Resin composition, cured product, prepreg, metal foil-clad laminate, single-layer resin sheet, laminated resin sheet, and printed wiring board

Abstract

[Problem] To provide a resin composition having excellent heat resistance and flame retardancy, a cured product, a prepreg, a metal foil-clad laminate, a single-layer resin sheet, a laminated resin sheet, and a printed wiring board. [Solution] The resin composition contains a cyanate ester compound (A) represented by formula (1), a cyclophosphazene compound (B), and an inorganic filler (C). Excellent heat resistance and dielectric properties can be obtained by the cyanate ester compound (A), and flame retardancy can be improved by the cyclophosphazene compound (B) and the inorganic filler (C).

Description

Technical Field

[0001] This invention relates to resin compositions, cured products thereof, prepregs using the same, metal foil laminates, single-layer resin sheets, laminated resin sheets, and printed circuit boards. Background Technology

[0002] In recent years, the miniaturization and high performance of information equipment have developed rapidly. Along with this, the requirements for materials used in the semiconductor and electronic component fields are higher than ever before. For example, in the semiconductor field, due to advancements in high-density mounting technology, the focus has shifted from surface mounting to area mounting, leading to new packaging methods such as BGA (Ball Grid Array) and CSP (Chip Size Package). Consequently, the requirements for high heat resistance and low thermal expansion in the insulating layers of printed circuit boards have further increased.

[0003] As materials constituting insulating layers of printed circuit boards, cyanate ester resins, for example (see Patent Document 1, for example), are conventionally known. Cyanate ester resins are thermosetting resins with excellent heat resistance and dielectric properties. However, while dicyclopentadiene-type cyanate ester resins have excellent heat resistance, low thermal expansion, dielectric properties, and water absorption, they suffer from significantly poor flame retardancy. In Patent Document 1, flame retardancy was improved by adding inorganic fillers, but further improvements in these properties are desired.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2009-298981 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] This invention was made in response to the problem that aims to provide resin compositions, cured products, prepregs, metal foil laminates, single-layer resin sheets, laminated resin sheets, and printed circuit boards with excellent heat resistance and flame retardancy.

[0009] Solution for solving the problem

[0010] The present invention is described below. [1]

[0012] A resin composition comprising a cyanate compound (A), a cyclophosphonitrile compound (B), and an inorganic filler (C) as shown in formula (1).

[0013]

[0014] (In equation (1), R) 1 (This represents a hydrocarbon group with 1 to 8 carbon atoms, where i is an integer from 0 to 3, n1 represents the repetition number, and the average value is a number from 0 to 5.) [2]

[0016] According to the resin composition of [1], wherein the aforementioned cyclophosphonitrile compound (B) comprises the compound shown in the following formula (2).

[0017]

[0018] (In formula (2), Z1 and Z2 each independently represent vinyl or hydrogen atoms, and n2 represents an integer from 3 to 8.) [3]

[0020] According to the resin composition of [1], wherein the aforementioned inorganic filler (C) comprises at least one selected from the group consisting of silica, alumina, magnesium hydroxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride and aluminum nitride. [4]

[0022] The resin composition according to [1] further comprises at least one of the following groups: cyanate compounds other than the aforementioned cyanate compound (A), epoxy compounds, phenolic compounds, maleimide compounds and polyphenylene ether compounds. [5]

[0024] According to the resin composition described in [1], the content of the aforementioned cyanate compound (A) is 10 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the resin solids. [6]

[0026] According to the resin composition described in [1], the content of the aforementioned cyclophosphonitrile compound (B) is 3 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the resin solids. [7]

[0028] According to the resin composition described in [1], the content of the aforementioned inorganic filler (C) is 50 parts by mass or more and 300 parts by mass or less relative to 100 parts by mass of the resin solids. [8]

[0030] A cured product is formed by curing the resin composition described in any one of [1] to [7]. [9]

[0032] A prepreg having a substrate and a resin composition [1] to [7] impregnated or coated on the aforementioned substrate.

[10]

[0034] A metal foil laminate comprising: a laminate formed by laminating one or more prepregs described [9], and a metal foil laminated on one or both sides of the aforementioned laminate.

[11]

[0036] A single-layer resin sheet is formed by molding the resin composition described in any one of [1] to [7] into a sheet shape.

[12]

[0038] A laminated resin sheet having a sheet substrate and a resin composition layer formed by coating one or both sides of the aforementioned sheet substrate with the resin composition described in any one of [1] to [7] and drying it.

[13]

[0040] A printed circuit board having an insulating layer and a conductor layer formed on one or both sides of the aforementioned insulating layer.

[0041] The aforementioned insulating layer comprises a cured product of the resin composition described in any one of [1] to [7].

[0042] The effects of the invention

[0043] According to the present invention, excellent heat resistance and flame retardancy can be obtained by including the cyanate compound (A) of formula (1), the cyclophosphonitrile compound (B) and the inorganic filler material (C). Detailed Implementation

[0044] Hereinafter, a method for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from its spirit.

[0045] It should be noted that in this specification, "~" is used to encompass the values ​​listed before and after it as the lower and upper limits.

[0046] In this specification, the description of groups (atomic groups) includes both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, the description of unsubstituted and unsubstituted groups is preferably unsubstituted.

[0047] Unless otherwise specified in this specification, "solid resin component in the resin composition" refers to the components in the resin composition other than fillers (including inorganic fillers) and solvents, and 100 parts by weight of solid resin component means that the total amount of resin components in the resin composition other than fillers and solvents is 100 parts by weight.

[0048] [Resin Composition]

[0049] The resin composition of this embodiment comprises a cyanate ester compound (A), a cyclophosphonitrile compound (B), and an inorganic filler (C) as shown in formula (1). Excellent heat resistance and dielectric properties are obtained by including the cyanate ester compound (A), and flame retardancy is improved by including the cyclophosphonitrile compound (B) and the inorganic filler (C). Furthermore, the resin composition of this embodiment preferably further comprises at least one compound selected from the group consisting of cyanate ester compound (D), epoxy compound (E), phenolic compound (F), maleimide compound (G), and polyphenylene ether compound (H), other than cyanate ester compound (A).

[0050]

[0051] (In equation (1), R) 1 (This represents a hydrocarbon group with 1 to 8 carbon atoms, where i is an integer from 0 to 3, n1 represents the repetition number, and the average value is a number from 0 to 5.)

