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

Abstract

To provide a resin composition improved in moldability while maintaining thermal conductivity of a cured product.SOLUTION: A resin composition includes an epoxy compound (A), a curing agent (B), a silane compound (C), and an inorganic filler (D). The silane compound (C) has a chain hydrocarbon group having 6 or more carbon atoms. The inorganic filler (D) includes: an inorganic filler (D1) having a modified Mohs hardness of less than 7; and an inorganic filler (D2) having a modified Mohs hardness of 7 or more. When a volume-based cumulative 50% particle diameter in the particle size distribution of the inorganic filler (D1) is d1(μm) and a volume-based cumulative 50% particle diameter in the particle size distribution of the inorganic filler (D2) is d2(μm), d1≠d2 is satisfied, and also the product of d1 and d2 (d1×d2) is 1.8 μm2 or more. The content of the inorganic filler (D) is 900-1,500 pts.mass based on 100 pts.mass of the total of the epoxy compound (A) and the curing agent (B).SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure generally relates to resin compositions, prepregs, resin films, metal foils with resin, metal-clad laminates, and wiring boards. More specifically, the present disclosure relates to resin compositions, prepregs, resin films, metal foils with resin, metal-clad laminates, and wiring boards containing epoxy compounds.

Background Art

[0002] Patent Document 1 discloses a sealing composition containing an epoxy resin, a curing agent, an inorganic filler containing silica particles having a specific surface area of 100 m 2 / g or more, and a silane compound having a structure in which a chain hydrocarbon group having 6 or more carbon atoms is bonded to a silicon atom. According to the technique of Patent Document 1, it is said that it is possible to achieve both obtaining a cured product with high thermal conductivity and improving fluidity.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In recent years, with the high functionality, high integration, and high-density mounting of semiconductors, as a heat dissipation technology for wiring boards against heat generation, it is desired that the cured product of the resin composition forming the insulating layer of the wiring board has high thermal conductivity. In addition, the miniaturization of semiconductors is accelerating more and more, and it is required to increase the resin fluidity and improve the moldability of the resin composition forming the insulating layer of the wiring board.

[0005] However, in Patent Document 1, no detailed examination has been made regarding the inorganic filler contained in the resin composition, and no measures for improving the moldability of the resin composition have been examined.

[0006] An object of the present disclosure is to provide a resin composition, a prepreg, a metal foil with resin, a metal-clad laminate, and a wiring board that can improve moldability while maintaining the thermal conductivity of the cured product.

Means for Solving the Problems

[0007] The resin composition according to one aspect of the present disclosure contains an epoxy compound (A), a curing agent (B), a silane compound (C), and an inorganic filler (D). The silane compound (C) has a linear hydrocarbon group having 6 or more carbon atoms. The inorganic filler (D) includes an inorganic filler (D1) having a modified Mohs hardness of less than 7 and an inorganic filler (D2) having a modified Mohs hardness of 7 or more. When the volume-based cumulative 50% particle diameter in the particle size distribution of the inorganic filler (D1) is d1 (μm) and the volume-based cumulative 50% particle diameter in the particle size distribution of the inorganic filler (D2) is d2 (μm), d1 ≠ d2, and the product (d1 × d2) of d1 and d2 is 1.8 μm 2 or more. The content of the inorganic filler (D) is 900 parts by mass or more and 1500 parts by mass or less with respect to 100 parts by mass in total of the epoxy compound (A) and the curing agent (B).

[0008] The prepreg according to one aspect of the present disclosure includes a resin layer containing the resin composition or a semi-cured product of the resin composition, and a fibrous substrate.

[0009] The resin film with resin according to one aspect of the present disclosure includes a resin layer containing the resin composition or a semi-cured product of the resin composition, and a support film.

[0010] The metal foil with resin according to one aspect 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.

[0011] The metal-clad laminate according to one aspect of the present disclosure includes an insulating layer containing a cured product of the resin composition or a cured product of the prepreg, and a metal foil.

[0012] The wiring board according to one aspect of the present disclosure includes an insulating layer containing a cured product of the resin composition or a cured product of the prepreg, and wiring.

Advantages of the Invention

[0013] According to the present disclosure, the moldability can be improved while maintaining the thermal conductivity of the cured product of the resin composition.

Brief Description of the Drawings

[0014]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Modes for Carrying Out the Invention

[0015] 1. Overview The resin composition according to the present embodiment is mainly used as a material for the wiring board 5 (see FIG. 5). The material for the wiring board 5 is not particularly limited, and examples thereof include a prepreg 1, a resin film 2, a metal foil with resin 3, and a metal-clad laminate 4 (see FIGS. 1 to 4).

[0016] The resin composition according to this embodiment contains an epoxy compound (A), a curing agent (B), a silane compound (C), and an inorganic filler (D). The silane compound (C) has a linear hydrocarbon group having 6 or more carbon atoms. The inorganic filler (D) includes an inorganic filler (D1) having a modified Mohs hardness of less than 7 and an inorganic filler (D2) having a modified Mohs hardness of 7 or more. When the volume-based cumulative 50% particle diameter in the particle size distribution of the inorganic filler (D1) is d1 (μm) and the volume-based cumulative 50% particle diameter in the particle size distribution of the inorganic filler (D2) is d2 (μm), d1 ≠ d2, and the product (d1 × d2) of d1 and d2 is 1.8 μm 2 or more. The content of the inorganic filler (D) is 900 parts by mass or more and 1500 parts by mass or less with respect to 100 parts by mass in total of the epoxy compound (A) and the curing agent (B).

[0017] According to the resin composition of this embodiment, the moldability can be improved while maintaining the thermal conductivity of the cured product.

[0018] The inventors have found that, in a resin composition containing an epoxy resin, by containing a silane compound having a specific group and using a specific amount of a plurality of types having different average particle diameters and hardnesses as the inorganic filler, the above problems can be solved, and the present disclosure has been completed.

