JP2012025845A - Method for manufacturing resin composition varnish, prepreg and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a resin composition varnish which is hard to cause settling and aggregation of a molybdenum compound, a prepreg having a low coefficient of thermal expansion and high drilling processability, and a laminate.SOLUTION: The method for manufacturing a resin composition varnish comprises a first dispersing and mixing step of dispersing and mixing a molybdenum compound (B) into a slurry (A) including silica particles having an average particle diameter of ≥0.01-≤0.1 μm and a specific surface area of ≥30-≤270 m/g, a second dispersing and mixing step of dispersing and mixing the slurry through the first dispersing and mixing step into a varnish including a thermosetting resin (C), and a third dispersing and mixing step of dispersing and mixing an inorganic filler (D) into the varnish through the second dispersing and mixing step and the prepreg and the laminate are obtained by using the manufacturing method.

Description

  TECHNICAL FIELD The present invention relates to a method for producing a resin composition varnish, and a prepreg and a laminate that are produced using the production method and are suitable for semiconductor packages and printed wiring boards.

  In recent years, demands for thinner and lighter electronic devices are increasing, and semiconductor packages and printed wiring boards are becoming thinner and higher in density. In order to carry out stable mounting corresponding to these, it is necessary to suppress warpage generated in a semiconductor package or a printed wiring board. One of the main causes of warpage occurring in a semiconductor package during mounting is a difference in thermal expansion coefficient between the laminated plate used in the semiconductor package and the silicon chip. For this reason, efforts are being made to bring the coefficient of thermal expansion close to that of a silicon chip, that is, to lower the coefficient of thermal expansion, in a laminated sheet for semiconductor packages.

Various methods for reducing the coefficient of thermal expansion of the laminate are conceivable. Among them, a method of increasing the filling rate of the inorganic filler in the resin composition used for producing the laminate is effective.
However, when a laminated board is produced by increasing the filling of the inorganic filler, there is a problem that the drillability of the laminated board deteriorates.

In order to solve this problem, the present inventors searched for an additive that can suppress the deterioration of drill workability even when the inorganic filler is highly filled, and found that the molybdenum compound has an excellent effect. It was.
However, since the specific gravity of the molybdenum compound is large, when it is directly added to the resin composition varnish used for the production of the laminated plate, it tends to settle, causing a manufacturing defect. Therefore, it is recommended to use particles (for example, Chemguard 911C, manufactured by Sherwin Williams Co., Ltd.) in which a molybdenum compound is supported on talc or the like (see, for example, Patent Document 1). There are disadvantages such as thickening and the tendency of the aggregation of molybdenum compound-carrying particles to occur, and satisfactory results have not been obtained.

JP 2000-264986 A

  The present invention has been made in view of such circumstances, and provides a method for producing a resin composition varnish that is unlikely to cause precipitation and aggregation of a molybdenum compound, and a prepreg and a laminate having a low thermal expansion coefficient and high drillability. is there.

  As a result of continual research, the inventors of the present invention have dispersed a molybdenum compound in a slurry in which specific silica particles are dispersed, and then added the slurry to a varnish containing a thermosetting resin, and then inorganic filling. It has been found that the above problems can be solved by producing a resin composition varnish by a method of blending materials, and the present invention has been completed. That is, the present invention is as follows.

[1] (A) A molybdenum compound is dispersed in a slurry containing silica particles having an average particle size of 0.01 μm or more and 0.1 μm or less and a specific surface area of 30 m ² / g or more and 270 m ² / g or less. A first dispersion mixing step of mixing;
(C) a second dispersion and mixing step in which the slurry that has undergone the first dispersion and mixing step is dispersed and mixed in a varnish containing a thermosetting resin;
(D) The 3rd dispersion | distribution mixing process which disperse-mixes the inorganic filler except the said silica particle and a molybdenum compound in the varnish which passed through the 2nd dispersion | distribution mixing process, The manufacturing method of the resin composition varnish.
[2] The method for producing a resin composition varnish according to [1], including a curing accelerator addition step of adding a curing accelerator to the varnish after the third dispersion mixing step.
[3] The resin composition according to [1] or [2], wherein the (B) molybdenum compound is one or a mixture of two or more selected from the group consisting of zinc molybdate, calcium molybdate, and magnesium molybdate. A method for manufacturing a varnish.

