JP5594128B2 - Resin composition for printed wiring board, prepreg, laminate, resin sheet, printed wiring board, and semiconductor device - Google Patents

Description

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

In recent years, with the demand for higher functionality of electronic devices, etc., high-density integration of electronic components, and further high-density mounting, etc. are progressing. Compared to the prior art, miniaturization, thinning, high density, and multilayering are progressing.
Therefore, the warpage of the substrate such as a printed wiring board greatly affects the reliability.
Therefore, studies have been made to reduce the linear expansion coefficient of the cured product of the resin composition for printed wiring boards and reduce the warpage of the printed wiring board (for example, Patent Document 1).

JP 2009-74036 A

However, conventionally used resin compositions using inorganic fillers such as aluminum hydroxide and silica cannot achieve a lower linear expansion coefficient than a semiconductor element made of silicon, so that the printed wiring board becomes thinner. In such a case, the warpage becomes large, and the semiconductor device using a thin printed wiring board has a problem that reliability such as connection reliability is lowered due to the influence of the warp.

The present invention has been accomplished in view of the above circumstances, and an object of the present invention is to provide a resin composition for a printed wiring board that is excellent in low thermal expansion and can reduce warping when used in a printed wiring board. To provide things.

The above object is achieved by the present invention described in the following items [1] to [9].
[1] A resin composition for printed wiring boards, comprising a zirconium compound.
[2] The printed wiring board resin composition according to [1], wherein the zirconium compound is at least one selected from the group consisting of a zirconium phosphate compound or a zirconium tungstate compound.
[3] The resin composition for printed wiring boards according to the above [1] or [2], wherein the resin composition for printed wiring boards further contains an inorganic filler having an average particle diameter of 5 to 100 nm.
[4] A prepreg obtained by impregnating a substrate with the resin composition for printed wiring boards according to any one of [1] to [3].
[5] A laminate having a metal foil on at least one side of the prepreg according to the above [4] or a laminate in which two or more prepregs are laminated.
[6] A resin sheet obtained by forming a resin layer made of the resin composition for printed wiring boards according to any one of [1] to [3] above on a film or a metal foil.
[7] A printed wiring board comprising the laminated board according to the above [6] for an inner layer circuit board.
[8] A printed wiring board obtained by laminating the prepreg according to the above [4] and / or the resin sheet according to the above [7] on the circuit of the inner layer circuit board.
[9] A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to the above [7] or [8].

According to the present invention, a printed wiring board having a low coefficient of thermal expansion can be obtained by using a resin composition for printed wiring boards containing a zirconium compound.

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 laminated board of this invention. It is the schematic which shows another example of the manufacturing method of the laminated board of this invention.

(Resin composition for printed wiring boards)
First, the resin composition for printed wiring boards will be described.
The resin composition for printed wiring boards of the present invention is characterized by containing a zirconium compound.
As a result, the linear expansion coefficient of the cured product of the resin composition for printed wiring boards can be lowered, and becomes a value close to the linear expansion coefficient of the semiconductor element. Therefore, the printed wiring board using the resin composition for printed wiring boards Reduces warping.
By reducing the warpage, a semiconductor device using the printed wiring board is excellent in reliability such as connection reliability.
Moreover, the laminated board using the resin composition for printed wiring boards containing the said zirconium compound is excellent in drill workability.
Furthermore, the outstanding flame retardance can also be expressed.

Although the said zirconium compound is not specifically limited, For example, zirconium compounds, such as a zirconium phosphate compound and a zirconium phosphate oxide, are mentioned. For example, zirconium phosphate compounds such as zirconium tungstate phosphate, zirconium tungstate, and zirconium phosphate, zirconium phosphate oxides such as zirconium tungstate phosphate, zirconium niobate phosphate, and zirconium tantalate phosphate. it can. Among these, zirconium phosphate (ZP) and zirconium tungstate phosphate (ZWP) are preferable from the viewpoint of low thermal expansion and drill workability.
Moreover, zirconium phosphate (ZP) and zirconium tungstate phosphate (ZWP) are excellent in fluidity.

