Resin composition

Abstract

The present invention addresses the problem of providing a resin composition with which it is possible to obtain a cured product having a good balance of flame retardancy, heat resistance, and high elongation, said resin composition having good resin fluidity before curing. [Solution] A resin composition comprising (A) a bifunctional or higher epoxy resin, (B) a curing agent, and (C) a flame retardant, the component (B) comprising (B-1) a benzoxazine-based curing agent, the component (C) comprising (C-1) a phosphazene compound having a phenolic hydroxyl group, and the content of the component (B) in the resin composition being 100% by mass. The phosphorus content is 0.6 mass% or more.

Description

Technical Field

[0001] This invention relates to resin compositions. It further relates to resin sheets, circuit boards, and semiconductor devices obtained using the resin compositions. Background Technology

[0002] In recent years, the miniaturization and high performance of electronic devices have continued to develop. In semiconductor packaging substrates, the stacked layers formed by insulating and conductive layers have become multilayered, and the miniaturization and high density of wiring have become a requirement. Consequently, the requirements for thinner semiconductor packaging have also increased, with the thickness of the core substrate needing to be below 100μm, and further, thin packaging such as coreless structures has become required.

[0003] For example, in applications such as automotive semiconductor packaging and semiconductor packaging for various components that utilize thin-film packaging, excellent durability against large temperature variations and resulting high reliability are required. Therefore, achieving high elongation and heat resistance of the insulating layer formed by the cured resin composition becomes important. Furthermore, with the increasing multilayering of thin-film packaging, ensuring flame retardancy is particularly necessary. In such products utilizing thin-film packaging, excellent reliability (heat resistance, high elongation) and flame retardancy are especially required.

[0004] To impart flame retardancy to resin compositions, flame retardants are typically included in the resin composition. As flame retardants, resin compositions using flame-retardant organic fillers with a phosphaphenanthrene skeleton, magnesium hydroxide, organosilicon fillers, phosphazene compounds, etc., have been reported to date (Patent Documents 1-5). Furthermore, from the viewpoint of easily imparting flame retardancy without hindering electrical properties and thermosetting resins, non-reactive solvent-soluble flame retardants have also been investigated (Patent Document 6).

[0005] In order to impart heat resistance to the resin composition, a formulation that contains a tetrafunctional epoxy resin was also investigated (Patent Document 7).

[0006] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2023-100866 Patent Document 2: Japanese Patent Application Publication No. 2023-024510 Patent Document 3: Japanese Patent Application Publication No. 2020-063392 Patent Document 4: Japanese Patent Application Publication No. 2022-179517 Patent Document 5: Japanese Patent Application Publication No. 2017-179013 Patent Document 6: Japanese Patent No. 7396443 Patent document 7: Japanese Patent No. 7060478. Summary of the Invention

[0007] The problem that the invention aims to solve To impart flame retardancy to resin compositions, flame retardants such as phenanthrene-based flame-retardant organic fillers and magnesium hydroxide, which have been studied to date, are used. However, since these are amorphous fillers, it is difficult to improve the elongation of the resin composition. Furthermore, if silicone fillers are used as flame retardants, the elastic modulus of the resin composition decreases. If non-reactive solvent-soluble flame retardants are used, the heat resistance (glass transition temperature Tg) decreases due to the lack of reactive groups. In subsequent reliability evaluations (thermal cycling tests), the embrittlement of the cured product accompanying the phase transition at the glass transition temperature (Tg) becomes a concern.

[0008] Furthermore, if a tetrafunctional epoxy resin is incorporated into the resin composition, while heat resistance can be guaranteed, it is difficult to maintain the elongation of the resin composition.

[0009] Therefore, in thin semiconductor packages with a core substrate thickness of less than 100μm, or even in thin semiconductor packages without a core structure, there is a strong requirement to meet both high reliability (elongation, heat resistance) and high flame retardancy. However, it is difficult to simultaneously achieve both high reliability (elongation, heat resistance) and high flame retardancy.

[0010] The present invention was made in view of the above-mentioned problems, and its object is to provide a resin composition that can ensure high flame retardancy while also having heat resistance and high elongation, a resin sheet containing the resin composition, a circuit board containing an insulating layer formed from the cured resin composition, and a semiconductor device.

[0011] Methods for solving problems In order to solve the aforementioned problems, the inventors conducted in-depth research and found that a resin composition containing a benzoxazine curing agent and a specific phosphazene compound as a flame retardant can solve the aforementioned problems, thus completing the present invention.

[0012] That is, the present invention includes the following inventions.

[0013] [1] A resin composition comprising (A) an epoxy resin with two or more functional groups, (B) a curing agent and (C) a flame retardant, wherein, (B) Components include (B-1) benzoxazine-based curing agent. (C) Component contains a phosphazene compound with a phenolic hydroxyl group (C-1). When the resin component in the resin composition is set to 100% by mass, the phosphorus content is 0.6% by mass or more.

[0014] [2] The resin composition according to [1], wherein component (A) comprises a biphenyl-type epoxy resin.

[0015] [3] The resin composition according to [1] or [2], wherein component (A) comprises an epoxy resin represented by formula (A1) below. [Chemistry 1] In equation (A1), R a1 R a2 and R a3 Each independently represents an alkylene group, an oxygen atom, or an alkylene group that may have substituents, R. a4 R indicates an alkyl or hydrogen atom that may have substituents. a5 This indicates an alkylene group that may have substituents.

[0016] [4] The resin composition according to any one of [1] to [3], wherein when the resin component in the resin composition is set to 100% by mass, the content of component (B-1) is 2% by mass or more.

[0017] [5] The resin composition according to any one of [1] to [4], wherein component (B) further comprises (B-2) other curing agent, wherein component (B-2) is a compound selected from active ester curing agents, phenol curing agents, cyanate ester curing agents and carbodiimide curing agents.

[0018] [6] The resin composition according to any one of [1] to [5] further comprises (D) a polymer component.

[0019] [7] The resin composition according to [6], wherein the weight average molecular weight of component (D) is 10,000 or more.

[0020] [8] According to the resin composition of [6] or [7], wherein when the resin component in the resin composition is set to 100% by mass, the content of component (D) is 1 to 25% by mass.

[0021] [9] The resin composition according to any one of [1] to [8] further comprises (E) an inorganic filler material.

[0022]

[10] The resin composition according to any one of [1] to [9] further comprises (F) a curing accelerator.

[0023]

[11] The resin composition according to any one of [1] to

[10] is used to form an insulating layer.

[0024]

[12] A resin sheet comprising a support and a resin composition layer comprising any one of the resin compositions described in [1] to

[11] disposed on the support.

[0025]

[13] The resin sheet according to

[12] , wherein the thickness of the resin composition layer is less than 100 μm.

[0026]

[14] A circuit board comprising an insulating layer formed from a cured resin composition of any one of [1] to

[11] .

[0027]

[15] The circuit board according to

[14] has a core substrate with a thickness of less than 100 μm, or does not have a core substrate.

[0028]

[16] A semiconductor device comprising the circuit board described in

[14] or

[15] .

[0029]

[17] The resin composition according to any one of [1] to

[11] is used to form an insulating layer of a circuit board having a core substrate with a thickness of less than 100 μm, or not having a core substrate.

[0030] Invention Effects According to the present invention, a resin composition capable of producing a cured product that has both high flame retardancy and heat resistance and high elongation is provided; a resin sheet comprising the resin composition; a circuit board and a semiconductor device comprising an insulating layer formed from the cured product of the resin composition. Detailed Implementation

[0031] The present invention will now be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be implemented in any way that is modified without departing from the scope of the claims and their equivalents.

[0032] [Resin Composition] The resin composition of the present invention is a resin composition comprising (A) an epoxy resin with two or more functional groups, (B) a curing agent and (C) a flame retardant, wherein, (B) Components include (B-1) benzoxazine-based curing agent. (C) Component contains (C-1) a phosphazene compound with phenolic hydroxyl groups.

[0033] The resin composition may further include, as needed, other curing agents (B-2) besides component (B-1) as curing agent, flame retardants besides component (C-1) as component (C), and may also include (D) polymer components, (E) inorganic fillers, (F) curing accelerators, and (G) other components, etc. The components contained in the resin composition are described in detail below.

[0034] (A) Epoxy resin The resin composition of the present invention comprises an epoxy resin with two or more functions as component (A).

[0035] Examples of components (A) include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol phenolic varnish type epoxy resin, phenol phenolic varnish type epoxy resin, tert-butylcatechol type epoxy resin, naphthol type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, cresol phenolic varnish type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spirocyclic rings, cyclohexanediol type epoxy resin, naphthyl ether type epoxy resin, tris(hydroxymethyl) type epoxy resin, tetraphenylethane type epoxy resin, and epoxy resin having a trifunctional aromatic structure.

[0036] When a biphenyl-type epoxy resin is included as component (A), the resulting resin composition exhibits excellent resin flowability, excellent thermosetting properties during curing, and excellent elongation as a cured product, and is therefore preferred.

[0037] Here, biphenyl-type epoxy resin refers to a divalent structure obtained by removing two hydroxyl groups from biphenyl phenol, which may have substituents; that is, an epoxy resin containing at least a portion of biphenyl. The substituents that can be present in the biphenyl group are not particularly limited as long as they achieve the effects of the present invention, and examples include halogen atoms, alkyl groups, alkenyl groups, cycloalkyl groups, alkoxy groups, cycloalkyloxy groups, aryl groups, aryloxy groups, arylalkyl groups, arylalkoxy groups, and monovalent heterocyclic groups. Examples of halogen atoms used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The alkyl group used as a substituent can be either linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8. The alkenyl group used as a substituent can be either linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 12, more preferably 2 to 10, and even more preferably 2 to 8. The number of carbon atoms in the cycloalkyl group used as a substituent is preferably 3 to 12, more preferably 3 to 10. The alkoxy group used as a substituent can be either straight-chain or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8. The number of carbon atoms in the cycloalkoxy group used as a substituent is preferably 3 to 12, more preferably 3 to 10. The number of carbon atoms in the aryl group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms in the aryloxy group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms in the arylalkyl group used as a substituent is preferably 7 to 15, more preferably 7 to 11. The number of carbon atoms in 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 the heterocycle of a heterocyclic compound. The number of carbon atoms in the monovalent heterocyclic group is preferably 3 to 15, more preferably 3 to 9. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl). From the viewpoint of further enjoying the effects of the present invention, the substituents that may be present in the biphenyl group are preferably selected from one or more of halogen atoms, alkyl groups, alkoxy groups, aryl groups, and aryloxy groups, more preferably selected from one or more of alkyl groups and aryl groups. When the biphenyl group has substituents, from the viewpoint of further enjoying the effects of the present invention, the number of substituents relative to each biphenyl structure is preferably one or more, more preferably two or more, three or more, or four or more, and the upper limit is preferably six or less. The (A-1) component preferably includes one or more of a disubstituted biphenyl having two substituents per biphenyl structure, a trisubstituted biphenyl having three substituents per biphenyl structure, and a tetrasubstituted biphenyl having four substituents per biphenyl structure.

