HK1171777B - Thermosetting resin composition, method for producing resin composition varnish, prepreg and laminate - Google Patents
Thermosetting resin composition, method for producing resin composition varnish, prepreg and laminate Download PDFInfo
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Abstract
Discloses are a thermosetting resin composition containing a maleimide compound including an unsaturated maleimide compound having a specified chemical structure, a thermosetting resin, an inorganic filler, and a molybdenum compound; a laminate plate for wiring boards obtained by coating a base material with a thermosetting resin composition containing a thermosetting resin, silica, and a specified molybdenum compound and then performing semi-curing to form a prepreg, and laminating and molding the prepreg; and a method for manufacturing a resin composition varnish including specified steps. According to the present invention, electronic components having low thermal expansion properties and excellent drilling processability and heat resistance, for example, a prepreg, a laminate plate, an interposer, etc., can be provided.
Description
Technical Field
The present invention particularly relates to a thermosetting resin composition suitable for use in electronic components and the like which have low thermal expansion and excellent drilling processability and heat resistance, a prepreg and a laminate using the composition, a laminate for wiring boards which requires drilling processing in the stage of production of wiring boards, a method for producing a varnish of the resin composition, and a prepreg and a laminate produced by the production method and suitable for use in semiconductor packages and printed wiring boards.
Background
In a wiring board used for a semiconductor package (hereinafter referred to as an "interposer"), a plurality of drilling processes are generally performed for interlayer connection of wirings. Therefore, the laminate for interposer is required to have high drilling workability.
However, conventionally, a curable resin composition composed of a bismaleimide compound and a cyanate resin has been widely used for a laminate for semiconductor packaging (for example, patent document 1). This is because the resin composition is excellent in heat resistance and therefore suitable as a resin composition for a laminate for semiconductor encapsulation which is exposed to high temperatures such as a reflow step in many cases at the time of mounting.
However, in recent years, as demands for reduction in thickness and weight of electronic devices have increased, reduction in thickness and increase in density of semiconductor packages have rapidly progressed, and even in laminated plates for semiconductor packages, higher characteristics have been demanded in a wide range of fields other than heat resistance.
Among these, in order to suppress an increase in warpage during mounting due to a reduction in thickness of a semiconductor package, it is strongly required to make the thermal expansion coefficient of a laminated plate for a semiconductor package close to that of a silicon chip, that is, to lower the thermal expansion.
Various methods are conceivable for reducing the thermal expansion of the laminate, but it is effective to reduce the thermal expansion of the resin itself for the laminate or to increase the filling of the inorganic filler in the resin composition. Therefore, it has been proposed to use a novolak type cyanate ester resin or to increase the content of an inorganic filler (for example, patent document 2).
However, the use of cyanate ester resins or the high filling of inorganic fillers reduces the machinability of the resin compositions, and there is a problem that the drilling workability of laminates using these resin compositions is significantly impaired.
Therefore, attempts have been made to prevent the reduction of the drilling processability by adding a plate-like filler such as calcined talc as an inorganic filler or reducing the content of the inorganic filler (for example, patent document 3), but there have been problems such that the effect of preventing the reduction of the drilling processability is insufficient or the warpage-suppressing effect of the semiconductor package is insufficient due to the low elasticity of the resin composition, and satisfactory results have not been obtained.
In order to reduce the thermal expansion of the laminate, it is effective to increase the content of a filler having a small thermal expansion coefficient, such as silica, in the inorganic filler in the resin composition for the laminate. However, if the content of a hard filler such as silica is increased, there is a problem that the drilling workability of the laminated plate is lowered.
In addition, in order to improve the drilling workability, an attempt has been made to add a metal dichalcogenide such as molybdenum disulfide as inorganic solid lubricant particles (for example, see patent document 4). However, when molybdenum disulfide is added, there is a problem that the electrical insulation of the laminate is significantly lowered, and satisfactory results cannot be obtained.
Therefore, in order to solve this problem, the present inventors have searched for additives that can suppress the deterioration of the drilling processability even with highly filled inorganic filler materials, and have found that molybdenum compounds have excellent effects.
However, since the molybdenum compound has a high specific gravity, if it is added directly to a resin composition varnish for laminate sheet production, it is likely to settle, which causes production defects. Therefore, it is recommended to use particles in which a molybdenum compound is supported on talc or the like (for example, Kemguard 911C manufactured by Sherwin Williams corporation) (for example, see patent document 1), but there are disadvantages that thickening occurs in a varnish of the resin composition, or aggregation between particles supported on a molybdenum compound is easily caused, and satisfactory results cannot be obtained.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 3-52773
Patent document 2: japanese patent No. 4132703
Patent document 3: japanese patent laid-open publication No. 2005-162787
Patent document 4: japanese Kohyo publication 2002-527538
Patent document 5: japanese laid-open patent publication No. 2000-264986
Disclosure of Invention
The present invention has been made in view of such a situation, and a first object of the present invention is to provide a thermosetting resin composition suitable for use in electronic components and the like having low thermal expansion and excellent drilling processability and heat resistance, and a prepreg and a laminate using the same, and a second object of the present invention is to provide a laminate for wiring boards having excellent drilling processability in the production of wiring boards, and having excellent electrical insulation properties and low thermal expansion.
Further, a third object of the present invention is to provide a method for producing a resin composition varnish in which precipitation or aggregation of a molybdenum compound is less likely to occur, and a prepreg and a laminate sheet having a low thermal expansion coefficient and high drilling processability.
The present inventors have made extensive studies and, as a result, have found that: the first object is achieved by a thermosetting resin composition containing an unsaturated maleimide compound having an acidic substituent group represented by a specific chemical formula, a thermosetting resin, an inorganic filler and a molybdenum compound, the second object is achieved by producing a laminate using a thermosetting resin composition containing a thermosetting resin, a specific amount of silica and a specific molybdenum compound, and the third object is achieved by dispersing and mixing a molybdenum compound in a slurry in which specific silica particles are dispersed, adding the slurry to a varnish containing a thermosetting resin, and then blending an inorganic filler to produce a resin composition varnish by the above-described method. The present invention has been completed based on the above findings.
That is, the present invention provides the following inventions 1 to 15 and 16:
1. a thermosetting resin composition characterized by containing: (A) a maleimide compound comprising an unsaturated maleimide compound having an acidic substituent represented by the following general formula (I) or (II), (B) a thermosetting resin, (C) an inorganic filler, and (D) a molybdenum compound.
[ solution 1]
[ solution 2]
(in the formula, R1Represents a hydroxyl group, a carboxyl group or a sulfonic acid group as an acidic substituent, R2、R3、R4And R5Independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group or a group represented by the following formula (III), X is an integer of 1 to 5, Y is an integer of 0 to 4, and the sum of X and Y is 5. )
[ solution 3]
2. The thermosetting resin composition according to 1, wherein the molybdenum compound (D) is at least one selected from molybdenum oxides and molybdic acid compounds, and the content of the molybdenum compound is 0.02 to 20 vol% based on the total amount of the resin composition.
3. The thermosetting resin composition according to 1 or 2, wherein the thermosetting resin (B) is an epoxy resin, the total content of the component (A) and the component (B) is 30 to 80 vol% of the total resin composition, and the mass ratio of the component (A) to the component (B) is 20 to 90 parts by mass when the total content of the component (A) and the component (B) is 100 parts by mass.
4. The thermosetting resin composition according to any one of the above 1 to 3, wherein the inorganic filler (C) is fused spherical silica, and the content of the inorganic filler is 10 to 60 vol% based on the total amount of the resin composition.
5. A prepreg obtained by impregnating or coating a base material with or with the thermosetting resin composition described in any one of 1 to 4 and then B-staging the impregnated or coated base material.
6. A laminate sheet obtained by laminating and molding the prepregs of the above 5.
7. The laminate sheet according to the above 6, which is a metal-clad laminate sheet obtained by laminating a metal foil on at least one surface of a prepreg and then performing hot press molding.
8. A laminate for a wiring board, which is obtained by applying a thermosetting resin composition containing (E) a thermosetting resin, (F) silica, and (G) a molybdenum compound selected from at least one of zinc molybdate, calcium molybdate, and magnesium molybdate to a film-like or fibrous substrate, semi-curing the applied thermosetting resin composition to obtain a prepreg, and laminating the prepreg and molding the prepreg, wherein the content of the silica in (F) is 20 to 60 vol%.
9. The laminate for a wiring board as described in the above 8, wherein the silica of (F) is a fused spherical silica having an average particle diameter of 0.1 μm or more and 1 μm or less, and the content of the molybdenum compound of (G) is 0.1 vol% or more and 10 vol% or less of the total amount of the resin composition.
10. The laminate for a wiring board according to claim 8 or 9, wherein the thermosetting resin composition is varnished.
11. The laminate for wiring boards according to any one of the above 8 to 10, wherein the film-like or fibrous base material is a glass cloth.
12. Preparation method of resin composition varnishThe method comprises the following steps: a first dispersing and mixing step of mixing a mixture containing (H) a polymer having an average particle diameter of 0.01 to 0.1 μm and a specific surface area of 30m2270m above g2(I) a molybdenum compound is dispersed and mixed in a slurry of silica particles of not more than g,
a second dispersion mixing step of dispersing and mixing the slurry having undergone the first dispersion mixing step in a varnish containing (J) a thermosetting resin,
and a third dispersion mixing step of dispersing (K) an inorganic filler other than the silica particles and the molybdenum compound in the varnish having passed through the second dispersion mixing step.
13. The method for producing a varnish of the resin composition as described in the above 12, which comprises a curing accelerator adding step of adding a curing accelerator to the varnish after the third dispersing and mixing step.
