WO2011010672A1 - 樹脂組成物、樹脂シート、プリプレグ、金属張積層板、プリント配線板及び半導体装置 - Google Patents
樹脂組成物、樹脂シート、プリプレグ、金属張積層板、プリント配線板及び半導体装置 Download PDFInfo
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- WO2011010672A1 WO2011010672A1 PCT/JP2010/062259 JP2010062259W WO2011010672A1 WO 2011010672 A1 WO2011010672 A1 WO 2011010672A1 JP 2010062259 W JP2010062259 W JP 2010062259W WO 2011010672 A1 WO2011010672 A1 WO 2011010672A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0212—Resin particles
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0263—Details about a collection of particles
- H05K2201/0266—Size distribution
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
Definitions
- the present invention relates to a resin composition, a resin sheet, a prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor device.
- printed wiring boards and the like for high-density mounting used for these are becoming smaller, thinner, higher density, and multi-layered than ever before. Accordingly, printed wiring boards and metal-clad laminates are required to have the following characteristics after satisfying basic requirements such as flame retardancy. That is, (1) In order to cope with the reduction in rigidity of the substrate itself due to the reduction in thickness, it has excellent low thermal expansion and low warpage, and dimensional deformation and warpage when connecting parts to a metal-clad laminate or printed wiring board by reflow. (2) Because it supports multi-layered printed wiring boards, it has excellent desmearing properties during the plating process, and sufficient electrical conductivity between the upper metal wiring and lower metal wiring can be secured. (3) Rapid mass production Therefore, it is required to have excellent drill workability and high productivity.
- a prepreg used for the production of a printed wiring board is generally prepared by dissolving a resin composition mainly composed of a thermosetting resin such as an epoxy resin in a solvent to make a varnish, impregnating this into a base material, and drying by heating. It is produced by making it.
- a resin composition containing an inorganic filler in order to improve heat resistance, low thermal expansion, low warpage, desmear resistance, etc. of prepregs, laminates and printed wiring boards, and drill workability of prepregs, etc.
- a prepreg is produced using a resin composition containing a flexible component for improvement.
- the resin composition disclosed in Patent Document 1 has an epoxy resin, a curing agent, an aluminum filler or an inorganic filler containing spherical silica and aluminum hydroxide, a core-shell structure, and a shell portion formed of the epoxy resin. It contains a flexible component composed of fine particles composed of a compatible resin, and has a thermal expansion coefficient ⁇ z in the thickness (Z) direction in a cured state of 48 or less. Patent Document 1 describes that a laminate produced using the resin composition has good dimensional stability and drilling workability and suppresses the generation of cracks during drilling.
- Patent Document 2 discloses a prepreg obtained by combining a thermosetting resin composition containing an aluminum hydroxide-boehmite composite product as an essential component with a base material.
- the technique described in Patent Document 2 uses a material having high heat resistance such as boehmite or an aluminum hydroxide-boehmite composite product as an inorganic filler in order to cope with an increase in solder reflow temperature.
- Patent Document 3 discloses a technique related to a filler that fills a through hole and / or a recess of a base material.
- it is a technique for the purpose of preventing the occurrence of cracks and improving drillability in a base material filled with a filler, and is a liquid filler containing at least a curing agent, an inorganic filler, an organic filler, and a liquid resin. Is disclosed.
- the varnish of the resin composition containing a large amount of inorganic filler fine particles or flexible component fine particles tends to impair the dispersibility of the fine particles and increases the viscosity (thixo). Therefore, it becomes difficult to impregnate the base material with a sufficient amount of the resin composition and to uniformly impregnate the base material into the base material.
- the unevenness of the prepreg and the pressure due to the fine particles vary, there is a problem that separation between the resin and the fine particles easily occurs, and streaky unevenness occurs in the obtained metal-clad laminate.
- an amorphous inorganic filler such as boehmite is used, there is a problem that the fluidity of the varnish of the resin composition is particularly likely to be lowered, and it is difficult to highly fill the inorganic filler.
- the present invention has been accomplished in view of the above circumstances, and an object of the present invention is to provide good properties for impregnation of the base material and characteristics imparted by the filler (for example, low warpage, flame retardancy). It is to provide a resin composition capable of producing a prepreg, a metal-clad laminate, and a printed wiring board, which are excellent in properties, such as properties, low thermal expansion properties, drill workability, and desmear resistance.
- Another object of the present invention is to provide a resin sheet produced using the resin composition, a prepreg produced using the resin composition, a metal-clad laminate produced using the resin composition or the prepreg, and the metal
- An object of the present invention is to provide a printed wiring board produced using at least one of a tension laminate, the prepreg, and the resin composition, and a semiconductor device excellent in performance produced using the printed wiring board. .
- a resin composition used for forming a laminated board which has an average particle size different from that of an epoxy resin, an amorphous first inorganic filler, and the first inorganic filler. And a second inorganic filler having a thickness of 10 to 100 nm.
- the weight ratio (w2 / w3) between the content (w2) of the second inorganic filler and the content (w3) of the third inorganic filler is 0.02 to 1.5.
- the weight ratio (w2 / w1) between the content (w1) of the first inorganic filler and the content (w2) of the second inorganic filler is 0.02 to 0.5.
- the epoxy resin is at least one selected from the group consisting of a biphenyl dimethylene type epoxy resin, a novolac type epoxy resin, a naphthalene-modified cresol novolac epoxy resin, and an anthracene type epoxy resin.
- the resin composition according to (14), wherein the silicone rubber fine particles are core-shell structure particles in which a core portion made of silicone rubber is coated with a silicone resin.
- the resin composition according to the above (14) or (15), wherein the silica nanoparticles have an average particle diameter of 40 nm to 100 nm.
- (22) A metal-clad laminate characterized by having a metal foil on at least one surface of a resin-impregnated base material layer obtained by impregnating the resin composition according to any one of (1) to (19) in a base material Board.
- (24) A printed wiring board comprising the metal-clad laminate according to (22) or (23) as an inner layer circuit board.
- (25) A printed wiring board obtained by using the prepreg described in (21) as an insulating layer on an inner layer circuit.
- (26) A printed wiring board obtained by using the resin composition according to any one of (1) to (19) as an insulating layer on an inner layer circuit.
- (27) A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to any one of (24) to (27).
- the first inorganic filler having an irregular shape and a first inorganic filler having a different average particle diameter from the first inorganic filler and having an average particle diameter of 10 to 100 nm are used in combination.
- this resin composition it is possible to obtain a varnish containing an amorphous first inorganic filler without impairing fluidity, and it is possible to suppress warpage of the metal-clad laminate.
- the second resin composition containing a combination of silicone rubber fine particles, boehmite particles, and silica nanoparticles a varnish containing a large amount of the three types of particles in a low viscosity state can be obtained.
- the resin composition has good impregnation into the substrate.
- Resin sheets, prepregs and metal-clad laminates produced using the resin composition are excellent in properties such as flame retardancy, low thermal expansion, drill workability, low warpage, and desmear resistance. Furthermore, a printed wiring board excellent in performance can be obtained using at least one of the metal-clad laminate, the prepreg, the resin sheet, and the resin composition. Further, according to the present invention, a semiconductor device having excellent performance can be obtained using the printed wiring board.
- the resin composition of the present invention and the resin sheet, prepreg, metal-clad laminate, printed wiring board, and semiconductor device using the resin composition will be described.
- the first to fifth resin compositions of the present invention can suppress a decrease in fluidity of a varnish obtained by mixing the resin composition with a solvent, despite containing a high ratio of filler. Therefore, the resin composition of the present invention has a good impregnation property to the substrate.
- the resin composition of the present invention provides effects obtained by using fillers, such as low warpage, flame retardancy, low thermal expansion, drilling workability, and desmear resistance in prepregs, laminates or printed wiring boards. The effect of improving the characteristics is high.
- the resin composition of the present invention includes multiple types of filler particles. These different kinds of filler particles contained in the resin composition of the present invention are selected to generate attractive forces between the particles. As a result, each filler particle is contained in a highly dispersed state in the resin composition, and a decrease in fluidity of the varnish is suppressed.
- the first to fifth resin compositions of the present invention have the common concept as described above.
- the filler particles to which the attractive force acts may exist in a state where there is a gap between the particles, or may exist in a state where they are adhered (contacted).
- the combination of different kinds of filler particles is a combination in which the attractive force acts strongly, the filler particles are adhered to each other, specifically, for example, the surface of the filler particles having a large particle diameter has a small particle diameter. It exists in the state which the filler particle adhered.
- the attractive force includes attractive force due to the surface potential (zeta potential) of the filler particles, attractive force due to van der Waals force, attractive force due to chemical bonding due to coupling agent treatment, etc., among which attractive force due to surface potential is preferable. .
- the 1st resin composition of this invention is a resin composition used in order to form a laminated board, Comprising: An epoxy resin, an amorphous 1st inorganic filler, the said 1st inorganic filler, and an average particle diameter And a second inorganic filler having an average particle size of 10 to 100 nm.
- the amorphous first inorganic filler and the second inorganic filler In the first resin composition including the epoxy resin, the amorphous first inorganic filler, and the second inorganic filler, the amorphous first inorganic filler and the second inorganic filler.
- the material eg, nano silica
- the second inorganic filler is present around the irregular first inorganic filler, and the second inorganic filler exhibits an action as a spacer of the irregular first inorganic filler.
- the attractive force due to the van der Waals force acting between the irregular first inorganic fillers is reduced, and aggregation thereof is prevented.
- the amorphous first inorganic filler is contained in the first resin composition in a highly dispersed state, and a decrease in fluidity of the varnish is suppressed.
- it is possible to obtain a resin composition that can suppress warping of a prepreg or a laminate without impairing the fluidity of a varnish even when an amorphous inorganic filler is used. it can.
- the first resin composition of the present invention contains an epoxy resin.
- the metal-clad laminated board and printed wiring board which are excellent in an electrical property can be obtained.
- it does not specifically limit as said epoxy resin,
- the thing which does not contain a halogen atom substantially is preferable.
- “substantially free of halogen atoms” means that the halogen derived from the halogen-based component used in the epoxy resin synthesis process remains in the epoxy resin even after the halogen removal step. Means to allow.
- it is preferable that the epoxy resin does not contain a halogen atom exceeding 30 ppm.
- Examples of the epoxy resin substantially free of halogen atoms include 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'- Cyclohexyldiene bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 '-(1,4) -phenylenediisopropylidene) bisphenol type epoxy resin), bisphenol M type epoxy resin (4,4'-(1 , 3-phenylenediisopropylidene) bisphenol type epoxy resin), phenol novolak type epoxy resin, cresol novolak type epoxy resin, etc.
- novolak type epoxy resin novolak type epoxy resin
- biphenyl type epoxy resin xylylene type Poxy resin
- phenol 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 tetrafunctional glycidylamines
- arylalkylene type epoxy resins such as tetramethylbiphenyl type epoxy resins
- naphthalene type epoxy resins such as naphthalene skeleton modified epoxy resins, methoxynaphthalene modified cresol novolac type epoxy resins, methoxynaphthalenedylene methylene type epoxy resins, etc.
- anthracene type epoxy resin phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluoro Emission type epoxy resin, flame-retardant epoxy resin or the like halogenated epoxy resins.
- One of these epoxy resins can be used alone, or two or more types of epoxy resins having different weight average molecular weights can be used in combination.
- One or more types of epoxy resins and epoxy A resin prepolymer can also be used in combination.
- epoxy resins at least one selected from the group consisting of biphenyl dimethylene type epoxy resins, novolac type epoxy resins, naphthalene-modified cresol novolac epoxy resins, and anthracene type epoxy resins is preferable.
- the moisture-absorbing solder heat resistance and flame retardancy of the resulting laminate and printed wiring board can be improved.
- the content of the epoxy resin is not particularly limited, but is preferably 5% by weight or more and 60% 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 reduced, or the moisture resistance of a prepreg or printed wiring board obtained using the resin composition may be reduced. Moreover, when the said upper limit is exceeded, the linear thermal expansion coefficient of a prepreg or a printed wiring board may become large, or heat resistance may fall.
- the content of the epoxy resin is particularly preferably 10% by weight or more and 50% by weight or less based on the entire resin composition.
- the weight average molecular weight of the epoxy resin is not particularly limited, but is preferably 1.0 ⁇ 10 2 or more and 2.0 ⁇ 10 4 or less. When the weight average molecular weight is less than the lower limit value, tackiness may occur on the surface of the insulating resin layer formed using the resin composition. 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, for example, by gel permeation chromatography (GPC) and specified as a weight molecular weight in terms of polystyrene.
- the first resin composition of the present invention contains an amorphous first inorganic filler.
- the amorphous first inorganic filler include crushed silica, zinc borate, talc, aluminum hydroxide, boehmite (alumina monohydrate obtained by modifying gibbsite) and the like. Among these, aluminum hydroxide and boehmite are preferable. It is because the heat resistance and drilling workability of the laminated board and printed wiring board obtained using the resin composition can be further improved.
- the average particle diameter of the first inorganic filler is not particularly limited, but is preferably 0.3 to 5 ⁇ m, particularly preferably 0.5 to 5 ⁇ m, and more preferably 0.5 to 3 ⁇ m. When the average particle size is within the above range, a resin composition that is particularly excellent in the high filling property and fluidity of the first inorganic filler can be obtained.
- the average particle diameter of the first inorganic filler can be measured by a laser diffraction scattering method.
- the inorganic filler is dispersed in water by ultrasonic waves, and the particle size distribution of the inorganic filler is created on a volume basis by a laser diffraction particle size distribution analyzer (HORIBA, LA-500).
- the median diameter is defined as the average particle diameter. It can be measured by doing. Specifically, the average particle diameter of the inorganic filler is defined by D50.
- the content of the first inorganic filler is not particularly limited, but is preferably 20 to 65% by weight, and particularly preferably 25 to 55% by weight of the entire resin composition. When the content is in the above range, the balance between heat resistance and fluidity is particularly excellent.
- the 1% thermal decomposition temperature of the first inorganic filler is preferably 260 ° C. or higher, and particularly preferably 300 ° C. or higher.
- the 1% pyrolysis temperature is defined by a differential thermal balance (TG / DTA) at a temperature increase rate of 10 ° C./min and a temperature at a point of 1% weight reduction from the initial weight.
- Examples of the first inorganic filler having a 1% thermal decomposition temperature of 300 ° C. or higher include boehmite.
- the first resin composition of the present invention includes a second inorganic filler having an average particle diameter different from that of the first inorganic filler and having an average particle diameter of 10 to 100 nm.
- the second inorganic filler include fused silica obtained by a dry method such as a combustion method, and sol-gel silica obtained by a wet method such as a precipitation method and a gel method.
- the first resin composition is prepared by dispersing a slurry in which the second inorganic filler is previously dispersed in an organic solvent. It is preferable to be prepared using. In particular, it is preferable to use a slurry in which nano-sized silica is previously dispersed in an organic solvent.
- nano-sized particles such as nano-sized silica tend to aggregate and often form secondary aggregates when blended into the resin composition. Such secondary agglomeration can be prevented, thereby preventing the fluidity from being lowered.
- aggregation prevention of the amorphous first inorganic filler due to the difference between the surface potential of the second inorganic filler (nano-sized silica) and the surface potential of the amorphous first inorganic filler described above. This is because the effect is enhanced.
- the average particle size of the second inorganic filler is particularly preferably 15 to 90 nm, and most preferably 25 to 75 nm. When the average particle diameter is within the above range, the high filling property of the second inorganic filler and the high fluidity of the varnish in the resin composition can be improved.
- the average particle diameter can be measured by, for example, an ultrasonic vibration current method (zeta potential), an ultrasonic attenuation spectroscopy (particle size distribution), a laser diffraction scattering method, or a dynamic light scattering method.
- an inorganic filler is dispersed in water by ultrasonic waves, and a particle size distribution of the inorganic filler is created on a volume basis by a dynamic light scattering particle size distribution device (HORIBA, LB-550), and the median diameter is averaged. It can measure by setting it as a particle diameter.
- the average particle size of the inorganic filler is defined by D50.
- the content of the second inorganic filler is not particularly limited, but is preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, and more preferably 0.5 to 5% by weight of the entire resin composition. preferable. When the content is within the above range, the impregnation property and moldability of the resin composition in the prepreg are particularly excellent.
- the weight ratio (w2 / w1) between the content (w1) of the first inorganic filler and the content (w2) of the second inorganic filler is not particularly limited, but is 0.02 to 0.5. It is preferable that it is 0.06 to 0.4. When the weight ratio is within the above range, the moldability can be particularly improved.
- the first resin composition is not particularly limited, but preferably contains a third inorganic filler having an average particle diameter of 0.2 to 3 ⁇ m.
- a third inorganic filler having the average particle diameter together with the first inorganic filler and the second inorganic filler, the heat resistance of the laminate and the printed wiring board obtained using the resin composition and Dimensional stability can be particularly improved.
- a submicron-order inorganic filler such as the third inorganic filler and a non-reactive material such as the first filler are used.
- the impregnation property of the resin varnish can be improved as compared with a conventional resin composition in combination with a regular inorganic filler.
- the average particle size of the third inorganic filler is particularly preferably 0.3 to 2.5 ⁇ m, and most preferably 0.4 to 1.5 ⁇ m. When the average particle size is within the above range, particularly high filling of the third inorganic filler in the resin composition and workability such as press molding of a prepreg obtained by using the resin composition and drilling of a laminated plate Balance can be improved.
- the average particle diameter of the third inorganic filler can be measured by a laser diffraction scattering method. Specifically, the average particle diameter of the third inorganic filler can be measured by the same method as that for the first inorganic filler.
- the maximum particle size of the third inorganic filler is not particularly limited, but is preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less. Thereby, the bit breakage rate at the time of drilling in printed wiring board production can be reduced.
- Examples of the third inorganic filler include silica, titanium oxide, silicon nitride, aluminum nitride, boron nitride, and alumina.
- silica is preferable, and spherical fused silica is particularly preferable. This is because such fused silica is excellent in low thermal expansion compared to other inorganic fillers.
- the manufacturing method of the said spherical silica is not specifically limited, It can obtain by a well-known method. Examples of the method for producing the spherical silica include a dry silica method, a wet silica method, and a sol-gel method.
- the weight ratio (w2 / w3) between the content (w2) of the second inorganic filler and the content (w3) of the third inorganic filler is not particularly limited, but is 0.02 to 1.5. Preferably, it is preferably 0.05 to 1.2. When the weight ratio is in the above range, the moldability of a laminate or a printed wiring board is particularly excellent when a prepreg using a resin composition is laminated.
- the specific surface area of the third inorganic filler (especially silica) is not particularly limited, but is preferably 1 m 2 / g or more and 250 m 2 / g or less. If the specific surface area exceeds the upper limit, the third inorganic fillers tend to aggregate together, and the structure of the resin composition may become unstable. Moreover, when it is less than the said lower limit, it may be difficult to fill the resin composition with the third inorganic filler.
- the specific surface area can be determined by the BET method.
- the third inorganic filler (particularly silica) may be used after surface treatment with functional group-containing silanes and / or alkylsilazanes in advance.
- aggregation of the third inorganic filler can be suppressed, and silica can be favorably dispersed in the resin composition of the present invention.
- the adhesiveness of the surface of an epoxy resin and a 3rd inorganic filler improves, the insulating layer excellent in mechanical strength is obtained.
- Suitable functional group-containing silanes such as the functional group-containing silanes and / or alkylsilazanes can be used.
- alkylsilazanes examples include hexamethyldisilazane (HMDS), 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexamethylcyclotrisilazane, and the like. It can. Among these, hexamethyldisilazane (HMDS) is preferable as the alkylsilazanes.
- HMDS hexamethyldisilazane
- the amount of the functional group-containing silanes and / or alkylsilazanes to be surface-treated in advance on the third inorganic filler is not particularly limited, but is 0.01% with respect to 100 parts by weight of the third inorganic filler. It is preferable that the amount is not less than 5 parts by weight. More preferably, it is 0.1 to 3 parts by weight. If the content of functional group-containing silanes and / or alkylsilazanes exceeds the upper limit, the insulating layer may crack in the production of the printed wiring board. If the content is less than the lower limit, 3 Bonding strength with the inorganic filler may be reduced.
- the method for surface-treating the third inorganic filler (especially silica) with functional group-containing silanes and / or alkylsilazanes is not particularly limited, but a wet method or a dry method is preferable.
- the wet method is particularly preferable.
- the wet method can uniformly treat the surface of the third inorganic filler.
- content of the said 3rd inorganic filler (especially silica) is not specifically limited, It is preferable that it is 20 to 85 weight% of the whole resin composition. More preferably, it is 25 to 75 weight%.
- content of the third inorganic filler is less than the lower limit, the linear thermal expansion coefficient of the cured product of the resin composition may increase or the water absorption rate may increase.
- moldability such as an insulating resin layer and a prepreg, may fall by the fall of the fluidity
- cured material of a resin composition can be 35 ppm or less.
- content with respect to the resin composition of a component makes 100 weight% the total amount of a component except the solvent contained for the purpose of melt
- the first resin composition is not particularly limited, but preferably contains a cyanate resin. Thereby, a flame retardance can be improved more.
- the cyanate resin is not particularly limited, and can be obtained, for example, by reacting a halogenated cyanide compound with phenols or naphthols and, if necessary, prepolymerizing by a method such as heating. Moreover, the commercial item prepared in this way can also be used.
- 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. can be mentioned. .
- the cyanate resin preferably has two or more cyanate groups (—O—CN) in the molecule.
- cyanate groups —O—CN
- phenol novolac-type cyanate resin is excellent in flame retardancy and low thermal expansion
- 2,2′-bis (4-cyanatophenyl) isopropylidene and dicyclopentadiene-type cyanate ester control the crosslinking density.
- a phenol novolac type cyanate resin is preferred from the viewpoint of low thermal expansion.
- other cyanate resins may be used alone or in combination of two or more, and are not particularly limited.
- the cyanate resin may be used alone, or two or more cyanate resins having different weight average molecular weights may be used in combination, or the cyanate resin and its prepolymer may be used in combination.
- 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 exhibited.
- the content of the cyanate resin is not particularly limited, but is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, and particularly preferably 10 to 40% by weight based on the solid content of the entire resin composition. % By weight. When the content is within the above range, the cyanate resin can effectively exhibit heat resistance and flame retardancy. If the content of the cyanate resin is less than the lower limit, the thermal expansibility increases and the heat resistance may decrease, and if it exceeds the upper limit, the strength of the prepreg produced using the resin composition may decrease. is there.
- a 1st resin composition is not specifically limited, It is preferable that a coupling agent is included. Thereby, the mechanical strength of the laminated board and printed wiring board obtained using a resin composition can be improved.
- aromatic aminosilane is preferably used as the coupling agent.
- the water absorption of the cured product of the resin composition can be further reduced by the synergistic effect of boehmite and aromatic aminosilane, and the multilayer printed wiring board obtained using this resin composition is tested after moisture absorption treatment. In, it is excellent in the adhesiveness between metal foil, a prepreg, and a prepreg.
- aromatic aminosilane examples include secondary aromatic aminosilanes such as N-phenyl-3-aminopropyltrimethoxysilane, (phenylaminomethyl) methyldimethoxysilane, and N-phenylaminomethyltriethoxysilane, and 3- ( and primary aromatic amines such as m-aminophenoxy) propyltrimethoxysilane, p-aminophenyltrimethoxysilane, and m-aminophenyltrimethoxysilane.
- secondary aromatic aminosilanes such as N-phenyl-3-aminopropyltrimethoxysilane are preferable.
- the content of the coupling agent is not particularly limited, but is preferably 0.05 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the first inorganic filler. More preferably, it is 0.2 parts by weight or more and 2.5 parts by weight or less.
- the content of the coupling agent exceeds the upper limit, the moldability of the prepreg formed by impregnating the first resin composition of the present invention may be lowered during the production of the laminate, and the lower limit. If it is less than the range, the adhesion between the circuit and the insulating layer formed from the first resin composition of the present invention may be reduced.
- the first resin composition can further use a phenolic curing agent.