[0038] (A) The biphenyl-type epoxy resin in component (A) may contain structures other than biphenyl. For example, in addition to the biphenyl, it may contain alkylene and / or arylene groups. Therefore, the biphenyl-type epoxy resin in component (A) may be a biphenyl phenolic varnish-type epoxy resin that contains not only biphenyls that may have substituents but also biphenyl aralkyl-type epoxy resins with a divalent structure composed of alkylene groups, or it may be a biphenyl aralkyl-type epoxy resin that contains biphenyls that may have substituents and biphenyl aralkyl-type epoxy resins with a divalent structure composed of alkylene groups and arylene groups.

[0039] Furthermore, as component (A), if it contains an epoxy resin with a trifunctional aromatic structure as shown in formula (A1), the minimum melt viscosity of the resulting resin composition can be reduced, and the glass transition temperature of the cured resin composition can be increased, which is therefore preferred.

[0040] [Chemistry 2] In equation (A1), R a1 R a2 and R a3 Each can be independently represented as an alkylene group, an oxygen atom, or an alkylene group that can be substituented, R. a4 R indicates an alkyl or hydrogen atom that may have substituents. a5 This indicates an alkylene group that may have substituents.

[0041] R a1 R a2 and R a3 Each can independently represent an alkylene group, an oxygen atom, or an alkylene group that can have substituents.

[0042] The alkylene group having substituents can be any of straight-chain, branched, or cyclic, preferably a straight-chain or branched hydrocarbon group, and more preferably a straight-chain group. As this alkylene group, it is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. This number of carbon atoms does not include the number of carbon atoms of the substituents. Examples of alkylene groups include methylene, 1,1-dimethylmethylene, ethylene, propylene, n-butylene, sec-butylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene, among which methylene, ethylene, and propylene are preferred, and methylene is more preferred.

[0043] The oxoalkylene group having substituents can be any of the following: linear, branched, or cyclic. It is preferably a linear or branched hydrocarbon group, and more preferably linear. As this oxoalkylene group, it is preferably an oxoalkylene group with 1 to 10 carbon atoms, more preferably an oxoalkylene group with 1 to 6 carbon atoms, and even more preferably an oxoalkylene group with 1 to 3 carbon atoms. This number of carbon atoms does not include the number of carbon atoms of the substituents. Examples of oxoalkylene groups include oxomethylene, oxoethylene, oxopropylene, oxo-n-butylene, oxo-sec-butylene, oxo-tert-butylene, oxopentylene, oxohexylene, oxo-heptylene, oxo-octylene, oxononylene, and oxodecylene, among which oxomethylene, oxoethylene, and oxopropylene are preferred, and oxomethylene is more preferred.

[0044] As R a1 R a2 and R a3 From the viewpoint of achieving significant effects of the present invention, it is preferable to represent each of the oxoalkylene groups that may have substituents independently, and more preferably to represent oxomethylene groups.

[0045] R a4 This indicates an alkyl group or hydrogen atom that may have substituents. The alkyl group that may have substituents can be linear, branched, or cyclic. The alkyl group is preferably an alkyl group with 1 to 6 carbon atoms, more preferably an alkyl group with 1 to 5 carbon atoms, more preferably an alkyl group with 1 to 3 carbon atoms, and particularly preferably an alkyl group with 1 or 2 carbon atoms. This number of carbon atoms does not include the number of carbon atoms of the substituents. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, etc., with methyl and ethyl being preferred, and methyl being more preferred.

[0046] As R a4 From the viewpoint of achieving significant effects of the present invention, alkyl groups that may have substituents are preferred, and methyl groups are more preferred.

[0047] R a5 Indicates an alkylene group that may have substituents, and R a1 The alkylene group represented is the same as the substituent group. As R a5 From the viewpoint of achieving significant effects of the present invention, methylene or 1,1-dimethylmethylene is preferred, and 1,1-dimethylmethylene is more preferred.

[0048] R a1 R a2 and R a3 The terms "alkylene", "oxoalkylene", and "R" indicate... a4 The alkyl group and R are indicated. 5The alkylene group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxyl groups, sulfonyl groups, cyano groups, nitro groups, hydroxyl groups, mercapto groups, oxo groups, etc.

[0049] As shown in formula (A1), resins can be exemplified below, but are not limited to this.

[0050] [Chemistry 3] As component (A), it may contain an epoxy resin that is solid at a temperature of 25°C (also referred to as "solid epoxy resin") alone, or it may contain a combination of solid epoxy resin and epoxy resin that is liquid at a temperature of 25°C (hereinafter referred to as "liquid epoxy resin").

[0051] In the case where both solid epoxy resin and liquid epoxy resin are used as component (A), their mass ratio (solid epoxy resin: liquid epoxy resin) is preferably in the range of 1:0.001 to 1:5, and more preferably in the range of 1:0.01 to 1:3.

[0052] Specific examples of solid epoxy resins include biphenyl-type epoxy resins such as "NC3000H", "NC3000", "NC3000L", and "NC3100" (biphenyl-type epoxy resins) manufactured by Nippon Kayaku Co., Ltd.; and "YX4000H", "YX4000", and "YL6121" (biphenyl-type epoxy resins) manufactured by Mitsubishi Chemical Co., Ltd.

[0053] Furthermore, as an epoxy resin with a trifunctional aromatic structure as shown in formula (A1), "VG3101L" manufactured by AIR WATER Co., Ltd. can be cited as an example.

[0054] In addition to these, specific examples of solid epoxy resins include: DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol phenolic varnish type epoxy resin); DIC's "N-695" (cresol phenolic varnish type epoxy resin); and DIC's "HP-720". 0", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthalene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (triphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC700" 0L (naphthol phenolic varnish type epoxy resin); Nippon Steel Chemical & Materials Co., Ltd.'s "ESN475V" (naphthol type epoxy resin); Nippon Steel Chemical & Materials Co., Ltd.'s "ESN485" (naphthol phenolic varnish type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "YX4000HK" (bi-xylenol type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "YX8800" (anthracite type epoxy resin); Osaka Gas Chemical Co., Ltd.'s "PG-100" and "CG-5" 00”; “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER1010” (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER1031S” (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “1031S” manufactured by Mitsubishi Chemical Corporation; “ZX-1542” manufactured by Nippon Steel Chemical & Materials Co., Ltd.; “EX-321” manufactured by Nagase ChemteX Co., Ltd.; “NC7000L”, “YL7890”, “YL7800”, “jER1010”, etc. manufactured by Mitsubishi Chemical Corporation.

[0055] Specific examples of liquid epoxy resins include: DIC Corporation's "HP4032", "HP4032H", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical Corporation's "828US", "828EL" (bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), and "jER152" (phenolic varnish type epoxy resin); Nippon Steel Chemical & Materials Co., Ltd.'s "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Corporation's "EX-721" (glycidyl ester type epoxy resin); Daicel Corporation's "Celloxide 2021P" (alicyclic epoxy resin with an ester skeleton) and "PB-3600" (an epoxy resin with a butadiene structure).

[0056] From the viewpoint of obtaining a cured product with a high glass transition temperature and a resin composition with the lowest possible melt viscosity, the epoxy equivalent of component (A) is 165 g / eq. or more, preferably 200 g / eq. or more, and more preferably 205 g / eq. or more. There is no particular upper limit, but it is preferably 5000 g / eq. or less, more preferably 3000 g / eq. or less, and even more preferably 2000 g / eq. or less, 1000 g / eq. or less, or 500 g / eq. or less. It should be noted that the epoxy equivalent can be determined according to JIS K7236 and is the mass of resin containing 1 equivalent of epoxy groups.

[0057] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of component (A) in the resin composition of the present invention is preferably 45% by mass or more, more preferably 48% by mass or more, and even more preferably 50% by mass or more when the resin content in the resin composition is set to 100% by mass. The upper limit of the content of component (A) is not particularly limited as long as the effects of the present invention can be achieved, and is preferably 70% by mass or less, more preferably 68% by mass or less, and even more preferably 65% ​​by mass or less.

[0058] In this invention, the term "resin component" in relation to the resin composition refers to the component constituting the resin composition excluding the inorganic filler material. Furthermore, "non-volatile component" refers to the component constituting the resin composition other than the organic solvent described later.

[0059] (B) Curing agent The resin composition of the present invention includes a curing agent as component (B), and component (B) includes a (B-1) benzoxazine curing agent.

[0060] (B-1) Benzooxazine-based curing agent The resin composition contains a (B-1) benzoxazine compound. The (B-1) benzoxazine compound is a compound having a benzoxazine ring as shown in the following formula (B1) in its molecule.

[0061] [Chemistry 4] From the viewpoint that even after environmental testing under high temperature and high humidity conditions, the high tightness is improved, the number of benzoxazine rings per molecule of (B-1) benzoxazine compound is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less.

[0062] (B-1) The benzoxazine compound preferably has an aromatic ring in addition to the benzoxazine ring. By having an aromatic ring in addition to the benzoxazine ring, high binding strength can be maintained even after environmental testing under higher temperature and humidity conditions. Examples of aromatic rings include benzene rings, naphthalene rings, anthracene rings, and biphenyl rings, with benzene rings being preferred. Furthermore, from the viewpoint of improving the aforementioned binding strength, the number of aromatic rings is preferably one or more, more preferably two or more, more preferably ten or less, and more preferably five or less.

[0063] As (B-1) benzoxazine compounds, benzoxazine compounds represented by the following general formula (B2) are preferred.

[0064] [Chemistry 5] In equation (B2), R b1 R represents an n-valent group. b2 Each element independently represents a halogen atom, alkyl group, or aryl group. n represents an integer from 2 to 4, and m represents an integer from 0 to 4.

[0065] R b1 This indicates an n-valent group. Preferably, such a group is an arylene, an alkylene, an oxygen atom, or an n-valent group composed of two or more of them; more preferably, it is an arylene or an n-valent group composed of two or more of them; and even more preferably, it is an n-valent group composed of two or more of them.