14. The method for producing a varnish of a resin composition as described in the above 12 or 13, wherein the molybdenum compound (I) is a mixture of 1 or 2 or more selected from the group consisting of zinc molybdate, calcium molybdate and magnesium molybdate.
15. A prepreg obtained by impregnating and coating a base material with a varnish of a resin composition obtained through the following steps: a first dispersing and mixing step comprising (H) a polymer having an average particle diameter of 0.01 to 0.1 μm and a specific surface area of 30m2270m above g2A step of dispersing and mixing (I) a molybdenum compound in a slurry of silica particles having a particle size of not more than g; a second dispersion mixing step of dispersing and mixing the slurry having undergone the first dispersion mixing step in a varnish containing (J) a thermosetting resin; and a third dispersion mixing step of dispersing and mixing (K) the inorganic filler in the varnish having passed through the second dispersion mixing step.
16. A laminate sheet obtained by laminating and molding the prepreg according to claim 15.
The thermosetting resin composition of the present invention is particularly suitable for use in electronic components and the like having low thermal expansibility and excellent drilling processability and heat resistance.
Therefore, according to the present invention, a prepreg, a laminate, or the like having excellent performance can be provided by using the thermosetting resin composition.
Further, according to the present invention, a laminated plate for a wiring board, which is excellent in drilling workability in the production of a wiring board and also has excellent electrical insulation properties and low thermal expansion properties, can be provided. Therefore, if the interposer is manufactured using the laminate for a wiring board of the present invention, a semiconductor package with less warpage and low cost can be obtained.
Further, according to the present invention, it is possible to provide a method for producing a resin composition varnish in which precipitation or aggregation of a molybdenum compound is less likely to occur, and a prepreg and a laminate sheet having a low thermal expansion coefficient and high drilling processability.
Detailed Description
First, the thermosetting resin composition of the present invention will be explained.
[ thermosetting resin composition ]
The thermosetting resin composition of the present invention is a resin composition containing, as essential components, (a) a maleimide compound comprising an unsaturated maleimide compound having an acidic substituent represented by the following general formula (I) or (II), (B) a thermosetting resin, (C) an inorganic filler, and (D) a molybdenum compound.
[ solution 4]
[ solution 5]
In the formula, R1Is a hydroxyl group, a carboxyl group or a sulfonic acid group as an acidic substituent, R2、R3、R4And R5Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, R2～R5May be the same or different. A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group or a group represented by the following formula (III), X is an integer of 1 to 5, Y is an integer of 0 to 4, and the sum of X and Y is 5.
[ solution 6]
First, the unsaturated maleimide compound having an acidic substituent represented by the general formula (I) or (II) of the component (a) can be produced, for example, by reacting a maleimide compound having at least 2N-substituted maleimide groups in 1 molecule with an amine compound having an acidic substituent represented by the following general formula (IV) in an organic solvent.
[ solution 7]
In the formula, R1Each independently represents a hydroxyl group, a carboxyl group or a sulfonic acid group as an acidic substituent, R2Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, X is an integer of 1 to 5, Y is an integer of 0 to 4, and the sum of X and Y is 5.
Examples of the maleimide compound having at least 2N-substituted maleimide groups in 1 molecule include bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, m-phenylene bismaleimide, and 2, 2-bis- (4- (4-maleimidophenoxy) phenyl) propane.
Among them, bis (4-maleimidophenyl) methane, m-phenylenebismaleimide and bis (4-maleimidophenyl) sulfone, which have a high reaction rate and can be more highly heat-resistant, are preferable, m-phenylenebismaleimide and bis (4-maleimidophenyl) methane are more preferable from the viewpoint of low cost, and bis (4-maleimidophenyl) methane is particularly preferable from the viewpoint of solubility in a solvent.
Examples of the amine compound having an acidic substituent represented by the general formula (IV) include, for example, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3, 5-dihydroxyaniline, 3, 5-dicarboxylaniline and the like, among which m-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3, 5-dihydroxyaniline are preferable from the viewpoint of solubility and yield of synthesis, and m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance.
The organic solvent used in the reaction is not particularly limited, and examples thereof include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide, and the like, and 1 or 2 or more of these solvents may be used in combination.
Among these organic solvents, cyclohexanone, propylene glycol monomethyl ether and methyl cellosolve are preferred from the viewpoint of solubility, cyclohexanone and propylene glycol monomethyl ether are more preferred from the viewpoint of low toxicity, and propylene glycol monomethyl ether which is highly volatile and hardly remains as a residual solvent in the production of a prepreg is particularly preferred.
The amount of the organic solvent used is preferably 10 to 1000 parts by mass, more preferably 100 to 500 parts by mass, and particularly preferably 200 to 500 parts by mass, based on 100 parts by mass of the total of the maleimide compound having at least 2N-substituted maleimide groups in 1 molecule and the amine compound having an acidic substituent represented by the general formula (IV).
When the amount of the organic solvent used is 10 parts by mass or more, the solubility becomes sufficient, and when the amount is 1000 parts by mass or less, the reaction time does not become excessively long.
Regarding the amounts of the maleimide compound having at least 2N-substituted maleimide groups in 1 molecule and the amine compound having an acidic substituent represented by the general formula (IV), the maleimide group equivalent of the maleimide compound and-NH-of the amine compound are used2The equivalent ratio of equivalents in terms of base is preferably within the range shown by the following formula,
1.0<(Maleimido equivalent)/(-NH)2Equivalent of base conversion) is less than or equal to 10.0
The equivalent ratio is more preferably in the range of 2.0 to 10.0. When the amount ratio is within the above range, insufficient solubility in a solvent or gelation does not occur, and the heat resistance of the thermosetting resin is not lowered.
In addition, the reaction temperature is preferably 50 to 200 ℃, the reaction time is preferably in the range of 0.1 to 10 hours, and more preferably in the range of 100 to 160 ℃ and 1 to 8 hours.
In this reaction, a reaction accelerator may be used as needed. Examples of the reaction accelerator include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and organophosphorous compounds such as triphenylphosphine, and 1 kind or 2 or more kinds of them may be mixed and used.
The thermosetting resin composition of the present invention contains, as the component (a), the unsaturated maleimide compound having an acidic substituent represented by the general formula (I) or (II) described above, and thus has low thermal expansibility and excellent heat resistance. (A) The component (A) may contain other maleimide compounds, but it is preferable that the content of the unsaturated maleimide compound having an acidic substituent represented by the general formula (I) or (II) in the component (A) is 60% by mass or more.
Examples of the thermosetting resin of the component (B) include epoxy resin, phenol resin, unsaturated imide resin, cyanate ester resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, and the like, and 1 of these resins or 2 or more of these resins may be used in combination.
Among them, epoxy resins are preferable from the viewpoint of moldability and electrical insulation properties. Examples of such epoxy resins include bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol a novolac type epoxy resins, bisphenol F novolac type epoxy resins, biphenyl type epoxy resins, xylene type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, polyfunctional phenols, polycyclic aromatic diglycidyl ether compounds such as anthracene, and the like, and 1 or 2 or more of these may be used by mixing.
When an epoxy resin is used as the thermosetting resin, a curing agent or a curing accelerator for the epoxy resin may be used as needed. Examples of the curing agent include polyfunctional phenol compounds such as phenol novolac resins and cresol novolac resins, amine compounds such as dicyandiamide, diaminodiphenylmethane and diaminodiphenylsulfone, acid anhydrides such as phthalic anhydride, pyromellitic anhydride, maleic anhydride and maleic anhydride copolymers, and 1 or 2 or more of these may be used by mixing.
Examples of the curing accelerator include imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, and the like, and 1 kind or 2 or more kinds of these may be mixed and used.
The total content of the component (A) and the component (B) is preferably 30 to 80 vol%, more preferably 40 to 70 vol%, based on the total amount of the resin composition. By setting the total content of the component (A) and the component (B) to 30 to 80 vol%, the moldability and low thermal expansion of the resin composition can be maintained satisfactorily.
The mass ratio of the component (a) to the component (B) is preferably 20 to 90 parts by mass, more preferably 30 to 80 parts by mass, based on 100 parts by mass of the total content of the component (a) and the component (B). The flame retardancy, adhesiveness and heat resistance of the resin composition can be maintained well by setting the content of the component (A) to 20 to 90 parts by mass.
Examples of the inorganic filler of component (C) include glass powders and hollow glass beads of silica, alumina, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, E glass, S glass, D glass, and the like, and 1 kind of these may be used or 2 or more kinds may be mixed and used.
Among them, silica is preferable from the viewpoint of low thermal expansion. Examples of the silica include precipitated silica which is produced by a wet process and has a high water content, and dry silica which is produced by a dry process and contains little bound water or the like, and examples of the dry silica include pulverized silica, fumed silica, and fused spherical silica according to different production methods. Among them, fused spherical silica is preferable in terms of low thermal expansion and high fluidity when filled in a resin.
When fused spherical silica is used as the inorganic filler of the component (C), the average particle diameter is preferably 0.1 to 10 μm, more preferably 0.3 to 8 μm.
By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity of the resin composition at the time of high filling of the fused spherical silica can be favorably maintained, and by setting the average particle diameter to 10 μm or less, the mixing probability of coarse particles can be reduced and the occurrence of defects due to the coarse particles can be suppressed.
Here, the average particle diameter refers to a particle diameter corresponding to a point having a volume of 50% when a cumulative power distribution curve based on the particle diameter is obtained with the total volume of the particles as 100%, and can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method or the like.