- a phenolic curing agent known or commonly used phenolic novolac resins, alkylphenol novolac resins, bisphenol A novolac resins, dicyclopentadiene type phenol resins, zyloc type phenol resins, terpene modified phenol resins, polyvinylphenols, etc. Can be used in combination.
- the blending amount of the phenolic curing agent is not particularly limited, but the equivalent ratio with the epoxy resin (phenolic hydroxyl group equivalent / epoxy group equivalent) is less than 1.0, preferably 0.1 or more. Thereby, the residue of an unreacted phenol type hardening
- additives other than the above components can be added as necessary as long as the characteristics are not impaired.
- components other than the above components include curing accelerators such as imidazoles, triphenylphosphine, and quaternary phosphonium salts, surfactants such as acrylates, colorants such as dyes, and pigments. .
- the resin composition of this invention is dissolved in a solvent and used as a varnish at the time of resin sheet production or prepreg production.
- the method for preparing the varnish is not particularly limited. For example, a slurry in which an epoxy resin, a first inorganic filler, and a second inorganic filler are dispersed in a solvent is prepared, and other resin composition components are added to the slurry. In addition, a method of adding the solvent and dissolving and mixing it may be mentioned.
- the solvent is not particularly limited, but a solvent that exhibits good solubility in the resin composition is preferable.
- a solvent that exhibits good solubility in the resin composition is preferable.
- acetone methyl ethyl ketone (MEK), cyclohexanone (ANON), methyl isobutyl ketone (MIBK), cyclopenta Non, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
- MEK methyl ethyl ketone
- ANON cyclohexanone
- MIBK methyl isobutyl ketone
- cyclopenta Non, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like you may use a poor solvent in the range which does not exert a bad influence.
- the solid content of the resin composition contained in the varnish is not particularly limited, but is preferably 30 to 80% by weight, particularly preferably 40 to 70% by weight. Thereby, the impregnation property to the base material of a resin composition can be improved.
- the second resin composition of the present invention comprises an epoxy resin, silicone rubber fine particles having an average particle size of 1 ⁇ m to 10 ⁇ m, boehmite fine particles having an average particle size of 0.2 ⁇ m to 5 ⁇ m, and silica nanoparticles having an average particle size of 10 nm to 100 nm. , Containing.
- the varnish of the resin composition is in a low-viscosity state, A large amount of three types of particles can be contained.
- the metal-clad laminate using the second resin composition and / or the prepreg containing the resin composition as described above although the flow of the resin composition varnish is low because the varnish of the resin composition is low, the resin
- the composition contains silicone rubber fine particles, boehmite particles, and silica nanoparticles in combination, the fluidity of these particles and the resin fluidity are well balanced, and the pressure exerted by the particles due to the cushioning effect of the silicone rubber fine particles. There is little variation in the surface, and there are very few uneven stripes on the surface.
- the silicone rubber fine particles are not particularly limited as long as they are elastic rubber fine particles formed of organopolysiloxane.
- the fine particles made of silicone rubber (organopolysiloxane crosslinked elastomer) itself, and the core portion made of silicone rubber are made of silicone resin. And core-shell structured particles coated with.
- the silicone rubber fine particles KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil E-500, Trefil E-600 (manufactured by Toray Dow Corning Co., Ltd.) Commercial products such as these can be used.
- the silicone rubber fine particles have an average particle diameter of 1 to 10 ⁇ m and are preferably 1 to 5 ⁇ m from the viewpoint of excellent impregnation properties.
- the content of the silicone rubber fine particles is not particularly limited, but is preferably 5 to 50% by weight based on the solid content of the entire resin composition, and particularly 10 to 40% by weight from the viewpoint of excellent impregnation properties. Is preferred.
- the boehmite particles are monohydrates of aluminum oxide, and are AOH-30, AOH-60 (both manufactured by Tesco), granular BMB series, plate-like BMT series, and scale-like BMF series (commercially available products such as Kawai Lime Industry Co., Ltd.) can also be used.
- the boehmite particles have an average particle diameter of 0.2 to 5 ⁇ m, and 0.5 to 4 ⁇ m is preferable from the viewpoint of excellent impregnation properties.
- the content of the boehmite particles is not particularly limited, but is preferably 5 to 50% by weight based on the solid content of the entire resin composition, and particularly 10 to 40% by weight from the viewpoint of excellent impregnation properties. preferable.
- the silica nanoparticles have an average particle size of 10 to 100 nm, and preferably 40 to 100 nm from the viewpoint of impregnation. This is because if the average particle size is less than 10 nm, the space between the filaments of the substrate cannot be expanded, and if it is greater than 100 nm, it may not be possible to enter between the filaments.
- silica nanoparticle for example, methods, such as combustion methods, such as VMC (Vaperized Metal Combution) method, PVS (Physical Vapor Synthesis) method, the melting method which flame-melts crushed silica, a sedimentation method, a gel method Can be used.
- combustion methods such as VMC (Vaperized Metal Combution) method, PVS (Physical Vapor Synthesis) method, the melting method which flame-melts crushed silica, a sedimentation method, a gel method
- the VMC method is particularly preferable.
- the VMC method is a method in which silica fine particles are formed by putting silicon powder into a chemical flame formed in an oxygen-containing gas, burning it, and then cooling it.
- the particle diameter of the silica fine particles to be obtained can be adjusted by adjusting the particle diameter of the silicon powder to be input, the input amount, the flame temperature, and the like.
- Commercially available products such as NSS-5N (manufactured by Tokuyama
- the content of the silica nanoparticles is not particularly limited, but is preferably 1 to 10% by weight, particularly 2 to 5% by weight, based on the solid content of the entire resin composition. When the content is within the above range, the impregnation property is particularly excellent.
- the weight ratio of the content of the silicone rubber fine particles to the content of the silica nanoparticles is not particularly limited, but is preferably 1 to 15, preferably 1 to 10. It is preferable that it is 2 to 5, in particular.
- the weight ratio of the boehmite particle content to the silica nanoparticle content is not particularly limited, but is preferably 1 to 50, and particularly 2 to 20. It is preferable.
- the moldability is particularly good. If it is larger or smaller than the above range, the impregnation property is deteriorated, and the solder failure heat resistance and the insulation reliability are easily lowered due to the generation of voids.
- the average particle diameter of the silicone rubber fine particles, the boehmite particles, and the silica nanoparticles can be measured by, for example, a laser diffraction scattering method and a dynamic light scattering method.
- particles are dispersed in water by ultrasonic waves, and a particle size distribution measuring device (manufactured by HORIBA, LA-500) or a dynamic light scattering particle size distribution measuring device (manufactured by HORIBA, LB-550) is used.
- the particle size distribution is measured on a volume basis, and the median diameter is defined as the average particle diameter.
- the average particle diameter of the silicone rubber fine particles, boehmite particles, and silica nanoparticles is defined by D50 (median diameter).
- the resin composition of the present invention may contain an inorganic filler such as silica, aluminum hydroxide, and talc as long as the characteristics are not impaired.
- the epoxy resin is not particularly limited.
- the epoxy resin is the same as the first resin composition, and thus the description thereof is omitted here.
- the above epoxy resins at least one selected from the group consisting of a biphenyl aralkyl type epoxy resin, a naphthalene skeleton modified epoxy resin, and a cresol novolak type epoxy resin is preferable.
- the content of the epoxy resin is not particularly limited, but is preferably 5 to 30% by weight based on the solid content of the entire resin composition.
- the content is less than the lower limit, the curability of the resin composition may decrease, or the prepreg obtained from the resin composition or the moisture resistance of the printed wiring board may decrease.
- the said upper limit is exceeded, the linear thermal expansion coefficient of a prepreg or a printed wiring board may become large, or heat resistance may fall.
- the weight average molecular weight of the epoxy resin is not particularly limited, but is preferably 40 to 18000. If the weight average molecular weight is less than the lower limit, the glass transition point is lowered, and if it exceeds the upper limit, the fluidity is lowered and the substrate may not be impregnated. By setting the weight average molecular weight within the above range, the impregnation property can be improved.
- the second resin composition is not particularly limited, but preferably contains a cyanate resin. Thereby, a flame retardance can be improved more.
- the cyanate resin is not particularly limited, and specific examples and contents thereof are the same as those of the first resin composition, and thus description thereof is omitted here.
- the second resin composition is not particularly limited, but preferably contains a maleimide resin.
- the maleimide resin is not particularly limited, but N, N ′-(4,4′-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2-bis [ And bismaleimide resins such as 4- (4-maleimidophenoxy) phenyl] propane.
- other maleimide resins may be used alone or in combination of two or more, and are not particularly limited.
- the maleimide resin may be used singly, maleimide resins having different weight average molecular weights may be used in combination, or the maleimide resin and its prepolymer may be used in combination.
- the content of the maleimide resin is not particularly limited, but is preferably 1 to 30% by weight, particularly preferably 5 to 20% by weight, based on the solid content of the entire resin composition.
- the second resin composition may contain at least one selected from the group consisting of a polyimide resin, a triazine resin, a phenol resin, and a melamine resin.
- a phenolic curing agent can be used for the second resin composition.
- curing agent is not specifically limited, Since a specific example and content are the same as that of the said 1st resin composition, description here is abbreviate
- additives other than the above components can be added as necessary as long as the characteristics are not impaired.
- Components other than the above components include, for example, epoxy silane coupling agents, cationic silane coupling agents, aminosilane coupling agents, titanate coupling agents, coupling agents such as silicone oil type coupling agents, imidazoles, and triphenyl. Examples thereof include curing accelerators such as phosphine and quaternary phosphonium salts, surface conditioners such as acrylic polymers, and colorants such as dyes and pigments.
- the third resin composition of the present invention is characterized by containing an epoxy resin, silicone rubber fine particles having an average particle diameter of 1 ⁇ m to 10 ⁇ m, and silica nanoparticles having an average particle diameter of 10 nm to 150 nm.
- the silicone fine particles having a positive surface zeta potential and silica nanoparticles having a negative surface zeta potential attract each other, so that the varnish has a low viscosity even when a large amount of particles are contained.
- a prepreg sufficiently impregnated with the resin composition can be obtained. .
- the obtained prepreg is excellent in flame retardancy, low thermal expansion, drill workability, and desmear resistance.
- the metal-clad laminate using the third resin composition and / or the prepreg containing the resin composition as described above has a large flow because the varnish of the resin composition has a low viscosity, but the resin Since the composition contains silicone rubber fine particles and silica nanoparticles in combination, the fluidity of these particles and the resin fluidity are well balanced, and the pressure variation due to the particles is small due to the cushioning effect of the silicone rubber fine particles. There are very few streaky irregularities on the surface.
- the silicone rubber fine particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane, and specific examples and contents thereof are the same as those of the second resin composition, and thus description thereof is omitted here. To do.
- the silica nanoparticles have an average particle diameter of 10 to 150 nm, and preferably 40 to 100 nm from the viewpoint of impregnation. This is because if the average particle size is less than 10 nm, the space between the filaments of the base material cannot be expanded, and if it is greater than 150 nm, it may not be possible to enter between the filaments.
- the silica nanoparticles are not particularly limited, and specific examples and contents thereof are the same as those of the second resin composition, and thus description thereof is omitted here.
- the weight ratio of the content of the silicone rubber fine particles to the content of the silica nanoparticles is not particularly limited, but is 1 to 50. In particular, it is preferably 2 to 20.
- the weight ratio is within the above range, the moldability can be particularly improved.
- the weight ratio is larger or smaller than the above range, the impregnation property is deteriorated, and the solder failure heat resistance and the insulation reliability are liable to be lowered due to the generation of voids.
- the average particle size of the silicone rubber fine particles and the silica nanoparticles can be measured by, for example, a laser diffraction scattering method and a dynamic light scattering method. Particles are dispersed in water by ultrasonic waves, and the particle size distribution of the particles is measured by volume using a laser diffraction particle size distribution analyzer (HORIBA, LA-500) or dynamic light scattering particle size distribution (HORIBA, LB-550). Measured by reference, the median diameter (D50) is taken as the average particle diameter.
- the third resin composition may contain an inorganic filler such as boehmite, silica, aluminum hydroxide, and talc as long as the characteristics are not impaired.
- an inorganic filler such as boehmite, silica, aluminum hydroxide, and talc as long as the characteristics are not impaired.
- epoxy resin A specific example is the same as that of the said 1st resin composition.
- epoxy resins at least one selected from the group consisting of a biphenyl aralkyl type epoxy resin, a naphthalene skeleton modified epoxy resin, and a cresol novolak type epoxy resin is preferable.
- a biphenyl aralkyl type epoxy resin a naphthalene skeleton modified epoxy resin
- cresol novolak type epoxy resin is preferable.
- the heat resistance and flame retardancy of prepregs, laminates and printed wiring boards are improved.
- about content of an epoxy resin since it is the same as that of the said 2nd resin composition, description is abbreviate
- the weight average molecular weight of the epoxy resin is not particularly limited, but is preferably 400 to 18,000. If the weight average molecular weight is less than the lower limit, the glass transition point is lowered, and if it exceeds the upper limit, the fluidity is lowered and the substrate may not be impregnated. By setting the weight average molecular weight within the above range, the impregnation property can be improved.
- the third resin composition is not particularly limited, but preferably contains a cyanate resin. Thereby, a flame retardance can be improved more.
- the cyanate resin is not particularly limited, and specific examples and contents thereof are the same as those of the first resin composition, and thus description thereof is omitted here.
- the third resin composition is not particularly limited, but preferably contains a maleimide resin. Thereby, heat resistance can be improved. Specific examples of the maleimide resin are the same as those of the second resin composition.
- the content of the maleimide resin is not particularly limited, but is preferably 1 to 30% by weight, more preferably 5 to 25% by weight, and still more preferably based on the solid content of the entire third resin composition. 5 to 20% by weight.
- the third resin composition may contain at least one selected from the group consisting of a polyimide resin, a triazine resin, a phenol resin, and a melamine resin.
- the third resin composition can use a phenolic curing agent.
- curing agent is not specifically limited, A specific example and content are the same as that of the said 1st resin composition.
- the third resin composition can be added with additives other than the above components as necessary within a range that does not impair the characteristics.
- Components other than the above components are the same as in the second resin composition.
- the fourth resin composition is characterized by containing an epoxy resin, barium sulfate particles having an average particle diameter of 10 nm to 150 nm, and an inorganic filler.
- barium sulfate particles having an average particle size of 10 nm to 150 nm in the epoxy resin composition By containing barium sulfate particles having an average particle size of 10 nm to 150 nm in the epoxy resin composition, a large amount of inorganic filler can be contained even when the resin varnish using the resin composition is in a highly viscous state. it can.
- the barium sulfate particles having an average particle diameter of 10 nm to 150 nm enter the gaps between the filaments of the base material to widen the gaps between the base materials, and can contain a larger amount of inorganic filler than before.
- the resin varnish can be brought into a low-viscosity state, and the inorganic filler can be contained in a larger amount. This is because the inorganic filler that attracts the barium sulfate particles in relation to the surface zeta potential can reduce the viscosity of the resin varnish as a whole, and is excellent in impregnation even if it contains a large amount of inorganic filler. I guess.
- the fourth resin composition having a low viscosity despite containing a large amount of the filler particles as described above a prepreg sufficiently impregnated with the resin composition is obtained. be able to.
- the obtained prepreg is excellent in flame retardancy, low thermal expansion, drill workability, and desmear resistance.
- the metal-clad laminate using the fourth resin composition and / or the prepreg containing the resin composition as described above although the flow of the resin composition varnish is low because the varnish of the resin composition is low, the resin By containing the silicone rubber fine particles and barium sulfate particles in combination, the composition has a good balance between the fluidity of these particles and the resin fluidity.
- a resin composition containing silicone rubber fine particles is used, a metal-clad laminate with little variation in pressure due to the particles due to the cushioning effect of the silicone rubber fine particles and very little surface streak unevenness can be obtained.
- the barium sulfate particles having an average particle diameter of 10 nm to 150 nm are not particularly limited, but preferably have a spherical shape. Thereby, the quantity of an inorganic filler can be increased further.
- the barium sulfate particles have an average particle diameter of 10 to 150 nm, and preferably 40 to 100 nm from the viewpoint of impregnation. This is because if the average particle size is less than 10 nm, the space between the filaments of the base material cannot be expanded, and if it is greater than 150 nm, it may not be possible to enter between the filaments.
- barium sulfate particles commercially available products such as BF-21 and BF-25 (manufactured by Sakai Chemical) can also be used.
- the content of the barium sulfate particles is not particularly limited, but is preferably 1 to 10% by weight, particularly 2 to 5% by weight, based on the solid content of the entire resin composition. When the content is within the above range, the impregnation property is particularly excellent.
- the inorganic filler used in the fourth resin composition is not particularly limited, and examples thereof include inorganic fillers such as boehmite, silica, aluminum hydroxide, and talc.
- the fourth resin composition preferably further contains silicone rubber fine particles. This improves drill wear and also reduces the linear expansion coefficient.
- the silicone rubber fine particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane, and specific examples and contents thereof are the same as those of the second resin composition, and thus description thereof is omitted here. To do.
- the weight ratio of the content of the silicone rubber fine particles to the content of the barium sulfate particles is not particularly limited, but is preferably 1 to 50, particularly 2 Preferably, it is ⁇ 20.
- the weight ratio is within the above range, the moldability can be particularly improved.
- the weight ratio is larger or smaller than the above range, the impregnation property is deteriorated, and the solder failure heat resistance and the insulation reliability are liable to be lowered due to the generation of voids.
- the average particle diameter of the silicone rubber fine particles and the barium sulfate particles can be measured by, for example, a laser diffraction scattering method and a dynamic light scattering method. Particles are dispersed in water by ultrasonic waves, and the particle size distribution of the particles is measured with a laser diffraction particle size distribution analyzer (HORIBA, LA-500) or a dynamic light scattering particle size distribution device (HORIBA, LB-550). It measures on a volume basis and the median diameter (D50) is taken as the average particle diameter.
- HORIBA laser diffraction particle size distribution analyzer
- HORIBA dynamic light scattering particle size distribution device
- epoxy resin used for a 4th resin composition Since the specific example is the same as that of the said 1st resin composition, description here is abbreviate
- epoxy resins biphenyl aralkyl type epoxy resins, naphthalene skeleton-modified epoxy resins, and cresol novolac type epoxy resins are particularly preferable. By using these epoxy resins, the heat resistance and flame retardancy of the prepreg, laminate and printed wiring board are improved.
- the weight average molecular weight of the said epoxy resin is not specifically limited, It is the same as that of the said 3rd resin composition.
- the fourth resin composition is not particularly limited, but preferably contains a cyanate resin. Thereby, a flame retardance can be improved more.
- the cyanate resin is not particularly limited, and specific examples and contents thereof are the same as those of the first resin composition, and thus description thereof is omitted here.
- the fourth resin composition is not particularly limited, but preferably contains a maleimide resin. Thereby, heat resistance can be improved.
- a specific example of the maleimide resin is the same as that of the second resin composition, and the content of the maleimide resin is the same as that of the third resin composition. Therefore, description thereof is omitted here.
- the fourth resin composition may contain at least one selected from the group consisting of a polyimide resin, a triazine resin, a phenol resin, and a melamine resin.
- the fourth resin composition can use a phenolic curing agent.
- curing agent is not specifically limited, Since a specific example and content are the same as that of the said 1st resin composition, description here is abbreviate
- the fourth resin composition can be added with additives other than the above components as necessary within a range that does not impair the characteristics. Since components other than the above components are the same as those of the second resin composition, description thereof is omitted here.
- the fifth resin composition includes (A) a filler formed by adhering (B) a second filler having a particle diameter smaller than that of the first filler (A) on the outer periphery of the first filler. It is characterized by that.
- the filler is uniformly dispersed in the resin composition by containing the filler formed by adhering the (B) second filler to the outer periphery of the first filler. Impregnation into the material is improved.
- a prepreg excellent in heat resistance, low expansibility and flame retardancy can be obtained.
- the first filler is not particularly limited, but the average particle size is preferably 0.2 ⁇ m to 10 ⁇ m. More preferably, the average particle size is 0.5 to 5 ⁇ m. By using the filler having the above average particle diameter, the impregnation property is further improved.
- the first filler is not particularly limited.
- oxides such as titanium oxide, alumina, silica, and fused silica
- carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite, aluminum hydroxide, and water
- Hydroxides such as magnesium oxide and calcium hydroxide, talc, calcined talc, calcined clay, unfired clay, mica
- silicates such as glass, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, nitriding Nitride such as aluminum, boron nitride, silicon nitride and carbon nitride, borate such as zinc borate, barium metaborate, aluminum borate, calcium borate and sodium borate
- titanium such as strontium titanate and barium titanate Acid salts
- silicones such as silicone rubber, and styrene butadiene rubber particles, Rubber particles such Kurirugomu particles can be
- the silicone is not particularly limited as long as it is a rubber elastic fine particle formed of an organopolysiloxane.
- examples thereof include core-shell structured particles coated with silicone mainly composed of a three-dimensional crosslinking type.
- the silicone rubber fine particles KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil E-500, Trefil E-600 (manufactured by Toray Dow Corning Co., Ltd.) Commercial products such as these can be used.
- the rubber particles are not particularly limited, but are preferably core-shell type rubber particles and cross-linked type rubber particles.
- the core-shell type rubber particle is a rubber particle having a core layer and a shell layer.
- the outer shell layer is a glassy polymer
- the inner core layer is a rubbery polymer, or an outer layer.
- a crosslinked rubber such as ethylene, propylene, styrene, butadiene, isopropylene, methyl acrylate, methyl methacrylate, and acrylonitrile
- a crosslinked rubber such as ethylene, propylene, styrene, butadiene, isopropylene, methyl acrylate, methyl methacrylate, and acrylonitrile
- the glassy polymer of the shell layer (outer layer) covering the core layer in the two-layer structure or the core layer in the three-layer structure methyl methacrylate, styrene, acrylonitrile, a copolymer thereof, or the like can be selected.
- An epoxy group, a carboxyl group or the like can be introduced into the glassy polymer as a functional group, and can be selected depending on the application.
- the crosslinked rubber particles include acrylonitrile butadiene rubber (NBR) particles, styrene butadiene rubber (SBR) particles, and acrylic rubber particles.
- NBR acrylonitrile butadiene rubber
- SBR styrene butadiene rubber
- acrylic rubber particles can also provide effects such as increasing the mechanical strength of the cured product of the fifth resin composition, relaxing the stress of the cured product, and reducing the thermal expansion of the cured product.
- the high heat resistance specifically means that the 1% thermal decomposition temperature of the inorganic filler is 260 ° C. or higher, and particularly preferably 300 ° C. or higher.
- the 1% pyrolysis temperature is defined by a differential thermal balance (TG / DTA) at a temperature increase rate of 10 ° C./min and a temperature at a point of 1% weight reduction from the initial weight.
- Examples of the filler having a 1% thermal decomposition temperature of 300 ° C. or higher include boehmite, alumina, talc, fired talc, and silica. Of these, boehmite, talc, and calcined talc are particularly preferable. Thereby, heat resistance and drill workability can be improved more.
- the organic fine particles such as the silicone and the rubber particles are not dissolved in the organic solvent when preparing the resin composition, and are not compatible with the components in the resin composition such as the resin. Accordingly, the organic fine particles are present in a dispersed state in the varnish of the resin composition.
- the content of the first filler is not particularly limited, but is preferably 40 to 75% by weight, particularly preferably 50 to 70% by weight, based on the entire resin composition. When the content is within the above range, the heat resistance and the fluidity are particularly excellent.
- the content of the silicone is not particularly limited, but is preferably 5 to 50% by weight of the entire resin composition, from the viewpoint of excellent impregnation properties. In particular, it is preferably 10 to 40% by weight. When the content exceeds 50% by weight, the rigidity of the obtained prepreg is lowered, and there is a concern that performance such as low warpage of the printed wiring board is deteriorated.
- the (B) second filler is not particularly limited as long as it adheres to the (A) first filler.
- the (B) second filler adhering to the (A) first filler is, for example, (A) one having a different sign of zeta potential of the first filler, one attracting by van de Swirl force, cup For example, it may be chemically bonded by a ring agent treatment or the like.
