Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and printed wiring board

Abstract

This resin composition contains a maleimide compound (A), a phosphine oxide compound (B), and an epoxy compound (C). The maleimide compound (A) includes a maleimide compound (A1) having an alkyl group having 6 or more carbon atoms and / or an alkylene group having 6 or more carbon atoms. The phosphine oxide compound (B) has a structure represented by formula (b0). (In formula (b0), X represents an alkylene group or a monovalent or divalent hydrocarbon group including at least one aromatic ring, and n represents 1 or 2).

Description

[Technical field]

[0001] The present disclosure generally relates to a resin composition, a prepreg, a resin-attached film, a resin-attached metal foil, a metal-clad laminate, and a printed wiring board. More specifically, the present disclosure relates to a resin composition containing a maleimide compound, and a prepreg, a resin-attached film, a resin-attached metal foil, a metal-clad laminate, and a printed wiring board using the resin composition. [Background technology]

[0002] Patent Document 1 discloses a flame-retardant resin composition used in the manufacture of printed wiring boards, etc. This flame-retardant resin composition contains a resin component containing a bismaleimide compound, a curing agent, a phosphorus-based flame retardant, and a fluororesin filler. The phosphorus-based flame retardant is at least one selected from the group consisting of cyclophosphazene-based flame retardants and phosphate-based flame retardants.

[0003] However, the phosphorus-based flame retardant of Patent Document 1 is easily thermally decomposed or hydrolyzed at a temperature lower than the temperature at which the flame is burned. If such a phosphorus-based flame retardant is contained in a flame-retardant resin composition, it may cause deterioration in flame resistance, chemical resistance, and electrical properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2018-044065 A Summary of the Invention

[0005] An object of the present disclosure is to provide a resin composition, a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a printed wiring board that can improve flame resistance, chemical resistance, and electrical properties.

[0006] A resin composition according to an embodiment of the present disclosure contains a maleimide compound (A), a phosphine oxide compound (B), and an epoxy compound (C). The maleimide compound (A) contains a maleimide compound (A1) having an alkyl group having 6 or more carbon atoms and / or an alkylene group having 6 or more carbon atoms. The phosphine oxide compound (B) has a structure represented by the following formula (b0).

[0007] [ka]

[0008] (In formula (b0), X is a monovalent or divalent hydrocarbon group containing at least one aromatic ring, or an alkylene group, and n is 1 or 2.)

[0009] A prepreg according to one embodiment of the present disclosure includes a substrate and a resin layer containing the resin composition or a semi-cured product of the resin composition impregnated into the substrate.

[0010] A resin-attached film according to one embodiment of the present disclosure comprises a resin layer containing the resin composition or a semi-cured product of the resin composition, and a support film supporting the resin layer.

[0011] A resin-coated metal foil according to one embodiment of the present disclosure includes a resin layer containing the resin composition or a semi-cured product of the resin composition, and a metal foil adhered to the resin layer.

[0012] A metal-clad laminate according to one embodiment of the present disclosure comprises an insulating layer including a cured product of the resin composition or a cured product of the prepreg, and a metal layer bonded to the insulating layer.

[0013] A printed wiring board according to one embodiment of the present disclosure includes an insulating layer including a cured product of the resin composition or a cured product of the prepreg, and a conductor wiring formed on the insulating layer. [Brief description of the drawings]

[0014] [Figure 1]FIG. 1 is a schematic cross-sectional view showing a prepreg according to one embodiment of the present disclosure. [Diagram 2] FIG. 2 is a schematic plan view showing a base material used in the prepreg. [Diagram 3] Fig. 3A is a schematic cross-sectional view showing a resin-attached film (without a protective film) according to an embodiment of the present disclosure, and Fig. 3B is a schematic cross-sectional view showing a resin-attached film (with a protective film) according to an embodiment of the present disclosure. [Figure 4] FIG. 4 is a schematic cross-sectional view showing a resin-coated metal foil according to one embodiment of the present disclosure. [Diagram 5] FIG. 5 is a schematic cross-sectional view showing a metal-clad laminate according to one embodiment of the present disclosure. [Figure 6] 6A and 6B are schematic cross-sectional views showing a printed wiring board (without interlayer connections) according to an embodiment of the present disclosure. [Figure 7] FIG. 7 is a schematic cross-sectional view showing a semiconductor package according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] 1. Overview The resin composition according to the present embodiment can be used as a substrate material, which is not particularly limited, and examples thereof include a prepreg 1, a resin-coated film 2, a resin-coated metal foil 3, a metal-clad laminate 4, and a printed wiring board 5 (see Figs. 1 to 6B).

[0016] The resin composition according to the present embodiment contains a maleimide compound (A), a phosphine oxide compound (B), and an epoxy compound (C). The present inventors have found that a specific phosphine oxide compound (B) is not easily thermally decomposed or hydrolyzed at a temperature lower than the temperature at which it is burned. They have also found that the specific phosphine oxide compound (B) is not easily degraded in the properties of the maleimide compound (A) and the epoxy compound (C). They have also found that a combination of a specific maleimide compound (A) and an epoxy compound (C) can contribute to improved flame resistance, chemical resistance, and electrical properties.

[0017] Therefore, the resin composition according to this embodiment can improve flame resistance, chemical resistance, and electrical properties.

[0018] 2.Details The resin composition according to the present embodiment will be described in detail below. Furthermore, the prepreg 1, the resin-attached film 2, the resin-attached metal foil 3, the metal-clad laminate 4, the printed wiring board 5, and the semiconductor package 100 according to the present embodiment will be described in detail with reference to the drawings. For convenience of explanation, arrows indicating mutually orthogonal X-direction, Y-direction, and Z-direction are shown in some of the drawings, but these arrows do not have any substance.

