JP2011178883A - Prepreg, laminated board, multilayer printed wiring board, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a prepreg and a laminated board excellent in impregnatability and drill wearability, and to provide a printed wiring board and a semiconductor device excellent in reliability. <P>SOLUTION: There are provided: a resin composition comprising a filler in which (B) a second filler having a smaller particle size than (A) a first filler is adhered on the outer periphery of (A) the first filler; a prepreg manufactured using the resin composition; and a laminated board, a printed wiring board and a semiconductor device manufactured using the prepreg. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a prepreg, a laminated board, a printed wiring board, and a semiconductor device.

2. Description of the Related Art In recent years, with the demand for higher functionality of electronic devices and the like, electronic components have been integrated at a high density and further at a high density mounting. For this reason, printed wiring boards and the like for high-density mounting used for these are becoming smaller and thinner and higher in density than ever before.
Particularly in the case of thinning, since the rigidity of the substrate itself is low, warping becomes a problem when components are connected by reflow. Therefore, the wiring board excellent in lower warpage and low thermal expansion tends to have a higher blending ratio of the filler.

However, if a large amount of the filler is filled in the resin composition, the resin composition is dispersed in the solvent, and when the resin varnish is adjusted, thixo is increased and the dispersibility of the filler is impaired. When the base material was impregnated with the resin varnish, the impregnation property was lowered.
In addition, a method of highly filling spherical silica has been proposed to improve thixotropy and dispersibility of the resin varnish, but the silica has a high hardness and has a problem with the wear of the drill.
Therefore, in order to achieve both drill wear and impregnation properties, talc and boehmite of aluminum hydroxide monohydrate (see, for example, Patent Document 1) and organosilicone (for example, Patent Document), which have lower hardness than silica. 2)), etc. have also been proposed, but it has not yet achieved a balance between drill wear and impregnation.

JP 2004-59643 A JP 2007-250966 A

  An object of the present invention is to provide a prepreg excellent in impregnation and drill wear, a laminated board having a small warpage, a printed wiring board, and a semiconductor device.

The object of the present invention is achieved by the present invention described in the following (1) to (10).
(1) (A) A resin composition containing a filler formed by adhering (B) a second filler having a particle diameter smaller than that of the first filler (A) on the outer periphery of the first filler is used. A prepreg characterized by that.
(2) The prepreg according to claim 1, wherein an average particle diameter of the first filler (A) is 0.2 μm to 10 μm.
(3) The prepreg according to (1) or (2), wherein the (B) second filler is inorganic filler fine particles having an average particle size of 10 to 100 nm.
(4) The prepreg according to any one of (1) to (3), wherein the second filler (B) is spherical silica.
(5) The first filler (A) is an oxide, carbonate, hydroxide, silicate, sulfate, sulfite, nitride, borate, titanate, silicone, and rubber particles. The prepreg according to any one of (1) to (4), which is at least one selected from the group consisting of:
(6) The prepreg according to any one of (1) to (5), wherein the (A) first filler is boehmite or silicone.
(7) The prepreg according to any one of (1) to (6), wherein the (B) second filler is surface-treated with a coupling agent.
(8) Laminated board using the prepreg according to any one of (1) to (7) (9) A printed wiring board using the laminated board according to (8).
(10) A semiconductor device in which a semiconductor element is mounted on the printed wiring board according to (9).

  According to the present invention, the prepreg is excellent in impregnation and drill wear, and the laminated board, printed wiring board, and semiconductor device obtained by using the prepreg have small warpage.

It is the schematic which shows an example of the impregnation coating equipment used for manufacture of the prepreg of this invention. It is the schematic which shows an example of the manufacturing method of the metal-clad laminated board of this invention. It is the schematic which shows another example of the manufacturing method of the metal-clad laminated board of this invention. It is a figure explaining the photograph which image | photographed the cross section of the laminated board obtained in Example 1. FIG. It is a figure explaining the photograph which image | photographed the cross section of the laminated board obtained in Example 9. FIG.

  Hereinafter, the prepreg, laminated board, printed wiring board, and semiconductor device of the present invention will be described.

  The prepreg of the present invention comprises (A) a resin composition containing a filler formed by adhering (B) a second filler having a particle diameter smaller than that of the first filler to the outer periphery of the first filler. It is characterized by using a thing.

  The prepreg of the present invention is obtained by impregnating a fiber base material with the above resin composition. Thereby, the prepreg excellent in heat resistance, low expansibility, and a flame retardance can be obtained. Examples of the base material include glass fiber base materials such as glass woven fabric, glass non-woven fabric, and glass paper, woven fabric and non-woven fabric made of synthetic fibers such as paper, aramid, polyester, aromatic polyester, and fluororesin, and metal fibers. Woven fabrics, nonwoven fabrics, mats and the like made of carbon fibers, mineral fibers, and the like. These substrates may be used alone or in combination. Among these, a glass fiber base material is preferable. Thereby, the rigidity and dimensional stability of a prepreg can be improved.

The resin composition may be dispersed in a solvent to form a resin varnish and impregnated into a fiber base material. Although it is desirable that the solvent used for these exhibits good solubility in the resin composition, a poor solvent may be used as long as it does not have an adverse effect. Examples of the solvent exhibiting good solubility include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. The solid content of the resin varnish is not particularly limited, but the solid content of the resin composition is preferably 30 to 80% by weight, and particularly preferably 40 to 70% by weight. Thereby, the impregnation property to the base material of the resin varnish can be improved.

Examples of the method of impregnating the base material with the resin composition include a method of immersing the base material in a resin varnish, a method of applying with various coaters, and a method of spraying with a spray. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved. In addition, when a base material is immersed in a resin varnish, a normal impregnation coating equipment can be used.

As another production method for impregnating the base material, a method using a long base material and a long metal foil or film as described in JP-A-8-150683 can be applied ( JP-A-8-150683, paragraphs 0005 and 0006, FIG. 1). In the case of this method, two are prepared: one obtained by winding a long base material in a roll form, and one obtained by winding a long metal foil or film in a roll form. And two metal foils or a film is separately sent out from a roll, a resin composition is apply | coated to each, and a resin layer is formed. When the resin composition is diluted with a solvent and used, it is dried after coating. Subsequently, the two metal foils or the insulating resin layer side of the film are opposed to each other, and one or two or more base materials are fed from the roll between the opposing surfaces, and laminated and adhered by a press roller. Subsequently, the resin layer can be made into a semi-cured state by continuously heating and pressing, and after cooling, a prepreg can be obtained by continuously winding with a roll, or by cutting to a predetermined length.

(Resin composition)
Next, the resin composition used for the prepreg of the present invention will be described.