[0019] The resin composition according to this embodiment uses a silane compound (C) having a chain hydrocarbon group with 6 or more carbon atoms in addition to an epoxy resin (A) and a curing agent (B), and as the inorganic filler (D), an inorganic filler (D1) with a modified Mohs hardness of less than 7 and an inorganic filler (D2) with a modified Mohs hardness of 7 or more are used. Regarding the average particle diameters d1 (μm) and d2 (μm) respectively, d1 ≠ d2, and the product (d1 × d2) of d1 and d2 is set to be not less than a specific value. Also, by setting the content of the inorganic filler (D) within a specific range, the moldability can be improved while maintaining the thermal conductivity of the cured product. Although the reason for the above effects when the resin composition of this embodiment has the above configuration is not necessarily clear, for example, it can be speculated as follows. By using the silane compound (C) having a chain hydrocarbon group with 6 or more carbon atoms, the highly hydrophobic silane compound (C) interacts with the inorganic filler (D), mainly enhancing the dispersibility of the inorganic filler (D2). In addition, as the inorganic filler (D), inorganic fillers (D1) and inorganic filler (D2) with different average particle diameters D50 are used. By using two types with appropriately different average particle diameters, as indicated by d1 × d2 being not less than a specific value, the inorganic filler (D) is more likely to be filled, thereby reducing the melt viscosity. As a result, it is considered that the resin composition has improved resin flowability and moldability.

[0020] The resin composition of this embodiment is excellent in moldability, and in addition to the cured product having high thermal conductivity, it is also excellent in drill processability and handling properties shown by D-10 bending, etc.

[0021] 2. Details <Resin Composition> The resin composition contains an epoxy compound (A), a curing agent (B), a silane compound (C), and an inorganic filler (D). The resin composition may further contain other components such as a curing catalyst. In this specification, "X and / or Y" means at least one of X and Y.

[0022] In other words, the resin composition is a formulation obtained by blending an epoxy compound (A), a curing agent (B), a silane compound (C), and an inorganic filler (D). In the resin composition which is a formulation, the silane compound (C) may interact with part or all of the inorganic filler (D) such as adsorbing and bonding to the surface.

[0023] The resin composition has thermosetting properties. When the resin composition is heated, it becomes a semi-cured product, and when further heated, it becomes a cured product. The semi-cured product is a substance in a semi-cured state, and the cured product is a substance in a cured state (insoluble and infusible state). Here, the semi-cured state means the state at the intermediate stage (B stage) of the curing reaction. The intermediate stage is the stage between the varnish state stage (A stage) and the cured state stage (C stage).

[0024] Hereinafter, the constituent components of the resin composition will be described.

[0025] ≪Epoxy Compound≫ The epoxy compound (A) is a compound having at least two or more epoxy groups in the molecule. The epoxy compound (A) is bifunctional or higher, preferably trifunctional or higher, and more preferably trifunctional. In this case, the heat resistance of the cured product of the resin composition can be improved. The epoxy compound (A) may be a monomer, an oligomer, or a polymer. The epoxy compound (A) may also be referred to as an epoxy resin. Generally, the term "resin" has two meanings: resin as a material before the cross-linking reaction and resin as a product (product) after the cross-linking reaction. In this specification, "resin" basically means the former.

[0026] The epoxy compound (A) is not particularly limited. For example, naphthalene-type epoxy compounds, cresol novolak-type epoxy compounds, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol S-type epoxy compounds, trisphenol methane-type epoxy compounds, phenol novolak-type epoxy compounds, alkylphenol novolak-type epoxy compounds, aralkyl-type epoxy compounds, biphenol-type epoxy compounds, dicyclopentadiene-type epoxy compounds, epoxy compounds that are condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups, triglycidyl isocyanurate, alicyclic epoxy compounds, etc. may be mentioned. The epoxy compound (A) may contain at least one epoxy compound selected from these groups. The epoxy compound (A) preferably contains a trisphenol methane-type epoxy compound, and more preferably contains a trifunctional trisphenol methane-type epoxy compound.

[0027] The content of the epoxy compound (A) is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more with respect to 100% by mass of the resin composition. In this case, the strength of the cured product can be improved. The content of the epoxy compound (A) is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less with respect to 100% by mass of the resin composition. In this case, the thermal conductivity of the resin composition can be further improved.

[0028] ≪Curing agent≫ The curing agent (B) is not particularly limited as long as it is a compound that can cause a curing reaction with the epoxy compound (A), that is, a compound having a curable functional group that can react with the epoxy group of the epoxy compound (A). Examples of the curable functional group include an amino group, a substituted amino group, a nitrogen-containing aromatic ring, an aromatic ring having a phenolic hydroxyl group, an acid anhydride group, etc.

[0029] Examples of the curing agent (B) include amine compounds, phenol compounds, acid anhydride compounds, polymercaptan compounds, Lewis acid-amine complexes, and the like. The curing agent (B) preferably contains at least one selected from the group consisting of amine compounds, phenol compounds, and acid anhydride compounds, and more preferably contains an amine compound. Since these curing agents (B) have appropriate curability, the melt viscosity of the resin composition can be further reduced, and as a result, the moldability of the resin composition can be further improved.

[0030] Examples of the amine compound include aliphatic polyamines such as dicyandiamide, diethylenetriamine, triethylenetetramine, and metaxylylenediamine; aromatic polyamines such as diaminodiphenylmethane, m-phenylenediamine, and diaminodiphenylsulfone; imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole; and hydrazides such as organic acid dihydrazide. Among these, dicyandiamide is preferred.

[0031] Examples of the phenol compound include novolak resins, aralkyl resins, polyfunctional phenol resins, dicyclopentadiene-type phenol resins, terpene-modified phenol resins, and bisphenol-type resins.

[0032] Examples of the novolak resin include phenol novolak resin, cresol novolak resin, naphthol novolak resin, and triazine-modified novolak resin. Examples of the aralkyl resin include phenol aralkyl resins having a phenylene skeleton or a biphenylene skeleton, and naphthol aralkyl resins having a phenylene skeleton or a biphenylene skeleton. Examples of the polyfunctional phenol resin include triphenolmethane-type resins. Examples of the dicyclopentadiene-type phenol resin include dicyclopentadiene-type phenol novolak resins and dicyclopentadiene-type naphthol novolak resins. Examples of the bisphenol type resin include bisphenol A type resin, bisphenol F type resin, and the like.