Although the particle diameter of the zirconium compound is not particularly limited, the average particle diameter is preferably 1 to 10 μm from the viewpoint of drilling workability and impregnation into a fiber base material, and from the viewpoint of insulation reliability, 1 ˜5 μm is preferred.

The content of the zirconium compound is not particularly limited, but is preferably 20 to 70% by weight based on the solid content of the entire resin composition for a printed wiring board, and has excellent insulation reliability (eg, excellent impregnation). ) To 20 to 50% by weight.

The resin composition for printed wiring boards containing a zirconium compound may use other inorganic fillers in addition to the zirconium compound.
Other inorganic fillers are not particularly limited. For example, talc, fired talc, fired clay, unfired clay, mica, silicates such as glass, oxides such as titanium oxide, alumina, silica, and fused silica, carbonic acid Carbonates such as calcium, magnesium carbonate, hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, Borates such as barium metaborate, aluminum borate, calcium borate and sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride, titanates such as strontium titanate and barium titanate Can be mentioned. One of these can be used alone, or two or more can be used in combination.

The average particle diameter of the other inorganic filler is preferably 1 to 10 μm from the viewpoint of drilling workability and impregnation into the fiber substrate, and 1 to 5 μm from the viewpoint of insulation reliability. Is preferred.
When it is desired to fill the base material with as much zirconium compound as possible, it is preferable to include an inorganic filler having an average particle diameter of 5 to 100 nm as the other inorganic filler together with the zirconium compound.
The thermal expansion coefficient of the prepreg obtained by these or a laminated board can be made small.

The content of the inorganic filler having an average particle diameter of 5 to 100 nm is not particularly limited, but is preferably 1 to 20 parts by volume with respect to 100 parts by volume of the zirconium compound.
Thereby, in addition to the impregnation property to a fiber base material, the prepreg and laminated board which are excellent in a moldability can be obtained.

Resin used for the resin composition for printed wiring boards containing a zirconium compound (it may only be called "the resin composition for printed wiring boards" hereafter) is although it does not specifically limit, An epoxy resin, a phenol resin, cyanate resin, A thermosetting resin such as a maleimide resin is preferable from the viewpoint of processability, heat resistance, and the like.
However, even when a thermoplastic resin such as polypropylene, polystyrene, or acrylonitrile butadiene styrene is used, a cured product having a low coefficient of linear expansion can be obtained as in the case of using a thermosetting resin.
When super engineering plastics such as amorphous polyarylate, polysulfone, polyethersulfone, polyphenylenesulfide, polyetheretherketone, polyimide, polyetherimide, fluororesin, liquid crystal polymer, etc. are used, heat resistance is improved with a low coefficient of linear expansion. An excellent cured product can be obtained.

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 resin, naphthalene skeleton modified epoxy resin, methoxynaphthalene modified cresol novolac type epoxy resin, naphthalene type epoxy resin such as methoxynaphthalenedylene methylene type epoxy resin 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 5-30 weight% on the solid content basis of the whole resin composition for printed wiring boards. 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 ⁴ 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 preferably contained in the printed wiring board resin composition from the viewpoint of flame retardancy.
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 cyanate resin is not particularly limited. For example, a novolak type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, a bisphenol type cyanate resin such as tetramethylbisphenol F type cyanate resin, and a naphthol aralkyl type cyanate resin. Can be mentioned.

  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. A naphthol aralkyl type cyanate resin is preferred from the viewpoint of mechanical strength and low water absorption. 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 heat reaction or the like, and is preferably used for adjusting the moldability and fluidity of the resin composition for a printed wiring board. Is.
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. If the content of the cyanate resin is less than the lower limit, the thermal expansibility may increase, and the heat resistance may decrease.If the content exceeds the upper limit, the strength of the prepreg produced using the resin composition for a printed wiring board is increased. May decrease.