[0052] [Cyanate compound (A)]

[0053] In equation (1), R is used as 1 The hydrocarbon group can be preferably alkyl, aryl, aralkyl, or allyl.

[0054] As an alkyl group, it can be any of the following: straight-chain, branched, or cyclic. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, hexyl, cyclohexyl, and methylcyclohexyl.

[0055] Examples of aryl groups include phenyl, tolyl, xylyl, and ethylphenyl.

[0056] Examples of aralkyl groups include benzyl and α-methylbenzyl.

[0057] Phenyl or methyl are preferred, with methyl being particularly preferred.

[0058] R 1 The substitution position relative to the cyanooxy group (-OCN) can be any of the ortho, meta, or para positions, with the ortho position being preferred.

[0059] In equation (1), i is the substitution number, preferably 1 or 2, more preferably 2.

[0060] In formula (1), n1 represents a number greater than or equal to 0, and its average value is 0 to 5, preferably 1.0 to 4.0, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2.5.

[0061] The weight-average molecular weight (Mw) of the cyanate ester compound (A), converted to polystyrene based on GPC, is preferably 400-2000, more preferably 400-1500. The number-average molecular weight (Mn), converted to polystyrene based on GPC, is preferably 350-1500, more preferably 400-1000. The content of the cyanate ester compound (A) relative to 100 parts by weight of the resin solids is preferably 10 parts by weight or more and 50 parts by weight or less, more preferably 15 parts by weight or more and 45 parts by weight or less, more preferably 25 parts by weight or more and 40 parts by weight or less. By setting it within this range, better heat resistance and higher dielectric properties can be obtained. Only one type of cyanate ester compound (A) may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

[0062] Cyanate ester compound (A) can be obtained, for example, by reacting a cyanide halide with a phenol under alkaline conditions. Alternatively, commercially available cyanate ester compound (A) can be used. Examples of cyanate ester compound (A) include CO3CO (dicyclopentadiene-type cyanate ester compound) manufactured by YANGZHOU TECHIAMATERIAL.

[0063] [Cyclophosphonitrile compound (B)]

[0064] Cyclophosphazene compound (B) functions as a flame retardant, and preferably comprises a compound represented by formula (2) below. By using cyclophosphazene compound (B) having phosphorus and nitrogen atoms, the flame retardancy can be further improved.

[0065]

[0066] (In formula (2), Z1 and Z2 each independently represent vinyl or hydrogen atoms, and n2 represents an integer from 3 to 8.)

[0067] Relative to 100 parts by weight of the resin solids, the content of cyclophosphonitrile compound (B) is preferably 3 parts by weight or more and 15 parts by weight or less, more preferably 3 parts by weight or more and 10 parts by weight or less, even more preferably 3 parts by weight or more and 9 parts by weight or less, and even more preferably 3 parts by weight or more and 8 parts by weight or less. This is because by setting it to the lower limit or above, superior flame retardancy can be obtained, and by setting it to the upper limit or below, superior moldability can be obtained. Only one type of cyclophosphonitrile compound (B) may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above-mentioned range.

[0068] The cyclophosphonitrile compound (B) shown in formula (2) can be obtained, for example, by using hexahalogenated cyclophosphonitriles such as hexachlorocyclotriphosphonitriles as raw materials and replacing the halogen atoms of the hexahalogenated cyclotriphosphonitriles with aryloxy groups. Alternatively, commercially available products can be used as cyclophosphonitrile compound (B). For example, Ravitle (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. is an example of cyclophosphonitrile compound (B).

[0069] [Inorganic filler material (C)]

[0070] The inorganic filler material (C) preferably comprises at least one material selected from the group consisting of silica, alumina, magnesium hydroxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride. Examples of silica types include natural silica, fused silica, synthetic silica, amorphous silica, AEROSIL, and hollow silica. Boehmite is preferred as the inorganic filler material (C) because of its excellent flame retardancy.

[0071] The average particle size (D50) of the inorganic filler (C) is preferably 0.1 to 3 μm, more preferably 0.2 to 2 μm, and even more preferably 0.3 to 1 μm. This is because, with the average particle size (D50) of the inorganic filler (C) within the above range, the dispersibility of the inorganic filler (C) in the resin composition is further improved, and the flow characteristics during molding are further improved. Here, "average particle size (D50)" refers to the particle size at which the particle size distribution of a specified amount of powder added to an aqueous dispersion medium is accumulated from the smallest particles using a laser diffraction particle size analyzer, reaching 50% of the total volume.

[0072] Relative to 100 parts by weight of the resin solids, the content of the aforementioned inorganic filler (C) is preferably 50 parts by weight or more and 300 parts by weight or less, and more preferably 70 parts by weight or more and 200 parts by weight or less. By setting it within this range, superior flame retardancy can be obtained. Only one type of inorganic filler (C) may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above-mentioned range.

[0073] [Cyanate ester compound (D)]

[0074] There are no particular limitations on the cyanate ester compound (D) other than cyanate ester compound (A), but compounds having two or more cyanooxy groups in the molecule are preferred. Specifically, examples include bisphenol A type cyanate compounds and their prepolymers, naphthol aralkyl type cyanate compounds, 1,3- or 1,4-dicyanoxybenzene, 1,3,5-tricyanoxybenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanoxynaphthalene, 1,3,6-tricyanoxynaphthalene, 4,4-dicyanoxybiphenyl, bis(4-dicyanoxyphenyl)methane, 2,2-bis(4-cyanoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-cyanoxyphenyl)propane, bis(4-cyanoxyphenyl) ether, bis(4-cyanoxyphenyl) sulfide, bis(4-cyanoxyphenyl) sulfone, tris(4-cyanoxyphenyl) phosphite, tris(4-cyanoxyphenyl) phosphate, and cyanate compounds obtained by reacting phenolic varnishes with cyanogen halides. Preferably, bisphenol A type cyanate compounds and their prepolymers, naphthol aralkyl type cyanate compounds, and more preferably at least one of bisphenol A type cyanate compounds and naphthol aralkyl type cyanate compounds. Using such cyanate compounds (D) tends to further improve heat resistance.