[0019] (1) Resin composition The resin composition according to the present embodiment contains a maleimide compound (A), a phosphine oxide compound (B), and an epoxy compound (C). Preferably, the resin composition further contains a styrene-based copolymer (D). Preferably, the resin composition further contains an inorganic filler (E). The resin composition may further contain other components (F). The components of the resin composition will be described below.

[0020] <Maleimide compound (A)> The maleimide compound (A) includes a maleimide compound (A1) having an alkyl group having 6 or more carbon atoms and / or an alkylene group having 6 or more carbon atoms. That is, the maleimide compound (A1) has at least one of an alkyl group having 6 or more carbon atoms and an alkylene group having 6 or more carbon atoms. The upper limit of the number of carbon atoms of the alkyl group is not particularly limited, but is, for example, 100 or less. The upper limit of the number of carbon atoms of the alkylene group is not particularly limited, but is, for example, 100 or less. Thus, the maleimide compound (A1) has a long chain of C6 or more, and therefore it is easy to improve the electrical properties of the substrate.

[0021] Here, the electrical characteristics mainly refer to the dielectric characteristics. In this embodiment, in particular, the dielectric loss tangent can be made small. This makes it possible to suppress the deterioration of the transmission characteristics at high frequencies.

[0022] Preferably, the maleimide compound (A) includes at least one selected from the group consisting of a maleimide compound (A3) represented by the following formula (a3), a maleimide compound (A4) represented by the following formula (a4), and a maleimide compound (A5) represented by the following formula (a5). By including such a maleimide compound (A) in the resin composition, the electrical properties of the substrate can be further improved.

[0023] [ka]

[0024] [ka]

[0025] (In formula (a4), n represents an integer of 1 to 10.)

[0026] [ka]

[0027] (In formula (a5), n represents an integer of 1 to 10.)

[0028] Preferably, the maleimide group equivalent of the maleimide compound (A1) is 400 g / eq or more. This can further improve the electrical properties of the substrate. The upper limit of the maleimide group equivalent is preferably 3000 g / eq or less, more preferably 2000 g / eq or less. The maleimide group equivalent is a value obtained by dividing the molecular weight of the maleimide compound (A) by the number of maleimide groups contained in the maleimide compound (A). In other words, the maleimide group equivalent is the molecular weight per maleimide group.

[0029] Preferably, the maleimide compound (A) further contains a maleimide compound (A2) having an equivalent of the maleimide group of less than 400 g / eq. This allows the glass transition temperature (Tg) of the substrate to be increased. By increasing the Tg of the substrate, cracks are less likely to occur in the substrate, and the reliability of the interlayer connection can be improved. That is, even if stress due to a thermal shock test or the like is applied to a substrate such as a multilayer printed wiring board, cracks are less likely to occur in the substrate, and the increase in the resistance value of the via hole and through hole is suppressed, and the reliability of the interlayer connection can be improved. In particular, in recent years, with the increase in density and miniaturization of wiring, the diameter of the via hole and through hole is also becoming smaller, so that increasing the Tg of the substrate is effective. The lower limit of the equivalent of the maleimide group of the maleimide compound (A2) is preferably 150 g / eq or more, more preferably 200 g / eq or more.

[0030] The maleimide compound (A2) having an equivalent weight of the maleimide group of less than 400 g / eq is not particularly limited, but includes, for example, the maleimide compound (A6) represented by the following formula (a6): The maleimide compound (A6) is 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide.

[0031] [ka]

[0032] When the maleimide compound (A) further contains a maleimide compound (A2), the content of the maleimide compound (A2) relative to the total mass of the maleimide compound (A) is preferably 20 mass% or more and 65 mass% or less, more preferably 25 mass% or more and 60 mass% or less.

[0033] <Phosphine oxide compound (B)> The phosphine oxide compound (B) mainly contributes to improving flame resistance (particularly self-extinguishing property). That is, the phosphine oxide compound (B) can impart flame resistance to the substrate by forming an oxygen barrier layer as a coating of a phosphoric acid layer generated by thermal decomposition during combustion, and by forming a carbon coating on the resin surface through a dehydration action, thereby blocking oxygen and heat.

[0034] The phosphine oxide compound (B) contains phosphorus, and therefore can be a flame retardant. Preferably, the phosphine oxide compound (B) is an additive flame retardant. Here, flame retardants are classified into reactive flame retardants and additive flame retardants. The reactive flame retardant is a flame retardant that chemically bonds with other components through a chemical reaction. On the other hand, the additive flame retardant is a flame retardant other than the reactive flame retardant. That is, the additive flame retardant is a flame retardant that is only added and does not chemically bond with other components. Since the phosphine oxide compound (B) is not a salt, it can suppress the decrease in chemical resistance due to alkalis and the like. Therefore, the cured product of the resin composition according to this embodiment is stable against various chemicals even if it comes into contact with these chemicals during the manufacture of a printed wiring board.

[0035] In addition, the phosphine oxide compound (B) is poorly compatible with the maleimide compound (A) and the epoxy compound (C), and therefore is unlikely to inhibit the curing reaction of the maleimide compound (A) and the epoxy compound (C). Therefore, it is presumed that the properties of the maleimide compound (A) and the epoxy compound (C) are unlikely to deteriorate.

[0036] The phosphine oxide compound (B) is an organic phosphorus compound represented by POR3 (R is an organic group such as an alkyl group or an aryl group). The molecular weight of the phosphine oxide compound (B) is not particularly limited, but is, for example, 400 or more and 700 or less.

[0037] The phosphine oxide compound (B) has a structure represented by the following formula (b0).

[0038] [ka]

[0039] (In formula (b0), X is a monovalent or divalent hydrocarbon group containing at least one aromatic ring, or an alkylene group, and n is 1 or 2.)

