JP5581640B2 - Resin composition, prepreg, laminate, multilayer printed wiring, and semiconductor device - Google Patents

Description

  The present invention relates to a resin composition, a prepreg, a laminate, a multilayer printed wiring, 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, various methods for reducing the coefficient of thermal expansion of the resin composition used and increasing the glass transition temperature have been studied.

  As a resin composition having both a low coefficient of thermal expansion and high heat resistance, a resin composition using a cyanate resin is generally known (for example, described in Patent Documents 1, 2 and 3). In order to fully develop a low coefficient of thermal expansion and high heat resistance, it is necessary for the cyanate group of the cyanate resin to react completely to form a cyclic structure. Since the reaction does not proceed sufficiently at low temperatures, it has been impossible to obtain a resin composition having a low coefficient of thermal expansion and sufficient heat resistance.

  It is also known to use lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, acetyla iron, etc. as a curing catalyst. (For example, patent document 4), there was nothing which can express the balance of sclerosis | hardenability and other characteristics at a high level.

JP 2007-277334 A JP 2007-138075 A JP 2004-59463 A JP 2009-132886 A

An object of the present invention is to provide a cyanate resin composition that promotes the reaction of a cyanate group at a low temperature, and the obtained cured product has low linear thermal expansion and is excellent in solder heat resistance.

The object of the present invention is achieved by the present invention described in the following items [1] to [ 7 ].
[1] Cyanate resin comprising (A) cyanate resin, and (B) acetylacetonatobis (ethylacetoacetate) aluminum or tris (8-quinolinolato) aluminum, and (C) an epoxy resin as essential components Composition.
[ 2 ] The cyanate resin composition according to [ 1 ], wherein the cyanate resin composition further includes (D) an inorganic filler.
[ 3 ] A prepreg obtained by impregnating a base material with the cyanate resin composition according to any one of [1] or [2] .
[ 4 ] A laminate having a metal foil on at least one side of a laminate in which at least one prepreg according to [ 3 ] is laminated.
[ 5 ] A resin sheet obtained by forming an insulating layer made of the cyanate resin composition according to any one of [1] or [2] on a film or a metal foil.
[6] The prepreg according to [3], laminate, and [5] a printed wiring board produced by using at least one selected from the group consisting of a resin sheet according to according to [4].
[ 7 ] A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to [ 6 ].

The cyanate resin composition of the present invention is cured even at a low temperature, and the cured product has low linear thermal expansion and excellent solder heat resistance.

Hereinafter, the cyanate resin composition, prepreg, laminate, printed wiring board, and semiconductor device of the present invention will be described.

The cyanate resin composition of the present invention can be impregnated in a substrate such as a glass fiber substrate and used for a prepreg and a laminate using the prepreg.
Moreover, since the cyanate resin composition of this invention has the outstanding insulation, it can be used for the insulating layer of a printed wiring board, for example.
Furthermore, since the cyanate resin composition of the present invention has low linear expansion and is excellent in heat resistance and adhesion to a conductor circuit, it can be used as an interposer for a semiconductor device.

As a printed wiring board of a semiconductor device, a mother board and an interposer are known. The interposer is a printed wiring board similar to the mother board, but is interposed between the semiconductor element (bare chip) or semiconductor package and the mother board and mounted on the mother board.
The interposer may be used as a substrate on which a semiconductor package is mounted in the same manner as a mother board. However, the interposer is used as a package substrate or a module substrate as a specific usage method different from the mother board.

The package substrate means that an interposer is used as a substrate of a semiconductor package. In a semiconductor package, a semiconductor element is mounted on a lead frame, both are connected by wire bonding and sealed with resin, and an interposer is used as a package substrate, and a semiconductor element is mounted on the interposer, There is a type that is connected by a method such as wire bonding and sealed with resin.

Next, details of the cyanate resin composition of the present invention will be described.