- the particle size of the (B) second filler is not particularly limited, but the average particle size is preferably 10 to 100 nm. Thereby, even if the varnish viscosity is high, the impregnation property is improved, the generation of voids can be suppressed, the solder heat resistance is excellent, and the insulation reliability is improved.
- a filler having an average particle diameter of 10 to 100 nm is used, it is preferably used as a slurry previously dispersed in an organic solvent. This is because a filler having an average particle size of 10 to 100 nm is likely to aggregate and may form a secondary aggregate or the like when blended in a resin composition, thereby reducing fluidity.
- the average particle diameter of the (B) second filler is particularly preferably 15 to 90 nm, and most preferably 25 to 75 nm. When the average particle size is within the above range, a resin composition having excellent high filling property and high fluidity can be obtained.
- the average particle size of the (A) first filler and (B) second filler is, for example, ultrasonic vibration current method (zeta potential), ultrasonic attenuation spectroscopy (particle size distribution), and laser diffraction scattering. It can be measured by the method.
- the (B) second filler is not particularly limited, and examples thereof include silicates such as talc, fired talc, fired clay, unfired clay, mica, and glass, titanium oxide, alumina, silica, and fused silica.
- a titanate etc. can be mentioned. One of these can be used alone, or two or more can be used in combination. Among these, silica is preferable from the viewpoint
- the shape of the second filler is not particularly limited, but is preferably spherical. Thereby, the impregnation property can be improved.
- the method of making the particles spherical There are no particular limitations on the method of making the particles spherical.
- the particles can be made spherical by using dry fused silica such as a combustion method or wet sol-gel silica such as a precipitation method or a gel method.
- the combination of the first filler and the second filler is not particularly limited.
- at least one selected from the group consisting of boehmite, talc, and silicone particles is used as the first filler.
- a combination using silica as a filler is preferable.
- the resin composition not only exhibits good impregnation properties to the substrate, but also has good drill workability, and can produce a laminate having a low thermal expansion coefficient.
- the weight ratio of the content of the (A) first filler and the content of the (B) second filler is not particularly limited, but the content of the (A) first filler (
- the weight ratio (w2 / w1) of the content (w2) of the (B) second filler to w1) is preferably 0.02 to 0.5, particularly 0.06 to 0.4. Preferably there is.
- the weight ratio is within the above range, the moldability can be particularly improved.
- the (A) first filler and / or (B) second filler may be, for example, an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent,
- a surface treatment may be performed with a functional group-containing silane such as a coupling agent such as a silicone oil coupling agent and / or an alkylsilazane.
- a functional group-containing silane such as a coupling agent such as a silicone oil coupling agent and / or an alkylsilazane.
- Suitable functional group-containing silanes such as the functional group-containing silanes and / or alkylsilazanes can be used.
- epoxy silane and vinyl silane More preferred are epoxy silane and vinyl silane.
- adhesion to an irregular inorganic filler such as boehmite and adhesion to a resin are improved.
- the amount of the functional group-containing silanes and / or the alkylsilazane functional group-containing silanes to be surface-treated in advance on the (A) first filler and / or the (B) second filler is not particularly limited. It is preferable that the amount is 0.01 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the filler ((A) first filler or (B) second filler). More preferably, it is 0.1 to 3 parts by weight.
- the content of the functional group-containing silanes and / or the functional group-containing silanes of the alkylsilazanes exceeds the upper limit, the heat resistance and insulation reliability may be reduced by an excess coupling agent, and the lower limit. If it is less than the range, the adhesion between the filler and the resin component is lowered, and the mechanical strength and resin composition fluidity of the cured product of the resin composition may be lowered.
- the method for surface-treating the (A) first filler and / or the (B) second filler with functional group-containing silanes and / or alkylsilazanes is not particularly limited, but is wet or dry The method is preferred.
- the wet method is particularly preferable. When compared with the dry method, the wet method can uniformly treat the surface.
- resin used for a 5th resin composition For example, an epoxy resin, a phenol resin, cyanate resin, maleimide resin etc. can be used.
- epoxy resin It does not specifically limit as said epoxy resin,
- the specific example is the same as that of the said 1st resin composition.
- at least one selected from the group consisting of a biphenyl aralkyl type epoxy resin, a naphthalene skeleton modified epoxy resin, and a cresol novolak type epoxy resin is preferable.
- the preferable content of the epoxy resin is the same as that of the second resin composition.
- the weight average molecular weight of the epoxy resin is not particularly limited, but a weight average molecular weight of 4.0 ⁇ 10 2 to 1.8 ⁇ 10 3 is preferable. When the weight average molecular weight is less than the lower limit, the glass transition point is lowered, and when it exceeds the upper limit, the fluidity is lowered and the substrate may not be impregnated. By setting the weight average molecular weight within the above range, the impregnation property can be improved.
- the cyanate resin is not particularly limited, and specific examples and contents thereof are the same as those of the first resin composition.
- the maleimide resin is not particularly limited, and specific examples thereof are the same as those of the second resin composition, and the contents thereof are the same as those of the third resin composition.
- the phenol resin is not particularly limited, and is the same as that exemplified as the phenolic curing agent in the first resin composition.
- additives other than the above components can be added as necessary as long as the characteristics are not impaired.
- the components other than the above components include curing accelerators such as imidazoles, triphenylphosphine, and quaternary phosphonium salts, surface conditioners such as acrylic polymers, and colorants such as dyes and pigments. .
- the resin sheet of the present invention is obtained by forming a resin layer containing the resin composition of the present invention on a substrate.
- the resin layer can be used as an insulating layer of a printed wiring board.
- the method for producing the resin sheet is not particularly limited.
- (1) a resin varnish obtained by dissolving and dispersing a resin composition in a solvent or the like is applied to a substrate using various coating apparatuses, Examples include a method of drying, and (2) a method in which the resin varnish is spray-coated on a substrate with a spray device and then dried.
- the method of drying the resin varnish after applying the resin varnish to the substrate using various coating apparatuses such as a comma coater and a die coater is preferable. Thereby, the resin layer which does not have a void and has a uniform thickness can be efficiently formed on the substrate.
- the thickness of the insulating layer is not particularly limited, but is preferably 5 to 100 ⁇ m. Thereby, when manufacturing a printed wiring board using this resin sheet, while being able to fill and shape the unevenness
- the solvent used in preparing the resin varnish desirably has good solubility in the resin component in the resin composition, but a poor solvent may be used as long as it does not have an adverse effect.
- the solvent exhibiting good solubility include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and tetrahydrofuran, and acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate.
- cellosolves such as cellosolve and butylcellosolve
- carbitols such as carbitol and butylcarbitol
- aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethylene glycol, and the like.
- the base material used for the resin sheet of the present invention is not particularly limited, for example, a polyester resin such as polyethylene terephthalate or polybutylene terephthalate; a fluororesin; a thermoplastic resin film having heat resistance such as a polyimide resin; Copper and / or copper alloys, aluminum and / or aluminum alloys, iron and / or iron alloys, silver and / or silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, Metal foils such as tin and tin-based alloys can be used.
- a polyester resin such as polyethylene terephthalate or polybutylene terephthalate
- a fluororesin such as a polyimide resin
- a thermoplastic resin film having heat resistance such as a polyimide resin
- the thickness of the base material is not particularly limited, but it is preferable to use a base material having a thickness of 10 to 70 ⁇ m because the handleability in producing a resin sheet is good.
- connects a resin layer is as small as possible. Thereby, when forming an insulating layer on a conductor circuit using this resin sheet, a fine wiring process becomes easy.
- the prepreg of the present invention is obtained by impregnating a base material with the resin composition and further heat-drying as necessary.
- the base material examples include glass fiber base materials such as glass woven fabric, glass non-woven fabric, and glass paper, paper, aramid, polyester, aromatic polyester, woven fabric and non-woven fabric made of synthetic fibers such as fluororesin, metal fibers, Examples thereof include woven fabrics, nonwoven fabrics and mats made of carbon fibers and mineral fibers. These substrates may be used alone or in combination. Among these, a glass fiber base material is preferable. Thereby, the rigidity and dimensional stability of a prepreg can be improved.
- the resin composition is dissolved in a solvent and used as a resin varnish.
- Examples of the method of impregnating the substrate with the resin composition include a method of immersing the substrate in a resin varnish, a method of applying the resin varnish to the substrate with various coaters, a method of spraying the resin varnish on the substrate by spraying, and the like. Can be mentioned. 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. For example, as shown in FIG.
- the base material 1 is immersed in the resin varnish 3 of the impregnation tank 2 to impregnate the base material 1 with the resin varnish 3.
- the base material 1 is immersed in the resin varnish 3 by the dip roll 4 (three in FIG. 1) with which the impregnation tank 2 is equipped.
- the base material 1 impregnated with the resin varnish 3 is pulled up in the vertical direction, and arranged between a pair of squeeze rolls or comma rolls (5 in FIG. 1 is a squeeze roll) arranged in parallel in the horizontal direction. Then, the application amount of the resin varnish 3 to the substrate 1 is adjusted.
- the base material 1 coated with the resin varnish 3 is heated at a predetermined temperature with a dryer 6 to volatilize the solvent in the coated varnish and to semi-cur the resin composition to produce the prepreg 7. .
- the upper roll 8 in FIG. 1 rotates in the same direction as the traveling direction of the prepreg 7 in order to move the prepreg 7 in the traveling direction.
- a semi-cured prepreg can be obtained by drying the solvent of the resin varnish impregnated in the substrate at a predetermined temperature, for example, 90 to 180 ° C.
- the metal-clad laminate of the present invention has a metal foil on at least one surface of a resin-impregnated base material layer formed by impregnating the base material with the above resin composition.
- the metal-clad laminate of the present invention can be produced, for example, by attaching a metal foil to at least one surface of the prepreg or a laminate obtained by superimposing one or more prepregs.
- the temperature to be heated is not particularly limited, but is preferably 120 to 250 ° C, particularly preferably 120 to 220 ° C, further preferably 150 to 220 ° C, and particularly preferably 150 to 200 ° C.
- the pressure to be pressurized is not particularly limited, but is preferably 0.5 to 5 MPa. If necessary, post-curing may be performed at a temperature of 150 to 300 ° C. in a high-temperature bath or the like.
- Another method for producing the metal-clad laminate of the present invention is a method for producing a metal-clad laminate using the metal foil with an insulating resin layer shown in FIG.
- a metal foil 10 with an insulating resin layer in which a uniform insulating resin layer 12 is coated on a metal foil 11 with a coater is prepared, and the metal foils 10 and 10 with an insulating resin layer are provided on both sides of a substrate 20 such as glass fiber.
- a prepreg 41 with a metal foil is obtained by a method in which an insulating resin layer is disposed inside (FIG. 2A) and laminate impregnation is performed in a vacuum at 60 to 130 ° C. and under a pressure of 0.1 to 5 MPa (FIG. 2). (B)).
- the metal-clad laminate 51 can be obtained by directly heat-pressing the prepreg 41 with metal foil (FIG. 2C). Furthermore, as another method for producing the metal-clad laminate of the present invention, a method for producing a metal-clad laminate using the polymer film sheet with an insulating resin layer shown in FIG. First, a polymer film sheet 30 with an insulating resin layer obtained by coating a uniform insulating resin layer 32 on the polymer film sheet 31 with a coater, and the polymer film sheet 30 with an insulating resin layer on both sides of the substrate 2; 30 is arranged with the insulating resin layer inside (FIG.
- a prepreg 42 with a polymer film sheet is obtained by laminating and impregnating in a vacuum at 60 to 130 ° C. and under a pressure of 0.1 to 5 MPa. Can be obtained (FIG. 3B).
- the metal foil 11 is arranged on the surface from which the polymer film sheet 31 is peeled (FIG. 3D).
- a metal-clad laminate 52 can be obtained by heating and pressing (FIG. 3E).
- peeling a double-sided polymer film sheet two or more sheets can be laminated
- a metal-clad laminate can be obtained by placing a metal foil or a polymer film sheet on the outermost upper and lower surfaces or one surface of the laminated prepregs and heating and pressing.
- the temperature for the heat and pressure molding is not particularly limited, but is preferably 120 to 250 ° C, particularly preferably 120 to 220 ° C, and particularly preferably 150 to 220 ° C.
- the pressure to be pressurized is not particularly limited, but is preferably 0.1 to 5 MPa, and particularly preferably 0.5 to 3 MPa.
- the prepreg is prepared with a base material, the surface smoothness of the prepreg is high and low-pressure molding is possible. If necessary, post-curing may be performed at a temperature of 150 to 300 ° C. in a high-temperature bath or the like.
- the metal-clad laminate shown in FIGS. 2 to 3 is not particularly limited, but is produced using, for example, an apparatus for producing a metal foil with an insulating resin layer and an apparatus for producing a metal-clad laminate.
- the metal foil can be supplied by, for example, using a long sheet product in the form of a roll, and continuously unwinding it.
- a predetermined amount of the liquid insulating resin is continuously supplied onto the metal foil by an insulating resin supply device.
- the liquid insulating resin a coating solution in which the resin composition of the present invention is dissolved and dispersed in a solvent is used.
- the coating amount of the insulating resin can be controlled by the clearance between the comma roll and the backup roll of the comma roll.
- the metal foil coated with a predetermined amount of insulating resin is transported inside a horizontal conveying type hot air dryer, and the organic solvent contained in the liquid insulating resin is substantially removed by drying.
- a metal foil with an insulating resin layer in which the curing reaction has been advanced halfway can be obtained.
- the metal foil with an insulating resin layer can be wound up as it is, but with a laminate roll, a protective film is superimposed on the side on which the insulating resin layer is formed, and the metal foil with an insulating resin layer laminated with the protective film is wound up.
- a metal foil with an insulating resin layer in a roll form is obtained.
- the apparatus for producing the metal-clad laminate is an apparatus that can perform the steps of FIGS. 2 (a) to 2 (b). For example, devices described in JP-A-8-150683, WO2007 / 040125, and the like are mentioned.
- the step (a) is performed using a laminating apparatus. Inside the laminating apparatus, the metal foil with an insulating resin layer obtained in the step (a) and the base material are installed so as to be continuously supplied. Since the protective film is laminated on the surface of the insulating resin layer, the metal foil with the insulating resin layer is continuously supplied while peeling off the protective film by a winding roll. Moreover, a base material is continuously supplied from the base material of a roll form.
- the metal foils with an insulating resin layer are overlaid in a form in which the fiber cloth is sandwiched on the insulating resin layer side, and bonded by heating and pressing with a laminate roll.
- the insulating resin layer is an uncured or semi-cured material in a substantially solvent-free state, but is fluidized by heat melting, so that the base material is impregnated.
- the joined product after joining can be sent to the next process as it is, and the joining temperature between the metal foil with insulating resin layer and the base material can be adjusted by applying temperature and pressure with a laminate roll.
- the bonded product after the bonding is transferred between horizontal conveying type hot air dryers and heat-treated at a temperature equal to or higher than the melting temperature of the insulating resin.
- the metal-clad laminate after the heat treatment can be formed into a roll-like metal-clad laminate by continuously winding the metal-clad laminate with pinch rolls.
- the laminate may be normal pressure or vacuum, but vacuum is preferred.
- the printed wiring board of the present invention uses the above metal-clad laminate as an inner layer circuit board. Moreover, the printed wiring board of this invention uses said prepreg for an insulating layer on an inner layer circuit. Moreover, the printed wiring board of this invention uses said resin composition for an insulating layer on an inner layer circuit.
- the printed wiring board is a circuit in which a circuit is formed of a conductive material such as a metal foil on an insulating layer, a single-sided printed wiring board (single layer board), a double-sided printed wiring board (double layer board), and a multilayer. Any of printed wiring boards (multilayer boards) may be used.
- a multilayer printed wiring board is a printed wiring board that is laminated in three or more layers by a plated through-hole method, a build-up method, or the like, and can be obtained by heating and press-molding an insulating layer on an inner circuit board. .
- the inner layer circuit board for example, a metal layer of the metal-clad laminate of the present invention in which a predetermined conductor circuit is formed by etching or the like and the conductor circuit portion is blackened can be suitably used.
- a prepreg of the present invention or a resin film made of the resin composition of the present invention can be used.
- the resin film which consists of the said prepreg or the said resin composition is used as the said insulating layer, the said inner layer circuit board does not need to consist of the metal-clad laminated board of this invention.
- a multilayer printed wiring board in which the metal-clad laminate of the present invention is used as an inner circuit board and the prepreg of the present invention and the resin sheet of the present invention are used as an insulating layer will be described.
- a commercially available resin sheet can also be used as the insulating layer.
- a circuit is formed on one or both sides of the metal-clad laminate to produce an inner layer circuit board. In some cases, through holes can be formed by drilling or laser processing, and electrical connection on both sides can be achieved by plating or the like.
- the insulating layer is formed by superposing the resin layer of the prepreg or the resin sheet on the inner layer circuit board and heating and pressurizing it.
- a multilayer printed wiring board can be obtained by alternately and repeatedly forming conductive circuit layers and insulating layers formed by etching or the like.
- the prepreg and the inner layer circuit board or the resin layer of the resin sheet and the inner layer circuit board are combined and vacuum heated and pressed using a vacuum pressurizing laminator apparatus, and then a hot air drying apparatus
- the insulating layer is cured by heating.
- the conditions for heat and pressure molding are not particularly limited, but for example, it can be carried out at a temperature of 60 to 160 ° C. and a pressure of 0.2 to 3 MPa.
- the conditions for heat curing are not particularly limited, but for example, the temperature can be set at 140 to 240 ° C. for 30 to 120 minutes.
- the prepreg is overlaid with the inner layer circuit board or the resin layer of the resin sheet on the inner layer circuit board, and this is heated and pressed with a flat plate press or the like.
- the conditions for the heat and pressure molding are not particularly limited, but for example, it can be carried out at a temperature of 140 to 240 ° C. and a pressure of 1 to 4 MPa.
- the insulating layer is heat-cured simultaneously with the heat and pressure forming.
- the curing of the insulating layer formed from the resin sheet or the prepreg may be left in a semi-cured state in order to facilitate the subsequent laser irradiation and removal of resin residue (smear) and improve desmearing properties.
- the first insulating layer is partially cured (semi-cured) by heating at a temperature lower than the normal heating temperature, and one or more insulating layers are further formed on the insulating layer to form a semi-cured insulating layer By heat-curing again to such an extent that there is no practical problem, the adhesion between the insulating layer and between the insulating layer and the circuit can be improved.
- the semi-curing temperature is preferably 80 ° C. to 200 ° C., more preferably 100 ° C. to 180 ° C.
- the insulating layer is irradiated with a laser to form an opening.
- a laser an excimer laser, a UV laser, a carbon dioxide gas laser, or the like can be used.
- desmear treatment it is preferable to perform a treatment for removing resin residues and the like (smear) after laser irradiation with an oxidizing agent such as permanganate and dichromate, that is, desmear treatment. If the desmear treatment is inadequate and the desmear resistance is not sufficiently secured, even if metal plating is applied to the opening, sufficient conductivity is ensured between the upper metal wiring and the lower metal wiring due to smear. There is a risk of disappearing. Further, the surface of the smooth insulating layer can be simultaneously roughened, and the adhesion of the conductive wiring circuit formed by subsequent metal plating can be improved.
- an oxidizing agent such as permanganate and dichromate
- the timing at which the substrate is peeled is not particularly limited.
- the peeling of the substrate may be performed either before or after the heat curing of the insulating layer, and before and after the formation of the opening by laser irradiation, the desmear treatment You may go either before or after.
- the base material of the resin sheet is a resin film
- (1) heat curing of the insulating layer, base material peeling, formation of apertures by laser irradiation, desmear treatment (2) Preference is given to the order of substrate peeling, heat curing of the insulating layer, formation of apertures by laser irradiation, and desmear treatment.
- the base material of the resin sheet is a metal foil
- (1) heat curing of the insulating layer, formation of apertures by laser irradiation, desmear treatment, base material peeling order, or (2) heat curing of the insulating layer is preferred.
- an outer layer circuit is formed.
- the insulating layers are connected by metal plating, and the outer layer circuit pattern is formed by etching.
- an insulating layer may be further laminated and a circuit may be formed in the same manner as described above.
- a solder resist layer is formed as the outermost layer after the circuit is formed.
- the method of forming the solder resist layer is not particularly limited. For example, a dry film type solder resist is laminated (laminated) on a circuit, exposed and developed, or a liquid resist is printed, exposed and developed. Methods and the like.
- the electrode part for a connection is provided in order to mount a semiconductor element.
- the connection electrode portion can be appropriately coated with a metal film such as gold plating, nickel plating, or solder plating.
- One of the typical gold plating methods is a nickel-palladium-gold electroless plating method.
- a pretreatment is performed on the connecting electrode portion by an appropriate method such as a cleaner, and then a palladium catalyst is applied. Thereafter, an electroless nickel plating process, an electroless palladium plating process, and an electroless gold plating process Are performed sequentially.
- the ENEPIG method is a method in which a displacement gold plating process is performed in the electroless gold plating process of the nickel-palladium-gold electroless plating process.
- the diffusion preventing property and the corrosion resistance of the conductor material in the connection electrode portion are improved. Since it is possible to prevent the diffusion of the underlying nickel plating film, the reliability of the Au-Au joint is improved and the nickel oxidation by gold can be prevented, so the reliability of the lead-free solder joint with a large thermal load is also improved. improves.
- the ENEPIG method it is usually necessary to perform surface treatment before performing electroless palladium plating to prevent the occurrence of poor conduction in the plating process. If the poor conduction is severe, a short circuit occurs between adjacent terminals. Cause.
- the printed wiring board of the present invention does not have the above-described conduction failure without performing surface treatment, and can be easily plated.
- solder bump is preferably made of an alloy made of tin, lead, silver, copper, bismuth or the like.
- connection method between the semiconductor element and the printed wiring board is to use a flip chip bonder or the like to align the connection electrode part on the substrate and the solder bump of the semiconductor element, and then to an IR reflow device, a heat plate, etc.
- the solder bumps are heated to a melting point or higher by using a heating device, and the printed wiring board and the solder bumps are connected by fusion bonding.
- a metal layer having a relatively low melting point, such as solder paste may be formed in advance on the connection electrode portion on the printed wiring board. Prior to this joining step, the connection reliability can be improved by applying a flux to the surface layer of the connection electrode portion on the solder bump and / or printed wiring board.
- Example A series Examples using the first resin composition are shown below.
- Example A1 (1) Preparation of resin composition-containing varnish (resin varnish) Novolak-type epoxy resin (EOCN-1020-75, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200) as an epoxy resin, 17.5% by weight, and a first inorganic filler Boehmite (manufactured by Kawai Lime Co., Ltd., product number BMT-3L, average particle size 2.9 ⁇ m, 1% thermal decomposition temperature 420 ° C.) 61.4% by weight and spherical nano silica (product number NSS-5N, Tokuyama as the second inorganic filler) 37.5% by weight, average particle size 70 nm), phenol resin (MEH7851-4L, manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent 187) 17.5% by weight, and imidazole (Shikoku Chemical Industries) as a curing accelerator Co., Ltd., product
- a commercially available resin film (also referred to as a build-up material) (Ajinomoto Fine Techno Co., ABF GX-13, thickness 40 ⁇ m) is laminated on the inner layer circuit using a vacuum laminator, at a temperature of 170 ° C. for 60 minutes.
- a laminate having an insulating layer was obtained by heat curing.
- an opening (blind via hole) having a diameter of 60 ⁇ m was formed on the prepreg of the obtained laminate using a carbonic acid laser device (manufactured by Hitachi Via Mechanics Co., Ltd .: LG-2G212), and a swelling liquid (70 ° C.) Soaked in Atotech Japan Co., Swelling Dip Securigant P) for 5 minutes, and further soaked in 80 ° C potassium permanganate aqueous solution (Atotech Japan Co., Concentrate Compact CP) for 15 minutes, neutralized and roughened Processed.
- a power feeding layer of about 0.5 ⁇ m was formed by an electroless copper plating film.