(C) The content of the inorganic filler of component (a) is preferably 10 to 60 vol%, more preferably 20 to 50 vol% of the total amount of the resin composition. By setting the content of the inorganic filler to 10 to 60 vol% of the total amount of the resin composition, the moldability and low thermal expansion of the resin composition can be favorably maintained.
Examples of the molybdenum compound as the component (D) include molybdenum oxides such as molybdenum trioxide, zinc molybdate, ammonium molybdate, magnesium molybdate, calcium molybdate, barium molybdate, sodium molybdate, potassium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, silicomolybdic acid, molybdic acid compounds, and inorganic molybdenum compounds such as molybdenum boride, molybdenum disilicide, molybdenum nitride, and molybdenum carbide. These may be used in a mixture of 1 or 2 or more.
Among them, molybdenum oxide and molybdic acid compound are preferable from the viewpoint of a good effect of preventing reduction in drilling workability, and zinc molybdate, calcium molybdate, and magnesium molybdate are particularly preferable from the viewpoint of low water solubility, low toxicity, and high electrical insulation.
When zinc molybdate, calcium molybdate, or magnesium molybdate is used as the component (D), precipitation prevention or improvement in dispersibility can be achieved when the resin composition is dissolved in an organic solvent and varnished by using talc, silica, zinc oxide, calcium carbonate, or magnesium hydroxide as a support for the molybdenum compound. Examples of such molybdenum compounds include KEMGARD 911C manufactured by SherwinWilliams corporation, in which zinc molybdate is supported on talc.
(D) The content of the molybdenum compound of component (B) is preferably 0.02 to 20% by volume, more preferably 0.1 to 15% by volume, based on the total amount of the resin composition. By setting the content of the molybdenum compound to 0.02 to 20 vol% of the total amount of the resin composition, the effect of preventing the reduction of the drilling workability while maintaining the adhesiveness of the resin composition is sufficiently obtained.
The thermosetting resin composition of the present invention may contain any known thermoplastic resin, elastomer, organic filler, flame retardant, ultraviolet absorber, antioxidant, adhesion improver, and the like to such an extent that the thermosetting properties as a resin composition are not impaired.
Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyether ether ketone resin, polyetherimide resin, silicone resin, tetrafluoroethylene resin, and the like.
Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxyl-modified acrylonitrile.
Examples of the organic filler include resin fillers having a uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, or the like; and a resin filler having a core-shell structure comprising a rubbery core layer made of an acrylate resin, a methacrylate resin, a conjugated diene resin, or the like, and a glassy shell layer made of an acrylate resin, a methacrylate resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like.
Examples of the flame retardant include halogen-containing flame retardants containing bromine or chlorine, phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, tris (dichloropropyl) phosphate, and red phosphorus, nitrogen flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers.
Examples of the antioxidant include hindered phenol-based or hindered amine-based antioxidants, and examples of the adhesion improver include silane-based, titanate-based, and aluminate-based coupling agents.
The thermosetting resin composition of the present invention is used by impregnating or coating a substrate with the composition, followed by B-staging to prepare a prepreg. When used for the prepreg, the respective components are preferably finally dissolved or dispersed in an organic solvent to form a varnish.
Examples of the organic solvent used in this case include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide can be used in a mixture of 1 or 2 or more.
Among them, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferable from the viewpoint of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity.
When the inorganic filler is blended in a varnish, it is preferable to pretreat the inorganic filler with a coupling agent such as a silane-based or titanate-based coupling agent or a surface treatment agent such as a silicone oligomer, or to perform a bulk mixing (integral blending) treatment.
The resin composition in the varnish to be finally obtained is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, of the total amount of the varnish. By setting the content of the resin composition in the varnish to 40 to 90 mass%, the coating property can be maintained well, and a prepreg with an appropriate amount of the resin composition can be obtained.
The prepreg of the present invention is obtained by impregnating or applying the thermosetting resin composition of the present invention to a substrate and then B-staging the impregnated or applied resin composition. That is, the prepreg of the present invention is produced by impregnating or applying the thermosetting resin composition of the present invention to a substrate, and then semi-curing (B-staging) the substrate by heating or the like. The prepreg of the present invention will be described in detail below.
As the base material used for the prepreg of the present invention, known materials used for various laminates for electrical insulating materials can be used. Examples of such a material include fibers of inorganic substances such as E glass, D glass, S glass, and Q glass, fibers of organic substances such as aramid, polyester, and polytetrafluoroethylene, and mixtures thereof.
These base materials have shapes such as woven cloth, nonwoven fabric, roving (roving), chopped strand mat (chopped strand mat), and surfacing mat (surfacing mat), but the material and shape may be selected according to the intended use and performance of the molded product, and 2 or more materials and shapes may be used alone or in combination as necessary.
The thickness of the substrate is not particularly limited, and for example, a substrate of about 0.01 to 0.2mm can be used, and a substrate subjected to surface treatment with a silane coupling agent or the like or a substrate subjected to mechanical opening treatment is preferable from the viewpoint of heat resistance, moisture resistance, and workability. The prepreg of the present invention can be obtained by impregnating or applying the resin composition to a substrate so that the amount of the resin composition adhering to the substrate is 20 to 90 mass% in terms of the resin content of the dried prepreg, and then performing heat drying at a temperature of 100 to 200 ℃ for 1 to 30 minutes to semi-cure (B-stage) the prepreg.
The laminate of the present invention is obtained by laminating and molding the prepreg of the present invention. That is, the prepreg of the present invention is formed by laminating, for example, 1 to 20 sheets of the prepreg, and arranging a metal foil such as copper or aluminum on one surface or both surfaces of the prepreg. The molding conditions can be applied to, for example, a method of laminating a laminate sheet or a multilayer sheet for an electrical insulating material, and molding can be performed at a temperature of 100 to 250 ℃, a pressure of 0.2 to 10mPa, and a heating time of 0.1 to 5 hours by using, for example, a multistage press, a multistage vacuum press, a continuous molding, an autoclave molding machine, or the like. Further, the prepreg of the present invention and the wiring board for inner layer may be combined and laminated to produce a multilayer board.
Next, the wiring board laminate of the present invention will be described.
[ laminate for Wiring Board ]
The laminate for wiring board of the present invention is as follows: the prepreg is obtained by applying a thermosetting resin composition containing (E) a thermosetting resin, (F) silica, and (G) at least one molybdenum compound selected from the group consisting of zinc molybdate, calcium molybdate, and magnesium molybdate, wherein the silica content of (F) is 20 to 60 vol.% to a film-like or fibrous substrate, semi-curing the composition to obtain a prepreg, and laminating and molding the prepreg.
Among them, examples of the thermosetting resin of the component (E) include epoxy resin, phenol resin, unsaturated imide resin, cyanate ester resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, and the like, and 1 kind of these resins or 2 or more kinds of them may be mixed and used.
Among them, epoxy resins are preferably used alone or in combination from the viewpoint of moldability and electrical insulation.
Examples of the epoxy resin used include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, bisphenol F novolac type epoxy resin, biphenyl type epoxy resin, xylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenol, polycyclic aromatic diglycidyl ether compounds such as anthracene, and the like, and 1 or 2 or more of these may be used by mixing.
When an epoxy resin is used as the thermosetting resin, a curing agent or a curing accelerator for the epoxy resin may be used as needed.
Examples of the curing agent include polyfunctional phenol compounds such as phenol novolac resins and cresol novolac resins, amine compounds such as dicyandiamide, diaminodiphenylmethane and diaminodiphenylsulfone, acid anhydrides such as phthalic anhydride, pyromellitic anhydride, maleic anhydride and maleic anhydride copolymers, and 1 or 2 or more of these may be used by mixing.
Examples of the curing accelerator include imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, and the like, and 1 kind or 2 or more kinds of these may be mixed and used.
Examples of the silica as the component (F) include precipitated silica which is produced by a wet process and has a high water content, and dry silica which is produced by a dry process and contains little bound water or the like. Examples of the dry-process silica include pulverized silica, fumed silica, and fused spherical silica depending on the production method. Among them, fused spherical silica is preferable from the viewpoint of low thermal expansion and high fluidity when blended in a resin.
When fused spherical silica is used as silica, the average particle diameter is preferably 0.1 μm or more and 1 μm or less. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity when blended in a resin can be favorably maintained, and by setting the average particle diameter to 1 μm or less, the wear of the drill blade at the time of drilling can be suppressed.
Here, the "average particle diameter" in the present specification means a particle diameter corresponding to a point of 50% by volume when a cumulative power distribution curve based on the particle diameter is obtained with the total volume of the particles as 100%, and can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method or the like.
The content of silica is required to be 20 vol% or more and 60 vol% or less of the total amount of the resin composition. The content of silica is set to 20 vol% or more of the total amount of the resin composition, whereby the thermal expansion of the laminate can be reduced, and the moldability and the drilling processability can be favorably maintained by setting the content to 60 vol% or less. The content of silica is preferably 30 vol% or more and 60 vol% or less, and more preferably 40 vol% or more and 56 vol% or less.
As the component (G), at least one molybdenum compound selected from zinc molybdate, calcium molybdate, and magnesium molybdate is used.
When these molybdenum compounds are used in a laminate sheet together with silica, the effect of preventing the reduction of drilling workability is greater than that of calcined talc or the like, and the electrical insulation is not significantly reduced as in molybdenum disulfide. When these molybdenum compounds are blended, these particles may be used as they are, or may be used by being supported on particles such as talc, silica, zinc oxide, calcium carbonate, and magnesium hydroxide. In this case, the average particle diameter of these particles is preferably 0.3 μm to 3 μm, more preferably 0.5 μm to 2 μm.