[0040] Here, the upper limit of the number of aromatic rings (benzene rings) contained in the hydrocarbon group in formula (b0) is not particularly limited, but is, for example, not more than 5. The number of carbon atoms in the hydrocarbon group is not particularly limited, but is, for example, 6 to 14 (C6 to C14).

[0041] The number of carbon atoms in the alkylene group in formula (b0) is not particularly limited, but is from 1 to 10 (C1 to C10).

[0042] Since the phosphine oxide compound (B) has a structure represented by the above formula (b0), it is less susceptible to thermal decomposition and hydrolysis. Furthermore, compared with general phosphate esters, the phosphine oxide compound (B) is less likely to inhibit the curing reaction of the maleimide compound (A) and the epoxy compound (C). Therefore, it is presumed that the phosphine oxide compound (B) is less likely to deteriorate the properties of the maleimide compound (A) and the epoxy compound (C).

[0043] Preferably, the phosphine oxide compound (B) includes at least one selected from the group consisting of a phosphine oxide compound (B1) represented by the following formula (b1), a phosphine oxide compound (B2) represented by the following formula (b2), a phosphine oxide compound (B3) represented by the following formula (b3), a phosphine oxide compound (B4) represented by the following formula (b4), a phosphine oxide compound (B5) represented by the following formula (b5), a phosphine oxide compound (B6) represented by the following formula (b6), a phosphine oxide compound (B7) represented by the following formula (b7), and a phosphine oxide compound (B8) represented by the following formula (b8).

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] The phosphine oxide compounds (B1) to (B8) are types of additive-type flame retardants. In particular, the phosphine oxide compound (B1) is effective in improving chemical resistance.

[0053] Here, chemical resistance mainly means alkali resistance, which means that the substrate is less likely to whiten even if it is subjected to an alkali treatment under high temperature and high concentration conditions during desmearing, repair, etc.

[0054] Preferably, the phosphine oxide compound (B) contains a phosphine oxide compound (B9) having a melting point of 280° C. or more. This makes it possible to increase the thermal decomposition temperature of the resin composition. The upper limit of the melting point of the phosphine oxide compound (B9) is not particularly limited, but is, for example, 400° C. or less.

[0055] Here, the phosphine oxide compound (B9) may include the phosphine oxide compounds (B1) to (B8). That is, the melting points of the phosphine oxide compounds (B1) to (B8) may be 280° C. or higher.

[0056] Preferably, the resin composition further contains a reactive flame retardant. The reactive flame retardant is a flame retardant that chemically bonds with the maleimide compound (A) and / or the epoxy compound (C). In this way, the reactive flame retardant is reacted with the maleimide compound (A) and / or the epoxy compound (C), thereby further improving the flame resistance.

[0057] Preferably, the reactive flame retardant is a phosphorus-containing compound (B10) having a structure represented by the following formula (b10):

[0058] [ka]

[0059] In formula (b10), s represents an integer of 1 to 10, Z represents an arylene group or an ester bond represented by formula (b10.1), and R 1 ~R 3 each independently represents a hydrogen atom or a monovalent organic group, and * represents a bond.

[0060] The monovalent organic group is not particularly limited, but examples thereof include alkyl groups, etc. The alkyl group is not particularly limited, but examples thereof include methyl groups, etc.

[0061] The structure represented by formula (b10) is preferably a structure represented by the following formula (b11.1) or (b11.2), which can further improve chemical resistance.

[0062] [ka]

[0063] (In formula (b11.1) and formula (b11.2), * indicates a bond.)

[0064] The phosphorus-containing compound (B10) preferably further has a structure represented by the following formula (b12.1) or (b12.2), which can further improve the chemical resistance.

[0065] [ka]

[0066] (In formula (b12.1) and formula (b12.2), * indicates a bond.)

[0067] Preferably, the phosphorus-containing compound (B10) has both the structure represented by formula (b11.1) or formula (b11.2) and the structure represented by formula (b12.1) or formula (b12.2). For example, the phosphorus-containing compound (B10) preferably includes the phosphorus-containing compound (B13) represented by the following formula (b13). The phosphorus-containing compound (B13) is diphenyl-2-methacryloyloxyethyl phosphate.

[0068] [ka]

[0069] The content of the phosphine oxide compound (B) is preferably 1 part by mass or more and 65 parts by mass or less, more preferably 5 parts by mass or more and 60 parts by mass or less, relative to 100 parts by mass in total of the maleimide compound (A) and the epoxy compound (C).

[0070] <Epoxy compound (C)> The epoxy compound (C) is a compound having at least one (preferably two or more) epoxy group in the molecule. The epoxy compound (C) is not particularly limited, but examples thereof include naphthalene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, and mesogen skeleton epoxy resin. The mesogen skeleton epoxy resin is an epoxy resin having at least one mesogen group in the molecule. The mesogen group is a rigid structure and is the minimum unit structure capable of forming a liquid crystal structure. The mesogen group is not particularly limited, but examples thereof include a biphenyl structure and a phenyl benzoate structure.

[0071] Preferably, the epoxy compound (C) contains an epoxy compound (C1) having an epoxy equivalent of 200 g / eq or more and 350 g / eq or less. This allows the glass transition temperature (Tg) of the substrate to be increased. As described above, by increasing the Tg of the substrate, cracks are less likely to occur in the substrate, and the reliability of interlayer connection can be improved.

[0072] Preferably, the mass ratio of the maleimide compound (A) to the epoxy compound (C) is 50:50 to 95:5. In other words, preferably, the content of the epoxy compound (C) is 5 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the total of the maleimide compound (A) and the epoxy compound (C). This makes it possible to reduce the water absorption rate of the substrate.

[0073] <Styrene-based copolymer (D)> Preferably, the resin composition further contains a styrene-based copolymer (D), which can reduce warping of the substrate.

