JP6405981B2 - Resin composition, prepreg, metal foil-clad laminate and printed wiring board - Google Patents

Description

  The present invention relates to a resin composition for printed wiring boards having high thermal conductivity, a prepreg, a metal foil-clad laminate, and a printed wiring board.

  In recent years, higher integration, higher functionality, and higher density mounting of semiconductors widely used in electronic devices, communication devices, personal computers, etc. are accelerating more and more than ever before. The demand is growing. In particular, a technology for radiating printed wiring boards against heat generation has been demanded. This is because the amount of heat generated from the semiconductor increases with the higher functionality of the semiconductor, and heat is likely to accumulate inside due to the effects of higher integration and higher density mounting.

  A thermosetting resin itself such as an epoxy resin used for an insulating layer of a printed wiring board has a low thermal conductivity. Then, in order to improve thermal conductivity as a printed wiring board, the method of highly filling the inorganic filler excellent in thermal conductivity to thermosetting resin is known (patent document 1).

  However, when the inorganic filler is highly filled in the thermosetting resin composition, the volume ratio of the thermosetting resin is decreased, the moldability is deteriorated, and cracks and voids are easily generated between the resin and the inorganic filler. In addition, a printed wiring board highly filled with an inorganic filler has a drawback that workability is poor, and particularly when drilling with a mechanical drill, there is a problem that the drill bit is significantly worn or broken. For such problems, it is effective to use a compound having high thermal conductivity and low hardness for the inorganic filler, and boehmite is one of the inorganic fillers that satisfy such characteristics (Patent Document). 2).

JP 2001-348488 A International Publication No. 2013/146700 Pamphlet

  However, the present inventors have found that the dielectric loss tangent of the resin composition is deteriorated when boehmite is highly filled as an inorganic filler in order to improve high thermal conductivity and workability.

  The present invention has been made in view of the above problems, and while maintaining high heat dissipation characteristics, formability and mechanical drilling workability, in addition, good glass transition temperature, thermal conductivity, dielectric constant and dielectric loss tangent. It aims at providing the resin composition used for the printed wiring board which has a characteristic, a prepreg using the same, a laminated board, and a metal foil tension laminated board.

  The inventors of the present invention have a partially aluminized boehmite (A) having an average particle size (D50) of 1 to 5 μm and a 700 ° C. dehydration amount of 13.0 to 14.5%, and an average particle size (D50). It contains a second inorganic filler (B) other than (A) that is 0.1 to 0.5 μm, and further contains an epoxy resin (C-1), a cyanate ester compound (C-2), and a maleimide compound ( C-3), phenol resin (C-4), acrylic resin (C-5), polyamide resin (C-6), polyamideimide resin (C-7) and thermosetting polyimide resin (C-8). A resin composition containing at least one thermosetting compound (C) selected from the group, the total content of the partially aluminized boehmite (A) and the second inorganic filler (B) However, it is 200-5 with respect to 100 mass parts of resin solid content in a resin composition. It has been found that the resin composition of 00 parts by mass solves the above-mentioned problems, and the present invention has been completed.

  The resin composition according to the present invention has good curability, and a laminate or a metal foil-clad laminate obtained by curing the obtained prepreg has a high glass transition temperature and high thermal conductivity and mechanical drill processability. However, it has good dielectric constant and dielectric loss tangent characteristics compared to a resin composition that is highly filled with boehmite as a filler. Therefore, it is suitable for printed wiring board materials for high integration and high density. The practicality is extremely high.

  Embodiments of the present invention will be described below. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

  In this embodiment, partially aluminized boehmite (A) having an average particle size (D50) of 1 to 5 μm and a 700 ° C. dehydration amount of 13.0 to 14.5%, and an average particle size of 0.1 to The second inorganic filler (B) other than (A), epoxy resin (C-1), cyanate ester compound (C-2), maleimide compound (C-3), phenol resin (0.5 μm) Any one selected from the group consisting of C-4), acrylic resin (C-5), polyamide resin (C-6), polyamideimide resin (C-7) and thermosetting polyimide resin (C-8). A resin composition containing the above thermosetting compound (C), wherein the total content of the partially aluminized boehmite (A) and the second inorganic filler (B) is a resin in the resin composition. Resin group which is 200 to 500 parts by mass with respect to 100 parts by mass of solid content It is an adult.

