Resin composition

Abstract

To provide a novel resin composition capable of providing a cured product exhibiting good adhesion to a conductor layer after exposure to a high-temperature, high-humidity environment, even when a composition contributing to good dielectric properties is used.SOLUTION: A resin composition contains an epoxy resin represented by formula (1), and an active ester resin. (In formula (1), R1 each independently represents a monovalent aliphatic group, L each independently represents a single bond or a divalent linking group, RS each independently represents a substituent, m each independently represents an integer of 0-3, and n represents an integer of 0-5.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition. Further, it relates to a resin sheet, a cured product, a circuit board, and a semiconductor device.

Background Art

[0002] A resin composition containing an epoxy resin and its curing agent has been widely used as an insulating material for circuit boards such as printed wiring boards and redistribution substrates for semiconductor chip packages because it provides a cured product excellent in insulation, heat resistance, adhesion, etc.

[0003] On the other hand, with the recent increase in communication speed, an insulating material for circuit boards is required to have excellent dielectric properties (low dielectric tangent) in order to reduce transmission loss when operating in a high-frequency environment. As an insulating material with excellent dielectric properties, a specific curing agent such as an active ester resin that can reduce and suppress the generation of polar groups such as secondary hydroxyl groups in the curing reaction of epoxy resin is used, or a high content of inorganic filler is used. Those adopting a specific composition are known (for example, Patent Documents 1 to 3).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] When an insulating layer is formed using a resin composition adopting a composition contributing to good dielectric properties as described in Patent Documents 1 to 3, it has been found that the adhesion of the insulating layer to the conductor layer tends to deteriorate after exposure to a high-temperature and high-humidity environment.

[0006] An object of the present invention is to provide a novel resin composition that can provide a cured product exhibiting good adhesion to a conductor layer even when exposed to a high-temperature and high-humidity environment, even when a composition contributing to good dielectric properties is employed.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors have found that the above problems can be solved by a resin composition having the following configuration, and have completed the present invention.

[0008] That is, the present invention includes the following. [1] A resin composition comprising an epoxy resin represented by the following formula (1) and an active ester resin.

Chemical formula

[10] The resin composition according to any one of [1] to [9], which is for an insulating layer of a circuit board.

[11] A resin sheet including a support and a layer of the resin composition according to any one of [1] to

[10] provided on the support.

[12] The resin sheet according to

[11] , wherein the support is a thermoplastic resin film or a metal foil.

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

[10] .

[14] A circuit board including an insulating layer made of a cured product of the resin composition according to any one of [1] to

[10] .

[15] A semiconductor device including the circuit board according to

[14] . [Effect of the Invention]

[0009] According to the present invention, even when a composition that contributes to good dielectric properties is adopted, a novel resin composition can be provided that can result in a cured product exhibiting good adhesion to a conductor layer when exposed to a high-temperature and high-humidity environment.

Mode for Carrying Out the Invention

[0010] <Explanation of Terms> In this specification, the term "optionally having a substituent" when referring to a compound or a group means both the case where the hydrogen atom of the compound or group is not substituted with a substituent and the case where some or all of the hydrogen atoms of the compound or group are substituted with a substituent.

[0011] In this specification, the term "substituent" means, unless otherwise specified, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a monovalent heterocyclic group, an alkylidene group, an acyl group, an acyloxy group, an amino group, a silyl group, a carboxy group, a sulfo group, a cyano group, a nitro group, a mercapto group, and an oxo group.

[0012] Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3. The alkenyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkenyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 or 3. The number of carbon atoms of the cycloalkyl group used as a substituent is preferably 3 to 12, more preferably 3 to 6. The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6. The number of carbon atoms of the cycloalkyloxy group used as a substituent is preferably 3 to 12, more preferably 3 to 6. The number of carbon atoms of the aryl group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms of the arylalkyl group used as a substituent is preferably 7 to 15, more preferably 7 to 11. The number of carbon atoms of the arylalkoxy group used as a substituent is preferably 7 to 15, more preferably 7 to 11. The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from a heterocyclic ring of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3 to 15, more preferably 3 to 9. The monovalent heterocyclic group includes a monovalent aromatic heterocyclic group (heteroaryl group). The alkylidene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms of the alkylidene group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The acyl group used as a substituent refers to a group represented by the formula: -C(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. The number of carbon atoms of the acyl group is preferably 2 to 13, and still more preferably 2 to 7.The acyloxy group used as a substituent is a group represented by the formula: -O-C(=O)-R (wherein R has the same meaning as described above). The number of carbon atoms of the acyloxy group is preferably 2 to 13, more preferably 2 to 7. The above-mentioned substituent may further have a substituent (which may be referred to as a "secondary substituent"). As the secondary substituent, the same ones as the above-mentioned substituents may be used unless otherwise specified.

[0013] In this specification, the term "aliphatic group" refers to a group obtained by removing one or more hydrogen atoms bonded to the aliphatic carbon of an aliphatic compound. Specifically, a monovalent aliphatic group refers to a group obtained by removing one hydrogen atom bonded to the aliphatic carbon of an aliphatic compound, and a divalent aliphatic group refers to a group obtained by removing two hydrogen atoms bonded to the aliphatic carbon of an aliphatic compound. Examples of the monovalent aliphatic group include an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, and an alkapolyenyl group which may have a substituent (the number of double bonds is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2). Examples of the divalent aliphatic group include an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, an alkenylene group which may have a substituent, a cycloalkenylene group which may have a substituent, and an alkapolyenylene group which may have a substituent (the number of double bonds is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2). Here, the alkyl group, alkenyl group, alkapolyenyl group, alkylene group, alkenylene group, and alkapolyenylene group may each be linear or branched. In this specification, unless otherwise specified, the number of carbon atoms of the aliphatic group is preferably 1 or more, more preferably 2 or more or 3 or more, and preferably 30 or less, more preferably 20 or less, still more preferably 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, or 6 or less. The number of carbon atoms of the substituent is not included in the number of carbon atoms.

[0014] In this specification, "C"p ~C q The term "」(where p and q are positive integers and p < q)" indicates that the number of carbon atoms in the organic group described immediately after this term is p to q. For example, "C1~C6 alkyl group" indicates an alkyl group having 1 to 6 carbon atoms, and "C6~C 10 cycloalkyl group" indicates a cycloalkyl group having 6 to 10 carbon atoms.

[0015] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0016] [Resin Composition] The resin composition of the present invention contains an epoxy resin represented by the following formula (1) and an active ester resin. [Chemical formula] (In formula (1), R 1 each independently represents a monovalent aliphatic group, L each independently represents a single bond or a divalent linking group, R S each independently represents a substituent, m each independently represents an integer from 0 to 3, n represents an integer from 0 to 5.)

[0017] As described above, when an insulating layer is formed using a conventional resin composition that contributes to good dielectric properties (for example, a resin composition that adopts a specific composition such as using a specific curing agent such as an active ester resin that can reduce or suppress the generation of polar groups such as secondary hydroxyl groups in the curing reaction of an epoxy resin, or highly compounding an inorganic filler), it has been found that the adhesion to the conductor layer tends to deteriorate after exposure to a high-temperature and high-humidity environment. Further, it has been confirmed that the deterioration of the adhesion to the conductor layer after exposure to a high-temperature and high-humidity environment becomes remarkable when a specific curing agent such as an active ester resin is highly compounded or an inorganic filler is more highly compounded in order to bring about better dielectric properties.

[0018] On the other hand, according to the present invention using a specific epoxy resin represented by the above formula (1) as the epoxy resin, even when a specific composition that contributes to good dielectric properties is adopted, a cured product can be obtained that exhibits good adhesion to the conductor layer when exposed to a high-temperature and high-humidity environment. Furthermore, it has been confirmed that according to the present invention using a specific epoxy resin represented by the above formula (1) as the epoxy resin, the dielectric properties themselves, such as a lower dielectric tangent, become better.

[0019] The resin composition of the present invention may contain other epoxy resins as long as it contains the epoxy resin represented by the above formula (1). Hereinafter, the epoxy resin represented by the above formula (1) is referred to as “(A-1) epoxy resin represented by formula (1)” or simply “(A-1) component”, and other epoxy resins are referred to as “(A-2) other epoxy resins” or simply “(A-2) component”. Further, these (A-1) component and (A-2) component are collectively referred to as “(A) epoxy resin” or simply “epoxy resin” or “(A) component”.

[0020] Hereinafter, each component will be described.

[0021] <(A) Epoxy Resin> The resin composition of the present invention is characterized in that it contains an epoxy resin as the (A) component, and the epoxy resin contains the epoxy resin represented by (A-1) formula (1). [Chemical formula] (In formula (1), R 1 each independently represents a monovalent aliphatic group, L each independently represents a single bond or a divalent linking group, R S each independently represents a substituent, m each independently represents an integer from 0 to 3, n represents an integer from 0 to 5.)

[0022] In formula (1), R 1 each independently represents a monovalent aliphatic group. As the monovalent aliphatic group represented by R 1 , as described above, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a cycloalkyl group which may have a substituent is preferable, and an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 12 carbon atoms which may have a substituent, or a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent is more preferable.

[0023] Among them, even when adopting a composition that contributes to good dielectric properties, from the viewpoint of realizing a cured product that exhibits even better adhesion to the conductor layer when exposed to a high-temperature and high-humidity environment, the monovalent aliphatic group represented by R 1 is preferably an alkyl group which may have a substituent, and more preferably an alkyl group. The number of carbon atoms of the alkyl group is as described above for the aliphatic group, preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6 or 1 to 4.