[0066] The preferred arylene group is one with 6 to 20 carbon atoms, more preferably one with 6 to 15 carbon atoms, and even more preferably one with 6 to 12 carbon atoms. Specific examples of arylene groups include phenylene, naphthylene, anthracene, and biphenylene, with phenylene being the most preferred.

[0067] The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples of alkylene groups include, for example, methylene, ethylene, propylene, etc., with methylene being the most preferred.

[0068] Examples of groups composed of two or more elements include groups formed by combining one or more arylene groups with one or more oxygen atoms, groups formed by combining one or more arylene groups with one or more alkylene groups, groups formed by combining one or more alkylene groups with one or more oxygen atoms, and groups formed by combining one or more arylene groups with one or more alkylene groups with one or more oxygen atoms. Groups formed by combining one or more arylene groups with one or more oxygen atoms, and groups formed by combining one or more arylene groups with one or more alkylene groups are preferred. Specific examples of groups composed of two or more elements include the following groups. In the formula, "*" indicates a bond.

[0069] [Chemistry 6] Arylenes and alkylenes can have substituents. There are no particular limitations on substituents; examples include halogen atoms, -OH, and -OC. 1-6 Alkyl, -N(C) 1-6 Alkyl)2, C 1-6 Alkyl, C 6-10 Aryl, -NH2, -CN, -C(O)OC 1-6 Alkyl groups, -COOH, -C(O)H, -NO2, etc. Here, the term "C" is used... p-q "(p and q are positive integers, satisfying p < q) indicates that the number of carbon atoms in the organic group immediately following the term is p to q. For example, "C 1-6 The term "alkyl" indicates an alkyl group having 1 to 6 carbon atoms.

[0070] The above-mentioned substituents may further have substituents (hereinafter, sometimes referred to as "secondary substituents"). As secondary substituents, the same substituents as the above-mentioned substituents may be used unless otherwise specified.

[0071] R b2 Each alkyl or aryl group independently represents a halogen atom, an alkyl group, or an aryl group. The alkyl group is preferably an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably an alkyl group with 1 to 3 carbon atoms. The aryl group is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms. The halogen atom represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The alkyl and aryl groups may have substituents. The substituents are the same as those that may be present in the aforementioned aryl groups.

[0072] n represents an integer from 2 to 4, preferably an integer from 2 to 3, and more preferably 2. m represents an integer from 0 to 4, preferably an integer from 0 to 3, and more preferably 0.

[0073] From the viewpoint of achieving the desired effects of the present invention, the benzoxazine compound represented by general formula (B2) is preferably at least one of the benzoxazine compounds represented by general formulas (B3) and (B4) below.

[0074] [Chemistry 7] The benzoxazine compound represented by general formula (B3) is preferably at least one of the benzoxazine compounds represented by general formula (B5) and general formula (B6), and the benzoxazine compound represented by general formula (B4) is preferably the benzoxazine compound represented by general formula (B7).

[0075] [Chemistry 8] The benzoxazine compound represented by general formula (B2) can be used alone or in a mixture of two or more compounds. For example, when the benzoxazine compound represented by general formula (B5) is used in a mixture with the benzoxazine compound represented by general formula (B6), the mass mixing ratio (general formula (B5): general formula (B6)) is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, and even more preferably 1:3 to 3:1. By keeping the mass mixing ratio within this range, the adhesion to the conductor layer after environmental testing can be improved.

[0076] Specific examples of (B-1) benzoxazine compounds include: "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazine-3-yl)phenyl]methane) manufactured by Shikoku Chemical Industry Co., Ltd.

[0077] From the viewpoint of improving adhesion, the molecular weight of the (B-1) benzoxazine compound is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less.

[0078] From the viewpoint of maintaining high elongation of the cured resin composition while ensuring high heat resistance, when the resin component in the resin composition is set to 100% by mass, the content of component (B-1) in the resin composition of the present invention is preferably 2% by mass or more, more preferably 2.2% by mass or more, even more preferably 2.5% by mass or more, preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less.

[0079] (B-2) Other curing agents The resin composition of the present invention may further contain other curing agents (B-2) as curing agent (B). As component (B-2), a compound capable of reacting with component (A) to cure the resin composition can be used, such as reactive ester-based curing agents, phenol-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, anhydride-based curing agents, amine-based curing agents, etc. Preferably, component (B-2) includes any one of reactive ester-based curing agents, phenol-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents, and more preferably, an reactive ester-based curing agent.

[0080] Examples of reactive ester-based curing agents include curing agents having one or more reactive ester groups per molecule. Among these, ester-based curing agents include compounds such as phenolic esters, thiophene esters, N-hydroxyamine esters, and heterocyclic hydroxyl esters, which have two or more highly reactive ester groups per molecule. This reactive ester-based curing agent is preferably obtained through a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, reactive ester-based curing agents obtained from carboxylic acid compounds and hydroxyl compounds are preferred, and even more preferably, reactive ester-based curing agents obtained from carboxylic acid compounds and phenolic compounds and / or naphthol compounds.

[0081] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0082] Examples of phenolic or naphthol compounds include, for example, hydroquinone, resorcinol, 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-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, trihydroxybenzene, dicyclopentadiene-type diphenol compounds, and phenolic varnishes. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two phenol molecules with one dicyclopentadiene molecule.

[0083] Preferred examples of reactive ester-based curing agents include: dicyclopentadiene-type reactive ester-based curing agents, naphthalene-type reactive ester-based curing agents containing naphthalene structures, reactive ester-based curing agents containing acetylated derivatives of phenolic varnishes, reactive ester-based curing agents containing benzoyl derivatives of phenolic varnishes, reactive ester-based curing agents containing acetylated derivatives of phenolic varnishes, and reactive ester-based curing agents containing styrene and naphthalene structures. As a dicyclopentadiene-type reactive ester-based curing agent, a reactive ester-based curing agent containing a dicyclopentadiene-diphenol structure is preferred. "Dicyclopentadiene-diphenol structure" indicates a divalent structural unit containing a phenylene-dicyclopentene-phenylene group.

[0084] Among them, the active ester curing agent is preferably selected from one or more active ester curing agents containing styrene and naphthalene structures, and naphthalene-type active ester curing agents containing naphthalene structures.

[0085] Commercially available reactive ester-based curing agents include, but are not limited to, those containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", and "EXB-8000L-65TM" (manufactured by DIC); naphthalene-type reactive ester-based curing agents containing a naphthalene structure include "HP-B-8151-62T", "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", and "HPC-8151-62T" (manufactured by DIC); and phosphorus-containing reactive ester compounds include "EXB9401". (Manufactured by DIC Corporation); Examples of active ester curing agents containing acetylated compounds of phenolic varnishes include "DC808" (manufactured by Mitsubishi Chemical Corporation); Examples of active ester curing agents containing benzoyl compounds of phenolic varnishes include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); Examples of active ester curing agents containing acetylated compounds of phenolic varnishes include "DC808" (manufactured by Mitsubishi Chemical Corporation); Examples of active ester curing agents containing benzoyl compounds of phenolic varnishes include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "EXB-8500-65T" (manufactured by DIC Corporation); Examples of active ester curing agents containing styrene and naphthalene structures include "PC1300-02-65MA" (manufactured by AIR WATER Corporation), etc.

[0086] Examples of phenolic curing agents include those having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring (benzene ring, naphthalene ring, etc.) in one molecule. Among these, compounds having hydroxyl groups bonded to a benzene ring are preferred. Furthermore, from the viewpoint of heat resistance and water resistance, phenolic curing agents having a phenolic varnish structure are preferred. Further, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and more preferably phenolic curing agents containing a triazine skeleton. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, phenolic varnish curing agents containing a triazine skeleton are preferred.

[0087] Specific examples of phenolic and naphthol-based curing agents include: "MEH-7700", "MEH-7810", and "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-495", "SN-495V", "SN-375", and "SN-395" manufactured by Nippon Steel Chemical & Materials Co., Ltd.; D The following are examples of products manufactured by IC Company: “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”; and “GDP-6115L”, “GDP-6115H”, “ELPC75”, etc.

[0088] Examples of cyanate ester-based curing agents include, for instance, bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether, etc., which are difunctional cyanate ester resins; polyfunctional cyanate ester resins derived from phenolic varnishes and cresol varnishes, etc.; prepolymers of some of these cyanate ester resins that have been triazineized; etc. Specific examples of cyanate ester-based curing agents include Lonza Japan's "PT30" and "PT60" (both phenolic varnish-type multifunctional cyanate ester resins); "ULL-950S" (multifunctional cyanate ester resin); "BA230" and "BA230S75" (prepolymers of bisphenol A dicyanate partially or completely triazineized to become trimers); etc.

[0089] Specific examples of carbodiimide-based curing agents include "V-03", "V-05", "V-07" and "V-11S" manufactured by Nisshinbo Chemical Co., Ltd.; and Stabaxol (registered trademark) P manufactured by Rhein-Chemie Co., Ltd.

[0090] Anhydride-based curing agents include those having one or more anhydride groups in one molecule. Specific examples of anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, and so on. Polymer-type anhydrides include benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic 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(dehydrated trimellitate), and styrene-maleic acid resin copolymerized from styrene and maleic acid. Commercially available anhydride-based curing agents can be used, such as "MH-700" manufactured by Shin Nippon Rikka Co., Ltd.

[0091] As amine-based curing agents, examples include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. From the viewpoint of achieving the desired effect of the present invention, aromatic amines are preferred. The amine-based curing agent is preferably a primary or secondary amine, more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyl diamino sulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino- 4-Hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Amine-based curing agents can be commercially available, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYABOND AA", "KAYABOND AB", "KAYABONDA-S" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Co., Ltd.

[0092] When the resin component in the resin composition is set to 100% by mass, the content of (B) curing agent is preferably 1% by mass or more, more preferably 1.5% by mass or more, even more preferably 2% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0093] (B) When the curing agent contains an active ester curing agent as component (B-2), and the resin component in the resin composition is set to 100% by mass, the content of the active ester curing agent is preferably 10% by mass or more, more preferably 12% by mass or more, more preferably 20% by mass or less, and more preferably 18% by mass or less.

[0094] The ratio of the number of epoxy groups in component (A) to the number of active groups in curing agent ((B) number of active groups in curing agent / (A) number of epoxy groups in component) × 100 [%) is preferably 4 or more, more preferably 10 or more, even more preferably 20 or more, preferably 60 or less, more preferably 50 or less, and even more preferably 45 or less.