The partially aluminized boehmite (A) in this embodiment has a 700 ° C. dehydration amount of 13.0 to 14.5%. Boehmite has an AlOOH structure, but when heated, the following dehydration reaction takes place and changes to alumina, and its mass decreases.
2AlOOH → Al ₂ O ₃ + H ₂ O
The 700 ° C. dehydration amount represents the mass reduction rate of water reduction when heated to 700 ° C. with the mass reduction rate at 100 ° C. being 0%. Note that when the dehydration reaction proceeds completely and all the boehmite is transformed into alumina, the 700 ° C. dehydration amount becomes 15%.
Boehmite AlOOH can also be expressed as AlO (OH), and deteriorates the dielectric loss tangent of a prepreg and a metal foil-clad laminate using a resin composition containing the hydroxyl group in the crystal structure.
However, when the boehmite is heat-treated for a short time, only the surface of the boehmite particles is transformed into a crystalline phase of alumina (Al ₂ O ₃ ), which is a completely dehydrated product, so that the electrical characteristics are improved.
The crystal structure of the surface alumina at this time includes γ-alumina, δ-alumina and α-alumina in the order of the phase transition, and is not particularly limited, but γ-alumina from the viewpoint of minimizing the aluminization inside the boehmite particles. It is preferable that
By using partially aluminized boehmite with a dehydration amount of 700 ° C. of 13.0 to 14.5%, when this is contained as an inorganic filler, the thermal conductivity and electrical properties of the laminate obtained by curing The characteristics can be improved, and higher mechanical drilling workability can be achieved. The amount of dehydration at 700 ° C. is particularly preferably 13.0 to 13.9% from the viewpoint of dielectric loss tangent.

In the partially aluminized boehmite (A) in the present embodiment, it is essential that the average particle diameter (D50) is 1 to 5 μm from the viewpoint of thermal conductivity and insulation reliability of the laminate.
Moreover, as the shape, in order to reduce the specific surface area, it is preferable to have a shape closer to a sphere. This is because the fluidity of the resin composition is improved as the particle shape is closer to a sphere, so that molding defects such as voids during molding can be reduced even in a composition that is highly filled with an inorganic filler.
In addition, the average particle diameter (D50) in the present invention means a median diameter, and is a diameter in which the larger side and the smaller side are equivalent when the particle size distribution of the measured powder is divided into two. The average particle diameter is generally measured by a wet laser diffraction / scattering method.

As what is used for the 2nd inorganic filler (B) of this embodiment, it is a thing other than the partially aluminized boehmite (A) of this embodiment, and an average particle diameter (D50) is 0.1-0. If it is 0.5 micrometer, it will not specifically limit, The common thing used in this industry can be used.
For example, silica such as natural silica, fused silica, amorphous silica, hollow silica, alumina, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, molybdenum oxide, zinc molybdate, etc. Molybdenum compound, zinc borate, aluminum nitride, aluminum hydroxide heat treated product (heat treated aluminum hydroxide and reduced part of crystal water), metal hydrate such as magnesium hydroxide, zinc stannate, Examples include clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass fibers (fine glass powders such as E glass and D glass), and hollow glass. Among these, silica, alumina, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride are preferably used from the viewpoint of the filling rate. By setting the average particle size in the above range, the inorganic filler in the resin composition can be obtained by entering the gaps in the partially aluminized boehmite (A) having a larger average particle size than the second inorganic filler (B). This is because the volume content of the material can be increased and the thermal conductivity can be further improved.
The mass ratio of the partially aluminized boehmite (A) and the second inorganic filler (B) is preferably 1: 0.03 to 1: 0.5. The reason for this is that, from the viewpoint of close packing, small particles are filled between large particles, so by combining the content ratio of the small particles and large particles, the particles can be packed closely without excess or deficiency, and the resin composition This is because the fluidity of the resin is improved and molding defects such as voids can be suppressed.
In addition, if the shape of the second inorganic filler (B) is spherical, the fluidity of the resin composition is improved. Therefore, even when the inorganic filler is highly filled, molding of voids and the like during molding is performed. This is desirable because defects can be reduced.

  The total content of the partially aluminized boehmite (A) and the second inorganic filler (B) in the resin composition of the present embodiment is 200 to 100 mass parts of the resin solid content in the resin composition. The inclusion of 500 parts by mass is necessary from the viewpoints of thermal conductivity and moldability. Among these, it is preferable that it is 300-500 mass parts especially. The “resin solid content in the resin composition” means a component in the resin composition excluding the solvent, partially aluminized boehmite (A), and the second inorganic filler (B) unless otherwise specified. The resin solid content of 100 parts by mass means that the total of the components excluding the solvent and the inorganic filler in the resin composition is 100 parts by mass.