- a 25 ⁇ m thick UV-sensitive dry film (AQ-2558 manufactured by Asahi Kasei Co., Ltd.) was bonded with a hot roll laminator, and a chromium vapor deposition was drawn in which a pattern with a minimum line width / line spacing of 20/20 ⁇ m was drawn.
- a 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 an aqueous sodium carbonate solution to form a plating resist.
- 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 ⁇ m.
- the plating resist was peeled off using a two-stage peeling machine.
- Each chemical solution is composed mainly 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 second stage oxidizing resin etchant.
- An aqueous solution of acidic amine (Mc. Dicer 9279, manufactured by Nihon McDermid) was used for neutralization.
- the power feeding layer was immersed in an ammonium persulfate aqueous solution (AD-485 manufactured by Meltex Co., Ltd.) to be removed by etching, and insulation between wirings was ensured.
- the insulating layer was finally cured at a temperature of 200 ° C. for 60 minutes, and finally a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) was formed on the circuit surface to obtain a printed wiring board.
- 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). The one formed by CRC-8300) was used.
- a flux material was uniformly applied to the solder bumps by a transfer method, and then, using a flip chip bonder device, the solder bumps were mounted on a printed wiring board by thermocompression bonding.
- a liquid sealing resin manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S
- the curing condition of the liquid sealing resin was a temperature of 150 ° C. for 120 minutes.
- Example A2 The procedure was the same as Example A1 except that the resin varnish was mixed as follows. 17.5% by weight of phenol novolac cyanate resin (Primaset PT-30, Lonza) as cyanate resin, and biphenyldimethylene type epoxy resin (NC3000, Nippon Kayaku, epoxy equivalent 275) 9.5 as epoxy resin
- phenol novolac cyanate resin Principal PT-30, Lonza
- biphenyldimethylene type epoxy resin NC3000, Nippon Kayaku, epoxy equivalent 275
- boehmite product number BMT-3L, average particle size 2.9 ⁇ m, 1% thermal decomposition temperature 420 ° C.
- a second inorganic filler Spherical nanosilica product number NSS-5N, manufactured by Tokuyama Corporation, average particle size 70 nm
- phenol resin MEH7851-4L, manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent 187) as a curing agent 8.1% by weight Used (W2 /
- Example A3 The procedure was the same as Example A1 except that the resin varnish was mixed as follows. 17.5% by weight of phenol novolac cyanate resin (Primaset PT-30, Lonza) as cyanate resin and biphenyldimethylene type epoxy resin (NC3000, Nippon Kayaku, epoxy equivalent 275) 9.5 as epoxy resin
- phenol novolac cyanate resin Principal cyanate resin
- NC3000 biphenyldimethylene type epoxy resin
- N3000 epoxy equivalent 275
- a first inorganic filler boehmite (manufactured by Kawai Lime Co., Ltd., product number BMT-3L, average particle size 2.9 ⁇ m, 1% thermal decomposition temperature 420 ° C.) 31.6% by weight, as a second inorganic filler Spherical nanosilica (product number NSS-5N, manufactured by Tokuyama Corp., average particle size 70 nm) 3.5% by weight and spherical silica (SO-31R (man
- Example A4 The second inorganic filler was the same as Example A3 except that the following was used.
- spherical nano silica product number Admanano, manufactured by Admatechs, average particle size 50 nm, 40 wt% cyclohexanone slurry
- the cyclohexanone slurry was blended in terms of dry powder of spherical nano silica.
- Example A5 The second inorganic filler was the same as Example A3 except that the following was used.
- spherical nano silica product number Admanano, manufactured by Admatechs, average particle size 25 nm, 30 wt% Anon slurry
- the cyclohexanone slurry was blended in terms of dry powder of spherical nano silica.
- Example A6 The second inorganic filler was the same as Example A3 except that the following was used.
- Spherical nanosilica product number PL-1, manufactured by Fuso Chemical Industry Co., Ltd., average particle size 15 nm, 12 wt% anon slurry
- the cyclohexanone slurry was blended in terms of dry powder of spherical nano silica.
- Example A7 The first inorganic filler was the same as Example A3 except that the following was used.
- Aluminum hydroxide product number ALH-3L, manufactured by Kawai Lime Co., Ltd., average particle diameter 4.5 ⁇ m, 1% thermal decomposition temperature 280 ° C.
- Example A8 The first inorganic filler was the same as Example A3 except that the following was used.
- talc product number LMS-400, manufactured by Fuji Talc Industrial Co., Ltd., average particle size 3.8 ⁇ m, 1% pyrolysis temperature 375 ° C.
- Example A9 The same procedure as in Example A3 was conducted except that the following epoxy resin was used.
- Naphthalene-modified cresol novolac epoxy resin HP-5000, manufactured by DIC, epoxy equivalent 250
- Example A10 The same procedure as in Example A3 was conducted except that the following epoxy resin was used.
- Example A11 The procedure was the same as Example A1 except that the resin varnish was mixed as follows. 17.5% by weight of phenol novolac cyanate resin (Primaset PT-30, Lonza) as cyanate resin, and biphenyldimethylene type epoxy resin (NC3000, Nippon Kayaku, epoxy equivalent 275) 9.5 as epoxy resin 2% by weight boehmite (manufactured by Kawai Lime, product number BMT-3L, average particle size 2.9 ⁇ m, 1% thermal decomposition temperature 420 ° C.) 21.1% by weight as the first inorganic filler, and as the second inorganic filler Spherical nanosilica (product number NSS-5N, manufactured by Tokuyama Corporation, average particle size 70 nm) 10.5% by weight and spherical silica (SO-31R (manufactured by Admatechs, specific surface area 4.5 m 2 / g) as the third inorganic filler.
- phenol novolac cyanate resin
- Example A12 The procedure was the same as Example A1 except that the resin varnish was mixed as follows. 17.5% by weight of phenol novolac cyanate resin (Primaset PT-30, Lonza) as cyanate resin, and biphenyldimethylene type epoxy resin (NC3000, Nippon Kayaku, epoxy equivalent 275) 9.5 as epoxy resin 4% by weight boehmite (manufactured by Kawai Lime, product number BMT-3L, average particle size 2.9 ⁇ m, 1% thermal decomposition temperature 420 ° C.) 45.6% by weight as the first inorganic filler, and as the second inorganic filler Spherical nanosilica (product number NSS-5N, manufactured by Tokuyama Corporation, average particle size 70 nm) 10.5% by weight and spherical silica (SO-31R (manufactured by Admatechs, specific surface area 4.5 m 2 / g) as the third inorganic filler.
- phenol novolac cyanate resin
- Example A1 The same procedure as in Example A1 was carried out except that the resin varnish was blended as follows without using the second inorganic filler. 17.5% by weight of phenol novolac cyanate resin (Primaset PT-30, Lonza) as cyanate resin, and biphenyldimethylene type epoxy resin (NC3000, Nippon Kayaku, epoxy equivalent 275) 9.5 as epoxy resin % By weight and 56.1% by weight of boehmite (product number BMT-3L, average particle size 2.9 ⁇ m, 1% pyrolysis temperature 420 ° C., manufactured by Kawai Lime Co., Ltd.) as the first inorganic filler, and as the third inorganic filler Spherical silica (SO-31R (manufactured by Admatechs, specific surface area 4.5 m 2 / g, average particle size 1.1 ⁇ m) 8.8 wt%, phenol resin (MEH7851-4L, Meiwa Kasei Co., Ltd.
- Example A2 Except having used the 1st inorganic filler, it carried out similarly to Example A1 except having mix
- the impregnation property of the resin varnish in the prepreg is obtained by curing the prepreg produced as described above in a hot air oven at a temperature of 180 ° C. for 1 hour, and at a cross section of 35 points at 15 mm intervals in the width direction of 530 mm. Were observed and evaluated. In the cross-sectional observation, a scanning electron microscope was used to observe the presence or absence of voids not impregnated with resin (unimpregnated voids). Each code
- surface is as follows. A: No non-impregnated void was observed at all points. O: Unimpregnated voids were found at locations of 1 and less than 5, but at a practical level. ⁇ : Unimpregnated voids were observed at locations of 5 or more and less than 30 and were not practical. X: Unimpregnated voids were observed at 30 or more points, and this was not practical.
- the heat resistance of the semiconductor device was evaluated by 260 ° C. multi-reflow. Specifically, in accordance with IPC / JEDEC J-STD-20, the semiconductor device obtained above is passed through a 260 ° C. reflow furnace, and an ultrasonic depth inspection device is used every 10 passes. The insulating layer peeling of the semiconductor device, the crack, the peeling of the back surface of the semiconductor element, the defect of the solder bump, and the conduction failure on a hot plate at 125 ° C. were evaluated. Each code is as follows. (Double-circle): There was no peeling of an insulating layer, etc., and conduction
- the plating soaking after drilling was evaluated as follows. First, two laminates having a thickness of 0.4 mm are overlapped, and then drilled 3,000 times with a drill having a diameter of 0.2 mm, and then the through-hole plating with a thickness of 25 ⁇ m is formed on the formed through-hole. Through holes were formed. The penetration depth of the plating solution from the inner wall of the through hole into the laminate was measured. In addition, the union seal product number KMC L253 was used for the drill, the drill rotation speed at the time of drilling was 250 krpm / min, and the tip load of the drill was 9.6 ⁇ m / rev. Each code
- surface is as follows.
- the penetration depth was less than 20 ⁇ m (good).
- ⁇ The penetration depth was 20 ⁇ m or more and less than 50 ⁇ m (substantially no problem).
- ⁇ The penetration depth was 50 ⁇ m or more and less than 100 ⁇ m (substantially unusable).
- X The penetration depth was 100 ⁇ m or more (unusable).
- the through-hole insulation reliability was evaluated as follows about the sample which carried out the through-hole process, through-hole plating, and the circuit process on the same conditions as the drill process in said (8). That is, a voltage of 20V is applied between two through-holes whose inner wall spacing is 0.2 mm at a temperature of 130 ° C. and a humidity of 85%, and the time until the insulation resistance value becomes less than 10 8 ⁇ . Continuous measurement was performed.
- surface is as follows. A: 500 hours or more until the insulation resistance value was less than 10 8 ⁇ (good). ⁇ : It was 200 hours or more and less than 500 hours until the insulation resistance value was less than 10 8 ⁇ (substantially no problem). ⁇ : It was 100 hours or more and less than 200 hours until the insulation resistance value was less than 10 8 ⁇ (substantially unusable). X: It was less than 100 hours until the insulation resistance value was less than 10 8 ⁇ (unusable).
- Warpage amount of the printed wiring board portion (package) of the semiconductor device was measured as follows.
- the semiconductor device is placed on a chamber that can be heated and cooled with the chip surface (semiconductor element surface) facing down, and the semiconductor device is exposed to an atmosphere of ⁇ 50 ° C. and 125 ° C., respectively.
- surface is as follows.
- the resin compositions obtained in Examples A1 to A12 were excellent in fluidity and suppressed the occurrence of warpage when formed into a laminated board (multilayer printed wiring board). Further, the resin varnishes obtained in Examples A1 to A12 were excellent in thixotropy and filler sedimentation. Therefore, the resin varnish is excellent in mass production stability and impregnation with a prepreg. Further, since the resin varnish is excellent in resin flowability, even when the inorganic filler is highly filled, the moldability at the time of producing the laminate is good. Moreover, the printed wiring board produced using the said resin varnish was excellent in heat resistance, a low linear expansion coefficient, and drill workability.
- the printed wiring board is excellent in through-hole insulation reliability and has a low PKG warpage due to its low linear expansion coefficient.
- the resin varnish obtained in Comparative Example A1 has a high thixo ratio and poor impregnation with prepreg and resin flowability, and therefore poor in moldability, heat resistance, and through-hole insulation reliability.
- Comparative Example A2 is inferior in drill workability, it is inferior in through-hole insulation reliability.
- epoxy resin Nippon Kayaku Co., Ltd., NC3000, biphenylaralkyl type epoxy resin, weight average molecular weight 1300, softening point 57 ° C., epoxy equivalent 276 g / eq) 25.4% by weight, cyanate resin (Lonza Japan) 5.
- the prepreg was laminated on the inner layer circuit using a vacuum laminating apparatus, and heat cured at a temperature of 170 ° C. for 60 minutes to obtain a laminated body. Thereafter, using the obtained laminate, a printed wiring board was produced in the same manner as in Example A1.
- the obtained printed wiring board was subjected to ENEPIG treatment on the connection electrode portion corresponding to the solder bump array of the semiconductor element.
- the ENEPIG process was performed according to the following procedures [1]-[8]. The metal precipitation between the thin wires of the printed wiring board produced by performing the ENEPIG process was confirmed by SEM observation.
- Cleaner treatment ACL-007 manufactured by Uemura Kogyo Co., Ltd. was used as a cleaner liquid, and the test piece was immersed in a cleaner liquid at a liquid temperature of 50 ° C. for 5 minutes and then washed with water three times.
- Soft Etching Treatment After the cleaner treatment, a mixed solution of sodium persulfate and sulfuric acid was used as a soft etching solution, and the test piece was immersed in a soft etching solution at a liquid temperature of 25 ° C. for 1 minute and then washed with water three times.
- Pickling treatment After the soft etching treatment, the test piece was immersed in sulfuric acid having a liquid temperature of 25 ° C.
- Pre-dip treatment After the pickling treatment, the test piece was immersed in sulfuric acid at a liquid temperature of 25 ° C. for 1 minute.
- Palladium catalyst application After the pre-dip treatment, KAT-450 manufactured by Uemura Kogyo Co., Ltd. was used as a palladium catalyst application liquid in order to apply a palladium catalyst to the terminal portion. The test piece was immersed in the palladium catalyst application solution having a liquid temperature of 25 ° C. for 2 minutes and then washed with water three times.
- Electroless Ni plating treatment After the palladium catalyst application step, the test piece was immersed in an electroless Ni plating bath (NPR-4 manufactured by Uemura Kogyo Co., Ltd.) at a liquid temperature of 80 ° C. for 35 minutes, and then washed three times with water. did.
- Electroless Pd plating treatment After the electroless Ni plating treatment, the test piece was immersed in an electroless Pd plating bath (TPD-30 manufactured by Uemura Kogyo Co., Ltd.) at a liquid temperature of 50 ° C., and then washed with water three times. did.
- Electroless Au plating treatment After the electroless Pd plating treatment, the test piece was immersed in an electroless Au plating bath (TWX-40 manufactured by Uemura Kogyo Co., Ltd.) at a liquid temperature of 80 ° C. for 30 minutes and then washed with water three times. did.
- an electroless Au plating bath TWX-40 manufactured by Uemura Kogyo Co., Ltd.
- Example B2 The components of the slurry were 32.4% by weight of silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-600, average particle size 5 ⁇ m), boehmite particles (manufactured by Tesco Co., Ltd., AOH-30, average particle size 1. 8 ⁇ m) 12.2 wt% and silica nano particles (Tokuyama Co., Ltd., NSS-5N, average particle diameter 70 nm), except for 2.4 wt%.
- silicone rubber fine particles manufactured by Shin-Etsu Chemical Co., Ltd., KMP-600, average particle size 5 ⁇ m
- boehmite particles manufactured by Tesco Co., Ltd., AOH-30, average particle size 1. 8 ⁇ m
- silica nano particles Tokuyama Co., Ltd., NSS-5N, average particle diameter 70 nm
- Example B3 To a slurry prepared in the same manner as in Example B1, an epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC3000, biphenyl aralkyl type epoxy resin, weight average molecular weight 1300, softening point 57 ° C., epoxy equivalent 276 g / eq) 18.6 % By weight, cyanate resin (manufactured by Lonza Japan Co., Ltd., PT30, novolac-type cyanate resin, weight average molecular weight 380) 34.4% by weight, and zinc octylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.02 weight as a curing catalyst % was dissolved and mixed, and stirred using a high-speed stirrer to obtain a resin varnish containing 70% by weight of the resin composition based on the solid content, and was the same as Example B1.
- an epoxy resin manufactured by Nippon Kayaku Co., Ltd., NC3000, bipheny
- Example B4 To a slurry prepared in the same manner as in Example B1, an epoxy resin (Nippon Kayaku Co., Ltd., NC3000, biphenylaralkyl epoxy resin, weight average molecular weight 1300, softening point 57 ° C., epoxy equivalent 276 g / eq) 19.6 %
- cyanate resin Likza Japan Co., Ltd., PT30, novolac-type cyanate resin, weight average molecular weight 380
- maleimide resin manufactured by KAI Kasei Co., Ltd., BMI-70, (3-ethyl- 5-methyl-4-maleimidophenyl) methane, bismaleimide resin
- zinc octylate manufactured by Tokyo Chemical Industry Co., Ltd.
- Example B5 To a slurry prepared in the same manner as in Example B1, an epoxy resin (manufactured by Toto Kasei Co., Ltd., ESN-375, naphthalene type epoxy resin, weight average molecular weight 700, softening point 75 ° C., epoxy equivalent 167 g / eq) 25.4 % By weight, cyanate resin (Lonza Japan Co., Ltd., PT30, novolac-type cyanate resin, weight average molecular weight 380) 21.2% by weight, and phenolic resin (manufactured by Nippon Kayaku Co., Ltd., GPH-103, Example B1 And so on.
- an epoxy resin manufactured by Toto Kasei Co., Ltd., ESN-375, naphthalene type epoxy resin, weight average molecular weight 700, softening point 75 ° C., epoxy equivalent 167 g / eq
- cyanate resin Lionza Japan Co., Ltd., PT30, no
- Example B6 To a slurry prepared in the same manner as in Example B1, an epoxy resin (Nippon Kayaku Co., Ltd., NC3000, biphenyl aralkyl epoxy resin, weight average molecular weight 1300, softening point 57 ° C., epoxy equivalent 276 g / eq) 25.4 % By weight, cyanate resin (Lonza Japan Co., Ltd., PT30, novolac-type cyanate resin, weight average molecular weight 380) 21.2% by weight, and phenol resin (Maywa Kasei Co., Ltd., MEH-7500, Tri) as a curing agent 6.4% by weight of phenylmethane type phenol resin, hydroxyl group equivalent 97 g / eq) was dissolved and mixed, and stirred using a high-speed stirrer to obtain a resin varnish containing 70% by weight of the resin composition based on solid content. Except for this, the procedure was the same as in Example B1.
- epoxy resin manufactured by Toto Kasei Co., Ltd., ESN-375, naphthalene type epoxy resin, weight average molecular weight 700, softening point 75 ° C., epoxy equivalent 167 g / eq) 38.0% by weight
- phenol as a curing agent Resin Maywa Kasei Co., Ltd., MEH-7500, triphenylmethane type phenolic resin, hydroxyl group equivalent 97 g / eq
- the procedure was the same as Reference Example D1, except that a resin varnish containing 70% by weight based on the solid content was obtained.
- Example B2 The components of the slurry were boehmite particles (Tesco Co., Ltd., AOH-30, average particle size 1.8 ⁇ m) 18.2% by weight, silica nanoparticles (Tokuyama Co., Ltd., NSS-5N, average particle size 70 nm) 2 Except that the amount was 4% by weight and 26.4% by weight of silica particles (manufactured by Admatechs, SO-25R, average particle size 0.5 ⁇ m), the same as Example B1.
- Example B3 The components of the slurry were silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-600, average particle diameter 5 ⁇ m) 18.2% by weight, silica nanoparticles (manufactured by Tokuyama Corporation, NSS-5N, average particle diameter 70 nm)
- the procedure was the same as Example B1, except that the content was 2.4 wt% and the silica particles (Admatex Co., Ltd., SO-25R, average particle size 0.5 ⁇ m) were 26.4 wt%.
- Example B4 The components of the slurry were boehmite particles (manufactured by Tesco Co., Ltd., AOH-30, average particle size 1.8 ⁇ m) 20.6% by weight, and silica particles (manufactured by Admatex Co., Ltd., SO-25R, average particle size 0). 0.5 ⁇ m) Same as Example B1 except 26.4% by weight.
- Example B5 The components of the slurry were boehmite particles (Tesco Co., Ltd., AOH-30, average particle size 1.8 ⁇ m) 44.6% by weight, and silica nanoparticles (Tokuyama Co., Ltd., NSS-5N, average particle size 70 nm) Except for 2.4% by weight, the procedure was the same as Example B1.
- Example A2 Flame retardancy In the same manner as in Example A1, a double-sided metal-clad laminate having a thickness of 1.02 mm was obtained. The copper foil of the obtained metal-clad laminate was etched, and the flame retardancy of a 1.0 mm-thick test piece was measured by the vertical method according to UL-94 standards. V-0: V-0 requirement of UL-94 standard is satisfied. Nonstandard: One or more of the five test pieces burned out.
- Drill wearability Three layers of the obtained metal laminates were stacked, and a drill bit (UV L0950) manufactured by Union Tool Co., Ltd. was used with a drill rotation speed of 160 rpm and a feed speed of 3.2 m / min. Drilling of ⁇ 150 was performed 3000 times (3000 holes). The drill blade width before use was set to 100%, the residual rate of the drill blade width after use was measured, and the drill wear resistance was evaluated.
- a drill bit UV L0950 manufactured by Union Tool Co., Ltd.
- the structure obtained by etching the copper foil of the above metal-clad laminate is etched with a ⁇ 60 ⁇ m via hole using a carbonic acid laser device (manufactured by Hitachi Via Mechanics Co., Ltd .: LG-2G212).
- 500 holes are formed, immersed in a swelling solution at 70 ° C. (Atotech Japan, Swelling Dip Securigant P) for 5 minutes, and further an aqueous potassium permanganate solution at 80 ° C. (Atotech Japan, Concentrate Compact CP) After 15 minutes, the sample was neutralized and subjected to a roughening treatment to carry out a desmear treatment.
- the thickness of the structure before and after the desmear treatment was measured, and the amount of film reduction [(thickness before treatment ⁇ thickness after treatment) / (thickness before treatment)] was evaluated.
- FIG. 5 shows (1) a photograph of the surface of the metal-clad laminate obtained in Example B1, and (2) the surface of the metal-clad laminate obtained in Comparative Example B1.
- photographed (3) and the figure explaining the photograph of the surface of the metal foil layer of a metal-clad laminated board are shown.
- streaky unevenness occurred on the surface of the metal foil layer of the metal-clad laminate of Comparative Example B1, but the surface of the metal foil layer of the metal-clad laminate of Example B1 was The unevenness of was not seen.
- Comparative Example B1 the numerical value of the drill wear resistance is equivalent to the result of the example, but the test piece contains a very large amount of voids and cannot be objectively compared with the example. Moreover, in the linear expansion coefficient test of Comparative Example B1, since the prepreg impregnation property of the test piece was poor, the portion having a high filling property was selected and measured.
- the resin compositions, prepregs, metal-clad laminates, printed wiring boards, and semiconductor devices obtained in Examples B1 to B6 have a coefficient of linear expansion, flame retardancy, drill wear, prepreg impregnation, and desmear resistance. , And ENEPIG properties were all good. Therefore, by using a resin composition characterized by containing epoxy resin, silicone rubber fine particles, boehmite particles, and silica nanoparticles specified in the present invention, a prepreg having excellent performance, a metal-clad laminate, It can be seen that a printed wiring board and a semiconductor device can be obtained.
- Reference examples using the third resin composition of the present invention are shown below.
- ANON cyclohexanone
- MIBK methyl isobutyl ketone
- the components of the slurry were 32.5% by weight of silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-600, average particle size 5 ⁇ m), silica nanoparticles (manufactured by Tokuyama Co., Ltd., NSS-5N, average particle size 70 nm).
- the procedure was the same as Reference Example C1, except that the content was 2.5% by weight and the silica particles (manufactured by Admatechs Co., Ltd., SO-25R, average particle size 0.5 ⁇ m) were 5.0% by weight.
- Reference Example C7 The components of the slurry were 37.5% by weight of silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-605, average particle size 2 ⁇ m), and silica nanoparticles (manufactured by Tokuyama Corp., NSS-5N, average particle size 70 nm). ) Same as Reference Example C1, except 2.5% by weight.