[0074] The styrene copolymer (D) has at least one structure derived from a styrene compound and / or a styrene derivative. The styrene compound and / or the styrene derivative are not particularly limited, but examples thereof include styrene, α-methylstyrene, p-methylstyrene, compounds in which a part of the hydrogen atoms in the aromatic rings of these are substituted with alkyl groups, and polymers thereof. The styrene copolymer (D) may further have a structure derived from a conjugated diene compound.

[0075] The styrene copolymer (D) may be a non-hydrogenated or hydrogenated product. A non-hydrogenated product means a substance that is not hydrogenated. A hydrogenated product means a substance that is hydrogenated. The weight average molecular weight of the styrene copolymer (D) is preferably 10,000 or more and 150,000 or less.

[0076] Preferably, the styrene copolymer (D) contains at least one selected from the group consisting of methylstyrene (ethylene / butylene) methylstyrene copolymer, methylstyrene (ethylene-ethylene / propylene) methylstyrene copolymer, styrene-isoprene copolymer, styrene-isoprene styrene copolymer, styrene (ethylene / butylene) styrene copolymer, styrene (ethylene-ethylene / propylene) styrene copolymer, and hydrogenated products thereof. By including such a styrene copolymer (D) in the resin composition, the warpage of the substrate can be further reduced.

[0077] When the resin composition further contains a styrene-based copolymer (D), the content of the styrene-based copolymer (D) is preferably 10 parts by mass or more and 40 parts by mass or less per 100 parts by mass of the total of the maleimide compound (A), the epoxy compound (C) and the styrene-based copolymer (D), thereby making it possible to further reduce warpage of the substrate.

[0078] <Inorganic filler (E)> Preferably, the resin composition further contains an inorganic filler (E), which can further improve the flame resistance of the substrate and reduce the linear expansion coefficient of the substrate.

[0079] Preferably, the inorganic filler (E) contains at least one selected from the group consisting of metal oxides, metal hydroxides, talc, aluminum borate, barium sulfate, calcium carbonate, and zinc molybdate. The metal oxides are not particularly limited, but include, for example, silica, alumina, titanium oxide, and mica. The metal hydroxides are not particularly limited, but include, for example, aluminum hydroxide and magnesium hydroxide.

[0080] Preferably, the inorganic filler (E) is surface-treated with a surface treatment agent. This improves wettability with the maleimide compound (A), the phosphine oxide compound (B), the epoxy compound (C), and the styrene-based copolymer (D), and can improve the dispersibility of the inorganic filler (E). The surface treatment agent is not particularly limited, but examples thereof include silane coupling agents, titanate coupling agents, fatty acids, and surfactants. Preferably, the silane coupling agent has at least one functional group selected from the group consisting of vinyl groups, epoxy groups, styryl groups, methacryl groups, acrylic groups, amino groups, isocyanurate groups, ureido groups, mercapto groups, isocyanate groups, and acid anhydride groups.

[0081] The inorganic filler (E) is preferably spherical in shape, which can improve the fluidity of the resin composition during molding.

[0082] The inorganic filler (E) has an average particle size of preferably 0.01 μm to 50 μm, more preferably 0.05 μm to 20 μm, where the average particle size means the particle size at an integrated value of 50% in the particle size distribution determined by a laser diffraction / scattering method.

[0083] When the resin composition further contains an inorganic filler (E), the content of the inorganic filler (E) is preferably 30 parts by mass or more and 200 parts by mass or less, more preferably 50 parts by mass or more and 150 parts by mass or less, based on 100 parts by mass in total of the maleimide compound (A), the epoxy compound (C) and the styrene-based copolymer (D). In this case, the resin composition does not necessarily contain the styrene-based copolymer (D).

[0084] <Others (F)> The resin composition may further contain other components (F). The other components (F) are not particularly limited, but may include, for example, catalytic curing agents, crosslinking agents, reaction initiators, resin modifiers, defoamers, heat stabilizers, antistatic agents, UV absorbers, dyes, pigments, lubricants, dispersants such as wetting dispersants, and leveling agents. The catalytic curing agents include imidazole compounds such as 2-ethyl-4-methylimidazole. The content of the other components (F) is not particularly limited as long as it does not impair the effects of this embodiment.

[0085] <Form> The form of the resin composition is not particularly limited. The resin composition may be liquid or solid. The liquid form includes a varnish form. The resin composition is stirred and mixed with a solvent to prepare a varnish. The solvent is not particularly limited, but examples thereof include toluene, methyl ethyl ketone, cyclohexanone, and propylene glycol monomethyl ether acetate.

[0086] (2) Prepreg FIG. 1 shows a prepreg 1 according to this embodiment. The prepreg 1 is generally in the form of a sheet or film. That is, the prepreg 1 extends in the X and Y directions. The prepreg 1 is used as a material for a metal-clad laminate 4, a material for a printed wiring board 5, and for multi-layering (build-up method) of the printed wiring board 5. When the prepreg 1 is heated or irradiated with light (ultraviolet rays), it hardens and becomes a hardened product. The hardened product is a substance in a hardened state (insoluble and unmeltable state). The hardened product of the prepreg 1 can form the insulating layer 40 of the metal-clad laminate 4 and the insulating layer 50 of the printed wiring board 5 (see FIGS. 5 to 6B).

[0087] The prepreg 1 includes a substrate 11 and a resin layer 10 containing a resin composition or a semi-cured product of a resin composition impregnated into the substrate 11. One prepreg 1 includes at least one substrate 11.

[0088] The base material 11 is not particularly limited, but examples thereof include woven fabric and nonwoven fabric.

[0089] The woven fabric is not particularly limited, but examples thereof include glass cloth, aramid cloth, and polyester cloth.

[0090] The nonwoven fabric is not particularly limited, but examples thereof include glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper.