  Furthermore, the total volume of the partially aluminized boehmite (A) and the second inorganic filler (B) in the resin composition of the present embodiment is 40 to 70% by volume with respect to the total volume of the resin composition. It is preferable that it is 50 to 70% by volume. This is because the thermal conductivity can be improved by partially adding the aluminized boehmite (A) and the second inorganic filler (B) with such a content.

In the resin composition of this embodiment, since it thermosets later and produces a prepreg and a metal foil tension laminated board, a thermosetting compound (C) is made essential.
The thermosetting compound (C) is not particularly limited as long as it is a compound that is cured by heat. For example, epoxy resin (C-1), cyanate ester compound (C-2), maleimide compound (C-3), phenol Resin (C-4), acrylic resin (C-5), polyamide resin (C-6), polyamideimide resin (C-7), thermosetting polyimide resin (C-8), and the like. A curable compound can also be used individually by 1 type or in combination of 2 or more types as appropriate.
Among these, as a thermosetting compound used for this embodiment, any 1 or more types chosen from an epoxy resin (C-1), a cyanate ester compound (C-2), and a maleimide compound (C-3) are included. Preferably used.
By using an epoxy resin, the laminate obtained by curing becomes a resin composition having excellent characteristics such as heat resistance, thermal conductivity, water absorption, etc., and by using a cyanate ester compound, This is because the laminate obtained by curing becomes a resin composition having excellent heat resistance, chemical resistance and curability, and is obtained by curing by using a maleimide compound. This is because the plate is excellent in characteristics such as heat resistance, chemical resistance and curability.
Furthermore, by simultaneously using an epoxy resin, a cyanate ester compound and a maleimide compound, the resulting laminate is excellent in flame retardancy, heat resistance, chemical resistance, thermal conductivity, water absorption, curability, and elastic modulus characteristics. This is particularly preferable because it is expected.

As an epoxy resin (C-1) in this embodiment, if it is a compound which has a 2 or more epoxy group in 1 molecule, there will be no restriction | limiting in particular and a well-known thing can be used. For example, biphenyl aralkyl type epoxy resin, polyoxynaphthylene type epoxy resin, triphenolmethane type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak Type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, Naphthol aralkyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester Compounds obtained by epoxidation of a double bond such as butadiene, compounds obtained by the reaction of a hydroxyl-group-containing silicon resin with epichlorohydrin.
Among these, biphenyl aralkyl type epoxy resin, polyoxynaphthylene type epoxy resin, triphenolmethane type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, Bisphenol A novolac type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin maintain heat resistance, It is excellent in properties such as moisture absorption heat resistance and can be suitably used. These epoxy resins (C-1) may be used alone or in appropriate combination of two or more.

  Content of the said epoxy resin (C-1) in this embodiment is in the resin composition containing an epoxy resin (C-1) from a heat resistant, heat conductive, and water-absorbing viewpoint of the laminated board obtained. It is preferable that 10-90 mass parts is contained with respect to a total of 100 mass parts of resin solid content, More preferably, it is 30-70 mass parts.

As the cyanate ester compound (C-2) used in the present embodiment, generally known cyanate ester compounds can be used. For example, a naphthol aralkyl cyanate ester compound represented by the general formula (1), a novolak cyanate ester represented by the general formula (2), a biphenylaralkyl cyanate ester represented by the general formula (3), 1 , 3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, bis (3,5-dimethyl4-cyanatophenyl) methane, 1,3-dicyanatonaphthalene, 1, 4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4, 4'-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, bis (4-cyanatophenyl) propane, bis (4-cyanana Tophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, 2,2′-bis (4-cyanatophenyl) propane, bis (3,5-dimethyl, 4-si Anatophenyl) methane and the like.
Among them, a naphthol aralkyl cyanate compound represented by the general formula (1), a novolak cyanate compound represented by the general formula (2), and a biphenylaralkyl cyanate ester represented by the general formula (3) The compound is particularly preferred because it has excellent flame retardancy, high curability, and a cured product has a low coefficient of thermal expansion.

(In the formula, each R1 independently represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 to 50.)

(In the formula, each R2 independently represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 to 50.)

(In the formula, each R3 independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 to 50.)