The maleimide resin is preferably contained in the printed wiring board resin composition from the viewpoint of improving heat resistance.
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 1-30 weight% on the solid content basis of the resin composition for printed wiring boards, More preferably, it is 5-25 weight%, More preferably 5 to 20% by weight.

  Furthermore, the resin composition for printed wiring boards of the present invention may contain at least one selected from the group consisting of a polyimide resin, a triazine resin, a phenol resin, and a melamine resin.

  A phenolic curing agent can be used for the resin composition for printed wiring boards of the present invention. As the phenolic curing agent, for example, a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a zyloc type phenol resin, a terpene modified phenol resin, a polyvinyl phenol or the like may be used alone or Two or more types can be used in combination.

Although content of the said phenol type hardening | curing agent is not specifically limited, The equivalent ratio (phenolic hydroxyl group equivalent / epoxy group equivalent) with an epoxy resin is less than 1.0 and 0.1 or more are preferable. As a result, there remains no unreacted phenolic curing agent, and the moisture absorption heat resistance is improved. Furthermore, when severe moisture absorption heat resistance is required, the range of 0.2 to 0.5 is particularly preferable. In addition, the phenol resin not only acts as a curing agent, but can promote curing of a cyanate group and an epoxy group.

  The resin composition for a printed wiring board of the present invention can be added with additives other than the above components as necessary within a range that does not impair the characteristics. Components other than the above components include, for example, epoxy silane coupling agents, cationic silane coupling agents, aminosilane coupling agents, titanate coupling agents, coupling agents such as silicone oil type coupling agents, imidazoles, and triphenyl. Examples thereof include curing accelerators such as phosphine and quaternary phosphonium salts, surface conditioners such as acrylic polymers, and colorants such as dyes and pigments.

The resin composition for a printed wiring board of the present invention is used as a varnish after being dissolved in a solvent when preparing a prepreg. The method for preparing the varnish is not particularly limited. For example, a slurry in which a zirconium compound and the inorganic filler are dispersed in a solvent is prepared, and other components are added to the slurry. The method of mixing etc. is mentioned. Nano-sized particles such as fine particles having an average particle diameter of 5 to 100 nm tend to aggregate and often form secondary aggregation when blended with the resin composition for printed wiring boards. By using a material, such secondary aggregation can be prevented, and dispersibility is improved.

  The solvent is not particularly limited, but a solvent that exhibits good solubility in the resin composition for a printed wiring board is preferable, for example, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, dimethylformamide, Examples thereof include dimethylacetamide and N-methylpyrrolidone. In addition, you may use a poor solvent in the range which does not exert a bad influence.

  Although the solid content of the resin composition for printed wiring boards contained in the varnish is not particularly limited, it is preferably 30 to 80% by weight, particularly preferably 40 to 70% by weight. Thereby, the impregnation property to the base material of the resin composition for printed wiring boards can be improved.

(Resin sheet)
Next, the resin sheet will be described.
The resin sheet of the present invention is formed by forming an insulating layer made of the resin composition for printed wiring board on a metal foil or a film.
Here, the method for forming the insulating layer made of the resin composition for a printed wiring board on a metal foil or film is not particularly limited. For example, the resin composition for a printed wiring board is dissolved and dispersed in a solvent or the like. After preparing a resin varnish and applying the resin varnish to the substrate using various coating devices, drying the resin varnish on the substrate with a spray device, drying the resin varnish The method of doing is mentioned.

  The solvent used in the resin varnish desirably exhibits good solubility in the resin component in the resin composition for printed wiring boards, but a poor solvent may be used as long as it does not adversely affect the resin varnish. . Examples of the solvent exhibiting good solubility include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve and carbitol.

  Although it does not specifically limit as solid content in the said resin varnish, 10 to 70 weight% is preferable and 20 to 55 weight% is especially preferable.