By setting the average particle diameter to 0.3 μm or more, the dispersibility when blended in a resin can be maintained well, and by setting the average particle diameter to 3 μm or less, rapid sedimentation when the resin composition is dissolved in an organic solvent and made into a varnish can be prevented.
The content of the molybdenum compound is preferably 0.1 vol% or more and 10 vol% or less, more preferably 0.2 vol% or more and 7 vol% or less, of the total amount of the resin composition.
By setting the content of the molybdenum compound to 0.1 vol% or more of the total amount of the resin composition, the drilling workability of the laminated plate can be favorably maintained, and by setting the content to 10 vol% or less, the reduction in the formability can be prevented.
In addition to the above, the thermosetting resin composition of the present invention may also contain any known thermoplastic resin, elastomer, inorganic filler, organic filler, flame retardant, ultraviolet absorber, antioxidant, adhesion improver, and the like.
Examples of such thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyether ether ketone resin, polyetherimide resin, silicone resin, tetrafluoroethylene resin, and the like.
Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxyl-modified acrylonitrile.
Examples of the inorganic filler include glass powders such as alumina, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, E glass, S glass, and D glass, and hollow glass beads.
Examples of the organic filler include resin particles having a uniform structure, which are made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, or the like; resin particles having a core-shell structure comprising a rubbery core layer made of an acrylate resin, a methacrylate resin, a conjugated diene resin, or the like, and glassy shell layers made of each of an acrylate resin, a methacrylate resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like.
Examples of the flame retardant include halogen-containing flame retardants containing bromine or chlorine, phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, tris (dichloropropyl) phosphate, and red phosphorus, nitrogen flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, hindered phenol-based or hindered amine-based antioxidants, and silane-based, titanate-based or aluminate-based coupling agents.
The laminate for a wiring board of the present invention can be obtained by coating a film-like or fibrous base material with the thermosetting resin composition of the present invention using the above components, and laminating and molding a product obtained by semi-curing the coated base material. When the thermosetting resin composition of the present invention is applied, the thermosetting resin composition is preferably dissolved in an organic solvent and then varnished for use. By varnish-forming the resin composition and then coating, a uniform laminated sheet with few defects such as voids can be obtained.
Examples of the organic solvent used for making the thermosetting resin composition into a varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; and sulfur atom-containing solvents such as dimethylsulfoxide, and the like, and 1 or 2 or more of these solvents may be used in combination.
Among them, methyl cellosolve, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferable from the viewpoint of solubility of the resin, and propylene glycol monomethyl ether, methyl isobutyl ketone, and cyclohexanone are more preferable from the viewpoint of low toxicity.
The proportion of the resin composition in the varnish is preferably 50 to 80 mass% of the total amount of the varnish. By setting the proportion of the resin composition in the varnish to 50 mass% or more and 80 mass% or less, the coating property to the substrate can be maintained well.
Examples of the substrate used for coating include metal foils such as copper and aluminum, organic films such as polyethylene terephthalate and polyimide, and examples of the fibrous substrate include woven fabrics, nonwoven fabrics, roving mats, chopped mats and surfacing mats of inorganic fibers such as E glass, S glass, D glass and Q glass, organic fibers such as aramid, polyester and polytetrafluoroethylene, or mixtures thereof.
Among them, woven cloth of inorganic fibers such as E glass, S glass, D glass, and Q glass, that is, glass cloth is preferably used. By using the glass cloth as the base material, both low thermal expansion and high drilling workability of the laminated plate can be achieved.
When a glass cloth is used as the substrate, a glass cloth subjected to mechanical fiber opening treatment or surface treatment with a coupling agent or the like may be used in a thickness of 0.01mm to 0.2 mm.
In order to apply a thermosetting resin composition varnish to a glass cloth and semi-cure the varnish to obtain a prepreg, for example, a method may be used in which the glass cloth is impregnated with the resin composition varnish, the amount of varnish attached is adjusted so that the ratio of the resin composition in the prepreg becomes 20 to 90 mass% using a cutting bar (cut bar), a squeeze roll (squeeze roll), or the like, and then the glass cloth is semi-cured in a drying oven at about 100 to 200 ℃ for about 1 to 30 minutes.
The prepreg thus obtained can be laminated and molded to obtain the laminate of the present invention, for example, by the following method: the prepreg is prepared by stacking 1 to 20 sheets of the prepreg so as to have a desired thickness, arranging a metal foil of copper, aluminum or the like on one surface or both surfaces, and subjecting the stack to a press treatment using a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine or the like at a temperature of: about 100-250 ℃ and pressure: and (3) a method of heating and pressing the mixture for about 0.1 to 5 hours under a pressure of about 0.2 to 10 MPa.
Next, a method for producing the resin composition varnish of the present invention will be described.
[ method for producing varnish of resin composition ]
The method for producing a varnish of a resin composition of the present invention comprises: a first dispersion mixing step of dispersing and mixing (I) a molybdenum compound in a slurry containing (H) predetermined silica particles; a second dispersion-mixing step of dispersing and mixing the slurry having undergone the first dispersion-mixing step in a varnish containing (J) a thermosetting resin, and a third dispersion-mixing step of dispersing and mixing (K) an inorganic filler in the varnish having undergone the second dispersion-mixing step.
(first Dispersion mixing step)
The silica particles in the slurry of (H) in the first dispersion mixing step need to have an average particle diameter of 0.01 to 0.1 μm and a specific surface area of 30m2270m above g2The ratio of the carbon atoms to the carbon atoms is less than g.
When the average particle diameter is 0.01 to 0.1 μm and the specific surface area is 30m2270m above g2When the molybdenum compound is dispersed and mixed, the molybdenum compound can be stably maintained in a sufficiently dispersed state without settling for a long period of time.
The "average particle diameter" referred to herein means a particle diameter corresponding to a point of 50% by volume when a cumulative power distribution curve based on the particle diameter is obtained with the total volume of the particles as 100%, and can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method or the like.
The "specific surface area" is the sum of the surface areas of all particles contained in a unit mass of the powder, and can be measured by a specific surface area measuring apparatus using a BET method or the like.
Examples of the organic solvent in the slurry include alcohols such as methanol, ethanol, propanol, and butanol; glycol ethers such as methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Among these, the same organic solvent as that used in the varnish containing the thermosetting resin (J) is preferable from the viewpoint of easily maintaining the dispersibility of the molybdenum compound in the second dispersion mixing step.
The amount of silica particles to be mixed in the slurry is preferably 10 mass% to 50 mass%, more preferably 20 mass% to 40 mass%. When the blending amount is 10 mass% or more and 50 mass% or less, the dispersibility of the silica particles in the slurry is excellent, and the dispersibility and stability of the molybdenum compound are good.
Examples of the silica slurry satisfying the above-described conditions include Admanano manufactured by Admatechs, Inc.
Examples of the molybdenum compound of (I) include molybdenum trioxide, zinc molybdate, ammonium molybdate, magnesium molybdate, calcium molybdate, barium molybdate, sodium molybdate, potassium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, silicomolybdic acid, molybdenum disulfide, molybdenum diselenide, molybdenum ditelluride, molybdenum boride, molybdenum disilicide, molybdenum nitride, and molybdenum carbide, and 1 or 2 or more of these compounds may be used in combination.
Among them, zinc molybdate, calcium molybdate, and magnesium molybdate are preferable from the viewpoint of the effect of greatly improving the drilling workability with low water solubility and toxicity, high electrical insulation properties, and the like.
The amount of the molybdenum compound added to the silica slurry is determined by a volume ratio (Mo compound/SiO) when the volume of the silica particles contained in the slurry is 12) In terms of the amount, it is preferably 0.2 to 5, more preferably 0.3 to 4. If the volume ratio is 0.2 or moreWhen the amount is 5 or less, the dispersibility and stability when the molybdenum compound is dispersed and mixed in the slurry become good.
As a method of dispersing and mixing the molybdenum compound in the silica slurry in the first dispersion mixing step, for example, a method of adding a small amount of the molybdenum compound at a time while stirring the slurry, sufficiently mixing the molybdenum compound, and then performing dispersion treatment using a media mill such as a bead mill or a ball mill, a rapid disperser such as a dissolver, a high-pressure homogenizer such as a nano homogenizer, a colloidal mill, an ultrasonic treatment machine, or the like is exemplified.
Among them, a method of treatment with a high-pressure homogenizer is preferred from the viewpoint of less contamination of impurities and efficient dispersion. Further, as the dispersant for dispersion mixing, silane-based, titanate-based, aluminate-based, and other coupling agents, polyether-modified silicone-based, polycarboxylic acid-based, urethane-based, or acrylic polymer dispersants, and the like can be added.
(second Dispersion mixing step)
Examples of the thermosetting resin (J) in the second dispersion mixing step include epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, and melamine resin, and 1 or 2 or more of these resins may be used in combination.
Among them, epoxy resins are preferable from the viewpoint of moldability and electrical insulation properties.
Examples of such epoxy resins include bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol a novolac type epoxy resins, bisphenol F novolac type epoxy resins, biphenyl type epoxy resins, xylene type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, polycyclic aromatic diglycidyl ether compounds such as polyfunctional phenols and anthracenes, and 1 or 2 or more of these may be used by mixing.
When an epoxy resin is used as the thermosetting resin, a curing agent for the epoxy resin may be used as needed.
Examples of the curing agent include polyfunctional phenol compounds such as phenol novolac resins and cresol novolac resins; amine compounds such as dicyandiamide, diaminodiphenylmethane and diaminodiphenylsulfone; anhydrides such as phthalic anhydride, pyromellitic anhydride, maleic anhydride, and maleic anhydride copolymers, and 1 or 2 or more of these may be used in combination.