[0075] Relative to 100 parts by weight of the resin solids, the content of cyanate ester compound (D) is preferably 15 parts by weight or more and 45 parts by weight or less, more preferably 25 parts by weight or more and 40 parts by weight or less. By setting it within this range, there is a tendency to further improve the electrical properties and flame retardancy. Only one type of cyanate ester compound (D) may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

[0076] [Epoxy compound (E)]

[0077] The epoxy compound (E) is not particularly limited, but non-halogenated compounds having two or more epoxy groups per molecule are preferred. Specifically, examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenolic varnish type epoxy resin, bisphenol A phenolic varnish type epoxy resin, biphenyl aryl alkyl type epoxy resin, cresol phenolic varnish type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene-modified epoxy resin, phenolic varnish type epoxy resin modified with a naphthalene skeleton, phenolic aryl alkyl type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, compounds formed by the epoxidation of double bonds of glycidylamine, glycidyl ester, butadiene, etc., and compounds obtained by the reaction of hydroxyl-containing silicone resins with epichlorohydrin, etc. Preferably, it is selected from any one or more of the group consisting of naphthalene-modified epoxy resin, cresol phenolic varnish type epoxy resin, and bisphenol A type epoxy resin. There is a tendency to further improve heat resistance by using such epoxy compounds (E).

[0078] Relative to 100 parts by weight of the resin solids, the content of epoxy compound (E) is preferably 25 parts by weight or more and 65 parts by weight or less, more preferably 30 parts by weight or more and 60 parts by weight or less, and 35 parts by weight or more and 55 parts by weight or less. By setting it within this range, there is a tendency to further improve metal adhesion, heat resistance, peel strength, and electrical properties. Only one type of epoxy compound (E) may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above-mentioned range.

[0079] [Phenolic compound (F)]

[0080] As a phenolic compound (F), a phenolic resin having two or more hydroxyl groups in one molecule is preferred, and commonly known phenolic resins can be used. Specific examples include bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenolic varnish type phenolic resin, bisphenol A phenolic varnish type phenolic resin, glycidyl ester type phenolic resin, aralkyl phenolic varnish type phenolic resin, biphenyl aralkyl type phenolic resin, cresol phenolic varnish type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol phenolic varnish resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified phenolic varnish type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, aminotriazine-containing phenolic varnish type phenolic resin, phosphorus-containing phenolic resin, hydroxyl-containing silicone resin, etc., without particular limitation. From the perspective of flame retardancy, biphenyl alkyl phenolic resin, naphthol alkyl phenolic resin, phosphorus-containing phenolic resin, and hydroxyl-containing silicone resin are preferred.

[0081] Relative to 100 parts by mass of the resin solids, the content of phenolic compound (F) is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or 2 parts by mass or more and 7 parts by mass or less. Only one type of phenolic compound (F) may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above-mentioned range.

[0082] [Maleimide compound (G)]

[0083] As a maleimide compound (G), there is no particular limitation as long as the molecule has one or more maleimide groups. Specifically, examples include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, maleimide compounds shown in formula (3) below, prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. Preferably, the compound (G) is selected from at least one of the groups consisting of 2,2'-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, and maleimide compounds represented by formula (3) below. By including such a maleimide compound (G), the physical property balance of the resulting cured product tends to become more excellent. From the same point of view, the maleimide compound (G) more preferably contains at least one of the groups consisting of maleimide compounds represented by formula (3) below.

[0084]

[0085] (In equation (3), R) 6 Each can independently represent a hydrogen atom or a methyl group, preferably a hydrogen atom. Furthermore, in formula (3), n3 represents an integer of 1 or more, preferably an integer of 10 or less, and more preferably an integer of 7 or less.

[0086] The content of maleimide compound (G) can be appropriately set according to the desired properties and is not particularly limited. From the viewpoint of further improving the balance of physical properties such as electrical properties, heat resistance, and thermal conductivity, it is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less, and even more preferably 10 parts by mass or more and 25 parts by mass or less, relative to 100 parts by mass of the resin solids. By keeping the content of maleimide compound (G) within the above range, there is a tendency to further reduce the coefficient of thermal expansion and further improve the heat resistance of the obtained cured product. Only one type of maleimide compound (G) can be used, or two or more types can be used. When two or more types are used, the total amount is preferably within the above range.

[0087] [Polyphenylene ether compound (H)]

[0088] The polyphenylene ether compound (H) is not particularly limited, but a polymer containing repeating units as shown in formula (4) is preferred. By containing such a polyphenylene ether compound (H), there is a tendency to obtain excellent low dielectric constant, low dielectric loss tangent, and uniform cured product. In addition, the polyphenylene ether compound (H) may further contain at least one of the repeating units shown in formula (5) and the repeating units shown in formula (6).

[0089]

[0090] (In formula (4), R1, R2, R3 and R4 each independently represent an alkyl, aryl, halogen atom or hydrogen atom with 6 or fewer carbon atoms.)

[0091]

[0092] (In formula (5), R5, R6, R7, R 11 and R 12 Each of these independently represents an alkyl or phenyl group with 6 or fewer carbon atoms, R8, R9, and R 10 Each can independently represent an alkyl group or phenyl group with 6 or fewer carbon atoms.

[0093]

[0094] (In equation (6), R) 13 R 14 R 15 R 16 R 17 R 18 R 19 and R 20 Each of these groups independently represents a hydrogen atom, an alkyl group with 6 or fewer carbon atoms, or a phenyl group. A represents a straight-chain, branched, or cyclic divalent hydrocarbon group with 20 or fewer carbon atoms.

[0095] Furthermore, the polyphenylene ether compound (H) may have substituents. There are no particular limitations on the substituents; examples include olefinic unsaturated groups such as vinylbenzyl, epoxy groups, amino groups, hydroxyl groups, mercapto groups, carboxyl groups, and silyl groups. Among these, olefinic unsaturated groups are preferred. Hereinafter, such a polyphenylene ether compound (H) with substituents will also be referred to as "modified polyphenylene ether".

[0096] The unsaturated groups of the aforementioned olefins are not particularly limited, and examples include alkenyl groups such as vinyl, allyl, methyl allyl, propenyl, butenyl, hexenyl, and octenyl; cycloalkenyl groups such as cyclopentenyl and cyclohexenyl; and alkenyl aryl groups such as vinylbenzyl and vinylnaphthyl. Among these, vinylbenzyl is preferred from the viewpoint of electrical properties and low water absorption.