The cyanate resin composition of the present invention comprises (A) a cyanate resin and (B) an aluminum complex as essential components. As a result, the curing reaction is accelerated even at a low temperature, and the resulting cured product has a low coefficient of thermal expansion and excellent heat resistance.

The cyanate resin composition may further contain (C) an epoxy resin.
As a result, when used for a printed wiring board or the like, the adhesiveness to the conductor circuit is excellent.
Furthermore, the cyanate resin composition may contain (D) an inorganic filler. As a result, the thermal expansion coefficient of the cured product can be further lowered, and the elastic modulus can be increased.
・

The (A) cyanate resin is not particularly limited, and can be obtained, for example, by reacting a cyanogen halide with a phenol and prepolymerizing it by a method such as heating as necessary. Moreover, the commercial item prepared in this way can also be used. Thereby, the linear thermal expansion of the cured | curing material of the cyanate resin composition obtained can be lowered | hung. Moreover, it will be excellent in heat resistance. Further, the flame retardancy can be further improved.

Although it does not specifically limit as said (A) kind of cyanate resin, For example, bisphenol type cyanate resin, such as a novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethylbisphenol F type cyanate resin, etc. are mentioned be able to.

The (A) 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, 1,3,6-tricyanatonaphthalene, 4, 4'-Dicia DOO biphenyl, and phenol novolak type, etc. cyanate resin obtained by the reaction of a polyhydric phenol with a cyanogen halide of cresol novolac type and the like. 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 control the crosslinking density. Excellent in moisture resistance and 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 (A) cyanate resin may be used alone, or may be used in combination with cyanate resins having different weight average molecular weights, or may be used in combination with the 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.
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.

Although content of the said (A) cyanate resin is not specifically limited, It is preferable that it is 1 to 50 weight% of the whole cyanate resin composition. More preferably, it is 3 to 30% by weight. Thereby, cyanate resin can express heat resistance and a flame retardance effectively. If the content of the cyanate resin is less than the lower limit value, the thermal expansibility increases and the heat resistance may decrease, and if the content exceeds the upper limit value, the strength of the prepreg using the resin composition may decrease. . The content of the cyanate resin is particularly preferably 5 to 25% by weight in the cyanate resin composition.

The (B) aluminum complex is not particularly limited, but a trivalent aluminum complex is preferable. Excellent storage stability compared to monovalent and divalent aluminum complexes.

The ligand of the (B) aluminum complex is not particularly limited. Examples include sadiamine, glycine, triglycine, naphthidiline, phenanthroline, pentanediamine, pyridine, salicylic acid, salicylaldehyde, salicylideneamine, porphyrin, thiourea complex, and the like.
Among these, acetylacetonate is preferable.

The (C) epoxy resin is not particularly limited. 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′-cyclohexene). Sidiene 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 resins), phenol novolac type epoxy resins, cresol novolac type epoxy resins and other novolak type epoxy resins, biphenyl type epoxy resins, xylylene type epoxy resins, Enol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl dimethylene type epoxy resin, trisphenol methane novolak type epoxy resin, glycidyl ethers of 1,1,2,2- (tetraphenol) ethane, trifunctional, or 4 Functional glycidylamines, arylalkylene type epoxy resins such as tetramethylbiphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy Examples thereof include resins and fluorene type 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 thereof and their prepolymers can be used in combination.
Among these (C) epoxy resins, cresol novolac type epoxy resins are particularly preferable. Thereby, moisture absorption solder heat resistance improves and a glass transition temperature becomes high.

The content of the (C) epoxy resin is not particularly limited, but is preferably 5% by weight or more and 50% by weight or less of the entire resin composition. If the content is less than the lower limit, the curability of the resin composition may be lowered, or the moisture resistance of the prepreg or multilayer printed wiring board obtained from the resin composition may be lowered. Moreover, when the said upper limit is exceeded, the linear thermal expansion coefficient of a prepreg or a multilayer printed wiring board may become large, or heat resistance may fall. The content of the epoxy resin is preferably 10% by weight or more and 40% by weight or less based on the entire resin composition.