[4] (A) Disperse (B) a molybdenum compound in a slurry containing silica particles having an average particle diameter of 0.01 μm or more and 0.1 μm or less and a specific surface area of 30 m ² / g or more and 270 m ² / g or less. (C) 2nd dispersion | distribution mixing process which disperse-mixes the slurry which passed through the 1st dispersion | distribution mixing process and 1st dispersion | distribution mixing process in the varnish containing a thermosetting resin, and 2nd dispersion | distribution mixing process A prepreg obtained by impregnating a base material with a resin composition varnish obtained through (D) a third dispersion mixing step in which an inorganic filler is dispersed and mixed in the varnish subjected to the above.
[5] A laminate obtained by laminating the prepreg according to [4] above.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the resin composition varnish which does not raise | generate precipitation and aggregation of a molybdenum compound, and a prepreg and a laminated board with a low thermal expansion coefficient and high drill workability can be provided.

  Hereafter, the manufacturing method of the resin composition varnish of this invention, a prepreg, and a laminated board are demonstrated in detail.

[Method for Producing Resin Composition Varnish]
In the method for producing the resin composition varnish of the present invention, (A) the first dispersion mixing step of dispersing and mixing (B) the molybdenum compound in the slurry containing the predetermined silica particles, and the first dispersion mixing step. The slurry is dispersed and mixed in a varnish containing (C) a thermosetting resin, and (D) an inorganic filler is dispersed and mixed in the varnish that has undergone the second dispersion and mixing step. And a dispersion mixing step.

(First dispersion mixing step)
The silica particles in the slurry (A) in the first dispersion mixing step need to have an average particle size of 0.01 μm to 0.1 μm and a specific surface area of 30 m ² / g to 270 m ² / g.
When the average particle diameter is 0.01 μm or more and 0.1 μm or less and the specific surface area is 30 m ² / g or more and 270 m ² / g or less, the molybdenum compound is stable so as not to settle for a long time in a finely dispersed state when dispersed and mixed. Can be kept in.

As used herein, “average particle size” refers to the particle size at a point corresponding to a volume of just 50% when a cumulative frequency distribution curve based on particle size is obtained with the total volume of particles being 100%. It can be measured with a particle size distribution measuring device using a laser diffraction scattering method.
The “specific surface area” is the total surface area of all particles contained in a unit weight of powder, and can be measured with a specific surface area measuring device using the BET method.

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, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Is mentioned.
Among these, it is preferable that the organic solvent used in the varnish containing the thermosetting resin (C) is the same as the molybdenum compound in the second dispersion mixing step because it is easy to maintain the dispersibility of the molybdenum compound.

  As a compounding quantity of the silica particle in a slurry, it is preferable that it is 10 to 50 mass%, and it is more preferable that it is 20 to 40 mass%. When the blending amount is 10% by mass or more and 50% by mass or less, the dispersibility of the silica particles in the slurry is excellent, and the dispersibility and stability of the molybdenum compound are improved.

  As a silica slurry satisfying the above conditions, for example, Adma Nano manufactured by Admatechs Co., Ltd. can be mentioned.

Examples of the molybdenum compound (B) include molybdenum trioxide, zinc molybdate, ammonium molybdate, magnesium molybdate, calcium molybdate, barium molybdate, sodium molybdate, potassium molybdate, phosphomolybdic acid, and phosphomolybdic acid. Ammonium, sodium phosphomolybdate, silicomolybdic acid, molybdenum disulfide, molybdenum diselenide, molybdenum ditelluride, molybdenum boride, molybdenum disilicide, molybdenum nitride, molybdenum carbide, etc., and one or two of these A mixture of seeds or more can be used.
Among these, zinc molybdate, calcium molybdate, and magnesium molybdate are preferable because they have low water solubility and toxicity, high electrical insulation, and a large effect of improving drill workability.