[0097] The position of the substituent is not particularly limited; examples include the two ends of the polyphenylene ether chain, the single end of the polyphenylene ether chain, the side chain of the polyphenylene ether chain, or combinations thereof. From the viewpoint of heat resistance, polyphenylene ether compounds having olefinically unsaturated groups at both ends are preferred. When a polyphenylene ether compound has two or more substituents, the substituents can be the same or different.

[0098] Of the modified polyphenylene ethers described above, those having olefinically unsaturated groups at both ends are preferred. There are no particular limitations on such modified polyphenylene ethers; for example, compounds represented by formula (7) can be cited. By using such modified polyphenylene ethers, there is a tendency to further improve heat resistance and low water absorption.

[0099]

[0100] (In formula (7), X represents the group shown in formula (8) or formula (9) below, Y independently represents the group shown in formula (10) below, a and b represent integers from 0 to 100, and at least one of them is 1 or more.)

[0101]

[0102] (In equation (8), R) 21 R 22 R 23 R 27 and R 28 Each independently represents an alkyl or phenyl group with 6 or fewer carbon atoms, R 24 R 25 R 26 Each can independently represent an alkyl group or phenyl group with 6 or fewer carbon atoms.

[0103]

[0104] (In equation (9), R) 29 R 30 R 31 R 32 R 33 R 34 R 35 and R 36 Each of these groups independently represents a hydrogen atom, an alkyl group with 6 or fewer carbon atoms, or a phenyl group. A represents a straight-chain, branched, or cyclic divalent hydrocarbon group with 20 or fewer carbon atoms.

[0105]

[0106] (In equation (10), R) 39 and R 40Each independently represents an alkyl or phenyl group with 6 or fewer carbon atoms. R 37 and R 38 Each can independently represent an alkyl group or phenyl group with 6 or fewer carbon atoms.

[0107] In formula (9), the divalent hydrocarbon group represented by A is not particularly limited, and can be listed as methylene, ethylene, 1-methyl ethylene, 1,1-propylene, 1,4-phenylenebis(1-methyl ethylene), 1,3-phenylenebis(1-methyl ethylene), cyclohexylene, phenylmethylene, naphthylmethylene, 1-phenyl ethylene, etc.

[0108] The compound shown in formula (7) may contain one group shown in formula (10) or two or more groups shown in formula (10). When it contains two or more groups shown in formula (10), the groups shown in formula (10) of different kinds may be arranged randomly or the groups shown in formula (10) of the same kind may be arranged in a block-like manner.

[0109] In the modified polyphenylene ether shown in formula (7), R is preferred. 21 R 22 R 23 R 27 R 28 R 39 R 40 For alkyl groups with 3 or fewer carbon atoms, R 24 R 25 R 26 R 29 R 30 R 31 R 32 R 33 R 34 R 35 R 36 R 37 R 38 Modified polyphenylene ethers having 3 or fewer hydrogen atoms or alkyl groups, particularly more preferably, where X in formula (8) or formula (9) is a group represented by formula (11), formula (12) or formula (13), and Y in formula (10) is a structure of formula (14) or formula (15), or a random arrangement of formula (14) and formula (15).

[0110]

[0111]

[0112] (In the above formula (12), R) 31 R 32 R33 R 34 Each group can be independently a hydrogen atom or a methyl group. The -A- group is a straight-chain, branched, or cyclic divalent hydrocarbon group with 20 or fewer carbon atoms.

[0113]

[0114] (In the above formula (13), A is a divalent hydrocarbon group with 20 or fewer carbon atoms, which is straight-chain, branched, or cyclic.)

[0115]

[0116]

[0117] There are no particular limitations on the method for manufacturing modified polyphenylene ether having the structure shown in formula (7) above. For example, a method can be listed where a difunctional phenolic compound is oxidatively coupled with a difunctional phenolic compound to obtain a difunctional phenylene ether oligomer, and the terminal phenolic hydroxyl group of the obtained difunctional phenylene ether oligomer is vinylbenzyl etherified.

[0118] Furthermore, there are no particular limitations on other methods for manufacturing modified polyphenylene ethers. For example, as a method for manufacturing modified polyphenylene ethers modified with vinyl benzyl groups, one could include: dissolving a difunctional phenylene ether oligomer and vinyl benzyl chloride in a solvent, and then adding an alkali to react them under heating and stirring. Another method for manufacturing modified polyphenylene ethers modified with carboxyl groups could include: melt-blending and reacting an unsaturated carboxylic acid, its functional derivative, and polyphenylene ether in the presence or absence of a free radical initiator; or, for carboxyl-modified polyphenylene ethers, dissolving at least one of an unsaturated carboxylic acid and its functional derivative in an organic solvent in the presence or absence of a free radical initiator, and then reacting them in solution.

[0119] The number-average molecular weight of the polyphenylene ether compound (H), converted from polystyrene based on the GPC method, is 500 to 5000, preferably 700 to 3500, and more preferably 900 to 2500. By having a number-average molecular weight of 500 or more, the polyphenylene ether compound (H) is less prone to stickiness when formed into a coating. Furthermore, by having a number-average molecular weight of 5000 or less, a decrease in solubility in solvents can be prevented.

[0120] Relative to 100 parts by weight of the resin solids, the content of polyphenylene ether compound (H) is preferably 1 part by weight or more and 60 parts by weight or less, more preferably 5 parts by weight or more and 50 parts by weight or less, and 10 parts by weight or more and 40 parts by weight or less. Only one type of polyphenylene ether compound (H) may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above-mentioned range.

[0121] The vinyl equivalent (g / eq.) of the polyphenylene ether compound (H) is preferably 250 to 2600 g / eq., more preferably 350 to 1800 g / eq., and even more preferably 450 to 1400 g / eq. By keeping the vinyl equivalent (g / eq.) of the polyphenylene ether compound (H) within the above range, there is a tendency to further improve its heat resistance and low water absorption.

[0122] [Other ingredients]

[0123] When using inorganic filler (C), from the viewpoint of improving the dispersibility of inorganic filler (C), the bonding strength between resin and inorganic filler (C), and glass cloth, silane coupling agents and wetting and dispersing agents can be used in combination.

[0124] (Silane coupling agent)

[0125] As a silane coupling agent, there are no particular limitations as long as it is a silane coupling agent commonly used for the surface treatment of inorganic materials. Specific examples include aminosilane compounds such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; epoxysilane compounds such as γ-epoxypropoxypropyltrimethoxysilane; vinylsilane compounds such as γ-methacryloyloxypropyltrimethoxysilane; cationic silane compounds such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; and phenylsilane compounds. One silane coupling agent or a suitable combination of two or more can be used.

