JP5929639B2 - Cyanate ester compound, resin composition, prepreg, laminate, resin sheet, multilayer printed wiring board, and semiconductor device - Google Patents

Description

  The present invention relates to a cyanate ester compound, a resin composition, a prepreg, a laminate, a resin sheet, a multilayer 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 conventional technology, miniaturization and high density are progressing. As a countermeasure for increasing the density of this printed wiring board, a multilayer printed wiring board by a build-up method is often employed (for example, see Patent Document 1).

  A thermosetting resin composition is usually used for the insulating layer of the multilayer printed wiring board by the build-up method. Considering reliability and the like, a resin composition having a low coefficient of thermal expansion and a high glass transition temperature is required for the insulating layer.

A resin composition (Patent Document 2) in which an inorganic filler is blended with a novolak cyanate ester resin has been proposed for the required characteristics required for the resin composition used for such an insulating layer. However, with the further miniaturization and miniaturization in the future, improvement in reliability is required. In particular, improvement in reliability after moisture absorption is required. Further, Patent Document 3 discloses a method for synthesizing cyanate esters with high yield, and cyanate esters having various structures are disclosed. However, disclosure including their useful methods of use has been made. Absent.

Japanese Patent Application Laid-Open No. 07-106767 JP 2006-191150 A Japanese Patent Laid-Open No. 9-249746 JP-A-11-255735 JP 2011-132167 A

  The present invention provides a cyanate ester compound excellent in moisture absorption resistance, high heat resistance, low dielectric properties, low thermal expansion, and flame retardancy, and a resin composition. The present invention provides a prepreg, a resin sheet, a laminate, a multilayer printed wiring board, and a semiconductor device that are excellent in the balance of the characteristics used.

Such an object is achieved by the present invention described in the following items [1] to [11].
[1] A cyanate ester compound represented by the following formula (1).
[Wherein R ₁ is any one of the following formulas (2) to (5). ]
[Wherein R ₂ represents any one of H, a C1-C3 aliphatic hydrocarbon, and a C6-C12 aromatic hydrocarbon. ]
[2] A fluorene-type cyanate compound obtained by reacting a fluorene-type phenol and a cyanogen halide.
[3] A resin composition comprising the cyanate ester compound according to [1] or [2] as an essential component.
[4] The resin composition according to [3], further comprising an epoxy resin and a curing agent.
[5] The resin composition according to [4], further including an inorganic filler.
[6] The resin composition according to [5], wherein the inorganic filler is at least one selected from the group consisting of silica, aluminum hydroxide, boehmite, talc, and calcium carbonate.
[7] A prepreg obtained by impregnating a base material with the resin composition according to any one of [3] to [6].
[8] A laminate obtained by molding one or more prepregs according to [7].
[9] A resin sheet having an insulating layer made of the resin composition according to any one of [3] to [6] and a carrier layer made of a film or metal foil.
[10] A multilayer printed wiring board produced using at least one of [7] prepreg, [8] laminate and [9] resin sheet.
[11] A semiconductor device comprising a semiconductor element mounted on the multilayer printed wiring board according to [10].

  When the resin composition containing the cyanate ester compound of the present invention is used for an insulating layer of a printed wiring board, the multilayer printed wiring board has flame resistance, heat resistance, low linear expansion, low dielectric property, and moisture absorption solder heat resistance. Excellent in properties.

  The present invention will be described in detail below.

First, the cyanate ester compound of the present invention will be described.

The cyanate ester compound can be obtained by reacting a cyanogen halide compound with a phenol compound.
The cyanate ester resin of the present invention can be obtained by reacting a fluorene type phenol compound represented by the following general formula (6) with cyanogen halide.
[Wherein R ₁ is any one of the following formulas (7) to (10). ]
[Wherein R ₂ represents any one of H, a C1-C3 aliphatic hydrocarbon, and a C6-C7 aromatic hydrocarbon. ]

  The cyanate ester compound may include a dimerized or trimerized compound.

  The synthesis conditions and method of the cyanate ester compound of the present invention are not particularly limited. For example, the fluorene type phenol resin represented by the general formula (6) is dissolved in an organic solvent, and the cyanogen halide compound is formed at a low temperature. Then, a basic compound such as a tertiary amine is added dropwise at a low temperature. The basic compound such as cyanogen halide and tertiary amine may be dropped alternately or simultaneously. By proceeding the reaction at a low temperature so that side reactions due to the exothermic reaction do not occur, a cyanate ester compound can be obtained in a high yield. Low temperature means below the temperature at which side reactions occur. Preferably, it is 0 ° C. or lower.

  In the synthesis conditions, the molar ratio of the fluorene type phenol resin and the cyanogen halide is preferably 1.0 to 3 cyanogen halides with respect to the phenolic hydroxyl group 1 of the fluorene type phenol resin.

