sulfo group, cyano group, nitro group, hydroxyl group, mercapto group and oxo group (oxo). Among them, the chain aliphatic hydrocarbon group represented by R ¹ preferably has no substituent.

As described above, (A) the long-chain aliphatic phenol resin contains not only a compound having a single structure but also one or more compounds selected from the group of compounds represented by formula (A-1). composition. Therefore, (A) the long-chain aliphatic phenol resin may contain one or more compounds represented by formula (A-1).

Therefore, R ¹ of formula (A-1) may contain various chain aliphatic hydrocarbon groups which may have substituents. Among them, the optionally substituted aliphatic hydrocarbon group represented by R ¹ includes an optionally substituted chain unsaturated aliphatic hydrocarbon group. Therefore, R ¹ may represent a combination of a chain saturated aliphatic hydrocarbon group which may have a substituent and a chain unsaturated aliphatic hydrocarbon group which may have a substituent, or a chain unsaturated aliphatic hydrocarbon group which may have a substituent.

The amount of the compound in which R ¹ represents a chain unsaturated aliphatic hydrocarbon group which may have a substituent is 70% relative to 100% by mass of the entire compound represented by the formula (A-1) in the long-chain aliphatic phenol resin (A). It is preferably at least 80% by mass, preferably at least 80% by mass, and particularly preferably at least 90% by mass, and usually at most 100% by mass.

R ¹ of formula (A-1) preferably contains a chain unsaturated aliphatic hydrocarbon group which may have a substituent and contains one carbon-carbon double bond. R ¹ represents a chain unsaturated fat which may have a substituent and contains one carbon-carbon double bond relative to 100% by mass of the entire compound represented by the formula (A-1) in the long-chain aliphatic phenol resin (A) The amount of the family hydrocarbon group compound is preferably 10 mass% or more, more preferably 20 mass% or more, particularly preferably 30 mass% or more, 60 mass% or less, preferably 50 mass% or less, particularly preferably 40% by mass or less.

R ¹ of formula (A-1) preferably contains a chain unsaturated aliphatic hydrocarbon group which may have a substituent and contains two carbon-carbon double bonds. R ¹ represents a chain unsaturated fat which may have a substituent and contains two carbon-carbon double bonds with respect to 100% by mass of the entire compound represented by the formula (A-1) in the long-chain aliphatic phenol resin (A) The amount of the family hydrocarbon group compound is preferably 5 mass% or more, more preferably 10 mass% or more, particularly preferably 15 mass% or more, 50 mass% or less, preferably 40 mass% or less, particularly preferably 30% by mass or less.

R ¹ of formula (A-1) preferably contains a chain unsaturated aliphatic hydrocarbon group which may have a substituent and contains three carbon-carbon double bonds. R ¹ represents a chain unsaturated fat which may have a substituent and contains three carbon-carbon double bonds with respect to 100% by mass of the entire compound represented by the formula (A-1) in the long-chain aliphatic phenol resin (A) The amount of the family hydrocarbon group compound is preferably 10 mass% or more, more preferably 20 mass% or more, particularly preferably 30 mass% or more, 70 mass% or less, more preferably 60 mass% or less, particularly preferably 50% by mass or less.

The amount of the compound in which R ¹ represents a chain saturated aliphatic hydrocarbon group which may have a substituent may be 0 mass % relative to 100 mass % of the total compound represented by the formula (A-1) of the long-chain aliphatic phenol resin (A). , can also be greater than 0 mass%. Specifically, the amount of the compound in which R ¹ represents a chain saturated aliphatic hydrocarbon group which may have a substituent is usually 0% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass. %the following.

In formula (A-1), R ² represents a hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. In addition, the aliphatic hydrocarbon group may be linear or branched, or may have a ring structure. The number of carbon atoms of the hydrocarbon group represented by R ² is preferably 1 to 20, more preferably 1 to 14, more preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.

Examples of the hydrocarbon group represented by R ² include: saturated aliphatic hydrocarbon groups such as alkyl groups and cycloalkyl groups; unsaturated aliphatic hydrocarbon groups such as alkenyl groups, alkynyl groups, polyalkenyl groups, and cycloalkenyl groups; and aromatic groups such as aryl groups. hydrocarbyl. Among them, a saturated aliphatic hydrocarbon group is preferred, and an alkyl group is preferred. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and nonyl. , and decyl group, with methyl group being particularly preferred.

The hydrocarbon group represented by R ² may have a substituent. Examples of the substituent in R ² include the same substituents as those in R ¹ . The hydrocarbon group represented by R ² preferably has no substituent.

In formula (A-1), n represents a number of 1 or more. This n can represent the average number of hydroxyl groups bonded to the benzene ring represented by formula (A-1). n is usually 1 or more and usually 2 or less. Therefore, n can be 1, 2, or a number greater than 1 and less than 2. When n is 1, examples of the compound represented by formula (A-1) include cardanol. When n is 2, examples of the compound represented by formula (A-1) include cardol, methylcardol, urushiol, and the like. Therefore, for example, when (A) the long-chain aliphatic phenol resin contains cardanol in combination with one or more selected from cardanol, methylcardanol, and urushiol, n may be greater than 1 and less than 2 number.

In Formula (A-1), m represents a number equal to or greater than 0. This m can represent the average number of R ² groups bonded to the benzene ring represented by formula (A-1). m can be 0 or a number greater than 0, preferably less than 1, preferably less than 1. When m is 0, examples of the compound represented by formula (A-1) include cardanol, cardanol, urushiol, and the like. When m is 1, examples of the compound represented by formula (A-1) include methylcardanol and the like. Therefore, for example, when (A) the long-chain aliphatic phenol resin contains at least one selected from cardanol, cardanol, and urushiol in combination with methylcardanol, m may be greater than 0 and less than 1 number.

Examples of (A) the long-chain aliphatic phenol resin include resins represented by any one of the following formulas (a-1) to formula (a-4), or combinations thereof.

[Chemistry 5] .

(In formulas (a-1) to (a-4), R ¹ has the same meaning as in formula (A-1)).

Examples of the long-chain aliphatic phenol resin (A) include cardanol (resin of formula (a-1)), cardanol (resin of formula (a-2)), and 2-methylcardanol. (resin of formula (a-3)), urushiol (resin of formula (a-4)). These are marketed, for example, as resins derived from natural organic matter.

(A) The phenolic hydroxyl equivalent of the long-chain aliphatic phenol resin is preferably 50g/eq.~3000g/eq., more preferably 100g/eq.~1000g/eq., more preferably 100g/eq.~500g /eq., the best is 100g/eq.～300g/eq. Phenolic hydroxyl equivalent represents the mass of resin corresponding to 1 equivalent of phenolic hydroxyl group. In addition, the phenolic hydroxyl group means a hydroxyl group bonded to a benzene ring.

When the epoxy group number of (B) epoxy resin is 1, the phenolic hydroxyl number of (A) long-chain aliphatic phenol resin is preferably 0.01 or more, more preferably 0.02 or more, particularly preferably 0.05 or more, and 1 or less is preferred, 0.5 or less is more preferred, and 0.3 or less is particularly preferred. "Number of phenolic hydroxyl groups of (A) long-chain aliphatic phenol resin" means the mass of non-volatile components of (A) long-chain aliphatic phenol resin present in the resin composition divided by the phenolic hydroxyl equivalent. The value obtained by adding up all the values. In addition, "the number of epoxy groups of (B) epoxy resin" means the total value obtained by dividing the mass of non-volatile components of (B) epoxy resin present in the resin composition by the epoxy equivalent. value. (A) When the number of phenolic hydroxyl groups of the long-chain aliphatic phenol resin is within the above range, the crack resistance and stain removal resistance of the cured product of the resin composition can be particularly good, and in general, the resin composition can be effectively improved. The minimum melt viscosity, the dielectric properties of the hardened material, and the adhesion to the conductor layer.

When the number of active ester groups of (C) the active ester compound is 1, the number of phenolic hydroxyl groups of (A) the long-chain aliphatic phenol resin is preferably 0.01 or more, more preferably 0.02 or more, more preferably 0.03 or more, and It is preferably 1 or less, more preferably 0.5 or less, more preferably 0.2 or less. "The number of active ester groups of (C) the active ester compound" means the total value obtained by dividing the mass of the non-volatile component of the (C) active ester compound present in the resin composition by the active ester group equivalent. value. (A) When the number of phenolic hydroxyl groups of the long-chain aliphatic phenol resin is within the above range, the crack resistance and stain removal resistance of the cured product of the resin composition can be particularly good, and in general, the resin composition can be effectively improved. The minimum melt viscosity, the dielectric properties of the hardened material, and the adhesion to the conductor layer.

(A) The weight average molecular weight of the long-chain aliphatic phenol resin is preferably 1,000 or less, more preferably 800 or less, and particularly preferably 500 or less. The lower limit is not particularly limited, and may be, for example, 50 or more, 100 or more, 150 or more, 186 or more, 200 or more, etc. The weight average molecular weight can be measured as a polystyrene-converted value using gel permeation chromatography (GPC).

The amount of (A) the long-chain aliphatic phenol resin is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and particularly preferably 0.2 mass%, based on 100 mass% of the non-volatile content of the resin composition. The above content is preferably 10 mass% or less, more preferably 5 mass% or less, and particularly preferably 3 mass% or less. (A) When the amount of the long-chain aliphatic phenol resin is within the above range, the crack resistance and stain removal resistance of the cured product of the resin composition can be particularly good, and further, the minimum melting point of the resin composition can generally be effectively improved. Viscosity, dielectric properties of the hardened material, and adhesion to the conductor layer.

The amount of the long-chain aliphatic phenol resin (A) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and particularly preferably 1 mass% or more, based on 100 mass% of the resin component of the resin composition. , preferably 20 mass% or less, more preferably 15 mass% or less, and particularly preferably 10 mass% or less. The resin component of the resin composition refers to components other than the (D) inorganic filler described below among the non-volatile components of the resin composition. (A) When the amount of the long-chain aliphatic phenol resin is within the above range, the crack resistance and stain removal resistance of the cured product of the resin composition can be particularly good, and further, the minimum melting point of the resin composition can generally be effectively improved. Viscosity, dielectric properties of the hardened material, and adhesion to the conductor layer.

The mass ratio of (A) long-chain aliphatic phenol resin and (B) epoxy resin ((A) long-chain aliphatic phenol resin/(B) epoxy resin) is preferably 0.01 or more, more preferably 0.02 or more, Especially good is 0.05 or more, 1 or less is better, more preferably is 0.5 or less, and particularly good is 0.3 or less. When the mass ratio ((A) long-chain aliphatic phenol resin/(B) epoxy resin) is within the above range, the crack resistance and stain removal resistance of the cured product of the resin composition can be particularly good, and in general, Effectively improve the minimum melt viscosity of the resin composition, the dielectric properties of the cured product, and the adhesion to the conductor layer.

[(B)Epoxy resin] The resin composition according to one embodiment of the present invention contains (B) epoxy resin as (B) component. (B) The epoxy resin may be a curable resin having an epoxy group. (B) The epoxy resin does not contain components corresponding to the above-mentioned (A).