The resin composition includes (A) a filler formed by adhering (B) a second filler having a particle diameter smaller than that of the first filler (A) to the outer periphery of the first filler.
Thereby, a filler is uniformly disperse | distributed in a resin composition and the impregnation property to a base material improves.

(A) Although a 1st filler is not specifically limited, It is preferable that an average particle diameter is 0.2 micrometer-10 micrometers. More preferably, the average particle size is 0.5 to 5 μm.
By using the filler having the above average particle diameter, the impregnation property is further improved.

(A) The first filler is not particularly limited. For example, oxides such as titanium oxide, alumina, silica, and fused silica, carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite, aluminum hydroxide, and water Hydroxides such as magnesium oxide and calcium hydroxide, talc, calcined talc, calcined clay, uncalcined clay, mica, silicates such as glass, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, nitriding Nitride such as aluminum, boron nitride, silicon nitride and carbon nitride, borate such as zinc borate, barium metaborate, aluminum borate, calcium borate and sodium borate, titanium such as strontium titanate and barium titanate Acid salt, silicone rubber, etc., and styrene butadiene rubber particles, Rubber particles such Kurirugomu particles can be exemplified.
As the filler, one of these can be used alone, or two or more can be used in combination.

The silicone is not particularly limited as long as it is a rubber elastic fine particle formed of an organopolysiloxane. For example, a fine particle composed of silicone rubber (organopolysiloxane crosslinked elastomer) itself, and a core portion composed of silicone mainly composed of two-dimensional crosslinking. Examples thereof include core-shell structured particles coated with silicone mainly composed of a three-dimensional crosslinking type. As the silicone rubber fine particles, KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefill E-500, Trefil E-600 (manufactured by Toray Dow Corning Co., Ltd.) Commercial products such as these can be used.

The rubber particles are not particularly limited, but are preferably core-shell type rubber particles and cross-linked type rubber particles.
The core-shell type rubber particle refers to a rubber particle having a core layer and a shell layer. For example, the outer shell layer is a glassy polymer and the inner core layer is a rubbery polymer, or an outer layer. The three-layer structure in which the shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. As the rubber-like polymer of the core layer, a crosslinked rubber such as ethylene, propylene, styrene, butadiene, isopropylene, methyl acrylate, methyl methacrylate, acrylonitrile and the like can be selected. As the shell layer covering the core layer, methyl methacrylate, styrene, acrylonitrile or a copolymer thereof can be selected. In the resin constituting the shell layer, an epoxy group, a carboxyl group or the like can be introduced as a functional group, and can be selected depending on the application.
Examples of the crosslinked rubber particles include acrylonitrile butadiene rubber (NBR) particles, styrene butadiene rubber (SBR) particles, and acrylic rubber particles.
In addition, such rubber particles can impart effects such as increasing the mechanical strength of the cured product, stress relaxation of the cured product, and reducing thermal expansion.

Among the first fillers, those having high heat resistance are particularly preferable. High heat resistance means that the 1% thermal decomposition temperature of the inorganic filler is 260 ° C. or higher, and particularly preferably 300 ° C. or higher. The 1% pyrolysis temperature is defined by a differential thermal balance (TG / DTA) at a temperature increase rate of 10 ° C./min and a temperature at a point of 1% weight reduction from the initial weight. Examples of the filler having a 1% thermal decomposition temperature of 300 ° C. or higher include boehmite, alumina, talc, calcined talc, and silica. Of these, boehmite, talc, and calcined talc are particularly preferable. Thereby, heat resistance and drill workability can be improved more.

The organic fine particles are not dissolved in an organic solvent when preparing the resin composition, and are not compatible with components in the resin composition such as a resin. Accordingly, the organic fine particles are present in a dispersed state in the varnish of the resin composition.

  Although content of said 1st filler is not specifically limited, It is preferable that it is 40 to 75 weight% of the whole said resin composition, and it is especially preferable that it is 50 to 70 weight%. When the content is within the above range, the heat resistance and the fluidity are particularly excellent.

Although content of the said silicone filler is not specifically limited, It is preferable that it is 5 to 50 weight% of the whole resin composition, and it is preferable that it is especially 10 to 40 weight% from the point which is excellent in impregnation property.

Next, the second filler will be described. The (B) second filler is not particularly limited as long as it adheres to the (A) first filler.
The (B) second filler adhering to the (A) first filler is, for example, (A) one having a different zeta potential sign of the first filler, one attracting by van de Swirl force, cup Examples include chemical bonding by ring agent treatment, etc.

The particle size of the (B) second filler is not particularly limited, but the average particle size is preferably 10 to 100 nm.
Thereby, even if the varnish viscosity is high, the impregnation property is improved, the generation of voids can be suppressed, the solder heat resistance is excellent, and the insulation reliability is improved.
In addition, when using a filler with an average particle diameter of 10-100 nm, it is preferable to use as a slurry previously disperse | distributed to the organic solvent. This is because the filler having an average particle size of 10 to 100 nm is likely to aggregate and may form a secondary aggregate or the like when blended into the resin composition, thereby reducing fluidity.

The average particle diameter of the (B) second filler is particularly preferably 15 to 90 nm, and most preferably 25 to 75 nm. When the average particle size is in the above range, high filling property and high fluidity are also excellent.

  The average particle diameter of the (A) first filler and (B) second filler is, for example, ultrasonic vibration current method (zeta potential), ultrasonic attenuation spectroscopy (particle size distribution), and laser diffraction scattering. It can be measured by the method.

The (B) second filler is not particularly limited, and examples thereof include silicates such as talc, fired talc, fired clay, unfired clay, mica, and glass, titanium oxide, alumina, silica, and fused silica. Oxides, carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, Borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride, carbon nitride, strontium titanate, barium titanate, etc. A titanate etc. can be mentioned. One of these can be used alone, or two or more can be used in combination.
Among these, silica is preferable from the viewpoint of lowering the linear thermal expansion coefficient of the laminate.

(B) The shape of the second filler is not particularly limited, but is preferably spherical.
Thereby, the impregnation property can be improved.
There are no particular limitations on the method of making the particles spherical. For example, in the case of silica, the particles can be made spherical by dry fused silica such as a combustion method or wet sol-gel silica such as a precipitation method or a gel method.

  The combination of the first filler and the second filler is not particularly limited. For example, the first filler may be at least one selected from the group consisting of boehmite, talc, and silicone particles, and the second filler. A combination using silica as the material is preferred. In the case of this combination, the resin composition not only exhibits good impregnation properties to the substrate, but also has good drill workability, and can produce a laminate having a low thermal expansion coefficient.