The weight average molecular weight of the (C) epoxy resin is not particularly limited, but a weight average molecular weight of 1.0 × 10 ² or more and 2.0 × 10 ⁴ or less is preferable. When the weight average molecular weight is less than the lower limit value, tackiness may occur on the surface of the insulating resin layer, and when the upper limit value is exceeded, solder heat resistance may decrease. By setting the weight average molecular weight within the above range, it is possible to achieve an excellent balance of these characteristics.
The weight average molecular weight of the epoxy resin can be measured by GPC, for example.

The (D) inorganic filler is not particularly limited. For example, talc, calcined clay, unfired clay, mica, silicates such as glass, oxides such as titanium oxide, alumina, silica, and fused silica, calcium carbonate, Carbonates such as magnesium carbonate and hydrotalcite, metal hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, zinc borate and metaborane Borates such as barium oxide, 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. Among these, silica is particularly preferable from the viewpoint of low thermal expansion and insulation reliability, and spherical fused silica is more preferable. Moreover, aluminum hydroxide is preferable in terms of flame resistance.

The particle diameter of the inorganic filler (D) is not particularly limited, but an inorganic filler having a monodispersed average particle diameter can also be used, and an inorganic filler having a polydispersed average particle diameter can be used. Furthermore, one or two or more inorganic fillers having an average particle size of monodisperse and / or polydisperse can be used in combination. Among these, when the width of the conductor circuit of the multilayer printed wiring board and the width (L / S) between the conductor circuits is less than 15/15 μm, the average particle size is 1.2 μm or less and 0.1 μm or more from the viewpoint of insulation reliability. In addition, those having a coarse grain cut of 5 μm or more are preferable. When L / S is 15 μm or more, it is preferable that the average particle size is 5 μm or less and 0.2 μm or more, and the coarse particles of 20 μm or more are 0.1% or less. If the average particle size is less than the lower limit, the fluidity is remarkably deteriorated and the moldability is lowered. Moreover, when the said upper limit is exceeded, the insulation of a conductor circuit may fall. The average particle diameter can be measured using a laser diffraction / scattering particle size distribution measuring apparatus (a general instrument such as Shimadzu SALD-7000).

Although content of the said (D) inorganic filler is not specifically limited, 40 to 80 weight% of the whole cyanate resin composition is preferable, and 60 to 75 weight% is preferable. When the content is within the above range, the prepreg impregnation and moldability are particularly excellent.

Next, the prepreg will be described.

The prepreg of the present invention is obtained by impregnating a base material with the cyanate resin composition. Thereby, the prepreg excellent in various characteristics, such as heat resistance, can be obtained.
Examples of the base material used in the prepreg of the present invention include glass fiber base materials such as glass fiber cloth and glass non-woven cloth, inorganic fiber base materials such as fiber cloth and non-fiber cloth containing inorganic compounds other than glass, and aromatic polyamide resins. And organic fiber base materials composed of organic fibers such as polyamide resin, aromatic polyester resin, polyester resin, polyimide resin, and fluororesin. Among these base materials, glass fiber base materials represented by glass woven fabric are preferable in terms of strength and water absorption.

Examples of the method of impregnating the base material with the cyanate resin composition include, for example, a method in which a cyanate resin composition is made into a resin varnish using a solvent, the base material is immersed in the resin varnish, a method of coating with various coaters, and a spraying method. Etc. 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.

The solvent used in the resin varnish desirably has good solubility in the cyanate resin composition, but a poor solvent may be used as long as it does not have an adverse effect. Examples of the solvent exhibiting good solubility include N-methylpyrrolidone and the like.
Although the solid content in the resin varnish is not particularly limited, the solid content of the cyanate resin composition is preferably 40 to 85% by weight, particularly preferably 65 to 80% by weight. Thereby, the impregnation property to the base material of a resin varnish can further be improved.
A prepreg can be obtained by impregnating the base material with the cyanate resin composition and drying at a predetermined temperature, for example, 80 to 200 ° C.