[0024] Therefore, in a preferred embodiment, R 1 each independently represents an alkyl group, and more preferably represents an alkyl group having 1 to 6 carbon atoms.

[0025] In formula (1), each L independently represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L include divalent organic groups composed of one or more (e.g., 1 to 50, 1 to 20, 1 to 10) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. Among them, divalent aliphatic groups are preferred. Therefore, in a preferred embodiment, each L independently represents a single bond or a divalent aliphatic group, and more preferably represents a divalent aliphatic group.

[0026] As described above, examples of the divalent aliphatic group represented by L include a divalent group composed of an alkylene group which may have a substituent, an alkenylene group which may have a substituent, a cycloalkylene group which may have a substituent, or a combination thereof. A divalent group composed of an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or a combination thereof is preferred.

[0027] Among them, from the viewpoint of realizing a cured product that exhibits better adhesion to the conductor layer even when exposed to a high-temperature and high-humidity environment, even when adopting a composition that contributes to good dielectric properties, the divalent aliphatic group represented by L is preferably a divalent group composed of an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, or a combination thereof. A divalent group composed of an alkylene group, a cycloalkylene group, or a combination thereof is more preferred, and an alkylene group or a cycloalkylene group is even more preferred. The number of carbon atoms of the alkylene group is as described above for the aliphatic group, preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6 or 1 to 4. The number of carbon atoms of the cycloalkylene group is as described above for the aliphatic group, preferably 6 to 12, and more preferably 6 to 10.

[0028] Therefore, in a preferred embodiment, L each independently represents a divalent group consisting of an alkylene group, a cycloalkylene group, or a combination thereof, and more preferably represents a divalent group consisting of an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or a combination thereof.

[0029] Even when adopting a composition that contributes to good dielectric properties, from the perspective of realizing a cured product that exhibits excellent adhesion to a conductor layer when exposed to a high-temperature and high-humidity environment, L is preferably each independently a divalent group represented by the following formula (2).

[0030]

Chemical formula

[0031] R 3 and R 4 The alkyl groups in are as described above for aliphatic groups, and preferably have 1 to 6 carbon atoms. Also, when R 3 and R 4 combine to form a ring, the formed ring is preferably a 4- to 10-membered saturated carbon ring, more preferably a 6- to 10-membered saturated carbon ring. The saturated carbon ring may have substituents derived from R 3 and R 4 .

[0032] R 3 and R 4 The substituents that the alkyl groups in may have are as described above. However, since the effects of the present invention can be more enjoyed, a halogen atom or an alkyl group is preferred.

[0033] For example, R 3 and R 4When both represent a hydrogen atom, the divalent group represented by the formula (2) is a methylene group. R 3 and R 4 When both represent a methyl group, the divalent group represented by the formula (2) is a propylene group (propane-2,2-diyl group). R 3 and R 4 When both represent a trifluoromethyl group, the divalent group represented by the formula (2) is a hexafluoropropylene group (hexafluoropropane-2,2-diyl group). R 3 and R 4 When they are integrated to form a 6-membered saturated carbon ring, the divalent group represented by the formula (2) is a cyclohexylene group (cyclohexane-1,1-diyl group). As described above, the saturated carbon ring may have substituents derived from R 3 and R 4 For example, as a 6-membered saturated carbon ring having a substituent, a trimethylcyclohexylene group (such as 3,3,5-trimethylcyclohexane-1,1-diyl group, etc.) can be mentioned.

[0034] In the formula (1), R S each independently represents a substituent. R S As the substituent represented by, as described above, from the viewpoint of being able to enjoy the effects of the present invention more, a halogen atom, an alkoxy group, or an aryl group is preferable, and a halogen atom is more preferable.

[0035] In the formula (1), m each independently represents an integer of 0 to 3. Even when adopting a composition that contributes to good dielectric properties, from the viewpoint of being able to realize a cured product that exhibits better adhesion to the conductor layer when exposed to a high-temperature and high-humidity environment, m each independently preferably represents an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0036] Even when adopting a composition that contributes to good dielectric properties, from the viewpoint of being able to realize a cured product that exhibits particularly good adhesion to the conductor layer when exposed to a high-temperature and high-humidity environment, and further from the viewpoint of being able to realize a cured product with even better dielectric properties such as a lower dielectric tangent, examples of the epoxy resin represented by the formula (1) that is particularly suitable are shown below.

[0037] In a preferred embodiment, in formula (1), R 1 each independently represents an alkyl group which may have a substituent, L each independently represents a divalent group consisting of (i) a single bond, or (ii) an alkylene group which may have a substituent, an alkenylene group which may have a substituent, a cycloalkylene group which may have a substituent, or a combination thereof, R S each independently represents a halogen atom, an alkoxy group, or an aryl group, m each independently represents 0 or 1, n represents an integer from 0 to 5.

[0038] In a more preferred embodiment, in formula (1), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms, L each independently represents a divalent group consisting of an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or a combination thereof, R S each independently represents a halogen atom, m each independently represents 0 or 1 (more preferably 0), n represents an integer from 0 to 5.

[0039] In an even more preferred embodiment, in formula (1), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms, L each independently represents a divalent group represented by the above formula (2), m each independently represents 0 or 1 (more preferably 0), n represents an integer from 0 to 5.

[0040] From the viewpoint of being able to more enjoy the effects of the present invention, the bonding position of L to the benzene ring specified in formula (1) is also the oxygen atom (R1 In relation to the bonding position with the oxygen atom bonded to the ortho position, the para position is preferred.

[0041] Even when adopting a composition that contributes to good dielectric properties, from the viewpoint of being able to realize a cured product that exhibits good adhesion to the conductor layer when exposed to a high-temperature and high-humidity environment, the epoxy equivalent of the component (A-1) is preferably 160 g / eq. or more, more preferably 170 g / eq. or more, 175 g / eq. or more, or 180 g / eq. or more, and the upper limit thereof is preferably 600 g / eq. or less, more preferably 500 g / eq. or less, 400 g / eq. or less, or 300 g / eq. or less. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy groups and can be measured in accordance with JIS K7236.

[0042] Hereinafter, an example of the synthesis procedure of the component (A-1), that is, the epoxy resin represented by the formula (1), will be shown.

[0043] In one embodiment, the component (A-1) is (x1) a divalent hydroxy compound represented by the following general formula (x1), and (x2) epihalohydrin and is a reaction product (epoxidized product).

[0044]

Chemical formula

[0045] -(x1) Divalent hydroxy compound- The divalent hydroxy compound (x1) may be appropriately determined in order to achieve the structure of the target component (A-1). Preferred examples of the structure of the component (A-1), that is, the structure represented by the formula (1), are as described above. For example, as such a divalent hydroxy compound (x1), in the positional relationship with the hydroxy group, R is in the ortho position 1A biphenyl compound to which R is bonded ortho to a hydroxy group, a bisphenol compound to which R is bonded, etc. may be mentioned. Specifically, 4,4'-methylenebis(2-C1-C6 alkylphenol) may be used as a compound that provides the structure of formula (1) in which R is a C1-C6 alkyl group, L is a methylene group, and m is 0. 1 A bisphenol compound to which R is bonded, etc. may be mentioned. Specifically, 1 2,2-bis(4-hydroxy-3-C1-C6 alkylphenyl)propane may be used as a compound that provides the structure of formula (1) in which R is a C1-C6 alkyl group, L is a propane-2,2-diyl group, and m is 0. 1 1,1-bis(4-hydroxy-3-C1-C6 alkylphenyl)cyclohexane may be used as a compound that provides the structure of formula (1) in which R is a C1-C6 alkyl group, L is a cyclohexane-1,1-diyl group, and m is 0. 1 -(x2) Epihalohydrin -

[0046] As the epihalohydrin (x2), epichlorohydrin or epibromohydrin may be used.

[0047] The reaction of the (x1) component and the (x2) component may be carried out by a conventionally known epoxidation reaction using a dihydroxy compound and an epihalohydrin. The reaction may proceed in a solvent-free system without using a solvent, or may proceed in an organic solvent system using an organic solvent. Examples of the organic solvent used in the reaction include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. The organic solvent may be used alone or in combination of two or more.

[0048] ​In the reaction, a base may be used. Examples of the base include alkali metal hydroxides such as sodium hydroxide (caustic soda) and potassium hydroxide; and tertiary amines such as triethylamine, pyridine, and N,N-dimethyl-4-aminopyridine (DMAP). The base may be used alone or in combination of two or more. In the reaction, a condensing agent or an interlayer transfer catalyst may also be used. Any conventionally known ones may be used for these.

[0049] The reaction temperature is not particularly limited as long as the reaction proceeds, and may be, for example, in the range of 50 to 150 °C. Also, the reaction time is not particularly limited as long as the structure of the target component (A-1) is achieved, and may be, for example, in the range of 1 to 10 hours.

[0050] In such a reaction, by adjusting the molar ratio of the component (x1) to the component (x2) etc., the degree of polymerization (n in formula (1); n tends to increase as the amount of the component (x2) decreases) can be adjusted, and the epoxy equivalent of the obtained component (A-1) can be adjusted. In order to efficiently achieve the structure of formula (1), the amount of the component (x2) needs to be more than the amount of the component (x1). Usually, the component (x2) is 2 moles or more, preferably 3 moles or more, per 1 mole of the component (x1).