  Although it does not specifically limit as said halogenated cyanide compound, For example, cyanogen chloride, cyanogen bromide, etc. can be used.

  The tertiary amine is not particularly limited, and may be any of alkylamine, arylamine, and cycloalkylamine, such as trimethylamine, triethylamine, methyldiethylamine, tripropylamine, tributylamine, and methyldibutylamine. .

  The organic solvent used for the synthesis is not particularly limited. For example, ketone solvents, aromatic solvents, ether solvents, halogenated hydrocarbon solvents, alcohol solvents, aprotic solvents, nitrile solvents, There are ester solvents and hydrocarbon solvents, and any of them can be used. These 1 type or 2 types or more can be used in combination.

  As a treatment after reacting the fluorene type phenol resin represented by the general formula (6) with a cyanogen halide, the precipitated hydrogen halide salt of a basic compound such as a tertiary amine is removed by filtration or washing with water. . Furthermore, in order to remove amines, separation washing can be performed using an acidic aqueous solution. Dilute hydrochloric acid is mainly used. Finally, anhydrous sodium sulfate or the like is used for dehydration. In the case of washing with water, it is necessary to select a solvent that can be separated. The content of ionic impurities after washing is preferably 30 ppm or less for Na ions, Br ions, and Cl ions. More preferably, it is 10 ppm or less. In the case of 30 ppm or more, when used for an insulating layer of a multilayer printed wiring board, the insulation reliability may be adversely affected.

  Below, the resin composition of this invention is demonstrated.

  The resin composition of the present invention is a resin composition containing the cyanate ester compound of the present invention. The resin composition of the present invention may contain other cyanate ester compounds, epoxy resins, curing agents, curing accelerators, inorganic fillers, release agents, and other additives, and other additives as necessary.

  The cyanate ester compound used in the resin composition of the present invention is not particularly limited as long as it contains a fluorene structure in its skeleton and two aromatic rings at the 9-position. For example, 9,9-bis ( 4-Hydroxyphenyl) -9H-fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) -9H-fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) -9H-fluorene 9 , 9-bis (3-propyl-4-hydroxyphenyl) -9H-fluorene, 9,9-bis (4-hydroxynaphthyl) -9H-fluorene, 9,9-bis (6-hydroxynaphthyl) -9H-fluorene Etc. One of these can be used alone, two or more of them can be used together, or a dimer thereof can be used.

Although content of a resin composition is not specifically limited, It is preferable to contain 5 to 60 weight% of the said resin composition whole. More preferably, it is 10 to 50% by weight, and particularly preferably 15 to 40% by weight. If the content is less than the lower limit, the heat resistance, low thermal expansibility, and flame retardancy are reduced. When the upper limit is exceeded, reliability in a HAST test or a PCT test, which is a reliability test under high temperature and high humidity, may be reduced.

  In addition to the cyanate ester compound of the present invention, other cyanate ester compounds can be used in combination with the resin composition of the present invention. Such a cyanate ester compound is not particularly limited. For example, bisphenol A dicyanate, bisphenol F dicyanate, bisphenol E dicyanate, phenol novolac cyanate, cresol novolac cyanate Examples include esters. One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more of these prepolymers can be used in combination.

  Among the other cyanate ester compounds, it is preferable to use bisphenol A type dicyanate resin, bisphenol E type dicyanate ester, and phenol novolac type cyanate ester. When bisphenol A type dicyanate or bisphenol E type dicyanate is used, the water absorption can be lowered, and the adhesion with copper after moisture absorption treatment is improved. Moreover, when a phenol novolac-type cyanate ester is used, a highly heat-resistant resin composition can be obtained.

  The epoxy resin used in the present invention is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, Bisphenol type epoxy resin such as bisphenol Z type epoxy resin, novolac type epoxy resin such as phenol novolac type epoxy resin, cresol novolac epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, arylalkylene 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 resin Carboxymethyl resins, epoxy resins such as a fluorene epoxy resin. One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more of these prepolymers can be used in combination. Among these, a biphenyl aralkyl type epoxy resin is particularly preferable. Thereby, the flame retardance of a printed wiring board improves.

Although the weight average molecular weight of the epoxy resin is not particularly limited, the weight average molecular weight is preferably 2.0 × 10 ^{2 to} 2.0 × 10 ⁴ , and particularly preferably 8.0 × 10 ^{2 to} 1.5 × 10 ⁴ . When the weight average molecular weight is less than the lower limit, tackiness may occur in the prepreg, and when the upper limit is exceeded, the impregnation property to the fiber base material is lowered during prepreg production, and a uniform product cannot be obtained. There is. The weight average molecular weight of the epoxy resin can be measured by GPC, for example.