  When the resin sheet of the present invention has two or more insulating layers, at least one of them is preferably the resin composition of the present invention. Moreover, it is preferable that the insulating layer which consists of a resin composition for printed wiring boards of this invention forms the insulating layer which consists of a resin composition for printed wiring boards of this invention directly on metal foil or a film. By doing so, the insulating layer made of the resin composition for a printed wiring board of the present invention can exhibit a high plating peel strength with the outer layer circuit conductor during the production of the printed wiring board.

The insulating layer made of the resin composition for a printed wiring board of the present invention preferably has a thickness of 0.5 to 10 μm. By setting the thickness of the insulating layer within the above range, high adhesion with the conductor circuit can be obtained.

  Although the film used for the resin sheet of the present invention is not particularly limited, for example, a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a thermoplastic resin film having heat resistance such as a fluorine resin, or a polyimide resin may be used. it can.

Although the metal foil used for the resin sheet of the present invention is not particularly limited, for example, copper and / or copper-based alloy, aluminum and / or aluminum-based alloy, iron and / or iron-based alloy, silver and / or silver-based alloy, Metal foils such as gold and gold-based alloys, zinc and zinc-based alloys, nickel and nickel-based alloys, tin and tin-based alloys, and the like can be used. In manufacturing the resin sheet of the present invention, the surface roughness (Rz) of the irregularities on the surface of the metal foil on which the insulating layer is laminated is preferably 2 μm or less. By forming an insulating layer made of the resin composition of the present invention on the surface of a metal foil having a surface roughness (Rz) of 2 μm or less, the surface roughness is small and adhesion (plating peel strength) is excellent. Can be.
The surface roughness (Rz) of the metal was measured at 10 points, and the average value was obtained. The surface roughness was measured based on JISB0601.

(Prepreg)
Next, the prepreg will be described.
The prepreg of the present invention is obtained by impregnating a substrate with the resin composition for printed wiring board and drying by heating. In the present invention, by containing a zirconium compound in combination with the epoxy resin composition, a resin composition for a printed wiring board having a low viscosity can be obtained despite containing a large amount of these particles. A prepreg in which the substrate is sufficiently impregnated with the resin composition for wiring boards can be obtained, and the obtained prepreg is excellent in low thermal expansion property, drill workability, and reliability.
Moreover, it is excellent in flame retardancy and desmear resistance.

The base material is not particularly limited, but for example, glass fiber base materials such as glass woven fabric, glass nonwoven fabric, and glass paper, woven fabric made of synthetic fibers such as paper, aramid, polyester, aromatic polyester, fluororesin, and the like Examples include woven fabrics, nonwoven fabrics, mats and the like made of nonwoven fabrics, metal fibers, 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 method for impregnating the substrate with the resin varnish is not particularly limited, and examples thereof include a method of immersing the substrate in the resin varnish, a method of applying with various coaters, and a method of spraying. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the epoxy 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 epoxy resin varnish 3 of the impregnation tank 2 to impregnate the base material 1 with the epoxy resin varnish 3. In that case, the base material 1 is immersed in the epoxy 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 epoxy resin varnish 3 is pulled up in the vertical direction, and a pair of squeeze rolls or comma rolls (5 in FIG. 1 is a squeeze roll) arranged in parallel in the horizontal direction. Through the interval, the application amount of the epoxy resin varnish 3 to the substrate 1 is adjusted. Thereafter, the base material 1 to which the epoxy resin varnish 3 is applied is heated at a predetermined temperature with a dryer 6 to volatilize the solvent in the applied varnish and to semi-cur the epoxy resin composition to prepare the prepreg 7. To manufacture. 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 epoxy resin varnish can obtain the semi-hardened prepreg 7 by making it dry at the temperature of 90-180 degreeC for 1 to 10 minutes of time.

(Laminated board)
Next, a laminated board is demonstrated.
The laminate of the present invention has a metal foil on at least one surface of a resin-impregnated substrate layer formed by impregnating a substrate with the above resin composition for printed wiring board.
The laminate of the present invention can be produced, for example, by attaching a metal foil to at least one surface of the prepreg or a laminate obtained by superposing two or more prepregs.
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 prepreg. 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, 120-250 degreeC is preferable and especially 150-220 degreeC is 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. Moreover, you may postcure at the temperature of 150-300 degreeC with a high temperature tank etc. as needed.