Next, the resin sheet will be described.
The resin sheet using the cyanate resin composition is obtained by forming an insulating layer made of the resin varnish on a carrier film or a metal foil.

The content of the cyanate resin composition in the resin varnish is not particularly limited, but is preferably 45 to 85% by weight, and particularly preferably 65 to 80% by weight.

Next, the resin varnish is coated on a carrier film or a metal foil using various coating apparatuses, and then dried. Or after spray-coating a resin varnish on a carrier film or metal foil with a spray apparatus, this is dried. A resin sheet can be produced by these methods.

Although the said coating apparatus is not specifically limited, For example, a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a comma coater, a curtain coater, etc. can be used. Among these, a method using a die coater, a knife coater, and a comma coater is preferable. Thereby, the resin sheet which does not have a void and has the thickness of a uniform insulating layer can be manufactured efficiently.
Since the carrier film forms an insulating layer on the carrier film, it is preferable to select one that is easy to handle. Moreover, since the carrier film is peeled after laminating the insulating layer of the resin sheet on the inner layer circuit board surface, it is preferable that the resin sheet is easily peeled after being laminated on the inner layer circuit board. Therefore, it is preferable to use a thermoplastic resin film having heat resistance such as a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a fluorine-based resin, or a polyimide resin, for example. Among these carrier films, a film made of polyester is most preferable. This facilitates peeling from the insulating layer with an appropriate strength.

  Although the thickness of the said carrier film is not specifically limited, 1-100 micrometers is preferable and 3-50 micrometers is especially preferable. When the thickness of the carrier film is within the above range, handling is easy and the flatness of the surface of the insulating layer is excellent.

Similar to the carrier film, the metal foil may be used after peeling a resin sheet on an inner circuit board and may be used after peeling the metal foil as a conductor circuit. The metal foil 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, gold and gold-based alloy, Metal foils such as zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys can be used.

The thickness of the metal foil is not particularly limited, but is preferably 0.1 μm or more and 70 μm or less. Further, it is preferably 1 μm or more and 35 μm or less, more preferably 1.5 μm or more and 18 μm or less. When the thickness of the metal foil is less than the above lower limit value, pinholes with scratches on the metal foil are generated, and when the metal foil is etched and used as a conductor circuit, plating variations at the time of circuit pattern formation, circuit disconnection, etching solution If the upper limit is exceeded, the thickness variation of the metal foil or the surface roughness variation of the roughened surface of the metal foil may increase. There is.

The metal foil may be an ultrathin metal foil with a carrier foil. The ultrathin metal foil with a carrier foil is a metal foil obtained by laminating a peelable carrier foil and an ultrathin metal foil. Since an ultra-thin metal foil layer can be formed on both sides of the insulating layer by using an ultra-thin metal foil with a carrier foil, for example, when forming a circuit by a semi-additive method, etc. By electroplating the metal foil directly as the power feeding layer, the ultrathin copper foil can be flash etched after the circuit is formed. By using an ultra-thin metal foil with a carrier foil, even with an ultra-thin metal foil having a thickness of 10 μm or less, for example, a reduction in handling properties of the ultra-thin metal foil in a pressing process, and cracking or cutting of the ultra-thin copper foil are prevented. Can do. The thickness of the ultrathin metal foil is preferably 0.1 μm or more and 10 μm or less. Furthermore, it is preferably 0.5 μm or more and 5 μm or less, more preferably 1 μm or more and 3 μm or less. When the thickness of the ultrathin metal foil is less than the lower limit, the ultrathin metal foil is damaged after peeling the carrier foil, the pinhole of the ultrathin metal foil is generated, and the circuit pattern is formed by the generation of the pinhole. Plating variation, disconnection of circuit wiring, penetration of chemicals such as etching liquid and desmear liquid, etc. may occur. If the above upper limit is exceeded, the thickness variation of the ultrathin metal foil will increase or the ultrathin metal foil There may be a case where the roughness of the roughened surface becomes large.