[0126] (Wetting and dispersing agent)

[0127] As a wetting and dispersing agent, dispersants commonly used in coatings can be used appropriately, and there is no particular limitation on the type. For example, wetting and dispersing agents such as Disperbyk-110, 111, 180, 161, BYK-W996, W9010, and W903 manufactured by BYK Corporation can be cited.

[0128] (Other polymer compounds, other flame retardant compounds, additives)

[0129] In the resin composition of this embodiment, other thermosetting resins, thermoplastic resins and their oligomers, elastomers, and other polymeric compounds, flame-retardant compounds, and additives may also be used as needed. These are not particularly limited as long as they are commonly used substances. For example, flame-retardant compounds may include phosphate esters, melamine phosphate, phosphorus-containing epoxy resins, nitrogen compounds such as melamine and / or benzoguanamine, compounds containing oxazine rings, and silicone compounds. As additives, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, dispersants, leveling agents, and gloss agents may be used in appropriate combinations as needed.

[0130] (Curing accelerator)

[0131] In the resin composition of this embodiment, curing accelerators may also be used in combination to appropriately adjust the curing speed as needed. Examples of such compounds include organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, and di-tert-butyl phthalate; azo compounds such as azobisnitrile; tertiary amines such as N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylaniline-ethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutylenediamine, and N-methylpiperidine; and tertiary amines such as 2-ethyl-4-methylimidazole. Imidazoles such as 2-phenyl-4-methylimidazole and triphenylimidazole; monomeric phenols such as phenol, xylenol, cresol, resorcinol, and catechol; organometallic salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octanoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; substances formed by dissolving these organometallic salts in hydroxyl-containing monomeric compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; organotin compounds such as dioctyltin oxide, other alkyltin compounds, and alkyltin oxides.

[0132] (solvent)

[0133] Furthermore, the resin composition of this embodiment may contain a solvent as needed. For example, if an organic solvent is used, the viscosity during the preparation of the resin composition decreases, improving workability and increasing the impregnation of the glass cloth. There is no particular limitation on the type of solvent, as long as it can dissolve part or all of the mixture of the cyanate compound (A) and the cyclophosphonitrile compound (B). Specific examples include ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, and cellosolves such as methyl cellosolve, propylene glycol methyl ether, and their acetates, but these are not particularly limited. One solvent may be used alone, or two or more may be used in combination.

[0134] [Preparation of Resin Composition]

[0135] The resin composition of this embodiment can be prepared by conventional methods. The preparation method is not particularly limited as long as it yields a resin composition uniformly containing cyanate compound (A), cyclophosphonitrile compound (B), inorganic filler (C), and any other components mentioned above as needed. For example, the resin composition of this embodiment can be easily prepared by sequentially mixing cyanate compound (A), cyclophosphonitrile compound (B), and inorganic filler (C) in a solvent and stirring thoroughly.

[0136] It should be noted that, during the preparation of the resin composition, known treatments (stirring, mixing, kneading, etc.) for uniformly dissolving or dispersing the components can be performed. For example, in the uniform dispersion of inorganic filler material (C), stirring and dispersion treatment using a stirring tank equipped with a stirrer having appropriate stirring capacity can improve the dispersibility of the resin composition. The aforementioned stirring, mixing, and kneading treatments can be appropriately performed using known devices such as ball mills, bead mills, or rotary / rotary mixing devices.

[0137] [use]

[0138] The resin composition of this embodiment is suitable for use as a cured product, prepreg, metal foil-coated laminate, single-layer resin sheet, laminated resin sheet, or printed circuit board. In these applications, properties such as heat resistance and flame retardancy are required. In this regard, the resin composition of this embodiment provides excellent heat resistance and flame retardancy, and is therefore useful. Hereinafter, prepreg, metal foil-coated laminate, single-layer resin sheet, laminated resin sheet, or printed circuit board will be described.

[0139] 〔Cured product〕

[0140] The cured product of this embodiment is obtained by curing the resin composition of this embodiment using heat, light, or the like. The cured product can be obtained by melting, dissolving, or dispersing the curable resin composition in a solvent, flowing it into a mold, removing the solvent by depressurization as needed, and then curing it under normal conditions. In the case of heat curing, it is preferable to cure the curable resin composition at 65°C to 250°C, more preferably at 120°C to 230°C, and even more preferably at 150°C to 200°C. By curing at the above temperatures, the decrease in the storage modulus of the cured product can be further suppressed, and the coefficient of linear expansion of the cured product is small even at high temperatures, resulting in a curable resin composition with excellent heat resistance. The curing temperature during heat curing is not particularly limited; it can be cured at a specific curing temperature, or it can be cured by a stepped curing process of holding the product at a certain temperature for a certain time twice or more during the heating process.

[0141] [Prepreg]

[0142] The prepreg of this embodiment has a substrate and the above-described resin composition impregnated or coated onto the substrate. The manufacturing method of the prepreg can be carried out according to conventional methods and is not particularly limited. For example, the prepreg of this embodiment can be produced by impregnating or coating the resin composition of this embodiment onto the substrate and then heating it in a dryer at 100°C to 200°C for 1 minute to 30 minutes for semi-curing (B-Stage).

[0143] The content of the resin composition (including inorganic filler) relative to the total amount of the prepreg is preferably 30% to 90% by mass, more preferably 35% to 85% by mass, and most preferably 40% to 80% by mass. By keeping the content of the resin composition within the above range, there is a tendency to further improve the moldability.

[0144] The substrate used in this embodiment is not particularly limited, and various known substrates used in printed circuit board materials can be appropriately selected according to the target application and performance. Specific examples are not particularly limited, but include glass fibers other than glass such as E-glass, D-glass, S-glass, Q-glass, spherical glass, NE-glass, L-glass, and T-glass; inorganic fibers other than glass such as quartz; fully aromatic polyamides such as poly(p-phenylene terephthalamide) (Kevlar, DuPont, Inc.), copoly(p-phenylene oxide / 3,4'-oxophenylene oxide / terephthalamide) (Technora, Hayami Industry Co., Ltd.); polyesters such as 2,6-hydroxynaphthenic acid·p-hydroxybenzoic acid (Vectran, KURARAY CO.,LTD.), and Zxion (KB SEIREN LTD.); organic fibers such as poly(p-phenylenebenzoxazole) (ZYLON, Toyobo Co., Ltd.); and polyimide. From the perspective of availability and low dielectric loss tangent, E-glass, NE-glass, and L-glass are preferred. These substrates can be used individually or in combination of two or more.