  Another method for producing the laminate of the present invention is a method for producing a laminate using the metal foil with resin shown in FIG. First, a metal foil 10 with resin 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 resin are attached to 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 it 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 laminated plate 51 can be obtained by directly heat-pressing the prepreg 41 with metal foil (FIG. 2C).

Furthermore, as another method for producing the laminate of the present invention, a method for producing a laminate using the polymer film sheet with resin shown in FIG. First, a polymer film sheet 30 with resin in which a uniform insulating resin layer 32 is coated on a polymer film sheet 31 with a coater is prepared, and the polymer film sheets 30 and 30 with resin on both sides of the substrate 2 are insulated with resin. The prepreg 42 with a polymer film sheet can be obtained by a method in which the layers are arranged inside (FIG. 3 (a)) and the laminate is impregnated with heating at a temperature of 60 to 130 ° C. and a pressure of 0.1 to 5 MPa in a vacuum. (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). )), The laminated plate 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 laminated sheet can be obtained by placing 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.
The laminate obtained by such a production method has high thickness accuracy, uniform thickness, and excellent surface smoothness.
In addition, since a laminated board with small molding strain can be obtained, a printed wiring board and a semiconductor device manufactured using the laminated board obtained by the manufacturing method have small warpage and small warpage variation.
Furthermore, a printed wiring board and a semiconductor device can be manufactured with high yield.

Although the temperature is not particularly limited as the conditions for the heat and pressure molding, 120 to 250 ° C is preferable, and 150 to 220 ° 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.
Furthermore, if necessary, post-curing may be performed at a temperature of 150 to 300 ° C. in a high-temperature tank or the like.

Although the laminated board of FIGS. 2-3 is not specifically limited, For example, it manufactures using the apparatus which manufactures the metal foil with resin, and the apparatus which manufactures a laminated board.
In the apparatus for producing the metal foil with resin, the metal foil can be supplied by, for example, using a long sheet product in the form of a roll, and thereby continuously unwinding. A predetermined amount of the liquid resin composition is continuously supplied onto the metal foil by a supply device. Here, as the liquid insulating resin, a coating solution in which the resin composition of the present invention is dissolved and dispersed in a solvent is used. The coating amount of the resin composition can be controlled by the clearance between the comma roll and the backup roll of the comma roll. The metal foil coated with a predetermined amount of the resin composition is transferred to the inside of the horizontal conveyance type hot air drying device, and the organic solvent contained in the liquid insulating resin is substantially removed by drying. Correspondingly, a resin-coated metal foil in which the curing reaction has been advanced halfway can be obtained. The metal foil with resin can be wound as it is, but with a laminating roll, a protective film is superimposed on the side on which the resin layer is formed, and the metal foil with resin laminated with the protective film is wound, Obtained metal foil with resin.

When a laminated board is obtained by such a production method, it is necessary to consider the impregnation property of the resin composition directly into the fiber substrate, not the varnish dissolved and dispersed in the solvent. By using an inorganic filler having an average particle diameter of 5 to 100 nm as another inorganic filler, the impregnation property to the fiber base material is particularly improved. Therefore, the flow of the resin composition in the laminate during the heat and pressure molding Since the non-uniform movement of the molten resin is suppressed, streaky unevenness on the surface of the laminated plate can be prevented and the thickness can be made uniform.

(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 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.
Moreover, the printed wiring board of this invention uses said epoxy resin composition 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 metal layer of the laminate of the present invention in which a predetermined conductor circuit is formed by etching or the like and the conductor circuit portion is blackened can be suitably used.
As the insulating layer, a prepreg of the present invention or a resin film made of the resin composition for a printed wiring board 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 for printed wiring boards as 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.