[0091] The glass fibers constituting the glass cloth and the glass nonwoven fabric are not particularly limited, but examples thereof include Q glass, NE glass, E glass, S glass, T glass, L glass, and L2 glass.

[0092] The thickness of the substrate 11 is preferably 5 μm or more and 300 μm or less, and more preferably 10 μm or more and 200 μm or less.

[0093] The surface of the substrate 11 may be surface-treated with a silane coupling agent. The silane coupling agent is not particularly limited, but examples thereof include silane coupling agents having at least one functional group selected from the group consisting of a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, an isocyanate group, and an acid anhydride group.

[0094] An example of the substrate 11 is shown in Fig. 2. The substrate 11 is a woven fabric made of warp threads 111 and weft threads 112. The direction of the warp threads 111 (X direction) and the direction of the weft threads 112 (Y direction) are perpendicular to each other. The substrate 11 extends in the X direction and the Y direction. A bias direction BD is a direction that intersects with the direction of the warp threads 111 (X direction). The angle between the bias direction BD and the direction of the warp threads 111 (X direction) is θ (e.g., 45°).

[0095] The resin layer 10 is divided into a case where it contains a resin composition (first case) and a case where it contains a semi-cured product of the resin composition (second case).

[0096] In the first case, the resin layer 10 is formed as follows. That is, the base material 11 is impregnated with a varnish of a resin composition, and then the solvent is volatilized to form the resin layer 10. This resin layer 10 is formed from an unreacted resin composition (dried product). Here, the unreacted state includes a state in which no reaction has occurred and a state in which almost no reaction has occurred. The resin layer 10 changes from an unreacted state to a cured state by being heated.

[0097] On the other hand, the resin composition in the second case is in a semi-cured state. Here, the semi-cured state means a state of an intermediate stage (B stage) of the curing reaction. The intermediate stage is a stage between the varnish state stage (A stage) and the cured state stage (C stage). The resin layer 10 in the second case is formed as follows. That is, after the varnish of the resin composition is impregnated into the substrate 11, the resin layer 10 can be formed by heating to volatilize the solvent and progressing the curing reaction of the resin composition to the intermediate stage. This resin layer 10 is formed of a resin composition in a semi-cured state (semi-cured product).

[0098] As described above, in the resin layer 10, the progress of the curing reaction may differ depending on the resin composition used.

[0099] The thickness of the prepreg 1 (thickness in the Z direction) is not particularly limited, but is, for example, 10 μm or more and 120 μm or less, which can realize a thin board.

[0100] As described above, the resin layer 10 of the prepreg 1 according to this embodiment is formed from the above-mentioned resin composition, and therefore can have improved flame resistance, chemical resistance, and electrical properties.

[0101] (3) Resin-coated film 3A shows a resin-attached film 2 according to this embodiment. The resin-attached film 2 is generally in the form of a film or sheet. The resin-attached film 2 includes a resin layer 20 containing a resin composition or a semi-cured product of a resin composition, and a support film 21 that supports the resin layer 20. The resin-attached film 2 is used for multi-layering of a printed wiring board 5 (build-up method), etc.

[0102] When heated or irradiated with light (ultraviolet light), the resin layer 20 hardens to form the insulating layer 40 of the metal-clad laminate 4 and the insulating layer 50 of the printed wiring board 5 (see FIGS. 5 to 6B). The resin layer 20 is similar to the resin layer 10 of the prepreg 1, except that it is not impregnated into the base material 11.

[0103] The thickness of the resin layer 20 is not particularly limited, but is, for example, 10 μm or more and 120 μm or less, which can realize a thin substrate.

[0104] The support film 21 supports the resin layer 20. This makes the resin layer 20 easier to handle. The support film 21 can be peeled off from the resin layer 20 as necessary. Preferably, after the resin layer 20 is cured to form the insulating layer 40, the support film 21 is peeled off from the insulating layer 40. The same applies when the insulating layer 50 is formed from the resin layer 20.

[0105] The support film 21 is, for example, an electrically insulating film, but is not particularly limited thereto. Specific examples of the support film 21 include a polyethylene terephthalate (PET) film, a polyimide film, a polyester film, a polyparabanic acid film, a polyether ether ketone film, a polyphenylene sulfide film, an aramid film, a polycarbonate film, and a polyarylate film. The support film 21 is not limited to these films.

[0106] In FIG. 3A, one side of the resin layer 20 is covered with the support film 21, but as shown in FIG. 3B, one side of the resin layer 20 may be covered with the support film 21 and the other side of the resin layer 20 may be covered with the protective film 22. Like the support film 21, the protective film 22 can also be peeled off from the resin layer 20 as necessary. By covering both sides of the resin layer 20 in this way, the resin layer 20 becomes even easier to handle. In addition, adhesion of foreign matter to the resin layer 20 can be suppressed.

[0107] The protective film 22 is, for example, an electrically insulating film, but is not limited thereto. Specific examples of the protective film 22 include a polyethylene terephthalate (PET) film, a polyolefin film, a polyester film, and a polymethylpentene film. The protective film 22 is not limited to these films.

[0108] As described above, the resin layer 20 of the resin-coated film 2 according to this embodiment is formed from the above-mentioned resin composition, and therefore can have improved flame resistance, chemical resistance, and electrical properties.

[0109] (4) Resin-coated metal foil 4 shows the resin-coated metal foil 3 according to this embodiment. The resin-coated metal foil 3 is generally in the form of a film or sheet. The resin-coated metal foil 3 includes a resin layer 30 containing a resin composition or a semi-cured product of the resin composition, and a metal foil 31 bonded to the resin layer 30. The resin-coated metal foil 3 is used for multi-layering of a printed wiring board 5 (build-up method), etc.