  The weight ratio of the content of the first filler (A) and the content of the second filler (B) is not particularly limited, but the content of the (B) first filler The weight ratio (w2 / w1) of the content (w2) of the (B) second filler to (w1) is preferably 0.02 to 0.5, particularly 0.06 to 0.4. It is preferable that When the weight ratio is within the above range, the moldability can be particularly improved.

The (A) first filler and (B) second filler are, for example, an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, a silicone in advance. You may surface-treat with functional group containing silanes, such as coupling agents, such as an oil type coupling agent, and / or alkyl silazane. By performing the surface treatment in advance, the adsorptivity of (A) the first filler and (B) the second filler can be improved. Moreover, the adhesiveness of resin used for a resin composition and (A) 1st filler, or (B) 2nd filler improves, and the prepreg or laminated board which is excellent in mechanical strength can be obtained.

  Known functional group-containing silanes such as the functional group-containing silanes and / or alkylsilazanes can be used. Preferably, epoxy silane, styryl silane, methacryloxy silane, acryloxy silane, mercapto silane, triethoxy silane, N-cyclohexylaminopropyltrimethoxy silane, methyl dimethoxy silane, vinyl silane, isocyanate silane, sulfide silane, chloropropyl silane, ureido Silane compound. More preferred are epoxy silane and vinyl silane. In particular, adhesion to an irregular inorganic filler such as boehmite and adhesion to a resin are improved.

  The amount of the functional group-containing silanes and / or alkylsilazanes functional group-containing silanes to be surface-treated in advance on (A) the first filler and (B) the second filler is not particularly limited, The amount is preferably 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the filler ((A) first filler or (B) second filler). More preferably, it is 0.1 to 3 parts by weight. When the content of the functional group-containing silanes and / or the functional group-containing silanes of the alkylsilazanes exceeds the upper limit, the heat resistance and insulation reliability due to the excess coupling agent may decrease, and the lower limit. If it is less than the range, the mechanical strength with the resin component and the resin fluidity may decrease.

  The method for surface-treating the (A) first filler or (B) the second filler with a functional group-containing silane and / or alkylsilazane is not particularly limited, but a wet method or a dry method may be used. preferable. The wet method is particularly preferable. When compared with the dry method, the wet method can uniformly treat the surface.

  Although it does not specifically limit as resin used for the said resin composition, For example, an epoxy resin, a phenol resin, cyanate resin, maleimide resin etc. can be used.

Although it does not specifically limit as said epoxy resin, For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol Z type epoxy resin (4,4'-cyclohexyl) Diene bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 ′-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol M type epoxy resin (4,4 ′-(1,3) -Phenylenediisopridiene) bisphenol type epoxy resin), etc., novolac type epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin. Xy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl dimethylene type epoxy resin, trisphenol methane novolac type epoxy resin, glycidyl ethers of 1,1,2,2- (tetraphenol) ethane, trifunctional , Or tetrafunctional glycidylamines, arylalkylene type epoxy resins such as tetramethylbiphenyl type epoxy resins, naphthalene skeleton modified epoxy resins, methoxynaphthalene modified cresol novolak type epoxy resins, naphthalene type epoxies such as methoxynaphthalenedylene methylene type epoxy resins Resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene Epoxy resins, flame-retarded epoxy resin or the like halogenated epoxy resins. One of these can be used alone, two or more having different weight average molecular weights can be used in combination, and one or two or more of these prepolymers can be used in combination.
Among these epoxy resins, at least one selected from the group consisting of biphenyl aralkyl type epoxy resins, naphthalene skeleton-modified epoxy resins, and cresol novolac type epoxy resins is preferable. Thereby, heat resistance and a flame retardance are improved.

Although content of the said epoxy resin is not specifically limited, It is preferable to set it as 5 to 30 weight% on the solid content basis of the whole epoxy resin composition. If the content is less than the lower limit, the curability of the epoxy resin may decrease, or the prepreg obtained from the epoxy resin composition or the moisture resistance of the printed wiring board may decrease. Moreover, when the said upper limit is exceeded, the linear thermal expansion coefficient of a prepreg or a printed wiring board may become large, or heat resistance may fall.

The weight average molecular weight of the epoxy resin is not particularly limited, but a weight average molecular weight of 4.0 × 10 ^{2 to} 1.8 × 10 ³ is preferable. If the weight average molecular weight is less than the lower limit, the glass transition point is lowered, and if it exceeds the upper limit, the fluidity is lowered and the substrate may not be impregnated. By setting the weight average molecular weight within the above range, the impregnation property can be improved.
The weight average molecular weight of the epoxy resin can be measured by gel permeation chromatography (GPC), for example, and can be specified as a weight molecular weight in terms of polystyrene.

The cyanate resin is not particularly limited, and can be obtained, for example, by reacting a halogenated cyanide compound with phenols or naphthols, and prepolymerizing by a method such as heating as necessary. Moreover, the commercial item prepared in this way can also be used.

The kind of the cyanate resin is not particularly limited. For example, bisphenol cyanate resin such as novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, and naphthol aralkyl type. And cyanate resin.

The cyanate resin preferably has two or more cyanate groups (—O—CN) in the molecule. For example, 2,2′-bis (4-cyanatophenyl) isopropylidene, 1,1′-bis (4-cyanatophenyl) ethane, bis (4-cyanato-3,5-dimethylphenyl) methane, 3-bis (4-cyanatophenyl-1- (1-methylethylidene)) benzene, dicyclopentadiene type cyanate ester, phenol novolac type cyanate ester, bis (4-cyanatophenyl) thioether, bis (4-cyanato) Phenyl) ether, 1,1,1-tris (4-cyanatophenyl) ethane, tris (4-cyanatophenyl) phosphite, bis (4-cyanatophenyl) sulfone, 2,2-bis (4-si Anatophenyl) propane, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1 Cyanate resin obtained by reaction of 3,6-tricyanatonaphthalene, 4,4-dicyanatobiphenyl, phenol novolac type, cresol novolac type polyhydric phenols with cyanogen halide, naphthol aralkyl type polyvalent naphthol And cyanate resin obtained by the reaction of a halogenated cyanide. Among these, phenol novolac-type cyanate resin is excellent in flame retardancy and low thermal expansion, and 2,2-bis (4-cyanatophenyl) isopropylidene and dicyclopentadiene-type cyanate ester are used to control the crosslinking density, Excellent moisture resistance reliability. In particular, a phenol novolac type cyanate resin is preferred from the viewpoint of low thermal expansion. Furthermore, other cyanate resins may be used alone or in combination of two or more, and are not particularly limited.