[0145] Examples of substrate shapes include woven fabrics, nonwoven fabrics, rovings, chopped strand mats, and surfacing mats. Examples of weaving methods include plain weave, basket weave, and twill weave. The shape and weave of the substrate can be appropriately selected from these known substrates depending on the intended use and performance requirements. Furthermore, materials with filament-opening treatments or glass fabrics with surface treatments such as silane coupling agents are preferred. The thickness and weight of the substrate are not particularly limited, but a substrate thickness of approximately 0.01 mm to 0.3 mm is generally preferred. Especially from the viewpoint of strength and water absorption, a substrate thickness of 200 μm or less and a weight of 250 g / m³ are preferred. 2 The glass fabrics described below are preferably glass fabrics made of E-glass glass fibers.

[0146] [Metal foil laminate]

[0147] The metal-clad laminate of this embodiment has one or more sheets of the aforementioned prepreg and metal foil laminated on one or both sides of the laminate. The manufacturing method of the metal-clad laminate can be carried out using conventional methods and is not particularly limited. For example, it can be obtained by overlapping at least one sheet of the aforementioned prepreg, placing metal foil on one or both sides, and then laminating it. More specifically, by overlapping one or more sheets of the aforementioned prepreg, placing copper, aluminum, or other metal foil on one or both sides as needed, and then laminating the resulting structure as needed, the metal-clad laminate of this embodiment can be manufactured.

[0148] The metal foil used here is not particularly limited as long as it is a metal foil used in printed circuit board materials; known copper foils such as rolled copper foil and electrolytic copper foil are preferred. Furthermore, the thickness of the metal foil is not particularly limited, but is preferably 2μm to 70μm, more preferably 2μm to 35μm. The forming method and conditions for the metal foil-clad laminate are also not particularly limited; methods and conditions commonly used for printed circuit board laminates and multilayer boards can be applied. For example, when forming the metal foil-clad laminate, multi-stage presses, multi-stage vacuum presses, continuous forming machines, autoclave forming machines, etc., can be used. Additionally, the temperature is typically 100℃ to 300℃, and the pressure is typically a surface pressure of 2 kgf / cm². 2 ~100kgf / cm 2The heating time is typically in the range of 0.05 hours to 5 hours. Furthermore, post-curing can be performed at a temperature of 150°C to 300°C, depending on the requirements. Additionally, a multilayer board can be manufactured by combining and laminating the prepreg of this embodiment with a separately manufactured inner layer circuit board. The metal foil laminate of this embodiment, by forming a predetermined circuit pattern, is suitable for use as a printed circuit board.

[0149] [Resin Sheets]

[0150] The laminated resin sheet of this embodiment has a sheet substrate and a resin composition layer formed by coating one or both sides of the sheet substrate with the above-described resin composition and then drying it. The manufacturing method of the laminated resin sheet can be carried out according to conventional methods and is not particularly limited. For example, it can be obtained by coating a solution obtained by dissolving or dispersing the resin composition of this embodiment in a solvent onto the sheet substrate and then drying it.

[0151] The substrate material used herein is not particularly limited, and examples include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and release films with release agents coated on the surface of these films, organic film substrates such as polyimide film, conductor foils such as copper foil and aluminum foil, glass plates, SUS plates, FRP and other plate-shaped substrates, but is not particularly limited to these.

[0152] As a coating method, for example, a method of coating a solution obtained by dissolving or dispersing the resin composition of this embodiment in a solvent onto a sheet substrate using a bar coater, a die coater, a doctor blade, a Beck coater, or the like.

[0153] Furthermore, the single-layer resin sheet of this embodiment is formed by molding the above-described resin composition into a sheet shape. The manufacturing method of the single-layer resin sheet can be carried out according to conventional methods and is not particularly limited. For example, in the above-described method for manufacturing a laminated resin sheet, the following methods can be listed: a solution in which the resin composition of this embodiment is dissolved or dispersed in a solvent is applied to a sheet substrate and dried, and then the sheet substrate is peeled off or etched from the laminated resin sheet. It should be noted that by supplying the solution in which the resin composition of this embodiment is dissolved or dispersed in a solvent to a mold having a sheet-shaped cavity and drying it, etc., a single-layer resin sheet (resin sheet) can also be obtained without using a sheet substrate.

[0154] It should be noted that in the production of the single-layer resin sheet or the laminated resin sheet in this embodiment, the drying conditions for removing the solvent are not particularly limited. If the temperature is low, the solvent is likely to remain in the resin composition. If the temperature is high, the resin composition will be cured. Therefore, it is preferable to perform the drying process at a temperature of 20°C to 170°C for 1 minute to 90 minutes.

[0155] Furthermore, the thickness of the resin composition layer of the single-layer or laminated sheet in this embodiment can be adjusted by the concentration of the resin composition solution and the coating thickness in this embodiment. There is no particular limitation. Generally speaking, when the coating thickness is thicker, solvent is more likely to remain during drying. Therefore, 0.1 μm to 500 μm is preferred.

[0156] Printed circuit boards

[0157] The printed circuit board of this embodiment has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, wherein the insulating layer contains a cured product of the aforementioned resin composition. The manufacturing method of the printed circuit board can be performed according to conventional methods and is not particularly limited. For example, it can be manufactured by the following method: First, a copper-clad laminate or a metal-clad laminate of this embodiment is prepared. An inner layer substrate is formed by etching the surface of the metal-clad laminate. On the surface of the inner layer circuit of the inner layer substrate, a surface treatment is performed as needed to improve adhesive strength. Then, a required number of sheets of the prepreg of this embodiment are overlapped on the surface of the inner layer circuit, and then metal foil for the outer layer circuit is laminated on its outer side. The substrate is then heated and pressurized to integrally form the laminate. By operating as described above, a multilayer laminate with an insulating layer formed of a substrate and a cured product of the resin composition is formed between the metal foil for the inner and outer layer circuits. Next, after opening holes for through holes and conductive holes are performed on the multilayer laminate, a descaling treatment is performed to remove resin residue, i.e., glue residue, from the resin component. Then, a plated metal film is formed on the wall of the hole to conduct the metal foil used for the inner layer circuit and the outer layer circuit. Then, the metal foil used for the outer layer circuit is etched to form the outer layer circuit and a printed circuit board is manufactured.