Examples of (B) epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol S type epoxy resin, Phenol AF type epoxy resin, dicyclopentadiene type epoxy resin, phenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl Base - Catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol Cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy Resin, heterocyclic epoxy resin, spiro-containing epoxy resin, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthyl ether-type epoxy resin, trimethylol-type epoxy resin Oxygen resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, etc. (B) Epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

From the viewpoint of obtaining a cured product having excellent heat resistance, the epoxy resin (B) preferably contains an epoxy resin containing an aromatic structure. Aromatic structures refer to chemical structures that are usually defined as aromatic, and also include polycyclic aromatic and aromatic heterocycles. Examples of the epoxy resin containing an aromatic structure include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, and dicyclopentadienyl. Vinyl type epoxy resin, phenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthalene type epoxy resin Phenolic epoxy resin, anthracene epoxy resin, bixylenol epoxy resin, glycidyl amine epoxy resin with aromatic structure, glycidyl ester type epoxy resin with aromatic structure, methane Phenol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with aromatic structure, epoxy resin with aromatic structure butadiene structure, alicyclic resin with aromatic structure Formula epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring with aromatic structure, cyclohexanedimethanol type epoxy resin with aromatic structure, naphthyl ether type epoxy resin, etc. Trimethylol-type epoxy resin with aromatic structure, tetraphenylethane-type epoxy resin with aromatic structure, etc.

In the resin composition, the epoxy resin (B) is based on an epoxy resin having two or more epoxy groups per molecule. The proportion of the epoxy resin having two or more epoxy groups per molecule is preferably 50 mass% or more, more preferably 60 mass% or more, based on 100 mass% of the non-volatile content of the epoxy resin (B). , the best value is more than 70% by mass.

Epoxy resin includes epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and epoxy resin that is solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resin"). Resin"). The resin composition may contain only liquid epoxy resin as the epoxy resin, or may contain only solid epoxy resin, or may contain liquid epoxy resin and solid epoxy resin in combination.

As the liquid epoxy resin, one having two or more epoxy groups per molecule is preferred.

As liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and cyclic epoxy resin with butadiene structure Oxygen resin is preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D" and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "828EL" and "828EL" manufactured by Mitsubishi Chemical Corporation jER828EL", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" manufactured by Mitsubishi Chemical Corporation "(phenol novolac type epoxy resin); "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycyrrhizol) manufactured by ADEKA (Glycirol) type epoxy resin); "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene) manufactured by ADEKA type epoxy resin); "ZX1059" made by Nippon Steel Chemical Materials Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" made by Nagase ChemteX Co., Ltd. (glycidol ester-based epoxy resin); "Celloxide 2021P" manufactured by Daicel Corporation (alicyclic epoxy resin with an ester skeleton); "PB-3600" manufactured by Daicel Corporation, "JP-100" manufactured by Nippon Soda Corporation ", "JP-200" (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd. wait. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is preferred. Better.

As solid epoxy resins, dixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol novolak-type epoxy resin, cresol novolak-type epoxy resin, dicyclopentane Diene type epoxy resin, ginseng type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl 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 resin, phenol benzopyrrolone type epoxy resin are preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation Resin); "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP- 7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", " EXA-7311-G4", "EXA-7311-G4S", "HP6000" (alkylene ether type epoxy resin); "EPPN-502H" (ginseng phenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Japan "NC7000L" (naphthol novolak type epoxy resin) manufactured by Nippon Chemical Industry Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Chemical Industry Co., Ltd. Resin); "ESN475V" (naphthol-type epoxy resin) and "ESN4100V" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd. ); "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation Resin); "YL6121" manufactured by Mitsubishi Chemical Corporation (biphenyl-type epoxy resin); "YX8800" manufactured by Mitsubishi Chemical Corporation (anthracene-type epoxy resin); "YX7700" manufactured by Mitsubishi Chemical Corporation (phenol aralkyl type Epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" manufactured by Mitsubishi Chemical Corporation (N-type epoxy resin); "jER1010" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Nippon Chemical Corporation "WHR991S" (phenol benzopyrrolone type epoxy resin) made by These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the (B) epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20. , the better is 10:1～1:10, the especially best is 7:1～1:7.

(B) The epoxy equivalent of the epoxy resin is preferably 50g/eq.～5,000g/eq., more preferably 60g/eq.～3,000g/eq., more preferably 80g/eq.～2,000g/ eq., the best range is 110g/eq.～1,000g/eq. The epoxy equivalent weight represents the mass of the resin corresponding to 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

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

The amount of (B) epoxy resin in the resin composition is preferably 1 mass% or more, more preferably 2 mass% or more, based on 100 mass% of non-volatile components in the resin composition, and particularly preferably 4% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. (B) When the amount of epoxy resin is within the above range, the crack resistance and stain removal resistance of the cured resin composition can be particularly good. Furthermore, the minimum melt viscosity and curing resistance of the resin composition can generally be effectively improved. The dielectric properties of the object and the adhesion to the conductor layer.

The amount of (B) epoxy resin in the resin composition is preferably 5 mass% or more, more preferably 10 mass% or more, and particularly preferably 20 mass%, based on 100 mass% of the resin component in the resin composition. Mass% or more, preferably 60 mass% or less, more preferably 50 mass% or less, particularly preferably 40 mass% or less. (B) When the amount of epoxy resin is within the above range, the crack resistance and stain removal resistance of the cured resin composition can be particularly good. Furthermore, the minimum melt viscosity and curing resistance of the resin composition can generally be effectively improved. The dielectric properties of the object and the adhesion to the conductor layer.

[(C) Active ester compound] The resin composition according to one embodiment of the present invention contains (C) active ester compound as (C) component. (C) The active ester compound does not include components corresponding to the above-mentioned (A) to (B). (C) The active ester compound reacts with (B) epoxy resin to harden the resin composition and functions as an epoxy resin hardener. (C) The active ester compound may be used individually by 1 type, and may be used in combination of 2 or more types.

As (C) the active ester compound, it is generally preferable to use esters having two or more highly reactive esters in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds. base compound. The active ester compound is preferably obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaloline, methylated bisphenol A, and methylated bisphenol. F. Methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, phloroglucinol, dicyclopentadiene-type diphenol compounds , phenolic phenolic resin (Phenolic Novolac), etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene into two molecules of phenol.

Specifically, as (C) the active ester compound, a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetate of a phenolic phenolic resin, a phenolic phenolic resin containing An active ester compound of a benzyl compound of a resin is preferred, and among these, at least one selected from the group consisting of a dicyclopentadiene-type active ester compound and a naphthalene-type active ester compound is also preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

Regarding commercially available products of (C) active ester compounds, for example, active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" ” (manufactured by DIC Corporation); examples of active ester compounds containing a naphthalene structure include “HP-B-8151-62T”, “EXB-8100L-65T”, “EXB-8150-60T”, and “EXB-8150- 62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); examples of active ester compounds containing phosphorus include " EXB9401" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is an acetate of a phenol-based phenolic resin; and an active ester compound that is a benzyl compound of a phenol-based phenolic resin. Examples of the compound include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); examples of the active ester compound containing a styrene group and a naphthalene structure include "PC1300-02-65MA" (Air Water company system), etc.

(C) The active ester group equivalent of the active ester compound is preferably 50g/eq.~500g/eq., more preferably 50g/eq.~400g/eq., more preferably 100g/eq.~300g/eq. . The active ester group equivalent represents the mass of the active ester compound corresponding to 1 equivalent of active ester group.

When the number of epoxy groups of (B) the epoxy resin is 1, the number of active ester groups of the (C) active ester compound is preferably 0.1 or more, more preferably 0.5 or more, more preferably 1 or more, and preferably 6 or less. , preferably 5 or less, particularly preferably 4 or less. (C) When the number of active ester groups of the active ester compound is within the above range, the crack resistance and stain removal resistance of the cured resin composition can be particularly good, and further, the minimum melt viscosity of the resin composition can generally be effectively improved. , the dielectric properties of the hardened material, and the adhesion to the conductor layer.

The amount of (C) active ester compound in the resin composition is preferably 1 mass % or more, more preferably 5 mass % or more, and particularly preferably 10 mass % with respect to 100 mass % of non-volatile components of the resin composition. % by mass or more and 40 mass % or less, preferably 30 mass % or less, particularly preferably 20 mass % or less. (C) When the amount of the active ester compound is within the above range, the crack resistance and stain removal resistance of the cured resin composition can be particularly good, and further, the minimum melt viscosity and curing resistance of the resin composition can be effectively improved. The dielectric properties of the object and the adhesion to the conductor layer.

The amount of (C) active ester compound in the resin composition is preferably 20 mass% or more, more preferably 30 mass% or more, and particularly preferably 40 mass%, based on 100 mass% of the resin component of the resin composition. % or more, preferably 80 mass% or less, more preferably 70 mass% or less, and particularly preferably 60 mass% or less. (C) When the amount of the active ester compound is within the above range, the crack resistance and stain removal resistance of the cured resin composition can be particularly good, and further, the minimum melt viscosity and curing resistance of the resin composition can be effectively improved. The dielectric properties of the object and the adhesion to the conductor layer.

The mass ratio of (C) active ester compound and (A) long-chain aliphatic phenol resin ((C) active ester compound/(A) long-chain aliphatic phenol resin) is preferably 1 or more, preferably 2 or more, Especially good is 5 or more, 50 or less is better, 40 or less is more preferred, and particularly good is 30 or less. When the mass ratio ((C) active ester compound/(A) long-chain aliphatic phenol resin) is within the above range, the crack resistance and stain removal resistance of the cured product of the resin composition can be particularly good, and in general, Effectively improve the minimum melt viscosity of the resin composition, the dielectric properties of the cured product, and the adhesion to the conductor layer.

[(D) Inorganic filler material] The resin composition according to one embodiment of the present invention may further contain (D) an inorganic filler as an optional component. The (D) inorganic filler which is the component (D) does not include those corresponding to the above-mentioned components (A) to (C). (D) The inorganic filler is usually contained in the resin composition in the form of particles.

As the material of (D) the inorganic filler, an inorganic compound is used. (D) Examples of the inorganic filler material include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate , bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these fats, silica and alumina are suitable, and silica is suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, as the silica, spherical silica is preferred. (D) Inorganic filler material may be used individually by 1 type, or in combination of 2 or more types.

(D) The inorganic filler material can be classified into a hollow inorganic filler material having pores inside and a solid inorganic filler material having no pores inside. As the (D) inorganic filler, only a hollow inorganic filler, only a solid inorganic filler, or a combination of the hollow inorganic filler and the solid inorganic filler may be used. When a hollow inorganic filler is used, the relative dielectric constant of the cured product of the resin composition can usually be made particularly low.

Since hollow inorganic filling materials have pores, they usually have a porosity greater than 0% by volume. From the viewpoint of reducing the relative dielectric constant of the insulating layer containing the cured product of the resin composition, the porosity of the hollow inorganic filler material is preferably 5% by volume or more, more preferably 10% by volume or more, and particularly preferably 15%. Volume% or more. In addition, from the viewpoint of the mechanical strength of the cured product of the resin composition, the porosity of the hollow inorganic filler is preferably 95 volume % or less, more preferably 90 volume % or less, and particularly preferably 85 volume % or less.

The porosity P (volume %) of a particle is defined as the volume of "the total volume of one or more pores existing inside the particle" relative to the "volume of the entire particle based on the outer surface of the particle" Base ratio (total volume of pores/volume of particles). The porosity P can be determined by the following formula (M1) using the measured value D _M (g/cm ³ ) of the actual density of the particles and the theoretical value D _T (g/cm ³ ) of the material density of the material forming the particles. to calculate.

[Number 1] .

The hollow inorganic filler material can be produced by the method described in Japanese Patent No. 5940188 and Japanese Patent No. 5864299, or a method based thereon, for example.