[0095] Here, "the number of epoxy groups in component (A)" refers to the sum of all values ​​obtained by dividing the mass of component (A) present in the resin composition by the epoxy equivalent. Furthermore, "the number of active groups in the curing agent (B)" refers to the sum of all values ​​obtained by dividing the mass of curing agent (B) present in the resin composition, i.e., components (B-1) and (B-2), by the active group equivalent of their respective compounds.

[0096] (C) Flame retardant The resin composition of the present invention comprises (C) a flame retardant, and as component (C), it comprises (C-1) a phosphazene compound having phenolic hydroxyl groups.

[0097] Among them, as component (C-1), a phosphazene compound having phenolic hydroxyl groups as shown in the following formula (C1) is preferred.

[0098] [Chemistry 9] In equation (C1), R c1 and R c2 Each of these groups independently represents a hydrogen atom, a hydroxyl group, an alkyl group with 1 to 6 carbon atoms that may have substituents, an alkoxy group with 1 to 6 carbon atoms that may have substituents, or a glycidyl group that may have substituents. A independently represents a single bond, an aryl group with 6 to 10 carbon atoms that may have substituents, a sulfonyl group, an alkylene group with 1 to 6 carbon atoms that may have substituents, or a divalent group composed of combinations thereof. n represents an integer from 3 to 25, and m1 and m2 independently represent integers from 1 to 5. R c1 R c2 When there are multiple A's, R c1 R c2 R can be the same as or different from A. c1 and R c2 At least one of them is a hydroxyl group.

[0099] R c1 and R c2 The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 6 carbon atoms can be any of straight-chain, branched, or cyclic, and is preferably a straight-chain or branched alkyl group. Examples of alkyl groups having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, etc.

[0100] R c1 and R c2The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably an alkoxy group having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include: methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, etc. The alkoxy group having 1 to 6 carbon atoms can be straight-chain, branched, or cyclic, and is preferably a straight-chain or branched alkoxy group.

[0101] R c1 and R c2 The alkyl, alkoxy, and glycidyl groups having 1 to 6 carbon atoms may have substituents.

[0102] There are no particular restrictions on the substituents used; examples include halogen atoms, -OH, and -OC. 1-6 Alkyl, -N(C) 1-6 Alkyl)2, C 1-6 Alkyl, C 6-10 Aryl, -NH2, -CN, -C(O)OC 1-6 Alkyl groups, -COOH, -C(O)H, -NO2, etc.

[0103] Here, the term "C" p-q "(p and q are positive integers, satisfying p < q) indicates that the number of carbon atoms in the organic group immediately following the term is p to q. For example, "C 1-6 The term "alkyl" indicates an alkyl group having 1 to 6 carbon atoms.

[0104] The above-mentioned substituents may further have substituents (hereinafter, sometimes referred to as "secondary substituents"). As secondary substituents, the same substituents as the above-mentioned substituents may be used unless otherwise specified.

[0105] Examples of arylene groups with 6 to 10 carbon atoms represented by A include phenylene and naphthylene.

[0106] The alkylene group represented by A, having 1 to 6 carbon atoms, is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. The alkylene group having 1 to 6 carbon atoms can be straight-chain, branched, or cyclic, and is preferably a straight-chain or branched alkylene group. Examples of alkylene groups having 1 to 6 carbon atoms include: methylene, ethylene, n-propylene, isopropylene, dimethylmethylene, n-butylene, tert-butylene, pentylene, neopentylene, hexylene, cyclohexylene, etc.

[0107] The group represented by A is not particularly limited to aryl, sulfonyl, alkylene, or divalent group consisting of 6 to 10 carbon atoms that may have substituents, or combinations thereof. Examples include phenylsulfonyl, 4-hydroxyphenylsulfonyl, phenyl dimethylmethylene, and 4-hydroxyphenyl dimethylmethylene.

[0108] The arylene group (A) with 6 to 10 carbon atoms and the alkylene group (A) with 1 to 6 carbon atoms can have substituents. As substituents, they can be associated with R. 1 The substituents that can be present in alkyl groups with 1 to 6 carbon atoms have the same meaning and the preferred range is also the same.

[0109] N represents an integer from 3 to 25, preferably an integer from 3 to 15, more preferably an integer from 3 to 10, and even more preferably 3.

[0110] m1 and m2 each independently represent an integer from 1 to 5, preferably an integer from 1 to 4, more preferably an integer from 1 to 3, even more preferably 1 or 2, and particularly preferably 1.

[0111] Furthermore, as component (C-1), a phosphazene compound represented by the following formula (C2) is preferred.

[0112] [Chemistry 10] In equation (C2), R 11 and R 21 Each of these groups independently represents a hydrogen atom, a hydroxyl group, an alkyl group with 1 to 6 carbon atoms that may have substituents, an alkoxy group with 1 to 6 carbon atoms that may have substituents, or a glycidyl group that may have substituents. n1 represents an integer from 3 to 25. Wherein, R... 11 and R 21 At least one of them is a hydroxyl group.

[0113] R 11 and R 21 R in equation (C1) 1 and R 2 The meanings are the same, and the preferred ranges are also the same. n1 has the same meaning as n in equation (C1), and the preferred ranges are also the same.

[0114] Specific examples of component (C-1) include phosphazene compounds with the following structures, but the present invention is not limited to them.

[0115] [Chemistry 11] [Chemistry 12] In equations (C3) and (C4), n2 represents an integer from 3 to 25.

[0116] [Chemistry 13] [Chemistry 14] (C-1) Commercially available products may be used, such as "SPH-100" and "SPB-100" manufactured by Otsuka Chemical Co., Ltd., and "FP-400", "FP-430", "FP-470", "FP-800H", "FP-900H" and "FP-4000" manufactured by Fushimi Pharmaceutical Co., Ltd., with "FP-400" and "FP-430" manufactured by Fushimi Pharmaceutical Co., Ltd. being preferred.

[0117] When the resin component in the resin composition is set to 100% by mass, the content of component (C-1) is preferably 3% by mass or more, more preferably 4% by mass or more, and even more preferably 5% by mass or more. Furthermore, there is no particular upper limit, but it is preferably 40% by mass or less, more preferably 30% by mass or less or 20% by mass or less, and even more preferably 15% by mass or less.

[0118] The lower limit of the ratio of the content of (B-1) benzoxazine compound to (C-1) phosphazene compound having a phenolic hydroxyl group (weight ratio of (C-1) component / (B-1) component) is preferably 0.2 or more, more preferably 0.4. The upper limit is preferably 17.0, more preferably 15.0.

[0119] The lower limit of the equivalent ratio of (B-1) benzoxazine compound to (C-1) phosphazene compound having a phenolic hydroxyl group (equivalent ratio of (C-1) component / (B) component) is preferably 0.1 or more, more preferably 0.3. The upper limit is preferably 15.0, more preferably 13.0.

[0120] From the viewpoint of possessing excellent flame retardancy, the resin composition of the present invention may further comprise (C-2) other flame retardants as component (C). Examples of components (C-2) include phosphorus-based flame retardants (e.g., phosphate ester compounds, phenanthrene phosphate compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide). Phosphorus-based flame retardants are preferred.

[0121] Phosphorus-based flame retardants, such as phenanthrene compounds and phosphazene compounds, are preferred.

[0122] Examples of phosphenanthrene compounds include those with phenolic hydroxyl groups. Commercially available products of such compounds are available, such as "HCA-HQ-HST" manufactured by Mikko Co., Ltd.

[0123] As component (C-2), i.e., the phosphazene compound, examples include phosphazene compounds other than those with phenolic hydroxyl groups as described in (C-1), such as phosphazene compounds without phenolic hydroxyl groups. Preferably, the phosphazene compound without phenolic hydroxyl groups is R in the aforementioned formula (C1). 1 and R 2 Phosphazene compounds that are not hydroxyl groups. Preferably, R in the aforementioned formula (C2) is a phosphazene compound that does not possess a phenolic hydroxyl group. 11 and R 21 Phosphazene compounds that are not hydroxyl groups.

[0124] As a phosphazene compound that does not have a phenolic hydroxyl group, commercially available products can be used, such as "FP-100", "FP-500", "FP-500F", "FP-700", "FP-700F", "FP-750", "FP-750F", "FP-800A", "FP-1000", and "FP-5000" manufactured by Fushimi Pharmaceutical Co., Ltd.

[0125] In the resin composition of the present invention, when the resin component in the resin composition is set to 100% by mass, the content of phosphorus-containing compounds is preferably 4.0% by mass or more, more preferably 5.0% by mass or more, preferably 35% by mass or less, more preferably 32% by mass or less.

[0126] When the resin component in the resin composition is set to 100% by mass, from the viewpoint of flame retardancy, the phosphorus content contained in the resin composition of the present invention is preferably 0.6% by mass or more, more preferably 0.8% by mass or more, and even more preferably 1.0% by mass or more. The upper limit is not particularly limited as long as the effects of the present invention can be achieved, but it is preferably 4.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 2.0% by mass or less.

[0127] The phosphorus content in the resin composition can be determined using the X-ray photoelectron spectrometry method described in the "Determination of Phosphorus Content" section of the following examples. Alternatively, the phosphorus content in the resin composition can also be determined using ICP-MS or electron probe microanalysis (EPMA).

[0128] (D) Polymer composition The resin composition of the present invention may contain a polymer component as component (D).

[0129] Examples of (D) polymer components include, for example, phenoxy resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamide-imide resins, polyether-imide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, polyester resins, and other thermoplastic resins.

[0130] (D) One polymer component may be used alone, or two or more may be used in combination.

[0131] Examples of phenoxy resins include those having one or more skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic varnish skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal group of the phenoxy resin can be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0132] Phenoxy resins can be commercially available, such as Mitsubishi Chemical's "1256" and "4250" (both containing a bisphenol A backbone); Mitsubishi Chemical's "YX8100" (containing a bisphenol S backbone); Mitsubishi Chemical's "YX6954" (containing a bisphenol acetophenone backbone); Nippon Steel & Sumitomo Metal Chemicals' "FX280" and "FX293"; Mitsubishi Chemical's "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30"; etc.

[0133] As the polyimide resin, resins having an imide structure (preferably a cyclic imide structure) can be used, such as imides of acid anhydrides and diamine compounds; imides of acid anhydrides and diisocyanate compounds; etc. Among these, imides of acid anhydrides and diamine compounds are preferred. Furthermore, the polyimide resin may contain an indane backbone such as a trimethylindane backbone; for example, the indane backbone may be contained in the structural unit formed by the polymerization of a diamine compound.