In the general formula (1), each of the substituents R1 independently represents a hydrogen atom or a methyl group. In particular, an α-naphthol aralkyl type cyanate ester compound in which the substituent R1 is hydrogen has heat resistance. While maintaining, it is excellent in properties such as water absorption and moisture absorption heat resistance, and can be suitably used.
In the above general formula (1), n1 represents an integer of 1 to 50, but a plurality of cyanate ester compounds (C-2) different in n1 are used singly or in appropriate combination of two or more. May be used.

  In the present embodiment, the content of the cyanate ester compound (C-2) is selected from the viewpoints of heat resistance of the obtained laminate, solvent solubility and curability of the resin composition, and cyanate ester compound (C-2). It is preferable that 10-90 mass parts is contained with respect to a total of 100 mass parts of resin solid content in the resin composition containing, and it is especially preferable that it is 30-70 mass parts.

  The maleimide compound (C-3) used in the present embodiment can be used without particular limitation as long as it is a compound having one or more maleimide groups in one molecule. For example, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl Examples include -5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, tris (4-maleimidophenyl) methane, and a maleimide compound represented by the formula (4). These maleimide compounds may be used singly or in appropriate combination of two or more. Moreover, not only the form of a monomer but the form of a prepolymer may be sufficient, and the form of the prepolymer of a maleimide compound and an amine compound may be sufficient. Among these, from the viewpoint of heat resistance, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4) -Maleimidophenyl) methane, a maleimide compound represented by the formula (4) can be preferably used.

In the maleimide compound represented by the formula (4), a maleimide compound in which the substituent R4 is hydrogen maintains heat resistance and is excellent in properties such as water absorption and moisture absorption heat resistance, and thus can be suitably used. Further, as the maleimide compound, a plurality of maleimide compounds having different n4 may be appropriately mixed and used.
(In the formula, each R4 independently represents a hydrogen atom or a methyl group, and n4 is an integer ranging from 1 to 10 as an average value.)

  The content of the maleimide compound (C-3) in the resin composition of the present embodiment is such that the resin solids in the resin composition containing the maleimide compound are from the viewpoint of the heat resistance of the resulting laminate and the curability of the resin composition. It is preferable that 10-90 mass parts is contained with respect to a total of 100 mass parts of minutes, More preferably, it is 30-70 mass parts.

  As other thermosetting compounds (C) used in the present embodiment, phenol resin (C-4), acrylic resin (C-5), polyamide resin (C-6), and polyamideimide resin (C-7) are further used. ), Thermosetting polyimide resin (C-8), and any generally known one can be used without particular limitation. Each component of these thermosetting compounds can be used singly or in appropriate combination of two or more according to the purpose. Among them, one or more kinds of phenol resin (C-4), acrylic resin (C-5), polyamide resin (C-6), polyamideimide resin (C-7), and thermosetting polyimide resin (C-8) are used. The combination which uses a component suitably with any 1 or more types of components chosen from an epoxy resin (C-1), a cyanate ester compound (C-2), and a maleimide compound (C-3) is used preferably.

In the resin composition of this embodiment, a molybdenum compound (D) can be further contained. It is preferable to contain the molybdenum compound (D) because the mechanical drill workability of the resulting laminated plate can be improved.
As the molybdenum compound (D), molybdenum may be contained in the molecule, for example, molybdic acid, zinc molybdate, ammonium molybdate, sodium molybdate, calcium molybdate, potassium molybdate, molybdenum trioxide, molybdenum disulfide. And molybdenum compounds. Of these, molybdic acid, ammonium molybdate, and molybdenum trioxide are preferred because they do not function as organometallic catalysts.

  The molybdenum compound (D) may be obtained by treating a commercially available molybdenum compound with an inorganic oxide by a method such as a sol-gel method or a liquid phase precipitation method. Molybdenum compounds whose surfaces are treated with inorganic oxides act on inorganic oxides on heat, and molybdenum compounds act on drills. This is particularly preferable because it is possible to achieve both.

  The inorganic oxide surface-treated with the molybdenum compound is not particularly limited, and examples thereof include silica, titania, alumina, zirconium oxide, and the like, and silica is preferable from the viewpoint of insulating characteristics.

  Moreover, the thickness of the surface inorganic oxide surface-treated to a molybdenum compound is although it does not specifically limit, It is preferable that it is 15-50 nm. This is because the heat resistance is good when the thickness is 15 nm or more, and cracks generated when the inorganic oxide is treated with respect to the molybdenum compound can be reduced when the thickness is 50 nm or less.