- Reference Example C8 The components of the slurry were 37.5% by weight of silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-597, average particle diameter 5 ⁇ m), and silica nanoparticles (manufactured by Tokuyama Corporation, NSS-5N, average particle diameter 70 nm). ) Same as Reference Example C1, except 2.5% by weight.
- epoxy resin manufactured by Toto Kasei Co., Ltd., ESN-375, naphthalene type epoxy resin, weight average molecular weight 700, softening point 75 ° C., epoxy equivalent 167 g / eq) 38.0% by weight
- phenol as a curing agent Resin Maywa Kasei Co., Ltd., MEH-7500, triphenylmethane type phenolic resin, hydroxyl group equivalent 97 g / eq
- the procedure was the same as Reference Example C1, except that a resin varnish containing 70% by weight based on the solid content was obtained.
- Reference Comparative Example C2 The components of the slurry were 37.5% by weight of silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-600, average particle size 5 ⁇ m), and silica particles (manufactured by Admatechs Co., Ltd., SO-25R, average particle size). 0.5 ⁇ m) Same as Reference Example C1, except 2.5% by weight.
- Reference Comparative Example C3 The components of the slurry were 37.5% by weight of silica particles (manufactured by Admatechs Co., Ltd., SO-25R, average particle size 0.5 ⁇ m), and silica nanoparticles (manufactured by Tokuyama Co., Ltd., NSS-5N, average particle size 70 nm). ) Same as Reference Example C1, except 2.5% by weight.
- Reference Comparative Example C4 The slurry was made in the same manner as Reference Example C1 except that the silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-600, average particle size 5 ⁇ m) were 40.0% by weight.
- FIG. 6 shows (1) a photograph of the surface of the metal-clad laminate obtained in Reference Example C1, and (2) a metal obtained in Reference Comparative Example C1.
- photographed the surface of the tension laminate sheet, and the figure explaining the photograph of the surface of the metal foil layer of (3) metal tension laminate sheet are shown.
- the surface of the metal foil layer of the metal-clad laminate of Reference Example C1 was No streak-like unevenness was observed.
- Reference Comparative Example C1, Reference Comparative Example C2, and Reference Comparative Example C4 have a numerical value of drill wear resistance that is equivalent to the results of Examples, but the test piece is in a state containing a very large amount of voids. It cannot be objectively compared with the reference embodiment. Moreover, in the linear expansion coefficient test of the reference comparative example C1, the reference comparative example C2, and the reference comparative example C4, since the prepreg impregnation property of a test piece was bad, it measured by selecting the part with high filling property.
- the resin compositions, prepregs, metal-clad laminates, printed wiring boards, and semiconductor devices obtained in Reference Examples C1 to C8 have a coefficient of linear expansion, flame retardancy, drill wear, prepreg impregnation, desmear The tolerance and ENEPIG properties were all good. Therefore, by using the silicone rubber fine particle-containing resin composition characterized by containing an epoxy resin, silicone rubber fine particles, and silica nanoparticles specified in the present invention, a prepreg having excellent performance, a metal-clad laminate, It can be seen that a printed wiring board and a semiconductor device can be obtained.
- Reference Example D1 (1) Preparation of resin composition-containing varnish (resin varnish) Epoxy resin (Nippon Kayaku Co., Ltd., NC3000, biphenyl aralkyl type epoxy resin, weight average molecular weight 1300, softening point 57 ° C., epoxy equivalent 276 g / eq) 21 0.0% by weight, cyanate resin (Lonza Japan Co., Ltd., PT30, novolac-type cyanate resin, weight average molecular weight 380) 39.0% by weight, zinc octylate (Tokyo Kasei Co., Ltd.) 0.02% by weight, Silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-605, average particle size 2 ⁇ m) 37.0% by weight, and barium sulfate particles (manufactured by Sakai Chemicals, BF-21,
- Epoxy resin manufactured by Toto Kasei Co., Ltd., ESN-375, naphthalene type epoxy resin, weight average molecular weight 700, softening point 75 ° C., epoxy equivalent 167 g / eq
- 21.0% by weight cyanate resin (Lonza Japan Co., Ltd.) , PT30, novolac-type cyanate resin, weight average molecular weight 380) 39.0% by weight
- zinc octylate manufactured by Tokyo Chemical Industry Co., Ltd.
- silicone rubber fine particles manufactured by Shin-Etsu Chemical Co., Ltd., KMP- 605, average particle size 2 ⁇ m
- barium sulfate particles manufactured by Sakai Chemicals, BF-21, average particle size 50 nm
- Epoxy resin (Nippon Kayaku Co., Ltd., NC3000, biphenyl aralkyl epoxy resin, weight average molecular weight 1300, softening point 57 ° C., epoxy equivalent 276 g / eq) 21.0% by weight, cyanate resin (Lonza Japan Co., Ltd.) , PT30, novolac-type cyanate resin, weight average molecular weight 380) 39.0% by weight, zinc octylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.02% by weight, silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP- 597, average particle size 5 ⁇ m) 37.0% by weight, barium sulfate particles (manufactured by Sakai Chemicals, BF-21, average particle size 50 nm) 3.0% by weight are dissolved and mixed in cyclohexanone and stirred using a high-speed stirr
- Naphthol aralkyl type cyanate resin 39.0% by weight, zinc octylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.02% by weight, silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP-605, average) (Particle diameter 2 ⁇ m) 37.0% by weight, barium sulfate particles (manufactured by Sakai Chemicals, BF-21, average particle size 50 nm) 3.0% by weight are dissolved and mixed in cyclohexanone, and stirred using a high-speed stirrer to give a resin.
- the procedure was the same as Reference Example D1, except that a resin varnish containing 70% by weight of the composition based on the solid content was obtained.
- Epoxy resin (Nippon Kayaku Co., Ltd., NC3000, biphenyl aralkyl epoxy resin, weight average molecular weight 1300, softening point 57 ° C., epoxy equivalent 276 g / eq) 21.0% by weight, cyanate resin (Lonza Japan Co., Ltd.) , PT30, novolac-type cyanate resin, weight average molecular weight 380) 39.0% by weight, zinc octylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.02% by weight, barium sulfate particles (manufactured by Sakai Chemicals, BF-21, average particles) 37.0% by weight of silica particles (manufactured by Admatechs Co., Ltd., SO-25R, average particle size 0.5 ⁇ m) of 37.0% by weight are dissolved and mixed in cyclohexanone and stirred using a high-speed stirrer. In the same manner as
- Epoxy resin (Nippon Kayaku Co., Ltd., NC3000, biphenyl aralkyl epoxy resin, weight average molecular weight 1300, softening point 57 ° C., epoxy equivalent 276 g / eq) 21.0% by weight, cyanate resin (Lonza Japan Co., Ltd.) , PT30, novolac-type cyanate resin, weight average molecular weight 380) 39.0% by weight, zinc octylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.02% by weight, silicone rubber fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP- 605, average particle size 2 ⁇ m) 37.0% by weight, silica particles (manufactured by Admatechs Co., Ltd., SO-25R, average particle size 0.5 ⁇ m) 3.0% by weight are dissolved and mixed in cyclohexanone, and a high-speed stirring device
- FIG. 7 shows (1) a photograph of the surface of the metal-clad laminate obtained in Reference Example D1, and (2) a metal obtained in Reference Comparative Example D1.
- photographed the surface of the tension laminate sheet, and the figure explaining the photograph of the surface of the metal foil layer of (3) metal tension laminate sheet are shown.
- streaky unevenness was generated on the surface of the metal foil layer of the metal-clad laminate of Reference Comparative Example D1, but the surface of the metal foil layer of the metal-clad laminate of Reference Example D1 was No streak-like unevenness was observed.
- Table D1 and Table D2 1) to 11) in Table D1 and Table D2 are as follows. 1) Nippon Kayaku Co., Ltd., NC3000 2) Made by Toto Kasei Co., Ltd., ESN-375 3) Lonza Japan, PT30 4) MEH-7851-H, manufactured by Meiwa Kasei Co., Ltd. 5) MEH-7500, manufactured by Meiwa Kasei Co., Ltd.
- the resin compositions, prepregs, metal-clad laminates, printed wiring boards, and semiconductor devices obtained in Reference Examples D1 to D9 have linear expansion coefficient, flame retardancy, prepreg impregnation properties, desmear resistance, and ENEPIG All of the characteristics were good. Accordingly, by using the barium sulfate particle-containing resin composition characterized by containing an epoxy resin and barium sulfate particles specified in the present invention, a prepreg having excellent performance, a metal-clad laminate, a printed wiring board, It can also be seen that a semiconductor device can be obtained.
- Reference Example E1 (1) Preparation of resin composition-containing varnish (resin varnish) 17.5% by weight of naphthalene-type tetrafunctional epoxy resin (product number HP-4700, manufactured by DIC, epoxy equivalent 165) as an epoxy resin, and biphenylalkylene as a phenol curing agent Type novolac resin (product number MEH-7785-3H, Meiwa Kasei Co., Ltd., hydroxyl equivalent 230) 17.3% by weight, imidazole (product number 2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) 0.1% by weight as a curing accelerator, Boehmite (product number BMT-3L, product number BMT-3L, average particle size 2.9 ⁇ m, 1% pyrolysis temperature 420 ° C.) 61.4% by weight as one filler, and spherical nano silica (product number NSS) as the
- Reference Examples E2 to E12 and Reference Comparative Example E1 were the same as Reference Example E1, except that the resin varnish was prepared according to the recipe shown in Table E1 and Table E2, and the resin varnish, prepreg, metal-clad laminate, A printed wiring board and a semiconductor device were produced. The raw materials used are shown below.
- Cyanate resin / Novolac type cyanate resin “Primaset PT-30” manufactured by Lonza Japan
- Cyanate equivalent 124 (2) Epoxy resin / naphthalene-type tetrafunctional epoxy resin: “DIC-4700” manufactured by DIC, epoxy equivalent of 165 g / eq (3) Epoxy resin / biphenyl dimethylene type epoxy resin: Nippon Kayaku Co., Ltd.
- Resin varnishes of reference examples and comparative examples Tables E1 and E2 show the evaluation results of prepregs, metal-clad laminates, printed wiring boards, semiconductor devices, and the like produced using the resin varnishes.
- FIG. 8 shows a cross-sectional FE-SEM photograph of the laminate obtained in Reference Example E1.
- FIG. 9 shows a cross-sectional FE-SEM photograph of the laminate obtained in Reference Example E9.
- the resin varnishes obtained in Reference Examples E1 to E12 were excellent in fluidity and suppressed the occurrence of warpage when formed into a laminate. Moreover, from FIG. 8, it can confirm that the spherical filler (silica) which is a 2nd filler has adsorb
- the resin varnishes obtained in Reference Examples E1 to E12 were excellent in thixotropy and filler sedimentation.
- the resin varnish is excellent in mass production stability and impregnation with a prepreg. Further, since the resin varnish is excellent in resin flowability, the moldability at the time of producing the laminated plate was good even when the inorganic filler was highly filled. Moreover, it was excellent in heat resistance, a low linear expansion coefficient, and drill workability when it was used as a printed wiring board. For this reason, the through-hole insulation reliability is excellent, and because of the low linear expansion coefficient, the amount of warpage of the printed wiring board portion of the semiconductor device is small and excellent. On the other hand, it is inferred that Reference Comparative Example E1 had high thixotropy, poor impregnation with prepreg, and resin flowability, resulting in poor moldability, heat resistance, and through-hole insulation reliability.
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Abstract
Description
従って、プリント配線板や金属張積層板には、難燃性等の基本要求を満たした上で、次のような特性が求められている。すなわち、(1)薄型化による基板自体の剛性の低下に対応するため、低熱膨張性や低反り性に優れ、リフローにより金属張積層板やプリント配線板に部品を接続する際に寸法変形や反りが小さい、(2)プリント配線板の多層化に対応するため、メッキプロセス時のデスミア性に優れ、上層金属配線と下層金属配線との通電性を十分に確保できること、(3)迅速な大量生産に対応するため、ドリル加工性等に優れ、生産性が高いことなどが求められている。
また、特許文献2には、水酸化アルミニウム-ベーマイト複合品を必須成分として含有する熱硬化性樹脂組成物を基材と組み合わせてなるプリプレグが開示されている。特許文献2に記載の技術は、半田リフロー温度の高温化に対応するために、無機充填材としてベーマイトや水酸化アルミニウム‐ベーマイト複合品のような耐熱性の高いものを用いている。
また、特許文献3には、基材の貫通孔及び/又は凹部に充填される充填材に関する技術が開示されている。具体的には、充填材を充填した基材においてクラックの発生防止やドリル加工性向上を目的とした技術であり、少なくとも硬化剤と無機フィラーと有機フィラーと液状の樹脂を含有する液状の充填材が開示されている。
また、ベーマイトのような不定形の無機充填材を用いる場合、樹脂組成物のワニスの流動性低下が特に生じやすく、無機充填材の高充填が困難になるという問題がある。
本発明の別の目的は、前記樹脂組成物を用いて作製した樹脂シート、前記樹脂組成物を用いて作製したプリプレグ、前記樹脂組成物又は前記プリプレグを用いて作製した金属張積層板、前記金属張積層板、前記プリプレグ、及び前記樹脂組成物のうち少なくともいずれか1つを用いて作製したプリント配線板、及び前記プリント配線板を用いて作製した性能に優れる半導体装置、を提供することにある。