[0110] When the resin layer 30 is heated or irradiated with light (ultraviolet light), it hardens and can form the insulating layer 40 of the metal-clad laminate 4 and the insulating layer 50 of the printed wiring board (see Figs. 5 to 6B). The resin layer 30 is similar to the resin layer 10 of the prepreg 1, except that it is not impregnated into the base material 11.

[0111] The thickness of the resin layer 30 is not particularly limited, but is, for example, 10 μm or more and 120 μm or less, which can realize a thin substrate.

[0112] The metal foil 31 is adhered to the resin layer 30. Specific examples of the metal foil 31 include, but are not limited to, copper foil, aluminum foil, and nickel foil. The metal foil 31 can be etched away to remove unnecessary portions in a subtractive method or the like to form conductor wiring 51 (see FIG. 6A, etc.).

[0113] The thickness of the metal foil 31 is not particularly limited, but is preferably, for example, not less than 0.2 μm and not more than 35 μm.

[0114] When the metal foil 31 is an ultra-thin metal foil, from the viewpoint of improving handling properties, the metal foil 31 is preferably a part of an ultra-thin metal foil with a carrier. The ultra-thin metal foil with a carrier includes the metal foil 31 (ultra-thin metal foil), a release layer, and a carrier. In this case, the thickness of the metal foil 31 is, for example, 10 μm or less. The release layer is a layer that temporarily bonds the metal foil 31 and the carrier. If necessary, the metal foil 31 is peeled off from the release layer. The carrier is a support that supports the metal foil 31. Specific examples of the carrier include copper foil and aluminum foil. The thickness of the carrier is thicker than that of the metal foil 31.

[0115] As described above, the resin layer 30 of the resin-coated metal foil 3 according to this embodiment is formed from the above-mentioned resin composition, and therefore can improve flame resistance, chemical resistance, and electrical properties.

[0116] (5)Metal-clad laminate 5 shows a metal-clad laminate 4 according to this embodiment. The metal-clad laminate 4 includes an insulating layer 40 and a metal layer 41 bonded to the insulating layer 40. The insulating layer 40 includes a cured product of a resin composition or a cured product of a prepreg 1. The metal-clad laminate 4 is used as a material for a printed wiring board 5, etc.

[0117] In FIG. 5, one insulating layer 40 has one substrate 42, but one insulating layer 40 may have two or more substrates 42.

[0118] The thickness of the insulating layer 40 is not particularly limited, but is, for example, 10 μm or more and 120 μm or less, which can realize a thin substrate.

[0119] 5, the metal layer 41 is bonded to both sides of the insulating layer 40, but it may be bonded to only one side. A metal-clad laminate 4 in which the metal layer 41 is bonded to both sides of the insulating layer 40 is a double-sided metal-clad laminate. A metal-clad laminate 4 in which the metal layer 41 is bonded to only one side of the insulating layer 40 is a single-sided metal-clad laminate.

[0120] The metal layer 41 is not particularly limited, but may be, for example, a metal foil, etc. The metal foil is not particularly limited, but may be, for example, a copper foil, an aluminum foil, a nickel foil, etc.

[0121] The thickness of the metal layer 41 is not particularly limited, but is, for example, 0.2 μm or more and 35 μm or less. When the metal layer 41 is an ultra-thin metal foil, from the viewpoint of improving the handling property, the metal layer 41 is preferably a part of the ultra-thin metal foil with a carrier. The ultra-thin metal foil with a carrier is as described above.

[0122] As described above, the insulating layer 40 of the metal-clad laminate 4 according to this embodiment is formed from the above-mentioned resin composition, and therefore can have improved flame resistance, chemical resistance, and electrical properties.

[0123] (6) Printed wiring board 6A and 6B show a printed wiring board 5 according to this embodiment. The printed wiring board 5 includes an insulating layer 50 and conductor wiring 51 formed on the insulating layer 50. The insulating layer 50 includes a cured product of a resin composition or a cured product of a prepreg 1.

[0124] The printed wiring board 5 shown in FIG. 6A has one insulating layer 50. In FIG. 6A, one insulating layer 50 has one base material 52, but one insulating layer 50 may have two or more base materials 52. On the other hand, the printed wiring board 5 shown in FIG. 6B has multiple (specifically, three) insulating layers 50. That is, the three insulating layers 50 are a first insulating layer 510, a second insulating layer 520, and a third insulating layer 530. These insulating layers 50 are stacked and bonded in order in the thickness direction. In FIG. 6B, each of the first insulating layer 510, the second insulating layer 520, and the third insulating layer 530 may not have a base material 52, or may have one or more base materials 52. In this way, the insulating layer 50 is similar to the insulating layer 40 of the metal-clad laminate 4 described above.

[0125] 6A, the conductor wiring 51 is formed on both sides of the insulating layer 50. The conductor wiring 51 may be formed on only one side of the insulating layer 50.

[0126] On the other hand, in the printed wiring board shown in FIG. 6B, the conductor wiring 51 includes an inner layer circuit 511 and an outer layer circuit 512. The inner layer circuit 511 is located between two insulating layers 50. That is, the inner layer circuit 511 is located between the first insulating layer 510 and the second insulating layer 520, and between the second insulating layer 520 and the third insulating layer 530. The outer layer circuit 512 is located outside the insulating layer 50. That is, the outer layer circuit 512 is formed on the surface of the first insulating layer 510 and the third insulating layer 530. The printed wiring board 5 shown in FIG. 6B further includes a via hole 8 and a blind via hole 9. The via hole 8 and the blind via hole 9 electrically connect the inner layer circuit 511 and the outer layer circuit 512. That is, the inner layer circuit 511 and the outer layer circuit 512 are interlayer-connected by the via hole 8 and the blind via hole 9.

[0127] The method for forming the conductor wiring 51 is not particularly limited, but examples thereof include a subtractive method and a semi-additive method (SAP: Semi-Additive Process).