[0051] After the reaction, the excess component (x2) can be distilled off to obtain the component (A-1). Also, the component (A-1) may be purified. For example, after the reaction, in order to remove by-produced salts and excess starting materials from the system, purification steps such as washing with water and microfiltration may be performed. Specifically, the residue obtained by distilling off the excess component (x2) may be dissolved in an organic solvent, filtered, washed with water to remove by-produced salts, and then the organic solvent may be distilled off to purify the component (A-1).

[0052] The resin composition of the present invention may contain the other epoxy resin (A-2) as long as it contains the above-mentioned component (A-1) as the epoxy resin.

[0053] (A-2) component is not particularly limited as long as it has one or more (preferably two or more) epoxy groups in one molecule. Examples of (A-2) component include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene skeleton type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, etc.

[0054] (A-2) component can be classified into an epoxy resin that is liquid at 20°C (hereinafter referred to as "liquid epoxy resin") and an epoxy resin that is solid at 20°C (hereinafter referred to as "solid epoxy resin"). When the resin composition of the present invention contains (A-2) component, it may further contain only the liquid epoxy resin, may further contain only the solid epoxy resin, or may further contain a combination of the liquid epoxy resin and the solid epoxy resin.

[0055] The epoxy equivalent of (A-2) component is preferably 50 g / eq. to 2000 g / eq., more preferably 60 g / eq. to 1000 g / eq., and still more preferably 80 g / eq. to 500 g / eq.

[0056] The weight average molecular weight (Mw) of (A-2) component is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The Mw of the epoxy resin can be measured as a value in terms of polystyrene by the GPC method.

[0057] Even when adopting a composition that contributes to good dielectric properties, from the viewpoint of realizing a cured product that exhibits good adhesion to a conductor layer when exposed to a high-temperature and high-humidity environment, the content of component (A-1) in the resin composition, that is, the epoxy resin represented by formula (1), is preferably 1% by mass or more, more preferably 2% by mass or more, 4% by mass or more, or 5% by mass or more, still more preferably 6% by mass or more, 8% by mass or more, 10% by mass or more, 11% by mass or more, or 12% by mass or more when the resin components in the resin composition are taken as 100% by mass. The upper limit of the content is not particularly limited and may be determined according to the properties required for the resin composition. However, from the viewpoint of realizing a cured product that exhibits even better dielectric properties in combination with the (B) active ester resin described later, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, or 40% by mass or less. Therefore, in one embodiment, the content of component (A-1) in the resin composition is 1% by mass or more and 45% by mass or less when the resin components in the resin composition are taken as 100% by mass.

[0058] In the present invention, the "resin components" referred to for the resin composition mean the components excluding the (D) inorganic filler described later among the non-volatile components constituting the resin composition.

[0059] When the resin composition of the present invention contains component (A-2), that is, other epoxy resins, when the total of component (A) (total of non-volatile components) is taken as 100% by mass, the content of component (A-1) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, or 30% by mass or more. The upper limit of the content of component (A-1) in the total of component (A) is not particularly limited and may be 100% by mass. However, for example, it may be 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, etc.

[0060] In the resin composition of the present invention, the total content of component (A) may be appropriately determined so as to satisfy the preferable ranges of the content of component (A-1) and the content of component (A-1) in the whole component (A). For example, when the resin component in the resin composition is 100% by mass, the total content of component (A) in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, 25% by mass or more, 26% by mass or more, 28% by mass or more, or 30% by mass or more. The upper limit of the content is not particularly limited and may be determined according to the properties required for the resin composition. However, from the viewpoint of realizing a cured product exhibiting better dielectric properties in combination with the (B) active ester resin described later, it may be preferably 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less, etc.

[0061] <(B) active ester resin> The resin composition of the present invention contains an active ester resin as component (B).

[0062] As the active ester resin, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester resin, compounds having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferable. The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.

[0063] 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.

[0064] Examples of the phenolic compound or naphtholic compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenolic compounds, phenol novolac, and the like. Here, the "dicyclopentadiene-type diphenolic compound" refers to a diphenolic compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0065] Specific examples of the active ester resin that are preferable from the viewpoint of more enjoying the effects of the present invention include an active ester resin containing a dicyclopentadiene-type diphenolic structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolac, and an active ester resin containing a benzoylated product of phenol novolac. Among them, in combination with the component (A-1), from the viewpoint of achieving a cured product that exhibits particularly good adhesion to the conductor layer and particularly good dielectric properties when exposed to a high-temperature and high-humidity environment, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene-type diphenolic structure are more preferable. The "dicyclopentadiene-type diphenolic structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

[0066] Examples of commercially available products of component (B) include, as active ester resins containing a dicyclopentadiene-type diphenol structure, "EXB-9451", "EXB-9460", "EXB-9460S", "HPC-8000-65T", "HPC-8000H-65TM", "HPC-8000L-65TM" (manufactured by DIC Corporation); as active ester resins containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "HP-B-8151-62T" (manufactured by DIC Corporation); as phosphorus-containing active ester resins, "EXB9401" (manufactured by DIC Corporation); as active ester resins that are acetylated products of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as active ester resins that are benzoylated products of phenol novolac, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and as active ester resins containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.), and the like.

[0067] Component (B) may be used alone or in combination of two or more in any ratio.

[0068] The active ester group equivalent of component (B) (in this specification, may be abbreviated as "active group equivalent") is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and even more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester resin per 1 equivalent of the active ester group.

[0069] From the viewpoint of easily realizing a resin composition having good dielectric properties, when the resin component in the resin composition is 100% by mass, the content of component (B) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, 35% by mass or more, or 40% by mass or more. The upper limit of the content is not particularly limited and may be determined according to the properties required for the resin composition. For example, it may be 70% by mass or less, 65% by mass or less, or 60% by mass or less.

[0070] In the resin composition of the present invention, the mass ratio of component (B) to component (A-1) ((B) component / (A-1) component) is preferably 1 or more, more preferably 1.2 or more, still more preferably 1.3 or more, 1.5 or more, 1.6 or more, 1.8 or more, or 2 or more from the viewpoint of providing a cured product having excellent dielectric properties. As described above, according to the resin composition of the present invention using component (A-1), even when component (B) is contained to such an extent that excellent dielectric properties can be realized, a cured product having good adhesion to a conductor layer when exposed to a high-temperature and high-humidity environment can be provided. For example, in the resin composition of the present invention, the mass ratio of component (B) to component (A-1) may be increased to 2.5 or more, 3 or more, or 3.5 or more. The upper limit of the mass ratio ((B) component / (A-1) component) may be, for example, 10 or less, 8 or less, 6 or less, 5 or less, etc.

[0071] In the resin composition of the present invention, the mass ratio of component (B) to component (A) ((B) component / (A) component) is preferably 0.8 or more, more preferably 1 or more from the viewpoint of providing a cured product having excellent dielectric properties. As described above, according to the resin composition of the present invention using component (A-1), even when component (B) is contained to such an extent that excellent dielectric properties can be realized, a cured product having good adhesion to a conductor layer when exposed to a high-temperature and high-humidity environment can be provided. For example, in the resin composition of the present invention, the mass ratio of component (B) to component (A) may be increased to 1.1 or more, 1.2 or more, or 1.3 or more. The upper limit of the mass ratio ((B) component / (A) component) may be, for example, 2 or less, 1.9 or less, 1.8 or less, etc.

[0072] <(C) Other curing agent> The resin composition of the present invention may further contain, as component (C), a curing agent other than component (B) (also referred to as "other curing agent").

[0073] Examples of component (C) include phenolic curing agents, naphtholic curing agents, acid anhydride curing agents, cyanate ester curing agents, carbodiimide curing agents, amine curing agents, etc. Component (C) may be used alone or in combination of two or more.

[0074] As the phenolic curing agent and naphtholic curing agent, those having a novolak structure are preferable from the viewpoints of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer, nitrogen-containing phenolic curing agents and nitrogen-containing naphtholic curing agents are preferable, and phenolic curing agents containing a triazine skeleton and naphtholic curing agents containing a triazine skeleton are more preferable.

[0075] Specific examples of the phenolic curing agent and naphtholic curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.; "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" manufactured by DIC Corporation; "GDP-6115L", "GDP-6115H", "ELPC75", etc. manufactured by Gunei Chemical Industry Co., Ltd.

[0076] Examples of the acid anhydride-based curing agent include curing agents having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as a styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available products of the acid anhydride-based curing agent include "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

[0077] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers in which part of these cyanate resins is triazine-ized; and the like. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", "BA230S75" (prepolymer in which part or all of bisphenol A dicyanate is triazine-ized to form a trimer), etc. manufactured by Lonza Japan Co., Ltd.

[0078] Specific examples of carbodiimide curing agents include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g / eq.), V-05 (carbodiimide group equivalent: 262 g / eq.), V-07 (carbodiimide group equivalent: 200 g / eq.); V-09 (carbodiimide group equivalent: 200 g / eq.) manufactured by Nisshinbo Chemical Inc.; and Stabaxol (registered trademark) P (carbodiimide group equivalent: 302 g / eq.) manufactured by Rhein Chemie.

[0079] Examples of the amine curing agent include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. The amine curing agent may be a commercially available product, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd., "EPICURE W" manufactured by Mitsubishi Chemical Corporation, and the like.