The said cyanate resin may be used independently, can also use together cyanate resin from which a weight average molecular weight differs, or can also use together the said cyanate resin and its prepolymer.
The prepolymer is usually obtained by, for example, trimerizing the cyanate resin by a heating reaction or the like, and is preferably used for adjusting the moldability and fluidity of the epoxy resin composition. .
The prepolymer is not particularly limited. For example, when a prepolymer having a trimerization rate of 20 to 50% by weight is used, good moldability and fluidity can be expressed.

The content of the cyanate resin is not particularly limited, but is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, and particularly preferably 10 to 50% by weight based on the solid content of the entire epoxy resin composition. 40% by weight. When the content is within the above range, the cyanate resin can effectively exhibit heat resistance and flame retardancy. When the cyanate resin content is less than the lower limit, thermal expansibility increases and heat resistance may decrease. When the upper limit value is exceeded, the strength of the prepreg produced using the epoxy resin composition decreases. There is.

The maleimide resin is not particularly limited, but N, N ′-(4,4′-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2-bis [ And bismaleimide resins such as 4- (4-maleimidophenoxy) phenyl] propane. Furthermore, other maleimide resins can be used alone or in combination of two or more, and are not particularly limited.

The maleimide resin may be used alone, or may be used in combination with maleimide resins having different weight average molecular weights, or may be used in combination with the maleimide resin and its prepolymer.

Although content of the said maleimide resin is not specifically limited, It is preferable that it is 1 to 30 weight% on the solid content basis of the whole epoxy resin composition, More preferably, it is 5 to 25 weight%, More preferably, it is 5 to 5 weight%. 20% by weight.

The phenol resin is not particularly limited. For example, a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a zylock type phenol resin, a terpene-modified phenol resin, a polyvinylphenol, and the like. A thing can be used individually or in combination of 2 or more types.

If necessary, the resin composition may contain additives other than the above components as long as the characteristics are not impaired. Examples of the components other than the above components include curing accelerators such as imidazoles, triphenylphosphine, and quaternary phosphonium salts, surface conditioners such as acrylic polymers, and colorants such as dyes and pigments. .

(Prepreg)
Next, the prepreg will be described.
The prepreg of the present invention is obtained by impregnating a base material with the above resin composition. In the present invention, by using a solid epoxy resin as a main component of the resin composition, a prepreg having low tackiness and easy handling can be obtained. Examples of the base material include glass fiber base materials such as glass woven fabric, glass non-woven fabric, and glass paper, paper, aramid, polyester, aromatic polyester, woven fabric and non-woven fabric made of synthetic fibers such as fluororesin, metal fibers, Examples thereof include woven fabrics, nonwoven fabrics and mats made of carbon fibers and mineral fibers. These substrates may be used alone or in combination. Among these, a glass fiber base material is preferable. Thereby, the rigidity and dimensional stability of a prepreg can be improved.

When the substrate is impregnated with the resin composition, the resin composition is dissolved in a solvent and used as a resin varnish. The solvent preferably has good solubility in the epoxy resin composition, but a poor solvent may be used as long as it does not adversely affect the solvent. Examples of the solvent exhibiting good solubility include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. The solid content of the resin varnish is not particularly limited, but is preferably 30 to 80% by weight, particularly preferably 40 to 70% by weight, based on the solid content of the epoxy resin composition. Thereby, the impregnation property to the base material of the resin varnish can be improved.

Examples of the method of impregnating the base material with the resin varnish include a method of immersing the base material in the resin varnish, a method of applying with various coaters, and a method of spraying with a spray. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved. In addition, when a base material is immersed in a resin varnish, a normal impregnation coating equipment can be used. As shown in FIG. 1, the base material 1 is immersed in the resin varnish 3 of the impregnation tank 2 to impregnate the base material 1 with the resin varnish 3. In that case, the base material 1 is immersed in the resin varnish 3 by the dip roll 4 (three in FIG. 1) with which the impregnation tank 2 is equipped. Next, the base material 1 impregnated with the resin varnish 3 is pulled up in the vertical direction, and arranged between a pair of squeeze rolls or comma rolls (5 in FIG. 1 is a squeeze roll) arranged in parallel in the horizontal direction. Then, the application amount of the resin varnish 3 to the substrate 1 is adjusted. Thereafter, the base material 1 coated with the resin varnish 3 is heated at a predetermined temperature with a dryer 6 to volatilize the solvent in the coated varnish and to semi-cur the resin composition to produce the prepreg 7. . Note that the upper roll 8 in FIG. 1 rotates in the same direction as the direction of travel of the prepreg 7 in order to move the prepreg 7 in the direction of travel. Moreover, the conditions which dry the solvent of the said resin varnish can obtain the semi-hardened prepreg 7 by drying at the temperature of 90-180 degreeC, and time 1 to 10 minutes.

(Laminated board)
Next, a laminated board is demonstrated.
The laminate of the present invention has a metal foil on at least one side of a laminate obtained by superposing at least one prepreg. Thereby, the laminated board excellent in heat resistance, low expansibility, and a flame retardance can be obtained. When one prepreg is used, the metal foil is overlapped on both the upper and lower surfaces or one surface. Two or more prepregs can be laminated. When two or more prepregs are laminated, a metal foil or film is laminated on the outermost upper and lower surfaces or one surface of the laminated prepregs. Next, a laminate can be obtained by heat-pressing a laminate of a prepreg and a metal foil.

  Although the temperature to heat is not specifically limited, 120-220 degreeC is preferable and especially 150-200 degreeC is preferable. Although the pressure to pressurize is not particularly limited, it is preferably 1.5 to 5 MPa, and particularly preferably 2 to 4 MPa. Moreover, you may perform post-curing at the temperature of 150-300 degreeC with a high-temperature soot as needed.