[0128] As described above, insulating layer 50 of printed wiring board 5 according to this embodiment is formed from the above-mentioned resin composition, and therefore can have improved flame resistance, chemical resistance, and electrical properties.

[0129] (7) Semiconductor packages FIG. 7 shows a semiconductor package 100 according to this embodiment. The semiconductor package 100 includes a printed wiring board 5 and a semiconductor chip 7 mounted on the printed wiring board 5. In this case, the printed wiring board 5 is also called a package substrate, a module substrate, or an interposer. The printed wiring board 5 has at least one insulating layer 50. The insulating layer 50 has at least one base material 52. The insulating layer 50 does not necessarily have to have the base material 52.

[0130] The insulating layer 50 has a conductor wiring 51. The conductor wiring 51 includes a pad 513. The pad 513 is formed on the surface of the insulating layer 50.

[0131] There is no particular limitation on the semiconductor chip 7. The semiconductor chip 7 has bumps 70. The bumps 70 are bonded to the pads 513. This allows the semiconductor chip 7 and the printed wiring board 5 to be electrically connected to each other.

[0132] An underfill resin layer 500 is formed between the semiconductor chip 7 and the printed wiring board 5. The underfill resin layer 500 is formed by filling the gap between the semiconductor chip 7 and the printed wiring board 5 with an underfill liquid sealing material and curing it.

[0133] As described above, the semiconductor package 100 according to this embodiment includes the above-mentioned printed wiring board 5, and therefore can have improved flame resistance, chemical resistance, and electrical characteristics. EXAMPLES

[0134] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to the examples.

[0135] (1) Resin composition The raw materials for the resin composition are as follows.

[0136] <Maleimide compound (A)> ≪(A1)(A3)≫ Maleimide compound (A3) represented by formula (a3), Designer Molecules Inc. (DMI), trade name "BMI-689", maleimide group equivalent weight 345 g / eq ≪(A1)(A4)≫ Maleimide compound (A4) represented by formula (a4), Designer Molecules Inc. (DMI), product name "BMI-1500", maleimide group equivalent weight 750 g / eq ≪(A1)(A5)≫ Maleimide compound (A5) represented by formula (a5), Designer Molecules Inc. (DMI), product name "BMI-3000", maleimide group equivalent weight 1500 g / eq ≪(A2)≫ Maleimide compound (A6) represented by formula (a6), Daiwa Chemical Industry Co., Ltd., product name “BMI-5100”, maleimide group equivalent weight 221 g / eq.

[0137] <Phosphine oxide compound (B)> <<(B1)(B9)>> ·Additive flame retardant, Shinichi Kako Co., Ltd., product name "PQ-60", melting point 330℃ ≪(B2)(B9)≫ Additive-type flame retardant, Katayama Chemical Industry Co., Ltd., product name "BPO-13", melting point 300℃ ≪(B10)≫ Reactive flame retardant, Sanko Co., Ltd., product name "SD-5", phosphorus content 11.8% by mass, melting point 130℃ <Phosphate ester> Additive flame retardant, non-halogen condensed phosphate ester (aromatic condensed phosphate ester), Daihachi Chemical Industry Co., Ltd., product name "PX-200".

[0138] <Phosphazene> Additive flame retardant, Otsuka Chemical Co., Ltd., product name "SPB-100L".

[0139] <Epoxy compound (C)> Naphthalene-type epoxy resin, DIC Corporation, product name "HP-9500" (epoxy equivalent: 230g / eq) Biphenyl type epoxy resin, Nippon Kayaku Co., Ltd., product name "NC-3000-H" (epoxy equivalent 280~300g / eq).

[0140] <Styrene-based copolymer (D)> Hydrogenated methylstyrene (ethylene / butylene) methylstyrene copolymer, hydrogenated styrenic thermoplastic elastomer (SEBS), Kuraray Co., Ltd., product name "Septon (registered trademark) V9827" (weight average molecular weight 92,000).

[0141] <Inorganic filler (E)> · Fused silica, Admatechs Co., Ltd., trade name "SC2050-MTX", average particle diameter 0.5 μm.

[0142] <Others (F)> · 2-Ethyl-4-methylimidazole, Shikoku Kasei Kogyo Co., Ltd., "2E4MZ".

[0143] <PPE resin> · Modified polyphenylene ether, Mitsubishi Gas Chemical Co., Inc., trade name "OPE-2St-1200".

[0144] The maleimide compound (A), phosphine oxide compound (B), phosphazene, epoxy compound (C), styrene copolymer (D), inorganic filler (E) and others (F) were blended in the blending amounts shown in Tables 1 and 2, and this was stirred and mixed with a mixed solvent of methyl ethyl ketone and toluene and homogenized to prepare a varnish of the resin composition.

[0145] (2) Prepreg After impregnating the above varnish into a glass cloth (Nitto Boseki Co., Ltd., #2116 type, WEA116E, E-glass, thickness 0.1 mm), it was heat-dried at 100 to 160 °C for about 2 to 8 minutes to produce a prepreg. Note that for some comparative examples, the resin could not be cured.

[0146] (3) Metal-clad laminate Two sheets of the above prepreg were overlapped, copper foils with a thickness of 12 μm were arranged on both sides thereof, and heating and pressing were performed under the conditions of a temperature of 220 °C, 2 hours, and a pressure of 3 MPa to produce a double-sided copper-clad laminate (double-sided metal-clad laminate) with a thickness of about 0.2 mm. The following tests were performed using this as an evaluation substrate.

[0147] (4) Tests (4.1) Flame resistance A test piece measuring 125 mm in length and 12.5 mm in width was cut out from the evaluation board. Then, a flame test (vertical flame test) was performed 10 times on this test piece in accordance with Underwriters Laboratories' "Test for Flammability of Plastic Materials - UL94". Specifically, the flame test was performed twice for each of the five test pieces. Flame resistance was evaluated based on the total duration of the flame test. If the flame continued to burn until the end, it is indicated as "burned" in Tables 1 and 2.