  Although content of the said epoxy resin is not specifically limited, 1 to 55 weight% of the whole resin composition is preferable, and 2 to 40 weight% is especially preferable. If the content is less than the lower limit, the reactivity of the cyanate resin may decrease, or the moisture resistance of the product obtained may decrease, and if the content exceeds the upper limit, the heat resistance may decrease.

  The curing agent used in the present invention is not particularly limited as long as it has a hydroxyl group in the molecule. For example, resol type phenol resins such as phenol novolac resin, cresol novolak resin, novolak type phenol resin such as bisphenol A novolac resin, unmodified resole phenol resin, oil modified resole phenol resin modified with tung oil, linseed oil, walnut oil, etc. Such as phenol resin and phenoxy resin. One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more of these prepolymers can be used in combination. Among these, novolac type phenol resins are preferable, and among them, biphenyl aralkyl type phenol resins are preferable. By using a biphenyl aralkyl type phenolic resin, a low water absorption laminated board can be obtained, and the obtained laminated board is excellent in flame retardancy.

  The number of repeating units of the biphenyl aralkyl type phenol resin is not particularly limited, but the number of repeating units is preferably 1 to 12, and particularly preferably 2 to 8. If the average number of repeating units is less than the lower limit, the heat resistance may decrease. Moreover, when the said upper limit is exceeded, compatibility with other resin will fall and workability | operativity may fall.

The weight average molecular weight of the phenol resin is not particularly limited, but is preferably 2.0 × 10 ^{2 to} 1.8 × 10 ⁴ , and more preferably 5.0 × 10 ^{2 to} 1.5 × 10 ⁴ . When the weight average molecular weight is less than the lower limit, tackiness may occur in the prepreg, and when the upper limit is exceeded, the impregnation property to the fiber base material is lowered during prepreg production, and a uniform product cannot be obtained. There is. The weight average molecular weight of the phenol resin can be measured by, for example, GPC.

  Although content of the said phenol resin is not specifically limited, 1 to 55 weight% of the whole resin composition is preferable, and 5 to 40 weight% is especially preferable. If the content is less than the lower limit, the heat resistance may be reduced, and if the content exceeds the upper limit, the characteristics of low thermal expansion may be impaired.

  The resin composition of the present invention preferably contains an inorganic filler. Thereby, even if it makes a laminated board thin (thickness 0.5 mm or less), it not only is excellent in intensity | strength, but the low thermal expansion of a laminated board and the improvement of a flame retardance can be aimed at.

  Examples of the inorganic filler include, but are not limited to, silicates such as talc, fired clay, unfired clay, mica, and glass, oxides such as titanium oxide, alumina, silica, and fused silica, calcium carbonate, and magnesium carbonate. , Carbonates such as hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, Examples include borates such as 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. it can. As the inorganic filler, one of these can be used alone, or two or more can be used in combination. Among these, silica is particularly preferable, and fused silica (particularly spherical fused silica) is preferable in terms of excellent low thermal expansion. The shape is crushed and spherical, but in order to reduce the melt viscosity of the resin composition in order to ensure the impregnation of the fiber substrate, a method of use that suits the purpose, such as using spherical silica, is adopted. .

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 to 5.0 μm, particularly preferably 0.1 to 2.0 μm. If the particle size of the inorganic filler is less than the lower limit, the varnish has a high viscosity, which may affect the workability during prepreg production. When the upper limit is exceeded, phenomena such as sedimentation of the inorganic filler may occur in the varnish. This average particle diameter can be measured, for example, by a particle size distribution meter (manufactured by HORIBA, LA-500).

  The inorganic filler is not particularly limited, but an inorganic filler having a monodispersed average particle diameter can 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.

  Furthermore, spherical silica (especially spherical fused silica) having an average particle size of 5.0 μm or less is preferable, and spherical fused silica having an average particle size of 0.1 to 2.0 μm is particularly preferable. Thereby, the filling property of an inorganic filler can be improved.

  Although content of the said inorganic filler is not specifically limited, 20 to 80 weight% of the whole resin composition is preferable, and 30 to 70 weight% is especially preferable. When the content is within the above range, the cured product of the resin composition obtained is particularly excellent in low thermal expansion and low water absorption.

  The resin composition of the present invention is not particularly limited, but it is preferable to use a coupling agent. The coupling agent improves the wettability of the interface between the thermosetting resin and the inorganic filler, thereby uniformly fixing the thermosetting resin or the like and the inorganic filler to the fiber substrate, Heat resistance, particularly solder heat resistance after moisture absorption can be improved.

  The coupling agent is not particularly limited, and examples thereof include an epoxy silane coupling agent, a cationic silane coupling agent, an amino silane coupling agent, a titanate coupling agent, and a silicone oil type coupling agent. One or two or more coupling agents selected from among them may be used. Thereby, the wettability with the interface of an inorganic filler can be made high, and thereby heat resistance can be improved more.