(1) 積層板を形成するために用いる樹脂組成物であって、エポキシ樹脂と、不定形の第1無機充填材と、前記第1無機充填材と平均粒子径が異なりかつその平均粒子径が10~100nmである第2無機充填材と、を含むことを特徴とする樹脂組成物。
(2) 前記第2無機充填材の含有量は、前記樹脂組成物全体の0.5~5重量%である上記(1)に記載の樹脂組成物。
(3) 前記第2無機充填材が予め有機溶媒に分散されたスラリーを用いて調製された上記(1)又は(2)に記載の樹脂組成物。
(4) 前記第2無機充填材は、シリカである上記(1)乃至(3)のいずれかに記載の樹脂組成物。
(5) 前記第1無機充填材は、ベーマイトである上記(1)乃至(4)のいずれかに記載の樹脂組成物。
(6) 前記第1無機充填材の平均粒径が、0.5~5μmである上記(1)乃至(5)のいずれかに記載の樹脂組成物。
(7) 前記前記第1無機充填材の含有量が、前記樹脂組成物全体の20~65重量%である上記(1)乃至(6)のいずれかに記載の樹脂組成物。
(8) さらに、平均粒子径が0.2~3μmの第3無機充填材を含むものである上記(1)乃至(7)のいずれかに記載の樹脂組成物。
(9) 前記第3無機充填材の最大粒子径が、10μm以下である上記(8)に記載の樹脂組成物。
(10) 前記第2無機充填材の含有量(w2)と、前記第3無機充填材の含有量(w3)との重量比(w2/w3)が、0.02~1.5である上記(8)又は(9)に記載の樹脂組成物。
(11) 前記第1無機充填材の含有量(w1)と、前記第2無機充填材の含有量(w2)との重量比(w2/w1)が、0.02~0.5である上記(1)乃至(10)のいずれかに記載の樹脂組成物。
(12) さらに、シアネート樹脂を含むものである上記(1)乃至(11)のいずれかに記載の樹脂組成物。
(13) 前記エポキシ樹脂は、ビフェニルジメチレン型エポキシ樹脂、ノボラック型エポキシ樹脂、ナフタレン変性クレゾールノボラックエポキシ樹脂、およびアントラセン型エポキシ樹脂よりなる群から選ばれる少なくとも1種である上記(1)乃至(12)のいずれかに記載の樹脂組成物。
(14) エポキシ樹脂と、平均粒子径1μm~10μmのシリコーンゴム微粒子と、平均粒子径0.2μm~5μmのベーマイト微粒子と、平均粒子径10nm~100nmのシリカナノ粒子と、を含有することを特徴とする、樹脂組成物。
(15) 前記シリコーンゴム微粒子は、シリコーンゴムからなるコア部を、シリコーン樹脂で被覆したコアシェル構造粒子である、上記(14)に記載の樹脂組成物。
(16) 前記シリカナノ粒子の平均粒子径が40nm以上100nm以下である上記(14)又は(15)に記載の樹脂組成物。
(17) さらに、シアネート樹脂を含むものである上記(14)乃至(16)のいずれかに記載の樹脂組成物。
(18) さらに、マレイミド樹脂を含むものである上記(14)乃至(17)のいずれかに記載の樹脂組成物。
(19) 前記エポキシ樹脂は、ビフェニルアラルキル型エポキシ樹脂、ナフタレン骨格変性エポキシ樹脂、及びクレゾールノボラック型エポキシ樹脂よりなる群から選ばれる少なくとも1種である上記(14)乃至(18)のいずれかに記載の樹脂組成物。
(20) 基材上に、上記(1)乃至(19)のいずれかに記載の樹脂組成物からなる樹脂層が形成されてなることを特徴とする、樹脂シート。
(21) 上記(1)乃至(19)のいずれかに記載の樹脂組成物を基材に含浸してなることを特徴とするプリプレグ。
(22) 基材中に上記(1)乃至(19)のいずれかに記載の樹脂組成物を含浸してなる樹脂含浸基材層の少なくとも片面に金属箔を有することを特徴とする金属張積層板。
(23) 上記(21)に記載のプリプレグ又は当該プリプレグを2枚以上重ね合わせた積層体の少なくとも片面に金属箔を重ね、加熱加圧することにより得られる上記(22)に記載の金属張積層板。
(24) 上記(22)又は(23)に記載の金属張積層板を内層回路基板に用いてなることを特徴とするプリント配線板。
(25) 内層回路上に、上記(21)に記載のプリプレグを絶縁層に用いてなるプリント配線板。
(26) 内層回路上に、上記(1)乃至(19)のいずれかに記載の樹脂組成物を絶縁層に用いてなるプリント配線板。
(27) 上記(24)乃至(27)のいずれかに記載のプリント配線板に半導体素子を搭載してなることを特徴とする半導体装置。
また、シリコーンゴム微粒子と、ベーマイト粒子と、シリカナノ粒子とを組み合わせて含有する第2の樹脂組成物を用いることによって、低粘度の状態で前記3種類の粒子を多量に含むワニスを得ることができ、前記樹脂組成物の基材への含浸性が良好である。また、前記第2の樹脂組成物を用いることによって、表面のスジ状ムラの発生が非常に少ない金属張積層板を得ることができる。
前記樹脂組成物を用いて作製した樹脂シート、プリプレグ及び金属張積層板は、難燃性、低熱膨張性、ドリル加工性、低反り性及びデスミア耐性等の特性に優れる。さらに、前記金属張積層板、前記プリプレグ、前記樹脂シート及び前記樹脂組成物のうち少なくとも1つを用いて、性能に優れるプリント配線板を得ることができる。また、本発明によれば、前記プリント配線板を用いて、性能に優れる半導体装置を得ることができる。
まず、本発明の樹脂組成物について説明する。
本発明の第1~第5の樹脂組成物は、充填材を高比率で含んでいるにも関わらず、該樹脂組成物を溶媒と混合したワニスの流動性の低下を抑制することができる。そのため、本発明の樹脂組成物は基材への含浸性が良好である。その結果、本発明の樹脂組成物は、充填材使用により得られる効果、例えば、プリプレグ、積層板又はプリント配線板における低反り性、難燃性、低熱膨張性、ドリル加工性、及びデスミア耐性等の特性向上効果が高い。
本発明の樹脂組成物のワニスが流動性を確保したまま、すなわち、該ワニスが低粘度の状態で、充填材を高比率で含むことが可能な理由は次のように考えられる。まず、本発明の樹脂組成物は、複数種の充填材粒子を含む。本発明の樹脂組成物に含有されるこれら異種の充填材粒子は、その粒子間に引力が生じるものが選択されている。その結果、樹脂組成物中、各充填材粒子が高分散状態で含有され、ワニスの流動性低下が抑制される。
本発明の第1~第5の樹脂組成物は、上記のような共通のコンセプトを有している。
また、上記引力は、充填材粒子の表面電位(ゼータ電位)による引力、ファンデアワールス力による引力、カップリング剤処理等による化学的結合による引力等が含まれるが、中でも表面電位による引力が好ましい。
本発明の第1の樹脂組成物は、積層板を形成するために用いる樹脂組成物であって、エポキシ樹脂と、不定形の第1無機充填材と、前記第1無機充填材と平均粒子径が異なりかつその平均粒子径が10~100nmである第2無機充填材と、を含むことを特徴とする。
以上のように、本発明によれば、不定形の無機充填材を用いた場合であってもワニスの流動性を損なうことなく、プリプレグや積層板の反りを抑制できる樹脂組成物を得ることができる。
前記エポキシ樹脂としては、特に限定されないが、実質的にハロゲン原子を含まないものが好ましい。ここで、「実質的にハロゲン原子を含まない」とは、エポキシ樹脂の合成過程において使用されたハロゲン系成分に由来するハロゲンが、ハロゲン除去工程を経ても尚、エポキシ樹脂に残存していることを許容することを意味する。通常、エポキシ樹脂中に30ppmを超えるハロゲン原子を含まないことが好ましい。
これらの中の1種類のエポキシ樹脂を単独で用いることもできるし、異なる重量平均分子量を有する2種類以上のエポキシ樹脂を併用することもできるし、1種類または2種類以上のエポキシ樹脂と、エポキシ樹脂のプレポリマーを併用することもできる。
これらエポキシ樹脂の中でも特に、ビフェニルジメチレン型エポキシ樹脂、ノボラック型エポキシ樹脂、ナフタレン変性クレゾールノボラックエポキシ樹脂、およびアントラセン型エポキシ樹脂よりなる群から選ばれる少なくとも1種が好ましい。これらのエポキシ樹脂を用いることにより、得られる積層板及びプリント配線板の吸湿半田耐熱性および難燃性を向上させることができる。
本発明において、前記エポキシ樹脂の重量平均分子量は、例えばゲル浸透クロマトグラフィー(GPC)で測定し、ポリスチレン換算の重量分子量として特定することができる。
前記不定形の第1無機充填剤としては、例えば破砕シリカ、硼酸亜鉛、タルク、水酸化アルミ、ベーマイト(ギブサイトを変性して得られるアルミナ一水和物)等が挙げられる。
これらの中でも水酸化アルミ、ベーマイトが好ましい。樹脂組成物を用いて得られる積層板及びプリント配線板の耐熱性およびドリル加工性をより向上させることができるからである。
前記第1無機充填材の平均粒子径の測定は、レーザー回折散乱法により測定することができる。無機充填材を水中で超音波により分散させ、レーザー回折式粒度分布測定装置(HORIBA製、LA-500)により、無機充填材の粒度分布を体積基準で作成し、そのメディアン径を平均粒子径とすることで測定することができる。具体的には、無機充填材の平均粒子径はD50で規定される。
前記第2無機充填材としては、例えば燃焼法などの乾式法により得られる溶融シリカや沈降法やゲル法などの湿式法により得られるゾルゲルシリカなどが挙げられる。
このような第2無機充填材(特にシリカ)を予め有機溶媒に分散したスラリーを用いることで、不定形の第1無機充填剤を用いた際に生じる、ワニスの流動性の低下を抑制することができる理由は、次のように考えられる。まず、ナノサイズのシリカのようなナノサイズの粒子は、凝集し易く、樹脂組成物に配合する際に2次凝集体等を形成してしまうことが多いが、スラリー状のものを用いることで、このような2次凝集を防止することができ、それによって流動性が低下するのを防止することができる。次に、上述した第2無機充填材(ナノサイズのシリカ)の表面電位と、前記不定形の第1無機充填剤の表面電位との相違による、前記不定形の第1無機充填剤の凝集防止効果が高まるからである。
前記平均粒子径は、例えば、超音波振動電流法(ゼータ電位)、超音波減衰分光法(粒度分布)、レーザー回折散乱法、動的光散乱法により測定することができる。
例えば、無機充填材を水中で超音波により分散させ、動的光散乱式粒度分布装置(HORIBA製、LB-550)により、無機充填材の粒度分布を体積基準で作成し、そのメディアン径を平均粒子径とすることで測定することができる。具体的には、無機充填材の平均粒子径はD50で規定される
前記第3無機充填材の平均粒子径の測定は、レーザー回折散乱法により測定することができる。具体的には、第1無機充填材と同様の方法により、第3無機充填材の平均粒子径を測定することができる。
尚、本発明において、含有成分の樹脂組成物に対する含有量とは、含有成分の溶解及び/又は分散を目的として含有させる溶剤を除いた成分の合計量を100重量%とするものである。
前記シアネート樹脂は、特に限定されないが、例えば、ハロゲン化シアン化合物とフェノール類やナフトール類とを反応させ、必要に応じて加熱等の方法でプレポリマー化することにより得ることができる。また、このようにして調製された市販品を用いることもできる。
これらの中で、フェノールノボラック型シアネート樹脂が難燃性、および低熱膨張性に優れ、2,2'-ビス(4-シアナトフェニル)イソプロピリデン、およびジシクロペンタジエン型シアネートエステルが架橋密度の制御、および耐湿信頼性に優れている。特に、フェノールノボラック型シアネート樹脂が低熱膨張性の点から好ましい。また、更に他のシアネート樹脂を1種類あるいは2種類以上併用したりすることもでき、特に限定されない。
前記プレポリマーは、通常、前記シアネート樹脂を加熱反応などにより、例えば3量化することで得られるものであり、樹脂組成物の成形性、流動性を調整するために好ましく使用されるものである。
前記プレポリマーは、特に限定されないが、例えば3量化率が20~50重量%のプレポリマーを用いた場合、良好な成形性、流動性を発現できる。
特に前記第1無機充填剤として、ベーマイトを用いる場合は、カップリング剤として、芳香族アミノシランを用いることが好ましい。これにより、ベーマイトと芳香族アミノシランの相乗効果により樹脂組成物の硬化物の吸水性をより低下させることができ、かつこの樹脂組成物を用いて得られる多層プリント配線板は、吸湿処理後の試験において、金属箔とプリプレグ、プリプレグ間の密着性に優れる。
次に、本発明の第2の樹脂組成物について説明する。
本発明の第2の樹脂組成物は、エポキシ樹脂と、平均粒子径1μm~10μmのシリコーンゴム微粒子と、平均粒子径0.2μm~5μmのベーマイト微粒子と、平均粒子径10nm~100nmのシリカナノ粒子と、を含有することを特徴とする。
第2の樹脂組成物では、前記シリコーンゴム微粒子と、前記ベーマイト粒子と、前記シリカナノ粒子とを併用して樹脂組成物に含有させることにより、前記樹脂組成物のワニスが低粘度の状態で、前記3種類の粒子を多量に含有させることができる。これは、正の表面ゼータ電位を有するベーマイト粒子の周囲に、負の表面ゼータ電位を有するシリカナノ粒子が選択的に付着し、同符号の表面ゼータ電位を有するシリコーンゴム微粒子とベーマイト粒子との反発力が弱まることにより、多量の粒子を含んでいてもワニスが低粘度となるからである。
また、上記のような充填材粒子を多量に含んでいるにも関わらず、粘度の低い、第2の樹脂組成物を用いることによって、当該樹脂組成物を充分に基材に含浸したプリプレグを得ることができる。得られたプリプレグは、難燃性、低熱膨張性、ドリル加工性、及びデスミア耐性に優れる。
また、NSS-5N(トクヤマ(株)製)、Sicastar43-00-501(Micromod社製)等の市販品を用いることもできる。
上記エポキシ樹脂の中でも特に、ビフェニルアラルキル型エポキシ樹脂、ナフタレン骨格変性エポキシ樹脂、及びクレゾールノボラック型エポキシ樹脂よりなる群から選ばれる少なくとも1種が好ましい。これらのエポキシ樹脂を用いることにより、得られるプリプレグ、積層板及びプリント配線板の耐熱性及び難燃性を向上させる。
前記シアネート樹脂は、特に限定されず、具体例や含有量は、上記第1の樹脂組成物と同様であるため、ここでの説明は省略する。
前記マレイミド樹脂としては、特に限定されないが、N,N’-(4,4’-ジフェニルメタン)ビスマレイミド、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン、2,2-ビス[4-(4-マレイミドフェノキシ)フェニル]プロパン等のビスマレイミド樹脂が挙げられる。また、更に他のマレイミド樹脂を1種類あるいは2種類以上併用したりすることもでき、特に限定されない。
次に、本発明の第3の樹脂組成物について説明する。
本発明の第3の樹脂組成物は、エポキシ樹脂と、平均粒子径1μm~10μmのシリコーンゴム微粒子と、平均粒子径10nm~150nmのシリカナノ粒子と、を含有することを特徴とする。
シリコーンゴム微粒子と、シリカナノ粒子とを併用して樹脂組成物に含有させることにより、前記樹脂組成物のワニスが低粘度の状態で、前記3種類の粒子を多量に含有させることができる。これは、正の表面ゼータ電位を有するシリコーン微粒子と、負の表面ゼータ電位を有するシリカナノ粒子とが引き合うことにより、多量の粒子を含んでいてもワニスが低粘度となるからである。
上記のような充填材粒子を多量に含んでいるにも関わらず、粘度の低い、第3の樹脂組成物を用いることによって、当該樹脂組成物を基材に充分含浸したプリプレグを得ることができる。得られたプリプレグは、難燃性、低熱膨張性、ドリル加工性、及びデスミア耐性に優れる。
上記エポキシ樹脂の中でも特に、ビフェニルアラルキル型エポキシ樹脂、ナフタレン骨格変性エポキシ樹脂、及びクレゾールノボラック型エポキシ樹脂よりなる群から選ばれる少なくとも1種が好ましい。これらのエポキシ樹脂を用いることにより、プリプレグ、積層板、プリント配線板の耐熱性及び難燃性を向上させる。
エポキシ樹脂の含有量については、上記第2の樹脂組成物と同様であるため説明は省略する。
前記シアネート樹脂は、特に限定されず、具体例や含有量は、上記第1の樹脂組成物と同様であるため、ここでの説明は省略する。
次に、本発明の第4の樹脂組成物について説明する。
第4の樹脂組成物は、エポキシ樹脂と、平均粒子径10nm~150nmの硫酸バリウム粒子と、無機充填材を含有することを特徴とする。
平均粒子径10nm~150nmの硫酸バリウム粒子をエポキシ樹脂組成物に含有させることにより、前記樹脂組成物を用いた樹脂ワニスが高粘度の状態であっても、無機充填材を多量に含有させることができる。これは平均粒子径10nm~150nmの硫酸バリウム粒子が、基材のフィラメントの隙間に入り込み基材間の隙間が広げられ、従来よりも多量の無機充填材を含むことができると推察する。
また無機充填材との組み合わせによっては、樹脂ワニスを低粘度の状態にすることができ無機充填材を、さらに多量に含有させることができる。これは、表面ゼータ電位との関係で、硫酸バリウム粒子とが引き合う無機充填材は、樹脂ワニス全体として粘度を下げることができことにより、多量の無機充填材を含んでいても含浸性に優れると推察する。
また、上記のような充填材粒子を多量に含んでいるにも関わらず、粘度の低い、第4の樹脂組成物を用いることによって、当該樹脂組成物を充分に基材に含浸したプリプレグを得ることができる。得られたプリプレグは、難燃性、低熱膨張性、ドリル加工性、及びデスミア耐性に優れる。
これにより更に無機充填材の量を多くすることができる。
これによりドリル磨耗性が向上するほか、線膨張係数を下げることができる。
上記エポキシ樹脂の中でも特に、ビフェニルアラルキル型エポキシ樹脂、ナフタレン骨格変性エポキシ樹脂、及びクレゾールノボラック型エポキシ樹脂が好ましい。これらのエポキシ樹脂を用いることにより、プリプレグ、積層板及びプリント配線板の耐熱性及び難燃性を向上させる。
また、前記エポキシ樹脂の重量平均分子量は、特に限定されず、上記第3の樹脂組成物同様である。
前記シアネート樹脂は、特に限定されず、具体例や含有量は、上記第1の樹脂組成物と同様であるため、ここでの説明は省略する。
次に、本発明の第5の樹脂組成物について説明する。
第5の樹脂組成物は、(A)第一の充填材の外周に、(A)第一の充填材より粒径の小さい(B)第二の充填材が付着してなる充填材を含むことを特徴とする。
上記の平均粒径の充填材を用いることにより、さらに含浸性が向上する。
(A)第一の充填材として、これらの中の1種類を単独で用いることもできるし、2種類以上を併用したりすることもできる。
コアシェル型ゴム粒子とは、粒子がコア層とシェル層を有するゴム粒子をいい、例えば、外層のシェル層がガラス状ポリマー、内層のコア層がゴム状ポリマーで構成される2層構造、または外層のシェル層がガラス状ポリマー、中間層がゴム状ポリマー、コア層がガラス状ポリマーで構成される3層構造のものなどが挙げられる。2層構造におけるコア層又は3層構造における中間層のゴム状ポリマーとして、エチレン、プロピレン、スチレン、ブタジエン、イソプロピレン、アクリル酸メチル、メタクリル酸メチル、アクリルニトリル等の架橋ゴムを選択することができる。また、2層構造においてコア層を被覆するシェル層(外層)又は3層構造におけるコア層のガラス状ポリマーとしては、メチルメタアクリレート、スチレン、アクリロニトリルあるいはその共重合体等を選択することができる。ガラス状ポリマーには、官能基としてエポキシ基、カルボキシル基等の導入も可能であり、用途により選択することができる。
架橋型ゴム粒子としては、例えば、アクリロニトリルブタジエンゴム(NBR)粒子、スチレンブタジエンゴム(SBR)粒子、アクリルゴム粒子などが挙げられる。
なお、このようなゴム粒子は、第5の樹脂組成物の硬化物の機械強度を高める、該硬化物の応力緩和、該硬化物の低熱膨張化などの効果を付与することもできる。
前記(A)第一の充填材に付着する(B)第二の充填材は、例えば、(A)第一の充填材のゼータ電位の符号が異なるもの、ファンデスワール力による引き付け合うもの、カップリング剤処理等により化学的に結合させる等が挙げられる。
これにより、ワニス粘度が高くとも含浸性が向上し、ボイド発生を抑えることができ、さらには半田耐熱性に優れ、絶縁信頼性が向上する。
なお、平均粒子径が10~100nmの充填材を用いる場合は、予め有機溶媒に分散したスラリーとして用いることが好ましい。平均粒子径が10~100nmの充填材は、凝集し易く、樹脂組成物に配合する際に二次凝集体等を形成し流動性を低下する場合があるからである。
この中でもシリカが、積層板の線熱膨張率を下げる点で好ましい。
球状にする方法は特に限定されないが、例えば、シリカの場合は、燃焼法などの乾式の溶融シリカや沈降法やゲル法などの湿式のゾルゲルシリカなどにより球状にすることができる。
上記エポキシ樹脂の中でも特に、ビフェニルアラルキル型エポキシ樹脂、ナフタレン骨格変性エポキシ樹脂、及びクレゾールノボラック型エポキシ樹脂よりなる群から選ばれる少なくとも1種が好ましい。これらのエポキシ樹脂を用いることにより、プリプレグ、積層板及びプリント配線板の耐熱性及び難燃性を向上させる。
前記エポキシ樹脂の重量平均分子量は、特に限定されないが、重量平均分子量4.0×102~1.8×103が好ましい。重量平均分子量が前記下限未満であると、ガラス転移点が低下し、前記上限値を超えると流動性が低下し、基材に含浸できない場合がある。重量平均分子量を前記範囲内とすることにより、含浸性に優れたものとすることができる。
本発明の樹脂シートは、前記本発明の樹脂組成物を含む樹脂層を基材上に形成してなるものである。該樹脂層は、プリント配線板の絶縁層として使用することができる。
樹脂シートを作製する方法は特に限定されないが、例えば、(1)樹脂組成物を溶剤などに溶解、分散させた樹脂ワニスを、各種塗工装置を用いて基材に塗工した後、これを乾燥する方法、(2)上記樹脂ワニスを、スプレー装置により基材に噴霧塗工した後、これを乾燥する方法、などが挙げられる。
これらの中でも、コンマコーター、ダイコーターなどの各種塗工装置を用いて、樹脂ワニスを基材に塗工した後、これを乾燥する方法が好ましい。これにより、ボイドがなく、均一な厚みを有する樹脂層を、基材上に効率よく形成することができる。
なお、本発明の樹脂シートを製造するにあたっては、樹脂層と接する基材面の凹凸は極力小さいものであることが好ましい。これにより、該樹脂シートを用いて、導体回路上に絶縁層を形成する際に、微細配線加工が容易となる。
次に、プリプレグについて説明する。
本発明のプリプレグは、前記樹脂組成物を基材に含浸し、さらに必要に応じて、加熱乾燥してなるものである。
例えば、図1に示すように、基材1を、含浸槽2の樹脂ワニス3中に浸漬して、基材1に樹脂ワニス3を含浸する。その際、含浸槽2が備えるディップロール4(図1では3本)によって基材1は樹脂ワニス3中に浸漬される。次いで、樹脂ワニス3を含浸した基材1を、垂直方向に引き上げて、水平方向に並設され、対向している1対のスクイズロール又は、コンマロール(図1の5はスクイズロール)の間を通して、基材1への樹脂ワニス3の塗布量を調整する。その後、樹脂ワニス3が塗布された基材1を、乾燥機6で所定の温度で加熱して、塗布されたワニス中の溶剤を揮発させると共に樹脂組成物を半硬化させてプリプレグ7を製造する。なお、図1中の上部ロール8はプリプレグ7を進行方向に移動させるために、プリプレグ7の進行方向と同方向に回転している。前記基材に含浸させた樹脂ワニスの溶剤を、所定温度、例えば90~180℃で乾燥させることにより半硬化のプリプレグを得ることができる。
次に、金属張積層板について説明する。
本発明の金属張積層板は、基材に上記の樹脂組成物を含浸してなる樹脂含浸基材層の少なくとも片面に金属箔を有するものである。
本発明の金属張積層板は、例えば、上記のプリプレグ又は当該プリプレグを1枚以上重ね合わせた積層体の少なくとも片面に金属箔を張り付けることで製造できる。
さらに、本発明の金属張積層板を製造する別の方法として、図3に示す絶縁樹脂層付き高分子フィルムシートを用いた金属張積層板の製造方法も挙げられる。まず、高分子フィルムシート31に、均一な絶縁樹脂層32をコーターで塗工した絶縁樹脂層付き高分子フィルムシート30を準備し、基材2の両側に絶縁樹脂層付き高分子フィルムシート30、30を絶縁樹脂層を内側にして配し(図3(a))、真空中で加熱60~130℃、加圧0.1~5MPaでラミネート含浸させる方法により、高分子フィルムシート付きプリプレグ42を得ることができる(図3(b))。次いで、高分子フィルムシート付きプリプレグ42の少なくとも片面の高分子フィルムシート31を剥離後(図3(c))、高分子フィルムシート31を剥離した面に金属箔11を配し(図3(d))、加熱加圧成形することで金属張積層板52を得ることができる(図3(e))。さらに、両面の高分子フィルムシートを剥離する場合は、前述のプリプレグ同様に、2枚以上積層することもできる。プリプレグを2枚以上積層するときは、積層したプリプレグの最も外側の上下両面もしくは片面に金属箔または高分子フィルムシートを配し、加熱加圧成形することで金属張積層板を得ることができる。前記加熱加圧成形する条件としては、温度は、特に限定されないが、120~250℃が好ましく、特に120~220℃が好ましく、特に150~220℃が好ましい。前記加圧する圧力は、特に限定されないが、0.1~5MPaが好ましく、特に0.5~3MPaが好ましい。本発明では、基材付きでプリプレグを作製するため、プリプレグの表面平滑性が高く低圧成形が可能となる。また、必要に応じて高温槽等で150~300℃の温度で後硬化を行ってもかまわない。
前記絶縁樹脂層付き金属箔を製造する装置において、金属箔は、例えば長尺のシート品を巻物形態にしたもの等を用い、これにより連続的に巻き出すことにより供給することができる。液状の絶縁樹脂は、絶縁樹脂の供給装置により、所定量が連続的に金属箔上に供給される。ここで液状の絶縁樹脂として、本発明の樹脂組成物を溶剤に溶解、分散させた塗布液が用いられる。絶縁樹脂の塗工量は、コンマロールと、当該コンマロールのバックアップロールとのクリアランスにより制御することができる。所定量の絶縁樹脂が塗工された金属箔は、横搬送型の熱風乾燥装置の内部を移送し、液状の絶縁樹脂中に含有される有機溶剤等を実質的に乾燥除去し、必要に応じて、硬化反応を途中まで進めた絶縁樹脂層付き金属箔とすることができる。絶縁樹脂層付き金属箔は、そのまま巻き取ることもできるがラミネートロールにより、絶縁樹脂層が形成された側に保護フィルムを重ね合わせ、当該保護フィルムがラミネートされた絶縁樹脂層付き金属箔を巻き取って、巻物形態の絶縁樹脂層付き金属箔を得ている。
次に、本発明のプリント配線板について説明する。
本発明のプリント配線板は、上記の金属張積層板を内層回路基板に用いてなる。
また、本発明のプリント配線板は、内層回路上に、上記のプリプレグを絶縁層に用いてなる。
また、本発明のプリント配線板は、内層回路上に、上記の樹脂組成物を絶縁層に用いてなる。
前記内層回路基板としては、例えば、本発明の金属張積層板の金属層に、エッチング等により所定の導体回路を形成し、導体回路部分を黒化処理したものを好適に用いることができる。
前記絶縁層としては、本発明のプリプレグ、又は本発明の樹脂組成物からなる樹脂フィルムを用いることができる。尚、前記絶縁層として、前記プリプレグ又は前記樹脂組成物からなる樹脂フィルムを用いる場合は、前記内層回路基板は本発明の金属張積層板からなるものでなくてもよい。
前記金属張積層板の片面又は両面に回路形成し、内層回路基板を作製する。場合によっては、ドリル加工、レーザー加工によりスルーホールを形成し、メッキ等で両面の電気的接続をとることもできる。この内層回路基板に前記プリプレグ又は樹脂シートの樹脂層を重ね合わせて加熱加圧形成することで絶縁層を形成する。同様にして、エッチング等で形成した導体回路層と絶縁層とを交互に繰り返し形成することにより、多層プリント配線板を得ることができる。
或いは、前記プリプレグを前記内層回路基板又は前記樹脂シートの樹脂層を前記内層回路基板に重ね合わせ、これを平板プレス装置等で加熱加圧成形する。ここで加熱加圧成形する条件としては特に限定されないが、一例を挙げると、温度140~240℃、圧力1~4MPaで実施することができる。このような平板プレス装置等による加熱加圧成形では、加熱加圧成形と同時に絶縁層の加熱硬化が行われる。
ENEPIG法は、前記ニッケル-パラジウム-金無電解メッキ法の無電解金メッキ処理段階において、置換金メッキ処理を行う方法である。下地メッキとしての無電解ニッケルメッキ皮膜と、無電解金メッキ皮膜との間に無電解パラジウムメッキ皮膜を設けることによって、接続用電極部における導体材料の拡散防止性、耐食性が向上する。下地ニッケルメッキ皮膜の拡散防止を図ることができるので、Au-Au接合の信頼性が向上し、また金によるニッケル酸化を防止することができるので、熱負荷の大きい鉛フリー半田接合の信頼性も向上する。ENEPIG法では、通常、無電解パラジウムメッキ処理を行う前に表面処理を行って、メッキ工程での導通不良の発生を防ぐ必要があり、導通不良が甚だしい場合には隣接する端子間でショートを起こす原因となる。一方、本発明のプリント配線板は、表面処理を行わなくても上記のような導通不良がなく、簡単にメッキ処理を行うことができる。
次に、本発明の半導体装置について説明する。