[0080] When the resin composition of the present invention contains the component (C), the content of the component (C) in the resin composition may be determined according to the properties required for the resin composition. When the resin component in the resin composition is 100% by mass, for example, it is 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. The upper limit of the content of the component (C) is not particularly limited, but may be, for example, 20% by mass or less, 15% by mass or less, 10% by mass or less, and the like.

[0081] As described above, from the viewpoint of providing a cured product having excellent dielectric properties, the resin composition of the present invention contains an active ester resin, that is, component (B). In the resin composition of the present invention, when the total of the non-volatile components of component (B) and component (C) is 100% by mass, the content of component (B) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, 75% by mass or more, or 80% by mass or more. The upper limit of the content of component (B) in the total of component (B) and component (C) is not particularly limited and may be 100% by mass, but may be, for example, 95% by mass or less, 90% by mass or less, etc.

[0082] <(D) Inorganic filler> The resin composition of the present invention may further contain an inorganic filler as component (D). By containing component (D), the linear thermal expansion coefficient and the dielectric tangent can be further reduced.

[0083] Examples of the material of component (D) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum silicate, 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, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. Also, spherical silica is preferred as the silica. Component (D) may be used alone or in combination of two or more.

[0084] Examples of commercially available products of component (D) include, for example, "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd.; "SP60-05", "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd.; "DAW-03", "FB-105FD" manufactured by Denka Co., Ltd.; "Selfiers", "MGH-005" manufactured by Taiheiyo Cement Corporation, etc.

[0085] The average particle size of component (D) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more. The average particle size of component (D) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution measuring device and taking the median diameter thereof as the average particle size. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample is measured for the volume-based particle size distribution of the inorganic filler in a flow cell method using a laser diffraction type particle size distribution measuring device with the wavelengths of the light sources used being blue and red, and the average particle size is calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0086] (D) The specific surface area of the component is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m2 3 m / g or more 2 5 m / g or more 2 or more. The upper limit of the specific surface area is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 80 m 2 / g or less, still more preferably 60 m 2 / g or less, 50 m 2 / g or less or 40 m 2 / g or less. The specific surface area of component (D) is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method and calculating the specific surface area using the BET multi-point method.

[0087] Component (D) is preferably surface-treated with a suitable surface treatment agent. By being surface-treated, the moisture resistance and dispersibility of component (D) can be enhanced. Examples of the surface treatment agent include silane coupling agents such as vinyl-based silane coupling agents, epoxy-based silane coupling agents, styryl-based silane coupling agents, (meth)acrylic-based silane coupling agents, amino-based silane coupling agents, isocyanurate-based silane coupling agents, ureido-based silane coupling agents, mercapto-based silane coupling agents, isocyanate-based silane coupling agents, and acid anhydride-based silane coupling agents; non-silane coupling - alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane; and silazane compounds. The surface treatment agent may be used alone or in combination of two or more.

[0088] Examples of commercially available products of the surface treatment agent include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0089] From the perspective of improving the dispersibility of the inorganic filler, it is preferable that the degree of surface treatment with the surface treatment agent falls within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2 to 5% by mass of the surface treatment agent.

[0090] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more from the perspective of improving the dispersibility of the inorganic filler, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, from the perspective of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and even more preferably 0.5 mg / m 2 or less. The amount of carbon per unit surface area of the component (D) can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. etc. can be used.

[0091] When the resin composition of the present invention contains the component (D), the content of the component (D) in the resin composition is, from the viewpoint of easily realizing a resin composition having better dielectric properties, when the non-volatile components in the resin composition are 100% by mass, for example, 40% by mass or more, preferably 50% by mass or more. As described above, according to the present invention using the component (A-1), even when adopting a specific composition that contributes to good dielectric properties, a cured product can be obtained that exhibits good adhesion to the conductor layer when exposed to a high-temperature and high-humidity environment. For example, in the resin composition of the present invention, the content of the component (D) may be increased to 60% by mass or more, 65% by mass or more, or 70% by mass or more. The upper limit of the content of the component (D) is not particularly limited, but may be, for example, 90% by mass or less, 85% by mass or less, etc.

[0092] <(E) Thermoplastic resin> The resin composition of the present invention may contain a thermoplastic resin as the component (E).

[0093] Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. The thermoplastic resin may be used alone or in combination of two or more.

[0094] The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured at a column temperature of 40 °C using LC-9A / RID-6A manufactured by Shimadzu Corporation as the measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as the column, and chloroform or the like as the mobile phase, and can be calculated using the calibration curve of standard polystyrene.

[0095] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both are bisphenol A skeleton-containing phenoxy resins), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation, and in addition, "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd., "YX7553", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation, etc.

[0096] Examples of the polyvinyl acetal resin include, for example, polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include, for example, "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denka Co., Ltd., and ESREC BH series, BX series, KS series, BL series, BM series, etc. manufactured by Sekisui Chemical Co., Ltd.

[0097] Specific examples of the polyimide resin include "Lica Coat SN20" and "Lica Coat PN20" manufactured by Nippon Rika Kogyo Co., Ltd. Specific examples of the polyimide resin also include modified polyimides such as linear polyimide obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compound and tetracarboxylic dianhydride (described in JP-A-2006-37083), and polyimide containing polysiloxane skeleton (described in JP-A-2002-12667 and JP-A-2000-319386, etc.).

[0098] Specific examples of the polyamideimide resin include "Vironmax HR11NN" and "Vironmax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimide "KS9100", "KS9300", etc. manufactured by Hitachi Chemical Co., Ltd.

[0099] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0100] Specific examples of the polysulfone resin include polysulfone "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers, LLC.

[0101] When the resin composition of the present invention contains the component (E), the content of the component (E) in the resin composition may be determined according to the properties required for the resin composition. However, when the resin component in the resin composition is 100% by mass, for example, it is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, 0.6% by mass or more, 0.8% by mass or more, or 1% by mass or more. The upper limit of the content of the component (E) is not particularly limited, but may be, for example, 20% by mass or less, 18% by mass or less, 16% by mass or less, 15% by mass or less, etc.

[0102] <(F) Radical polymerizable resin> The resin composition of the present invention may contain a radical polymerizable resin as the component (F).

[0103] The type of the radical polymerizable resin is not particularly limited as long as it has one or more (preferably two or more) radical polymerizable unsaturated groups in one molecule. Examples of the radical polymerizable resin include resins having one or more selected from maleimide groups, vinyl groups, allyl groups, styryl groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, fumaroyl groups, and maleoyl groups as radical polymerizable unsaturated groups. Among them, from the viewpoint of providing a cured product having even better dielectric properties, the radical polymerizable resin is preferably one or more selected from maleimide resins, (meth)acrylic resins, and styryl resins.

[0104] As the maleimide resin, as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule, its type is not particularly limited. Examples of the maleimide resin include (1) maleimide resins containing an aliphatic skeleton (preferably an aliphatic skeleton having 36 carbon atoms derived from dimer diamine) such as "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", "BMI-689" (all manufactured by Designer Molecules), "SLK6895-T90" (manufactured by Shin-Etsu Chemical Co., Ltd.); (2) maleimide resins containing an indane skeleton described in JP-A No. 2020-500211 of the Japan Institute of Invention and Innovation; (3) maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group such as "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), "BMI-80" (manufactured by KAI Chemical Co., Ltd.).

[0105] (As the (meth)acrylic resin, as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule, its type is not particularly limited, and it may be a monomer or an oligomer. Here, the term "(meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group. Examples of the methacrylic resin include, in addition to (meth)acrylate monomers, (meth)acrylic resins such as "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

[0106] As the styryl resin, as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule, its type is not particularly limited, and it may be a monomer or an oligomer. Examples of the styryl resin include, in addition to styrene monomer, styryl resins such as "OPE-2St", "OPE-2St 1200", "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0107] When the resin composition of the present invention contains the component (F), the content of the component (F) in the resin composition may be determined according to the properties required for the resin composition. However, when the resin component in the resin composition is 100% by mass, for example, it is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more or 0.6% by mass or more. The upper limit of the content of the component (F) is not particularly limited, but may be, for example, 10% by mass or less, 8% by mass or less, 6% by mass or less, etc.

[0108] <(G) Curing accelerator> The resin composition of the present invention may contain a curing accelerator as the component (G).

[0109] Examples of the component (G) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, peroxide-based curing accelerators, and the like. The curing accelerator may be used alone or in combination of two or more.

[0110] When the resin composition of the present invention contains the component (G), the content of the component (G) in the resin composition, when the resin component in the resin composition is 100% by mass, is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass or less or 1% by mass or less.

[0111] <Optional additive> The resin composition of the present invention may further contain optional additives. Such additives include, for example, radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as benton and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; 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-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic-based flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers, etc. The content of such additives may be determined according to the properties required for the resin composition.

[0112] <Organic solvent> The resin composition of the present invention may further contain an organic solvent as a volatile component. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The organic solvent may be used alone or in combination of two or more.

[0113] The resin composition of the present invention can be produced, for example, by adding the component (A-1), the component (B), and, if necessary, the component (A-2), the component (C), the component (D), the component (E), the component (F), the component (G), other additives, and an organic solvent to an arbitrary preparation container in an arbitrary order and / or partially or entirely simultaneously, and then mixing them. Also, during the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or throughout the process. Further, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring device such as a mixer or a shaking device to be uniformly dispersed. Also, defoaming may be performed under low-pressure conditions such as under vacuum simultaneously with stirring or shaking.