  The addition amount of the coupling agent is not particularly limited because it depends on the specific surface area of the inorganic filler, but is preferably 0.05 to 3 parts by weight, particularly 0.1 to 2 parts per 100 parts by weight of the inorganic filler. Part by weight is preferred. If the content is less than the lower limit, the inorganic filler cannot be sufficiently coated, and thus the effect of improving the heat resistance may be reduced. If the content exceeds the upper limit, the reaction is affected, and the bending strength is reduced. There is a case.

  You may use a hardening accelerator for the resin composition of this invention as needed. A well-known thing can be used as said hardening accelerator. For example, organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), triethylamine, tributylamine, diazabicyclo [2, 2,2] tertiary amines such as octane, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxy Examples include imidazoles such as imidazole and 2-phenyl-4,5-dihydroxyimidazole, phenolic compounds such as phenol, bisphenol A, and nonylphenol, organic acids such as acetic acid, benzoic acid, salicylic acid, and paratoluenesulfonic acid, and mixtures thereof. It is done. As the curing accelerator, one kind including these derivatives can be used alone, or two or more kinds including these derivatives can be used in combination.

  Although content of the said hardening accelerator is not specifically limited, 0.05 to 5 weight% of the whole resin composition containing the said fluorene-type cyanate ester resin is preferable, and 0.2 to 2 weight% is especially preferable. When the content is less than the lower limit, the effect of promoting curing may not appear, and when the content exceeds the upper limit, the storability of the prepreg may deteriorate.

  The resin composition of the present invention includes thermoplastic resins such as phenoxy resin, polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyethersulfone resin, polyester resin, polyethylene resin, polystyrene resin, styrene-butadiene copolymer, styrene- Polystyrene thermoplastic elastomers such as isoprene copolymers, polyolefin thermoplastic elastomers, polyamide elastomers, thermoplastic elastomers such as polyester elastomers, diene elastomers such as polybutadiene, epoxy modified polybutadiene, acrylic modified polybutadiene, and methacrylic modified polybutadiene May be used in combination. The resin composition containing the fluorene-type cyanate ester resin may include a pigment, a dye, an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, and an ion scavenger as necessary. You may add additives other than the said components, such as.

  Next, the prepreg of the present invention will be described.

  The prepreg of the present invention is obtained by impregnating a base material with the above resin composition. Thereby, it is possible to obtain a prepreg suitable for manufacturing a printed wiring board excellent in various characteristics such as dielectric characteristics, mechanical and electrical connection reliability under high temperature and high humidity.

  The base material is not particularly limited, but glass fiber base materials such as glass woven fabric and glass nonwoven fabric, polyamide resin fibers, aromatic polyamide resin fibers, polyamide resin fibers such as wholly aromatic polyamide resin fibers, polyester resin fibers, Synthetic fiber substrate, kraft paper, cotton linter composed of woven or non-woven fabric mainly composed of aromatic polyester resin fiber, polyester resin fiber such as wholly aromatic polyester resin fiber, polyimide resin fiber, fluororesin fiber, etc. Examples thereof include organic fiber base materials such as paper base materials mainly composed of paper, mixed paper of linter and kraft pulp, and the like. Among these, a glass fiber base material is preferable. Thereby, the intensity | strength of a prepreg can improve, a water absorption can be lowered | hung, and a thermal expansion coefficient can be made small.

  Although the glass which comprises the said glass fiber base material is not specifically limited, For example, E glass, C glass, A glass, S glass, D glass, NE glass, T glass, H glass etc. are mentioned. Among these, E glass, T glass, or S glass is preferable. Thereby, the high elasticity of a glass fiber base material can be achieved and a thermal expansion coefficient can also be made small.

  The method for producing the prepreg is not particularly limited. For example, a resin varnish is prepared using the epoxy resin composition described above, the substrate is immersed in the resin varnish, the coating method is applied by various coaters, and sprayed. Methods and the like. 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 exhibits good solubility in the resin component in the resin composition, but a poor solvent may be used within a range that does not adversely affect the resin varnish. Examples of the solvent exhibiting good solubility include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, and carbitol.

  The solid content of the resin varnish is not particularly limited, but the solid content of the resin composition is preferably 50 to 80% by weight, and particularly preferably 60 to 78% by weight. Thereby, the impregnation property to the base material of a resin varnish can further be improved. Although it does not specifically limit the predetermined temperature which impregnates the said resin composition to the said base material, A prepreg can be obtained by drying at 90-220 degreeC etc., for example.

Next, the laminated board of this invention is demonstrated.

  The laminate of the present invention is formed by molding at least one prepreg described above. Thereby, the laminated board excellent in the dielectric property and the mechanical and electrical connection reliability in high temperature and high humidity can be obtained.