Another method for producing the metal-clad laminate of the present invention is a method for producing a metal-clad laminate using the metal foil with an insulating resin layer shown in FIG. First, a metal foil 10 with an insulating resin layer in which a uniform insulating resin layer 12 is coated on a metal foil 11 with a coater is prepared, and the metal foils 10 and 10 with an insulating resin layer are provided on both sides of a substrate 20 such as glass fiber. A prepreg 41 with a metal foil is obtained by a method of laminating and impregnating with an insulating resin layer inside (FIG. 2 (a)) and heating in a vacuum at 60 to 130 ° C. and a pressure of 0.1 to 5 MPa (FIG. 2). (B)). Next, the metal-clad laminate 51 can be obtained by directly heat-pressing the prepreg 41 with metal foil (FIG. 2C).
Furthermore, as another method for producing the metal-clad laminate of the present invention, a method for producing a metal-clad laminate using the polymer film sheet with an insulating resin layer shown in FIG. First, a polymer film sheet 30 with an insulating resin layer obtained by coating a uniform insulating resin layer 32 on the polymer film sheet 31 with a coater, and the polymer film sheet 30 with an insulating resin layer on both sides of the substrate 2; 30 with an insulating resin layer inside (FIG. 3 (a)), and a prepreg 42 with a polymer film sheet is obtained by laminating and impregnating in a vacuum at 60 to 130 ° C. and under a pressure of 0.1 to 5 MPa. Can be obtained (FIG. 3B). Next, after peeling the polymer film sheet 31 on at least one side of the prepreg 42 with the polymer film sheet (FIG. 3C), the metal foil 11 is arranged on the surface from which the polymer film sheet 31 is peeled (FIG. 3D). )), A metal-clad laminate 52 can be obtained by heating and pressing (FIG. 3E). Furthermore, when peeling a double-sided polymer film sheet, two or more sheets can be laminated | stacked like the above-mentioned prepreg. When two or more prepregs are laminated, a metal-clad laminate can be obtained by placing a metal foil or a polymer film sheet on the outermost upper and lower surfaces or one surface of the laminated prepregs and heating and pressing. Although the temperature is not particularly limited as the conditions for the heat and pressure molding, 120 to 220 ° C is preferable, and 150 to 200 ° C is particularly preferable. Although the pressure to pressurize is not particularly limited, 0.1 to 5 MPa is preferable, and 0.5 to 3 MPa is particularly preferable. In the present invention, since the prepreg is prepared with a base material, the surface smoothness of the prepreg is high and low-pressure molding is possible. Moreover, you may perform post-curing at the temperature of 150-300 degreeC with a high temperature tank etc. as needed.

As another method for producing the laminate of the present invention, a method using a long base material and a long metal foil as described in JP-A-8-150683 can also be applied (JP-A-8 No. 8). -150683, paragraphs 0005 and 0006, FIG. 1). In the case of this method, two are prepared: one obtained by winding a long base material in a roll form and one obtained by winding a long metal foil in a roll form. Then, the two metal foils are separately fed from the roll, and the resin composition of the present invention is applied to each to form an insulating resin layer. When the resin composition is diluted with a solvent and used, it is dried after coating. Subsequently, the insulating resin layer sides of the two metal foils are made to face each other, and one or two or more base materials are sent out from the rolls facing each other, and laminated and bonded with a press roller. Next, the insulating resin layer is made into a semi-cured state by continuously heating and pressing, and after cooling, it is wound up with a roll or cut into a predetermined length. According to this method, since the lamination is continuously performed while the long base material and the metal foil are transferred onto the line, a long semi-cured laminate is obtained during the production. A metal-clad laminate is obtained by heating and pressing the cut semi-cured laminate with a press.
A film may be used instead of the metal foil.

(Printed wiring board)
Next, the printed wiring board of the present invention will be described.
The printed wiring board of the present invention uses the above-described laminated board as an inner layer circuit board.
Moreover, the printed wiring board of this invention uses said prepreg for an insulating layer on an inner layer circuit.

In the present invention, a printed wiring board is a circuit in which a circuit is formed of a conductive material such as a metal foil on an insulating layer, a single-sided printed wiring board (single-layer board), a double-sided printed wiring board (double-layer board), and a multilayer. Any of printed wiring boards (multilayer boards) may be used. A multilayer printed wiring board is a printed wiring board that is laminated in three or more layers by a plated through hole method, a build-up method, or the like, and can be obtained by heating and press-molding an insulating layer on an inner circuit board. .
As the inner layer circuit board, for example, a predetermined conductor circuit formed by etching or the like on the metal layer of the laminate having the metal foil of the present invention, and the conductor circuit portion blackened can be suitably used.
As the insulating layer, a prepreg of the present invention or a resin film made of the resin composition of the present invention can be used. In addition, when using the resin film which consists of the said prepreg or the said resin composition as the said insulating layer, the said inner layer circuit board does not need to consist of a laminated board of this invention.

Hereinafter, as a representative example of the printed wiring board of the present invention, a multilayer printed wiring board in which the laminated board of the present invention is used as an inner circuit board and the prepreg of the present invention is used as an insulating layer will be described.
A circuit is formed on one side or both sides of the laminate to produce an inner layer circuit board. In some cases, through holes can be formed by drilling or laser processing, and electrical connection on both sides can be achieved by plating or the like. The insulating layer is formed by superposing the prepreg on the inner layer circuit board and forming it by heating and pressing. Similarly, a multilayer printed wiring board can be obtained by alternately and repeatedly forming conductive circuit layers and insulating layers formed by etching or the like.

Specifically, the prepreg and the inner layer circuit board are combined and subjected to vacuum heating and pressing using a vacuum pressurizing laminator device or the like, and then the insulating layer is heated and cured using a hot air drying device or the like. Although it does not specifically limit as conditions to heat-press form here, If an example is given, it can implement at the temperature of 60-160 degreeC, and the pressure of 0.2-3 MPa. Moreover, it is although it does not specifically limit as conditions to carry out heat hardening, If an example is given, it can implement in temperature 140-240 degreeC and time 30-120 minutes.

In the next step, laser is irradiated to form an opening in the insulating layer, but it is necessary to peel off the substrate before that. There is no particular problem in peeling the base material either after the insulating layer is formed, before heat curing, or after heat curing.

  Next, the insulating layer is irradiated with laser to form an opening. As the laser, an excimer laser, a UV laser, a carbon dioxide gas laser, or the like can be used.

It is preferable to perform a treatment for removing resin residues (smear) after laser irradiation with an oxidizing agent such as permanganate or dichromate, that is, desmear treatment. If the desmear treatment is inadequate and the desmear resistance is not sufficiently secured, even if metal plating is applied to the opening, sufficient conductivity is ensured between the upper metal wiring and the lower metal wiring due to smear. There is a risk of disappearing. Further, the surface of the smooth insulating layer can be simultaneously roughened, and the adhesion of the conductive wiring circuit formed by subsequent metal plating can be improved.

  Next, an outer layer circuit is formed. The outer layer circuit is formed by connecting the insulating resin layers by metal plating and forming an outer layer circuit pattern by etching.

Further, an insulating layer may be stacked and a circuit may be formed in the same manner as described above. However, in a multilayer printed wiring board, a solder resist is formed on the outermost layer after the circuit is formed. The method of forming the solder resist is not particularly limited. For example, a method of laminating (laminating) a dry film type solder resist and forming it by exposure and development, or a method of printing a liquid resist by exposure and development It is done by the method to do. In addition, when using the obtained multilayer printed wiring board for a semiconductor device, the electrode part for a connection is provided in order to mount a semiconductor element. The connection electrode portion can be appropriately coated with a metal film such as gold plating, nickel plating, or solder plating.