Next, a laminated board is demonstrated.

The laminate of the present invention is formed by molding at least one prepreg described above. Thereby, the laminated board which has the outstanding heat resistance and adhesiveness, and whose dielectric constant and dielectric loss tangent are low can be obtained.

In the case of a single prepreg, a metal foil or a carrier film is stacked on both 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. In addition, what is used for the said resin sheet can be used for the metal foil or carrier film used for a laminated board.

Next, a laminate can be obtained by heating and pressurizing a laminate of a prepreg and a metal foil and / or a carrier film.
The heating temperature is not particularly limited, but is preferably 150 to 240 ° C, and particularly preferably 180 to 220 ° C.
Moreover, the pressure to pressurize is not particularly limited, but is preferably 2 to 5 MPa, and particularly preferably 2.5 to 4 MPa.

Next, although a printed wiring board is demonstrated, the manufacturing method of a printed wiring board is not specifically limited. For example, it can be manufactured as follows.

A laminated board having copper foil on both sides obtained above is prepared, a through hole is formed by a drill or the like, and after filling the through hole by plating, a predetermined conductor circuit ( The inner layer circuit board is manufactured by forming the inner layer circuit) and subjecting the conductor circuit to a roughening process such as a blackening process.

When the cyanate resin composition of the present invention is used, fine through-holes can be formed with a high yield as compared with the conventional case, and the unevenness of the wall after the formation of the through-hole is very small.

Next, the above-described resin sheet or the above-described prepreg is formed on the upper and lower surfaces of the inner layer circuit board, and is heated and pressed.
Specifically, the resin sheet or prepreg and the inner layer circuit board are combined and subjected to vacuum heating and pressing using a vacuum pressurizing laminator apparatus or the like. Thereafter, the insulating layer can be formed on the inner circuit board by heat-curing with 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 heat-harden, If an example is given, it can implement in temperature 140-240 degreeC and time 30-120 minutes.

Alternatively, the insulating layer can also be formed on the inner layer circuit board by superimposing the resin sheet or prepreg on the inner layer circuit board and then heat-pressing the resin sheet or prepreg using a flat plate press apparatus 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 140-240 degreeC, and the pressure of 1-4 MPa.

The laminated body obtained by the above-described method can form a new conductive wiring circuit by metal plating after roughening the surface of the insulating layer with an oxidizing agent such as permanganate or dichromate. it can.

When the cyanate resin composition of the present invention is used, it is excellent in fine wiring processing as compared with the prior art, and forms a wiring with a very narrow conductor width (line) and conductor (space) when a conductor circuit is formed with a high yield. be able to.

Thereafter, the insulating layer is cured by heating. Although the temperature to harden | cure is not specifically limited, For example, it can be made to harden | cure in the range of 150 to 240 degreeC. Preferably it is made to harden | cure at 180 to 220 degreeC.
Next, an opening is provided in the insulating layer by using a carbonic acid laser device, and an outer layer circuit is formed on the surface of the insulating layer by electrolytic copper plating to achieve conduction between the outer layer circuit and the inner layer circuit. The outer layer circuit is provided with a connection electrode portion for mounting a semiconductor element.
After that, a solder resist is formed on the outermost layer, the connection electrode part is exposed so that a semiconductor element can be mounted by exposure / development, nickel gold plating treatment is performed, and it is cut into a predetermined size to obtain a multilayer printed wiring board. Can do.

When the cyanate resin composition of the present invention is used, the nickel gold plating does not remain in the insulating layer as compared with the case of using the conventional epoxy resin composition at the time of nickel gold plating.