Examples of the organic solvent used in the thermosetting resin-containing varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide can be used in a mixture of 1 or 2 or more.
Among them, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are preferable from the viewpoint of excellent solubility and low toxicity of the thermosetting resin.
The solid content concentration of the varnish containing the thermosetting resin is preferably 40 mass% to 90 mass%, more preferably 50 mass% to 80 mass%. By setting the solid content of the varnish to 40 mass% or more and 90 mass% or less, the dispersibility and stability of the molybdenum compound in the second dispersion mixing step can be maintained well.
The amount of the molybdenum compound dispersed in the slurry in the varnish is preferably 0.1 vol% to 10 vol% when the total resin composition is 100 vol% from which the organic solvent contained in the resin composition varnish is finally removed. By setting the amount of the molybdenum compound to 0.1 vol% or more and 10 vol% or less, the resin composition can be made to have low thermal expansion while maintaining good drilling workability.
The slurry in which the molybdenum compound is dispersed in the second dispersion mixing step is dispersed and mixed in a varnish containing a thermosetting resin. For example, a method of adding a small amount of the slurry each time while stirring the varnish and sufficiently mixing the slurry can be mentioned.
(third Dispersion mixing step)
As the inorganic filler (K) in the third dispersion mixing step, various materials can be used in addition to the silica particles of the component (H) and the molybdenum compound of the component (I) described above. Examples thereof include glass powders and hollow glass beads such as silica, alumina, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, E glass, S glass, and D glass, and 1 of these or 2 or more of them may be mixed and used.
Among them, silica is preferable from the viewpoint of low thermal expansion coefficient.
Examples of the silica include precipitated silica which is produced by a wet process and has a high water content, and dry-process dioxide which is produced by a dry process and contains almost no bound water; the dry-process silica further includes pulverized silica, fumed silica, and fused spherical silica, which are different depending on the production method. Among them, fused spherical silica is preferable from the viewpoint of excellent fluidity when filled in a resin.
When fused spherical silica is used as the inorganic filler, the average particle diameter is preferably 0.1 μm or more and 10 μm or less, more preferably 0.3 μm or more and 8 μm or less. By setting the average particle diameter of the fused spherical silica to 0.1 μm or more, the fluidity at the time of filling into the resin can be maintained well, and by setting the average particle diameter to 10 μm or less, the probability of mixing of coarse particles can be reduced, and the occurrence of defects can be suppressed.
The average particle size is larger than the silica particles of the component (H).
The amount of the inorganic filler to be incorporated in the varnish is preferably 20 vol% or more and 60 vol% or less, more preferably 30 vol% or more and 55 vol% or less, based on 100 vol% of the total resin composition excluding the organic solvent contained in the final resin composition varnish. By setting the blending amount of the inorganic filler to 20 vol% or more and 60 vol% or less, the resin composition can be made to have a low thermal expansion coefficient while maintaining good moldability.
Examples of the method of dispersing and mixing the inorganic filler in the varnish containing the molybdenum compound and the thermosetting resin in the third dispersion and mixing step include a method of directly adding and mixing the inorganic filler, and a method of dispersing the inorganic filler in an organic solvent in advance to prepare a slurry, and then adding and mixing the slurry.
Among them, from the viewpoint of dispersibility of the inorganic filler in the varnish, a method of slurrying the inorganic filler and then adding it is preferable. When the inorganic filler is slurried, the inorganic filler is preferably subjected to a pretreatment in advance with a silane-based or titanate-based coupling agent, or a surface treatment agent such as a silicone oligomer, or a whole mixing treatment.
The resin composition varnish produced through the above steps may be used by adding, in addition to the above components, a curing accelerator, a thermoplastic resin, an elastomer, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, an adhesion improver, and the like.
Examples of the curing accelerator include imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, and the like, and 1 kind or 2 or more kinds of these may be mixed and used.
Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyether ether ketone resin, polyetherimide resin, silicone resin, tetrafluoroethylene resin, and the like.
Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxyl-modified acrylonitrile.
Examples of the organic filler include resin fillers having a uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, or the like; the resin filler has a core-shell structure comprising a rubbery core layer made of an acrylate resin, a methacrylate resin, a conjugated diene resin, or the like, and a glassy shell layer made of an acrylate resin, a methacrylate resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like.
Examples of the flame retardant include halogen-containing flame retardants containing bromine or chlorine, phosphorus-containing flame retardants such as triphenyl phosphate, tricresyl phosphate, tris (dichloropropyl) phosphate, and red phosphorus; nitrogen flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide.
Other examples include benzotriazole-based ultraviolet absorbers as examples of ultraviolet absorbers, hindered phenol-based or hindered amine-based antioxidants as examples of antioxidants, and silane-based, titanate-based, aluminate-based coupling agents as examples of adhesion improvers.
It is preferable that these components be added to the resin composition varnish after the third dispersion mixing step. The solid content of the finally obtained resin composition varnish is preferably 40 to 80% by mass, more preferably 45 to 75% by mass.
When the solid content is 40 to 80% by mass, the coating property of the varnish becomes good, and a prepreg having an appropriate amount of the resin composition can be obtained.
[ prepreg and laminate ]
Next, a prepreg and a laminate using the resin composition varnish will be described.
(prepreg)
The prepreg of the present invention was obtained as follows: the resin composition varnish obtained by the above-described method for producing a resin composition varnish of the present invention is impregnated and applied to a substrate, and then semi-cured by heating or the like.
Examples of the base material used in the prepreg of the present invention include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as aramid resin, polyester resin, and tetrafluoroethylene resin, and mixtures thereof.
These base materials have shapes such as woven cloth, nonwoven fabric, roving, chopped strand mat, and surfacing mat, and the material and shape may be selected according to the intended use and performance of the laminate, and 1 or 2 or more kinds of materials and shapes may be combined as necessary. In addition, from the viewpoint of heat resistance, moisture resistance, and processability, a substrate subjected to surface treatment with a silane coupling agent or the like, or a substrate subjected to mechanical opening treatment is preferable. The thickness of the substrate may be, for example, 0.01 to 0.2 mm.
(laminated plate)
The laminate of the present invention is formed by laminating and molding the prepreg of the present invention. For example, the prepreg of the present invention is laminated by 1 to 20 sheets and has a structure in which a metal foil such as copper or aluminum is disposed on one surface or both surfaces thereof, and the metal foil-clad laminate can be produced by laminating and molding the prepreg at a temperature of about 100 to 250 ℃, a pressure of about 0.2 to 10MPa, and a heating time of about 0.1 to 5 hours, using a press, a vacuum press, a continuous molding machine, an autoclave, or the like.
The metal foil is not particularly limited as long as it is used for electronic components. Further, a multilayer board can be produced by combining the prepreg of the present invention and an inner layer wiring board and performing lamination molding.
The prepreg and the laminate of the present invention described above have low thermal expansion coefficient and high drilling workability.
Examples
The present invention will be further illustrated by the following examples, but the present invention is not limited to these examples.
Production example 1: production of Maleimide Compound (A-1)
In a reaction vessel having a capacity of 2 liters, which can be heated and cooled, and which is equipped with a thermometer, a stirring device, and a moisture meter having a reflux condenser, bis (4-maleimidophenyl) methane: 358.0g, p-aminophenol: 54.5g and propylene glycol monomethyl ether: 412.5g, and the reaction was carried out under reflux for 5 hours to obtain a solution of the maleimide compound (A-1).
Production example 2: production of Maleimide Compound (A-2)
In a heatable and coolable 2 l reaction vessel with thermometer, stirring device, water content meter with reflux condenser, bis (4-maleimidophenyl) methane: 358.0g, p-aminobenzoic acid: 68.5g and N, N-dimethylacetamide: 322.5g was reacted at 140 ℃ for 5 hours to obtain a solution of maleimide compound (A-2).
Examples 1 to 3
The unsaturated maleimide compound having an acidic substituent (a) obtained in production example 1 or 2, the thermosetting resin (B) described below, the curing accelerator, (C) the inorganic filler, and the molybdenum compound (D) were dispersed in propylene glycol monomethyl ether at the blending ratios shown in table 1 and dissolved to obtain a uniform varnish having a resin composition content of 70 mass%. The varnish of the resin composition was applied by impregnation to an E glass cloth (manufactured by Nindon textile Co., Ltd., WEA116E) having a thickness of 0.1mm, and dried at 150 ℃ for 5 minutes to obtain a prepreg containing 50% by mass of the resin composition. 4 sheets of the prepreg were stacked, 18 μm electrolytic copper foil was placed on the upper and lower sides, and vacuum pressing was performed at 185 ℃ and 3.5MPa for 90 minutes to obtain a copper-clad laminate.
The obtained copper-clad laminate was measured and evaluated for drilling workability, thermal expansion coefficient, and heat resistance by the methods shown below, and the results are shown in table 1.
(B) Thermosetting resin
B-1: biphenylalkyl epoxy resin [ Nippon Kabushiki Kaisha, NC-3000 ]
B-2: phenol novolak type epoxy resin [ EPICLON-770, available from DIC corporation ]
B-3: cresol novolak type phenol resin [ PHENOLITEKA-1165, available from DIC corporation ]
Curing accelerator: 2-Ethyl-4-methylimidazole [ 2E4MI, a product of Siguo Kagaku K.K. ]
(C) Inorganic filler
C-1: molten spherical silica slurry (available from Admatechs corporation, SC2050-KC, average particle diameter 0.5 μm, solid content 70% by mass)
C-2: aluminum hydroxide (manufactured by Sumitomo chemical Co., Ltd., CL-310)
C-3: calcined Talc [ Fuji Talc, ST-100 ]
(D) Molybdenum compound
D-1: zinc molybdate (Strem Chemicals reagent)
D-2: talc with zinc molybdate (Sherwin Williams Co., Ltd., Chemguard911C, Zinc molybdate 20% by mass)
D-3: calcium molybdate (Strem Chemicals reagent)
Comparative example 1
A copper-clad laminate using the resin composition was obtained in the same manner as in example 1, except that the molybdenum compound (D) was not blended. The measurement and evaluation results are shown in table 1.