  As a method for producing a molybdenum compound whose surface is treated with an inorganic oxide, for example, a molybdenum compound powder is dispersed in an alcohol solution in which a metal alkoxide is dissolved, such as silicon alkoxide or aluminum alkoxide, and water and alcohol and A mixed solution of the catalyst is dropped to hydrolyze the alkoxide, thereby forming a film of silicon oxide or aluminum oxide as a film on the powder surface. Thereafter, the powder is subjected to solid-liquid separation and vacuum drying, followed by heat treatment as described above. By this operation, a molybdenum compound having a film on the surface of the powder is obtained.

  The content of the molybdenum compound (D) in the present embodiment is a total of 100 mass of resin solids in the resin composition containing the molybdenum compound (D), from the viewpoint of the hole workability and reactivity of the obtained laminate. It is preferable that 0.1-10 mass parts is contained with respect to a part, More preferably, it is 1-5 mass parts.

In the resin composition of this embodiment, in addition to the above-described components, other components may be included as long as desired properties are not impaired.
For example, a silane coupling agent may be included. The silanol group of the silane coupling agent exhibits affinity and reactivity with a material having a hydroxyl group on the surface, and therefore has an effect on the organic-inorganic bond, and the surface of the inorganic filler reacts with the silane coupling agent. In this case, the adhesion between the thermosetting resin and the inorganic filler is improved. That is, the peel strength, the elastic modulus, the moisture absorption heat resistance, and the effect of improving the appearance of the cured product are expected.
The silane coupling agent used is not particularly limited as long as it is a silane coupling agent generally used for inorganic surface treatment. Specific examples include aminosilanes such as γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ -Vinyl silanes such as methacryloxypropyltrimethoxysilane, cationic silanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, phenylsilanes, etc. One kind can be used alone, or two or more kinds can be used in appropriate combination.

  The content of the silane coupling agent in the resin composition of the present embodiment is 3 to 30 parts by mass with respect to a total of 100 parts by mass of resin solids in the resin composition containing the silane coupling agent. Is preferred. This is because the adhesiveness between the resin and the inorganic filler can be improved without lowering the glass transition temperature by setting this range.

  Moreover, in the resin composition of this embodiment, it is also possible to use a wet dispersing agent together as long as the desired characteristics are not impaired. By containing the wetting and dispersing agent, the dispersibility of the inorganic filler can be improved. These wetting and dispersing agents are not particularly limited as long as they are dispersion stabilizers used for coatings. For example, wet dispersing agents such as Disperbyk-110, 111, 161, 180, and W903 manufactured by Big Chemie Japan Co., Ltd. can be mentioned, and one kind can be used alone or two or more kinds can be used in appropriate combination.

  Moreover, in order to adjust a cure rate suitably, the hardening accelerator may be contained. Any curing accelerator can be used without particular limitation as long as it is generally used as a curing accelerator for the thermosetting compound. For example, organometallic salts such as copper, zinc, cobalt, nickel and manganese, imidazoles and derivatives thereof, tertiary amines and the like can be mentioned. Moreover, you may use the above-mentioned hardening accelerator individually by 1 type or in combination of 2 or more types as appropriate. The content of the curing accelerator can be appropriately adjusted from the viewpoints of the degree of curing of the resin and the viscosity of the resin composition, and is usually based on 100 parts by mass of the total resin solids in the resin composition containing the curing accelerator. About 0.01 to 15 parts by mass.

  Also, other thermosetting compounds other than the above (C), thermoplastic compounds, various polymer compounds such as oligomers and elastomers thereof, other flame retardant compounds, additives, etc. may be added. Good. These can be used without particular limitation as long as they are generally used. For example, examples of the flame retardant compound include phosphorus compounds such as phosphate esters and melamine phosphate, nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, and silicone compounds. Additives include UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, brighteners A polymerization inhibitor and the like, and one type may be used alone or two or more types may be used in appropriate combination as necessary.

  The resin composition of the present embodiment may contain an organic solvent as necessary. The organic solvent is used to lower the viscosity of the resin composition, improve handling properties, and improve impregnation properties with glass cloth. Any organic solvent can be used without particular limitation as long as the mixture of the thermosetting compounds is compatible. Examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, and xylene, and amides such as dimethylformamide and dimethylacetamide, but are not limited thereto. is not. Moreover, you may use these organic solvents individually by 1 type or in combination of 2 or more types.