前記で得られたプリント配線板に半田バンプを有する半導体素子を実装し、半田バンブを介して、前記プリント配線板との接続を図る。そして、プリント配線板と半導体素子との間には液状封止樹脂を充填し、半導体装置を形成する。半田バンプは、錫、鉛、銀、銅、ビスマス等からなる合金で構成されることが好ましい。
以下、第1の樹脂組成物を用いた実施例を示す。
(実施例A1)
(1)樹脂組成物含有ワニス(樹脂ワニス)の調製
エポキシ樹脂としてノボラック型エポキシ樹脂(EOCN-1020-75、日本化薬社製、エポキシ当量200)17.5重量%と、第1無機充填材としてベーマイト(河合石灰社製、品番BMT-3L、平均粒子径2.9μm、1%熱分解温度420℃)61.4重量%と、第2無機充填材として球状ナノシリカ(品番NSS-5N、トクヤマ社製、平均粒子径70nm)3.5重量%と、硬化剤としてフェノール樹脂(MEH7851-4L、明和化成社製、水酸基当量187)17.5重量%と、硬化促進剤としてイミダゾール(四国化成工業社製、品番2E4MZ)0.1重量%とを、メチルイソブチルケトンに溶解、混合させた。次いで、得られた混合物を、高速撹拌装置を用い撹拌し、樹脂ワニスを調製した(W2/W1=0.06)。
前記樹脂ワニスをガラス織布(厚さ94μm、日東紡績製Eガラス織布、WEA-2116)に含浸し、150℃の加熱炉で2分間乾燥して、プリプレグ中のワニス固形分が約50重量%のプリプレグを得た。
得られたプリプレグを4枚重ね、その両面に12μmの銅箔(三井金属鉱業社製3EC-VLP箔)を重ねて、圧力3MPa、温度220℃で2時間加熱加圧成形し、両面に銅箔を有する、厚さ0.40mmの金属張積層板を得た。
両面に銅箔を有する前記金属張積層板を、ドリル機で開孔した後、無電解めっきにより上下銅箔間の導通を図った。さらに、両面の銅箔をエッチングすることにより内層回路を両面に形成した(L(導体回路幅)/S(導体回路間幅)=120/180μm、クリアランスホール1mmφ、3mmφ、スリット2mm)。
次に、内層回路に、過酸化水素水と硫酸を主成分とする薬液(旭電化工業(株)製テックSO-G)をスプレー吹き付けする粗化処理によって凹凸形成を行った。
次に脱脂、触媒付与、活性化の工程を経た後、無電解銅メッキ皮膜により約0.5μmの給電層を形成した。この給電層の表面に、厚さ25μmの紫外線感光性ドライフィルム(旭化成社製AQ-2558)をホットロールラミネーターにより貼り合わせ、最小線幅/線間が20/20μmのパターンが描画されたクロム蒸着マスク(トウワプロセス社製)を使用して、位置を合わせ、露光装置(ウシオ電機社製UX-1100SM-AJN01)にて露光、炭酸ソーダ水溶液にて現像し、めっきレジストを形成した。
得られたプリント配線板は、半導体素子の半田バンプ配列に相当するニッケル金メッキ処理が施された接続用電極部を配した後、50mm×50mmの大きさに切断し使用した。半導体素子(TEGチップ、サイズ15mm×15mm、厚み0.8mm)は、Sn/Pb組成の共晶で形成された半田バンプを有し、半導体素子の回路保護膜はポジ型感光性樹脂(住友ベークライト社製CRC-8300)で形成されたものを使用した。
半導体装置の組み立ては、まず、半田バンプにフラックス材を転写法により均一に塗布し、次にフリップチップボンダー装置を用い、半田バンプをプリント配線板上に加熱圧着により搭載した。次に、IRリフロー炉で半田バンプを溶融接合した後、液状封止樹脂(住友ベークライト社製、CRP-4152S)を充填し、液状封止樹脂を硬化させることで半導体装置を得た。尚、液状封止樹脂の硬化条件は、温度150℃、120分の条件であった。
樹脂ワニスの配合を以下のようにした以外は、実施例A1と同様にした。
シアネート樹脂としてフェノールノボラックシアネート樹脂(プリマセットPT-30、ロンザ社製)17.5重量%と、エポキシ樹脂としてビフェニルジメチレン型エポキシ樹脂(NC3000、日本化薬社製、エポキシ当量275)9.5重量%と、第1無機充填材としてベーマイト(河合石灰社製、品番BMT-3L、平均粒子径2.9μm、1%熱分解温度420℃)61.4重量%と、第2無機充填材として球状ナノシリカ(品番NSS-5N、トクヤマ社製、平均粒子径70nm)3.5重量%と、硬化剤としてフェノール樹脂(MEH7851-4L、明和化成社製、水酸基当量187)8.1重量%とを、用いた(W2/W1=0.06)。
樹脂ワニスの配合を以下のようにした以外は、実施例A1と同様にした。
シアネート樹脂としてフェノールノボラックシアネート樹脂(プリマセットPT-30、ロンザ社製)17.5重量%と、エポキシ樹脂としてビフェニルジメチレン型エポキシ樹脂(NC3000、日本化薬社製、エポキシ当量275)9.5重量%と、第1無機充填材としてベーマイト(河合石灰社製、品番BMT-3L、平均粒子径2.9μm、1%熱分解温度420℃)31.6重量%と、第2無機充填材として球状ナノシリカ(品番NSS-5N、トクヤマ社製、平均粒子径70nm)3.5重量%と、第3無機充填材として球状シリカ(SO-31R(アドマテックス社製、比表面積4.5m2/g、平均粒子径1.2μm)29.8重量%と、硬化剤としてフェノール樹脂(MEH7851-4L、明和化成社製、水酸基当量187)8.1重量%とを、用いた(W2/W1=0.11、W2/W3=0.12)。
第2無機充填材として、以下のものを用いた以外は、実施例A3と同様にした。
第2無機充填材として球状ナノシリカ(品番アドマナノ、アドマテックス社製、平均粒子径50nm、40wt%シクロヘキサノンスラリー)を用いた(W2/W1=0.11、W2/W3=0.12)。尚、上記シクロヘキサノンスラリーは、球状ナノシリカの乾粉換算で配合した。
第2無機充填材として、以下のものを用いた以外は、実施例A3と同様にした。
第2無機充填材として球状ナノシリカ(品番アドマナノ、アドマテックス社製、平均粒子径25nm、30wt%アノンスラリー)を用いた(W2/W1=0.11、W2/W3=0.12)。尚、上記シクロヘキサノンスラリーは、球状ナノシリカの乾粉換算で配合した。
第2無機充填材として、以下のものを用いた以外は、実施例A3と同様にした。
第2無機充填材として球状ナノシリカ(品番PL-1、扶桑化学工業社製、平均粒子径15nm、12wt%アノンスラリー)を用いた(W2/W1=0.11、W2/W3=0.12)。尚、上記シクロヘキサノンスラリーは、球状ナノシリカの乾粉換算で配合した。
第1無機充填材として、以下のものを用いた以外は、実施例A3と同様にした。
第1無機充填材として水酸化アルミ(品番ALH-3L、河合石灰社製、平均粒子径4.5μm、1%熱分解温度280℃)を用いた(W2/W1=0.11、W2/W3=0.12)。
第1無機充填材として、以下のものを用いた以外は、実施例A3と同様にした。
第1無機充填材としてタルク(品番LMS-400、富士タルク工業社製、平均粒子径3.8μm、1%熱分解温度375℃)を用いた(W2/W1=0.11、W2/W3=0.12)。
エポキシ樹脂として、以下のものを用いた以外は、実施例A3と同様にした。
エポキシ樹脂としてナフタレン変性クレゾールノボラックエポキシ樹脂(HP-5000、DIC社製、エポキシ当量250)を用いた(W2/W1=0.11、W2/W3=0.12)。
エポキシ樹脂として、以下のものを用いた以外は、実施例A3と同様にした。
エポキシ樹脂としてアントラセン型エポキシ樹脂(YX8800、ジャパンエポキシレジン、エポキシ当量181)を用いた(W2/W1=0.11、W2/W3=0.12)。
樹脂ワニスの配合を以下のようにした以外は、実施例A1と同様にした。
シアネート樹脂としてフェノールノボラックシアネート樹脂(プリマセットPT-30、ロンザ社製)17.5重量%と、エポキシ樹脂としてビフェニルジメチレン型エポキシ樹脂(NC3000、日本化薬社製、エポキシ当量275)9.5重量%と、第1無機充填材としてベーマイト(河合石灰社製、品番BMT-3L、平均粒子径2.9μm、1%熱分解温度420℃)21.1重量%と、第2無機充填材として球状ナノシリカ(品番NSS-5N、トクヤマ社製、平均粒子径70nm)10.5重量%と、第3無機充填材として球状シリカ(SO-31R(アドマテックス社製、比表面積4.5m2/g、平均粒子径1.2μm)33.3重量%と、硬化剤としてフェノール樹脂(MEH7851-4L、明和化成社製、水酸基当量187)8.1重量%とを、用いた(W2/W1=0.5、W2/W3=0.32)。
樹脂ワニスの配合を以下のようにした以外は、実施例A1と同様にした。
シアネート樹脂としてフェノールノボラックシアネート樹脂(プリマセットPT-30、ロンザ社製)17.5重量%と、エポキシ樹脂としてビフェニルジメチレン型エポキシ樹脂(NC3000、日本化薬社製、エポキシ当量275)9.5重量%と、第1無機充填材としてベーマイト(河合石灰社製、品番BMT-3L、平均粒子径2.9μm、1%熱分解温度420℃)45.6重量%と、第2無機充填材として球状ナノシリカ(品番NSS-5N、トクヤマ社製、平均粒子径70nm)10.5重量%と、第3無機充填材として球状シリカ(SO-31R(アドマテックス社製、比表面積4.5m2/g、平均粒子径1.2μm)8.8重量%と、硬化剤としてフェノール樹脂(MEH7851-4L、明和化成社製、水酸基当量187)8.1重量%とを、用いた(W2/W1=0.23、W2/W3=1.2)。
第2無機充填材を用いずに、樹脂ワニスの配合を以下のようにした以外は、実施例A1と同様にした。
シアネート樹脂としてフェノールノボラックシアネート樹脂(プリマセットPT-30、ロンザ社製)17.5重量%と、エポキシ樹脂としてビフェニルジメチレン型エポキシ樹脂(NC3000、日本化薬社製、エポキシ当量275)9.5重量%と、第1無機充填材としてベーマイト(河合石灰社製、品番BMT-3L、平均粒子径2.9μm、1%熱分解温度420℃)56.1重量%と、第3無機充填材として球状シリカ(SO-31R(アドマテックス社製、比表面積4.5m2/g、平均粒子径1.1μm)8.8重量%と、硬化剤としてフェノール樹脂(MEH7851-4L、明和化成社製、水酸基当量187)8.1重量%とを、用いた。
第1無機充填材を用いずに、樹脂ワニスの配合を以下のようにした以外は、実施例A1と同様にした。
シアネート樹脂としてフェノールノボラックシアネート樹脂(プリマセットPT-30、ロンザ社製)17.5重量%と、エポキシ樹脂としてビフェニルジメチレン型エポキシ樹脂(NC3000、日本化薬社製、エポキシ当量275)9.5重量%と、第2無機充填材として球状ナノシリカ(品番NSS-5N、トクヤマ社製、平均粒子径70nm)10.5重量%と、第3無機充填材として球状シリカ(SO-31R(アドマテックス社製、比表面積4.5m2/g、平均粒子径1.1μm)54.4重量%と、硬化剤としてフェノール樹脂(MEH7851-4L、明和化成社製、水酸基当量187)8.1重量%とを、用いた(W2/W3=0.19)。
樹脂ワニスのチキソ性は、E型粘度計(円錐平板型回転粘度計)を用いてJIS K7117-2に準拠して測定した。具体的には、樹脂ワニス1mlを測定カップ中央に入れ粘度を測定し、5rpm/20rpmの粘度比を評価した。
樹脂ワニスを作製した後、100ccのメスシリンダーに10cm高さまで注ぎ静置した。24時間後、分離した透明部分の長さ(cm)を目視で確認した。(10-透明部分長さ)/10×100%を算出し、フィラー沈降性を評価した。
樹脂流れ性は、JIS C 6521に準拠して、温度170℃及び圧力15kgf/cm2で5分間、加熱加圧し、フローアウト量を評価した。尚、試験試料は、実施例で得られたワニスを12μm銅箔の粗面にキャスティングし、温度150℃時間5分乾燥後、得られた30μmの銅箔付き樹脂フィルムを5枚重ねたものを用いた。
プリプレグにおける樹脂ワニスの含浸性は、上記で作製した作製したプリプレグを、温度180℃で1時間、熱風オーブン中で硬化後、幅方向530mmにおいて、15mm間隔で35点の断面を観察し評価した。断面観察では、走査電子顕微鏡を用い、樹脂が含浸されていないボイド(未含浸ボイド)の有無を観察した。表中の各符号は、以下の通りである。
◎:全点の箇所で、未含浸ボイドは見られなかった。
○:1以上5未満の箇所で、未含浸ボイドが見られたが、実用可能レベルであった。
△:5以上30未満の箇所で、未含浸ボイドが見られ、実用不可であった。
×:30点以上の箇所で、未含浸ボイドが見られ、実用不可であった。
上記で作製したプリプレグを4枚重ね、その両面に12μmの銅箔(三井金属鉱業社製3EC-VLP箔)を重ねて、圧力3MPa、温度220℃で2時間加熱加圧成形し、両面に銅箔を有する、厚さ0.40mmの金属張積層板を得た。尚、温度120℃の時に、5分で3MPaまで昇圧した。
得られた積層板(510mm×510mmサイズ)の銅箔全面を、エッチングで除去した後、その成形性を目視で評価した。
表中の各符号は、以下の通りである。
◎:ボイドが、無かった。
○:10mm端部にのみ、10μm未満のボイドが有ったが、実用可能レベルであった。
△:10μmを超えるボイドが有り、実用不可であった。
×:ボイドが多数有り、実用不可であった。
半導体装置の耐熱性は、260℃マルチリフローで評価した。
具体的には、上記で得られた半導体装置を、IPC/JEDECのJ-STD-20に準拠して、260℃のリフロー炉を通過させ、通過10回毎に、超音波深傷検査装置で半導体装置の絶縁層の剥離、クラック、半導体素子裏面の剥離、および半田バンプの欠損、並びに125℃の熱板上で導通不良を評価した。各符号は以下の通りである。
◎:40回以上の通過で、絶縁層の剥離等、および導通不良が無かった。
○:20回以上40回未満の通過で、絶縁層の剥離等、および導通不良が無かった。
△:10回以上20回未満の通過で、絶縁層の剥離等、および導通不良が発生した。
×:10回未満の通過で、絶縁層の剥離等、および導通不良が発生した。
得られた金属張積層板の銅箔をエッチングで除去し、厚さが100μm、面積4mm×40mmのテストピースを切り出し、TMA装置(TAインスツルメント社製)を用いて、5℃/分で昇温し、25℃から150℃の範囲における線熱膨張係数を測定した。
ドリル加工後のめっき染み込みは、次のようにして評価した。まず、厚さ0.4mmの上記積層板を2枚重ね合わせ、次に、直径0.2mmのドリルにて3,000回穴あけ加工を施した後、形成した貫通孔に厚み25μmのスルーホールメッキを施してスルーホールを形成した。このスルーホールの内壁から積層板中へのメッキ液の染み込み深さを測定した。尚、ドリルは、ユニオンシール製、品番KMC L253を用い、穴あけ時のドリルの回転数は250krpm/min、ドリルのチップロードは9.6μm/revとした。表中の各符号は、以下の通りである。
◎:染み込み深さが、20μm未満であった(良好)。
○:染み込み深さが、20μm以上50μm未満であった(実質上問題なし)。
△:染み込み深さが、50μm以上100μm未満であった(実質上使用不可)。
×:染み込み深さが、100μm以上であった(使用不可)。
上記(8)におけるドリル加工と同様の条件で、スルーホール加工、スルーホールメッキおよび回路加工したサンプルについて、以下のようにしてスルーホール絶縁信頼性を評価した。すなわち、互いの内壁間の間隔が0.2mmである2つのスルーホール間に、温度130℃湿度85%の下、電圧20Vを印加し、絶縁抵抗値が108Ω未満になるまでの時間を連続測定した。
表中の各符号は以下の通りである。
◎:絶縁抵抗値が108Ω未満となるまで、500時間以上であった(良好)。
○:絶縁抵抗値が108Ω未満となるまで、200時間以上500時間未満であった(実質上問題なし)。
△:絶縁抵抗値が108Ω未満となるまで、100時間以上200時間未満であった(実質上使用不可)。
×:絶縁抵抗値が108Ω未満となるまで、100時間未満であった(使用不可)。
上記で作製した半導体装置のプリント配線板部(パッケージ)の反り量を以下のようにして測定した。
半導体装置のチップ面(半導体素子面)を下にして加熱冷却可能なチャンバー上に置いて、半導体装置を-50℃と125℃の雰囲気下にそれぞれさらし、半導体装置の裏面のプリント配線板部(プリント配線板部のサイズ:50mm×50mm)、すなわち、BGA面を上にして、48mm×48mmの範囲のプリント配線板部の反り量の変化を測定した。表中の各符号は、以下の通りである。
◎:反り量の変化が、200μm未満であった(良好)。
○:反り量の変化が、200μm以上300μm未満であった(実質上問題なし)。
△:反り量の変化が、300μm以上350μm未満であった(実質上使用不可)。
×:反り量の変化が、350μm以上であった(使用不可)。
前記プリプレグを10枚重ね、その両面に12μmの銅箔を重ねて、圧力3MPa、温度200℃で2時間加熱加圧成形し、厚さ0.12mmの両面銅張積層板を得た。得られた銅張積層板の銅箔をエッチングし、UL-94規格に従い、1.0mm厚のテストピースの難燃性を垂直法により測定した。尚、表中の「V-0」はUL-94規格のV-0の要件を満たすことを示す。
また、実施例A1~A12で得られた樹脂ワニスは、チキソ性、およびフィラー沈降性に優れていた。そのため、該樹脂ワニスは量産安定性、およびプリプレグでの含浸性に優れる。また、該樹脂ワニスは樹脂流れ性にも優れるため、無機充填材を高充填にしても積層板作製時の成形性が良好であった。また、上記樹脂ワニスを用いて作製したプリント配線板は耐熱性、低線膨張率、ドリル加工性に優れていた。そのため、該プリント配線板はスルーホール絶縁信頼性に優れ、低線膨張率のため、PKG反り量も小さく優れていた。
それに比べて、比較例A1で得られた樹脂ワニスは、チキソ比が高く、プリプレグでの含浸性、および樹脂流れ性に劣るため、上記成形性、および耐熱性、スルーホール絶縁信頼性に劣る。また、比較例A2は、ドリル加工性に劣るため、スルーホール絶縁信頼性に劣る。
以下、第2の樹脂組成物を用いた実施例を示す。
(1)樹脂組成物含有ワニスの調製
まず、シリコーンゴム微粒子(信越化学工業(株)製、KMP-600、平均粒子径5μm)26.4重量%、ベーマイト粒子(テスコ(株)製、AOH-30、平均粒子径1.8μm)18.2重量%、及びシリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.4重量%をANON:MIBK=1:1(v/v)である溶媒に分散させて、濃度65重量%のスラリーを調製した。
このスラリーに、エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)25.4重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)21.2重量%、及び硬化剤としてフェノール樹脂(日本化薬(株)製、GPH-103、ビフェニルアラルキル型フェノール樹脂)6.4重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た。
前記樹脂ワニスをガラス織布(厚さ94μm、日東紡績製Eガラス織布、WEA-2116)に含浸し、180℃の加熱炉で2分間乾燥して、プリプレグ中の樹脂組成物が固形分基準で約49重量%のプリプレグを得た。
得られたプリプレグを用い、実施例A1と同様にして、厚さ0.130mmの両面金属張積層板を得た。
得られた両面金属張積層板に、実施例A1と同様にして、内層回路を両面に形成[L(導体回路幅(μm))/S(導体回路間幅(μm))=50/50]した後、内層回路に粗化処理による凹凸形成を行った。
その後、得られた積層体を用いて、実施例A1と同様にして、プリント配線板を作製した。
得られたプリント配線板は、半導体素子の半田バンプ配列に相当する接続用電極部にENEPIG処理を施した。ENEPIG処理は、以下の[1]-[8]の手順で行った。
ENEPIG工程を行って作製したプリント配線板の細線間の金属析出をSEM観察により確認した。
クリーナー液として上村工業(株)製ACL-007を用い、上記テストピースを液温50℃のクリーナー液に5分間浸漬した後、3回水洗した。
[2]ソフトエッチング処理
クリーナー処理後、ソフトエッチング液として過硫酸ソーダと硫酸の混液を用い、上記テストピースを液温25℃のソフトエッチング液に1分間浸漬した後、3回水洗した。
[3]酸洗処理
ソフトエッチング処理後、上記テストピースを液温25℃の硫酸に1分間浸漬した後、3回水洗した。
[4]プレディップ処理
酸洗処理後、上記テストピースを液温25℃の硫酸に1分間浸漬した。
[5]パラジウム触媒付与
プレディップ処理後、端子部分にパラジウム触媒を付与するために、パラジウム触媒付与液として上村工業(株)製KAT-450を用いた。上記テストピースを、液温25℃の当該パラジウム触媒付与液に2分間浸漬した後、3回水洗した。
[6]無電解Niめっき処理
パラジウム触媒付与工程の後、上記テストピースを液温80℃の無電解Niめっき浴(上村工業(株)製NPR-4)に35分間浸漬した後、3回水洗した。
[7]無電解Pdめっき処理
無電解Niめっき処理後、上記テストピースを液温50℃の無電解Pdめっき浴(上村工業(株)製TPD-30)に5分間浸漬した後、3回水洗した。
[8]無電解Auめっき処理
無電解Pdめっき処理後、上記テストピースを液温80℃の無電解Auめっき浴(上村工業(株)製TWX-40)に30分間浸漬した後、3回水洗した。
得られたENEPIG処理を施されたプリント配線板を、50mm×50mmの大きさに切断したものを使用し、実施例A1同様、半導体素子を作製した。
スラリーの成分を、シリコーンゴム微粒子(信越化学工業(株)製、KMP-600、平均粒子径5μm)32.4重量%、ベーマイト粒子(テスコ(株)製、AOH-30、平均粒子径1.8μm)12.2重量%、及びシリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.4重量%とした以外は、実施例B1と同様にした。
実施例B1と同様にして調製したスラリーに、エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)18.6重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)34.4重量%、及び硬化触媒としてオクチル酸亜鉛(東京化成(株)製)0.02重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た以外は、実施例B1と同様にした。
実施例B1と同様にして調製したスラリーに、エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)19.6重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)13.3重量%、マレイミド樹脂(ケイアイ化成(株)製、BMI-70、(3-エチル-5-メチル-4-マレイミドフェニル)メタン、ビスマレイミド樹脂)20.1重量%、及び硬化触媒としてオクチル酸亜鉛(東京化成(株)製)0.02重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た以外は、実施例B1と同様にした。
実施例B1と同様にして調製したスラリーに、エポキシ樹脂(東都化成(株)製、ESN-375、ナフタレン型エポキシ樹脂、重量平均分子量700、軟化点75℃、エポキシ当量167g/eq)25.4重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)21.2重量%、及び硬化剤としてフェノール樹脂(日本化薬(株)製、GPH-103、ビフェニルアラルキル型フェノール樹脂)6.4重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た以外は、実施例B1と同様にした。
実施例B1と同様にして調製したスラリーに、エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)25.4重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)21.2重量%、及び硬化剤としてフェノール樹脂(明和化成(株)製、MEH-7500、トリフェニルメタン型フェノール樹脂、水酸基当量97g/eq)6.4重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た以外は、実施例B1と同様にした。
シリコーンゴム微粒子(信越化学工業(株)製、KMP-600、平均粒子径5μm)37.5重量%、及びシリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)2.5重量%をANON:MIBK=1:1(v/v)の溶媒に分散させて、濃度65重量%のスラリーを調製した。
このスラリーに、エポキシ樹脂(東都化成(株)製、ESN-375、ナフタレン型エポキシ樹脂、重量平均分子量700、軟化点75℃、エポキシ当量167g/eq)38.0重量%、及び硬化剤としてフェノール樹脂(明和化成(株)製、MEH-7500、トリフェニルメタン型フェノール樹脂、水酸基当量97g/eq)22.0重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た以外は、参考実施例D1と同様にした。
スラリーの成分を、ベーマイト粒子(テスコ(株)製、AOH-30、平均粒子径1.8μm)18.2重量%、シリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.4重量%、及びシリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)26.4重量%とした以外は、実施例B1と同様にした。
スラリーの成分を、シリコーンゴム微粒子(信越化学工業(株)製、KMP-600、平均粒子径5μm)18.2重量%、シリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.4重量%、及びシリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)26.4重量%とした以外は、実施例B1と同様にした。
スラリーの成分を、ベーマイト粒子(テスコ(株)製、AOH-30、平均粒子径1.8μm)20.6重量%、及びシリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)26.4重量%とした以外は、実施例B1と同様にした。
スラリーの成分を、ベーマイト粒子(テスコ(株)製、AOH-30、平均粒子径1.8μm)44.6重量%、及びシリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.4重量%とした以外は、実施例B1と同様にした。
得られた結果を表B1に示す。
得られた金属張積層板の銅箔をエッチングにより除去し、評価用試料として2mm×2mmを切り出し、TMA装置(TAインスツルメント社製)を用いて、10℃/分の条件で、30~150℃まで昇温させ、50~100℃における厚み方向(Z方向)の線熱膨張係数(CTE)を測定した。
実施例A1と同様にして、厚さ1.02mmの両面金属張積層板を得た。得られた金属張積層板の銅箔をエッチングし、UL-94規格に従い、1.0mm厚のテストピースの難燃性を垂直法により測定した。
V-0:UL-94規格のV-0の要件を満たす。
規格外:全焼するものが5本のテストピース中1本以上あった。
得られた金属積層板を3枚重ねて、ユニオンツール(株)製ドリルビット(UV L0950)により、ドリル回転速度160rpm、送り速度3.2m/分のドリル加工条件で、φ150の孔あけ加工を3000回(3000穴)行った。使用前のドリル刃幅を100%とし、使用後のドリル刃幅の残存率を測定し、ドリル摩耗性を評価した。
得られた金属張積層板の断面観察を行った。断面観察は、走査電子顕微鏡を用いた。含浸性は、断面観察結果において、観察されたボイドの面積で評価した。
○:全面積10%未満の箇所で、未含浸ボイドが見られたが、実用可能レベルであった。
△:全面積10~30%の箇所で、未含浸ボイドが見られ、実用不可であった。
×:全面積50%以上の箇所で、未含浸ボイドが見られ、実用不可であった。
上記金属張積層板の銅箔をエッチングにより除去して得られた構造体に対して、炭酸レーザー装置(日立ビアメカニクス(株)製:LG-2G212)を用いてφ60μmのビアホール500穴を形成し、70℃の膨潤液(アトテックジャパン社製、スウェリングディップ セキュリガント P)に5分間浸漬し、さらに80℃の過マンガン酸カリウム水溶液(アトテックジャパン社製、コンセントレートコンパクト CP)に15分浸漬後、中和して粗化処理を行うことでデスミア処理を行った。デスミア処理前後の構造体の厚みを測定し、減膜量[(処理前厚み-処理後厚み)/(処理前厚み)]を評価した。
図5に、(1)実施例B1で得られた金属張積層板の表面を撮影した写真、(2)比較例B1で得られた金属張積層板の表面を撮影した写真、及び(3)金属張積層板の金属箔層の表面の写真を説明する図を示す。写真に示すように、比較例B1の金属張積層板の金属箔層の表面には、スジ状のムラが発生したが、実施例B1の金属張積層板の金属箔層の表面は、スジ状のムラが見られなかった。
ENEPIG処理を行って作製した上記プリント配線板の細線間の金属析出をSEM観察し、実施例Aシリーズ同様評価により確認した。
比較例B1では、本発明で特定したシリカナノ粒子及びベーマイト粒子を用いなかったことに起因し、プリプレグ含浸性が悪いため、線膨張係数、難燃性、デスミア耐性、及びENEPIG特性が実用可能なレベルに達していなかった。