[0158] Alternatively, the laminated resin sheet or single-layer resin sheet of this embodiment can be used instead of the metal foil laminate or prepreg. When the laminated resin sheet or single-layer resin sheet of this embodiment is overlapped on the surface of the inner layer circuit, a multilayer laminate is manufactured in which an insulating layer formed of a cured resin composition is formed between the metal foils for the inner layer circuit and the outer layer circuit.

[0159] Thus, according to this embodiment, since the resin composition contains the cyanate compound (A), cyclophosphonitrile compound (B), and inorganic filler (C) shown in formula (1), excellent heat resistance and flame retardancy can be obtained.

[0160] Example

[0161] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way.

[0162] (Example 1)

[0163] 30 parts by weight of the cyanate compound (A) shown in formula (1) (dicyclopentadiene type cyanate compound (DCPD type CN) CO3COYANGZHOU TECHIA MATERIAL Co., Ltd.), 40 parts by weight of the biphenyl aralkyl type epoxy resin (NC-3000FH, manufactured by Nippon Kayaku Co., Ltd.) as epoxy compound (E), 10 parts by weight of the cresol phenolic varnish type epoxy resin (N680, manufactured by DIC Co., Ltd.), 3.0 parts by weight of the aminotriazine-containing phenolic varnish type phenolic resin (LA-3018, manufactured by DIC Co., Ltd.) as phenolic compound (F), and the phenolic varnish type phenolic resin (LA-3018, manufactured by DIC Co., Ltd.) as a phenolic compound (F), and the phenolic varnish type phenolic resin (LA-3018, manufactured by DIC Co., Ltd.) as a phenolic compound (F), and the phenolic varnish type phenolic resin (LA-3018, manufactured by DIC Co., Ltd.) as a phenolic compound, and the phenolic varnish type phenolic resin (C ... 12 parts by weight of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (BMI-5100, manufactured by Yamato Kasei Corporation) as imide compound (G), 5.0 parts by weight of hexaphenoxycyclotriphosphazene (Ravitle (registered trademark) FP-110, manufactured by Fushimi Pharmaceutical Co., Ltd.) as cyclophosphazene compound (B), and 150 parts by weight of boehmite (Apyral AOH60, manufactured by Nabaltec Co., Ltd.) as inorganic filler material (C) were mixed, and the solids were diluted to 60% by weight with methyl ethyl ketone to obtain a varnish. The composition of the resin composition is shown in Table 1.

[0164] The obtained varnish was impregnated and coated onto a 0.09 mm thick (IPC No. #2116) E-glass cloth, and dried at 170°C for 5 minutes using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Manufacturing Co., Ltd.) to obtain a prepreg containing 49% by weight of the resin composition. Eight sheets of this prepreg were overlapped, with 12 μm copper foil (3EC-VLP, manufactured by Mitsui Metals & Minerals Co., Ltd.) placed on both sides, and then dried under a pressure of 30 kg / cm². 2 A 12μm copper-clad laminate with a thickness of 0.8mm was obtained by vacuum pressing at 210℃ for 150 minutes. The copper foil on both sides of the obtained copper-clad laminate was removed by etching to obtain the laminate itself. The flame retardancy and formability of the obtained copper-clad laminate were evaluated.

[0165] (Flame retardancy)

[0166] The aforementioned laminated plate was cut into 125mm × 13mm × 0.8mm dimensions to obtain 5 test samples. Following the UL94 vertical test method, the test samples were vertically mounted in a fixture, and the burning time was measured by subjecting them to two 10-second contact flames using a 20mm flame.

[0167] (Moldability)

[0168] The aforementioned laminated plate was cut into 300mm × 300mm × 0.8mm dimensions. Both sides of the resulting sample were observed to confirm the presence or absence of flow marks. If flow marks were present, the longest value of the flow mark originating from the end of the sample was measured.

[0169] The results are shown in Table 1.

[0170] (Example 2)

[0171] Except for the changes in the resin composition as shown in Table 1, the varnish and copper-clad laminate were prepared in the same manner as in Example 1, and the flame retardancy and moldability were evaluated in the same way as in Example 1. In Example 2, the content of cyclophosphonitrile compound (B) relative to 100 parts by weight of the resin solids was set to 3.0 parts by weight. The composition of the resin composition, the evaluation of flame retardancy, and the evaluation of moldability are shown in Table 1.

[0172] (Example 3)

[0173] Except for the changes in the resin composition as shown in Table 1, the varnish and copper-clad laminate were prepared in the same manner as in Example 1, and the flame retardancy and moldability were evaluated in the same way as in Example 1. In Example 3, the content of cyclophosphonitrile compound (B) relative to 100 parts by weight of the resin solids was set to 8.0 parts by weight. The composition of the resin composition, the evaluation of flame retardancy, and the evaluation of moldability are shown in Table 1.

[0174] (Example 4)

[0175] Except for the changes in the resin composition as shown in Table 1, the varnish and copper-clad laminate were prepared in the same manner as in Example 1, and the flame retardancy and moldability were evaluated in the same way as in Example 1. In Example 4, the content of cyclophosphonitrile compound (B) relative to 100 parts by weight of the resin solids was set to 9.0 parts by weight. The composition of the resin composition, the evaluation of flame retardancy, and the evaluation of moldability are shown in Table 1.

[0176] (Example 5)

[0177] Except for the changes in the resin composition as shown in Table 1, the varnish and copper-clad laminate were prepared in the same manner as in Example 1, and the flame retardancy and moldability were evaluated in the same way as in Example 1. In Example 5, the content of cyclophosphonitrile compound (B) relative to 100 parts by weight of the resin solids was set to 9.9 parts by weight. The composition of the resin composition, the evaluation of flame retardancy, and the evaluation of moldability are shown in Table 1.

[0178] (Example 6)

[0179] Except for the changes in the resin composition as shown in Table 2, the varnish and copper-clad laminate were prepared in the same manner as in Example 1, and the flame retardancy and moldability were evaluated in the same way as in Example 1. In Example 6, the content of cyclophosphonitrile compound (B) relative to 100 parts by weight of the resin solids was set to 10.0 parts by weight. The composition of the resin composition, the evaluation of flame retardancy, and the evaluation of moldability are shown in Table 2.