(D) Commercially available products of the inorganic filler include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; and "YC100C", "YA050C" and "YA050C" manufactured by Admatechs. -MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1"; "UFP-30", "DAW-03", "FB-105FD" made by DENKA "; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; "Espherique" manufactured by Nikko Catalyst Co., Ltd.; "MG-005", "CellSpheres" manufactured by Pacific Cement Co., Ltd. "wait.

From the viewpoint of significantly obtaining the desired effect of the present invention, the average particle diameter of (D) the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.2 μm. Above, it is preferably 10 μm or less, more preferably 5 μm or less, and more preferably 3 μm or less.

(D) The average particle size of the inorganic filler material can be measured using a laser diffraction-scattering method based on Mie scattering theory. Specifically, the measurement can be performed by using a laser diffraction and scattering particle size distribution measuring device to prepare the particle size distribution of the inorganic filler material on a volume basis, and taking the median particle size as the average particle size. The measurement sample can be used: weigh 100 mg of the inorganic filler material and 10 g of methyl ethyl ketone into a vial, and disperse it using ultrasonic waves for 10 minutes. For the measurement sample, use a laser diffraction particle size distribution measuring device, set the wavelength of the light source to blue and red, and measure the volume-based particle size distribution of the inorganic filler material by a flow cell method. It can be obtained by The average particle size was calculated as the median particle size of the particle size distribution. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

The specific surface area of (D) the inorganic filler is preferably 0.1 m ² /g or more, more preferably 0.5 m 2 /g or more, and more preferably 1 m ² from the viewpoint of significantly obtaining the desired effect of the present invention. ² /g or more, particularly preferably 3m ² /g or more, preferably 100m ² /g or less, more preferably 70m ² /g or less, more preferably 50m ² /g or less, particularly preferably 40m ² /g or less. The specific surface area of the inorganic filler material can be measured by adsorbing nitrogen gas on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mounttech) according to the BET method, and calculating the specific surface area using the BET multi-point method.

From the viewpoint of improving moisture resistance and dispersibility, (D) the inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include: fluorine-containing silane coupling agent, aminosilane coupling agent, epoxysilane coupling agent, mercaptosilane coupling agent, silane coupling agent, alkoxysilane, and organosilazane compounds, titanate coupling agents, etc. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM803" (3-mercaptosilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Propyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM573" (N-phenyl-3-aminopropyl) manufactured by Shin-Etsu Chemical Industries, Ltd. Trimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM" manufactured by Shin-Etsu Chemical Industries, Ltd. -4803" (long-chain epoxy silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., etc.

From the viewpoint of improving the dispersibility of the inorganic filler material, it is preferable to control the degree of surface treatment by the surface treatment agent within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, more preferably 0.2% to 3% by mass of a surface treatment agent, and more preferably Jia carried out surface treatment with 0.3% by mass to 2% by mass of surface treatment agent.

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

(D) The carbon amount per unit surface area of the inorganic filler material can be measured after washing the surface-treated inorganic filler material with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent can be added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning can be performed at 25° C. for 5 minutes. The supernatant liquid was removed, the solid content was dried, and the carbon amount per unit surface area of the inorganic filler material was measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

The amount of (D) inorganic filler in the resin composition may be 0% by mass or more than 0% by mass relative to 100% by mass of non-volatile components of the resin composition, and may be 20% by mass or more. Good, more preferably 40 mass% or more, particularly good 60 mass% or more, preferably 90 mass% or less, preferably 85 mass% or less, particularly good 80 mass% or less. (D) When the amount of the inorganic filler is within the above range, the crack resistance and stain removal resistance of the cured resin composition can be particularly good. Furthermore, the minimum melt viscosity and curing resistance of the resin composition can generally be effectively improved. The dielectric properties of the object and the adhesion to the conductor layer.

[(E) Optional hardener] The resin composition according to one embodiment of the present invention may further contain (E) any curing agent as an optional component. Those corresponding to the above-mentioned components (A) to (D) are not included in the optional curing agent (E) as the component (E). Therefore, (E) any hardener means an epoxy resin hardener that reacts with (B) epoxy resin to harden the resin composition except (A) long-chain aliphatic phenol resin and (C) active ester compound. ingredients. (E) Arbitrary hardening agents may be used individually by 1 type, or in combination of 2 or more types.

(E) Any curing agent, as mentioned above, has the ability to react with (B) epoxy resin to harden the resin composition, similarly to (A) long-chain aliphatic phenol resin and (C) active ester compound. function. Examples of the optional curing agent (E) include: phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, and cyanate ester curing agents. agents, and mercaptan hardeners. Among them, the phenol-based hardener classified as (E) any hardener does not include a substance belonging to (A) long-chain aliphatic phenol resin. Among these, it is preferable to use one or more types of hardeners selected from the group consisting of phenol-based hardeners and carbodiimide-based hardeners.

As the phenolic curing agent, one having one or more, preferably two or more hydroxyl groups (phenolic hydroxyl groups) bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. From the viewpoint of heat resistance and water resistance, a phenolic hardener having a novolac structure is preferred. In addition, from the viewpoint of adhesion, a nitrogen-containing phenol-based hardener is preferred, and a triazine skeleton-containing phenol-based hardener is more preferred. Among them, phenolic novolac resin containing a triazine skeleton is preferred from the viewpoint of satisfying high heat resistance, water resistance and adhesion. Specific examples of phenolic hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. , "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", manufactured by Nippon Steel Chemical Materials Co., Ltd. "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090" made by DIC Corporation -60M" etc.

As the carbodiimide-based hardener, a hardener having one or more, preferably two or more carbodiimide structures in one molecule can be used. Specific examples of carbodiimide-based hardeners include tetramethylene-bis(tert-butylcarbodiimide), cyclohexanebis(methylene-tert-butylcarbodiimide), etc. Aliphatic biscarbodiimides; aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide) and other biscarbodiimides; polyhexamethylenecarbodiimide, polytrimethylmethane Aliphatic polycarbons such as hexamethylene carbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide) Diimines; poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide) amine), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide) Phenylcarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), Poly[methylenebis(methylphenylene)carbodiimide] and other aromatic polycarbodiimides and other polycarbodiimides. Examples of commercially available carbodiimide hardeners include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", and "CARBODILITE V-07" manufactured by Nisshinbo Chemical Co., Ltd. and "CARBODILITE V-09"; "Stabaxol P", "Stabaxol P400", "Hycasyl 510" manufactured by Rhein Chemie, etc.

As the acid anhydride-based curing agent, one having one or more acid anhydride groups per molecule can be used, and preferably one having two or more acid anhydride groups per molecule. Specific examples of acid anhydride-based hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Phthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro- 3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic acid Dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyltetracarboxylic dianhydride, 1,3,3a,4,5, 9b-Hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(phenylene glycol) Polymeric acid anhydrides such as tricarboxylic anhydride ester) and styrene-maleic acid resin copolymerized with styrene and maleic acid. Examples of commercially available acid anhydride-based hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Nippon Rika Co., Ltd.; Mitsubishi Chemical Corporation "YH-306" and "YH-307" made by Hitachi Chemical Co., Ltd.; "HN-2200" and "HN-5500" made by Hitachi Chemical Co., Ltd.; "EF-30", "EF-40" and "EF" made by Crevelli Co., Ltd. -60", "EF-80", etc.

As the amine-based curing agent, one having one or more, preferably two or more amine groups in one molecule can be used. Examples of amine-based curing agents include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like. Among them, aromatic amines are also preferred. The amine hardener is preferably a primary amine or a secondary amine, with primary amine being more preferred. Specific examples of the amine-based hardener include: 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4' -Diaminodiphenyl terine, 3,3'-diaminodiphenyl terine, m-phenylenediamine, m-phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxy Benzidine, 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)benzene Benzene, bis(4-(4-aminophenoxy)phenyl)sine, bis(4-(3-aminophenoxy)phenyl)sine, etc. Examples of commercially available amine-based hardeners include "SEIKACURE-S" manufactured by SEIKA; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", and "KAYABOND C-100" manufactured by Nippon Kayaku Co., Ltd. KAYAHARD AB", "KAYAHARD AS"; "EPICURE W" made by Mitsubishi Chemical Corporation; "DTDA" made by Sumitomo Seika Co., Ltd., etc.

Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; " P-d", "F-a", etc.

Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4 ,4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2 , 2-bis(4-cyanato)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylbenzene) methyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatophenyl)sulfide, and bis(4- Difunctional cyanate ester resins such as cyanate ester phenyl ether; multifunctional cyanate ester resins derived from phenol novolac resin and cresol novolak resin; part of these cyanate ester resins are triazinized The resulting prepolymer, etc. Specific examples of cyanate-based hardeners include "PT30" and "PT60" manufactured by Lonza Japan (both are phenol novolac-type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (dual A prepolymer in which part or all of phenol A dicyanate is triazinized to form a trimer), etc.

Examples of thiol-based hardeners include trimethylolpropane (3-mercaptopropionate), pentaerythritol (3-mercaptobutyrate), and ginseng (3-mercaptopropyl)isocyanuric acid. Ester etc.

(E) The active group equivalent of any hardener is preferably 50g/eq.~3000g/eq., preferably 100g/eq.~1000g/eq., more preferably 100g/eq.~500g/eq. , the best range is 100g/eq.～300g/eq. Active group equivalent represents the mass of hardener corresponding to 1 equivalent of active group.

When the epoxy group number of (B) the epoxy resin is 1, the reactive group number of the optional hardener (E) is preferably 0.01 or more, more preferably 0.1 or more, more preferably 0.2 or more, and preferably 3 or less. , preferably 2 or less, particularly preferably 1 or less. "(E) The number of active groups of any hardener" means the total value obtained by dividing the mass of the non-volatile components of (E) any hardener present in the resin composition by the active group equivalent. value.

The amount of the optional hardener (E) in the resin composition may be 0% by mass, may be greater than 0% by mass, and may be 0.01% by mass or more relative to 100% by mass of the non-volatile components of the resin composition. It is good, preferably 0.1 mass% or more, particularly preferably 1 mass% or more, preferably 20 mass% or less, preferably 10 mass% or less, and particularly preferably 5 mass% or less.

The amount of the optional hardener (E) in the resin composition may be 0% by mass or more than 0% by mass relative to 100% by mass of the resin component of the resin composition, preferably 0.1% by mass or more. , preferably 1 mass % or more, particularly preferably 5 mass % or more, preferably 50 mass % or less, preferably 40 mass % or less, and particularly preferably 30 mass % or less.

[(F) Hardening accelerator] The resin composition according to one embodiment of the present invention may further contain (F) a hardening accelerator as an optional component. The hardening accelerator (F) which is the component (F) does not include those corresponding to the above-mentioned components (A) to (E). The (F) hardening accelerator functions as a hardening catalyst that accelerates hardening of the (B) epoxy resin.

Examples of the (F) hardening accelerator include phosphorus-based hardening accelerators, urea-based hardening accelerators, guanidine-based hardening accelerators, imidazole-based hardening accelerators, metal-based hardening accelerators, and amine-based hardening accelerators. Among them, imidazole-based hardening accelerators are also preferred. (F) The hardening accelerator may be used individually by 1 type, or in combination of 2 or more types.