Comparative example 2
A copper-clad laminate using a resin composition was obtained in the same manner as in example 1, except that the unsaturated maleimide compound (a) having an acidic substituent was not blended. The measurement and evaluation results are shown in table 1.
Comparative example 3
A copper-clad laminate using a resin composition was obtained in the same manner as in example 1, except that the inorganic filler (C) was not blended. The measurement and evaluation results are shown in table 1.
< evaluation of drilling processability, thermal expansion Rate and Heat resistance of copper-clad laminate >
(1) Evaluation of drilling workability
An aluminum foil having a thickness of 0.1mm was disposed on the upper side of a product obtained by stacking 2 copper-clad laminates, and a paper phenol plate having a thickness of 1.5m was disposed on the lower side thereof, and a drill having a diameter of 0.2mm was used to open 6000 holes using a drill puncher (Hitachi Via Mechanics, Ltd., ND-1V212) under conditions of a rotational speed of 160krpm, a transport speed of 2m/min, and a chip load (chip load) of 12.5 μm/rev, and the amount of blade wear and hole position accuracy of the drill were measured by the following methods, thereby evaluating the drilling workability.
A) Amount of wear of drill bit blade
The drill blade portions before and after the hole was drilled were observed from the center axis of the hole using an inspection microscope (MX 50, olympus corporation), and the wear retraction amount of the blade tip was measured as the drill blade wear amount.
B) Hole location accuracy
In the copper-clad laminate having 2 sheets stacked, the amount of offset position of the hole on the lower side (the side of the drilled hole outlet) of the 2 nd sheet was measured by using a hole position accuracy measuring machine [ Hitachi ViaMechanics, Ltd., HT-1Am ], and the average of the amounts of offset position of the holes at 4001 to 6000 th was calculated as +3 σ (σ: standard deviation) as the hole position accuracy.
(2) Measurement of thermal expansion Rate
After removing the copper foil of the copper-clad laminate with an etching solution, the laminate was cut into a size of 5mm square to prepare a test piece. The thermal expansion coefficient of the test piece in the longitudinal direction (the longitudinal direction of the glass cloth) at 50 to 20 ℃ was measured at a temperature rise rate of 10 ℃/min using a TMA test apparatus (TMA 2940, manufactured by TA INSTRUMENTS Co., Ltd.).
(3) Evaluation of Heat resistance (glass transition temperature)
After removing the copper foil of the copper-clad laminate with an etching solution, the laminate was cut into a size of 5mm square to prepare a test piece. The temperature-dimensional change curve in the thickness direction of the test piece was measured at a temperature increase rate of 10 ℃/min using a TMA test apparatus [ TMA2940 manufactured by dupont corporation ], and the temperature of the intersection of the low-temperature side approximate line and the high-temperature side approximate line of the temperature-dimensional change curve was determined as the glass transition temperature, and used as the evaluation of heat resistance.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Use amount (parts by mass) | ||||||
| A: unsaturated maleimide compound having acidic substituent | ||||||
| A-1 (production example 1) | 65 | 65 | 65 | 65 | ||
| A-2 (preparation example 2) | 50 | |||||
| B: thermosetting resin | ||||||
| B-1 (Biphenylalkyl type epoxy resin) | 35 | 35 | 35 | 35 | ||
| B-2 (phenol/novolac type epoxy resin) | 50 | 61 | ||||
| B-3 (cresol/novolac type epoxy resin) | 39 | |||||
| Curing accelerator: 2-ethyl-4-methylimidazole | 0.5 | 0.25 | 0.5 | 0.5 | 0.15 | 0.5 |
| C: inorganic filler | ||||||
| C-1 (fused spherical silica slurry: SC 2050-K)C) | 199 | 124 | 81 | 199 | 124 | |
| C-2 (aluminium hydroxide: CL-310) | 34 | 34 | ||||
| C-3 (calcined talc: ST-100) | 48 | 54 | ||||
| D: molybdenum compound | ||||||
| D-1 (Zinc molybdate) | 86 | 154 | ||||
| D-2 (Zinc molybdate with talc 10% loading) | 6.0 | 6.0 | ||||
| D-3 (calcium molybdate) | 5.6 | |||||
| Composition (volume%) | ||||||
| A + B: unsaturated maleimide compound + thermosetting resin | 50 | 60 | 79 | 50 | 60 | 70 |
| C: inorganic filler | 38 | 38.5 | 20 | 38 | 38.5 | |
| D: molybdenum compound | 12 | 1.5 | 1.0 | 12 | 1.5 | 30 |
| Measurement and evaluation | ||||||
| (1) Workability in drilling | ||||||
| Abrasion loss of drill blade (mum) | 11 | 9 | 7 | 31 | 8 | 5 |
| Hole position accuracy (mum) | 31 | 30 | 28 | 48 | 29 | 25 |
| (2) Thermal expansion coefficient (10)-6/℃) | 10.8 | 11.4 | 11.7 | 10.7 | 14.1 | 14.5 |
| (3) Heat resistance (glass transition temperature:. degree. C.) | 210 | 220 | 215 | 212 | 175 | 199 |
The amount (parts by mass) used in table 1 is the amount of each component shown in parts by mass when the total amount of (a) the unsaturated maleimide compound having an acidic substituent and (B) the thermosetting resin is 100 parts by mass for the resin compositions of examples and comparative examples. However, in comparative example 2, since the maleimide compound (a) was not blended, the total blending amount of the thermosetting resin (B) and the cresol novolak type phenol resin was shown as 100 parts by mass.
As is clear from table 1, the examples of the present invention have a low soaking expansion ratio and excellent drilling workability and heat resistance.
On the other hand, comparative example 1 has a low thermal expansion coefficient and excellent heat resistance, but does not contain the molybdenum compound (D) of the present invention, and therefore, the drilling workability is significantly deteriorated.
In comparative examples 2 and 3, although the drilling processability was excellent, since the unsaturated maleimide compound (a) having an acidic substituent or the inorganic filler (C) of the present invention was not contained, the thermal expansion coefficient was high and the heat resistance was poor.
Examples 4, 6 and 7, and comparative example 4
In the formulations shown in tables 2 and 3, the thermosetting resin (E) and the curing agent (E) were completely dissolved in the organic solvent, and then the silica slurry (F) was added thereto and stirred until both were sufficiently mixed. Then, the molybdenum compound (G) was added in small amounts each time, the stirring was continued until the agglomerates disappeared, and finally the curing accelerator was added, and the stirring was continued for 1 hour to make the varnish entirely uniform.
The thus obtained thermosetting resin composition varnish was applied to E glass cloth (manufactured by Nindon textile Co., Ltd., WEA116E) having a thickness of 0.1mm by impregnation and then dried at 160 ℃ for 5 minutes to be semi-cured, thereby obtaining a prepreg having a resin composition ratio of 48 mass%.
A predetermined number of the prepregs were stacked to obtain a desired thickness, and electrolytic copper foils having a thickness of 12 μm (manufactured by Kogawa electric industries Co., Ltd., GTS-12) were disposed on both surfaces, and the resultant was pressed by vacuum at a temperature of: 185 ℃ and pressure: and then, the copper clad laminate was heated and pressed at 4MPa for 90 minutes to obtain a copper clad laminate.
Example 5 and comparative example 5
A copper-clad laminate was obtained in the same manner as in "examples 4, 6, and 7 and comparative example 4" except that, when a thermosetting resin composition varnish was mixed, the silica slurry (F) was added, and then the inorganic filler (aluminum hydroxide) was added before the molybdenum compound (G) was added, followed by sufficiently stirring and mixing.
Comparative examples 6 and 7
In the case of blending a thermosetting resin composition varnish, (F) a silica slurry was added, then an inorganic filler (calcined talc or molybdenum disulfide) was added, and the mixture was stirred until the aggregate disappeared, and finally a curing accelerator was added, and the mixture was stirred for 1 hour to make the varnish uniform, and a copper-clad laminate was obtained in the same manner as in "examples 4, 6, 7 and comparative example 4".
TABLE 2
TABLE 3
Here, the blending amounts of the respective components in tables 2 and 3 are shown in parts by mass with the total blending amount of the thermosetting resin of (E) being 100. However, regarding the silica of (F) and the molybdenum compound of (G), the values of volume% with respect to the total amount of the resin composition are also shown in parentheses. The following substances were used for each of the components in tables 2 and 3.