  In the case of a single prepreg, a metal foil or 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. Next, a laminate can be obtained by heating and pressurizing a laminate of a prepreg and a metal foil. Although the temperature to heat is not specifically limited, 120-260 degreeC is preferable and 150-240 degreeC is especially preferable. Moreover, the pressure to pressurize is not particularly limited, but is preferably 1 to 8 MPa, and particularly preferably 1.5 to 7 MPa.

  The metal foil includes, for example, copper and a copper alloy, aluminum and an aluminum alloy, silver and a silver alloy, gold and a gold alloy, zinc and a zinc alloy, nickel and a nickel alloy, tin and a tin alloy, iron and Examples thereof include iron-based alloys. Examples of the film include polyethylene, polypropylene, polystyrene resin, polyethylene naphthalate, polyethylene terephthalate, polyimide, and fluorine resin.

  Next, the resin sheet of the present invention will be described.

  The resin sheet of the present invention is formed by forming an insulating layer made of a resin composition on a film or a carrier layer made of a metal foil.

  The method of forming the insulating layer made of the resin composition on the carrier layer is not particularly limited. For example, the resin composition is dissolved and dispersed in a solvent to prepare a resin varnish, and various coating apparatuses are used. Examples thereof include a method in which a resin varnish is applied to a substrate and then dried, and a method in which the resin varnish is spray-coated on a substrate with a spray device and then dried. Among these, it is preferable to apply a resin varnish to a substrate using various coating apparatuses such as a comma coater and a die coater and then dry the resin varnish. Thereby, the resin sheet which does not have a void and has the thickness of a uniform insulating layer can be manufactured efficiently.

  The solvent used in the resin varnish desirably exhibits good solubility in the resin component in the resin composition, but a poor solvent may be used within a range that 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, 30 to 80 weight% is preferable and especially 40 to 70 weight% is preferable.

  In the resin sheet of the present invention, the thickness of the insulating layer formed by forming the resin composition on the carrier layer is not particularly limited, but is preferably 5 to 120 μm. More preferably, it is 10-80 micrometers. Thereby, when manufacturing a multilayer printed wiring board using this resin sheet, while being able to fill the unevenness | corrugation of an inner-layer circuit and to shape | mold, suitable insulating layer thickness can be ensured. Moreover, generation | occurrence | production of the crack of the insulating layer part of a resin sheet can be suppressed, and powder fall at the time of cutting can be decreased.

  The film or metal foil used for the resin sheet of the present invention is not particularly limited, and examples thereof include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polystyrene resins, fluorine resins, and polyimide resins. Heat-resistant thermoplastic resin film, or 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.

  Although it does not specifically limit as thickness of the said carrier layer, When the thing of 10-120 micrometers is used, the handleability at the time of manufacturing a resin sheet is favorable, and it is preferable.

  Next, an embodiment of the multilayer printed wiring board of the present invention will be described.

  A laminate having metal 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 (by etching or the like is formed on both sides of the laminate. 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.

  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 be formed on the inner layer circuit board by superposing the resin sheet or the prepreg on the inner layer circuit board and then heat-pressing it using a flat plate press 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 substrate 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.

  Thereafter, the insulating layer is cured by heating. Although the temperature to harden | cure is not specifically limited, For example, it can be hardened in the range of 100 to 260 degreeC. Preferably it is made to harden | cure at 150 to 230 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.

Next, an embodiment of the semiconductor device of the present invention will be described.
A semiconductor device can be manufactured by mounting a semiconductor element on a multilayer 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.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  A synthesis example of the fluorene type cyanate ester resin of the present invention is shown below. In addition, the synthesis example shown below is an illustration and is not limited to the following method.

(Synthesis Example 1)
(1) Synthesis of biscresol fluorene-type cyanate compound 22.8 g (0.06 mol, trade name BCF, manufactured by JFE Chemical, hydroxyl equivalent 380 g / eq) of bisphenol fluorene and 150 ml of tetrahydrofuran (hereinafter referred to as THF) were charged and dried N2. Dissolve with stirring under atmosphere. After dissolution, it was cooled to -20 ° C. Cyanogen bromide (hereinafter BrCN) 19.1 g (purity 95%, 0.18 mol) was charged at -20 ° C., and the internal temperature was controlled to -15 to -20 ° C., while trimethylamine (hereinafter TEA) 18 0.2 g (0.18 mol) was added dropwise over 1 hour. After completion of the dropwise addition, stirring was further continued for 12 hours to complete the reaction.