  The method for producing the resin composition of the present embodiment is a method in which a resin composition is produced by partially combining aluminized boehmite (A), the second inorganic filler (B), and the thermosetting compound (C). There is no particular limitation. For example, a part of the aluminized boehmite (A) and the second inorganic filler (B) are dispersed in the epoxy resin (C-1) with a homomixer or the like, and the cyanate ester compound (C-2) and maleimide are dispersed therein. The method etc. which mix | blend a compound (C-3) are mentioned. Furthermore, it is desirable to add an organic solvent in order to lower the viscosity, improve the handling property and improve the impregnation property into the glass cloth.

  Next, a prepreg, a laminate, and a metal foil-clad laminate produced using the resin composition will be described in detail.

The manufacturing method of the prepreg of this embodiment includes a partly aluminized boehmite (A), a second inorganic filler (B), an epoxy resin (C-1), a cyanate ester compound (C-2), a maleimide compound ( C-3), phenol resin (C-4), acrylic resin (C-5), polyamide resin (C-6), polyamideimide resin (C-7) and thermosetting polyimide resin (C-8). There is no particular limitation as long as it is a method for producing a prepreg by combining a base material and a resin composition containing at least one thermosetting compound (C) selected from the group as an essential component.
For example, after impregnating or apply | coating the said resin composition to a base material, it semi-hardens by the method of heating for 1 to 60 minutes in a 100-200 degreeC dryer, etc., and the method of manufacturing a prepreg etc. are mentioned. The amount of the resin composition attached to the substrate is preferably in the range of 40 to 95 mass% in terms of the amount of the resin composition (including the inorganic filler) relative to the total amount of the prepreg.

The base material used when manufacturing the prepreg of this embodiment can use the well-known thing used for various printed wiring board materials. Examples thereof include inorganic fibers such as E glass, T glass, L glass, D glass, S glass, NE glass, and quartz, and organic fibers such as polyimide, polyamide, and polyester, and can be appropriately selected depending on the intended use and performance.
Examples of the shape include woven fabric, non-woven fabric, roving, chopped strand mat, and surfacing mat. Although it does not restrict | limit especially about thickness, Usually, it is 0.01-0.3 mm, for example, the range of 0.01-0.2 mm is suitable for a laminated board use.

  The above-described base material may be subjected to a surface treatment from the viewpoint of adhesion to the resin and moisture absorption heat resistance. For example, the surface of the base material can be surface-treated with a silane coupling agent or the like. Moreover, when using a woven fabric as a base material, you may physically open the woven fabric. When using a film as the substrate, it is preferable to surface-treat the substrate by plasma treatment or the like from the viewpoint of adhesion to the resin.

The laminated board of this embodiment is formed by lamination using the above-described prepreg. Specifically, it is manufactured by laminating one or a plurality of the prepregs described above and laminating and forming a metal foil such as copper or aluminum on one or both sides as desired. The metal foil to be used is not particularly limited as long as it is used for a printed wiring board material. As a molding condition, a general laminated board for a printed wiring board and a multilayer board can be applied. For example, using a multi-stage press, multi-stage vacuum press, continuous molding, autoclave molding machine, etc., the temperature is generally 100 to 300 ° C., the pressure is ^{2 to} 100 kgf / cm ² , and the heating time is generally in the range of 0.05 to 5 hours. It is. Moreover, it is also possible to make a multilayer board by combining the prepreg of the present invention and a separately produced wiring board for the inner layer and laminate molding.

  The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The metal foil-clad laminate of the present invention has a low coefficient of thermal expansion, good moldability and chemical resistance, and is particularly effectively used as a printed wiring board for semiconductor packages that require such performance. be able to.

The printed wiring board in the present invention can be manufactured, for example, by the following method. First, a metal foil-clad laminate such as a copper-clad laminate of the present invention is prepared. Etching is performed on the surface of the metal foil-clad laminate to form an inner layer circuit, thereby producing an interior substrate. The inner layer circuit surface of the inner layer substrate is subjected to surface treatment to increase the adhesive strength as necessary, and then a predetermined number of prepregs of the present invention are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is formed on the outer surface. Laminate and heat and press to form one piece. In this way, a multilayer laminate is produced in which an insulating layer made of a cured material of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after this multi-layer laminate is subjected to through-hole or via-hole drilling, desmear treatment is performed to remove smear, which is a resin residue derived from the resin component contained in the cured product layer. Is called. After this, a plated metal film is formed on the wall surface of this hole to connect the inner layer circuit and the metal foil for the outer layer circuit, and further, the outer layer circuit is formed by etching the metal foil for the outer layer circuit. Manufactured.
The prepreg of the present invention (base material and the resin composition of the present invention attached thereto) and the resin composition layer (layer comprising the resin composition of the present invention) of the metal foil-clad laminate are the resin composition of the present invention. An insulating layer containing is formed.