(E) Thermosetting resin
E-1: phenol novolak type epoxy resin [ EPICLON-770, available from DIC corporation ]
E-2: bisphenol A novolak type epoxy resin [ EPICLON-865, available from DIC corporation ]
E-3: biphenylalkyl epoxy resin [ Nippon Kabushiki Kaisha, NC-3000 ]
Curing agent: cresol novolak type phenol resin [ PHENOLITEKA-1165, available from DIC corporation ]
Curing accelerator: 2-Ethyl-4-methylimidazole [ キュアゾール 2E4MZ, a product of Siguo Kagaku K.K. ]
(F) Silicon dioxide
F-1: molten spherical silica slurry [ SC2050-KC, manufactured by Admatechs, having an average particle diameter of 0.5 μm and a solid content of 70% by mass ]
F-2: slurry of fused spherical silica [ SC4050-KNA, manufactured by Admatechs, Ltd., average particle diameter 1.0 μm, solid content 70% by mass ]
(G) Molybdenum compound
G-1: zinc molybdate [ Strem Chemicals reagent, average particle size 2 μm ]
G-2: zinc molybdate-supported talc [ Sherwin Williams, Chemguard911C, average particle diameter 3 μm ]
G-3: calcium molybdate [ Strem Chemicals reagent, average particle size 2 μm ]
G-4: magnesium molybdate [ Sanjin and chemical reagent, average particle size 3 μm ]
Inorganic filler 1: calcined Talc (BST, product of Japan Talc Co., Ltd.)
Inorganic filler 2: molybdenum disulfide (DAIZO NICHIMOLY, A powder)
Inorganic filler 3: aluminum hydroxide (manufactured by Sumitomo chemical industry Co., Ltd., C-303)
Organic solvent: cyclohexanone (manufactured by GODO K.K.)
The characteristics of the copper-clad laminates obtained in the above examples and comparative examples were measured and evaluated by the following methods. The measurement and evaluation results are shown in tables 4 and 5.
(1) Evaluation of drilling workability
A paper phenol board having a thickness of 0.4mm was placed on the upper side and a paper phenol board having a thickness of 1.5mm was placed on the lower side of a product obtained by stacking 2 copper-clad laminates having a thickness of 0.4mm, 6000 holes were drilled by a drill having a diameter of 0.2mm using a drill puncher [ Hitachi Via Mechanics, Ltd., ND-1V212 ] under conditions of a rotational speed of 160Krpm, a conveying speed of 1.8m/min and a cutting resistance of 11.25 μm/rev, and the amount of blade wear and hole position accuracy of the drill were measured by the following methods to evaluate the drilling workability.
a) Amount of wear of drill bit blade
The new product (before drilling) and the drill blade portion after drilling were observed from the center axis of the drilled hole using a scanning electron microscope (S-4700, manufactured by Hitachi, Ltd.), and the wear retraction amount of the blade tip was measured as the drill blade wear amount.
b) Hole location accuracy
In the copper-clad laminate having 2 sheets stacked, the amount of hole misalignment on the lower side (the side of the drilled hole outlet) of the 2 nd sheet was measured using a hole position accuracy measuring machine [ Hitachi ViaMechanics, Ltd., HT-1AM ], and the average of the amounts of hole misalignment hitting 4001 to 6000 (σ: standard deviation) was calculated as the hole position accuracy. If the hole position accuracy is 35 μm or less, there is no practical problem, and good results are obtained.
(2) Measurement of thermal expansion Rate
The copper foil of the copper-clad laminate having a thickness of 0.8mm was removed by an etching solution, and the laminate was cut into a size of 5mm square to prepare a test piece. The average linear thermal expansion coefficient in the longitudinal direction (the longitudinal direction of the glass cloth) of the test piece at 50 to 120 ℃ was measured at a temperature rise rate of 10 ℃/min using a TMA test apparatus (TA INSTRUMENTENTS Co., Ltd., TMA 2940). The closer the thermal expansion coefficient is to that of the silicon chip (4-5 × 10)-6/. degree. C.), the better the results.
(3) Measurement of electrical insulation
A round portion having a diameter of 20mm remaining on the copper foil on one surface of a copper-clad laminate having a thickness of 0.1mm was removed by an etching solution, and the laminate was cut into a size of 50mm square with the round portion at the center to prepare a test piece. The test piece was immersed in fluorinert (manufactured by Sumitomo 3M Co., Ltd.), and an insulation breakdown test was carried out using a voltage withstand meter (manufactured by Toyo electric wave industries Co., Ltd., PT-1011) at a voltage increase rate of 5kV/10 sec, and the insulation breakdown voltage was measured. If the dielectric breakdown voltage is 6kV or more, no problem arises in use, and good results are obtained.
(4) Evaluation of moldability
A copper-clad laminate having a thickness of 0.4mm was cut into a size of 5mm square, a mold was made with a mold resin, and the cut surface was polished to prepare a test piece for cross-section observation. The polished cross section of the test piece was polished with a Flatmilling apparatus (E-3200, manufactured by Hitachi, Ltd.), and then observed with a scanning electron microscope (S-4700, manufactured by Hitachi, Ltd.), to observe the presence or absence of voids and evaluate moldability.
TABLE 4
TABLE 5
As is clear from table 4, the examples of the present invention are all excellent in drilling workability and low thermal expansion property, and have no problem in electrical insulation property and moldability.
On the other hand, as is clear from table 5, in comparative example 4, since the content of silica exceeds 60 vol% of the total amount of the resin composition, moldability is remarkably deteriorated, and drilling processability and electrical insulation are also deteriorated. In comparative example 5, since the content of silica is less than 20% by volume of the total amount of the resin composition, there is a problem that the thermal expansion coefficient is large. In comparative example 6, since the molybdenum compound of the present invention was not contained, the drilling workability was significantly deteriorated. Similarly, in comparative example 7, since molybdenum disulfide was contained instead of the molybdenum compound of the present invention, the electrical insulation was significantly deteriorated.
Examples 8 and 9, and comparative examples 8 and 9
In the compounding of the resin composition varnish shown in Table 6, first, the molybdenum compound of (I) was added to the silica slurry of (H) in small amounts at a time with stirring, and mixed so that no agglomeration could occur. The silica slurry containing the molybdenum compound was treated 3 times with a nano homogenizer (NM 2000-AR, manufactured by Jitian Kogyo Co., Ltd.) under an air pressure of 0.5MPa to sufficiently disperse and mix the molybdenum compound and the silica particles.
Next, the molybdenum compound-dispersed silica slurry was added to the resin varnish prepared by dissolving the thermosetting resin and the curing agent of (J) in an organic solvent in small amounts each time with stirring, and after the completion of the addition of all the components, the mixture was stirred for 1 hour until all the components were uniform.
Then, the inorganic filler slurry (K) was added to the resin varnish while stirring, and the curing accelerator was further added thereto, and the mixture was stirred for 1 hour until the whole mixture became uniform, thereby preparing a resin composition varnish.
The solid content concentration of the varnish of the resin compositions of examples 8 and 9 and comparative examples 8 and 9 was 70% by mass.
Comparative example 10
In the compounding of the resin composition varnishes shown in table 6, the molybdenum compound of (I) was added to the resin varnish prepared by dissolving the thermosetting resin of (J) and the curing agent in an organic solvent in small amounts at a time while stirring, and after the completion of the addition of all the molybdenum compound, the mixture was stirred for 1 hour until all the molybdenum compound was homogeneous.
Then, the inorganic filler slurry (K) was added to the resin varnish while stirring, and the curing accelerator was further added thereto, and the mixture was stirred for 1 hour until the whole mixture became uniform, thereby preparing a resin composition varnish.
The resin composition varnish of comparative example 10 had a solid content concentration of 70 mass%.
Comparative example 11
In the compounding of the resin composition varnish shown in Table 6, first, the molybdenum compound of (I) was added to the silica slurry of (H) in small amounts at a time with stirring and mixed so that agglomeration could not occur. The silica slurry containing the molybdenum compound was treated 3 times with a nano homogenizer (NM 2000-AR, manufactured by Jitian Kogyo Co., Ltd.) under an air pressure of 0.5MPa to sufficiently disperse and mix the molybdenum compound and the silica particles.
Then, the molybdenum compound-dispersed silica slurry was added to the inorganic filler slurry of (K) in small amounts each time with stirring, and after the completion of the addition of all the materials, the mixture was stirred for 1 hour until the mixture was completely uniform.
Then, the slurry was added to a resin varnish prepared by dissolving the thermosetting resin and the curing agent of (J) in an organic solvent with stirring, and a curing accelerator was further added thereto, and the mixture was stirred for 1 hour until the whole mixture became uniform, thereby preparing a resin composition varnish.
The resin composition varnish of comparative example 11 had a solid content concentration of 70 mass%.
The resin composition varnishes prepared in the examples and comparative examples were each impregnated with E glass cloth (WEA 116E, manufactured by Nindon textile Co., Ltd.) having a coating thickness of 0.1mm, and dried by heating at 160 ℃ for 5 minutes to obtain a prepreg having a resin composition content of 48 mass%. Each of 4 sheets of the prepregs was stacked, and 12 μm electrolytic copper foils were placed on the upper and lower sides, and vacuum-pressed at 185 ℃ and 3.8MPa for 90 minutes to obtain a copper-clad laminate.
The resin composition varnish and the copper-clad laminate obtained in this way were used, and the settleability of the resin composition varnish, the presence or absence of aggregates in the varnish, and the drilling processability and thermal expansion coefficient of the copper-clad laminate were measured and evaluated by the following methods, and the evaluation results are shown in table 7.
(1) Evaluation of Settlability of varnish of resin composition
Collecting 500cm of varnish of the resin composition in a settling tank made of glass having a diameter of 5cm and a length of 35cm3The mixture was allowed to stand at room temperature of 25 ℃ and the time until the precipitate stayed at the bottom of the settling tube was measured to evaluate the settling property.
(2) Evaluation of the Presence of agglomerates in the varnish of the resin composition
The varnish of the resin composition was collected in a flask to 100cm3400cm of the same organic solvent as used in the varnish was added thereto3And fully oscillating. The diluted varnish was filtered through a nylon mesh having a mesh opening of 20 μm, and the presence of residue on the mesh was visually checked to evaluate the presence of aggregates.