One of the typical gold plating methods is a nickel-palladium-gold electroless plating method. In this method, a pretreatment is performed on the connecting electrode portion by an appropriate method such as a cleaner, and then a palladium catalyst is applied. Thereafter, an electroless nickel plating treatment, an electroless palladium plating treatment, and an electroless gold plating treatment are further performed. Are performed sequentially.
The ENEPIG method is a method in which a substitution gold plating process is performed in the electroless gold plating process stage of the nickel-palladium-gold electroless plating process. By providing the electroless palladium plating film between the electroless nickel plating film as the base plating and the electroless gold plating film, the diffusion preventing property and the corrosion resistance of the conductor material in the connection electrode portion are improved. Since it is possible to prevent the diffusion of the underlying nickel plating film, the reliability of the Au-Au joint is improved and the nickel oxidation due to gold can be prevented. improves. In the ENEPIG method, it is usually necessary to perform surface treatment before performing electroless palladium plating to prevent the occurrence of poor conduction in the plating process. If the poor conduction is severe, a short circuit occurs between adjacent terminals. Cause. On the other hand, the printed wiring board of the present invention does not have the above-described conduction failure without performing surface treatment, and can be easily plated.

(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.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

The raw materials used in Examples and Comparative Examples are as follows.
(1) Epoxy resin / biphenyl type epoxy resin: Nippon Kayaku Co., Ltd. NC-3000, epoxy equivalent 275
(2) Phenolic curing agent / biphenyl type novolak resin: Nippon Kayaku Co., Ltd. GPH-103, hydroxyl group equivalent 231
(3) Cyanate resin / Novolac type cyanate resin: Lonza Japan Co., Ltd. Primaset PT-30, cyanate equivalent 124
(4) Polyimide resin: V-8003 manufactured by DIC
(5) Zirconium particles A: Zirconium tungstate phosphate manufactured by Kyoritsu Materials Co., Ltd., average particle diameter of 3 to 6 μm
(6) Zirconium particles B: Zirconium phosphate manufactured by Kyoritsu Materials Co., Ltd., average particle diameter of 3 to 6 μm
(7) Spherical silica: Admatech's SO-32R, average particle size 1.0 μm
(8) Aluminum hydroxide / Gibsite: BE-033 manufactured by Nippon Light Metal Co., Ltd. Average particle size 2.2 μm BET specific surface area 3.6 m ² / g
(9) Imidazole: 2E4MZ manufactured by Shikoku Chemicals

Example 1
(1) Preparation of resin composition-containing varnish for printed wiring board 6.5 parts by weight of epoxy resin (NC-3000 manufactured by Nippon Kayaku Co., Ltd.), 6.5 weight of phenolic curing agent (GPH-103 manufactured by Nippon Kayaku Co., Ltd.) Parts, zirconium particles (Kyoritsu Material Co., Ltd. zirconium phosphate tungstate, average particle size 3 to 6 um) 86.9 parts by weight, imidazole (Shikoku Kasei 2E4MZ) 0.1 parts by weight dissolved in γ-butyrolactone. The mixture was mixed and stirred using a high-speed stirring device to obtain a varnish having a resin composition for a printed wiring board of 70% by weight based on the solid content.

(2) Preparation of prepreg The varnish was impregnated into a glass woven fabric (thickness 94 μm, E glass woven fabric manufactured by Nittobo Co., Ltd., WEA-2116), dried in a heating furnace at 180 ° C. for 2 minutes, and epoxy in the prepreg A prepreg having a resin composition based on solid content of about 49% by weight was obtained.

(3) Fabrication of laminated plate Four prepregs are stacked, and 12 μm copper foil (3EC-VLP foil, manufactured by Mitsui Mining & Smelting Co., Ltd.) is stacked on both sides of the prepreg, followed by heat pressing at 3 MPa and 220 ° C. for 2 hours. And the laminated board which has a copper foil on both surfaces with a thickness of 0.4 mm of an insulating resin layer was obtained.