  Hereinafter, the present invention will be specifically described with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited thereto.

(Synthesis Example 1)
α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g / eq., manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .: n includes 1 to 5) 0.47 mol (OH group equivalent) After dissolving in 500 ml, 0.7 mol of triethylamine was added to this solution, and 300 g of 0.93 mol of cyanogen chloride in chloroform was added dropwise at −10 ° C. over 1.5 hours, followed by stirring for 30 minutes. Further, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise and stirred for 30 minutes to complete the reaction. After the produced triethylamine hydrochloride was filtered off, the obtained filtrate was washed with 500 ml of 0.1N hydrochloric acid, and then washed with 500 ml of water four times. This was dried over sodium sulfate, evaporated at 75 ° C., and degassed under reduced pressure at 90 ° C. to obtain an α-naphthol aralkyl type cyanate ester compound represented by the above formula (I) as a brown solid. It was. When the obtained cyanate ester compound was analyzed by an infrared absorption spectrum, absorption of a cyanate ester group was confirmed in the vicinity of 2264 cm ⁻¹ .

( Reference Example 1)
30 parts by mass of α-naphthol aralkyl cyanate ester compound obtained in Synthesis Example 1 and 15 parts by mass of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70, manufactured by KAI Kasei Co., Ltd.) , 15 parts by mass of maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), 20 parts by mass of biphenyl aralkyl type epoxy resin (NC-3000-FH, manufactured by Nippon Kayaku Co., Ltd.), polyoxynaphthylene type epoxy Resin (HP6000, manufactured by DIC Corporation) 20 parts by mass, Silane coupling agent (OFS 6040, manufactured by Toray Dow Corning Co., Ltd.) 20 parts by mass, wetting and dispersing agent (BYK-W903, manufactured by Big Chemie Japan Co., Ltd.) 5 Mass parts are dissolved and mixed with methyl ethyl ketone, and partially aluminized boehmite (Boehmite MM01 manufactured by Kawai Lime Industry Co., Ltd.) Heat-treated product, average particle size 2.6 μm, 700 ° C. dehydration amount 14.3%) 300 parts by mass, average particle size 0.3 μm alumina (ASFP-20, manufactured by Denki Kagaku Kogyo Co., Ltd.) 100 parts by mass, Zinc molybdate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) 1 part by mass, Nikka octix manganese (Mn content 8 mass%) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 0.01 part by mass, 2, 4, 5 -Triphenylimidazole (product made from Tokyo Chemical Industry Co., Ltd.) 0.5 mass part was mixed, and the varnish was obtained. The average particle size was measured with a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation) after dispersing the inorganic filler with methyl ethyl ketone, followed by a dispersion treatment for 3 minutes with an ultrasonic homogenizer. The 700 ° C. dehydration amount was calculated from the dehydration amount of 100 ° C. to 700 ° C. using a differential heat-mass simultaneous measurement device (Bruker AXS Co., Ltd.). This varnish was diluted with methyl ethyl ketone, impregnated with 47.2 g / m ² of E glass cloth (manufactured by Asahi Kasei E-Materials Co., Ltd.), dried by heating at 150 ° C. for 3 minutes, and a filler content of 76 mass. % Prepreg was obtained. Next, 8 sheets of this prepreg were stacked and 12 μm electrolytic copper foils were placed one above the other and pressed at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes to obtain a 0.8 mm thick copper-clad laminate. .

  The obtained copper-clad laminate was evaluated for thermal conductivity, glass transition temperature, dielectric constant and dielectric loss tangent. The results are shown in Table 1.