(Semiconductor device)
Next, the semiconductor device of the present invention will be described.
A semiconductor element having solder bumps is mounted on the printed wiring board obtained above, and connection to the printed wiring board is attempted through the solder bump. A liquid sealing resin is filled between the printed wiring board and the semiconductor element to form a semiconductor device. The solder bump is preferably made of an alloy made of tin, lead, silver, copper, bismuth or the like.

The connection method between the semiconductor element and the printed wiring board is to use a flip chip bonder or the like to align the connection electrode part on the substrate and the solder bump of the semiconductor element, and then to an IR reflow device, a heat plate, etc. The solder bumps are heated to a melting point or higher by using a heating device, and the printed wiring board and the solder bumps are connected by fusion bonding. In order to improve connection reliability, a metal layer having a relatively low melting point, such as solder paste, may be formed in advance on the connection electrode portion on the printed wiring board. Prior to this joining step, the connection reliability can be improved by applying a flux to the surface layer of the connection electrode portion on the solder bump and / or printed wiring board.

The connection reliability can also be improved by applying flux to.
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

Example 1
(1) Preparation of resin varnish Naphthalene type tetrafunctional epoxy resin (product number HP-4700, manufactured by DIC, epoxy equivalent 165) as epoxy resin is 17.5% by weight, and biphenylalkylene type novolak resin (product number MEH-) is used as a phenol curing agent. 7851-3H, Meiwa Kasei Co., Ltd., hydroxyl equivalent 230) 17.3% by weight, imidazole (product number 2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) 0.1% by weight as a curing accelerator, boehmite (1st filler) Kawai Lime Co., Ltd., product number BMT-3L, average particle size 2.9 μm, 1% pyrolysis temperature 420 ° C. 61.4% by weight, spherical nano silica (product number NSS-5N, manufactured by Tokuyama Co., Ltd.), Average particle size 70nm, vinylsilane treated product) 3.5wt% and epoxy silane (Part No. A-187, GE East) as coupling agent Manufactured by Silicone Co., Ltd.) 0.2 wt%, it was dissolved and mixed in methyl isobutyl ketone. Subsequently, it stirred using the high-speed stirring apparatus and prepared the resin varnish.

(2) Preparation of prepreg The resin varnish was impregnated into a glass woven fabric (thickness 94 μm, Nittobo E glass woven fabric, WEA-2116), dried in a heating furnace at 150 ° C. for 2 minutes, and varnish in the prepreg A prepreg having a solid content of about 50% by weight was obtained.

(3) Production of Laminate 4 layers of the above prepregs, 12 μm copper foil (3EC-VLP foil manufactured by Mitsui Mining & Smelting Co., Ltd.) are layered on both sides, and heated and pressure-molded at a pressure of 3 MPa and a temperature of 220 ° C. for 2 hours. A laminate having copper foil on both sides having a thickness of 0.40 mm was obtained.

(4) Manufacture of printed wiring board Using a laminated board having copper foil on both sides, after drilling with a drilling machine, conducting conduction between upper and lower copper foils by electroless plating and etching the copper foils on both sides Thus, inner layer circuits were formed on both sides. (L (conductor circuit width) / S (conductor circuit width) = 120/180 μm, clearance holes 1 mmφ, 3 mmφ, slit 2 mm)
Next, the inner layer circuit was sprayed with a chemical solution mainly composed of hydrogen peroxide and sulfuric acid (Tech SO-G manufactured by Asahi Denka Kogyo Co., Ltd.) to form irregularities by roughening treatment.

  Next, a commercially available resin film (also referred to as a build-up material) (Ajinomoto Fine Techno Co., ABF GX-13, thickness 40 μm) is laminated on the inner circuit using a vacuum laminator, temperature 170 ° C., time 60 minutes. Heat-cured to obtain a laminate having an insulating layer.

  Thereafter, an opening portion (blind via hole) having a diameter of 60 μm was formed in the insulating layer of the laminate obtained above using a carbonic acid laser device, and a swelling liquid (Swelling Dip Securigant manufactured by Atotech Japan Co., Ltd.) at 70 ° C. P) was immersed for 5 minutes, further immersed in an aqueous solution of potassium permanganate at 80 ° C. (manufactured by Atotech Japan Co., Ltd., Concentrate Compact CP) for 15 minutes, and then neutralized and roughened. Next, after passing through degreasing, catalyst application, and activation steps, an electroless copper plating film was formed with a power supply layer of about 0.5 μm. Next, a 25 μm thick UV-sensitive dry film (AQ-2558 manufactured by Asahi Kasei Co., Ltd.) is bonded to the surface of the power supply layer with a hot roll laminator, and a chromium having a pattern with a minimum line width / line spacing of 20/20 μm is drawn. Using a vapor deposition mask (manufactured by Towa Process Co., Ltd.), the position was adjusted, exposure was performed with an exposure apparatus (UX-1100SM-AJN01 manufactured by USHIO INC.), And development was performed with a sodium carbonate aqueous solution to form a plating resist.

  Next, electrolytic copper plating (81-HL manufactured by Okuno Pharmaceutical Co., Ltd.) was performed at 3 A / dm 2 for 30 minutes using the power feeding layer as an electrode to form a copper wiring having a thickness of about 25 μm. Here, the plating resist was peeled off using a two-stage peeling machine. Each chemical solution is mainly composed of monoethanolamine solution (R-100 manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the first stage alkaline aqueous solution layer, and potassium permanganate and sodium hydroxide as the main ingredients in the second stage oxidizing resin etchant. An aqueous solution of acidic amine (Mc. Dicer 9279, manufactured by Nihon McDermid Co., Ltd.) was used for neutralization.

  Then, the power feeding layer was immersed in an ammonium persulfate aqueous solution (AD-485 manufactured by Meltex Co., Ltd.) to remove it by etching and ensure insulation between the wirings. Next, the insulating layer was finally cured at a temperature of 200 ° C. for 60 minutes, and finally a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) was formed on the circuit surface to obtain a printed wiring board.

(5) Manufacture of Semiconductor Device The multilayer printed wiring board was used by cutting the connection electrode portion subjected to nickel gold plating corresponding to the solder bump arrangement of the semiconductor element into a size of 50 mm × 50 mm. . A semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm) has a solder bump formed of a eutectic of Sn / Pb composition, and a circuit protective film of the semiconductor element is a positive photosensitive resin (Sumitomo Bakelite). What was formed by company CRC-8300) was used. In assembling the semiconductor device, first, a flux material was uniformly applied to the solder bumps by a transfer method, and then mounted on a multilayer printed wiring board by thermocompression bonding using a flip chip bonder device. Next, after solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The curing condition of the liquid sealing resin was a temperature of 150 ° C. and 120 minutes.