[0114] As described above, even when the resin composition of the present invention containing the component (A-1) adopts a specific composition that contributes to good dielectric properties, it can provide a cured product that exhibits good adhesion to a conductor layer when exposed to a high-temperature and high-humidity environment.

[0115] In one embodiment, the cured product of the resin composition of the present invention is characterized by a low dielectric tangent (Df). For example, when measured at 5.8 GHz and 23°C as described in the <Measurement of Dielectric Tangent> section to be described later, the dielectric tangent (Df) of the cured product of the resin composition of the present invention can preferably be 0.008 or less, 0.006 or less, 0.004 or less, 0.0038 or less, 0.0036 or less, 0.0034 or less, 0.0032 or less, or 0.003 or less.

[0116] In one embodiment, the cured product of the resin composition of the present invention is characterized by high adhesion to a conductor layer when exposed to a high-temperature and high-humidity environment. For example, when exposed to high-temperature and high-humidity conditions of 130°C and 85% RH for 100 hours as described in the <Measurement of Copper Foil Peel Strength after High-Temperature and High-Humidity Environment Test (HAST)> section to be described later, the adhesion strength to the conductor foil after exposure to the high-temperature and high-humidity conditions is preferably 0.4 kgf / cm or more, 0.42 kgf / cm or more, 0.44 kgf / cm or more, or 0.45 kgf / cm or more.

[0117] In one embodiment, the cured product of the resin composition of the present invention exhibits the characteristic of having high adhesion to the plated conductor layer. For example, when the plated conductor layer is formed as described in the <Measurement of Peel Strength of Plated Conductor Layer> section to be described later, the adhesion strength to the plated conductor layer is preferably 0.4 kgf / cm or more, 0.42 kgf / cm or more, 0.44 kgf / cm or more, or 0.45 kgf / cm or more.

[0118] As described above, even when the resin composition of the present invention adopts a specific composition that contributes to good dielectric properties, it can provide a cured product that exhibits good adhesion to the conductor layer when exposed to a high-temperature and high-humidity environment. Furthermore, according to the present invention, it has also been confirmed that the dielectric properties themselves, such as a lower dielectric tangent, are even better. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), and can be more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for interlayer insulating layer of printed wiring board). The resin composition of the present invention can also be suitably used when the printed wiring board is a component-embedded circuit board. The resin composition of the present invention can also be suitably used as a resin composition for forming an insulating layer of a redistribution substrate of a semiconductor package (resin composition for insulating layer of redistribution substrate). In the present invention, printed wiring boards and redistribution substrates are collectively referred to as "circuit boards", and therefore the resin composition of the present invention can be suitably used for the insulating layer of the circuit board.

[0119] The resin composition of the present invention can be widely used in applications where a resin composition is required, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, hole filling resins, encapsulating resins, component embedding resins, and the like.

[0120] [Sheet-like Laminated Material (Resin Sheet, Prepreg)] The resin composition of the present invention can be used as it is, or it may be used in the form of a sheet-like laminated material containing the resin composition.

[0121] As the sheet-like laminated material, the resin sheets and prepregs shown below are preferable.

[0122] In one embodiment, the resin sheet includes a support and a layer of a resin composition provided on the support (hereinafter simply referred to as "resin composition layer"), and the resin composition layer is formed from the resin composition of the present invention.

[0123] The thickness of the resin composition layer varies depending on the application, and may be appropriately determined according to the application. For example, from the viewpoint of thinning printed wiring boards and semiconductor packages, the thickness of the resin composition layer is preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, or 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may usually be 1 μm or more, 5 μm or more, etc.

[0124] Examples of the support include thermoplastic resin films, metal foils, and release papers, and thermoplastic resin films and metal foils are preferable. Therefore, in a preferred embodiment, the support is a thermoplastic resin film or a metal foil.

[0125] When using a thermoplastic resin film as the support, examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

[0126] When using a metal foil as the support, examples of the metal foil include, for example, copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0127] The support may be subjected to a mat treatment, a corona treatment, or an antistatic treatment on the surface that joins the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface that joins the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a release layer, a commercially available product may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc.

[0128] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferred, and a range of 10 μm to 60 μm is more preferred. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0129] When using a metal foil as the support, a metal foil with a support substrate in which a support substrate that can be peeled off is laminated on a thin metal foil may be used. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When using a metal foil with a support substrate as the support, the resin composition layer is provided on the metal foil.

[0130] In the metal foil with a support substrate, the material of the support substrate is not particularly limited, and examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, and the like. When using copper foil as the support substrate, it may be an electrolytic copper foil or a rolled copper foil. Further, the release layer is not particularly limited as long as the metal foil can be peeled from the support substrate, and examples thereof include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic film, and the like.

[0131] In the metal foil with a support substrate, as the material of the metal foil, for example, copper foil and copper alloy foil are preferable.

[0132] In the metal foil with a support substrate, the thickness of the support substrate is not particularly limited, but a range of 10 μm to 150 μm is preferable, and a range of 10 μm to 100 μm is more preferable. Further, the thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0133] In one embodiment, the resin sheet may further include an arbitrary layer as necessary. Examples of such an arbitrary layer include a protective film and the like provided on a surface of the resin composition layer that is not joined 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 the protective film, it is possible to suppress the adhesion of dust and the like and scratches on the surface of the resin composition layer.

[0134] The resin sheet can be produced, for example, by directly using a liquid resin composition or preparing a resin varnish in which the resin composition is dissolved in an organic solvent, applying this onto a support using a die coater or the like, and further drying to form a resin composition layer.

[0135] Examples of the organic solvent include the same ones as the organic solvents described as components of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0136] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but drying is carried out so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% to 60% by mass of the organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0137] The resin sheet can be wound up and stored in a roll shape. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0138] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

[0139] The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of thinning printed wiring boards and semiconductor chip packages, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10 μm or more.

[0140] The prepreg can be manufactured by known methods such as the hot melt method and the solvent method.

[0141] The thickness of the prepreg can be in the same range as the resin composition layer in the above-mentioned resin sheet.

[0142] The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board). The sheet-like laminated material of the present invention can also be suitably used for forming an insulating layer of a redistribution substrate of a semiconductor package (for the insulating layer of a redistribution substrate). That is, the sheet-like laminated material of the present invention can be suitably used as an insulating layer for a circuit board.

[0143] [Circuit board] An insulating layer of a circuit board can be formed using the resin composition of the present invention. The present invention also provides such a circuit board, that is, a circuit board including an insulating layer made of a cured product of the resin composition of the present invention.

[0144] [Printed wiring board] In one embodiment, the circuit board of the present invention is a printed wiring board.

[0145] A printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the above resin sheet. (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate (II) A step of curing (for example, thermally curing) the resin composition layer to form an insulating layer

[0146] The "inner layer substrate" used in step (I) is a member serving as the substrate of a printed wiring board. Examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Further, the substrate may have conductor layers on one or both of its surfaces, and these conductor layers may be pattern-processed. An inner layer substrate having conductor layers (circuits) formed on one or both surfaces of the substrate may be referred to as an "inner layer circuit board". Also, in the production of a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the "inner layer substrate" as referred to in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate incorporating components may be used.

[0147] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (such as a SUS roll). Note that the thermocompression bonding member may be pressed directly against the resin sheet, or may be pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate.

[0148] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination can preferably be carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

[0149] The lamination can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichco Materials Co., Ltd., a batch type vacuum pressure laminator, and the like.

[0150] After lamination, under normal pressure (atmospheric pressure), for example, by pressing a heat-bonding member from the support side, a smoothing process of the laminated resin sheet may be performed. The pressing conditions for the smoothing process can be the same as the heat-bonding conditions for the above lamination. The smoothing process can be performed by a commercially available laminator. Note that the lamination and the smoothing process may be continuously performed using the above-mentioned commercially available vacuum laminator.

[0151] The support may be removed between step (I) and step (II), or may be removed after step (II). Note that when a metal foil is used as the support, a conductor layer may be formed using the metal foil without peeling the support. Also, when a metal foil with a support substrate is used as the support, the support substrate (and the release layer) may be peeled off. And a conductor layer can be formed using the metal foil.

[0152] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer composed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions usually employed when forming an insulating layer of a printed wiring board may be used.

[0153] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, etc. In one embodiment, the curing temperature is preferably 140°C to 250°C, more preferably 150°C to 240°C, and still more preferably 180°C to 230°C. The curing time can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and still more preferably 15 minutes to 120 minutes.

[0154] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 140°C, preferably 60°C to 135°C, more preferably 70°C to 130°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes.

[0155] When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing printed wiring boards. When removing the support after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

[0156] In another embodiment, the printed wiring board of the present invention can be manufactured using the above-described prepreg. The manufacturing method is basically the same as the case of using a resin sheet.

[0157] Step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, a laser, a plasma, etc., according to the composition of the resin composition used for forming the insulating layer. The dimensions and shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0158] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), removal of smear (desmear) is also performed. The procedures and conditions for the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0159] The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution. Preferably, it is an alkaline solution, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Security P" and "Swelling Dip Security SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but for example, it can be performed by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0160] The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd.

[0161] Also, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferable, and examples of commercially available products include "Reduction Solution Security P" manufactured by Atotech Japan Co., Ltd.