(Evaluation method)
1) Thermal conductivity: The density of the obtained eight-layer copper-clad laminate is measured, the specific heat is measured by DSC (TA Instrument Q100 type), and further, the heat is measured by a xenon flash analyzer (Bruker: LFA447 Nanoflash). The diffusivity was measured. And thermal conductivity was computed from the following formula | equation.
Thermal conductivity (W / m · K) = density (kg / m ³ ) × specific heat (kJ / kg · K) × thermal diffusivity (m ² / S) × 1000
2) Glass transition temperature (Tg): The obtained 8-layer copper-clad laminate was measured using a dynamic viscoelasticity analyzer (TA Instruments) according to JIS C6481.
3) Dielectric constant (Dk), dielectric loss tangent (Df): Using a test piece from which a copper foil of a copper-clad laminate having a thickness of 0.8 mm is removed, a cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies) The measurement of the dielectric constant and dielectric loss tangent at 1 GHz was performed three times, and the average value was calculated.

(Example 2)
Instead of the partially aluminized boehmite used in Reference Example 1, partially aluminized boehmite (average particle size 2.3 μm, 700 ° C. dehydrated amount 13.9) in which the filler was heated to further promote the aluminization of the surface. %) Was carried out in the same manner as in Reference Example 1 to obtain a copper-clad laminate having a thickness of 0.8 mm. The physical property measurement results of the obtained laminate are shown in Table 1.

(Example 3)
Instead of the partially aluminized boehmite used in Example 2, partially aluminized boehmite (average particle size 2.4 μm, 700 ° C. dehydrated amount 13.1) in which the filler was heated to further promote the aluminization of the surface. %) Was used in the same manner as in Reference Example 1 to obtain a copper-clad laminate having a thickness of 0.8 mm. The physical property measurement results of the obtained laminate are shown in Table 1.

(Comparative Example 1)
The same as Reference Example 1 except that 300 parts by weight of boehmite (MM011, Kawai Lime Industry Co., Ltd., average particle size 2.8 μm, 700 ° C. dehydrated amount 15.0%) was used without using some aluminized boehmite. To obtain a copper-clad laminate having a thickness of 0.8 mm. The physical property measurement results of the obtained laminate are shown in Table 1.

Claims (10)

Partially aluminized boehmite (A) having an average particle size (D50) of 1 to 5 μm and a dehydration amount (700 ° C. dehydration amount) of 13.0 to 13.9 % when heated to 100 to 700 ° C., average Contains a second inorganic filler (B) other than (A) having a particle size (D50) of 0.1 to 0.5 μm, and further contains an epoxy resin (C-1) and a cyanate ester compound (C- 2), maleimide compound (C-3), phenol resin (C-4), acrylic resin (C-5), polyamide resin (C-6), polyamideimide resin (C-7) and thermosetting polyimide resin ( C-8) a resin composition containing at least one thermosetting compound (C) selected from the group consisting of the partially aluminized boehmite (A) and a second inorganic filler ( The total content of B) is the resin solid content in the resin composition 200 to 500 parts by mass per 00 parts by weight, the resin composition. The second inorganic filler (B) is one or more selected from the group selected from silica, alumina, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride. The resin composition according to claim 1, wherein The cyanate ester compound (C-2) is represented by the naphthol aralkyl cyanate ester compound represented by the general formula (1), the novolak cyanate ester compound represented by the general formula (2), and the general formula (3). of the group selected from biphenyl aralkyl type cyanate ester compound is any one or more, the resin composition according to claim 1 or 2.
(In the formula, each R1 independently represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 to 50.)
(In the formula, each R2 independently represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 to 50.)
(In the formula, each R3 independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 to 50.) The maleimide compound (C-3) is bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4- The resin composition according to any one of claims 1 to 3 , wherein the resin composition is at least one selected from the group selected from maleimide phenyl) methane and a maleimide compound represented by formula (4).
(In the formula, each R4 independently represents a hydrogen atom or a methyl group, and n4 is an integer ranging from 1 to 10 as an average value.) Furthermore, the resin composition as described in any one of Claims 1-4 containing a molybdenum compound (D). The resin composition according to claim 5 , wherein the content of the molybdenum compound (D) is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the resin solid content in the resin composition. The resin composition according to claim 5 or 6 , wherein the molybdenum compound (D) has a surface treated with an inorganic oxide. A prepreg obtained by impregnating or coating the substrate with the resin composition according to any one of claims 1 to 7 . A metal foil-clad laminate obtained by laminating and curing the prepreg according to claim 8 and a metal foil. An insulating layer, wherein a printed wiring board comprising an insulating layer conductor layer formed on the surface of the printed wiring board comprising a resin composition, wherein the insulating layer is in any one of claims 1-7 .