[0134] As an acid anhydride used in the manufacture of polyimide resins, tetracarboxylic acid anhydrides are preferred. Examples of tetracarboxylic acid anhydrides include aromatic tetracarboxylic acid dianhydrides and aliphatic tetracarboxylic acid dianhydrides, with aromatic tetracarboxylic acid dianhydrides being preferred. Examples of aromatic tetracarboxylic acid dianhydrides include benzoyltetracarboxylic acid dianhydrides, naphthalenetetracarboxylic acid dianhydrides, anthracenetetracarboxylic acid dianhydrides, and bis(phthalic acid) dianhydrides, with bis(phthalic acid) dianhydrides being preferred. Examples of bis(phthalic acid) dianhydrides include 3,3',4,4'-benzophenone tetracarboxylic acid dianhydrides, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydrides, 3,3',4,4'-diphenyl sulfone tetracarboxylic acid dianhydrides, 3,3',4,4'-biphenyltetracarboxylic acid dianhydrides, 2,2',3,3'-biphenyltetracarboxylic acid dianhydrides, 2,3,3',4'-biphenyltetracarboxylic acid dianhydrides, 2, 3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 4,4'-oxophthalic anhydride, methylene-4,4'-diphthalic anhydride, 1,1-ethynyl-4,4'-diphthalic anhydride Anhydride, 2,2-propylidene-4,4'-diphthalic anhydride, 1,2-ethylidene-4,4'-diphthalic anhydride, 1,3-trimethylene-4,4'-diphthalic anhydride, 1,4-tetramethylene-4,4'-diphthalic anhydride, 1,5-pentamethylene-4,4'-diphthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride Examples of phthalic anhydride include 1,4-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic anhydride.

[0135] Examples of diamine compounds used in the manufacture of polyimide resins include aliphatic diamine compounds and aromatic diamine compounds, with aromatic diamine compounds being preferred. Examples of diphenylamine compounds include, for instance, 4,4'-diamino-2,2'-bis(trifluoromethyl)-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl-4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)propane, etc. [4,4'-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluoreneyl)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindene, etc.

[0136] Commercially available polyimide resins can be used, such as Shin-Etsu Chemical Co., Ltd.'s "SLK-6100", Shin Nippon Rika Co., Ltd.'s "RIKACOAT SN20" and "RIKACOAT PN20", and Arakawa Chemical Co., Ltd.'s "PIAD150H". Examples of polyimide resins also include linear polyimides (those described in Japanese Patent Application Publication No. 2006-37083) obtained by reacting difunctional hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic anhydrides, and modified polyimides containing a polysiloxane backbone (those described in Japanese Patent Application Publication Nos. 2002-12667 and 2000-319386, etc.).

[0137] Examples of polyvinyl acetal resins include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Commercially available polyvinyl acetal resins can be used, such as the S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemicals Co., Ltd.

[0138] Examples of polyolefin resins include low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, and other ethylene-based copolymers; as well as polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

[0139] Examples of polybutadiene resins include: resins containing a hydrogenated polybutadiene backbone, hydroxyl-containing polybutadiene resins, phenolic hydroxyl-containing polybutadiene resins, carboxyl-containing polybutadiene resins, acid anhydride-containing polybutadiene resins, epoxy-containing polybutadiene resins, isocyanate-containing polybutadiene resins, urethane-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins.

[0140] Commercially available polyamide-imide resins can be used, such as "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane backbone) manufactured by Hitachi Chemical Co., Ltd.

[0141] Commercially available polyethersulfone resins can be used, such as "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0142] Commercially available polysulfone resins can be used, such as polysulfones "P1700" and "P3500" manufactured by Olvay Advanced Polymers.

[0143] Commercially available polyphenylene ether resins can be used, such as SABIC's "NORYL SA90". Specific examples of polyetherimide resins include GE's "ULTEM".

[0144] Examples of polycarbonate resins include: hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, anhydride-containing carbonate resins, isocyanate-containing carbonate resins, and urethane-containing carbonate resins. Commercially available polycarbonate resins can be used, such as Mitsubishi Gas Chemical's "FPC0220," Asahi Kasei Chemicals' "T6002" and "T6001" (polycarbonate diol), and Kuraray's "C-1090," "C-2090," and "C-3090" (polycarbonate diol). Specific examples of polyetheretherketone (PEEK) resins include Sumitomo Chemical's "SUMIPLOYK."

[0145] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, and polycyclohexanedimethyl terephthalate resin.

[0146] From the viewpoint of improving film-forming properties, flexibility in the semi-cured state (stage B), and elongation of the cured product, the weight-average molecular weight (Mw) of the thermoplastic resin as the (D) polymer component is preferably 10,000 or more, more preferably 12,000 or more, further preferably 15,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less.

[0147] When the resin component in the resin composition is set to 100% by mass, the content of the polymer component (D) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, preferably 25% by mass or less, more preferably 24% by mass or less, and even more preferably 23% by mass or less.

[0148] (E) Inorganic filler materials The resin composition of the present invention may contain inorganic filler as component (E). By containing inorganic filler (E) in the resin composition, a cured product with superior dielectric properties can be obtained.

[0149] Inorganic compounds are used as inorganic filler materials. Examples of inorganic filler materials include: silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silica is particularly suitable. Examples of silica include, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. Furthermore, spherical silica is preferred as silica. (E) Components can be used alone or in combination of two or more.

[0150] Commercially available products that are components (E) include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; and "CELLSPHERES" and "MGH-005" manufactured by Pacific Cement Co., Ltd.

[0151] From the viewpoint of achieving the desired effect of the present invention, the average particle size of component (E) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0152] The average particle size of component (E) can be determined using laser diffraction and scattering based on the Mie scattering theory. Specifically, a laser diffraction and scattering particle size distribution measuring device can be used to prepare the particle size distribution of the inorganic filler material based on volume, and the median diameter can be set as the average particle size for measurement. The sample to be measured can be obtained by weighing 100 mg of inorganic filler material and 10 g of methyl ethyl ketone into a small bottle and dispersing it ultrasonically for 10 minutes. Using a laser diffraction and scattering particle size distribution measuring device, the particle size distribution of the inorganic filler material based on volume is measured in a flow cell mode with the light source wavelength set to blue and red. The average particle size, as the median diameter, is calculated from the obtained particle size distribution. Examples of laser diffraction and scattering particle size distribution measuring devices include, for example, the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0153] From the viewpoint of significantly achieving the desired effects of the present invention, the specific surface area of ​​component (E) is preferably 1 m². 2 / g or more, preferably 2m 2 / g or more, preferably 3m 2 / g or more. There is no specific upper limit, but 60mg is preferred. 2 / g or less, 50m 2 / g or less or 40m 2 / g or less. The specific surface area can be obtained by using a BET fully automated specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH) to adsorb nitrogen gas onto the sample surface and calculate the specific surface area using the BET multi-point method, thereby determining the specific surface area of ​​the inorganic filler material.

[0154] From the viewpoint of improving moisture resistance and dispersibility, component (E) is preferably treated with a surface treatment agent. Examples of surface treatment agents include, for instance, fluorinated silane coupling agents such as 3,3,3-trifluoropropyltrimethoxysilane; aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; epoxysilane coupling agents such as 3-epoxypropoxypropyltrimethoxysilane; mercaptosilane coupling agents such as 3-mercaptopropyltrimethoxysilane; silane coupling agents; alkoxysilanes such as phenyltrimethoxysilane; organosilazane compounds such as hexamethyldisilazane; and titanate coupling agents. Furthermore, a single surface treatment agent can be used, or two or more can be used in any combination.

[0155] Commercially available surface treatment agents include, for example, "KBM403" (3-epoxypropoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0156] From the viewpoint of improving the dispersibility of inorganic fillers, the degree of surface treatment using the surface treatment agent is preferably controlled within a specified range. Specifically, 0.2 to 5 parts by mass of the surface treatment agent is preferably used to surface treat 100 parts by mass of the inorganic filler, more preferably 0.2 to 3 parts by mass, and more preferably 0.3 to 2 parts by mass.

[0157] The degree of surface treatment using surface treatment agents can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m³. 2 The above, and more preferably, is 0.1 mg / m³ 2 The above, and more preferably, is 0.2 mg / m³ 2 That's all. On the other hand, from the viewpoint of suppressing the increase in melt viscosity of the resin varnish and melt viscosity in sheet form, 1 mg / m³ is preferred. 2The following, more preferably, is 0.8 mg / m 2 The following, and more preferably, is 0.5 mg / m². 2 the following.

[0158] (E) The carbon content per unit surface area of ​​component (E) can be determined after washing the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the surface-treated inorganic filler material, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. can be used.

[0159] From the viewpoint of significantly obtaining the effects of the present invention, when the content of the non-volatile component in the resin composition is set to 100% by mass, it is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less.

[0160] (F) Curing accelerator The resin composition of the present invention may further contain a curing accelerator as component (F).

[0161] Examples of components (F) include, for example, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Additionally, free radical polymerization initiators can also be used as curing accelerators. Component (F) can be used alone or in combination of two or more.

[0162] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0163] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0164] Examples of imidazole-based curing accelerators include, for example, 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine, 2,4- Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazolium and 1-benzyl-2-phenylimidazolium.

[0165] As an imidazole-based curing accelerator, commercially available products can be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation and "1B2PZ-10M" manufactured by Shikoku Chemical Industry Co., Ltd.

[0166] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

[0167] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) and cobalt(III) acetylacetone, organocopper complexes such as copper(II) acetylacetone, organozinc complexes such as zinc(II) acetylacetone, organoiron complexes such as iron(III) acetylacetone, organonickel complexes such as nickel(II) acetylacetone, and organomanganese complexes such as manganese(II) acetylacetone. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0168] Free radical polymerization initiators can be, for example, thermal polymerization initiators that generate free radicals upon heating. Free radical polymerization initiators can also be polymerization initiators with free radical reactive groups. A single free radical polymerization initiator can be used alone, or two or more can be used in any combination.

[0169] Examples of free radical polymerization initiators include peroxide-based free radical polymerization initiators and azo-based free radical polymerization initiators. Among these, peroxide-based free radical polymerization initiators are preferred.