[0180] (Example 7)

[0181] Except for the changes in the resin composition shown in Table 2, the varnish and copper-clad laminate were prepared in the same manner as in Example 1, and the flame retardancy and moldability were evaluated in the same way as in Example 1. In Example 7, the content of cyclophosphonitrile compound (B) relative to 100 parts by weight of the resin solids was set to 15.0 parts by weight. The composition of the resin composition, the evaluation of flame retardancy, and the evaluation of moldability are shown in Table 2.

[0182] (Example 8)

[0183] Except for the changes in the resin composition shown in Table 2, the varnish and copper-clad laminate were prepared in the same manner as in Example 1, and the flame retardancy and moldability were evaluated in the same way as in Example 1. In Example 8, 150 parts by weight of silica (manufactured by Denka Co., Ltd., SFP-130MC) were mixed in place of boehmite as inorganic filler (C). The composition of the resin composition, the evaluation of flame retardancy, and the evaluation of moldability are shown in Table 2.

[0184] (Comparative Example 1)

[0185] Without adding cyclophosphonitrile compound (B), the composition ratio was changed as shown in Table 2. Otherwise, the varnish and copper-clad laminate were prepared in the same manner as in Example 1, and the flame retardancy and moldability were evaluated in the same way as in Example 1. The composition of the resin composition, the evaluation of flame retardancy, and the evaluation of moldability are shown in Table 2.

[0186] (Comparative Example 2)

[0187] Instead of cyclophosphonitrile compound (B), an aromatic condensed phosphate ester (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.) was used as a flame retardant. Otherwise, the varnish and copper-clad laminate were prepared in the same manner as in Example 1, and the flame retardancy and moldability were evaluated in the same way as in Example 1. The composition of the resin composition, the evaluation of its flame retardancy, and the evaluation of its moldability are shown in Table 2.

[0188] [Table 1]

[0189]

[0190] [Table 2]

[0191]

[0192] (Results of the Examples and Comparative Examples)

[0193] As shown in Tables 1 and 2, according to Examples 1-8 with added cyclophosphinitron compound (B), compared with Comparative Example 1 without added flame retardant and Comparative Example 2 with added aromatic condensed phosphate ester instead of cyclophosphinitron compound (B) as flame retardant, the maximum burning time and average burning time can be significantly shortened, achieving sufficient flame retardancy. Regarding the judgment of flame retardancy, a maximum burning time of less than 10 seconds and an average burning time of less than 5 seconds is considered sufficient flame retardancy, denoted as "V-0", while a maximum burning time of 10 seconds to 30 seconds or an average burning time of 10 seconds to 25 seconds is considered insufficient flame retardancy, denoted as "V-1". It was observed that the degree of flame retardancy tends to increase with the increase of the content of cyclophosphinitron compound (B). That is, it can be seen that excellent flame retardancy can be obtained by adding cyclophosphinitron compound (B).

[0194] Furthermore, as shown in Tables 1 and 2, good moldability was also obtained according to Examples 1 to 8. Regarding the evaluation of moldability, a flow mark of less than 8.5 cm was considered the best moldability and was marked "◎"; a flow mark of 8.5 cm or more but less than 11.5 cm was considered good moldability and was marked "〇"; and a flow mark of 11.5 cm or more was considered poor moldability and was marked "×". That is, it can be seen that the content of cyclophosphonitrile compound (B) relative to 100 parts by mass of the resin solids is preferably set to 3 parts by mass or more and 15 parts by mass or less.

[0195] Furthermore, as shown in Tables 1 and 2, in Example 1 where boehmite was used as the inorganic filler material (C) and in Example 8 where silica was used as the inorganic filler material (C), substantially the same results were obtained regarding flame retardancy and formability. That is, it can be seen that regardless of the type of inorganic filler material (C), the effects resulting from the addition of cyclophosphonitrile compound (B) can be obtained.

[0196] Industrial availability

[0197] The resin composition of the present invention is industrially applicable as a material for cured products, prepregs, metal foil laminates, single-layer resin sheets, laminated resin sheets, printed circuit boards, etc.

Claims

1. A resin composition comprising a cyanate compound (A) of the following formula (1), a cyclophosphonitrile compound (B), and an inorganic filler (C). In equation (1), R 1 Independently represent hydrocarbon groups with 1 to 8 carbon atoms, i is an integer from 0 to 3, n1 represents the repetition number, and its average value is a number from 0 to 5.

2. The resin composition according to claim 1, wherein, The cyclophosphonitrile compound (B) comprises the compound shown in formula (2) below. In equation (2), Z1 and Z2 each independently represent vinyl or hydrogen atoms, and n2 represents an integer from 3 to 8.

3. The resin composition according to claim 1, wherein, The inorganic filler material (C) comprises at least one selected from the group consisting of silica, alumina, magnesium hydroxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride.

4. The resin composition according to claim 1, further comprising at least one selected from the group consisting of cyanate compounds other than said cyanate compound (A), epoxy compounds, phenolic compounds, maleimide compounds, and polyphenylene ether compounds.

5. The resin composition according to claim 1, wherein, The content of the cyanate compound (A) is 10 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the resin solids.

6. The resin composition according to claim 1, wherein, The content of the cyclophosphonitrile compound (B) is 3 parts by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the resin solids.

7. The resin composition according to claim 1, wherein, The content of the inorganic filler material (C) is 50 parts by mass or more and 300 parts by mass or less, relative to 100 parts by mass of the resin solids.

8. A cured product formed by curing the resin composition according to any one of claims 1 to 7.

9. A prepreg having a substrate and a resin composition of any one of claims 1 to 7 impregnated or coated on said substrate.

10. A metal foil laminate comprising: a laminate formed by laminating one or more sheets of the prepreg as described in claim 9, and a metal foil laminated on one or both sides of the laminate.

11. A single-layer resin sheet, which is formed by molding the resin composition according to any one of claims 1 to 7 into a sheet shape.

12. A laminated resin sheet having a sheet substrate and a resin composition layer formed by coating one or both sides of the sheet substrate with the resin composition of any one of claims 1 to 7 and drying it.

13. A printed circuit board having an insulating layer and a conductor layer formed on one or both sides of the insulating layer, The insulating layer comprises a cured product of the resin composition according to any one of claims 1 to 7.

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