[0162] The treatment with the neutralizing liquid can be performed by immersing the treated surface, which has been roughened with the oxidizing agent, in the neutralizing liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with the oxidizing agent in the neutralizing liquid at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0163] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on an insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single-metal layer or an alloy layer. Examples of the alloy layer include layers formed from 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, from the viewpoints of versatility, cost, ease of patterning, etc. of conductor layer formation, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single-metal layer of copper is even more preferred.

[0164] The conductor layer may have a single-layer structure or a multilayer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0165] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0166] In one embodiment, the conductor layer may be formed by plating. From the viewpoint of easy formation of fine wiring, it is preferably formed by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0167] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0168] In another embodiment, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably carried out 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 lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as the modified semi-additive method.

[0169] The metal foil can be manufactured by a known method such as an electrolytic method or a rolling method. Examples of commercially available metal foils include HLP foil, JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, 3EC-III foil, TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd., and the like.

[0170] Alternatively, as described above, when a metal foil or a metal foil with a support substrate is used as the support of the resin sheet, the conductor layer may be formed using the metal foil.

[0171] <Redistribution Substrate of Semiconductor Package> In one embodiment, the circuit board of the present invention is a redistribution substrate (redistribution layer) of a semiconductor package. Hereinafter, an explanation will be given in accordance with a method for manufacturing a semiconductor package.

[0172] The semiconductor package includes an insulating layer made of a cured product of the resin composition of the present invention as an insulating layer of the rewiring substrate. Note that the semiconductor package may include a sealing layer made of a cured product of the resin composition of the present invention.

[0173] The semiconductor package can be manufactured, for example, by a method including the following steps (1) to (6) using the resin composition and resin sheet of the present invention. The resin composition and resin sheet of the present invention may be used to form the rewiring formation layer (insulating layer for forming the rewiring substrate) in step (5) or the sealing layer in step (3). Hereinafter, an example of forming the rewiring formation layer and the sealing layer using the resin composition and resin sheet is shown. However, the technology for forming the rewiring formation layer and the sealing layer of the semiconductor package is known, and those skilled in the art can manufacture the semiconductor package according to the known technology using the resin composition and resin sheet of the present invention. (1) Step of laminating a temporary fixing film on a base material (2) Step of temporarily fixing a semiconductor chip on the temporary fixing film (3) Step of forming a sealing layer on the semiconductor chip (4) Step of peeling the base material and the temporary fixing film from the semiconductor chip (5) Step of forming a rewiring formation layer as an insulating layer on the surface of the base material and the temporary fixing film of the semiconductor chip from which they have been peeled, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0174] - Step (1) - The material used for the base material is not particularly limited. Examples of the base material include semiconductor wafers such as silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates impregnated with an epoxy resin or the like in glass fibers and subjected to thermosetting treatment (for example, FR-4 substrates); substrates made of bismaleimide triazine resin (BT resin), and the like.

[0175] The temporary fixing film can be peeled off from the semiconductor chip in step (4) and the material is not particularly limited as long as it can temporarily fix the semiconductor chip. Commercial products can be used as the temporary fixing film. Examples of commercial products include Rivar Alpha manufactured by Nitto Denko Corporation.

[0176] - Step (2)- The temporary fixing of the semiconductor chip can be performed using known devices such as a flip chip bonder or a die bonder. The layout and the number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production quantity of the target semiconductor package, etc. For example, they can be temporarily fixed in a matrix arrangement with multiple rows and multiple columns.

[0177] - Step (3)- The resin composition layer of the resin sheet of the present invention is laminated on the semiconductor chip, or the resin composition of the present invention is applied on the semiconductor chip and cured (for example, thermally cured) to form a sealing layer.

[0178] For example, the lamination of the semiconductor chip and the resin sheet can be performed by removing the protective film of the resin sheet and then thermocompression bonding the resin sheet to the semiconductor chip from the support side. Examples of the member for thermocompression bonding the resin sheet to the semiconductor chip (hereinafter also referred to as "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). It should be noted that it is preferable to press through an elastic material such as a heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the semiconductor chip instead of directly pressing the thermocompression bonding member against the resin sheet. The lamination of the semiconductor chip and the resin sheet may be performed by a vacuum lamination method, and the lamination conditions are the same as the lamination conditions described in relation to the manufacturing method of the printed wiring board, and the preferable range is also the same.

[0179] After lamination, the resin composition is thermally cured to form a sealing layer. The thermal curing conditions are the same as the thermal curing conditions described in relation to the manufacturing method of the printed wiring board.

[0180] The support of the resin sheet may be peeled off after laminating and thermosetting the resin sheet on the semiconductor chip, or the support may be peeled off before laminating the resin sheet on the semiconductor chip.

[0181] When forming the sealing layer by applying the resin composition of the present invention, the coating conditions are the same as those for forming the resin composition layer described in relation to the resin sheet of the present invention, and the preferred ranges are also the same.

[0182] - Step (4) - The method of peeling the base material and the temporary fixing film can be appropriately changed according to the material of the temporary fixing film, etc. For example, methods such as heating and foaming (or expanding) the temporary fixing film to peel it off, and irradiating ultraviolet rays from the base material side to reduce the adhesive force of the temporary fixing film and peel it off can be mentioned.

[0183] In the method of heating and foaming (or expanding) the temporary fixing film to peel it off, the heating conditions are usually 100 to 250 °C for 1 to 90 seconds or 5 to 15 minutes. Also, in the method of irradiating ultraviolet rays from the base material side to reduce the adhesive force of the temporary fixing film and peel it off, the irradiation amount of ultraviolet rays is usually 10 mJ / cm 2 ~1000 mJ / cm 2 is.

[0184] - Step (5) - The resin composition and resin sheet of the present invention are used to form a redistribution formation layer (insulating layer of the redistribution substrate).

[0185] After forming the redistribution formation layer, in order to layer-connect the semiconductor chip and the conductor layer described later, via holes may be formed in the redistribution formation layer. The via holes may be formed by a known method according to the material of the redistribution formation layer.

[0186] - Step (6) - The formation of the conductor layer on the rewiring formation layer may be carried out in the same manner as in step (V) described in relation to the method for manufacturing a printed wiring board. Note that steps (5) and (6) may be repeated to alternately stack (build up) the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer).

[0187] In manufacturing a semiconductor package, (7) a step of forming a solder resist layer on the conductor layer (rewiring layer), (8) a step of forming bumps, and (9) a step of dicing a plurality of semiconductor packages into individual semiconductor packages may be further carried out. These steps may be carried out according to various methods known to those skilled in the art used for manufacturing semiconductor packages.

[0188] Even when a composition that contributes to good dielectric properties is adopted, by forming a rewiring formation layer (insulating layer) using the resin composition and resin sheet of the present invention that can provide a cured product having good adhesion to a conductor layer when exposed to a high-temperature and high-humidity environment, a semiconductor package with extremely low transmission loss can be realized regardless of whether it is a Fan-In type package or a Fan-Out type package, without concern about a decrease in conductor adhesion. In one embodiment, the semiconductor package of the present invention is a Fan-Out type package. The resin composition and resin sheet of the present invention can be applied regardless of whether it is a Fan-Out panel level package (FOPLP) or a Fan-Out wafer level package (FOWLP). In one embodiment, the semiconductor package of the present invention is a Fan-Out panel level package (FOPLP) or a Fan-Out wafer level package (FOWLP).

[0189] [Semiconductor device] The semiconductor device of the present invention includes a layer made of a cured product of the resin composition layer of the present invention. The semiconductor device of the present invention can be manufactured using the circuit board of the present invention.

[0190] Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes).

Examples

[0191] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "mass %", respectively, unless otherwise specified.

[0192] <Synthesis Example 1: Synthesis of Epoxy Resin A> 100 g of 2,2-bis(4-hydroxy-3-methylphenyl)propane was dissolved in 1050 g of epichlorohydrin, 0.25 g of benzyltriethylammonium chloride was added, and 90 g of a 48% aqueous sodium hydroxide solution was added dropwise at 70 °C under reduced pressure over 5 hours. The generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the dropwise addition, the reaction was continued for 2 hours, and then the generated salt was removed by filtration. After further washing with water, epichlorohydrin was distilled off. The obtained epoxy resin was dissolved in 400 g of methyl isobutyl ketone, and 10 g of a 10% aqueous sodium hydroxide solution was added at 85 °C and reacted for 2 hours. After the reaction, filtration and washing with water were carried out, and methyl isobutyl ketone was distilled off to obtain 129 g of a light yellow liquid epoxy resin A. The epoxy resin A has a structure represented by the following formula (A) (where n is 0 to 5), and its epoxy equivalent was 193.

[0193]

Chemical formula

[0194] <Synthesis Example 2: Synthesis of Epoxy Resin B> Instead of 100 g of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 90 g of 4,4'-methylenebis(2-methylphenol) was used, and 145 g of a single yellow liquid epoxy resin B was obtained in the same procedure as in Synthesis Example 1. The epoxy resin B has a structure represented by the following formula (B) (where n is 0 to 5), and its epoxy group equivalent was 184.

[0195]

Chemical formula

[0196] <Synthesis Example 3: Synthesis of Epoxy Resin C> Instead of 100 g of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 116 g of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane was used, and 155 g of a single yellow solid epoxy resin C was obtained in the same procedure as in Synthesis Example 1. The epoxy resin C has a structure represented by the following formula (C) (where n is 0 to 5), and its epoxy group equivalent was 220.