The triethylamine salt was removed from the resulting solution by filtration with a filter paper (5C), and slowly poured into 600 ml of isopropanol cooled to −20 ° C. to obtain a precipitate. After filtration, it was washed again with 600 ml of isopropanol cooled to −20 ° C., filtered with a filter paper (5C), and then dried with a vacuum dryer (60 ° C., 1 torr). 22.0 g (yield 90%) of resin Got. Fluorene type cyanate ester obtained in this way is by infrared absorption spectrum measurement (Shimadzu IR Prestige-21, KBr transmission method), and the disappearance of absorption attributable hydroxyl groups of 3200~3500cm ^-1 2265cm ^-1 The absorption derived from cyanate ester was confirmed.

(Synthesis Example 2)
(2) Synthesis of bisphenolfluorene-type cyanate ester compound 21.1 g (0.06 mol, trade name BPFL, manufactured by JFE Chemical, hydroxyl equivalent 176 g / eq) of bisphenolfluorene and 150 ml of tetrahydrofuran (hereinafter THF) were charged in a dry N2 atmosphere. Dissolve under stirring. After dissolution, it was cooled to -20 ° C. Cyanogen bromide (hereinafter BrCN) 19.1 g (purity 95%, 0.18 mol) was charged at -20 ° C., and the internal temperature was controlled to -15 to -20 ° C., while trimethylamine (hereinafter TEA) 18 0.2 g (0.18 mol) was added dropwise over 1 hour. After completion of the dropwise addition, stirring was further continued for 12 hours to complete the reaction.

The triethylamine salt was removed from the resulting solution by filtration with a filter paper (5C), and slowly poured into 600 ml of isopropanol cooled to −20 ° C. to obtain a precipitate. After filtration, it was washed again with 600 ml of isopropanol cooled to −20 ° C., filtered through a filter paper (5C), and then dried with a vacuum dryer (60 ° C., 1 torr) to obtain 23.9 g (yield 92%) of resin. Got. Fluorene type cyanate ester obtained in this way is by infrared absorption spectrum measurement (Shimadzu IR Prestige-21, KBr transmission method), and the disappearance of absorption attributable hydroxyl groups of 3200~3500cm ^-1 2265cm ^-1 The absorption derived from cyanate ester was confirmed.

(Synthesis Example 3)
(3) Synthesis of bisphenol-type fluorene-type cyanate compound 22.7 g of bisphenol-type fluorene (0.06 mol, trade name CP-001, manufactured by Osaka Gas Chemical Co., Ltd., hydroxyl equivalent 176 g / eq) and tetrahydrofuran (hereinafter THF) 150 ml is charged and dissolved under stirring in a dry N2 atmosphere. After dissolution, it was cooled to -20 ° C. Cyanogen bromide (hereinafter BrCN) 19.1 g (purity 95%, 0.18 mol) was charged at -20 ° C., and the internal temperature was controlled to -15 to -20 ° C., while trimethylamine (hereinafter TEA) 18 0.2 g (0.18 mol) was added dropwise over 1 hour. After completion of the dropwise addition, stirring was further continued for 12 hours to complete the reaction.

The triethylamine salt was removed from the resulting solution by filtration with a filter paper (5C), and slowly poured into 600 ml of isopropanol cooled to −20 ° C. to obtain a precipitate. After filtration, the sample was again washed with 600 ml of isopropanol cooled to −20 ° C., filtered through a filter paper (5C), and then dried with a vacuum dryer (60 ° C., 1 torr) to obtain 24.7 g (yield 95%) of resin. Got. Fluorene type cyanate ester obtained in this way is by infrared absorption spectrum measurement (Shimadzu IR Prestige-21, KBr transmission method), and the disappearance of absorption attributable hydroxyl groups of 3200~3500cm ^-1 2265cm ^-1 The absorption derived from cyanate ester was confirmed.

  Below, the resin composition using the cyanate ester compound of the present invention will be described with reference to Examples and Comparative Examples. The present invention is not limited to this.

(1) Preparation of resin varnish 20 parts by weight of the biscleresol cyanate ester compound obtained in Synthesis Example 1, 15 parts by weight of biphenyldimethylene type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000H, epoxy equivalent 275) Parts, 15 parts by weight of a biphenyldimethylene type phenol resin (Maywa Kasei Co., Ltd., MEH-7851-3H, hydroxyl group equivalent 230), and an epoxy silane type coupling agent (GE Toshiba Silicone Co., Ltd., A-187). 3 parts by weight is dissolved in methyl ethyl ketone at room temperature, 49.7 parts by weight of spherical fused silica (manufactured by Admatechs Co., Ltd., spherical fused silica, SO-25R, average particle size 0.5 μm) is added, and a high-speed stirrer is used. For 10 minutes to obtain a resin varnish.

(2) Production of prepreg The glass woven fabric (thickness 94 μm, manufactured by Nitto Boseki Co., Ltd., WEA-2116) is impregnated with the resin varnish, and dried in a heating furnace at 170 ° C. for 2 minutes, so that the varnish solid content in the prepreg is about A 50% by weight prepreg was obtained.