As a compounding amount of the molybdenum compound in the silica slurry, when the volume of the silica particles contained in the slurry is 1, the volume ratio (Mo compound / SiO ₂ ) is preferably 0.2 or more and 5 or less, More preferably, it is 0.3 or more and 4 or less. When the volume ratio is 0.2 or more and 5 or less, dispersibility and stability when the molybdenum compound is dispersed and mixed in the slurry are improved.

As a method of dispersing and mixing the molybdenum compound in the silica dispersion in the first dispersion mixing step, for example, the molybdenum compound is first added little by little while stirring the slurry, and then mixed well, and then a media mill such as a bead mill or a ball mill, Examples thereof include a high-speed disperser such as a dissolver, a high-pressure homogenizer such as a nanomizer, a colloid mill, and an ultrasonic treatment machine.
Among these, a method of treating with a high-pressure homogenizer is preferable from the viewpoint that impurities are less mixed and can be efficiently dispersed. In addition, as a dispersant during dispersion mixing, coupling agents such as silane, titanate, and aluminate, modified silicones such as polyether-modified polysiloxane, polycarboxylic acids, urethane-based and acrylic polymer dispersants Etc. can also be added.

(Second dispersion mixing step)
Examples of the thermosetting resin (C) in the second dispersion and mixing step include epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, non-resin, and the like. A saturated polyester resin, an allyl resin, a dicyclopentadiene resin, a silicone resin, a triazine resin, a melamine resin, and the like can be given, and one or more of these can be mixed and used.

Among these, an epoxy resin is preferable from the viewpoint of moldability and electrical insulation.
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, and bisphenol F novolacs. Type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols and anthracene The diglycidyl ether compound of a kind etc. are mentioned, These 1 type (s) or 2 or more types can be mixed and used.

When an epoxy resin is used as the thermosetting resin, a curing agent for the epoxy resin can be used as necessary.
Examples of curing agents include, for example, polyfunctional phenol compounds such as phenol novolak and cresol novolak, amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenyl sulfone, phthalic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride Examples thereof include acid anhydrides such as copolymers, and one or two or more of these may be used in combination.

Examples of the organic solvent used in the varnish containing a thermosetting resin include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Ketone solvents, ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. A nitrogen atom-containing solvent, a sulfur atom-containing solvent such as dimethyl sulfoxide, and the like can be mentioned, and one kind or a mixture of two or more kinds can be used.
Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are preferable from the viewpoint of excellent solubility of the thermosetting resin and low toxicity.

  The solid content concentration of the varnish containing the thermosetting resin is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 80% by mass or less. 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 kept good.

  The amount of the slurry in which the molybdenum compound is dispersed in the varnish is 0.1 vol% when the total resin composition excluding the organic solvent contained in the resin composition varnish is 100 vol%. The amount is preferably 10% by volume or less. By making the amount of the molybdenum compound 0.1 volume% or more and 10 volume% or less, it is possible to reduce the thermal expansion of the resin composition while maintaining good drill workability.

  Examples of the method of dispersing and mixing the slurry in which the molybdenum compound is dispersed in the second dispersion mixing step in the varnish containing the thermosetting resin include, for example, a method of adding the slurry little by little while stirring the varnish and mixing sufficiently. It is done.

(Third dispersion mixing step)
As the inorganic filler (D) in the third dispersion mixing step, various materials can be used except the silica particles as the component (A) and the molybdenum compound as the component (B). For example, 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 Glass powder such as E glass, S glass, D glass, hollow glass beads, and the like can be used, and one or more of these can be mixed and used.

Of these, silica is preferred because of its low coefficient of thermal expansion.
Examples of the silica include a precipitated silica produced by a wet method and having a high water content, and a dry method silica produced by a dry method and containing almost no bound water. The dry method silica further includes differences in production methods. Examples include crushed silica, fumed silica, and fused spherical silica. Among these, 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 size is preferably 0.1 μm or more and 10 μm or less, and more preferably 0.3 μm or more and 8 μm or less. By making the average particle diameter of the fused spherical silica 0.1 μm or more, the fluidity when filled in the resin can be kept good, and by making the average particle diameter 10 μm or less, the mixing probability of coarse particles is reduced and defective. Occurrence can be suppressed.
In addition, an average particle diameter shall be larger than the silica particle which is the above-mentioned (A) component.