[0197]

Chemical formula

[0198] [Example 1] (1) Preparation of Resin Composition 10 parts of the epoxy resin A synthesized in Synthesis Example 1 and 20 parts of a biphenyl-type epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd., epoxy group equivalent of about 277) were dissolved by heating with stirring in 20 parts of toluene and 20 parts of MEK. After cooling the obtained solution to room temperature, 65 parts of an active ester resin ("HP-B-8151-62T" manufactured by DIC Corporation, active group equivalent 238, toluene solution with a solid content of 62% by mass), 6 parts of a triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%), 10 parts of a phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation, MEK / cyclohexanone mixed solution with a solid content of 30%), 5 parts of a curing accelerator (MEK solution with a solid content of 10% of "1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.), and 210 parts of an inorganic filler (spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) were mixed and uniformly dispersed with a high-speed rotary mixer to obtain a resin composition.

[0199] (2) Manufacture of resin sheet As a support, a polyethylene terephthalate film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130°C) having a release treatment on the surface with an alkyd resin-based release agent ("AL-5" manufactured by Lintec Corporation) was prepared. On this support, the resin composition was uniformly applied with a die coater so that the thickness of the resin composition layer after drying would be 40 μm, and dried at 70°C to 100°C for 3 minutes to form a resin composition layer on the support. Next, the rough surface of a polypropylene film ("Alpha MA-411" manufactured by Oji Fibrex Co., Ltd., thickness 15 μm) was laminated as a protective film on the surface of the resin composition layer that was not joined to the support. Thereby, a resin sheet having a layer structure of support / resin composition layer / protective film was obtained.

[0200] [Example 2] A resin composition was prepared and a resin sheet was obtained in the same manner as in Example 1, except that 6 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Inc., active group equivalent of about 216, toluene solution with a solid content of 50%) was further added.

[0201] [Example 3] A resin composition was prepared in the same manner as in Example 1 except that 3 parts of a bismaleimide resin (“BMI-689” manufactured by Designer Molecules, maleimide group equivalent weight of about 345) was further added to obtain a resin sheet.

[0202] [Example 4] A resin composition was prepared in the same manner as in Example 1 except that 3 parts of a bismaleimide resin (“BMI-1500” manufactured by Designer Molecules, maleimide group equivalent weight of about 750) was further added to obtain a resin sheet.

[0203] [Example 5] A resin composition was prepared in the same manner as in Example 1 except that 4.3 parts of a MEK solution (solid content: 70% by mass) of a maleimide resin (hereinafter also referred to as “maleimide resin C”) synthesized by the method described in Synthesis Example 1 of JP-A No. 2020-500211 of the Japan Institute of Invention and Innovation was further added to obtain a resin sheet.

[0204] [Example 6] (1) Preparation of resin composition 10 parts of the epoxy resin B synthesized in Synthesis Example 2 and 20 parts of a biphenyl-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "NC3000", epoxy equivalent weight of about 277) were dissolved by heating with stirring in 20 parts of toluene and 20 parts of MEK. After cooling the obtained solution to room temperature, 65 parts of an active ester resin (manufactured by DIC Corporation, "HP-B-8151-62T", active group equivalent weight of 238, toluene solution with a solid content of 62% by mass), 6 parts of a triazine skeleton-containing phenolic curing agent (manufactured by DIC Corporation, "LA-3018-50P", hydroxyl equivalent weight of about 151, 2-methoxypropanol solution with a solid content of 50%), 10 parts of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX6954BH30", MEK / cyclohexanone mixed solution with a solid content of 30%), 6 parts of a carbodiimide-based curing agent (manufactured by Nisshinbo Chemical Inc., "V-03", active group equivalent weight of about 216, toluene solution with a solid content of 50%), 3 parts of a bismaleimide resin (manufactured by Designer Molecules, "BMI-1500", maleimide group equivalent weight of about 750), 5 parts of a curing accelerator (MEK solution with a solid content of 10% of "1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.), and 210 parts of an inorganic filler (spherical silica (manufactured by Admatechs Co., Ltd., "SO-C2", average particle size of 0.5 μm) surface-treated with an amine-based silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573")) were mixed and uniformly dispersed with a high-speed rotary mixer to obtain a resin composition.

[0205] (2) Production of resin sheet Using the resin composition prepared in (1) above, a resin sheet was produced in the same manner as in Example 1.

[0206] [Example 7] A resin composition was prepared in the same manner as in Example 2, except that 10 parts of the epoxy resin C synthesized in Synthesis Example 3 was used instead of 10 parts of the epoxy resin A, and a resin sheet was obtained.

[0207] [Example 8] Instead of 65 parts of an active ester resin (toluene solution of "HP - B - 8151 - 62T" manufactured by DIC, active group equivalent 238, solid content 62% by mass), 62 parts of an active ester resin (toluene solution of "HPC - 8000 - 65T" manufactured by DIC, active group equivalent about 223 g, solid content 65% by mass) were used, and a resin composition was prepared in the same manner as in Example 4 to obtain a resin sheet.

[0208] [Example 9] (1) Preparation of resin composition 10 parts of epoxy resin A synthesized in Synthesis Example 1 and 20 parts of a biphenyl - type epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd., epoxy group equivalent about 277) were dissolved by heating with stirring in 20 parts of toluene and 20 parts of MEK. After the obtained solution was cooled to room temperature, 62 parts of an active ester resin (toluene solution of "HPC - 8000 - 65T" manufactured by DIC, active group equivalent about 223 g, solid content 65% by mass), 6 parts of a triazine - skeleton - containing phenolic curing agent ("LA - 3018 - 50P" manufactured by DIC, hydroxyl group equivalent about 151, 2 - methoxypropanol solution with solid content 50%), 50 parts of a phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation, MEK - cyclohexanone mixed solution with solid content 30%), 5 parts of a curing accelerator (MEK solution with 10% solid content of "1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.), and 105 parts of an inorganic filler (spherical silica (average particle size 0.3 μm, specific surface area 30.7 m 2 / g, "UFP - 30" manufactured by Denka Co., Ltd.) surface - treated with a phenylaminosilane - based coupling agent ("KBM573" manufactured by Shin - Etsu Chemical Co., Ltd.) were mixed and uniformly dispersed with a high - speed rotating mixer to obtain a resin composition.

[0209] (2) Manufacture of resin sheet Using the resin composition prepared in (1) above, a resin sheet was manufactured in the same manner as in Example 1.

[0210] [Example 10] (1) Preparation of resin composition 30 parts of the epoxy resin A synthesized in Synthesis Example 1 and 10 parts of a biphenyl-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "NC3000", epoxy group equivalent of about 277) were dissolved by heating with stirring in 20 parts of toluene and 20 parts of MEK. After cooling the resulting solution to room temperature, 65 parts of an active ester resin (manufactured by DIC Corporation, "HP-B-8151-62T", active group equivalent of 238, toluene solution with a solid content of 62% by mass), 6 parts of a triazine skeleton-containing phenolic curing agent (manufactured by DIC Corporation, "LA-3018-50P", hydroxyl group equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%), 6 parts of a carbodiimide-based curing agent (manufactured by Nisshinbo Chemical Co., Ltd., "V-03", active group equivalent of about 216, toluene solution with a solid content of 50%), 16.7 parts of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX6954BH30", MEK / cyclohexanone mixed solution with a solid content of 30%), 5 parts of a curing accelerator (MEK solution with a solid content of 10% of "1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.), and 105 parts of an inorganic filler (spherical silica (average particle size 0.3 μm, specific surface area 30.7 m 2 / g, manufactured by Denka Co., Ltd., "UFP-30") surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") were mixed and uniformly dispersed with a high-speed rotary mixer to obtain a resin composition.

[0211] (2) Production of resin sheet Using the resin composition prepared in (1) above, a resin sheet was produced in the same manner as in Example 1.

[0212] [Comparative Example 1] A resin composition was prepared and a resin sheet was obtained in the same manner as in Example 1, except that 10 parts of a bisphenol-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, "828US", epoxy group equivalent of about 188) was used instead of 10 parts of epoxy resin A.

[0213] [Comparative Example 2] A resin composition was prepared and a resin sheet was obtained in the same manner as in Example 1, except that 10 parts of a bixylenol-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX4000HK", epoxy group equivalent of about 185) was used instead of 10 parts of epoxy resin A.

[0214] [Comparative Example 3] A resin composition was prepared in the same manner as in Example 9, except that 10 parts of a bisphenol type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy group equivalent weight of about 188) was used instead of 10 parts of epoxy resin A, and a resin sheet was obtained.

[0215] <Measurement of average particle size of inorganic filler> 100 mg of an inorganic filler, 0.1 g of a dispersant ("SN9228" manufactured by San Nopco), and 10 g of methyl ethyl ketone were weighed into a vial and dispersed by ultrasonic waves for 10 minutes. Using a laser diffraction particle size distribution measuring device ("LA-960" manufactured by Horiba, Ltd.), with the wavelength of the light source used being blue and red, the particle size distribution based on volume was measured by the flow cell method, and the average particle size was calculated as the median diameter from the obtained particle size distribution.

[0216] <Measurement of dielectric loss tangent> The protective film was peeled off from the resin sheets obtained in the examples and comparative examples, heated at 200 °C for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The obtained cured product was cut into test pieces with a width of 2 mm and a length of 80 mm. For the test pieces, the dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C by the cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies. Measurements were performed on three test pieces, and the average value was calculated.