(3) Manufacture of resin sheet The resin varnish was coated on PET (polyethylene terephthalate, Purex film 36um made by Teijin DuPont Films) and dried for 2 minutes with a dryer at 150 ° C to obtain a resin sheet.

(4) Manufacture of laminated board Two prepregs as described above are stacked, 18 μm copper foil is stacked on both sides, and heated and pressure-molded at a pressure of 4 MPa and a temperature of 220 ° C. for 2 hours. A laminate having copper clad was obtained.

(5) Production of Multilayer Printed Wiring Board After the through-hole processing was performed using the 0.1 mm drill bit on the laminated board having copper clad on both sides obtained above, the through-hole was filled by plating. Further, a circuit was formed on both sides by etching and used as an inner layer circuit board. On the front and back of the inner layer circuit board, a commercially available resin film (sometimes referred to as a build-up material) (Ajinomoto Fine Techno Co., ABF GX-13, thickness 40 μm) is used on the inner layer circuit using a vacuum laminating apparatus. Laminated and heat cured at a temperature of 170 ° C. for 60 minutes to obtain a laminate.

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

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

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

(6) Fabrication of semiconductor device As described above, an opening is provided in the insulating layer of the multilayer printed wiring board using a carbonic acid laser device, an outer layer circuit is formed on the surface of the insulating layer by electrolytic copper plating, and conduction between the outer layer circuit and the inner layer circuit is performed. I planned. Note that the outer layer circuit was provided with a connection electrode part for mounting a semiconductor element. Thereafter, a solder resist (manufactured by Taiyo Ink, PSR4000 / AUS308) is formed on the outermost layer, the connection electrode part is exposed so that a semiconductor element can be mounted by exposure and development, and nickel gold plating treatment is performed, and the size is 50 mm × 50 mm. A multilayer printed wiring board was obtained by cutting. Thereafter, in the semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm), the solder bump is formed of a eutectic of Sn / Pb composition, and the circuit protective film is a positive photosensitive resin (CRC- manufactured by Sumitomo Bakelite Co., Ltd.). 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 the 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 liquid sealing resin was cured at a temperature of 150 ° C. for 120 minutes.

In Examples 2 to 13 and Comparative Example 1, a prepreg, a resin sheet, a laminated board, a multilayer printed wiring board, and a semiconductor device were prepared in the same manner as in Example 1 except that a resin varnish was prepared according to the recipe shown in Table 1. Produced. The raw materials used in Examples 2 to 13 and Comparative Example 1 other than the raw materials used in Example 1 (excluding Synthesis Examples 2 and 3) are shown below.
(1) Cyanate resin / Novolac type cyanate resin: Lonza Japan Co., Ltd. “Primaset PT-30”, cyanate equivalent 124
(2) Cyanate resin / bisphenol A type cyanate resin: Lonza Japan Co., Ltd. “Primaset BA-230”, cyanate equivalent 232
(3) Epoxy resin / biphenyl dimethylene type epoxy resin: Nippon Kayaku Co., Ltd. “NC-3000H”, epoxy equivalent 275
(4) Epoxy resin / naphthalene type bifunctional epoxy resin: manufactured by DIC, “HP-4032D”, epoxy equivalent 140 g / eq
(5) Epoxy resin / naphthalene type tetrafunctional epoxy resin: manufactured by DIC, “HP-4700”, epoxy equivalent of 165 g / eq
(6) Phenol resin / biphenylalkylene type novolak resin: “MEH-7851-3H” manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent 230
(7) Inorganic filler / spherical silica; manufactured by Admatechs Co., Ltd. “SO-25R”, average particle size 0.5 μm
(8) Inorganic filler / spherical silica; manufactured by Admatechs Co., Ltd. “SO-31R”, average particle size 1.0 μm
(9) Inorganic filler / spherical silica; “NSS-5N” manufactured by Tokuyama Corporation, average particle 70 nm
(10) Inorganic filler / boehmite; “BMT-3L” manufactured by Kawai Lime Co., Ltd., average particle 2.9 μm
(11) Inorganic filler / boron nitride; made by Mizushima Alloy Iron Co., Ltd. “HP-P1”, average particle size 2.0 μm
(12) Inorganic filler / alumina; manufactured by Nippon Light Metal Co., Ltd. “LS-22”, average particle size 2.4 μm
(13) Inorganic filler / talc; “LMS-200” manufactured by Fuji Talc Co., Ltd., average particle size 6.0 μm
(14) Coupling agent / epoxysilane; manufactured by GE Toshiba Silicone Co., Ltd. “A-187”

Table 1 shows the blending of resin varnishes of Examples and Comparative Examples, and the evaluation results are shown in Table 1 and Table 2.