[0170] Examples of peroxide-based free radical polymerization initiators include: hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide compounds such as tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; and dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl) peroxide. Diacyl peroxide compounds such as dicarbonates; peroxide ester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl)2-ethylperhexanoate, tert-butyl-2-ethylperhexanoate, tert-butyl-3,5,5-trimethylperhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, and tert-butyl peroxymaleic acid; etc.

[0171] Examples of azo radical polymerization initiators include: 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-nitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 2-phenylazo-4-methoxy-2,4-dimethylpentanonitrile, and other azo nitrile compounds; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis( Azoamide compounds such as [hydroxymethyl]ethyl]propionamide, 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); alkyl azo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane); etc.

[0172] Commercially available free radical polymerization initiators include, for example, those manufactured by Nippon Oil Company such as "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", "PERBUTYL O", "PERBUTYL ND", "PERBUTYL Z", "PERBUTYL I", "PERCUMYL P", "PERCUMYL D", "PERHEXYL D", "PERHEXYL A", "PERHEXYL LI", "PERHEXYL Z", "PERHEXYL ND", "PERHEXYL O", and "PERHEXYL PV".

[0173] When the resin composition of the present invention contains component (F), from the viewpoint of significantly obtaining the desired effect of the present invention, the content of component (F) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, preferably 1.2% by mass or less, and more preferably 1.0% by mass or less when the resin component in the resin composition is set to 100% by mass.

[0174] (G) Other ingredients In addition to the components described above, the resin composition of the present invention may also contain any other components within the range that achieve the desired effect. Examples of such components include elastomers, organic fillers, thickeners, defoamers, leveling agents, and adhesion promoters. These components may be used individually or in combination of two or more in any ratio.

[0175] <Organic Solvents> The resin composition of the present invention may further comprise an organic solvent as a volatile component. Examples of organic solvents include, for instance, 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; and 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and ethyl diglycol acetate. Ether-ester solvents such as 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; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. Organic solvents can be used alone or in combination of two or more.

[0176] [Preparation of the resin composition] The resin composition can be manufactured, for example, by mixing the above-mentioned components in any order. Furthermore, during the mixing of the components, heating and / or cooling can be performed by appropriately adjusting the temperature. Additionally, during or after mixing the components, stirring equipment such as a mixer can be used to stir the mixture to ensure uniform dispersion of the components. Furthermore, the resin composition can be degassed as needed.

[0177] [Characteristics of the Resin Composition] The resin composition of the present invention comprises component (A), component (B-1), and component (B-2), and therefore its cured product exhibits characteristics of maintaining high elongation and high flame retardancy. For example, for the cured product obtained by curing the resin composition under the conditions described in the later examples (heat curing at 200°C for 90 minutes), when a tensile test is performed according to Japanese Industrial Standard (JIS K 7127), the elongation (%) of the cured product at 23°C is preferably 3.5% or more, more preferably 4.0% or more, and even more preferably 4.5% or more. The elongation of the cured product can be determined according to the method described in <Test Example 4: Evaluation of Elongation Based on Tensile Test> of the later examples.

[0178] The cured resin composition of the present invention has excellent flame retardancy. For example, it is preferably “V-0” or better in the UL fire resistance test specification (UL-94). The flame retardancy can be evaluated according to the method described in <Test Example 5: Evaluation of Flame Retardancy> in the following examples.

[0179] The resin composition of the present invention is characterized by producing a cured product with suppressed coefficient of linear thermal expansion. Therefore, when using the resin composition of the present invention to form an insulating layer used in semiconductor components, an insulating layer with suppressed coefficient of linear thermal expansion can be obtained. For example, as described in <Experimental Example 2: Determination of Coefficient of Linear Thermal Expansion (CTE)> in the following embodiments, when a layered cured product obtained by uniformly coating a resin composition in the form of a PET film with a dried thickness of 30 μm is thermo-cured at 200°C for 90 minutes, the average coefficient of linear thermal expansion from 25°C to 150°C is preferably 50 ppm / °C or less, more preferably 45 ppm / °C or less, by thermomechanical analysis using the tensile-weighted method. The lower limit is not particularly limited and can be 1 ppm / °C or more, 2 ppm / °C or more, 3 ppm / °C or more, etc.

[0180] The cured resin composition of the present invention can increase its glass transition temperature (Tg). Therefore, an insulating layer with excellent heat resistance can be obtained from the cured resin composition. For example, as described in <Experimental Example 3: Evaluation of Glass Transition Temperature (Tg)> of the following examples, when the glass transition temperature (Tg) is measured using a thermomechanical analysis apparatus (DMA, Seiko Instruments Co., Ltd. "DMS-6100") in "stretch mode" at a temperature increase of 5°C / min and a range of 25°C to 240°C, the glass transition temperature (Tg) is preferably 150°C or higher, 155°C or higher, or 160°C or higher.

[0181] From the viewpoint of achieving good wiring embedding performance, the minimum melt viscosity of the resin composition layer in the resin sheet obtained from the resin composition of the present invention is preferably 6000 poise or less, more preferably 5000 poise or less, even more preferably 4000 poise or less, 3500 poise or less, or 3000 poise or less. The lower limit of this minimum melt viscosity is preferably 100 poise or more, more preferably 200 poise or more, and even more preferably 250 poise or more.

[0182] The minimum melt viscosity of the resin composition layer refers to the lowest viscosity exhibited by the resin composition layer when the resin melts. Specifically, when the resin composition layer is heated at a constant heating rate to melt the resin, in the initial stage, the melt viscosity decreases as the temperature rises. Then, if a certain level is exceeded, the melt viscosity increases with increasing temperature. The minimum melt viscosity refers to the melt viscosity at this minimum point. The minimum melt viscosity of the resin composition layer can be determined by a dynamic viscoelastic method, for example, by the method described in <Experimental Example 1: Determination of Minimum Melt Viscosity> in the following examples.

[0183] [Uses of the resin composition] The resin compositions of the present invention can provide cured products that combine high flame retardancy with heat resistance and elongation. Therefore, the resin compositions of the present invention can be suitably used as resin compositions for forming insulating layers on highly multilayered, high-density, thin, or coreless circuit boards (including printed wiring boards) of semiconductor devices and semiconductor packages, and can be further suitably used as resin compositions for forming interlayer insulating layers on which conductor layers are formed by plating.

[0184] Furthermore, the resin composition of the present invention can also be suitably used in automotive semiconductor packaging requiring high-temperature operation and in semiconductor packaging for various components.

[0185] [Resin Sheets] The resin sheet of the present invention comprises a support and a resin composition layer formed of the resin composition of the present invention disposed on the support.

[0186] From the viewpoint of achieving thinner circuit boards and providing a cured product with excellent insulation even when the cured resin composition is a thin film, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, further preferably 60 μm or less, and particularly preferably 50 μm or less. The lower limit of the resin composition layer thickness is not particularly limited and can generally be set to 1 μm or more, 5 μm or more, 10 μm or more, etc.

[0187] Examples of supports include films, metal foils, and release paper made of plastic materials, with films and metal foils made of plastic materials being more preferred.

[0188] When a film formed of a plastic material is used as a support, examples of plastic materials include, for example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0189] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. Copper foil can be used as the copper foil, either as a single metal of copper or as an alloy of copper with other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0190] The support can be treated with matte finish, corona treatment, or antistatic treatment on the surface that bonds to the resin composition layer.

[0191] Furthermore, as a support, a support with a release layer can be used on the surface bonded to the resin composition layer. Examples of release agents used in the release layer of the support with a release layer include, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Commercially available products can be used as the support with a release layer, such as PET films having a release layer primarily composed of an alkyd resin-based release agent, i.e., LINTEC's "SK-1", "AL-5", and "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and UNITIKA's "Unipeel".

[0192] The thickness of the support is not particularly limited, but is preferably in the range of 5μm to 75μm, more preferably in the range of 10μm to 60μm. It should be noted that when using a support with a release layer, the overall thickness of the support with the release layer is preferably within the above range.

[0193] When using a metal foil as a support, a metal foil with a carrier foil can also be used, which is formed by bonding a peelable carrier foil to a thin metal foil. In one embodiment, the metal foil with a carrier foil includes a carrier foil, a release layer disposed on the carrier foil, and a metal foil disposed on the release layer. When using a metal foil with a carrier foil as a support, a resin composition layer is disposed on the metal foil.

[0194] In metal foils with a carrier foil, the material of the carrier foil is not particularly limited, and examples include copper foil, aluminum foil, stainless steel foil, titanium foil, and copper alloy foil. When copper foil is used as the carrier foil, it can be electrolytic copper foil or rolled copper foil. Furthermore, the release layer is not particularly limited as long as it can peel the metal foil from the carrier foil, and examples include alloy layers selected from elements selected from Cr, Ni, Co, Fe, Mo, Ti, W, and P; organic coatings, etc.

[0195] In a metal foil with a carrier foil, the preferred material for the metal foil is, for example, copper foil or copper alloy foil.

[0196] In the metal foil with a carrier foil, the thickness of the carrier foil is not particularly limited, but is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm. Furthermore, the thickness of the metal foil can be set, for example, in the range of 0.1 μm to 10 μm.

[0197] In one embodiment, the resin sheet may further include other layers as needed. Examples of such other layers include, for instance, a protective film based on the support provided on the side not bonded to the support of the resin composition layer (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion of dust or the formation of scratches on the surface of the resin composition layer can be suppressed.

[0198] Resin sheets can be manufactured, for example, by dissolving a resin composition in an organic solvent to prepare a resin varnish, coating the resin varnish onto a support using a film coating machine or the like, and then drying it to form a resin composition layer.

[0199] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetates such as ethyl acetate, butyl acetate, acetic acid solvents, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as solvents and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. Organic solvents can be used alone or in combination of two or more.

[0200] Drying can be carried out using known methods such as heating or blowing hot air. Drying conditions are not particularly limited, but drying is generally carried out when the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. The drying method also varies depending on the boiling point of the organic solvent in the resin varnish. For example, when using a resin varnish containing 30% to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0201] Resin sheets can be stored in rolls. When resin sheets have a protective film, they can be used by peeling off the protective film.

[0202] [Circuit board] The resin composition of the present invention can be used to form the insulating layer of a circuit board. The present invention also provides the aforementioned circuit board, namely, a circuit board comprising an insulating layer formed from a cured product of the resin composition of the present invention.

[0203] Printed wiring board In one embodiment, the circuit board of the present invention is a printed wiring board. The printed wiring board includes an insulating layer formed by curing a cured product obtained by curing the above-described resin composition.