(Examples 2 to 12 and Comparative Example 1)
Examples 2 to 12 and Comparative Example 1 were resin varnishes, prepregs, laminates, multilayer printed wiring boards, as in Example 1 except that resin varnishes were prepared according to the recipes shown in Table 1 and Table 2. A semiconductor device was manufactured.
The raw materials used are shown below.
(1) Cyanate resin / Novolac type cyanate resin: Lonza Japan Co., Ltd. “Primaset PT-30”, cyanate equivalent 124
(2) Epoxy resin / naphthalene type tetrafunctional epoxy resin: manufactured by DIC, “HP-4700”, epoxy equivalent of 165 g / eq
(3) Epoxy resin / biphenyl dimethylene type epoxy resin: Nippon Kayaku Co., Ltd. “NC-3000H”, epoxy equivalent 275
(4) Phenol curing agent / biphenylalkylene type novolak resin: “MEH-7851-3H” manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent 230
(5) Curing accelerator / imidazole: “2E4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.
(6) First filler / boehmite; Kawai Lime Co., Ltd. “BMT-3L”, average particle 2.9 μm
(7) 1st filler / heat-resistant aluminum hydroxide; manufactured by Kawai Lime Co., Ltd. “AHL-F”, average particle 3 μm
(8) First filler / talc; “LMS-200” manufactured by Fuji Talc, average particle size 5.0 μm
(9) First filler / spherical silica; manufactured by Admatechs Co., Ltd. “SO-25R”, average particle size 0.5 μm
(10) First filler / spherical silica; “SO-31R” manufactured by Admatechs, average particle diameter of 1.0 μm
(11) First filler / silicone powder; “KMP-605” manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 2 μm
(12) First filler / silicone powder; “KMP-600” manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 5 μm
(13) Second filler / spherical silica; “NSS-5N” manufactured by Tokuyama Corporation, average particle 70 nm, vinylsilane treated product (14) Second filler / spherical silica; “NSS-5N” manufactured by Tokuyama Corporation , Average particle 70 nm, epoxy silane-treated product (15) second filler / spherical silica; manufactured by Admatex, “Admanano”, average particle 50 nm, vinyl silane-treated product (16) second filler / spherical silica; "Admanano", average particle size 25nm, vinyl silane-treated product (17) coupling agent / epoxysilane; GE Toshiba Silicone "A-187"

Example and comparative resin varnish recipes, and resin varnishes prepared according to the recipe, prepregs produced using the resin varnishes, metal-clad laminates, printed wiring boards, semiconductor devices, etc. It shows in Table 1 and Table 2.

The contents of the evaluation items described in Tables 1 and 2 will be described below. Moreover, the cross-sectional FE-SEM photograph of the laminated board obtained in Example 1 is shown in FIG. Moreover, the cross-sectional FE-SEM photograph of the laminated board obtained in Example 9 is shown in FIG.

(1) Thixotropic E-type viscometer (conical plate type rotational viscometer) was used for thixotropic measurement. In accordance with JIS K7117-2, 1 ml of resin varnish was placed in the center of the measuring cup, and measurement was performed at 5 rpm / 50 rpm. As for thixotropy, a viscosity ratio of 5 rpm / 50 rpm was evaluated.

(2) Dispersibility (grain gauge)
The dispersibility was evaluated using a particle gauge (Kortec Co., Ltd., KP-2020-2 manufactured by Elcometer). In particular. After placing the grain gauge horizontally and pouring the resin varnish into the deeper groove, the scraper was pulled to zero depth at a uniform speed in the direction perpendicular to the groove in 1-2 seconds. Observation was performed within 3 seconds at a right angle to the groove direction and at an angle of 20 to 30 °, and the points at which significant spots appeared were measured. The symbols shown in Tables 1 and 2 are as follows.
A: There was no aggregate of 20 μm or more.
Δ: There was an aggregate of 20 μm or more and less than 50 μm.
X: There was an aggregate of 50 μm or more.

(3) Dispersibility (particle size distribution)
For the dispersibility, a laser diffraction particle size distribution analyzer (manufactured by HORIBA, LB-550) was used. About 100 μl of resin varnish was put into an evaluation cell filled with a ketone organic solvent, and the value after stabilization was read. The particle size distribution of the filler was created on a volume basis, and the median diameter was evaluated as the average particle diameter. The symbols shown in Tables 1 and 2 are as follows.
A: There was no aggregate of 20 μm or more.
Δ: There was an aggregate of 20 μm or more and less than 50 μm.
X: There was an aggregate of 50 μm or more.

(4) Impregnation Impregnation of the prepreg was determined by curing the prepregs obtained in the above examples and comparative examples at a temperature of 180 ° C. for 1 hour in a hot air oven, and measuring 35 cross sections at 15 mm intervals in the width direction of 530 mm. Observed and evaluated. The symbols shown in Tables 1 and 2 are as follows.
A: No non-impregnated void was observed at all points.
○: Unimpregnated voids were observed at locations of 1 and less than 5.
Δ: Unimpregnated voids were observed at 5 or more and less than 30.
X: Unimpregnated voids were observed at 30 or more points.

(5) Formability The moldability was evaluated using the laminates (510 mm × 510 mm square) obtained in the examples and comparative examples. The laminate was divided into about 250 mm × 250 mm squares by a shear and divided into 4 parts, and then the copper foil was removed by etching. The surface was visually observed and evaluated.
The symbols shown in Tables 1 and 2 are as follows.
A: There were no voids.
○: There was a void of less than 10 μm only at the 10 mm end.
Δ: There was a void exceeding 10 μm.
X: There were many voids.

(6) Heat resistance Heat resistance was evaluated by 260 ° C multi-reflow.
The semiconductor devices obtained in the examples and comparative examples were passed through a reflow 260 ° C. reflow furnace in accordance with IPC / JEDEC J-STD-20. Layer peeling, cracking, peeling of the back surface of the semiconductor element, chipping of solder bumps, and poor copper passage on a hot plate at 125 ° C. were evaluated. The symbols shown in Tables 1 and 2 are as follows.
(Double-circle): There was no peeling of an insulating layer and copper penetration defect 40 times or more.
○: There were no peeling of the insulating layer or copper penetration failure at 20 times or more and less than 40 times.
(Triangle | delta): The peeling of the insulating layer or the copper penetration defect generate | occur | produced 10 times or more and less than 20 times.
X: Less than 10 times Insulation layer peeling or copper penetration failure occurred.