Examples of the phosphorus-based hardening accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (Tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrohexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl Aliphatic phosphonium salts such as ]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenyl Phenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetra Phenylborate, tetraphenylphosphonium tetraphenylborate, triphenylethylphosphonium tetraphenylborate, ginseng(3-methylphenyl)ethylphosphonium tetraphenylborate, ginseng(2- Methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate Aromatic phosphonium salts such as salts; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone additions such as triphenylphosphine-p-benzoquinone addition reactants Reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, Aliphatic phosphines such as tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexane Hexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, ginseng (4-ethylphenyl)phosphine, ginseng (4-propylphenyl)phosphine, ginseng (4 -isopropylphenyl)phosphine, ginseng(4-butylphenyl)phosphine, ginseng(4-tert-butylphenyl)phosphine, ginseng(2,4-dimethylphenyl)phosphine, ginseng(2, 5-dimethylphenyl)phosphine, ginseng(2,6-dimethylphenyl)phosphine, ginseng(3,5-dimethylphenyl)phosphine, ginseng(2,4,6-trimethylbenzene) base) phosphine, ginseng (2,6-dimethyl-4-ethoxyphenyl) phosphine, ginseng (2-methoxyphenyl) phosphine, ginseng (4-methoxyphenyl) phosphine, ginseng ( 4-ethoxyphenyl)phosphine, ginseng (4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphine)ethane, 1,3 -Bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,2-bis(diphenylphosphine)acetylene, 2,2'-bis(diphenylphosphine)bis Aromatic phosphines such as phenyl ethers, etc.

Examples of urea-based hardening accelerators include: 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, and 3-cyclohexyl -aliphatic dimethylureas such as 1,1-dimethylurea and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-( 4-Chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylbenzene) base)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethyl Urea, 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 base)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl base)phenyl]-1,1-dimethylurea, N,N-(1,4-phenyl)bis(N',N'-dimethylurea), N,N-(4-methyl Aromatic dimethylureas such as methyl-1,3-phenyl)bis(N',N'-dimethylurea) [toluene bisdimethylurea], etc.

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

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4- Methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 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-diamine Base-6-[2'-Undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuride 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, Imidazole compounds such as 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins. Examples of commercially available imidazole-based hardening accelerators include "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", " 2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A"; "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. .

Examples of metal-based hardening accelerators 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 organic cobalt complexes such as cobalt acetyl acetonate (II) and cobalt acetyl acetonate (III), organic copper complexes such as copper acetyl acetonate (II), ethanol acetonate, etc. Organic zinc complexes such as zinc acetyl acetonate (II), organic iron complexes such as iron acetyl acetonate (III), organic nickel complexes such as nickel acetyl acetonate (II), and organic manganese acetyl acetonate (II). Manganese complexes, etc. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-gin( Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. As the amine-based hardening accelerator, commercially available products can be used, and examples include "MY-25" manufactured by Ajinomoto Fine Chemicals Co., Ltd.

The amount of (F) hardening accelerator in the resin composition may be 0% by mass or more than 0% by mass relative to 100% by mass of non-volatile components of the resin composition, preferably 0.01% by mass or more. , preferably 0.02 mass% or more, particularly preferably 0.03 mass% or more, preferably 2 mass% or less, preferably 1 mass% or less, and particularly preferably 0.5 mass% or less.

The amount of (F) hardening accelerator in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably 0.01% by mass or more, based on 100% by mass of the resin component of the resin composition. More preferably, it is 0.05% by mass or more, particularly preferably 0.1% by mass or more, more preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[(G)Thermoplastic resin] The resin composition according to one embodiment of the present invention may further contain (G) a thermoplastic resin as an optional component. The thermoplastic resin (G) as the component (G) does not include those corresponding to the above-mentioned components (A) to (F).

Examples of (G) thermoplastic resin include phenoxy resin, polyamide imide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamide imine resin, and polyether. Imide resin, polystyrene resin, polyether styrene resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. (G) Thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of the phenoxy resin include those having a structure selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenolic skeleton, a biphenyl skeleton, a fluorine skeleton, and a dicyclopentadiene skeleton. Phenoxy resin with one or more skeletons from the group consisting of skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (containing a bisphenol A skeleton) Phenoxy resin with phenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical Materials Corporation; Mitsubishi Chemical Company-made "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30"; etc.

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

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C" and "Denka Butyral 6000-EP" manufactured by Denka Chemical Industry Co., Ltd. "; S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series manufactured by Sekisui Chemical Industry Co., Ltd.; etc.

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

Examples of the polybutadiene resin include a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl group-containing polybutadiene resin, a phenolic hydroxyl group-containing polybutadiene resin, and a carboxyl group-containing polybutadiene resin. , polybutadiene resin containing anhydride groups, polybutadiene resin containing epoxy groups, polybutadiene resin containing isocyanate groups, polybutadiene resin containing urethane groups, polyphenylene ether - Polybutadiene resin, etc.

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

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

Specific examples of polystyrene resins include polystyrene "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 Corporation, and the like.

Examples of the polycarbonate resin include hydroxyl group-containing carbonate resin, phenolic hydroxyl group-containing carbonate resin, carboxyl group-containing carbonate resin, acid anhydride group-containing carbonate resin, isocyanate group-containing carbonate resin, Carbonate resin containing urethane groups, etc. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., and "C-" manufactured by Kuraray Co., Ltd. 1090", "C-2090", "C-3090" (polycarbonate diol), etc. Specific examples of the polyetheretherketone resin include "SUMIPLOY K" manufactured by Sumitomo Chemical Corporation.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, and polybutylene naphthalate resin. Resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethanol terephthalate resin, etc.

(G) The weight average molecular weight (Mw) of the thermoplastic resin is preferably greater than 5,000, more preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, more preferably The best price is less than 60,000, and the best price is less than 50,000. The weight average molecular weight can be measured as a polystyrene-converted value using gel permeation chromatography (GPC).

The amount of (G) thermoplastic resin in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably 0.01% by mass or more, based on 100% by mass of non-volatile components of the resin composition. More preferably, it is 0.05% by mass or more, particularly preferably 0.1% by mass or more, more preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

The amount of (G) thermoplastic resin in the resin composition may be 0% by mass, or more than 0% by mass, preferably 0.01% by mass or more, relative to 100% by mass of the resin component of the resin composition. Preferably it is 0.05 mass% or more, particularly preferably it is 0.1 mass% or more, 10 mass% or less is more preferred, more preferably it is 5 mass% or less, and particularly preferably it is 3 mass% or less.

[(H) Radically polymerizable compound] The resin composition according to one embodiment of the present invention may further contain (H) any radically polymerizable compound as an optional component. The (H) radically polymerizable compound as the component (H) does not include those corresponding to the above-mentioned components (A) to (G). (H) A radical polymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more types.

(H) The radically polymerizable compound may contain an ethylenically unsaturated bond. Therefore, the (H) radically polymerizable compound may have a radically polymerizable group containing an ethylenically unsaturated bond. Examples of radically polymerizable groups include vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, and 3-vinylbenzene. group, 4-vinylphenyl and other unsaturated hydrocarbon groups; acrylyl, methacrylyl, maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrole-1 - group) and other α, β-unsaturated carbonyl groups, etc. (H) The radically polymerizable compound preferably has two or more radically polymerizable groups.

Examples of (H) radically polymerizable compounds include: (meth)acrylic radically polymerizable compounds, styrene radically polymerizable compounds, allyl radically polymerizable compounds, and maleic acid compounds. Amine-based radically polymerizable compounds, etc.

The (meth)acrylic radical polymerizable compound is, for example, a compound having one or more, preferably two or more acryl groups and/or methacryl groups. Examples of the (meth)acrylic radical-polymerizable compound include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, ) Acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexane Diol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glyceryl tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. Low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds; dioxanediol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate acrylate, 3,6,9-triox undecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate )acrylate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]fluoride, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol Low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as A di(meth)acrylate; ginseng (3-hydroxypropyl)isocyanurate tri(meth)acrylate, Isocyanurate containing low molecular weight (molecular weight less than 1000) such as ginseng (2-hydroxyethyl) isocyanurate tri(meth)acrylate and ethoxylated isocyanurate tri(meth)acrylate (meth)acrylate compounds of acid esters; (meth)acrylic modified polyphenylene ether resin and other high molecular weight (molecular weight is 1000 or more) acrylate compounds, etc. Examples of commercially available (meth)acrylic radical polymerizable compounds include "A-DOG" (dioxanediol diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd. "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Nippon Kayaku Co., Ltd. "KAYARAD R-684" ( Tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxanediol diacrylate), "SA9000" and "SA9000-111" (methacrylic modified) manufactured by SABIC Innovative Plastics polyphenylene ether) etc.

The styrenic radical 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 styrenic radical polymerizable compounds include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4 '-Divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether, etc. Low molecular weight (molecular weight less than 1,000) styrenic compounds; vinyl benzyl modified polyphenylene ether resin, styrene-divinylbenzene copolymer and other high molecular weight (molecular weight 1,000 or more) styrenic compounds, etc. Examples of commercially available styrenic radical polymerizable compounds include "ODV-XET (X03)", "ODV-XET (X04)", "ODV-XET (X05)" manufactured by Nippon Steel Chemical Materials Co., Ltd. )" (styrene-divinylbenzene copolymer), "OPE-2St 1200" and "OPE-2St 2200" (vinyl benzyl modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

The allyl radical polymerizable compound is, for example, a compound having one or more, preferably two or more allyl groups. Examples of the allyl radical polymerizable compound include diallyl diphenate, triallyl trimellitate, diallyl phthalate, and isophthalic acid. Diallyl, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, diallyl 2,3-naphthalenedicarboxylate and other aromatic carboxylic acid allyl ester compounds; 1,3 , 5-triallyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate and other allyl isocyanurate compounds; 2,2-bis[3- Allyl-4-(glycidyloxy)phenyl]propane and other aromatic allyl compounds containing epoxy groups; bis[3-allyl-4-(3,4-dihydro-2H- 1,3-Benzoxazin-3-yl)phenyl]methane and other benzoxazine-containing aromatic allyl compounds; 1,3,5-triallyl etherbenzene and other ether-containing aromatic alkenes Propyl compounds; allylsilane compounds such as diallyldiphenylsilane, etc. Examples of commercially available allyl-based radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd. and Nittouch Technology Finesse. "DAD" (diallyl diphenate) manufactured by a chemical company, "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., and "DAND" manufactured by Nippon Distillation Industry Co., Ltd. "(Diallyl 2,3-naphthalenedicarboxylate), "ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd. (Bis[3-allyl-4-(3,4-dihydro-2H-1,3 -Benzoxazin-3-yl)phenyl]methane), "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)benzene) manufactured by Nippon Kayaku Co., Ltd. propane), "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemicals Co., Ltd., etc.

The maleimide radical polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimine-based radically polymerizable compound may be an aliphatic maleimine compound containing an aliphatic amine skeleton, or an aromatic maleimine compound containing an aromatic amine skeleton. Examples of commercially available maleimide radical polymerizable compounds include "SLK-2600" manufactured by Shin-Etsu Chemical Industry Co., Ltd., "BMI-1500" manufactured by Designer Molecules, " "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing a dimer diamine structure), "BMI-6100" manufactured by Design Corporation ( Aromatic maleimide compound), "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aralkyl maleimide compound) manufactured by Nippon Chemical Co., Ltd., manufactured by KI Chemicals Co., Ltd. "BMI-70", "BMI-80", "BMI-2300", "BMI-TMH" made by Daiwa Chemical Industry Co., Ltd., etc. In addition, as the maleimide-based radical polymerizable compound, the maleimide resin (maleimide resin containing an indan ring skeleton) disclosed in the Japan Invention Association Technical Publication No. 2020-500211 can be used. amine compounds).