[0033] Examples of the acid anhydride compound include alicyclic acid anhydrides such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride; aromatic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, phthalic anhydride, and the like.

[0034] The content of the curing agent (B) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and still more preferably 3 part by mass or more with respect to 100 parts by mass of the epoxy compound (A). The content of the curing agent (B) is preferably 100 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 7 parts by mass or less with respect to 100 parts by mass of the epoxy compound (A). In these cases, the curing rate can be made appropriate.

[0035] The equivalent of the curing agent (B) with respect to 1 equivalent of the epoxy compound (A), that is, the ratio of the number of moles of the curable functional group of the curing agent (B) to 1 mole of the epoxy group of the epoxy compound (A) is, for example, 0.6 or more and 1.4 or less.

[0036] ≪Silane compound≫ The silane compound (C) is a compound having a silicon atom. The silane compound (C) has a chain hydrocarbon group having 6 or more carbon atoms. By having a chain hydrocarbon group having 6 or more carbon atoms, the silane compound (C) can disperse the inorganic filler (D) such as the inorganic filler (D2) more in the resin composition.

[0037] Examples of the chain hydrocarbon group having 6 or more carbon atoms include an alkyl group having 6 or more carbon atoms, an alkenyl group having 6 or more carbon atoms, an alkynyl group having 6 or more carbon atoms, an alkylene group having 6 or more carbon atoms, an alkenylene group having 6 or more carbon atoms, an alkynylene group having 6 or more carbon atoms, and the like. The silane compound (C) preferably has at least one selected from the group consisting of an alkyl group having 6 or more carbon atoms and an alkylene group having 6 or more carbon atoms.

[0038] Examples of the alkyl group having 6 or more carbon atoms include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like. Examples of the alkylene group having 6 or more carbon atoms include a hexylene group, an octylene group, a nonylene group, a decylene group, and the like.

[0039] The carbon number of the chain hydrocarbon group is preferably 7 or more, more preferably 8 or more. The carbon number of the chain hydrocarbon group is, for example, 20 or less, preferably 15 or less, and more preferably 10 or less.

[0040] Examples of the silane compound (C) include a silane monomer compound, a siloxane compound having an Si—O bond, a polysiloxane compound, and the like.

[0041] The silane compound (C) preferably has at least one selected from the group consisting of an epoxy group, a vinyl group, a (meth)acrylic group, a phenylamino group, and a hydrolyzable silyl group, and more preferably has at least one selected from the group consisting of an epoxy group, a vinyl group, a methacrylic group, and a phenylamino group. In this case, the silane compound (C) is likely to be adsorbed and bonded to the surface of the inorganic filler (D). The (meth)acrylic group means at least one of an acrylic group and a methacrylic group. Examples of the hydrolyzable silyl group include -SiR 1 m (OR 2 ) 3-m (R 1 is a hydrogen atom, a methyl group or an ethyl group. R 2is a methyl group or an ethyl group. m is an integer from 0 to 2. Examples thereof include a group represented by ().

[0042] The content of the silane compound (C) is preferably 4 parts by mass or more, more preferably 4.5 parts by mass or more, still more preferably 5 parts by mass or more, particularly preferably 5.5 parts by mass or more, even more particularly preferably 7 parts by mass or more, and most preferably 9 parts by mass or more with respect to 100 parts by mass in total of the epoxy compound (A) and the curing agent (B). In this case, the moldability of the resin composition can be further improved. The upper limit of the content of the silane compound (C) is not particularly limited, but is, for example, 30 parts by mass or less, preferably 20 parts by mass or less with respect to 100 parts by mass in total of the epoxy compound (A) and the curing agent (B).

[0043] The content of the silane compound (C) is preferably 0.9 parts by mass or more, more preferably 1.0 parts by mass or more, still more preferably 1.1 parts by mass or more, particularly preferably 1.4 parts by mass or more, even more particularly preferably 1.8 parts by mass or more, and most preferably 20 parts by mass or more with respect to 100 parts by mass of the inorganic filler (D2). In this case, the moldability of the resin composition can be further improved. The upper limit of the content of the silane compound (C) with respect to 100 parts by mass of the inorganic filler (D2) is not particularly limited, but is, for example, 10 parts by mass or less, preferably 5 parts by mass or less.

[0044] The content of the silane compound (C) is preferably 0.45 parts by mass or more, more preferably 0.55 parts by mass or more, and still more preferably 0.9 parts by mass or more with respect to 100 parts by mass of the inorganic filler (D). The content of the silane compound (C) with respect to 100 parts by mass of the inorganic filler (D) is not particularly limited, but is, for example, 5 parts by mass or less.

[0045] ≪Inorganic filler≫ The "inorganic filler" refers to a filler (filler material) composed of an inorganic material.

[0046] The inorganic filler (D) includes an inorganic filler (D1) with a modified Mohs hardness of less than 7 and an inorganic filler (D2) with a modified Mohs hardness of 7 or more.

[0047] The "modified Mohs hardness" considers integer values from 1 to 15 as a measure of hardness, sets corresponding standard substances for each, and measures the hardness by rubbing the standard substance with the sample substance to be measured for hardness and determining the presence or absence of scratches. As standard minerals for modified Mohs hardness, for example, calcite is used for "modified Mohs hardness 3", fluorite is used for "modified Mohs hardness 4", quartz (crystal) is used for "modified Mohs hardness 8", fused alumina is used for "modified Mohs hardness 12", silicon carbide is used for "modified Mohs hardness 13", and diamond is used for the hardest "modified Mohs hardness 15".

[0048] Examples of the inorganic filler (D1) include magnesium carbonate filler, glass filler, etc. Examples of the inorganic filler (D2) include aluminum oxide filler, silicon dioxide filler, zirconium oxide filler, silicon filler, etc.

[0049] The volume-based cumulative 50% particle diameter (D50) in the particle size distribution of the inorganic filler (D) is, for example, a value measured by a laser diffraction particle size distribution measuring device. As the laser diffraction particle size distribution measuring device, for example, "SALD-2300" manufactured by Shimadzu Corporation can be used.

[0050] Let the D50 of the inorganic filler (D1) be d1 (μm) and the D50 of the inorganic filler (D2) be d2 (μm).