  The blending amount of the inorganic filler in the varnish is 20% by volume or more and 60% by volume or less when the total resin composition excluding the organic solvent finally contained in the resin composition varnish is 100% by volume. Is preferable, and it is more preferable that it is 30 volume% or more and 55 volume% or less. By setting the blending amount of the inorganic filler to 20% by volume or more and 60% by volume or less, it is possible to reduce the thermal expansion coefficient of the resin composition while maintaining good moldability.

Examples of the method of dispersing and mixing the inorganic filler in the third dispersion mixing step in the varnish containing the molybdenum compound and the thermosetting resin include, for example, a method in which the inorganic filler is added as it is, and the inorganic filler is previously added to the organic solvent. There is a method in which the mixture is dispersed into a slurry and then added and mixed.
Among these, from the viewpoint of dispersibility of the inorganic filler in the varnish, a method of adding the inorganic filler after slurrying is preferable. When slurrying the inorganic filler, it is preferable to pre-treat the inorganic filler with a surface treatment agent such as a silane-based or titanate-based coupling agent, a silicone oligomer, or an integral blend.

  In addition to the above components, the resin composition varnish produced through the above steps includes a curing accelerator, a thermoplastic resin, an elastomer, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, and an adhesion improver. Can be used.

  Examples of curing accelerators include, for example, imidazoles and derivatives thereof, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, and the like, one or two of these. A mixture of seeds or more can be used.

  Examples of 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, poly Examples include ether ether ketone resins, polyether imide resins, silicone resins, and tetrafluoroethylene resins.

  Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.

  Examples of organic fillers include resin fillers of uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, acrylate ester resin, methacrylate ester resin, conjugated diene resin And a core-shell resin filler having a rubbery core layer and a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, etc. It is done.

  Examples of flame retardants include halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, red phosphorus and other phosphorus flame retardants, guanidine sulfamate, melamine sulfate, polyphosphorus Nitrogen flame retardants such as acid melamine and melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, and inorganic flame retardants such as antimony trioxide.

  Other examples of UV absorbers include benzotriazole UV absorbers, examples of antioxidants include hindered phenols and hindered amines, and examples of adhesion improvers include silanes, titanates, and aluminates. Coupling agents such as systems can be mentioned.

In addition, it is preferable to add these components to the resin composition varnish after the third dispersion mixing step. Moreover, it is preferable that it is 40-80 mass%, and, as for solid content of the resin composition varnish finally obtained, it is more preferable that it is 45-75 mass%.
When the solid content is 40 to 80% by mass, the coatability of the varnish is improved, and a prepreg having an appropriate resin composition adhesion amount can be obtained.

[Prepregs and laminates]
Next, the prepreg and laminate using the above resin composition varnish will be described.

(Prepreg)
The prepreg of the present invention is obtained by impregnating and applying a resin composition varnish obtained by the above-described method for producing a resin composition varnish of the present invention to a base material and then semi-curing it by heating or the like.

  Examples of the substrate used for 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, for example, woven fabric, non-woven fabric, roving, chopped strand mat, and surfacing mat, and the material and shape are selected depending on the intended use and performance of the laminate, and one kind is necessary. Alternatively, two or more kinds of materials and shapes can be combined. Moreover, the thing surface-treated with the silane coupling agent etc. and the thing which performed the fiber opening process are preferable from the point of heat resistance, moisture resistance, and workability. For example, a substrate having a thickness of 0.01 to 0.2 mm can be used.

(Laminated board)
The laminate of the present invention is formed by laminate molding using the prepreg of the present invention. For example, 1 to 20 prepregs of the present invention are stacked, and a metal foil such as copper or aluminum is arranged on one or both sides thereof, using a press, a vacuum press, a continuous molding machine, an autoclave, or the like, at a temperature of 100 to 250. A metal foil-clad laminate can be produced by lamination molding at a temperature of 0 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.