(H) The ethylenically unsaturated bond equivalent of the radical polymerizable compound is preferably 20 g/eq. to 3,000 g/eq., more preferably 50 g/eq. to 2,500 g/eq., more preferably 70 g/eq. .～2,000g/eq., the best is 90g/eq.～1,500g/eq. The ethylenically unsaturated bond equivalent represents the mass of the radically polymerizable compound per equivalent of the ethylenically unsaturated bond.

(H) The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 40,000 or less, more preferably 10,000 or less, more preferably 5,000 or less, particularly preferably 3,000 or less. The lower limit is not particularly limited, and may be 150 or more, for example. The weight average molecular weight can be measured as a polystyrene-converted value using gel permeation chromatography (GPC).

The amount of the (H) radically polymerizable compound in the resin composition may be 0% by mass relative to 100% by mass of the non-volatile components in the resin composition, or may be greater than 0% by mass, and may be 0.01% by mass. The above is preferred, more preferably 0.1 mass % or more, particularly preferably 0.5 mass % or more, 10 mass % or less is preferred, 5 mass % or less is preferred, and particularly preferably 2 mass % or less.

The amount of (H) radically polymerizable compound in the resin composition may be 0% by mass, may be greater than 0% by mass, and may be 0.01% by mass or more relative to 100% by mass of the resin component in the resin composition. It is better, preferably 0.1 mass % or more, particularly preferably 1 mass % or more, 15 mass % or less, preferably 10 mass % or less, and particularly preferably 5 mass % or less.

[(I) Optional additives] The resin composition according to one embodiment of the present invention may further contain (I) any additive as an optional component. (I) Optional additives include, for example, organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, iodine green, and diazo yellow , crystal violet, titanium oxide, carbon black and other colorants; hydroquinone, catechol, pyrogallol, phenothiazine and other polymerization inhibitors; silicone leveling agent, acrylic polymer leveling agent Leveling agents such as agents; Thickeners such as Benton and montmorillonite; Defoaming agents such as silicone defoamer, acrylic defoamer, fluorine defoamer, vinyl resin defoamer; UV absorbers such as azole-based UV absorbers; adhesion improving agents such as ureasilane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents ; Antioxidants such as hindered phenol antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus-based flame retardants (such as phosphate ester compounds, phosphazenes) Compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic-based flame retardants (such as antimony trioxide) and other flame retardants; phosphate ester dispersants, Dispersants such as polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; borate ester stabilizers, titanate ester stabilizers, and aluminate esters Stabilizers such as zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers. (I) Arbitrary additives may be used individually by 1 type, and may be used in combination of 2 or more types.

[(J)Solvent] The resin composition according to one embodiment of the present invention may further contain a solvent (J) as an optional volatile component in addition to non-volatile components such as the above-mentioned components (A) to (I). As the (J) solvent, generally, an organic solvent is used. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and acetic acid. Isoamyl propionate, methyl propionate, ethyl propionate, γ-butyrolactone and other ester solvents; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl Ether solvents such as methyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether, acetic acid ester, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (ethyl diglycol acetate), γ-butyrolactone, methyl methoxypropionate and other ether ester solvents; lactic acid Methyl ester, ethyl lactate, methyl 2-hydroxyisobutyrate and other ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, Ether alcohol solvents such as ethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone Isoamide solvents; dimethyl styrene and other styrene solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane and other aliphatic hydrocarbon solvents; benzene , toluene, xylene, ethylbenzene, trimethylbenzene and other aromatic hydrocarbon solvents. (J) Solvent may be used individually by 1 type, or in combination of 2 or more types.

(J) The amount of the solvent is not particularly limited, but may be, for example, 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 15 mass% or less based on 100 mass% of the total components of the resin composition. , 10% by mass or less, or 0% by mass.

[Production method of resin composition] The resin composition according to one embodiment of the present invention can be produced by mixing the above-mentioned components, for example. Some or all of the above-mentioned components may be mixed simultaneously, or may be mixed sequentially. During the mixing of the components, the temperature can be appropriately set, so that heating and/or cooling can be performed temporarily or continuously. In addition, stirring or shaking may be performed during mixing of the ingredients.

[Characteristics of resin composition] A cured product can be obtained by curing the resin composition according to one embodiment of the present invention. When performing the above-mentioned hardening, the resin composition can usually be heated. Therefore, generally, among the components contained in a lipid composition, volatile components such as (J) solvents evaporate due to heat during curing, but non-volatile components such as components (A) to (I) do not evaporate due to heat during curing. The heat evaporates. Therefore, the cured product of the resin composition may contain non-volatile components of the resin composition or reaction products thereof.

The cured product of the resin composition according to one embodiment of the present invention has excellent crack resistance. Therefore, when an insulating layer is formed from this hardened material, an insulating layer excellent in crack resistance can be obtained. For example, when the crack resistance is evaluated using the method explained in <Test Example 5: Evaluation of Crack Resistance> in the Examples described later, the yield can be preferably 40% or more, more preferably 60% or more, which is particularly preferred. More than 80%. Generally, the larger the value of the yield, the better the crack resistance.

The cured product of the resin composition according to one embodiment of the present invention has excellent stain removal resistance. Therefore, when the insulating layer is formed from the hardened material, the surface roughness of the insulating layer after the decontamination treatment can be reduced. For example, when the arithmetic mean roughness Ra of the surface of the insulating layer after the decontamination treatment is measured using the method described in <Test Example 3: Measurement of Arithmetic Mean Roughness (Ra)> of the Examples described later, it is possible to use The arithmetic mean roughness Ra is preferably 95 nm or less, more preferably 90 nm or less. Generally, the smaller the arithmetic mean roughness Ra is, the better the stain removal properties are.

The cured product of the resin composition according to one embodiment of the present invention can generally have excellent dielectric properties. For example, the relative dielectric constant of the hardened material is preferably 4.0 or less, more preferably 3.6 or less, and particularly preferably 3.4 or less. The lower limit of the relative dielectric constant is not particularly limited, but may be, for example, 1.5 or more, 2.0 or more, or the like. In addition, for example, the dielectric loss tangent of the hardened material is preferably 0.0040 or less, more preferably 0.0035 or less, more preferably 0.0030 or less, and particularly preferably 0.0027 or less. The lower limit of the dielectric loss tangent is not particularly limited, but may be, for example, 0.0010 or more. The relative permittivity and dielectric loss tangent of the hardened material can be measured by the method explained in <Test Example 1: Measurement of relative permittivity (Dk) and dielectric loss tangent (Df)> of the Examples described later. .

The cured product of the resin composition according to one embodiment of the present invention can generally have high adhesion to the conductor layer when a conductor layer is formed on the cured product. For example, when a conductor layer is formed on an insulating layer made of a hardened material using the method described in <Test Example 4: Measurement of Peel Strength (Peel Strength) of a Plated Conductor Layer> in Examples described later, the insulation The peeling strength between the layer and the conductor layer is preferably 0.30kgf/cm or more, more preferably 0.38kgf/cm or more, and particularly preferably 0.40kgf/cm or more. The higher the upper limit, the better, but it is usually 0.8kgf/cm or less. Peeling strength represents the amount of force required to peel the conductor layer from the insulating layer. Therefore, generally, the greater the peel strength, the better the adhesion.

The resin composition according to one embodiment of the present invention can generally have a low minimum melt viscosity. For example, when the minimum melt viscosity is measured using the method explained in <Test Example 2: Measurement of Minimum Melt Viscosity> in the Examples described later, the minimum melt viscosity is preferably 2,500 poise or less, more preferably 2,000 poise or less. The best value is under 1,500 berths. From the viewpoint of smoothly forming a thick insulating layer, the lower limit may be, for example, 500 poise or more, 700 poise or more, or the like.

[Application of resin composition] The resin composition according to one embodiment of the present invention can be used as a resin composition for insulating purposes. In particular, it can be suitably used as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer). For example, the resin composition of this embodiment can be used as a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package), and for forming a circuit board (including a printed wiring board). It is suitably used as a resin composition for an insulating layer (a resin composition for an insulating layer of a circuit board). In particular, the resin composition is suitable for forming an interlayer insulating layer provided between conductor layers. In addition, the resin composition is particularly suitable as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board).

Examples of semiconductor chip packages include FC-CSP, MIS-BGA package, ETS-BGA package, fan-out type WLP (Wafer Level Package), fan-in (Fan- in) type WLP, fan-out type PLP (Panel Level Package), fan-in type PLP.

In addition, the above-mentioned resin composition can be used as an underfill material. For example, it can be used as a material for MUF (Molding Under Filling) used after connecting a semiconductor wafer to a substrate.

Furthermore, the above-mentioned resin composition can be used in a wide range of applications that use the resin composition, such as resin sheets, sheet-like laminate materials such as prepregs, solder resists, wafer bonding materials, semiconductor sealing materials, hole-filling resins, and component embedding resins.

[Sheet-like laminated material] The resin composition can be applied and used in a varnish state, but industrially, it is suitably used in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminated material, resin sheets and prepregs shown below are preferred.

In one embodiment, the resin sheet includes a support body and a resin composition layer formed on the support body. The resin composition layer is formed from the above-mentioned resin composition. Therefore, the resin composition layer usually contains the resin composition, preferably only the resin composition.

From the viewpoint of thinning and the ability to provide a thin cured product with excellent insulation properties from the resin composition, the thickness of the resin composition layer is preferably 50 μm or less, and more preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be 5 μm or more, 10 μm or more, or the like.

Examples of the support include a film, a metal foil, and a release paper made of a plastic material, and a film or a metal foil made of a plastic material is preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate Polyesters such as ester (hereinafter sometimes referred to as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, tris Acetylcellulose (TAC), polyether sulfide (PES), polyetherketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

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

As the support body, a support body with a release layer having a release layer on a surface bonded to the resin composition layer can be used. Examples of the release agent used in the release layer of the support with the release layer include one selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. The above release agent. A commercial product can be used as a support with a release layer. For example, "SK-1" produced by Lintec Corporation, which is a PET film having a release layer containing an alkyd resin release agent as a main component, can be used. ", "AL-5", "AL-7", "Lumirror T60" made by Toray, "Purex" made by Teijin, "Unipeel" made by UNITIKA, etc.

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

In one embodiment, the resin sheet may further include any layers as needed. Examples of the optional layer include, for example, a protective film selected according to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating a protective film, it is possible to prevent dust from adhering to the surface of the resin composition layer and causing damage to the surface of the resin composition layer.

The resin sheet can be produced, for example, by directly applying a liquid (varnish-like) resin composition onto a support using a coating device such as a die coater, or by dissolving the resin composition in a solvent. A liquid (varnish-like) resin composition is prepared, and is applied on a support using a coating device such as a die coater, and then dried to form a resin composition layer.

Examples of the solvent include the same solvents as the solvent (J) described as a component of the resin composition. One type of solvent may be used alone, or two or more types may be used in combination.

Drying can be implemented by drying methods such as heating and blowing hot air. Drying conditions are not particularly limited, and drying is performed so that the content of the solvent in the resin composition layer becomes usually 10 mass% or less, preferably 5 mass% or less. Although it differs depending on the boiling point of the solvent in the resin composition, for example, when using a resin composition containing 30% to 60% by mass of a solvent, drying can be performed at 50°C to 150°C for 3 to 10 minutes. , thereby forming a resin composition layer.

Resin sheets can be rolled into rolls for storage. When the resin sheet has a protective film, it can usually be used by peeling off the protective film.

In one embodiment, the prepreg can be formed by impregnating the above-mentioned resin composition into a sheet-like fiber base material.

As for the sheet-like fiber base material used in the prepreg, for example, glass cloth, aromatic polyamide (aramid) non-woven fabric, liquid crystal polymer non-woven fabric, etc., which are commonly used as base materials for prepregs, can be used. material. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited, but is usually 10 μm or more.