(3) Evaluation of drilling processability of copper-clad laminate
An aluminum sheet having a thickness of 0.15mm was placed on the upper side of a product obtained by stacking 2 copper-clad laminated sheetsFoil, paper phenolic plate with thickness of 1.5mm arranged at lower side, and use thereofThe drill (2) was drilled into 6000 holes using a drill drilling machine (ND-1V 212, manufactured by Hitachi Via Mechanics, Ltd.) at a rotation speed of 160krpm, a conveying speed of 2m/min and a cutting resistance of 12.5 μm/rev, and the amount of wear of the drill and the hole position accuracy were measured by the following methods to evaluate the drilling workability.
a) Amount of wear of drill bit blade
The drill blade portions before and after drilling were observed from the center axis of the drilled hole using a scanning electron microscope (S-4700, manufactured by Hitachi, Ltd.), and the wear retraction amount of the blade tip was measured as the drill blade wear amount.
b) Hole location accuracy
In the copper-clad laminated plates having 2 laminated sheets, the amount of the deviated position of the hole on the lower side (the drilled hole outlet side) of the 2 nd sheet was measured by using a hole position accuracy measuring machine (Hitachi via mechanics, ltd. product, HT-1Am), and the average of the amounts of the deviated position of the holes at 4001 to 6000 th was calculated as +3 σ (σ: standard deviation) as the hole position accuracy.
(4) Measurement of thermal expansion Rate of copper-clad laminate
After removing the copper foil of the copper-clad laminate with an etching solution, the laminate was cut into a size of 5mm square to prepare a test piece. The thermal expansion coefficient of the test piece in the longitudinal direction (the longitudinal direction of the glass cloth) at 50 to 120 ℃ was measured at a temperature rise rate of 10 ℃/min using a TMA test apparatus (TMA 2940, manufactured by TAINSTRUMENTS Co., Ltd.).
TABLE 6
Unit is mass portion (wherein, the bracket is volume%)
In table 6, the resin composition varnishes produced by the production methods of examples and comparative examples are shown in parts by mass with the amount of the thermosetting resin (J) added being 100 parts by mass. However, the slurry in which the silica particles of (H) are dispersed in an organic solvent and the inorganic filler of (K) show the blending amounts of the organic solvents contained in them as well as being combined. Among them, (K) is also indicated in parentheses when the volume% of the inorganic filler is assumed to be 100 volume% with respect to the entire resin composition from which the organic solvent contained in the varnish of the resin composition is removed. In the case of using particles in which the molybdenum compound is supported on another substance, the molybdenum compound of (I) is not the amount of the molybdenum compound alone but the amount of the molybdenum compound supported on the particles.
The following materials were used for each component in table 6.
(H) Silica slurry H-1: the average particle diameter was adjusted to 0.05. mu.m, and the specific surface area was adjusted to 55m2(g) a slurry containing 30 mass% silica dispersed in propylene glycol monomethyl ether (manufactured by Admatech, Inc.; Admanano)
(H) Silica slurry H-2: the average particle diameter was adjusted to 0.025 μm and the specific surface area was adjusted to 110m2(g) a slurry containing 20 mass% silica dispersed in propylene glycol monomethyl ether (manufactured by Admatech, Admanano)
(H) Silica slurry H-3: average particle diameter of 0.5 μm and specific surface area of 7m2(ii) silica (SO-25R, manufactured by Admatechs corporation) was dispersed in propylene glycol monomethyl ether in a slurry in which the silica content was 50 mass%
(H) Silica slurry H-4: the average particle diameter was 0.05. mu.m, and the specific surface area was 380m2(380, available from Nippon Aerosil corporation) in a silica content of 10% by mass, in propylene glycol monomethyl ether
(I) Molybdenum Compound I-1: zinc molybdate (Strem Chemicals reagent)
(I) Molybdenum compound I-2: calcium molybdate (Strem Chemicals reagent)
(I) Molybdenum Compound I-3: talc supporting zinc molybdate, zinc molybdate content 10 mass% (Chemguard 911C manufactured by SherwinWilliams Co., Ltd.)
(J) Thermosetting resin: phenol novolac type epoxy resin (EPICLON-770, available from DIC corporation)
Curing agent: cresol novolak type phenol resin (PhenoliteKA-1165, product of DIC corporation)
Curing accelerator: 2-Ethyl-4-methylimidazole (2E 4MI, product of Siguo Kagaku Co., Ltd.)
Organic solvent: propylene glycol monomethyl ether (GODO product of Kabushiki Kaisha)
(K) Inorganic filler material: fused spherical silica slurry, average particle diameter 0.5 μm, specific surface area 7m2(ii)/g, silica mixing amount 70 mass% (SC 2050-KC manufactured by Admatechs Co., Ltd.)
TABLE 7
As is clear from table 7, the examples of the present invention are excellent in all of the settleability of the resin composition varnish, the presence or absence of aggregates, and the drilling processability and thermal expansion rate of the copper-clad laminate.
On the other hand, in comparative example 8, since the average particle diameter of the silica particles in the slurry of (H) was large and the specific surface area was small, the settleability of the resin composition varnish was significantly deteriorated.
In comparative example 9, since the specific surface area of the silica particles in the slurry of (H) was large, aggregates remained in the resin composition varnish, and the accuracy of the pore position was slightly deteriorated. In comparative example 10, since the talc supporting the molybdenum compound was directly added to the resin varnish, the settleability of the resin composition varnish was deteriorated and aggregates remained. Further, the hole position accuracy is also slightly deteriorated. In comparative example 11, since the slurry of silica dispersed in a molybdenum compound was added to the inorganic filler slurry and then added to the resin varnish, aggregates remained in the resin composition varnish.
If a printed wiring board is produced in a state where aggregates remain in the varnish of the resin composition, abnormal precipitation or the like is likely to occur due to molybdenum plating during the production of the printed wiring board, and the reliability of the printed wiring board as an electronic device may be impaired, which is not preferable.
According to the present invention, a resin composition varnish in which the molybdenum compound is less likely to precipitate or aggregate can be produced, and by using the varnish, a prepreg or a laminate suitable for a semiconductor package or a printed wiring board can be obtained which has a low thermal expansion coefficient and high drilling processability.
Industrial applicability
The thermosetting resin composition of the present invention is particularly preferably used for electronic components and the like having low thermal expansibility and excellent drilling processability and heat resistance. In addition, the laminated plate for a wiring board of the present invention is excellent in drilling workability in the production of a wiring board, and can provide a laminated plate for a wiring board having excellent electrical insulation properties and low thermal expansion. Further, the varnish obtained by the method for producing a resin composition varnish of the present invention can provide a prepreg and a laminated plate having high drilling processability.
Claims (9)
1. A thermosetting resin composition characterized by containing:
(A) a maleimide compound comprising an unsaturated maleimide compound having an acidic substituent represented by the following general formula (I) or (II), (B) a thermosetting resin, (C) an inorganic filler and (D) a molybdenum compound,
(D) the molybdenum compound is at least one selected from molybdenum oxide and molybdic acid compound, and the content of the molybdenum compound is 0.1-15 vol% of the total resin composition
In the formula, R1Represents a hydroxyl group, a carboxyl group or a sulfonic acid group as an acidic substituent, R2、R3、R4And R5Independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group or a group represented by the following formula (III), X is an integer of 1 to 5, Y is an integer of 0 to 4, and the sum of X and Y is 5,
2. the thermosetting resin composition according to claim 1, wherein,
(B) the thermosetting resin is an epoxy resin, and the total content of the component (A) and the component (B) is 30 to 80 vol% of the total amount of the resin composition, and the mass ratio of the component (A) to the component (B) is 20 to 90 parts by mass when the total content of the component (A) and the component (B) is 100 parts by mass.
3. The thermosetting resin composition according to claim 1 or 2,
(C) the inorganic filler is fused spherical silica, and the content of the inorganic filler is 10 to 60 vol% of the total resin composition.
4. A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition according to any one of claims 1 to 3 and then B-staging the impregnated or coated base material.
5. A laminate obtained by laminating the prepregs according to claim 4.
6. The laminate according to claim 5, which is a metal-clad laminate obtained by laminating a metal foil on at least one surface of a prepreg and then performing hot press molding.
7. A prepreg comprising a substrate impregnated with or coated with the thermosetting resin composition according to claim 1 and a B-staged resin composition prepared by the method.
8. Use of a prepreg according to claim 4 in the manufacture of a laminate, wherein the prepreg according to claim 4 is formed by lamination.
9. Use of the prepreg according to claim 4 for producing a metal-clad laminate, wherein the prepreg is formed by applying a metal foil to at least one surface of the prepreg according to claim 4 and then heating and pressing the metal foil.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-296058 | 2009-12-25 | ||
| JP2009296058A JP5682110B2 (en) | 2009-12-25 | 2009-12-25 | Thermosetting resin composition, prepreg and laminate using the same |
| JP2010160979A JP5556466B2 (en) | 2010-07-15 | 2010-07-15 | Laminate board for wiring boards |
| JP2010-160979 | 2010-07-15 | ||
| JP2010-165556 | 2010-07-23 | ||
| JP2010165556A JP5593915B2 (en) | 2010-07-23 | 2010-07-23 | Method for producing resin composition varnish, prepreg, laminate |
| PCT/JP2010/073376 WO2011078339A1 (en) | 2009-12-25 | 2010-12-24 | Thermosetting resin composition, method for producing resin composition varnish, prepreg and laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1171777A1 HK1171777A1 (en) | 2013-04-05 |
| HK1171777B true HK1171777B (en) | 2015-11-13 |
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