(4) Preparation of resin sheet The varnish obtained in the example was cast on a 38 μm polyethylene terephthalate substrate (hereinafter referred to as PET substrate), and the solvent was evaporated and dried at a temperature of 140 ° C. for 10 minutes. The thickness of the resin layer was set to 30 μm.

(5) Manufacture of printed wiring board After opening the laminated board having copper foils on both sides with a drilling machine, the upper and lower copper foils are connected by electroless plating, and the inner layer circuit is etched by etching the copper foils on both sides. L (conductor circuit width (μm)) / S (width between conductor circuits (μm)) = 50/50.
Next, the chemical | medical solution (Asahi Denka Kogyo Co., Ltd. make, Tech SO-G) which has hydrogen peroxide water and a sulfuric acid as a main component was spray-sprayed to the inner layer circuit, and the unevenness | corrugation formation by a roughening process was performed.

Next, the prepreg was laminated on the inner layer circuit using a vacuum laminating apparatus, and was cured by heating at a temperature of 170 ° C. for 60 minutes to obtain a laminated body.
Thereafter, an opening (blind via hole) having a diameter of 60 μm is formed on the prepreg of the obtained laminate using a carbonic acid laser device (manufactured by Hitachi Via Mechanics Co., Ltd .: LG-2G212), and a swelling liquid at 70 ° C. (Atotech Japan Co., Swelling Dip Securigant P) for 5 minutes, and further immersed in an aqueous solution of potassium permanganate at 80 ° C. (Atotech Japan Co., Concentrate Compact CP) for 15 minutes, neutralized and roughened The treatment was performed.
Next, after the steps of degreasing, applying a catalyst, and activating, a power supply layer of about 0.5 μm was formed by an electroless copper plating film. Chromium vapor deposition in which a 25 μm thick UV photosensitive dry film (AQ-2558, manufactured by Asahi Kasei Co., Ltd.) is pasted on the surface of the power feeding layer with a hot roll laminator, and a pattern with a minimum line width / line spacing of 20/20 μm is drawn. The position was adjusted using a mask (manufactured by Towa Process Co., Ltd.), exposure was performed with an exposure apparatus (UX-1100SM-AJN01 manufactured by Ushio Electric Co., Ltd.), and development was performed with an aqueous sodium carbonate 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 Mcder Mid 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 the 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 (manufactured by Taiyo Ink Co., PSR4000 / AUS308) was formed on the circuit surface to obtain a printed wiring board.
In addition, the ENEPIG process was performed to the connection electrode part of the said printed wiring board corresponded to the solder bump arrangement | sequence of a semiconductor element.
ENEPIG treatment includes [1] cleaner treatment, [2] soft etching treatment, [3] pickling treatment, [4] pre-dip treatment, [5] palladium catalyst application, [6] electroless nickel plating treatment, [7] The electroless palladium plating treatment and [8] electroless gold plating treatment were performed.

(6) Manufacture of Semiconductor Device A printed wiring board subjected to ENEPIG treatment was cut into a size of 50 mm × 50 mm and used. 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 the company make, 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 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 effect condition of the liquid sealing resin was a temperature of 150 ° C. for 120 minutes.

<Examples 2-4 and Comparative Examples 1-2>
A prepreg, a laminate, a printed wiring board, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1 with the blending amounts shown in Table 1.
The following evaluation items were evaluated for the prepreg, laminate, multilayer printed wiring board, and semiconductor device obtained above. Table 1 shows the composition of the resin compositions of Examples and Comparative Examples, each physical property value, and evaluation results. In the table, each compounding amount represents “parts by weight”.

(1) Linear thermal expansion coefficient As for the linear thermal expansion coefficient, a test piece of 4 mm × 20 mm was prepared using a TMA (thermomechanical analysis) apparatus (TA Instruments, Q400), and the temperature range was 30 to 300. The linear expansion coefficient (CTE) at 50 to 100 ° C. in the second cycle was measured under the conditions of 10 ° C./min and a load of 5 g. In addition, a sample uses two prepregs obtained in each Example and Comparative Example, and the second resin layer is face-to-face and pressed and laminated under the conditions of a temperature of 220 ° C., a pressure of 1 MPa, and a time of 120 minutes. What removed the foil was used.