[0051] In the inorganic filler (D), it is important that d1 ≠ d2, that is, d1 and d2 are different. "d1 and d2 are different" means that the value obtained by dividing d1 by d2 (d1 / d2) is 1.05 or more, or 0.95 or less.

[0052] In the inorganic filler (D), it is preferable that d1 > d2. In this case, by making the particle diameter of the inorganic filler (D1) with a lower hardness larger than the particle diameter of the inorganic filler (D2) with a higher hardness, the moldability can be further improved.

[0053] The lower limit of d1 of the inorganic filler (D1) is, for example, 0.1 μm or more, preferably 5 μm or more, more preferably 6 μm or more, and still more preferably 7 μm or more. The upper limit of d1 is, for example, 30 μm or less, preferably 20 μm or less, and more preferably 10 μm or less.

[0054] The lower limit of d2 of the inorganic filler (D2) is preferably 0.1 μm or more, more preferably 0.15 μm or more, and still more preferably 0.20 μm or more. The upper limit of d2 is, for example, 4 μm or less, preferably 2 μm or less, and more preferably 1 μm or less.

[0055] In the inorganic filler (D), the product of d1 and d2 (d1 × d2) is 1.8 μm 2 or more, which is important. d1 × d2 is preferably 2.0 μm 2 or more, more preferably 2.1 μm 2 or more, and still more preferably 2.2 μm 2 or more. The upper limit of d1 × d2 is not particularly limited, but for example, it is 5 μm 2 or less, and preferably 3 μm 2 or less.

[0056] The mass ratio (D2 / D1) of the inorganic filler (D2) to the inorganic filler (D1) is preferably 20 / 100 or more and 130 / 100 or less. By setting the mass ratio (D2 / D1) within the above range, the inorganic filler (D) can be densely filled. By densely filling, the apparent volume ratio of the inorganic filler (D) in the composition can be further reduced. As a result, the influence of the liquid component becomes stronger, the fluidity increases, and as a result, the moldability of the resin composition can be further improved. The mass ratio (D2 / D1) is more preferably 50 / 100 or more, and even more preferably 80 / 100 or more. The mass ratio (D2 / D1) is more preferably 120 / 100 or less, and even more preferably 110 / 100 or less.

[0057] The content of the inorganic filler (D) is 900 parts by mass or more and 1500 parts by mass or less with respect to a total of 100 parts by mass of the epoxy compound (A) and the curing agent (B). The content of the inorganic filler (D) is preferably 930 parts by mass or more, more preferably 960 parts by mass or more, even more preferably 990 parts by mass or more, and particularly preferably 1000 parts by mass or more. The content of the inorganic filler (D) is preferably 1300 parts by mass or less, more preferably 1100 parts by mass or less, and even more preferably 1050 parts by mass or less with respect to a total of 100 parts by mass of the epoxy compound (A) and the curing agent (B).

[0058] The content rate of the inorganic filler (D) is preferably 85% by mass or more, more preferably 88% by mass or more, and even more preferably 90% by mass or more with respect to 100% by mass of the resin composition. The upper limit of the content rate of the inorganic filler (D) is not particularly limited, but is, for example, 95% by mass or less with respect to 100% by mass of the resin composition.

[0059] <<Other Components>> The other components are components other than the above-mentioned epoxy resin (A), curing agent (B), silane compound (C), and inorganic filler (D). Examples of the other components include a curing catalyst, a dispersant, a dye, a surfactant, a leveling agent, a resin other than the epoxy compound (A), etc. The other components may include only one type or two or more types.

[0060] The curing catalyst is synonymous with a curing accelerator. The curing catalyst is not particularly limited, and examples thereof include organic phosphines such as triphenylphosphine, diphenylphosphine, and phenylphosphine; tetra-substituted phosphonium·tetra-substituted borate such as tetraphenylphosphonium·ethyltriphenylborate; and tetraphenylboron salts such as 2-ethyl-4-methylimidazole·tetraphenylborate.

[0061] When the resin composition contains a curing catalyst, the content of the curing catalyst is not particularly limited, but is, for example, 0.1 part by mass or more and 5 parts by mass or less with respect to a total of 100 parts by mass of the epoxy resin (A) and the curing agent (B).

[0062] <Prepreg> FIG. 1 shows a prepreg 1 according to this embodiment. The prepreg 1 is in a sheet form. The prepreg 1 includes at least one sheet-like fibrous substrate 12 and a resin layer 11. The fibrous substrate 12 is impregnated with the resin composition. The resin layer 11 contains the resin composition. The resin composition is a semi-cured product.

[0063] The fibrous substrate 12 is a reinforcing material and is not particularly limited. The thickness of the fibrous substrate 12 is not particularly limited, but is preferably in the range of 10 μm or more and 300 μm or less, and more preferably in the range of 30 μm or more and 200 μm or less.

[0064] Specific examples of the fibrous substrate 12 include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and lint paper. As for the type of glass cloth, #7628, #1501, #2116, #1080, #1078, and #106 are preferable.

[0065] In manufacturing the prepreg 1, it is preferable that the glass cloth is treated with a coupling agent before impregnating with the resin composition at the A stage. Thus, when the glass cloth is treated with a coupling agent, the adhesion between the glass cloth and the resin composition can be improved. The coupling agent is not particularly limited, and examples thereof include silane coupling agents.

[0066] The manufacturing method of the prepreg includes a step of impregnating the fibrous substrate 12 with the resin composition at the A stage, and a step of heating until the resin composition impregnated in the fibrous substrate 12 becomes the B stage. Here, the A stage refers to an initial stage where the resin composition is soluble and fusible in a certain liquid. That is, the resin composition at the A stage is a varnish.

[0067] <Resin-coated film> FIGS. 2A and 2B show the resin-coated film 2 according to the present embodiment. The resin-coated film 2 is used for the multilayer formation (build-up method) of the wiring board 5 and the like. The resin-coated film 2 is in a film shape as a whole. The resin-coated film 2 includes a resin layer 21 and a support film 22. FIG. 2A shows the resin-coated film 2 without the protective film 23. FIG. 2B shows the resin-coated film 2 further including the protective film 23. When the protective film 23 is peeled off from the resin-coated film 2 shown in FIG. 2B, it can become the resin-coated film 2 shown in FIG. 2A.