[0204] Printed wiring boards can be manufactured, for example, using the aforementioned resin sheet by a method comprising the steps (I) and (II) described below.

[0205] (I) Step of laminating resin sheets on a core substrate to bond the resin composition layer of the resin sheets to the core substrate; (II) Step of curing the resin composition layer to form an insulating layer. The "core substrate" used in step (I) refers to a component that serves as the substrate of a printed wiring board, such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, etc. Furthermore, the core substrate may have a metal layer such as copper foil on its surface as part of the core substrate. For example, a core substrate with a peelable first metal layer and a second metal layer on both surfaces can also be used. When using such a core substrate, a conductor layer serving as a wiring layer is typically formed on the surface of the second metal layer opposite to the first metal layer, which functions as a loop wiring layer. Examples of core substrates with such metal layers include, for example, the ultra-thin copper foil ("Micro Thin") with carrier copper foil manufactured by Mitsui Mining & Metals Co., Ltd.

[0206] In addition, the core substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned.

[0207] From the viewpoint of thinning, the thickness of the core substrate is preferably 100 μm or less, more preferably 80 μm or less, even more preferably 70 μm or less, and even more preferably 60 μm or less. The lower limit of the core substrate thickness is not particularly limited, and can typically be set to 10 μm or more, 15 μm or more, 20 μm or more, etc.

[0208] After preparing the core substrate, a resin composition layer is formed on the core substrate. When a conductor layer is formed on the surface of the core substrate, the formation of the resin composition layer is preferably carried out in a manner in which the conductor layer is embedded in the resin composition layer.

[0209] The formation of the resin composition layer is typically achieved by laminating a resin sheet and a core substrate. The lamination of the core substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet onto the core substrate from the support side. Examples of components for heating and pressing the resin sheet onto the core substrate (hereinafter also referred to as "heat-pressing components") include, for example, heated metal plates (SUS end plates, etc.) or metal rollers (SUS rollers, etc.). It should be noted that the heat-pressing component is not pressed directly onto the resin sheet; rather, it is preferable to press it using an elastic material such as heat-resistant rubber so that the resin sheet fully conforms to the surface irregularities of the inner substrate.

[0210] The lamination of the core substrate and the resin sheet can be performed using a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C; the heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa; and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination can preferably be performed under reduced pressure conditions below 26.7 hPa.

[0211] Lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include, for instance, the vacuum pressure laminator manufactured by Meiki Seisakusho, the vacuum dressing device manufactured by Nikko-Materials, and the intermittent vacuum pressure laminator.

[0212] After lamination, the laminated resin sheets can be smoothed by applying pressure to the heated pressing members under atmospheric pressure, for example, from the support side. The pressure conditions for smoothing can be the same as the heating and pressing conditions for lamination described above. Smoothing can be performed using a commercially available laminating machine. It should be noted that lamination and smoothing can be performed continuously using the aforementioned commercially available vacuum laminating machine.

[0213] The support for the resin sheet can be peeled off after the resin sheet is laminated onto the core substrate and thermocured (i.e., after step (II)), or before the resin sheet is laminated onto the core substrate (i.e., before step (I)). Alternatively, the support can be peeled off before the roughening treatment step (step (IV)) described later.

[0214] In step (II), the resin composition layer is cured to form an insulating layer comprising the cured resin composition. The curing conditions for the resin composition layer are not particularly limited, and the conditions used when forming the insulating layer of a printed wiring board can be used. The resin composition layer can be cured by irradiation with active energy rays such as ultraviolet light, or typically by heat curing.

[0215] For example, the thermosetting conditions of the resin composition layer vary depending on the type of resin composition. In one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0216] Before heat curing the resin composition layer, the resin composition layer can be preheated at a temperature lower than the curing temperature. For example, before heat curing the resin composition layer, it can be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for at least 5 minutes, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0217] The method for manufacturing a printed wiring board may further include: (III) the step of creating holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer. Additionally, it may include (VI) the step of removing the core substrate.

[0218] Step (III) is the step of creating holes in the insulating layer, thereby forming vias, through holes, etc., in the insulating layer. Step (III) can be carried out using, for example, a drill bit, laser, plasma, etc., depending on the composition of the resin composition used in the formation of the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the printed circuit board.

[0219] Step (IV) is a roughening treatment of the insulation layer. Typically, smear removal is also performed in this step (IV). The roughening treatment steps and conditions are not particularly limited. For example, the insulation layer can be roughened sequentially by swelling treatment using a swelling solution, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing solution.

[0220] Examples of swelling solutions used in the roughening process include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Sodium hydroxide solution and potassium hydroxide solution are more preferred as alkaline solutions. Commercially available swelling solutions include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN. The swelling treatment using the swelling solution is not particularly limited; for example, it can be performed by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to a suitable level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0221] Examples of oxidants used in roughening treatments include alkaline permanganate solutions obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using oxidants such as alkaline permanganate solutions is preferably performed by immersing the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Commercially available oxidants include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by ATOTECH JAPAN.

[0222] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and commercially available examples include, for instance, "Reduction Solution Securiganth P" manufactured by ATOTECH JAPAN. The treatment using the neutralizing solution can be performed by immersing the roughened surface treated with the oxidant in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From an operability perspective, it is preferable to immerse the roughened object treated with the oxidant in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0223] Step (V) is the step of forming a conductor layer, which is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). From the viewpoints of versatility, cost, and ease of patterning in 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. More preferably, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, is even more preferred. A single metal layer of copper is even more preferred.

[0224] The conductor layer can be a single-layer structure or a multi-layer structure consisting of two or more single-metal or alloy layers of different types of metals or alloys. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0225] The thickness of the conductor layer depends on the desired printed wiring board design, typically 3μm to 35μm, preferably 5μm to 30μm.

[0226] The conductor layer is preferably formed by plating. For example, the conductor layer with the desired wiring pattern can be formed by plating the surface of the insulating layer using methods such as semi-additive or fully additive methods. From the viewpoint of ease of manufacturing, it is preferable to form it by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0227] 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, exposing a portion of the seed layer corresponding to the desired wiring pattern. After forming a metal layer on the exposed seed layer by electrolytic plating, the mask pattern is removed. Then, the unwanted portion of the seed layer is removed by etching or the like, thus forming a conductor layer with the desired wiring pattern.

[0228] <Step (VI)> The circuit board of the present invention can be a coreless structure with the core substrate removed.

[0229] There is no particular limitation on the method for removing the core substrate. A preferred embodiment is to peel the core substrate off from the circuit board at the interface between the first and second metal layers, and then etch away the second metal layer using, for example, an aqueous solution of copper chloride. If necessary, the core substrate can also be peeled off while the conductor layer is protected by a protective film.

[0230] When the circuit board of the present invention has a core substrate, the ratio (T1 / T2) of the total thickness (T1) of the resin composition layers (insulating layers) on both sides of the core substrate to the thickness (T2) of the core substrate is preferably 2 to 10.

[0231] [Semiconductor Devices] A semiconductor device according to one embodiment of the present invention includes the above-described circuit substrate (including a printed wiring board). The semiconductor device can be manufactured using the above-described circuit substrate.

[0232] Examples of semiconductor devices include various semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and airplanes). Example

[0233] The following examples illustrate the present invention. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" to indicate quantities refer to "parts by mass" and "% by mass," respectively, unless otherwise specified. Furthermore, the operations described below are performed under normal temperature and pressure conditions unless otherwise specified.

[0234] [Example 1] (1) Preparation of resin composition Eight parts of bisphenol type epoxy resin (Nippon Steel Chemical Co., Ltd. "ZX1059", epoxy equivalent approximately 165 g / eq.) and trifunctional epoxy resin (AIR) were mixed. 18 parts of WATER's "VG3101L" epoxy equivalent (210 g / eq.), 25 parts of biphenyl-type epoxy resin (Nippon Kayaku Co., Ltd.'s "NC-3000L", epoxy equivalent approximately 271 g / eq.), 8 parts of phosphazene compound containing phenolic hydroxyl groups (Fushimi Pharmaceutical Co., Ltd.'s "FP-400", phenol equivalent approximately 247 g / eq., phosphorus content 12.5 wt%), 10 parts of benzoxazine-based curing agent (Shikoku Kasei Kogyo Co., Ltd.'s "Pd", benzoxazine equivalent 217 g / eq.), 17 parts of reactive ester resin (DIC Co., Ltd.'s "HP-C-8000L-65TM", reactive ester equivalent approximately 219 g / eq., 65 wt% solids in a toluene-methyl ethyl ketone mixed solution), benzene A varnish was prepared by uniformly dispersing 27 parts of an oxy-resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", MEK with 30% solid content and cyclohexanone solution), 3 parts of an imidazole curing accelerator (Shikoku Kasei Co., Ltd. "1B2PZ-10M", MEK solution with 10% by mass solid content), 25 parts of methyl ethyl ketone (MEK), and 70 parts of an inorganic filler material (Admatechs Co., Ltd. "SO-C2", surface-treated with an amino-based silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) using a mixer.

[0235] The phosphorus content in the resin composition was determined using the method described later in "Determination of Phosphorus Content". The phosphorus content in the obtained resin compositions in Examples 2-12 and Comparative Examples 1-3 were also determined in the same manner.

[0236] (2) Preparation of resin sheets A varnish of the resin composition prepared in (1) above is uniformly applied to a PET film (LINTEC "AL5", 38 μm thick) using a die coater to achieve a dried thickness of 30 μm. Then, it is dried in an oven to produce a resin sheet having a resin composition layer / PET film layer structure.

[0237] [Example 2] The epoxy resin was 50 parts, the phosphazene compound containing phenolic hydroxyl groups was 6 parts, and 2 parts of the phosphazene compound containing phenolic hydroxyl groups (Sanko Co., Ltd.'s "HCA-HQ-HST", phenol equivalent 162 g / wq., phosphorus content 9.5 wt%) were added. Otherwise, the resin sheet was prepared in the same manner as in Example 1.

[0238] [Example 3] The epoxy resin was 50 parts, and the phosphazene compound containing phenolic hydroxyl groups was 4.5 parts. Otherwise, the resin sheet was prepared in the same manner as in Example 1.

[0239] [Example 4] The resin sheet was prepared in the same manner as in Example 1, with 50 parts epoxy resin, 15 parts phenoxy resin, and 68 parts inorganic filler.

[0240] [Example 5] The resin sheet was prepared in the same manner as in Example 1, with 50 parts epoxy resin, 45 parts phenoxy resin, and 78 parts inorganic filler.