Next, a semiconductor device will be described.
A semiconductor device can be manufactured by mounting a semiconductor element on a printed wiring board manufactured by the method described above. The mounting method and the sealing method of the semiconductor element are not particularly limited. For example, a semiconductor element and a multilayer printed wiring board are used, and a flip-chip bonder or the like is used to align the connection electrode portions on the multilayer printed wiring board and the solder bumps of the semiconductor element. Thereafter, the solder bump is heated to the melting point or higher by using an IR reflow device, a hot plate, or other heating device, and the multilayer printed wiring board and the solder bump are connected by fusion bonding. And a semiconductor device can be obtained by filling and hardening a liquid sealing resin between a multilayer printed wiring board and a semiconductor element.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

( Reference Example 1 )
1. Preparation of resin varnish 22.0% by weight of novolak-type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30), 13.0% by weight of cresol novolak-type epoxy resin (N-690, manufactured by Dainippon Ink & Chemicals, Inc.) As an inorganic filler, 65.0% by weight of spherical silica (average particle diameter 1 μm), 0.11% by weight of tris (acetylacetonate) aluminum and mixed with methyl isobutyl ketone and cyclohexanone so that the solid content is 78%. A resin varnish was obtained.

2. Preparation of Prepreg The resin varnish prepared as described above was impregnated into a base material and dried at 150 ° C. for 5 minutes to obtain a 0.1 mm prepreg.

3. Fabrication of laminated plate A 12 μm thick copper foil (3EC-M3VLP made by Mitsui Metals) was superimposed on both sides of the prepreg produced as described above, and heat-press molded at 220 ° C. and 3 MPa, and a 0.1 mm copper foil was formed on both sides. The laminated board which has is obtained.
The thickness of the laminated board was 0.4 mm.

4). Fabrication of Printed Wiring Board The laminated board obtained above was subjected to through hole processing using a 0.1 mm drill bit, and then filled with through holes by plating. Further, a circuit was formed on both sides by etching and used as an inner layer circuit board. The prepreg obtained above was superposed on the front and back of the inner layer circuit board, and this was subjected to vacuum heating and pressing at a temperature of 100 ° C. and a pressure of 1 MPa using a vacuum pressurizing laminator apparatus. This was heated and cured at 170 ° C. for 60 minutes in a hot air drying apparatus to obtain a laminate.

Next, the surface electrolytic copper foil layer was subjected to blackening treatment, and a φ60 μm via hole for interlayer connection was formed by a carbon dioxide gas laser. Next, it is immersed in a swelling solution 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. (Concentrate Compact CP, manufactured by Atotech Japan) for 15 minutes. Then, it neutralized and the desmear process in a via hole was performed. Next, after the surface of the electrolytic copper foil layer is etched by about 1 μm by flash etching, electroless copper plating is performed with a thickness of 0.5 μm, a resist layer for electrolytic copper plating is formed with a thickness of 18 μm, and pattern copper plating is performed. The film was post-cured by heating at 60 ° C. for 60 minutes. Next, the plating resist was peeled off and the entire surface was flash etched to form a pattern of L / S = 20/20 μm.
Finally, a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) having a thickness of 20 μm was formed on the circuit surface to obtain a printed wiring board.

5. Manufacturing of Semiconductor Device A printed wiring board used for manufacturing a semiconductor device is the printed wiring board obtained as described above, and provided with a connecting electrode portion subjected to nickel gold plating corresponding to a solder bump arrangement of a semiconductor element. The thing 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 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.