(2) Drill wear resistance

Three of the resulting laminates are stacked, with an entry board (LE812F3 manufactured by Mitsubishi Gas Chemical Co., Ltd.) on top and a backboard (paper phenol plate with a thickness of 1.5 mm) on the bottom, drill made by Union Tool Co., Ltd. Using a bit (KMC L506, diameter 150 μm), drilling of φ150 (through-hole: 3000 under drilling conditions of drill rotation speed 200 krpm, feed rate 2.5 m / min, tip load 12.5 μm / rev Hole).
Evaluation of drill wearability was performed by measuring the remaining ratio of the drill blade width after use with the drill blade width before use being 100%.
The symbols are as follows: ◎: When the remaining rate of the drill blade width after use is 65% or more ○: When the remaining rate of the drill blade width after use is 50% or more and less than 65% ×: Drill blade width after use If the residual rate of the product is less than 50%

(3) Warpage of Semiconductor Device The warpage amount of the semiconductor device is determined by placing the semiconductor element surface of the semiconductor device obtained above on a chamber that can be heated and cooled, and in an atmosphere of −50 ° C. and 125 ° C. The change in the amount of warpage in a 48 mm × 48 mm portion on the substrate (size: 50 mm × 50 mm) on the back surface (surface on which no semiconductor element is mounted) of the printed wiring board portion of the apparatus was measured.
The sample used was the semiconductor device manufactured in the above example. Each code is as follows.
◎: When the change in warpage is less than 200 μm ○: When the change in warpage is 200 μm or more and less than 300 μm Δ: When the change in warpage is 300 μm or more and less than 350 μm ×: Warpage amount When the change of 350μm or more

From the evaluation results described in Table 1, Examples 1 to 4 using a zirconium compound had a low linear expansion coefficient, excellent drill wearability, and small warpage of the semiconductor device.
However, Comparative Example 1 using silica as the inorganic filler had a coefficient of thermal expansion of 11 ppm, and the warp of the semiconductor device was large. Drill wear was also reduced.
In Comparative Example 2 using aluminum hydroxide, although the drill wearability was good, the coefficient of thermal expansion was large and the warp of the semiconductor device was large.

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 resin 11 ... Metal foil 12 ... Insulating resin layer 20 ... Base material DESCRIPTION OF SYMBOLS 30 ... Polymer film sheet with resin 31 ... Polymer film sheet 32 ... Insulating resin layer 40 ... Prepreg 41 ... Prepreg with metal foil 42 ... Prepreg with polymer film sheet 51 ... Laminate plate 52 ... Laminate plate

Claims (8)

A resin composition for a printed wiring board, comprising 100% by weight of the resin composition for a printed wiring board, containing 53% by weight to 87% by weight of a zirconium compound ,
The resin composition for printed wiring boards , wherein the zirconium compound is at least one selected from the group consisting of a zirconium phosphate compound or a zirconium tungstate compound . The resin composition for printed wiring boards according to claim 1, wherein the resin composition for printed wiring boards further contains an inorganic filler having an average particle diameter of 5 to 100 nm. Prepreg characterized by being obtained by impregnating the printed circuit board resin composition according to the substrate to claim 1 or 2. A laminate having a metal foil on at least one surface of the prepreg according to claim 3 or a laminate in which two or more prepregs are stacked. The resin sheet formed by forming the insulating layer which consists of a resin composition for printed wiring boards of Claim 1 or 2 on a film or metal foil. A printed wiring board comprising the laminated board according to claim 4 as an inner circuit board. A printed wiring board obtained by laminating the prepreg according to claim 3 and / or the resin sheet according to claim 5 on a circuit of an inner layer circuit board. Wherein a formed by mounting a semiconductor element on a printed wiring board according to claim 6 or 7.