  The metal foil is not particularly limited as long as it is used for electronic parts. Moreover, the prepreg of the present invention and the inner layer wiring board can be laminated and molded to produce a multilayer board.

  The prepreg and laminate of the present invention as described above have the characteristics that the coefficient of thermal expansion is low and the drillability is high.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited by these Examples.

(Examples 1-2 and Comparative Examples 1-2)
Among the blends of the resin composition varnishes shown in Table 1, first, the molybdenum compound of (B) was added to the silica slurry of (A) little by little while stirring so as not to form an agglomerate. The silica slurry mixed with this molybdenum compound is treated three times under the condition of air pressure 0.5 MPa using a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd., NM2000-AR) to sufficiently disperse the molybdenum compound and the silica particles. Mixed.

  Next, this molybdenum compound-dispersed silica slurry is added little by little to a resin varnish prepared by dissolving the thermosetting resin (C) and the curing agent in an organic solvent. Stir until 1 hour.

Thereafter, the inorganic filler slurry (D) was added to the resin varnish while stirring, a curing accelerator was further added, and the mixture was stirred for 1 hour until the whole became uniform to prepare a resin composition varnish.
The solid content concentration of the resin composition varnishes of Examples 1-2 and Comparative Examples 1-2 was 70% by mass.

(Comparative Example 3)
Among the blends of the resin composition varnishes shown in Table 1, the molybdenum compound of (B) was gradually stirred while stirring in a resin varnish prepared by dissolving the thermosetting resin and curing agent of (C) in an organic solvent. In addition, the mixture was stirred for 1 hour until the whole became uniform after the addition of the entire amount.
Thereafter, the inorganic filler slurry (D) was added to the resin varnish while stirring, a curing accelerator was further added, and the mixture was stirred for 1 hour until the whole became uniform to prepare a resin composition varnish.
The solid content concentration of the resin composition varnish of Comparative Example 3 was 70% by mass.

(Comparative Example 4)
Among the blends of the resin composition varnishes shown in Table 1, first, the molybdenum compound of (B) was added to the silica slurry of (A) little by little while stirring so as not to form an agglomerate. The silica slurry mixed with this molybdenum compound is treated three times under the condition of air pressure of 0.5 MPa using a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd., NM2000-AR) to sufficiently disperse the molybdenum compound and the silica particles. Mixed.
Next, this molybdenum compound-dispersed silica slurry was added little by little to the inorganic filler slurry of (D) while stirring, and stirred for 1 hour until the whole became uniform after the addition of the entire amount.
Thereafter, the slurry is added to a resin varnish prepared by dissolving the thermosetting resin (C) and the curing agent in (C) in an organic solvent, and a curing accelerator is further added until the whole becomes uniform. The resin composition varnish was produced by stirring for a period of time.
The solid content concentration of the resin composition varnish of Comparative Example 4 was 70% by mass.

  The resin composition varnishes produced in the above Examples and Comparative Examples were impregnated and coated on 0.1 mm thick E glass cloth (manufactured by Nitto Boseki Co., Ltd., WEA116E) and dried at 160 ° C. for 5 minutes. Thus, a prepreg having a resin composition content of 48% by mass was obtained. Four prepregs were stacked, 12 μm electrolytic copper foils were placed one above the other, and vacuum-pressed at a temperature of 185 ° C. and a pressure of 3.8 MPa for 90 minutes to obtain a copper-clad laminate.

  Using the resin composition varnish and copper-clad laminate obtained in this way, the resin composition varnish sedimentation and the presence or absence of aggregates in the varnish, the copper-clad laminate drillability and thermal expansion coefficient are as follows: Measurement and evaluation were carried out by the methods described above, and the evaluation results are summarized in Table 2.

(1) Evaluation of sedimentation property of resin composition varnish 500 cm ^{3 of} resin composition varnish was placed in a glass sedimentation tube having a diameter of 5 cm and a length of 35 cm, and left at room temperature of 25 ° C., and settled at the bottom of the sedimentation tube. The time until the product accumulated was measured to evaluate the sedimentation property.