( Reference Example 2 )
A resin varnish was prepared in the same manner as in Reference Example 1 except that tris (acetylacetonato) aluminum was used in an amount of 0.15 parts by weight to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

( Reference Example 3 )
A resin varnish was prepared in the same manner as in Reference Example 1 , except that tris (acetylacetonato) aluminum was changed to 0.06 part by weight, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

( Reference Example 4)
A resin varnish was prepared in the same manner as in Reference Example 1, except that 0.14 parts by weight of tris (ethylacetoacetate) aluminum was used instead of tris (acetylacetonate) aluminum, and a prepreg, a resin sheet, a laminate, a print A wiring board and a semiconductor device were obtained.

(Example 5)
A resin varnish was prepared in the same manner as in Reference Example 1 except that 0.13 parts by weight of acetylacetonatobis (ethylacetoacetate) aluminum was used instead of tris (acetylacetonato) aluminum, and a prepreg, a resin sheet, and a laminate were prepared. A board, a printed wiring board, and a semiconductor device were obtained.

(Example 6)
A resin varnish was prepared in the same manner as in Reference Example 1 except that 0.16 parts by weight of tris (8-quinolinolato) aluminum was used instead of tris (acetylacetonato) aluminum, and a prepreg, resin sheet, laminate, print A wiring board and a semiconductor device were obtained.

( Reference Example 7 )
2,2′-bis (4-cyanatophenyl) isopropylidene (manufactured by Huntsman Co., Ltd., B-40S, trimerization rate 40%) 22.0% by weight, cresol novolac type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc.) N-690) 13.0% by weight, spherical silica (average particle size 1 μm) 65.0% by weight as an inorganic filler, tris (acetylacetonate) aluminum 0.06% by weight and solid content 78% Thus, it was mixed with methyl isobutyl ketone and cyclohexanone to obtain a resin varnish.

(Comparative Example 1)
A resin varnish was prepared in the same manner as in Reference Example 1 except that tris (acetylacetonato) cobalt (III) was changed to 0.12 parts by weight instead of tris (acetylacetonato) aluminum, and a prepreg, a resin sheet, and a laminate were prepared. A board, a printed wiring board, and a semiconductor device were obtained.

(Comparative Example 2)
A resin varnish was prepared in the same manner as in Reference Example 1 except that bis (acetylacetonato) zinc (II) was replaced by 0.09 parts by weight instead of tris (acetylacetonato) aluminum, and a prepreg, a resin sheet, and a laminate were prepared. A board, a printed wiring board, and a semiconductor device were obtained.

(Comparative Example 3)
A resin varnish was prepared in the same manner as in Reference Example 1 , except that 0.11 part by weight of aluminum chloride was used instead of tris (acetylacetonate) aluminum, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor were prepared. Got the device.

(Comparative Example 4)
A resin varnish was prepared in the same manner as in Reference Example 1 except that 0.09 part by weight of 2-phenylimidazole (manufactured by Nippon Synthetic Chemical Co., Ltd.) was used instead of tris (acetylacetonato) aluminum, and a prepreg, a resin sheet, A laminated board, a printed wiring board, and a semiconductor device were obtained.

The following evaluations were made on the resin varnishes, prepregs, laminates, printed wiring boards, and semiconductor devices obtained in the examples, reference examples, and comparative examples. The evaluation results are shown in Table 1.

(Evaluation method)
The evaluation was performed by the following method.

(1) Glass transition temperature The copper foil of the laminated board which has copper foil on the both surfaces obtained above is etched on the whole surface, a sample of a predetermined size is cut out, and 5 using a DMA apparatus (DMA 2980 manufactured by TA Instruments). While increasing the temperature at a rate of ° C./minute, a dynamic viscoelasticity was measured by applying a strain of a frequency of 1 Hz. The glass transition temperature was a temperature at which tan δ exhibited a maximum value.

(2) Solder heat resistance After the obtained laminate was cut into a 50 mm × 50 mm grinder saw, a sample in which only 1/4 of the copper foil was left by etching was prepared and measured in accordance with JIS C 6481. In the measurement, after performing a PCT moisture absorption treatment at 121 ° C., 100% for 2 hours, it was immersed in a solder bath at 288 ° C. for 30 seconds, and then the presence or absence of appearance abnormality was examined.