[0148] (4.2) Chemical resistance (alkali resistance) First, a 15% by mass sodium aqueous solution was heated to 80°C. Meanwhile, the copper foil on both sides of the evaluation board was removed by etching to obtain an unclad plate. Next, the unclad plate was immersed in the sodium aqueous solution heated to 80°C for 15 minutes. After that, the unclad plate was taken out of the sodium aqueous solution. The unclad plate was visually observed, and the chemical resistance was evaluated according to the following criteria.

[0149] "A": No whitening "B": Bleaching present.

[0150] When the unclad plate was originally white and it was difficult to visually determine whether or not there was whitening, the chemical resistance was evaluated according to the following criteria.

[0151] "A": The mass loss rate of the unclad plate before and after immersion is less than 0.5% by mass "B": The mass loss rate of the unclad plate before and after immersion is 0.5% by mass or more.

[0152] The mass loss rate of the unclad plate before and after immersion is the ratio of the difference in mass of the unclad plate before and after immersion to the mass of the unclad plate before immersion ((mass before immersion-mass after immersion) / mass before immersion x 100).

[0153] (4.3) Heat resistance A test piece measuring 5 cm x 5 cm was cut out from the evaluation board. This test piece was then placed in a dryer at 290°C for 1 hour. After that, the test piece was removed from the dryer and visually observed, and the heat resistance was evaluated according to the following criteria.

[0154] "A": No swelling "B": Swelling present.

[0155] (4.4) Dielectric tangent The dielectric loss tangent of the evaluation board at 1 GHz was measured in accordance with IPC-TM650-2.5.5.9. Specifically, an impedance analyzer (RF impedance analyzer HP4291B manufactured by Agilent Technologies) was used to measure the dielectric loss tangent of the evaluation board at 1 GHz.

[0156] (4.5) Glass transition temperature (Tg) First, the copper foil on both sides of the evaluation board was removed by etching to obtain an unclad board. Next, the glass transition temperature (Tg) of the unclad board was measured using a viscoelasticity spectrometer "DMS100" manufactured by Seiko Instruments Inc. At this time, dynamic viscoelasticity measurement (DMA) was performed with a bending module at a frequency of 10 Hz, and the temperature at which the loss tangent (tan δ) was maximized when the temperature was raised from room temperature to 320°C at a heating rate of 5°C / min was taken as the glass transition temperature (Tg).

[0157] [Table 1]

[0158] [Table 2] [Explanation of symbols]

[0159] 1 Prepreg 10 Resin layer 11 Base material 2 Resin-coated film 20 Resin layer 21 Support film 3. Metal foil with resin 30 Resin layer 31 Metal foil 4 Metal-clad laminate 40 Insulating layer 41 Metal layer 5. Printed Wiring Boards 50 Insulating layer 51 Conductor wiring

Claims

1. Contains a maleimide compound (A), a phosphine oxide compound (B), and an epoxy compound (C), The maleimide compound (A) includes a maleimide compound (A1) having an alkyl group having 6 or more carbon atoms and / or an alkylene group having 6 or more carbon atoms, The phosphine oxide compound (B) has a structure represented by the following formula (b0): Resin composition. 【Chemistry 1】 In formula (b0), X is a monovalent or divalent hydrocarbon group containing at least one aromatic ring, or an alkylene group, and n is 1 or 2.

2. The phosphine oxide compound (B) includes a phosphine oxide compound (B9) having a melting point of 280° C. or higher. The resin composition according to claim 1.

3. Further containing a reactive flame retardant, The resin composition according to claim 1 or 2.

4. The maleimide compound (A1) has a maleimide group equivalent of 400 g / eq or more. The resin composition according to any one of claims 1 to 3.

5. The maleimide compound (A) further includes a maleimide compound (A2) having an equivalent weight of a maleimide group of less than 400 g / eq. The resin composition according to any one of claims 1 to 4.

6. The maleimide compound (A) includes at least one selected from the group consisting of a maleimide compound (A3) represented by the following formula (a3), a maleimide compound (A4) represented by the following formula (a4), and a maleimide compound (A5) represented by the following formula (a5): The resin composition according to any one of claims 1 to 5. 【Chemistry 2】 【Chemistry 3】 (In formula (a4), n represents an integer of 1 to 10.) 【Chemistry 4】 (In formula (a5), n represents an integer of 1 to 10.)

7. The mass ratio of the maleimide compound (A) to the epoxy compound (C) is 50:50 to 95:

5. The resin composition according to any one of claims 1 to 6.

8. The epoxy compound (C) includes an epoxy compound (C1) having an epoxy equivalent of 200 g / eq or more and 300 g / eq or less. The resin composition according to any one of claims 1 to 7.

9. Further containing a styrene-based copolymer (D), The resin composition according to any one of claims 1 to 8.

10. The present invention comprises a substrate and a resin layer containing the resin composition according to any one of claims 1 to 9 or a semi-cured product of the resin composition impregnated in the substrate. Prepreg.

11. The present invention comprises a resin layer containing the resin composition according to any one of claims 1 to 9 or a semi-cured product of the resin composition, and a support film supporting the resin layer. Resin-coated film.

12. The present invention comprises a resin layer containing the resin composition according to any one of claims 1 to 9 or a semi-cured product of the resin composition, and a metal foil adhered to the resin layer. Metal foil with resin.

13. The present invention comprises an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 9 or a cured product of the prepreg according to claim 10, and a metal layer bonded to the insulating layer. Metal-clad laminate.

14. The present invention comprises an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 9 or a cured product of the prepreg according to claim 10, and a conductor wiring formed on the insulating layer. Printed wiring board.

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