(7) Coefficient of thermal expansion The copper foil of the obtained laminate was removed by etching, a test piece having a thickness of 100 μm, 4 mm × 40 mm was cut out, and 25 ° C. to 150 ° C. under a tensile condition of 5 ° C./min using TMA. The linear thermal expansion coefficient in the range of ° C. was measured.

(8) Plating penetration after drilling Plating penetration after drilling is performed by stacking two of the above-mentioned laminate plates having a thickness of 0.4 mm and drilling 3000 times with a drill having a diameter of 0.2 mm. A through hole having a thickness of 25 μm was formed on the through hole of the laminated plate to form a through hole, and the penetration depth of the plating solution from the inner wall of the through hole into the laminated plate was evaluated. In addition, the union seal product number KMC L253 was used for the drill, the rotation speed of the drill at the time of drilling was 250 krpm / min, and the tip load of the drill was 9.6 μm / rev. Each code is as follows.
A: The penetration depth was less than 20 μm.
○: The penetration depth was 20 μm or more and less than 50 μm.
(Triangle | delta): The penetration depth was 50 micrometers or more and less than 100 micrometers.
X: The penetration depth was 100 μm or more.

(9) Through-hole insulation reliability The through-hole insulation reliability was evaluated by continuous measurement under conditions of 0.2 mm between through-hole walls, applied voltage of 20 V, temperature of 130 ° C. and humidity of 85%. In addition, the sample which carried out the through hole process, the through hole plating, and the circuit process on the conditions similar to the above-mentioned drill process was used. The process was terminated when the insulation resistance value was less than 10 ⁸ Ω.
Each code is as follows.
A: It was 500 hours or more until the insulation resistance value was less than 10 ⁸ Ω.
○: It was 200 hours or more and less than 500 hours until the insulation resistance value was less than 10 ⁸ Ω.
Δ: It was 100 hours or more and less than 200 hours until the insulation resistance value was less than 10 ⁸ Ω.
X: It was less than 100 hours until the insulation resistance value was less than 10 ⁸ Ω.

(10) Warpage of printed wiring board portion The amount of warpage of the printed wiring board portion of the semiconductor device manufactured in the above example is set so that the semiconductor element surface is in contact with the lower surface in the chamber that can be heated and cooled. Changes in the amount of warpage at a 48 mm × 48 mm portion of the printed wiring board portion (printed wiring board portion (size: 50 mm × 50 mm) on the back surface of the semiconductor device) were measured under an atmosphere of ° C. Tables 1 and 2 Each code is as follows.
(Double-circle): The change of curvature amount was less than 200 micrometers.
A: The amount of warpage was 200 μm or more and less than 300 μm.
(Triangle | delta): The change of the curvature amount was 300 micrometers or more and less than 350 micrometers.
X: The change of the curvature amount was 350 μm or more.

(11) Flame retardancy In the production of the laminate, 4 sheets of the prepreg are stacked, 12 μm copper foil is stacked on both sides thereof, and pressure-molded for 2 hours at a pressure of 3 MPa and a temperature of 200 ° C. A 4 mm double-sided copper-clad laminate was obtained. The copper foil of the laminated board obtained above was etched, and a test piece having a thickness of 0.4 mm was measured by a vertical method according to the UL-94 standard.

As is clear from Table 1, the resin varnishes obtained in Examples 1 to 12 were excellent in fluidity and suppressed the occurrence of warpage when formed into a laminate. Moreover, it can confirm that the spherical filler (silica) which is a 2nd filler has adsorb | sucked to the outer periphery of a 1st filler (boehmite in FIG. 1) from FIG. Also in FIG. 2, it can be confirmed that the spherical filler (silica) as the second filler is adsorbed on the outer periphery of the silicone as the first filler.
The resin varnishes obtained in Examples 1 to 12 were excellent in thixotropy and filler sedimentation. Therefore, it is excellent in mass production stability and impregnation with a prepreg. Moreover, since it is excellent also in resin flowability, the moldability at the time of making a laminated board was favorable even if the inorganic filler was highly filled. Moreover, it was excellent in heat resistance, a low linear expansion coefficient, and drill workability when it was used as a printed wiring board. Therefore, the through-hole insulation reliability is excellent, and the PKG warp amount is small and excellent because of the low linear expansion coefficient.
In comparison, Comparative Example 1 is presumed to have a high thixotropy, inferior impregnation with prepreg, and resin flowability, resulting in inferior moldability, heat resistance, and through-hole insulation reliability.

When the resin composition of the present invention is used as a prepreg, the prepreg can maintain the conventional low linear thermal expansion coefficient, high glass transition temperature, high elastic modulus, and flame retardancy.
Furthermore, the multilayer printed wiring board using the prepreg has excellent solder heat resistance after moisture absorption treatment, excellent through-hole workability and insulation reliability in the manufacturing process of the multilayer printed wiring board, and further the multilayer printed circuit board. A semiconductor device using a rewiring board can show good results even in a reflow test at a high temperature of 280 ° C.

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Impregnation tank 3 ... Resin varnish 4 ... Dip roll 5 ... Squeeze roll 6 ... Dryer 7 ... Prepreg 8 ... Upper roll 10 ... Metal foil with an insulating resin layer 11 ... Metal foil 12 ... Insulating resin layer 20 ... Substrate 30 ... polymer film sheet with insulating resin layer 31 ... polymer film sheet 32 ... insulating resin layer 40 ... prepreg 41 ... prepreg with metal foil 42 ... prepreg with polymer film sheet 51 ... metal-clad laminate 52 ... metal-clad laminate Laminated board

Claims (10)

(A) A resin composition containing a filler formed by adhering (B) a second filler having a particle diameter smaller than that of the first filler (A) on the outer periphery of the first filler is used. A prepreg. 2. The prepreg according to claim 1, wherein an average particle diameter of the (A) first filler is 0.2 μm to 10 μm. The prepreg according to claim 1 or 2, wherein the (B) second filler is inorganic filler fine particles having an average particle size of 10 to 100 nm. The prepreg according to any one of claims 1 to 3, wherein the (B) second filler is spherical silica. The (A) first filler is a group consisting of oxide, carbonate, hydroxide, silicate, sulfate, sulfite, nitride, borate, titanate, silicone, and rubber particles. The prepreg according to any one of claims 1 to 4, which is at least one selected from the group consisting of: The prepreg according to any one of claims 1 to 5, wherein the (A) first filler is boehmite or silicone. The prepreg according to any one of claims 1 to 6, wherein the (B) second filler is surface-treated with a coupling agent. A laminate comprising the prepreg according to any one of claims 1 to 7. A printed wiring board using the laminated board according to claim 8. A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to claim 9.