(2) Evaluation of presence / absence of aggregates in resin composition varnish 100 cm ^{3 of} resin composition varnish was taken in a flask, and 400 cm ³ of the same organic solvent used in the varnish was added thereto and shaken well. The diluted varnish was filtered through a nylon mesh having an opening of 20 μm, and whether or not a residue remained on the mesh was visually confirmed to evaluate the presence or absence of aggregates.

(3) Evaluation of drillability of copper-clad laminate A 0.15 mm thick aluminum foil is placed on a stack of two copper-clad laminates, and a 1.5 mm thick paper phenol plate is placed underneath. Drilling 6000 holes with a 2 mm drill using a drilling machine (ND-1V212, manufactured by Hitachi Via Mechanics Co., Ltd.) at a rotation speed of 160 krpm, a feed rate of 2 m / min, and a chip load of 12.5 μm / rev. The drill workability was evaluated by measuring the amount of wear of the cutting edge of the drill and the hole position accuracy by the following method.

a) Amount of drill cutting edge wear The drill cutting edge before and after drilling was observed from above the center axis of the drill using a scanning electron microscope (manufactured by Hitachi, Ltd., S-4700). The wear retraction amount was measured and used as the drill cutting edge wear amount.
b) Hole position accuracy Of the two-layered copper-clad laminate, the hole position accuracy measurement machine (HT-1AM, manufactured by Hitachi Via Mechanics Co., Ltd.) And the average of the positional deviations of the holes in the 4001st to 6000th shots + 3σ (σ: standard deviation) was calculated to obtain the hole position accuracy.

(4) Measurement of coefficient of thermal expansion of copper-clad laminate After removing the copper foil of the copper-clad laminate with an etching solution, it was cut into a size of 5 mm square to prepare a test piece. The thermal expansion coefficient in the vertical direction (longitudinal direction of the glass cloth) at 50 ° C. to 120 ° C. of this test piece was measured using a TMA test apparatus (TA Instruments, TMA2940) at a heating rate of 10 ° C. / Measured in min.

  Table 1 shows the composition of resin composition varnishes produced by the production methods of Examples and Comparative Examples in terms of parts by mass when the amount of thermosetting resin (C) is 100 parts by mass. It is. However, about the slurry in which the silica particle of (A) was disperse | distributed in the organic solvent, and the inorganic filler of (D), the organic solvent contained in them has also shown the compounding quantity. About this (D), the volume% of the inorganic filler when the total resin composition excluding the organic solvent contained in the resin composition varnish is 100% by volume is also indicated in parentheses. Moreover, about the molybdenum compound of (B), when using the particle | grains with which the molybdenum compound was carry | supported by another substance, the compounding quantity as a support particle is shown instead of a molybdenum compound alone.

The following were used for each component in Table 1.
(A) Silica slurry A-1: Slurry in which silica having an average particle size of 0.05 μm and a specific surface area of 55 m ² / g is dispersed in propylene glycol monomethyl ether at a silica blending amount of 30 mass% (manufactured by Admatechs, Admanano)
(A) Silica slurry A-2: A slurry in which silica having an average particle size of 0.025 μm and a specific surface area of 110 m ² / g is dispersed in propylene glycol monomethyl ether at a silica blending amount of 20 mass% (manufactured by Admatechs, Admanano)
(A) Silica slurry A-3: Silica having an average particle size of 0.5 μm and a specific surface area of 7 m ² / g (manufactured by Admatechs Co., Ltd., SO-25R) in 50% by mass of silica in propylene glycol monomethyl ether Dispersed slurry (A) Silica slurry A-4: Silica (manufactured by Nippon Aerosil Co., Ltd., 380) having an average particle size of 0.05 μm and a specific surface area of 380 m ² / g in a silica content of 10% by mass and propylene glycol monomethyl ether Slurry dispersed in