Prepregs can be manufactured using methods such as hot melt method and solvent method.

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

The sheet-like laminated material is suitably used, for example, for forming an insulating layer (insulating resin sheet for semiconductor wafer packages) in the production of semiconductor wafer packages. Examples of applicable semiconductor chip packages include fan-out WLP, fan-in WLP, fan-out PLP, fan-in PLP, and the like. In addition, the sheet-like laminated material can be used, for example, to form an insulating layer of a circuit board (a resin sheet for an insulating layer of a circuit board). Furthermore, the sheet-like laminated material can be used as a material for the MUF used after connecting the semiconductor wafer to the substrate. In particular, sheet-like laminated materials are suitable for forming interlayer insulating layers.

[Circuit board] A circuit board according to one embodiment of the present invention contains a cured product of a resin composition. Generally, a circuit board is provided with an insulating layer formed of a cured product of a resin composition. The insulating layer contains the cured product of the above-mentioned resin composition, and preferably contains only the cured product of the above-mentioned resin composition. The circuit substrate can be manufactured, for example, by a manufacturing method including the following steps (I) and (II): (1) The step of forming a resin composition layer on the inner substrate; (II) The step of hardening the resin composition layer to form an insulating layer.

The "inner layer substrate" used in step (I) is a member that serves as the base material of the circuit substrate. Examples include: glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermal substrate Hardened polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner-layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes called an "inner-layer circuit substrate." In addition, when manufacturing a circuit substrate, an intermediate product on which an insulating layer and/or a conductor layer is to be further formed is also included in the above-mentioned "inner layer substrate". When the circuit board is a circuit board with built-in components, an inner substrate with built-in components can be used.

When the conductor layer included in the inner layer substrate is patterned, from the viewpoint of effectively utilizing the advantage of excellent crack resistance, it is preferable that the minimum line width/space ratio of the conductor layer is small. "Line width" refers to the circuit width of the conductor layer, and "line pitch" refers to the spacing between circuits. The range of the minimum line width/line space ratio is preferably below 50/50 μm (that is, the pitch is below 100 μm), preferably below 30/30 μm, more preferably below 20/20 μm, and more preferably below 15/15 μm. or less, more preferably 10/10 μm or less. The lower limit may be, for example, 0.5/0.5 μm or more. The spacing may be uniform or non-uniform over the entire conductor layer. The minimum pitch of the conductor layer may be, for example, 100 μm or less, 60 μm or less, 40 μm or less, 36 μm or less, or 30 μm or less.

The resin composition layer can be formed on the inner layer substrate by laminating the inner layer substrate and the resin sheet, for example. Lamination of the inner-layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet to the inner-layer substrate from the support side. Examples of a member for heat and pressure bonding the resin sheet to the inner substrate (hereinafter also referred to as "heat and pressure bonding member") include a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller, etc.) . Furthermore, it is preferable not to directly pressurize the resin sheet with the heating and pressing member, but to pressurize the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface irregularities of the inner substrate.

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

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

After lamination, the laminated resin sheets can be smoothed by applying pressure from the support side under normal pressure (atmospheric pressure), for example, using a heating and crimping member. The pressure conditions for the smoothing treatment can be set to the same conditions as those for the heat and pressure bonding of the lamination described above. Smoothing treatment can be performed by a commercially available laminator. In addition, lamination and smoothing processing can be performed continuously using the above-mentioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is hardened to form an insulating layer composed of a hardened product of the resin composition. The resin composition layer is usually hardened by thermal hardening. Specific hardening conditions of the resin composition layer may differ depending on the type of resin composition. In one example, the hardening temperature is preferably 120°C to 240°C, preferably 150°C to 220°C, and more preferably 170°C to 210°C. The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, still more preferably 15 minutes to 100 minutes.

The manufacturing method of the circuit board preferably includes preheating the resin composition layer at a temperature lower than the curing temperature before thermal hardening of the resin composition layer. For example, before thermally hardening the resin composition layer, the resin composition layer is subjected to a temperature of usually 50°C to 150°C, preferably 60°C to 140°C, and more preferably 70°C to 130°C for usually more than 5 minutes. Preferably, it takes 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes for preheating.

When manufacturing the circuit substrate, the steps of (III) opening holes in the insulating layer, (IV) decontaminating the insulating layer, and (V) forming the conductor layer may be further performed. These steps (III) to (V) can be implemented according to various methods known to those skilled in the art that can be used for manufacturing circuit substrates. Furthermore, in the case where the support is removed after step (II), the removal of the support may be between step (II) and step (III), between step (III) and step (IV), or between step (IV). ) and step (V). If necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) can be repeated to produce a circuit board having a multilayer structure such as a multilayer printed wiring board.

In other embodiments, the circuit substrate can be manufactured using the above-mentioned prepreg. The manufacturing method can be basically the same as in the case of using a resin sheet.

Step (III) is a step of opening holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) can be implemented using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used in forming the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the circuit board.

Step (IV) is a step of removing possible contamination (resin residue) on the insulating layer. Generally, in this step (IV), since the surface of the insulating layer is roughened, the decontamination treatment is sometimes called "roughening treatment". The steps and conditions of the decontamination treatment are not particularly limited, and known steps and conditions generally used when forming an insulating layer of a circuit board can be adopted. For example, a swelling treatment based on a swelling liquid, a roughening treatment based on an oxidizing agent, and a neutralization treatment based on a neutralizing liquid may be performed in sequence, and the insulating layer may be subjected to a decontamination treatment.

Examples of the swelling liquid used in the decontamination treatment include an alkali solution, a surfactant solution, and the like, and an alkali solution is preferred. As the alkali solution, sodium hydroxide solution and potassium hydroxide solution are preferred. Examples of commercially available swelling solutions include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN. The swelling treatment based on the swelling liquid can be performed, for example, by immersing the insulating layer in a swelling liquid of 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid of 40° C. to 80° C. for 5 minutes to 15 minutes.

Examples of the oxidizing agent used in the decontamination treatment include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment based on an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Corporation.

An acidic aqueous solution is preferred as the neutralizing liquid used in the decontamination treatment. An example of a commercially available product is "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. The treatment by the neutralizing liquid can be performed by immersing the treated surface that has completed the roughening treatment by the oxidizing agent in a neutralizing liquid of 30°C to 80°C for 5 to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the object that has been roughened by an oxidizing agent in a neutralizing liquid at 40° C. to 70° C. for 5 to 20 minutes.

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes 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. metal. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a nickel-chromium The alloy layer of alloy, copper-nickel alloy, copper-titanium alloy is better, and the single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or the alloy layer of nickel-chromium alloy is selected. Preferably, a single metal layer of copper is even better.

The conductor layer may have a single-layer structure, a single metal layer composed 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 desired design of the circuit board, but is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer may be formed by plating. For example, conventionally known techniques such as a semi-additive method and a fully additive method can be used to perform plating on the surface of the insulating layer to form a conductor layer having a desired wiring pattern. From the viewpoint of ease of production, the semi-additive method is preferred. Below, an example of forming a conductor layer by a semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a part of the plating seed layer in accordance with a desired wiring pattern. On the exposed plated seed layer, electrolytic plating is used to form a metal layer, and then the mask pattern is removed. Then, the unnecessary plating seed layer is 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 foil. When the conductor layer is formed using metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The resin composition layer and the metal foil can be laminated by a vacuum lamination method. The conditions for lamination may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, the metal foil on the insulating layer can be used to form a conductor layer with a desired wiring pattern by conventionally known techniques such as the subtractive method and the improved semi-additive method.

The metal foil can be produced by known methods such as electrolysis and rolling. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Metals Co., Ltd., and the like.

[Semiconductor chip packaging] A semiconductor chip package according to one embodiment of the present invention includes a cured product of a resin composition. Generally, a semiconductor chip package includes an insulating layer formed of a hardened product of a resin composition. The insulating layer contains the cured product of the above-mentioned resin composition, and preferably contains only the cured product of the above-mentioned resin composition. Examples of the semiconductor chip package include the following.

The semiconductor chip package of the first example includes the above-mentioned circuit substrate and a semiconductor chip mounted on the circuit substrate. The semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit substrate.

The bonding conditions between the circuit board and the semiconductor wafer can be any condition in which the terminal electrodes of the semiconductor wafer and the circuit wiring of the circuit board can be conductively connected. For example, conditions used in flip-chip mounting of semiconductor wafers can be adopted. In addition, for example, the semiconductor wafer and the circuit board may be bonded via an insulating adhesive.

An example of the bonding method is a method of press-bonding a semiconductor wafer to a circuit board. As the crimping conditions, the crimping temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the crimping time is usually in the range of 1 second to 60 The range of seconds (preferably the range of 5 seconds to 30 seconds).

Another example of the bonding method is a method of bonding the semiconductor wafer to the circuit board by reflow soldering. Reflow conditions can be set within the range of 120°C to 300°C.

After the semiconductor wafer is bonded to the circuit substrate, the semiconductor wafer may be filled with a molded underfill material. As the molding underfill material, the above-mentioned resin composition can be used.

The semiconductor chip package of the second example includes a semiconductor chip and an insulating layer formed of a cured product of a resin composition. Examples of the semiconductor chip package of the second example include fan-out WLP, fan-out PLP, and the like.

FIG. 1 is a cross-sectional view schematically showing a fan-out WLP as an example of a semiconductor chip package according to an embodiment of the present invention. For example, as shown in FIG. 1 , a semiconductor chip package 100 as a fan-out WLP includes a semiconductor wafer 110 , a sealing layer 120 formed to cover the periphery of the semiconductor wafer 110 , and a sealing layer provided on the semiconductor wafer 110 . 120 on the opposite side: a rewiring formation layer 130 as an insulating layer; a rewiring layer 140 as a conductor layer; a solder resist layer 150; and a bump 160.

The manufacturing method of this type of semiconductor chip package includes: (i) The step of laminating the temporary fixing film on the base material; (ii) the step of temporarily fixing the semiconductor wafer on the temporary fixing film; (iii) the step of forming a sealing layer on the semiconductor wafer; (iv) The step of peeling the base material and the temporary fixing film from the semiconductor wafer; (v) The step of forming a rewiring formation layer on the surface of the semiconductor wafer from which the base material and the temporary fixing film are peeled off; (vi) a step of forming a rewiring layer as a conductor layer on the rewiring forming layer; and, (vii) the step of forming a solder resist layer on the rewiring layer, In addition, the above-mentioned manufacturing method of semiconductor chip packaging may include: (viii) A step of cutting a plurality of semiconductor wafer packages into individual semiconductor wafer packages and singulating them.

(step (i)) Step (i) is a step of laminating the temporary fixing film on the base material. The lamination conditions of the base material and the temporary fixing film may be the same as the lamination conditions of the inner layer substrate and the resin sheet in the manufacturing method of the circuit board.

Examples of the base material include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); and rings impregnated with glass fibers such as FR-4 substrates. A substrate obtained by thermally curing oxy resin, etc.; a substrate made of bismaleimide triazine resin such as BT resin; etc.

As the temporary fixing film, any material that can be peeled off from the semiconductor wafer and can temporarily fix the semiconductor wafer can be used. Examples of commercially available products include "REVALPHA" manufactured by Nitto Denko Co., Ltd.