[0068] The resin layer 21 contains a resin composition. The resin composition is a semi-cured product. The semi-cured product becomes a cured product when heated. Thus, the resin layer 21 can form an insulating layer.

[0069] The thickness of the resin layer 21 is not particularly limited, but is preferably 50 μm or more and 150 μm or less, more preferably 60 μm or more and 140 μm or less, and still more preferably 70 μm or more and 130 μm or less. Thereby, higher thermal conductivity and higher insulation reliability can be realized.

[0070] The support film 22 supports the resin layer 21. Thus, since the support film 22 supports the resin layer 21, it becomes easier to handle the resin layer 21.

[0071] The support film 22 is, for example, an electrically insulating film. The support film 22 is not particularly limited, and examples thereof include polyethylene terephthalate (PET) film, polyimide film, polyester film, polypyromellitic acid film, polyether ether ketone film, polyphenylene sulfide film, aramid film, polycarbonate film, polyarylate film, and the like.

[0072] A release agent layer (not shown) may be provided on the surface of the support film 22 that supports the resin layer 21. By the release agent layer, the support film 22 can be peeled from the resin layer 21 as necessary.

[0073] In FIG. 2A, one surface of the resin layer 21 is covered with the support film 22, but as shown in FIG. 2B, the other surface of the resin layer 21 may be covered with the protective film 23. Thus, by covering both surfaces of the resin layer 21 with the support film 22 and the protective film 23, it becomes even easier to handle the resin layer 21. Also, it is possible to suppress foreign matter from adhering to the resin layer 21.

[0074] The protective film 23 is, for example, an electrically insulating film. The protective film 23 is not particularly limited, and examples thereof include polyethylene terephthalate (PET) film, polyolefin film, polyester film, polymethylpentene film, and the like.

[0075] A release agent layer (not shown) or a slightly adhesive layer (not shown) may be provided on the surface of the resin layer 21 of the protective film 23 that is overlapped. By the release agent layer, the protective film 23 can be peeled from the resin layer 21 as needed. By the slightly adhesive layer, the protective film 23 can be moderately adhered to the resin layer 21.

[0076] <Metal foil with resin> FIG. 3 shows a metal foil with resin 3 according to this embodiment. The metal foil with resin 3 is in the form of a film as a whole. The metal foil with resin 3 includes a resin layer 31 and a metal foil 32. The metal foil with resin 3 is used for the multilayer formation (build-up method) of the wiring board 5 and the like.

[0077] The resin layer 31 contains a resin composition. The resin composition is a semi-cured product. The semi-cured product can become a cured product by being heated. Thus, the resin layer 31 can form an insulating layer.

[0078] The thickness of the resin layer 31 is not particularly limited, but is preferably 50 μm or more and 150 μm or less, more preferably 60 μm or more and 140 μm or less, still more preferably 70 μm or more and 130 μm or less. Thereby, higher thermal conductivity and higher insulation reliability can be realized.

[0079] The metal foil 32 is adhered to the resin layer 31. Specific examples of the metal foil 32 include, but are not limited to, copper foil. The metal foil 32 can form the wiring 53 by removing unnecessary portions by etching in the subtractive method or the like.

[0080] The thickness of the metal foil 32 is not particularly limited, but is preferably 35 μm or less, more preferably 18 μm or less. The thickness of the metal foil 32 is preferably 5 μm or more.

[0081] The metal foil 32 may be composed of an extremely thin metal foil (e.g., an extremely thin copper foil) of a so-called carrier-attached extremely thin metal foil (not shown). The carrier-attached extremely thin metal foil has a three-layer structure. That is, the carrier-attached extremely thin metal foil includes a carrier, a release layer provided on the surface of the carrier, and an extremely thin metal foil provided on the surface of the release layer. The extremely thin metal foil is so extremely thin that it is difficult to handle alone and is, of course, thinner than the carrier. The carrier is a metal foil (e.g., a copper foil) having a role of protecting and supporting the extremely thin metal foil. Since the carrier-attached extremely thin metal foil has a certain thickness, it is easy to handle. The thicknesses of the extremely thin metal foil and the carrier are not particularly limited. For example, the thickness of the extremely thin metal foil is in the range of 1 μm or more and 10 μm or less, and the thickness of the carrier is in the range of 18 μm or more and 35 μm or less. The extremely thin metal foil can be peeled off from the release layer as needed.

[0082] When using the carrier-attached extremely thin metal foil, the resin-attached metal foil 3 can be manufactured as follows. That is, a resin composition is applied to the surface of the extremely thin metal foil of the carrier-attached extremely thin metal foil and heated to form a resin layer 31. Then, the carrier is peeled off from the extremely thin metal foil. The extremely thin metal foil is adhered as the metal foil 32 to the surface of the resin layer 31. The release layer is preferably peeled off together with the carrier and does not remain on the surface of the extremely thin metal foil. However, even if it remains, it can be easily removed. The extremely thin metal foil adhered to the surface of the resin layer 31 can be used as a seed layer in the Modified Semi Additive Process (MSAP), and a wiring 53 can be formed by performing an electrolytic plating process on this seed layer.

[0083] <Metal-clad laminate> FIG. 4A and FIG. 4B show a metal-clad laminate 4 according to the present embodiment. The metal-clad laminate 4 includes an insulating layer 41 and a metal layer 43. In the metal-clad laminate 4 of FIG. 4A, the insulating layer 41 includes a cured product of a resin composition. In the metal-clad laminate 4 of FIG. 4B, the insulating layer 41 includes a cured product of at least one or more prepregs. The cured product of the prepreg includes a fibrous substrate 42. Thus, the metal-clad laminate 4 of FIG. 4B can be manufactured using a prepreg as a material. The insulating layer 41 has electrical insulation and is a layer in an insoluble and infusible state. The metal layer 43 is adhered to the insulating layer 41.

[0084] The metal layer 43 is not particularly limited as long as it is a layer containing a metal. A specific example of the metal layer 43 is a copper foil. The thickness of the metal layer 43 is preferably in the range of 18 μm or more and 210 μm or less. The ten-point average roughness Rzjis of the metal layer 43 is preferably 5.0 μm or more. In this case, the adhesion between the insulating layer 41 and the metal layer 43 can be further improved.