Evaluation methods are shown in the following (1) to (7).
(1) Glass transition temperature:
A copper-clad laminate having copper foil on both sides with a thickness of 0.1 mm was etched all over, a 10 mm × 60 mm test piece was cut out from the obtained laminate, and a dynamic viscoelasticity measuring apparatus (TA Instruments, The temperature was increased at 3 ° C./min using DMA983) and measured. The glass transition temperature was the temperature at the peak position of tan δ.

(2) Linear expansion coefficient:
A laminated board having a copper foil on both sides having a thickness of 0.1 mm is entirely etched, and a 2 mm × 2 mm test piece is cut out from the obtained laminated board, and the thickness direction (XY) is obtained using TMA (TA Instruments). Direction) was measured. The measurement was performed in a pulling mode under a nitrogen atmosphere at a rate of temperature increase of 5 ° C./min, a temperature of 25 to 300 ° C., a load of 5 g, and two cycles. The coefficient of thermal expansion was the average linear thermal expansion coefficient at a temperature of 50 to 100 ° C. in the second cycle.

(3) Relative permittivity:
A laminated plate having copper foil on both sides with a thickness of 0.1 mm is etched on the entire surface by the triplate line resonator method, and a test piece of 20 mm × 50 mm is cut out from the obtained laminated plate to obtain a 1.6 mm thickness by stacking 16 pieces. The value of 1 GHz was measured.

(4) Flame retardancy:
In accordance with the UL-94 standard, a laminated board having copper foil on both sides with a thickness of 0.1 mm is etched on the entire surface, and a 13 mm × 125 mm test piece is cut out from the obtained laminated board, and a 0.1 mm thick test piece is obtained by a vertical method It was measured.

(5) Water absorption rate:
A laminated board having a copper foil on both sides having a thickness of 0.1 mm was etched on the entire surface, and a 50 mm × 50 mm test piece was cut out from the obtained laminated board and measured according to JIS6481.

(6) Hygroscopic solder heat resistance:
A test piece was prepared by cutting out a 50 mm × 50 mm from a laminate having a copper foil on both sides having a thickness of 0.1 mm and performing half-side etching in accordance with JIS 6481.
After treating for 24 hours at 121 ° C. using a pressure cooker, it was immersed in 288 ° C. solder for 60 seconds, and the presence or absence of swelling was observed. Each code | symbol is as follows.
○: No abnormality ×: Swelling occurred

(7) Moisture absorption multi-reflow The multilayer printed wiring board obtained above was passed through a 260 ° C. reflow furnace after pretreatment at a temperature of 85 ° C. and a humidity of 60% for 168 hours in accordance with J-STD-20 of IPC / JEDEC. Every five times, peeling of the insulating layer of the multilayer printed wiring board and defect of cracks were evaluated with an ultrasonic deep flaw inspection apparatus.
Each code is as follows.
A: No peeling of the insulating layer and generation of cracks 20 times or more.
○: Peeling or cracking occurred 10 times or more and less than 20 times.
Δ: Peeling or cracking occurred 5 times or more and less than 10 times.
X: Less than 5 times Insulating layer peeling or cracking occurred.

  The laminates obtained in each example have excellent flame retardancy despite the absence of halogen-based flame retardants and phosphorus compounds, and have the heat resistance and low thermal expansion required for recent electronic devices. It can be seen that it has an excellent balance of rate, low dielectric property and moisture absorption resistance. Moreover, the reflow heat resistance after moisture absorption of the multilayer printed wiring board was excellent. On the other hand, Comparative Example 1 could not obtain good results in flame retardancy, water absorption, and solder resistance.

  Since the resin composition using the cyanate ester compound of the present invention has a low coefficient of thermal expansion and excellent fluidity, it can be suitably used for a prepreg. The prepreg has no appearance defects such as stripes, and is excellent in formability and workability.

Claims (7)

The cyanate ester compound represented by the following formula (1) is an essential component,
Furthermore, the resin composition characterized by including an epoxy resin and a hardening | curing agent.
[Wherein R ₁ is any one of the following formulas (2) to (5). ]
[Wherein R ₂ represents any one of H, a C1-C3 aliphatic hydrocarbon, and a C6-C12 aromatic hydrocarbon. ] The resin composition of claim 1 further comprising an inorganic filler. The resin composition according to claim 2 , wherein the inorganic filler is at least one selected from the group consisting of silica, aluminum hydroxide, boehmite, talc, and calcium carbonate. Prepreg comprising a resin composition by impregnating a base material according to any one of claims 1 to 3. A laminate obtained by molding one or more prepregs according to claim 4 . The resin sheet which has an insulating layer which consists of a resin composition in any one of Claim 1 thru | or 3 , and a carrier layer which consists of a film or metal foil. A multilayer printed wiring board produced using at least one of the prepreg according to claim 4, the laminate according to claim 5, and the resin sheet according to claim 6 .