(step (ii)) Step (ii) is a step of temporarily fixing the semiconductor wafer on the temporary fixing film. The semiconductor wafer can be temporarily fixed using, for example, a flip chip bonder (flip chip bonder), a die bonder (die bonder), or other equipment. The layout and number of semiconductor wafers can be appropriately set according to the shape and size of the temporary fixing film, the target production number of semiconductor wafer packages, and the like. For example, the semiconductor wafers may be arranged in a matrix of multiple rows and columns and temporarily fixed.

(step (iii)) Step (iii) is a step of forming a sealing layer on the semiconductor wafer. The sealing layer can be formed of, for example, a photosensitive resin composition or a thermosetting resin composition. The sealing layer can be formed from a cured product of the resin composition of the above embodiment. The sealing layer can generally be formed by a method including the steps of forming a resin composition layer on a semiconductor wafer, and hardening the resin composition layer to form the sealing layer.

(step (iv)) Step (iv) is a step of peeling off the base material and the temporary fixing film from the semiconductor wafer. As for the peeling method, it is desirable to use an appropriate method suitable for the material of the temporary fixing film. Examples of the peeling method include a method of peeling the temporarily fixed film by heating, foaming or expanding it. Examples of the peeling method include a method of irradiating the temporarily fixed film with ultraviolet rays through the base material to reduce the adhesive force of the temporarily fixed film and then peeling the film.

When the base material and the temporary fixing film are peeled off from the semiconductor wafer as described above, the surface of the sealing layer is exposed. The manufacturing method of the semiconductor wafer package may include the step of grinding the exposed surface of the sealing layer. By grinding, the surface smoothness of the sealing layer can be improved.

(step (v)) Step (v) is a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor wafer from which the base material and the temporary fixing film are peeled off. Typically, the rewiring formation layer is formed on the semiconductor wafer and the sealing layer. The rewiring forming layer can be formed from a cured product of the resin composition of the above embodiment. The rewiring forming layer can generally be formed by a method including the steps of forming a resin composition layer on a semiconductor wafer and hardening the resin composition layer to form the rewiring forming layer. The resin composition layer can be formed on the semiconductor wafer by, for example, the same method as the method for forming the resin composition layer on the inner layer substrate described in the above-mentioned manufacturing method of the circuit board, except that the semiconductor wafer is used instead of the inner layer substrate. to proceed.

After the resin composition layer is formed on the semiconductor wafer, the resin composition layer is cured to obtain a rewiring formation layer as an insulating layer containing a cured product of the resin composition. The curing conditions of the resin composition layer can be the same as the curing conditions of the resin composition layer in the manufacturing method of the circuit board. When the resin composition layer is thermally cured, before the thermal curing, the resin composition layer may be subjected to a preheating process of heating at a temperature lower than the curing temperature. The processing conditions of this preheating process can be the same as those of the preheating process in the manufacturing method of a circuit board. Generally, after the rewiring forming layer is formed, holes are formed in the rewiring forming layer in order to connect the semiconductor wafer and the rewiring layer.

(step (vi)) Step (vi) is a step of forming a rewiring layer as a conductor layer on the rewiring formation layer. The method of forming the rewiring layer on the rewiring formation layer may be the same as the method of forming the conductor layer on the insulating layer in the manufacturing method of the circuit board. In addition, steps (v) and (vi) can be repeated to alternately build up rewiring layers and rewiring formation layers.

(step (vii)) Step (vii) is a step of forming a solder resist layer on the rewiring layer. The solder resist layer may be made of any insulating material. Among these, photosensitive resin compositions and thermosetting resin compositions are preferred from the viewpoint of ease of manufacturing semiconductor chip packages. The solder resist layer can be formed from a cured product of the resin composition of the above embodiment.

In addition, in step (vii), bump processing may be performed to form bumps if necessary. Bump processing can be performed using methods such as solder balls and solder plating. In addition, the formation of the through hole in the bump processing can be performed in the same manner as in step (v).

(step (viii)) In addition to steps (i) to (vii), the manufacturing method of semiconductor chip packaging may also include step (viii). Step (viii) is a step of cutting a plurality of semiconductor wafer packages into individual semiconductor wafer packages and singulating them. The method of cutting the semiconductor wafer package into individual semiconductor wafer packages is not particularly limited.

[Semiconductor device] The semiconductor device includes the above-mentioned circuit board or semiconductor wafer package. Examples of semiconductor devices include those used in electrical products (such as computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions, etc.) and vehicles (such as , various semiconductor devices such as locomotives, automobiles, trams, ships and aircraft, etc. Example

Hereinafter, an Example is shown and this invention is demonstrated concretely. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass" respectively, unless otherwise specified. In addition, the temperature conditions and pressure conditions unless otherwise specified are room temperature (25° C.) and atmospheric pressure (1 atm). In the following description, "L/S" means the line width/line space ratio of the wiring pattern unless otherwise specified.

＜Description of reagents＞ Long-chain aliphatic phenol resin ("LB-7000" manufactured by Tohoku Chemical Co., Ltd., active group equivalent: approximately 262g/eq.) contains 90% cardanol represented by the following formula (a-1-1), and the following formula 10% cardanol resin shown in (a-2-1); Long-chain aliphatic phenol resin ("LB-7250" manufactured by Tohoku Chemical Co., Ltd., active group equivalent: approximately 273 g/eq.) contains 95% cardanol represented by the following formula (a-1-1), and the following formula A 5% cardanol resin shown in (a-2-1).

[Chemical 6] .

(In the above formula, "*" represents the bonding point).

<Synthesis Example 1: Synthesis of phenolic hydroxyl-containing polybutadiene resin (elastomer X)> Into the reaction vessel, 69 g of bifunctional hydroxyl-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxyl equivalent = 1800 g/eq.) and aromatic hydrocarbon mixed solvent ( 40g of "Ipzole 150" (manufactured by Idemitsu Kosan Co., Ltd.) and 0.005g of dibutyltin laurate were mixed to dissolve evenly. After becoming uniform, the temperature was raised to 60°C, and 8 g of isophorone diisocyanate ("IPDI" manufactured by Evonik Japan, isocyanate group equivalent = 113 g/eq.) was added while stirring, and the reaction was carried out for about 3 hours.

Next, 23 g of cresol novolac resin ("KA-1160" manufactured by DIC Corporation, hydroxyl equivalent = 117g/eq.) and diethylene glycol monoethyl ether acetate (manufactured by Daicel Corporation) were added to the reactant. 60g, while stirring, the temperature was raised to 150°C, and the reaction was carried out for about 10 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. Based on the confirmation that the NCO peak disappeared, it was regarded as the end point of the reaction, and the reactant was cooled to room temperature. Then, the reaction product was filtered through a 100-mesh filter cloth to obtain elastomer X having a butadiene structure and a phenolic hydroxyl group (butadiene resin containing a phenolic hydroxyl group: non-volatile content 50% by mass). The number average molecular weight of elastomer X is 5900, and the glass transition temperature is -7°C.

<Example 1> While stirring, combine 15 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Chemical Materials Co., Ltd., epoxy equivalent: approximately 269g/eq.) and bisphenol-type epoxy resin ("ZX1059" manufactured by Nippon Chemical Materials Co., Ltd., double A 1:1 mixture of phenol A type and bisphenol F type, with an epoxy equivalent of about 169g/eq.), was heated and dissolved in 25 parts of solvent naphtha to obtain a solution. The solution was cooled to room temperature to prepare a dissolved composition of the epoxy resin.

In the dissolved composition of the epoxy resin, 2 parts of a long-chain aliphatic phenol resin ("LB-7000" manufactured by Tohoku Chemical Co., Ltd., active group equivalent: approximately 262 g/eq.), and an active ester compound ("HPC" manufactured by DIC Corporation -8150-62T", 68 parts of a toluene solution with an active ester group equivalent of about 220g/eq. and a non-volatile content rate of 62% by mass, a phenolic hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation , active group equivalent of approximately 151g/eq., 5 parts of 2-methoxypropanol solution with a non-volatile content rate of 50%, carbodiimide-based hardener ("V-03" manufactured by Nissinbo Chemical Co., Ltd., active group equivalent Approximately 216 g/eq., 50% non-volatile content ratio of toluene solution) 12 parts, spherical silica (Admatechs "SO- C2", average particle diameter 0.5 μm, specific surface area 5.8 m ² /g) 200 parts, imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd., 1-benzyl-2-phenylimidazole) 0.3 parts, Four parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass) were mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin composition.

<Example 2> In Example 1, 15 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is about 269g/eq.) was substituted with bisphenol-type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Materials Co., Ltd. , a 1:1 mixture of bisphenol A type and bisphenol F type, with an epoxy equivalent of about 169g/eq.) 5 parts, and a naphthalene type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, 1, 6-Bis(glycidyloxy)naphthalene, epoxy equivalent weight is about 145g/eq.) 20 parts. In addition, the amount of long-chain aliphatic phenol resin ("LB-7000" manufactured by Tohoku Chemical Co., Ltd., active group equivalent: approximately 262 g/eq.) was increased from 2 parts to 4 parts. Furthermore, instead of 68 parts of the active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, a toluene solution with an active ester group equivalent weight of approximately 220 g/eq. and a non-volatile content ratio of 62% by mass), an active ester compound (DIC Corporation) was used. Prepare 62 parts of "HPC-8000-65T", a toluene solution with an active ester group equivalent weight of about 223g/eq. and a non-volatile content rate of 65%. Except for the above matters, a resin composition was prepared in the same manner as in Example 1.

<Example 3> In Example 1, instead of 15 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: approximately 269g/eq.), naphthol-type epoxy resin ("NC3000L" manufactured by Nippon Chemical Materials Co., Ltd.) was used ESN475V", epoxy equivalent is about 330g/eq.) 15 parts. In addition, instead of 2 parts of long-chain aliphatic phenol resin ("LB-7000" manufactured by Tohoku Chemical Co., Ltd., active group equivalent: approximately 262g/eq.), another long-chain aliphatic phenol resin ("LB-7250" manufactured by Tohoku Chemical Co., Ltd. ", the active group equivalent is about 273g/eq.) 2 parts. Except for the above matters, a resin composition was prepared in the same manner as in Example 1.

<Example 4> In Example 3, instead of 2 parts of long-chain aliphatic phenol resin ("LB-7250" manufactured by Tohoku Chemical Co., Ltd., active group equivalent: about 273 g/eq.), another long-chain aliphatic phenol resin (manufactured by Tokyo Chemical Industry Co., Ltd. "Urushiol", active group equivalent is about 174g/eq.) 2 parts. Except for the above matters, a resin composition was prepared in the same manner as in Example 3.

<Example 5> In Example 1, biphenyl aralkyl novolak-type maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK/toluene mixed solution with a non-volatile content rate of 70%) was added to the resin composition. )4 parts. Except for the above matters, a resin composition was prepared in the same manner as in Example 1.

<Example 6> In Example 1, 3 parts of a bismaleimide-terminated polyimide compound ("BMI-1500" manufactured by DMI Corporation) was added to the resin composition. Except for the above matters, a resin composition was prepared in the same manner as in Example 1.

<Example 7> In Example 1, 3 parts of methacrylic modified polyphenylene ether ("SA9000-111" manufactured by SABIC Innovative Plastics) was added to the resin composition. Except for the above matters, a resin composition was prepared in the same manner as in Example 1.

<Example 8> In Example 1, 4 parts of vinyl benzyl modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content rate of 65%) was added to the resin composition. Except for the above matters, a resin composition was prepared in the same manner as in Example 1.

＜Comparative example 1＞ In Example 1, 2 parts of long-chain aliphatic phenol resin ("LB-7000" manufactured by Tohoku Chemical Co., Ltd., active group equivalent weight is approximately 262 g/eq.) was not used. Except for the above matters, a resin composition was prepared in the same manner as in Example 1.