[0085] The manufacturing method of the metal-clad laminate 4 of FIG. 4B includes, for example, a step of laminating a metal layer 43 such as a metal foil on one or both sides of a laminate composed of one prepreg 1 or two or more prepregs 1 and heating and pressing. Preferably, before laminating the metal layer 43 on the laminate, the surface of the metal layer 43 (at least the surface overlapping the laminate) is treated with a coupling agent. Thus, when the metal layer 43 is surface-treated with a coupling agent, the coupling agent can further improve the adhesion between the insulating layer 41 and the metal layer 43 by bonding the organic material in the prepreg 1 and the metal layer 43. Examples of the coupling agent include a silane coupling agent. The conditions for heating and pressing are not particularly limited. FIG. 4B shows a metal-clad laminate 4 obtained through a step of laminating metal layers 43 on both sides of a laminate composed of one prepreg 1 and heating and pressing.

[0086] <Wiring board> FIG. 5A and FIG. 5B show a wiring board 5 according to the present embodiment. The wiring board 5 includes at least one or more insulating layers 51 and at least one or more conductor layers 530.

[0087] In the wiring board 5 of FIG. 5A, the insulating layer 51 includes a cured product of a resin composition. In the wiring board 5 of FIG. 5B, the insulating layer 51 includes a cured product of at least one or more prepregs. The cured product of the prepreg includes a fibrous substrate 52. The insulating layer 51 has electrical insulation and is a layer in an insoluble and infusible state.

[0088] The conductor layer 530 is adhered to the insulating layer 51. In this specification, the "conductor layer" means a layer having conductivity such as a signal layer, a power supply layer, and a ground layer. The conductor layer 530 includes wiring 53.

[0089] The wiring board 5 is a concept including a wiring board having two or fewer conductor layers 530 and a multilayer wiring board having three or more conductor layers 530. Note that FIGS. 5A and 5B show a wiring board having two conductor layers 530 and one insulating layer 51.

[0090] The wiring board 5 can be manufactured, for example, by using a subtractive method with a metal-clad laminate 4 as a material. Further, the wiring board 5 may be made multilayer by a build-up method using a resin film 2 with resin and a metal foil 3 with resin.

[0091] The wiring board 5 may have one or more through-hole plating 54. The through-hole plating 54 is formed, for example, by drilling a hole in the insulating layer 51, performing a desmear treatment, and then applying copper plating or the like to the inner wall of this hole. The desmear treatment can be performed, for example, by the permanganate method. Although not shown, the wiring board 5 may have one or more blind vias. Note that the hole may be a through-hole or a non-through-hole.

Example

[0092] Hereinafter, the present disclosure will be specifically described by way of examples. However, the present disclosure is not limited to the examples.

[0093] [Raw materials] The following were used as raw materials for the resin compositions of each example and comparative example.

[0094] <Epoxy Compound (A)> · Epoxy Compound 1: Manufactured by Printec Co., Ltd., Product Number: VG3101, trifunctional epoxy resin.

[0095] <Hardener (B)> · Hardener 1: Manufactured by Nippon Carbide Industries Co., Ltd., Product Number: Dicy, dicyandiamide.

[0096] <Silane Compound (C)> · Silane Compound 1: Manufactured by Shin-Etsu Chemical Co., Ltd., Product Number: KBM-4803, 8-glycidoxy octyltrimethoxysilane: having an 8-glycidoxy octyl group (having a chain hydrocarbon group with 6 or more carbon atoms (octylene group)). · Silane Compound a: Manufactured by Shin-Etsu Chemical Co., Ltd., Product Number: KBE-403, 3-glycidoxypropyltriethoxysilane: having a 3-glycidoxypropyl group (not having a chain hydrocarbon group with 6 or more carbon atoms). · Silane Compound b: Manufactured by Shin-Etsu Chemical Co., Ltd., Product Number: X-12-981S, organosilane having an epoxy group (not having a chain hydrocarbon group with 6 or more carbon atoms). · Silane Compound c: Manufactured by Shin-Etsu Chemical Co., Ltd., Product Number: KR-516, siloxane having an epoxy group (not having a chain hydrocarbon group with 6 or more carbon atoms).

[0097] <Inorganic Filler (D)> [Inorganic Filler (D1)] · Inorganic Filler 1-1: Manufactured by Kojima Chemical Industry Co., Ltd., Product Number: Magthermo MS-PS, magnesium carbonate (synthetic magnesite), D50: 11 μm, Modified Mohs hardness: 3.5. · Inorganic Filler 1-2: Manufactured by Kojima Chemical Industry Co., Ltd., Product Number: MS-L, magnesium carbonate, D50: 8 μm, Modified Mohs hardness: 3.5. [Inorganic Filler (D2)] · Inorganic Filler 2: Manufactured by Admatechs Co., Ltd., Product Number: AO-502, alumina, D50: 0.2 μm, Modified Mohs hardness: 12.

[0098] [Preparation of Resin Composition] The above raw materials were compounded in the composition shown in Table 1, and this compound was dissolved or dispersed in methyl ethyl ketone, which is a solvent, so that the solid content became 80 to 95% by mass, and was stirred with a planetary mixer to prepare varnishes containing the resin compositions of each example and comparative example.

[0099] [Manufacture of Resin-Coated Film] After applying the above varnish to a PET film, which is a support film, it was heated at about 150 °C for 4 to 5 minutes to make the resin composition into a semi-cured product, thereby manufacturing a resin-coated film. The thickness of the resin layer was adjusted to 100 μm.