[0241] [Example 6] The resin sheet was prepared in the same manner as in Example 1, with 50 parts epoxy resin, 8 parts phenoxy resin, and 68 parts inorganic filler.

[0242] [Example 7] The resin sheet was prepared in the same manner as in Example 1, with 50 parts epoxy resin, 55 parts phenoxy resin, and 80 parts inorganic filler.

[0243] [Example 8] The resin sheet was prepared in the same manner as in Example 1, with 16 parts of a phenolic hydroxyl-containing phosphazene compound and 2 parts of a benzoxazine curing agent.

[0244] [Example 9] The resin sheet was prepared in the same manner as in Example 1, with 28 parts of a phenolic hydroxyl-containing phosphazene compound, 2 parts of a benzoxazine curing agent, and no active ester.

[0245] [Example 10] As a benzoxazine-based curing agent, 10 parts of "Pd" (manufactured by Shikoku Chemical Industry Co., Ltd., benzoxazine equivalent 217 g / eq.) were replaced with 10 parts of "JBZ-OP100D" (manufactured by JFE Chemical Co., Ltd., benzoxazine equivalent 218 g / eq.), and resin sheets were prepared in the same manner as in Example 1.

[0246] [Example 11] As a benzoxazine-based curing agent, 10 parts of "Pd" (manufactured by Shikoku Chemical Industry Co., Ltd., benzoxazine equivalent 217 g / eq.) were replaced with 10 parts of "ALP-d" (manufactured by Shikoku Chemical Industry Co., Ltd., benzoxazine equivalent 257 g / eq.), and resin sheets were prepared in the same manner as in Example 1.

[0247] [Example 12] The epoxy resin was 50 parts, the phosphazene compound containing phenolic hydroxyl groups was 4.5 parts, and the phenoxy resin was 15 parts of flexible polyimide (a cyclohexanone-methylcyclohexanone solution with 30% solid content of "PIAD150H" manufactured by Arakawa Chemical Co., Ltd.). Otherwise, the resin sheet was prepared in the same manner as in Example 1.

[0248] [Comparative Example 1] Eight parts of a phosphazene compound containing phenolic hydroxyl groups were replaced with eight parts of a phosphaphenanthrene compound containing phenolic hydroxyl groups (Sanko Co., Ltd.'s "HCA-HQ-HST", phenol equivalent 162 g / wq., phosphorus content 9.5 wt%). Otherwise, resin sheets were prepared in the same manner as in Example 1.

[0249] [Comparative Example 2] Eight parts of a phosphazene compound containing phenolic hydroxyl groups (Fushimi Pharmaceutical Co., Ltd.'s "FP-400", phenol equivalent of approximately 247 g / eq., phosphorus content of 12.5 wt%) were replaced with eight parts of a phosphazene compound without phenolic hydroxyl groups (Fushimi Pharmaceutical Co., Ltd.'s "FP-100", phosphorus content of 13.4 wt%). Otherwise, resin sheets were prepared in the same manner as in Example 1.

[0250] [Comparative Example 3] The epoxy resin was 50 parts, the phosphazene compound containing phenolic hydroxyl groups was 2 parts, and "Pd" (manufactured by Shikoku Chemical Industry Co., Ltd., benzoxazine equivalent 217 g / eq.) as a benzoxazine curing agent was 15.3 parts. Otherwise, the resin sheet was prepared in the same manner as in Example 1.

[0251] <Preparation of solidified products> The resin sheets prepared in the examples and comparative examples were vacuum-pressed at 100°C for 30 seconds using a vacuum pressurized laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), and then pressed from the support (PET film) with heat-resistant rubber for 30 seconds at 100°C and a pressure of 0.7 MPa, thereby being laminated onto a polyimide film ("Kapton H" manufactured by Toray DuPont Co., Ltd., 50 μm thick). The film was then thermo-cured at 200°C for 90 minutes to obtain the cured resin sheet.

[0252] <Determination of Phosphorus Content> The obtained cured material was placed on a scanning X-ray photoelectron spectrophotometer (XPS, manufactured by Albackfield Co., Ltd., PHIQuantes SXM), and the phosphorus content was evaluated by measuring the peak components with peak positions in the range of 130–135 eV from the binding energy of the intrinsic 2p orbitals of phosphorus atoms. The measured phosphorus content was evaluated according to the following criteria.

[0253] Evaluation Criteria: 〇: Phosphorus content is 0.6% or higher ×: Phosphorus content is less than 0.6% <Experimental Example 1: Determination of Minimum Melt Viscosity> The resin sheets prepared in the examples and comparative examples were cut into 18 mm diameter pieces, and 20 sheets were stacked to obtain samples for testing. The lowest melt viscosity of the obtained samples was measured using a dynamic viscoelasticity measuring apparatus (Yu-Bee-Em Co., Ltd. "Rheosol-G3000"). Specifically, the temperature was increased within a temperature range of 60°C to 200°C, the dynamic viscoelastic modulus was measured, and the lowest melt viscosity (poise) was calculated. The test conditions were set as follows: heating rate 5°C / min, temperature interval 2.5°C, vibration frequency 1 Hz, and strain 1 degree. The measured lowest melt viscosity was evaluated according to the following criteria.

[0254] Evaluation Criteria: 〇: Melt viscosity below 6000 poise △: Melt viscosity greater than 6000 poise and less than 8000 poise ×: Melt viscosity greater than 8000 poise <Experimental Example 2: Evaluation of the Coefficient of Linear Thermal Expansion (CTE)> The cured product obtained in the above-described "Preparation of Cured Product" section was measured using a thermomechanical analysis apparatus (TMA, Hitachi High-Tech Science "TMA / SS7100") under a 1N load in "tensile mode". The measurement was performed twice: the first time with a temperature increase of 5°C / min within the range of 25°C to 200°C, and the second time within the range of 25°C to 260°C. The linear thermal expansion coefficient (ppm / °C) for the second measurement from 30°C to 150°C was calculated. The linear thermal expansion coefficient was then evaluated based on the following evaluation criteria.

[0255] Evaluation Criteria: 〇: Linear thermal expansion coefficient is below 50ppm / ℃ ×: The linear thermal expansion coefficient is greater than 50 ppm / ℃ <Experimental Example 3: Evaluation of Glass Transition Temperature (Tg)> The resulting cured products were measured using a thermomechanical analysis apparatus (DMA, Seiko Instruments Co., Ltd. "DMS-6100") in "tensile mode". Measurements were performed at a temperature increase of 5°C / min within a range of 25°C to 240°C. The glass transition temperature was then evaluated based on the following criteria.

[0256] Evaluation Criteria: 〇: Glass transition temperature is above 150℃ ×: Glass transition temperature less than 150℃ <Experimental Example 4: Evaluation of Elongation Based on Tensile Test> Tensile tests were conducted on the cured resin composites according to Japanese Industrial Standard (JIS K7127) using a precision universal testing machine (Shimadzu Autograph AGS-X). The elongation (%) of the cured resin composite layer at 23°C was measured. The elongation was evaluated based on the following evaluation criteria.

[0257] Evaluation Criteria: 〇: Elongation rate of 4.0% or more △: Elongation rate of 3.5% or more but less than 4.0 ×: Elongation less than 3.5% <Example 5: Evaluation of Flame Retardancy> The resin sheets prepared in each example and comparative example were overlapped to a thickness of 150 μm using a manual lamination chamber (Nikko-Materials "V-160"). Then, using the same lamination chamber, they were laminated onto both sides of a 56 μm inner substrate (EMC "EM526") with copper foil removed from both sides. The resin sheets were then thermocured at 190°C for 90 minutes, and a flammability test was conducted according to the UL94 vertical burning test. Flame retardancy was evaluated based on the following evaluation criteria.

[0258] Evaluation Criteria: 〇: The evaluation result of the UL94 vertical flame retardancy test is equivalent to V-0. ×: The evaluation result of the UL94 vertical flame retardancy test is not equivalent to V-0. The results of experiments 1-5 are shown in Table 1.

[0259] [Table 1] Table 1-1 Table 1-2

Claims

1. A resin composition comprising (A) an epoxy resin with two or more functional groups, (B) a curing agent and (C) a flame retardant, wherein, (B) Components include (B-1) benzoxazine-based curing agent. (C) Component contains a phosphazene compound with a phenolic hydroxyl group (C-1). When the resin component in the resin composition is set to 100% by mass, the phosphorus content is 0.6% by mass or more.

2. The resin composition according to claim 1, wherein, (A) The component contains biphenyl-type epoxy resin.

3. The resin composition according to claim 1, wherein, (A) The component contains the epoxy resin shown in the following formula (A1). [Chemistry 1] In equation (A1), R a1 R a2 and R a3 Each independently represents an alkylene group, an oxygen atom, or an alkylene group that may have substituents, R. a4 R indicates an alkyl or hydrogen atom that may have substituents. a5 This indicates an alkylene group that may have substituents.

4. The resin composition according to claim 1, wherein, When the resin component in the resin composition is set to 100% by mass, the content of component (B-1) is 2% by mass or more.

5. The resin composition according to claim 1, wherein, (B) component further includes (B-2) other curing agents, which are compounds selected from active ester curing agents, phenol curing agents, cyanate ester curing agents and carbodiimide curing agents.

6. The resin composition according to claim 1, further comprising (D) a polymer component.

7. The resin composition according to claim 6, wherein, (D) The weight-average molecular weight of component (D) is above 10,000.

8. The resin composition according to claim 6 or 7, wherein, When the resin component in the resin composition is set to 100% by mass, the content of component (D) is 1 to 25% by mass.

9. The resin composition according to claim 1, further comprising (E) an inorganic filler material.

10. The resin composition according to claim 1, further comprising (F) a curing accelerator.

11. The resin composition according to claim 1, used to form an insulating layer.

12. A resin sheet comprising a support and a resin composition layer comprising the resin composition of any one of claims 1 to 11 disposed on the support.

13. The resin sheet according to claim 12, wherein, The thickness of the resin composition layer is less than 100 μm.

14. A circuit board comprising an insulating layer formed from a cured resin composition according to any one of claims 1 to 11.

15. The circuit board according to claim 14, wherein it has a core substrate with a thickness of less than 100 μm, or does not have a core substrate.

16. A semiconductor device comprising the circuit board of claim 14 or 15.

17. The resin composition according to claim 1, used to form an insulating layer of a circuit board having a core substrate with a thickness of less than 100 μm, or without a core substrate.

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