＜Comparative example 2＞ In Example 2, instead of 4 parts of long-chain aliphatic phenol resin ("LB-7000" manufactured by Tohoku Chemical Co., Ltd., active group equivalent: approximately 262 g/eq.), a novolak type phenolic hardener ("TD manufactured by DIC Corporation" was used) -2090", active radical equivalent is about 105g/eq.) 4 parts. Except for the above matters, a resin composition was prepared in the same manner as in Example 2.

＜Comparative Example 3＞ In Example 1, instead of 2 parts of long-chain aliphatic phenol resin ("LB-7000" manufactured by Tohoku Chemical Co., Ltd., active group equivalent: about 262 g/eq.), an epoxidized polybutadiene resin ( "PB3600M" manufactured by Daicel has an epoxy equivalent of about 193g/eq.) 2.5 parts. Except for the above matters, a resin composition was prepared in the same manner as in Example 1.

＜Comparative Example 4＞ In Example 1, the elastomer prepared in Synthesis Example 1 was used as a stress relaxation component instead of 2 parts of long-chain aliphatic phenol resin ("LB-7000" manufactured by Tohoku Chemical Co., Ltd., active group equivalent: approximately 262 g/eq.) X 10 servings. Except for the above matters, a resin composition was prepared in the same manner as in Example 1.

＜Manufacturing of resin sheets＞ As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. The resin composition obtained in the above-mentioned Example and Comparative Example was uniformly applied on the release layer of the support so that the thickness of the dried resin composition layer became 40 μm. Then, the resin composition is dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet including a support and a resin composition layer.

<Test Example 1: Measurement of relative dielectric constant (Dk) and dielectric loss tangent (Df)> The above-mentioned resin sheet is heated at 200° C. for 90 minutes to thermally harden the resin composition layer, and then the support is peeled off to obtain a cured product film formed of a cured product of the resin composition. The cured material film was cut into a width of 2 mm and a length of 80 mm to obtain cured material A for evaluation.

For the obtained hardened material A for evaluation, "HP8362B" manufactured by Agilent Technologies was used to measure the relative dielectric constant (( Dk value) is tangent to the dielectric loss angle (Df value). Three test pieces were measured and the average value was calculated.

<Test Example 2: Measurement of Minimum Melt Viscosity> The resin composition layers of 25 of the above-mentioned resin sheets were stacked to obtain a 1 mm thick resin composition layer. This resin composition layer was punched into a diameter of 20 mm, and a measurement sample was prepared. For the prepared measurement sample, a dynamic viscoelasticity measuring device ("Rheogel-G3000" manufactured by UBM) was used, and the temperature rise rate was 5°C/min from the starting temperature to 200°C, and the measurement temperature interval was 2.5°C. , the dynamic viscoelastic modulus is measured under the measurement conditions of a vibration frequency of 1Hz, and the minimum melt viscosity (Poise) is obtained.

<Test example 3: Measurement of arithmetic mean roughness (Ra)> (1) Base treatment of inner substrate: As the inner substrate, a glass cloth-based epoxy resin double-sided copper-clad laminate with copper foil on the surface was prepared (the thickness of the copper foil is 18 μm, the thickness of the substrate is 0.8 mm, "R1515A" manufactured by Panasonic Corporation). Using a microetchant ("CZ8101" manufactured by MEC Corporation), the copper foil on the surface of the inner layer substrate was etched with a copper etching amount of 1 μm and roughened. Then, drying was performed at 190°C for 30 minutes.

(2) Lamination and hardening of resin sheets: Using a batch-type vacuum pressure laminating machine (2-stage stacking laminator "CVP700" manufactured by Nikko-Materials), the above-mentioned resin sheets are laminated on the inner-layer substrate in such a manner that the resin composition layer is bonded to the above-mentioned inner-layer substrate. both sides. This lamination was performed by depressurizing for 30 seconds until the air pressure became 13 hPa or less, and then performing pressure bonding for 30 seconds under the conditions of a temperature of 100°C and a pressure of 0.74MPa.

Next, the laminated resin sheets were heat-pressed for 60 seconds under atmospheric pressure, 100° C., and a pressure of 0.5 MPa to smooth them. Furthermore, it was put into the oven of 130 degreeC, and heated for 30 minutes, and then it was moved to the oven of 170 degreeC, and heated for 30 minutes. By the above-mentioned heating, the resin composition layer is hardened to form an insulating layer.

(3) Formation of through holes: Use a CO ₂ laser processing machine (LK-2K212/2C) manufactured by Via Mechanics, with a frequency of 2000Hz, a pulse width of 3 microseconds, and an output power of 0.95W. , processing the insulating layer under the condition that the number of shots is 3 to form a through hole. The opening diameter (top diameter, diameter) of the through hole on the surface of the insulating layer is 50 μm, and the diameter of the through hole on the bottom surface of the insulating layer is 40 μm. Then, the polyethylene terephthalate film as the support was peeled off to obtain a sample substrate having a layer structure of insulating layer/inner layer substrate/insulating layer.

(4) Decontamination treatment: The sample substrate was immersed in Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd. as a swelling liquid at 60° C. for 10 minutes. Next, the sample substrate was immersed in Concentrate Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Atotech Japan Corporation as a roughening liquid at 80° C. for 20 minutes. Finally, the sample substrate was immersed in Reduction Solution Securiganth P manufactured by Atotech Japan Co., Ltd. as a neutralizing solution at 40° C. for 5 minutes to obtain evaluation substrate A as a sample substrate after the decontamination process.

(5) Determination of arithmetic mean roughness (Ra): The arithmetic mean roughness of the surface of the insulating layer of the evaluation substrate A was measured using a non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments) under the measurement conditions of VSI mode, 50x lens, and measurement range of 121 μm × 92 μm. Degree Ra. For each evaluation substrate A, the arithmetic mean roughness Ra was measured at 10 randomly selected points, and the average value was calculated.

<Test Example 4: Measurement of Peel Strength (Peel Strength) of the Plated Conductor Layer> The evaluation substrate A obtained in the step "(4) Decontamination treatment" by the same method as the above-mentioned Test Example 3 was prepared. The plate was immersed in an electroless plating solution of PdCl ₂ at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. After heating and annealing at 150° C. for 30 minutes, an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm on the insulating layer. Next, annealing was performed at 200° C. for 60 minutes to obtain evaluation substrate B.

On the conductor layer of the evaluation substrate B, a cut was formed surrounding a portion with a width of 10 mm and a length of 150 mm. One end of this part was peeled off and clamped with the clamp of a tensile testing machine (AUTO COM type testing machine "AC-50C-SL" manufactured by TSE Corporation). The insulation layer was stretched in the vertical direction at a speed of 50 mm/min at room temperature (25°C), and the load [kgf/cm] when peeling off 100 mm was measured as the peel strength.

<Test Example 5: Evaluation of Crack Resistance> (1) Lamination of resin sheets: An inner-layer substrate having circuit conductors (copper) formed in a wiring pattern of L/S=8 μm/8 μm on both sides was prepared (Hitachi Chemical Co., Ltd. "MCL-E700G" is manufactured, the thickness of the conductor layer is 35μm, the total thickness is 0.4mm, and the residual copper rate is 40%). Resin sheets are laminated on both sides of the inner layer substrate so that the resin composition layer is in contact with the inner layer substrate. This lamination is performed in the following manner: using a vacuum pressurized laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), vacuum suction is performed at a temperature of 120°C for 30 seconds, and then the temperature is 120°C and the pressure is Under the condition of 7.0kg/ ^cm2 , apply pressure for 30 seconds from the support through the heat-resistant rubber. Next, under atmospheric pressure, pressurization was performed for 60 seconds using a SUS end plate at a temperature of 120°C and a pressure of 5.5kg/ ^cm2 .

(2) Thermal hardening of the resin composition layer: Heating was performed at 130° C. for 30 minutes, and then heated at 170° C. for 30 minutes to thermally harden the resin composition layer, thereby obtaining an insulating layer as a hardened material layer formed of a hardened product of the resin composition. Then, the support body was peeled off to obtain a sample substrate having a layer structure of insulating layer/inner layer substrate/insulating layer.

(3) Roughening treatment: The insulating layer of the sample substrate is roughened. Specifically, the sample substrate was immersed in Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd. as a swelling liquid 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) manufactured by Atotech Japan Co., Ltd. as a roughening liquid at 80° C. for 20 minutes. Finally, it was immersed in Reduction Solution Securiganth P manufactured by Atotech Japan Co., Ltd. as a neutralizing solution at 40° C. for 5 minutes.

(4) Evaluation of cracks: The parts on the surface of the roughened insulating layer and on the wiring pattern of the inner substrate were observed. It was confirmed whether cracks (cracks) were generated on the surface of the insulating layer along the pattern shape of 100 inner-layer substrates, and the ratio of the number of portions on the pattern where no cracks occurred was calculated. This ratio is calculated as "yield". In addition, the calculated yield was scored according to the following criteria: 1 point: above 0% and less than 20% 2 points: more than 20% and less than 40% 3 points: more than 40% and less than 60% 4 points: more than 60% and less than 80% 5 points: above 80% A score of 3 or more is evaluated as "○", and a score of 2 or less is evaluated as "×".

＜Result＞ The results of the above-mentioned Examples and Comparative Examples are shown in the following table.

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100:Semiconductor chip packaging 110:Semiconductor wafer 120:Sealing layer 130:Rewiring formation layer 140:Rewiring layer 150: Solder mask 160: Bump

[Fig. 1] is a cross-sectional view schematically showing a fan-out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention.

100:Semiconductor chip packaging

110:Semiconductor wafer

120:Sealing layer

130:Rewiring formation layer

140:Rewiring layer

150: Solder mask

160: Bump

Claims (16)

A resin composition comprising (A) a resin represented by the following formula (A-1), (B) an epoxy resin, and (C) an active ester compound, In the formula (A-1), R ¹ represents a chain aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent, R ² represents a hydrocarbon group which may have a substituent, n represents a number of 1 or more, and m represents 0 or more. number, wherein R ¹ includes a chain unsaturated aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent. The resin composition of claim 1, wherein component (A) has a weight average molecular weight of 1,000 or less. The resin composition of claim 1, wherein component (A) is a resin represented by any one of formula (a-1) to formula (a-4) or a combination thereof, In the formulas (a-1) to (a-4), R ¹ represents a chain aliphatic hydrocarbon group having 7 or more carbon atoms that may have a substituent, wherein R ¹ includes a chain aliphatic hydrocarbon group having 7 or more carbon atoms that may have a substituent. chain unsaturated aliphatic hydrocarbon group. The resin composition of claim 1, wherein the amount of component (A) is 0.01 mass% or more and 10 mass% or less based on 100 mass% of non-volatile components in the resin composition. The resin composition of claim 1, which contains (D) an inorganic filler material. The resin composition of Claim 1, which contains (E) hardener in addition to component (A) and component (C). The resin composition of claim 1, which contains (F) a hardening accelerator. The resin composition of claim 1, which contains (G) thermoplastic resin. The resin composition of claim 1 is used to form an insulating layer of a printed wiring board. A hardened product of the resin composition according to any one of claims 1 to 9. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 9. A resin sheet is provided with a support body and a resin composition layer formed on the support body, and the resin composition layer includes the resin composition according to any one of claims 1 to 9. A circuit board provided with an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor chip package comprising a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor device provided with the circuit substrate according to claim 13. A semiconductor device provided with the semiconductor chip package of claim 14.

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