[0100] [Manufacture of Copper-Clad Laminate] Eight of the above resin-coated films were stacked with the support film peeled off, and these films were sandwiched between the roughened surfaces of two copper foils (thickness 35 μm) and heated and pressed at 200 °C, 2.94 MPa (30 kgf / cm 2 ) for 60 minutes to manufacture a copper-clad laminate (CCL) with an overall insulation layer thickness of 800 μm. [Evaluation] (Moldability) Regarding the moldability of the resin composition, the resin fluidity of the resin composition was evaluated by measuring the melt viscosity. The melt viscosity of the resin composition was measured using a high-temperature type flow tester ("CFT-100" manufactured by Shimadzu Corporation) under the conditions where the temperature of the flow tester was 130 °C and the pressure was 1.96 MPa (20 kgf / cm 2 ) using a nozzle diameter of 1 mm and a thickness of 1 mm. The measured values (Pa·s) of the melt viscosity are shown in Table 1. The moldability was evaluated according to the following criteria. ○ (Good): The melt viscosity was less than 3000 Pa·s. △ (Somewhat good): The melt viscosity was 3000 Pa·s or more and less than 3800 Pa·s. × (Poor): The melt viscosity was 3800 Pa·s or more.

[0101] (Thermal Conductivity) The thermal conductivity of the insulating layer of the manufactured copper-clad laminate was measured by the flash method defined in JIS R 1611. The thermal conductivity was evaluated according to the following criteria. ○ (Good): The thermal conductivity was 2.3 W / m·K or more. × (Poor): The thermal conductivity was less than 2.3 W / m·K.

[0102] (Drillability) The resin composition was heat-cured in the atmosphere to obtain a molded body for evaluation (100 mm × 100 mm × thickness 1.0 mm). The heating conditions were 130 °C for 2 hours.

[0103] Next, using a drill bit with the trade name "NEU L088BW" manufactured by Union Tool Co., Ltd. (diameter 0.15 mm, length 3 mm, carbide drill), 1000 through holes were drilled in the molded body for evaluation. Specifically, while rotating the above drill bit at a rotational speed of 80,000 min -1 (rpm), drilling was performed at a feed rate of 0.8 m / min and a pitch of 1.0 mm.

[0104] The wear rate (%) of the drill bit was calculated from the images of the tip of the drill bit before and after drilling. The drillability was evaluated according to the following criteria.

[0105] ○ (Good): The wear rate of the drill bit was less than 60%. × (Poor): The wear rate of the drill bit was 60% or more.

[0106] (Handling property) As an evaluation of the handling property, an R-10 bending evaluation was performed on the resin-coated film manufactured above. The R-10 bending evaluation was performed by winding the resin-coated film around a cylinder with a diameter of φ10 mm. The handling property was evaluated according to the following criteria. ○ (Good): No cracks occurred when the film was wound. × (Poor): Cracks occurred when the film was wound.

[0107]

Table 1

[0108] (Summary) As is apparent from the above-described embodiments and examples, the resin composition according to the first aspect of the present disclosure is a resin composition containing an epoxy compound (A), a curing agent (B), a silane compound (C), and an inorganic filler (D). The silane compound (C) has a linear hydrocarbon group having 6 or more carbon atoms. The inorganic filler (D) includes an inorganic filler (D1) having a modified Mohs hardness of less than 7 and an inorganic filler (D2) having a modified Mohs hardness of 7 or more. When the cumulative 50% particle diameter based on volume in the particle size distribution of the inorganic filler (D1) is d1 (μm) and the cumulative 50% particle diameter based on volume in the particle size distribution of the inorganic filler (D2) is d2 (μm), d1 ≠ d2, and the product (d1 × d2) of d1 and d2 is 1.8 μm 2 or more. The content of the inorganic filler (D) is 900 parts by mass or more and 1500 parts by mass or less with respect to 100 parts by mass in total of the epoxy compound (A) and the curing agent (B).

[0109] According to the first aspect, it is possible to obtain a resin composition capable of improving moldability while maintaining the thermal conductivity of the cured product.

[0110] In the second aspect of the present disclosure, in the first aspect, d1 > d2.

[0111] According to the second aspect, the resin composition can further improve moldability by making the particle diameter of the inorganic filler (D1) having a low hardness larger than the particle diameter of the inorganic filler (D2) having a high hardness.

[0112] In the third aspect of the present disclosure, in the first or second aspect, d1 is 5 μm or more and 30 μm or less, and d2 is 0.1 μm or more and 4 μm or less.

[0113] According to the third aspect, the resin composition can further improve the moldability by setting the particle diameters of the inorganic filler (D1) and the inorganic filler (D2) within the above ranges, respectively.

[0114] In the fourth aspect of the present disclosure, in any one of the first to third aspects, the content of the silane compound (C) is 1.0 part by mass or more with respect to 100 parts by mass of the inorganic filler (D2).

[0115] According to the fourth aspect, the resin composition can further improve the moldability by setting the ratio of the silane compound (C) to the inorganic filler (D2) within the above range.

[0116] In the fifth aspect of the present disclosure, in any one of the first to fourth aspects, the mass ratio of the inorganic filler (D1) to the inorganic filler (D2) is 20 / 100 or more and 130 / 100 or less.

[0117] According to the fifth aspect, the resin composition can further improve the moldability by setting the mass ratio of the inorganic filler (D1) to the inorganic filler (D2) within the above range.

[0118] In the sixth aspect of the present disclosure, in any one of the first to fifth aspects, the content of the silane compound (C) is 5 parts by mass or more with respect to 100 parts by mass in total of the epoxy compound (A) and the curing agent (B).

[0119] According to the sixth aspect, the resin composition can further improve the moldability by setting the ratio of the silane compound (C) to the epoxy compound (A) and the curing agent (B) within the above range.

[0120] In the seventh aspect of the present disclosure, in any one of the first to sixth aspects, the chain hydrocarbon group of the silane compound (C) contains at least one selected from the group consisting of an alkyl group and an alkylene group.

[0121] According to the seventh aspect, the resin composition can further improve the moldability by using the chain hydrocarbon group of the silane compound (C) as the above group.

[0122] In the eighth aspect of the present disclosure, in any one of the first to seventh aspects, the silane compound (C) has at least one selected from the group consisting of an epoxy group, a vinyl group, a methacryl group, and a phenylamino group.

[0123] According to the eighth aspect, the resin composition can further improve the moldability by the silane compound (C) having the above group.

[0124] In the ninth aspect of the present disclosure, in any one of the first to eighth aspects, the curing agent (B) contains at least one selected from the group consisting of an amine compound, a phenol compound, and an acid anhydride compound.