[0217] <Measurement of peel strength of plated conductor layer> (1) Preparation of inner layer substrate Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness of 18 μm, substrate thickness of 0.8 mm, "R1515A" manufactured by Panasonic) with an inner layer circuit formed were etched with a micro-etching agent ("CZ8101" manufactured by Meck) by 1 μm to perform roughening treatment of the copper surface.

[0218] (2) Lamination of resin sheet The protective film was peeled off from the resin sheets obtained in the examples and comparative examples to expose the resin composition layer. Using a batch-type vacuum pressure laminator (manufactured by Nippon Materials Co., Ltd., 2-stage build-up laminator "CVP700"), the resin composition layer was laminated on both sides of the inner layer substrate so that it was in contact with the inner layer substrate. Lamination was carried out by reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then pressure-bonding at 120 °C and a pressure of 0.74 MPa for 30 seconds. Subsequently, heat pressing was performed at 100 °C and a pressure of 0.5 MPa for 60 seconds to smooth it.

[0219] (3) Thermal curing of the resin composition layer Thereafter, the inner layer substrate with the resin sheet laminated thereon was put into an oven at 130 °C and heated for 30 minutes, and then transferred to an oven at 180 °C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Thereafter, the support was peeled off to obtain a cured substrate having a structure of insulating layer / inner layer substrate / insulating layer.

[0220] (4) Roughening treatment The cured substrate was subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out. (Wet desmear treatment) The cured substrate was immersed in a swelling solution (manufactured by Atotech Japan Co., Ltd. "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 °C for 5 minutes, then immersed in an oxidizing agent solution (manufactured by Atotech Japan Co., Ltd. "Concentrate Compact CP", an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 °C for 15 minutes, and finally immersed in a neutralizing solution (manufactured by Atotech Japan Co., Ltd. "Reduction Solution Securigant P", an aqueous sulfuric acid solution) at 40 °C for 5 minutes. Thereafter, it was dried at 80 °C for 15 minutes. The obtained substrate is referred to as a roughened substrate.

[0221] (5) Formation of the conductor layer A conductor layer was formed on the surface of the roughened substrate according to the semi-additive method. That is, the roughened substrate was immersed in an electroless plating solution containing PdCl2 at 40 °C for 5 minutes, and then immersed in an electroless copper plating solution at 25 °C for 20 minutes. After annealing by heating at 150 °C for 30 minutes, an etching resist was formed, and patterning was performed by etching. Then, electrolytic copper sulfate plating was performed to form a conductor layer with a thickness of 30 μm, and annealing treatment was performed at 200 °C for 60 minutes. The obtained substrate is referred to as evaluation substrate A.

[0222] (6) Measurement of peel strength of plated conductor layer The measurement of the peel strength of the plated conductor layer was carried out in accordance with Japanese Industrial Standard (JIS C6481). Specifically, a cut was made in a 10 mm wide and 100 mm long portion of the conductor layer of evaluation substrate A, one end of this was peeled off and grasped with a gripping tool, and the load (kgf / cm) when peeling 35 mm vertically at a speed of 50 mm / min at room temperature was measured. A tensile testing machine ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[0223] <Measurement of copper foil peel strength after high-temperature and high-humidity environment test (HAST)> (1) Substrate treatment of copper foil The shiny surface of "3EC-III" (electrolytic copper foil, 35 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. was etched with a micro-etching agent ("CZ8101" manufactured by Meck) by 1 μm to perform roughening treatment of the copper surface, and then rust prevention treatment (CL8300) was performed. Further, heat treatment was performed in an oven at 130 °C for 30 minutes. The obtained copper foil is called CZ copper foil.

[0224] (2) Preparation of inner layer substrate Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, "R1515A" manufactured by Panasonic) on which an inner layer circuit was formed were etched with a micro-etching agent ("CZ8101" manufactured by Meck) by 1 μm to perform roughening treatment of the copper surface.

[0225] (3) Fabrication of evaluation substrate The protective film was peeled off from the resin sheets obtained in the examples and comparative examples to expose the resin composition layer. Using a batch-type vacuum pressure laminator (manufactured by Nichco Materials Co., Ltd., two-stage build-up laminator "CVP700"), it was laminated on both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. Lamination was carried out by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then crimping at 120 °C and a pressure of 0.74 MPa for 30 seconds. Subsequently, it was heat-pressed at 100 °C and a pressure of 0.5 MPa for 60 seconds to smooth it. After smoothing, the support was peeled off. The treated surface of the CZ copper foil was laminated on the exposed resin composition layer under the same conditions as above. Then, an evaluation substrate B having a structure of CZ copper foil / insulating layer / inner layer substrate / insulating layer / CZ copper foil was produced by curing the resin composition layer under curing conditions of 200 °C for 90 minutes to form an insulating layer.

[0226] (4) Measurement of copper foil peel strength after HAST Regarding the obtained evaluation substrate B, a high-temperature and high-humidity environmental test was carried out for 100 hours under the conditions of 130 °C and 85% RH using a highly accelerated life test device ("PM422" manufactured by Kusumoto Chemical Co., Ltd.). Then, in the same manner as when measuring the peel strength of the plated conductor layer described above, the peel strength of the copper foil was measured in accordance with JIS C6481. That is, one end of the copper foil was peeled off and grasped with a gripping tool (manufactured by T.S.E. Co., Ltd., auto-comb type testing machine, "AC-50C-SL"), and using an Instron universal testing machine, the load (kgf / cm) when peeling 35 mm vertically at a speed of 50 mm / min at room temperature was measured.

[0227] The results of Examples 1 to 10 and Comparative Examples 1 to 3 are shown in Table 1.

[0228]

Table 1

Claims

1. Contains an epoxy resin and an active ester resin, The epoxy resin includes an epoxy resin represented by the following formula (1) and other epoxy resins: A resin composition, wherein the mass ratio of the active ester resin to the epoxy resin [active ester resin / epoxy resin] is 1.2 or more. 【Chemical 1】 (In formula (1), R １ each independently represents a monovalent aliphatic group, L each independently represents a single bond or a divalent linking group; R Ｓ each independently represents a halogen atom, an alkoxy group, or an aryl group; m's each independently represent an integer of 0 to 3; n represents an integer of 0 to 5.

2. The epoxy resin is represented by the following formula (1), and the active ester resin is included, and the thermoplastic resin is included, A resin composition, wherein the mass ratio of the active ester resin to the epoxy resin represented by formula (1) [active ester resin / epoxy resin represented by formula (1)] is 1.2 or more. 【Chemistry 2】 (In formula (1), R １ each independently represents a monovalent aliphatic group, L each independently represents a single bond or a divalent linking group; R Ｓ each independently represents a halogen atom, an alkoxy group, or an aryl group; m's each independently represent an integer of 0 to 3; n represents an integer of 0 to 5.

3. A resin composition as described in claim 2, wherein the thermoplastic resin comprises at least one selected from the group consisting of phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin.

4. A resin composition as described in claim 2, wherein the content of thermoplastic resin is 0.1 mass% or more and 20 mass% or less, when the resin component in the resin composition is 100 mass%.

5. The epoxy resin includes an epoxy resin, an active ester resin, and a maleimide resin represented by the following formula (1): A resin composition, wherein the mass ratio of the active ester resin to the epoxy resin represented by formula (1) [active ester resin / epoxy resin represented by formula (1)] is 1.2 or more. 【Chemistry 3】 (In formula (1), R １ each independently represents a monovalent aliphatic group, L each independently represents a single bond or a divalent linking group; R Ｓ each independently represents a halogen atom, an alkoxy group, or an aryl group; m's each independently represent an integer of 0 to 3; n represents an integer of 0 to 5.

6. A resin composition as described in claim 5, wherein the content of maleimide resin is 0.1 mass% or more and 10 mass% or less, when the resin component in the resin composition is 100 mass%.

7. The resin composition according to claim 1, wherein each R 1 independently represents an alkyl group.

8. The resin composition according to claim 1, wherein each R 1 independently represents an alkyl group having 1 to 6 carbon atoms.

9. A resin composition described in any one of claims 1 to 6, wherein L each independently represents a divalent aliphatic group.

10. The resin composition according to claim 1, wherein L each independently represents a divalent group selected from an alkylene group, a cycloalkylene group, or a combination thereof.

11. A resin composition described in any one of claims 1 to 6, further containing an inorganic filler.

12. A resin composition as described in claim 11, wherein the content of inorganic filler is 40 mass% or more when the non-volatile components in the resin composition are 100 mass%.

13. A resin composition described in any one of claims 1 to 6, wherein when the resin component in the resin composition is 100 mass%, the content of the epoxy resin represented by formula (1) is 1 mass% or more and 45 mass% or less.

14. A resin composition described in any one of claims 1 to 6, which is for use as an insulating layer in a circuit board.

15. A resin sheet comprising a support and a layer of the resin composition described in any one of claims 1 to 6 provided on the support.

16. A resin sheet as described in claim 15, wherein the support is a thermoplastic resin film or a metal foil.

17. A cured product of the resin composition described in any one of claims 1 to 6.

18. A circuit board comprising an insulating layer made of a cured product of the resin composition described in any one of claims 1 to 6.

19. A semiconductor device comprising the circuit board described in claim 18.

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