(B) Molybdenum compound B-1: Zinc molybdate (reagent manufactured by Strem Chemicals Co., Ltd.)
(B) Molybdenum compound B-2: Calcium molybdate (reagent manufactured by Strem Chemicals Co., Ltd.)
(B) Molybdenum compound B-3: Zinc molybdate-carrying talc, zinc molybdate content 10% by mass (manufactured by Sherwin Williams, Chemguard 911C)

(C) Thermosetting resin: phenol novolac type epoxy resin (DIC Corporation, Epicron N-770)

Curing agent: cresol novolac type phenolic resin (manufactured by DIC Corporation, Phenolite KA-1165)
Curing accelerator: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2E4MI)
Organic solvent: Propylene glycol monomethyl ether (Gordo Co., Ltd.)

(D) Inorganic filler: fused spherical silica slurry, average particle size 0.5 μm, specific surface area 7 m ² / g, silica content 70 mass% (manufactured by Admatechs, SC2050-KC)

As is apparent from Table 2, the examples of the present invention are excellent without any problems in all of the sedimentation property of the resin composition varnish and the presence or absence of aggregates, the drillability of the copper-clad laminate, and the thermal expansion coefficient.
On the other hand, in Comparative Example 1, since the average particle diameter of the silica particles in the slurry (A) is large and the specific surface area is small, the sedimentation property of the resin composition varnish is remarkably inferior.
Moreover, since the specific surface area of the silica particle in the slurry of (A) is large in the comparative example 2, the aggregate remains in the resin composition varnish, and the hole position accuracy is also slightly deteriorated. In Comparative Example 3, since the molybdenum compound-carrying talc is directly added to the resin varnish, the sedimentation property of the resin composition varnish is inferior, and aggregates remain. Furthermore, the hole position accuracy is slightly deteriorated. In Comparative Example 4, since the molybdenum compound-dispersed silica slurry is added to the inorganic filler slurry and then added to the resin varnish, aggregates remain in the resin composition varnish.
In addition, if a printed wiring board is produced in a state where aggregates remain in the resin composition varnish, abnormal deposition of plating due to molybdenum is likely to occur during the production, and reliability as an electronic device is impaired. Is not preferable.

  As described above, according to the present invention, it is possible to produce a resin composition varnish that is unlikely to cause precipitation or aggregation of a molybdenum compound. By using this, a low thermal expansion coefficient and high drill workability are suitable for semiconductor packages and printed wiring boards. Prepregs and laminates can be obtained.

Claims (5)

(A) (B) A molybdenum compound is dispersedly mixed in a slurry containing silica particles having an average particle diameter of 0.01 μm or more and 0.1 μm or less and a specific surface area of 30 m ² / g or more and 270 m ² / g or less. 1 dispersion mixing step;
(C) a second dispersion and mixing step in which the slurry that has undergone the first dispersion and mixing step is dispersed and mixed in a varnish containing a thermosetting resin;
(D) The 3rd dispersion | distribution mixing process which disperse-mixes the inorganic filler except the said silica particle and a molybdenum compound in the varnish which passed through the 2nd dispersion | distribution mixing process, The manufacturing method of the resin composition varnish.   The manufacturing method of the resin composition varnish of Claim 1 including the hardening accelerator addition process which adds a hardening accelerator to the varnish after a 3rd dispersion | distribution mixing process.   (B) The method for producing a resin composition varnish according to claim 1 or 2, wherein the molybdenum compound is one or a mixture of two or more selected from the group consisting of zinc molybdate, calcium molybdate, and magnesium molybdate. . (A) (B) A molybdenum compound is dispersedly mixed in a slurry containing silica particles having an average particle diameter of 0.01 μm or more and 0.1 μm or less and a specific surface area of 30 m ² / g or more and 270 m ² / g or less. (C) a second dispersion and mixing step in which the slurry that has undergone the first dispersion and mixing step is dispersed and mixed in a varnish containing a thermosetting resin, and a varnish that has undergone the second dispersion and mixing step. A prepreg obtained by impregnating a base material with a resin composition varnish obtained through (D) a third dispersion mixing step of dispersing and mixing an inorganic filler.   A laminate obtained by laminating the prepreg according to claim 4.