[0125] According to the ninth aspect, the resin composition can further reduce the melt viscosity by using the above compound with appropriate curability as the curing agent (B), and as a result, can further improve the moldability of the resin composition.

[0126] The prepreg (1) according to the tenth aspect of the present disclosure includes a resin layer (11) containing the resin composition or a semi-cured product of the resin composition according to any one of the first to ninth aspects, and a fibrous substrate (12).

[0127] According to the tenth aspect, by using the resin composition with improved moldability, a prepreg (1) having a fine resin layer (11) capable of forming an insulating layer having high thermal conductivity can be obtained.

[0128] The resin film (2) according to the eleventh aspect of the present disclosure includes a resin layer (21) containing the resin composition or a semi-cured product of the resin composition according to any one of the first to ninth aspects, and a support film (22).

[0129] According to the 11th aspect, by using a resin composition with improved moldability, a resin film (2) having a fine resin layer (21) capable of forming an insulating layer with high thermal conductivity can be obtained.

[0130] The metal foil with resin (3) according to the 12th aspect of the present disclosure includes a resin layer (31) containing the resin composition according to any one of the 1st to 9th aspects or a semi-cured product of the resin composition, and a metal foil (32).

[0131] According to the 12th aspect, by using a resin composition with improved moldability, a metal foil with resin (3) having a fine resin layer (31) capable of forming an insulating layer with high thermal conductivity can be obtained.

[0132] The metal-clad laminate (4) according to the 13th aspect of the present disclosure includes an insulating layer (41) containing a cured product of the resin composition according to any one of the 1st to 9th aspects, and a metal layer (43).

[0133] According to the 13th aspect, by using a resin composition with improved moldability, a metal-clad laminate (4) having a fine insulating layer (41) with high thermal conductivity can be obtained.

[0134] The metal-clad laminate (4) according to the 14th aspect of the present disclosure includes an insulating layer (41) containing a cured product of the prepreg (1) according to the 10th aspect, and a metal layer (43).

[0135] According to the 14th aspect, by using a resin composition with improved moldability, a metal-clad laminate (4) having a fine insulating layer (41) with high thermal conductivity can be obtained.

[0136] The wiring board (5) according to the 15th aspect of the present disclosure includes an insulating layer (51) containing a cured product of the resin composition according to any one of the 1st to 9th aspects, and a wiring (53).

[0137] According to the 15th aspect, by using a resin composition with improved moldability, a wiring board (5) having a fine insulating layer (51) with high thermal conductivity can be obtained.

[0138] The wiring board (5) according to the 16th aspect of the present disclosure includes an insulating layer (51) containing a cured product of the prepreg (1) according to the 10th aspect and wiring (53).

[0139] According to the 16th aspect, by using a resin composition with improved moldability, a wiring board (5) having a fine insulating layer (51) with high thermal conductivity can be obtained.

Explanation of reference numerals

[0140] 1 Pre-preg 11 Resin layer 12 Fibrous base material 2 Resin-coated film 21 Resin layer 22 Support film 3 Resin-coated metal foil 31 Resin layer 32 Metal foil 4 Metal-clad laminate 41 Insulating layer 43 Metal layer 5 Wiring board 51 Insulating layer 53 Wiring

Claims

1. An epoxy compound (A), a curing agent (B), a silane compound (C), and an inorganic filler (D) are contained, the silane compound (C) has a chain hydrocarbon group having 6 or more carbon atoms, the inorganic filler (D) includes an inorganic filler (D1) having a modified Mohs hardness of less than 7 and an inorganic filler (D2) having a modified Mohs hardness of 7 or more, when the cumulative 50% particle diameter based on volume in the particle size distribution of the inorganic filler (D1) is d1 (μm) and the cumulative 50% particle diameter based on volume in the particle size distribution of the inorganic filler (D2) is d2 (μm), the d1 ≠ the d2, and the product (d1 × d2) of the d1 and the d2 is 1.8 μm ２ or more, the content of the inorganic filler (D) is 900 parts by mass or more and 1500 parts by mass or less with respect to 100 parts by mass in total of the epoxy compound (A) and the curing agent (B), a resin composition.

2. the d1 > the d2, the resin composition according to Claim 1.

3. the d1 is 5 μm or more and 30 μm or less, the d2 is 0.1 μm or more and 4 μm or less, the resin composition according to Claim 2.

4. the content of the silane compound (C) is 1.0 part by mass or more with respect to 100 parts by mass of the inorganic filler (D2), the resin composition according to Claim 1 or 2.

5. the mass ratio of the inorganic filler (D2) to the inorganic filler (D1) is 20 / 100 or more and 130 / 100 or less, the resin composition according to Claim 1 or 2.

6. The content of the silane compound (C) is 5 parts by mass or more with respect to 100 parts by mass in total of the epoxy compound (A) and the curing agent (B). The resin composition according to claim 1 or 2.

7. The chain hydrocarbon group of the silane compound (C) contains at least one selected from the group consisting of an alkyl group and an alkylene group. The resin composition according to claim 1 or 2.

8. The silane compound (C) has at least one selected from the group consisting of an epoxy group, a vinyl group, a methacrylic group, and a phenylamino group. The resin composition according to claim 1 or 2.

9. The curing agent (B) contains at least one selected from the group consisting of an amine compound, a phenol compound, and an acid anhydride compound. The resin composition according to claim 1 or 2.

10. A prepreg comprising a resin layer containing the resin composition according to claim 1 or 2 or a semi-cured product of the resin composition, and a fibrous substrate.

11. A resin-coated film comprising a resin layer containing the resin composition according to claim 1 or 2 or a semi-cured product of the resin composition, and a support film.

12. A resin-coated metal foil comprising a resin layer containing the resin composition according to claim 1 or 2 or a semi-cured product of the resin composition, and a metal foil.

13. A metal-clad laminate comprising an insulating layer containing a cured product of the resin composition according to claim 1 or 2, and a metal layer.

14. A metal-clad laminate comprising an insulating layer containing a cured product of the prepreg according to claim 10, and a metal layer.

15. A wiring board comprising an insulating layer containing a cured product of the resin composition according to claim 1 or 2, and a wiring.

16. A wiring board comprising an insulating layer containing a cured product of the prepreg according to claim 10 and a wiring.

Images