(3) Water absorption rate The water absorption rate was a sample in which the obtained laminate was cut to 50 mm x 50 mm with a grinder saw and then the entire surface was etched, and was measured according to JIS C 6481. The measurement is carried out by measuring the weight after drying in an oven at 130 ° C. for 2 hours, measuring the weight after performing moisture absorption treatment at 121 ° C., 100% for 2 hours, and using the difference as the amount of moisture absorption, Asked.

(4) Peel strength A 100 mm × 20 mm test piece was prepared from the double-sided copper clad laminate having a thickness of 0.4 mm obtained in the examples and comparative examples, and the peel strength at 23 ° C. was measured.
The peel strength was measured according to JIS C 6481.

(5) Reaction rate The reaction rate was calculated | required by measuring using DSC apparatus (Differential scanning calorimetry DSC2920 by TA Instruments).
It calculated | required by following Formula (I) by comparing the area of the exothermic peak by reaction of DSC about both the unreacted cyanate resin composition and the hardened | cured material of a cyanate resin composition. In addition, the measurement was performed in a nitrogen atmosphere at a heating rate of 10 ° C./min.
Reaction rate (%) = (1-reaction peak area of cured product of cyanate resin composition / reaction peak area of unreacted cyanate resin composition) × 100 (I)
Here, the exothermic peak of the cured product of the unreacted cyanate resin composition was impregnated into the base material with the varnish comprising the resin compositions of Examples and Comparative Examples of the present invention, air-dried at 40 ° C. for 10 minutes, and then 40 ° C. This is an exothermic peak obtained when DSC measurement was performed using a sample from which the solvent was removed in 1 hour under a vacuum of 1 kPa.
The exothermic peak of the cured product of the cyanate resin composition is the exothermic peak when DSC measurement was performed using a sample obtained by etching the copper foil of the double-sided copper-clad laminate of the examples and comparative examples and scraping off the resin from the surface. It is.

  As is clear from Table 1, Examples 1 to 7 are laminated plates using the cyanate resin composition of the present invention, characterized by having cyanate resin and an aluminum complex as essential components. Other performance was excellent.

On the other hand, Comparative Examples 1 and 2 using a different metal complex as a catalyst instead of the aluminum complex had a large water absorption rate, and swollen in the solder heat resistance test.

Moreover, it turned out that the comparative example 3 which used the inorganic aluminum compound as a catalyst instead of an aluminum complex does not have sufficient reaction from the result of the reaction rate, and cannot shape | mold on the press conditions for 180 minutes at 220 degreeC.

Further, in Comparative Example 4 in which an imidazole compound was used as a catalyst instead of the aluminum complex, it was found from the results of the reaction rate that the reaction was not sufficient and could not be molded under the pressing conditions at 220 ° C. for 180 minutes.

The cyanate resin composition of the present invention has low linear thermal expansion and excellent solder heat resistance, so that it can be usefully used for interposers and semiconductor devices that are thinner and require higher performance.

Claims (7)

A cyanate resin composition comprising (A) a cyanate resin and (B) acetylacetonatobis (ethylacetoacetate) aluminum or tris (8-quinolinato) aluminum, and (C) an epoxy resin as essential components. The cyanate resin composition according to claim 1 , wherein the cyanate resin composition further comprises (D) an inorganic filler. Claim 1 or prepreg formed by impregnating a cyanate resin composition according to the substrate either 2. A laminate having a metal foil on at least one side of a laminate in which at least one prepreg according to claim 3 is laminated. The resin sheet formed by forming the insulating layer which consists of a cyanate resin composition in any one of the said Claim 1 or 2 on a film or metal foil. The prepreg according to claim 3, laminate of claim 4, and at least one printed wiring board produced by using selected from the group consisting of a resin sheet according to claim 5. A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to claim 6 .