比較例B2では、本発明で特定したシリコーンゴム微粒子及びシリカナノ粒子を用いなかったことに起因し、プリプレグ含浸性が悪いため、デスミア耐性、及びENEPIG特性が実用可能なレベルに達していなかった。
尚、比較例B1は、ドリル摩耗性の数値は実施例の結果と同等であるものの、テストピースはボイドが非常に多量に含んだ状態であり、実施例と客観的に対比することはできない。
また、比較例B1の線膨張係数試験では、テストピースのプリプレグ含浸性が悪かったため、充填性の高い部分を選定して測定を行った。
以下に、本発明の第3の樹脂組成物を用いた参考実施例を示す。
(参考実施例C1)
(1)樹脂組成物含有ワニス(樹脂ワニス)の調製
まず、シリコーンゴム微粒子(信越化学工業(株)製、KMP-600、平均粒子径5μm)37.5重量%、及びシリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.5重量%を、シクロヘキサノン(ANON):メチルイソブチルケトン(MIBK)=1:1(v/v)である溶媒に分散させて、濃度65重量%のスラリーを調製した。
このスラリーに、エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)28.7重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)24.0重量%、硬化剤としてフェノール樹脂(日本化薬(株)製、GPH-103、ビフェニルアラルキル型フェノール樹脂)7.3重量%を、溶解、混合した。次いで、高速撹拌装置を用い撹拌し、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た。
前記樹脂ワニスを用いて、実施例B1と同様にして、プリプレグを得た。
得られたプリプレグを用い、実施例A1と同様にして、厚さ0.130mmの両面金属張積層板を得た。
得られた両面金属張積層板を用いて、実施例B1と同様にして、プリント配線板を作製し、ENEPIG処理を施した。
得られたENEPIG処理を施されたプリント配線板を、50mm×50mmの大きさに切断したものを使用し、実施例A1同様、半導体装置を作製した。
スラリーの成分を、シリコーンゴム微粒子(信越化学工業(株)製、KMP-600、平均粒子径5μm)32.5重量%、シリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.5重量%、及びシリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)5.0重量%とした以外は、参考実施例C1と同様にした。
シリコーンゴム微粒子(信越化学工業(株)製、KMP-600、平均粒子径5μm)37.5重量%、及びシリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.5重量%をANON:MIBK=1:1(v/v)の溶媒に分散させて、濃度65重量%のスラリーを調製した。
このスラリーに、エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)21.0重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)39.0重量%、及び硬化触媒としてオクチル酸亜鉛(東京化成(株)製)0.02重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た以外は、参考実施例C1と同様にした。
参考実施例C3と同様にして調製したスラリーに、エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)22.2重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)15.0重量%、マレイミド樹脂(ケイアイ化成(株)製、BMI-70、(3-エチル-5-メチル-4-マレイミドフェニル)メタン、ビスマレイミド樹脂)22.8重量%、及び硬化触媒としてオクチル酸亜鉛(東京化成(株)製)0.02重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た以外は、参考実施例C1と同様にした。
参考実施例C3と同様にして調製したスラリーに、エポキシ樹脂(東都化成(株)製、ESN-375、ナフタレン型エポキシ樹脂、重量平均分子量700、軟化点75℃、エポキシ当量167g/eq)28.7重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)24.0重量%、及び硬化剤としてフェノール樹脂(日本化薬(株)製、GPH-103、ビフェニルアラルキル型フェノール樹脂)7.3重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た以外は、参考実施例C1と同様にした。
参考実施例C3と同様にして調製したスラリーに、エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)28.7重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)24.0重量%、及び硬化剤としてフェノール樹脂(明和化成(株)製、MEH-7500、トリフェニルメタン型フェノール樹脂、水酸基当量97g/eq)7.3重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た以外は、参考実施例C1と同様にした。
スラリーの成分を、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)37.5重量%、及びシリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.5重量%とした以外は、参考実施例C1と同様にした。
スラリーの成分を、シリコーンゴム微粒子(信越化学工業(株)製、KMP-597、平均粒子径5μm)37.5重量%、及びシリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.5重量%とした以外は、参考実施例C1と同様にした。
シリコーンゴム微粒子(信越化学工業(株)製、KMP-600、平均粒子径5μm)37.5重量%、及びシリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)2.5重量%をANON:MIBK=1:1(v/v)の溶媒に分散させて、濃度65重量%のスラリーを調製した。
このスラリーに、エポキシ樹脂(東都化成(株)製、ESN-375、ナフタレン型エポキシ樹脂、重量平均分子量700、軟化点75℃、エポキシ当量167g/eq)38.0重量%、及び硬化剤としてフェノール樹脂(明和化成(株)製、MEH-7500、トリフェニルメタン型フェノール樹脂、水酸基当量97g/eq)22.0重量%を溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た以外は、参考実施例C1と同様にした。
スラリーの成分を、シリコーンゴム微粒子(信越化学工業(株)製、KMP-600、平均粒子径5μm)37.5重量%、及びシリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)2.5重量%とした以外は、参考実施例C1と同様にした。
スラリーの成分を、シリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)37.5重量%、及びシリカナノ粒子(トクヤマ(株)製、NSS-5N、平均粒子径70nm)2.5重量%とした以外は、参考実施例C1と同様にした。
スラリーの成分を、シリコーンゴム微粒子(信越化学工業(株)製、KMP-600、平均粒子径5μm)40.0重量%とした以外は、参考実施例C1と同様にした。
得られた結果を表C1に示す。
(5)デスミア耐性は、デスミア処理を、上記プリプレグを4枚重ねた積層体に対して行うこと以外は、実施例Bシリーズと同様である。
(6)スジ状ムラの発生状況については、図6に、(1)参考実施例C1で得られた金属張積層板の表面を撮影した写真、(2)参考比較例C1で得られた金属張積層板の表面を撮影した写真、及び(3)金属張積層板の金属箔層の表面の写真を説明する図を示す。写真に示すように、参考比較例C1の金属張積層板の金属箔層の表面には、スジ状のムラが発生したが、参考実施例C1の金属張積層板の金属箔層の表面は、スジ状のムラが見られなかった。
参考比較例C1及び参考比較例C2では、本発明の第3の樹脂組成物で特定したシリカナノ粒子を用いなかったことに起因し、プリプレグ含浸性が悪いため、線膨張係数、難燃性、デスミア耐性、及びENEPIG特性が実用可能なレベルに達していなかった。
参考比較例C3では、本発明の第3の樹脂組成物で特定したシリコーンゴム微粒子を用いなかったことに起因し、ドリル摩耗性が実用可能なレベルに達していなかった。
参考比較例C4では、本発明の第3の樹脂組成物で特定したシリコーンゴム微粒子を多量に用いたことに起因し、線膨張係数は良好であるものの、本発明の第3の樹脂組成物で特定したシリカナノ粒子を用いなかったことに起因し、プリプレグ含浸性が悪いため、難燃性、デスミア耐性、及びENEPIG特性が実用可能なレベルに達していなかった。
尚、参考比較例C1、参考比較例C2、及び参考比較例C4は、ドリル摩耗性の数値は実施例の結果と同等であるものの、テストピースはボイドが非常に多量に含んだ状態であり、参考実施例と客観的に対比することはできない。
また、参考比較例C1、参考比較例C2、及び参考比較例C4の線膨張係数試験では、テストピースのプリプレグ含浸性が悪かったため、充填性の高い部分を選定して測定を行った。
参考実施例C1~C8で得られた本発明の樹脂組成物、プリプレグ、金属張積層板、プリント配線板、及び半導体装置は、線膨張係数、難燃性、ドリル摩耗性、プリプレグ含浸性、デスミア耐性、及びENEPIG特性のすべてが良好であった。従って、本発明で特定した、エポキシ樹脂と、シリコーンゴム微粒子と、シリカナノ粒子とを含むことを特徴とするシリコーンゴム微粒子含有樹脂組成物を用いることにより、性能の優れたプリプレグ、金属張積層板、プリント配線板、及び半導体装置を得られることがわかる。
以下に、本発明の第4の樹脂組成物を用いた参考実施例を示す。
(参考実施例D1)
(1)樹脂組成物含有ワニス(樹脂ワニス)の調製
エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)21.0重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)39.0重量%、オクチル酸亜鉛(東京化成(株)製)0.02重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)37.0重量%、及び硫酸バリウム粒子(堺化学製、BF-21、平均粒子径50nm)3.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得た。
前記樹脂ワニスを用いて、実施例B1と同様にして、プリプレグを得た。
得られたプリプレグを用い、実施例A1と同様にして、厚さ0.430mmの両面金属張積層板を得た。
得られた両面金属張積層板を用いて、実施例B1と同様にして、プリント配線板を作製し、ENEPIG処理を施した。
得られたENEPIG処理を施されたプリント配線板を、50mm×50mmの大きさに切断したものを使用し、実施例A1同様、半導体装置を作製した。
エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)21.0重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)39.0重量%、オクチル酸亜鉛(東京化成(株)製)0.02重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)32.0重量%、硫酸バリウム粒子(堺化学製、BF-21、平均粒子径50nm)3.0重量%、及びシリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)5.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)22.2重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)15.0重量%、マレイミド樹脂(ケイアイ化成(株)製、BMI-70、(3-エチル-5-メチル-4-マレイミドフェニル)メタン、ビスマレイミド樹脂)22.8重量%、オクチル酸亜鉛(東京化成(株)製)0.02重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)37.0重量%、及び硫酸バリウム粒子(堺化学製、BF-21、平均粒子径50nm)3.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)28.7重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)24.0重量%、フェノール樹脂(明和化成(株)製、MEH-7851-H、ビフェニルアラルキル型フェノール樹脂)7.3重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)37.0重量%、硫酸バリウム粒子(堺化学製、BF-21、平均粒子径50nm)3.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)28.7重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)24.0重量%、フェノール樹脂(明和化成(株)製、MEH-7500、トリフェニルメタン型フェノール樹脂、水酸基当量97g/eq)7.3重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)37.0重量%、硫酸バリウム粒子(堺化学製、BF-21、平均粒子径50nm)3.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
エポキシ樹脂(東都化成(株)製、ESN-375、ナフタレン型エポキシ樹脂、重量平均分子量700、軟化点75℃、エポキシ当量167g/eq)21.0重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)39.0重量%、オクチル酸亜鉛(東京化成(株)製)0.02重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)37.0重量%、硫酸バリウム粒子(堺化学製、BF-21、平均粒子径50nm)3.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)21.0重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)39.0重量%、オクチル酸亜鉛(東京化成(株)製)0.02重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-597、平均粒子径5μm)37.0重量%、硫酸バリウム粒子(堺化学製、BF-21、平均粒子径50nm)3.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)21.0重量%、シアネート樹脂(特開2009-35728の方法で合成、ナフトールアラルキル型シアネート樹脂)39.0重量%、オクチル酸亜鉛(東京化成(株)製)0.02重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)37.0重量%、硫酸バリウム粒子(堺化学製、BF-21、平均粒子径50nm)3.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)21.0重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)39.0重量%、オクチル酸亜鉛(東京化成(株)製)0.02重量%、硫酸バリウム粒子(堺化学製、BF-21、平均粒子径50nm)3.0重量%、シリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)37.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
エポキシ樹脂(東都化成(株)製、ESN-375、ナフタレン型エポキシ樹脂、重量平均分子量700、軟化点75℃、エポキシ当量167g/eq)38.0重量%、フェノール樹脂(明和化成(株)製、MEH-7500、トリフェニルメタン型フェノール樹脂、水酸基当量97g/eq)22.0重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)37.0重量%、シリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)3.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)21.0重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)39.0重量%、オクチル酸亜鉛(東京化成(株)製)0.02重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)37.0重量%、シリカ粒子(アドマテックス(株)製、SO-25R、平均粒子径0.5μm)3.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
エポキシ樹脂(日本化薬(株)製、NC3000、ビフェニルアラルキル型エポキシ樹脂、重量平均分子量1300、軟化点57℃、エポキシ当量276g/eq)21.0重量%、シアネート樹脂(ロンザジャパン(株)製、PT30、ノボラック型シアネート樹脂、重量平均分子量380)39.0重量%、オクチル酸亜鉛(東京化成(株)製)0.02重量%、シリコーンゴム微粒子(信越化学工業(株)製、KMP-605、平均粒子径2μm)40.0重量%をシクロヘキサノンに溶解、混合し、高速撹拌装置を用い撹拌して、樹脂組成物を固形分基準で70重量%含有する樹脂ワニスを得たこと以外は、参考実施例D1と同様にした。
得られた結果を表D1、及び表D2に示す。
尚、(2)難燃性について、表中の「全焼」は、5本のテストピース中、全焼するものが1本以上あったことを示す。
(6)スジ状ムラの発生状況については、図7に、(1)参考実施例D1で得られた金属張積層板の表面を撮影した写真、(2)参考比較例D1で得られた金属張積層板の表面を撮影した写真、及び(3)金属張積層板の金属箔層の表面の写真を説明する図を示す。写真に示すように、参考比較例D1の金属張積層板の金属箔層の表面には、スジ状のムラが発生したが、参考実施例D1の金属張積層板の金属箔層の表面は、スジ状のムラが見られなかった。
1) 日本化薬(株)製、NC3000
2) 東都化成(株)製、ESN-375
3) ロンザジャパン(株)製、PT30
4) 明和化成(株)製、MEH-7851-H
5) 明和化成(株)製、MEH-7500
6) ケイアイ化成(株)製、BMI-70
7) 東京化成(株)製、試薬
8) 信越化学工業(株)製、KMP-605、平均粒子径2μm
9) 信越化学工業(株)製、KMP-597、平均粒子径5μm
10) 堺化学製、BF-21、平均粒子径50nm
11) アドマテックス(株)製、SO-25R、平均粒子径0.5μm
参考比較例D1及び参考比較例D2では、本発明で特定した硫酸バリウム粒子を用いなかったことに起因し、プリプレグ含浸性が悪いため、線膨張係数、難燃性、デスミア耐性、及びENEPIG特性が実用可能なレベルに達していなかった。
参考比較例D3では、シリコーンゴム微粒子を多量に用いたことに起因し、線膨張係数は良好であるものの、本発明で特定した硫酸バリウム粒子を用いなかったことに起因し、プリプレグ含浸性が悪いため、難燃性、デスミア耐性、及びENEPIG特性が実用可能なレベルに達していなかった。
参考実施例D1~D9で得られた本発明の樹脂組成物、プリプレグ、金属張積層板、プリント配線板、及び半導体装置は、線膨張係数、難燃性、プリプレグ含浸性、デスミア耐性、及びENEPIG特性のすべてが良好であった。従って、本発明で特定した、エポキシ樹脂と、硫酸バリウム粒子とを含むことを特徴とする硫酸バリウム粒子含有樹脂組成物を用いることにより、性能の優れたプリプレグ、金属張積層板、プリント配線板、及び半導体装置を得られることがわかる。
以下に、本発明の第5の樹脂組成物を用いた参考実施例を示す。
(参考実施例E1)
(1)樹脂組成物含有ワニス(樹脂ワニス)の調製
エポキシ樹脂としてナフタレン型4官能エポキシ樹脂(品番HP-4700、DIC社製、エポキシ当量165)17.5重量%と、フェノール硬化剤としてビフェニルアルキレン型ノボラック樹脂(品番MEH-7851-3H、明和化成社製、水酸基当量230)17.3重量%と、硬化促進剤としてイミダゾール(四国化成工業社製、品番2E4MZ)0.1重量%と、第一の充填材としてベーマイト(河合石灰社製、品番BMT-3L、平均粒子径2.9μm、1%熱分解温度420℃)61.4重量%と、第二の充填材として球状ナノシリカ(品番NSS-5N、トクヤマ社製、平均粒子径70nm、ビニルシラン処理品)3.5重量%と、カップリング剤としてエポキシシラン(品番A-187、GE東芝シリコーン社製)0.2重量%とを、メチルイソブチルケトンに溶解、混合した。次いで、得られた混合物を、高速撹拌装置を用いて撹拌し、樹脂ワニスを調製した。
前記樹脂ワニスを用いて、実施例A1と同様にして、プリプレグを得た。
得られたプリプレグを用いて、実施例A1と同様にして、厚さ0.40mmの両面金属張積層板を得た。
両面に銅箔を有する前記金属張積層板を用いて、実施例A1と同様にしてプリント配線板を得た。
得られたプリント配線板を用いて、実施例A1と同様にして半導体装置を作製した。
参考実施例E2~E12、参考比較例E1は、表E1、および表E2に記載の配合表に従い樹脂ワニスを調製した以外は、参考実施例E1と同様に樹脂ワニス、プリプレグ、金属張積層板、プリント配線板、及び半導体装置を作製した。
尚、用いた原料を以下に示す。
(1)シアネート樹脂/ノボラック型シアネート樹脂:ロンザジャパン社製・「プリマセットPT-30」、シアネート当量124
(2)エポキシ樹脂/ナフタレン型4官能エポキシ樹脂:DIC社製・「HP-4700」、エポキシ当量165g/eq
(3)エポキシ樹脂/ビフェニルジメチレン型エポキシ樹脂:日本化薬社製・「NC-3000H」、エポキシ当量275
(4)フェノール硬化剤/ビフェニルアルキレン型ノボラック樹脂:明和化成社製「MEH-7851-3H」、水酸基当量230
(5)硬化促進剤/イミダゾール:四国化成工業社製・「2E4MZ」
(6)第一の充填材/ベーマイト;河合石灰社製・「BMT-3L」、平均粒子2.9μm
(7)第一の充填材/耐熱性水酸化アルミニウム;河合石灰社製・「AHL-F」、平均粒子3μm
(8)第一の充填材/タルク;富士タルク社製・「LMS-200」、平均粒子径5.0μm
(9)第一の充填材/球状シリカ;アドマテックス社製・「SO-25R」、平均粒子径0.5μm
(10)第一の充填材/球状シリカ;アドマテックス社製・「SO-31R」、平均粒子径1.0μm
(11)第一の充填材/シリコーンパウダー;信越化学工業社製・「KMP‐605」、平均粒子径2μm
(12)第一の充填材/シリコーンパウダー;信越化学工業社製・「KMP‐600」、平均粒子径5μm
(13)第二の充填材/球状シリカ;トクヤマ社製・「NSS-5N」、平均粒子70nm、ビニルシラン処理品
(14)第二の充填材/球状シリカ;トクヤマ社製・「NSS-5N」、平均粒子70nm、エポキシシラン処理品
(15)第二の充填材/球状シリカ;アドマテックス社製・「Admanano」、平均粒子50nm、ビニルシラン処理品
(16)第二の充填材/球状シリカ;アドマテックス社製・「Admanano」、平均粒子25nm、ビニルシラン処理品
(17)カップリング剤/エポキシシラン;GE東芝シリコーン社製・「A‐187」
樹脂ワニスのチキソ性を実施例Aシリーズと同様にして評価した。
樹脂ワニスの分散性は、粒ゲージ(コーテック株式会社、エルコメーター製KP-2020-2)を用いて評価した。具体的には、粒ゲージ(グラインドゲージ)を水平に置き、深い方の溝に樹脂ワニスを流しこんだ後、スクレーバーを溝に対して垂直方向に均等な速度で深さゼロまで1~2秒で引いた。3秒以内に溝方向に対して直角、及び角度20~30°で観察を行い、顕著な斑点が現れる目盛(凝集物の粒径)を測定した。表E1、およびE2に記載の各符号は、以下の通りである。
○:20μm以上の凝集物がなかった。
△:20μm以上、50μm未満の凝集物があった。
×:50μm以上の凝集物があった。
樹脂ワニスの分散性は、レーザー回折式粒度分布測定装置(HORIBA製、LA-500)を用いて評価した。具体的には、樹脂ワニス約100μlをケトン系有機溶剤で満たされた評価セルに投入し、安定した後の値を読み取った。充填材の粒度分布を体積基準で作成し、そのメディアン径を平均粒子径とすることで評価した。表E1、およびE2に記載の各符号は、以下の通りである。
○:20μm以上の凝集物がなかった。
△:20μm以上、50μm未満の凝集物があった。
×:50μm以上の凝集物があった。
プリプレグの含浸性は、実施例Aシリーズと同様にして、評価した。
参考実施例及び参考比較例で得られた積層板(510mm×510mm角)の成形性を評価した。具体的には、得られた積層板をシャーにより約250mm×250mm角に4等分した後、銅箔をエッチング除去した。目視で積層板表面を観察し評価した。
表E1、およびE2に記載の各符号は、以下の通りである。
◎:ボイドが、無かった。
○:10mm端部にのみ、10μm未満のボイドが有った。
△:10μmを超えるボイドがあった。
×:ボイドが多数あった。
半導体の耐熱性を、実施例Aシリーズと同様にして評価した。
得られた金属張積層板を用いて、実施例Aシリーズと同様にして、線熱膨張係数を測定した。
得られた金属張積層板を用いて、実施例Aシリーズと同様にして、ドリル加工後のめっき染み込みを評価した。
得られた金属張積層板を用いて、実施例Aシリーズと同様にして、スルーホール絶縁信頼性を評価した。
上記作製した半導体装置のプリント配線板部の反り量を、実施例Aシリーズと同様にして、測定した。
上記積層板の製造において、加熱加圧成形の温度を200℃で行ったこと以外は同様にして、厚さ0.4mmの両面銅張積層板を得た。得られた銅張積層板の銅箔をエッチングし、UL-94規格に従い、0.4mm厚のテストピースの難燃性を垂直法により測定した。
参考実施例E1~E12で得られた樹脂ワニスは、チキソ性、およびフィラー沈降性に優れていた。そのため、該樹脂ワニスは量産安定性、およびプリプレグでの含浸性に優れる。また、該樹脂ワニスは樹脂流れ性にも優れるため、無機充填材を高充填にしても積層板作製時の、成形性が良好であった。また、プリント配線板にした際の耐熱性、低線膨張率、ドリル加工性に優れていた。そのため、スルーホール絶縁信頼性に優れ、低線膨張率のため、半導体装置のプリント配線板部の反り量も小さく優れていた。
それに比べて、参考比較例E1は、チキソ性が高く、プリプレグでの含浸性、および樹脂流れ性に劣るため、成形性、および耐熱性、スルーホール絶縁信頼性に劣る結果となったと推察する。
2…含浸槽
3…樹脂ワニス
4…ディップロール
5…スクイズロール
6…乾燥機
7…プリプレグ
8…上部ロール
10…絶縁樹脂層付き金属箔
11…金属箔
12…絶縁樹脂層
20…基材
30…絶縁樹脂層付き高分子フィルムシート
31…高分子フィルムシート
32…絶縁樹脂層
40…プリプレグ
41…金属箔付きプリプレグ
42…高分子フィルムシート付きプリプレグ
51…金属張積層板
52…金属張積層板
Claims (27)
- 積層板を形成するために用いる樹脂組成物であって、
エポキシ樹脂と、不定形の第1無機充填材と、前記第1無機充填材と平均粒子径が異なりかつその平均粒子径が10~100nmである第2無機充填材と、を含むことを特徴とする樹脂組成物。 - 前記第2無機充填材の含有量は、前記樹脂組成物全体の0.5~5重量%である請求の範囲第1項に記載の樹脂組成物。
- 前記第2無機充填材が予め有機溶媒に分散されたスラリーを用いて調製された請求の範囲第1項又は第2項に記載の樹脂組成物。
- 前記第2無機充填材は、シリカである請求の範囲第1項乃至第3項のいずれかに記載の樹脂組成物。
- 前記第1無機充填材は、ベーマイトである請求の範囲第1項乃至第4項のいずれかに記載の樹脂組成物。
- 前記第1無機充填材の平均粒径が、0.5~5μmである請求の範囲第1項乃至第5項のいずれかに記載の樹脂組成物。
- 前記前記第1無機充填材の含有量が、前記樹脂組成物全体の20~65重量%である請求の範囲第1項乃至第6項のいずれかに記載の樹脂組成物。
- さらに、平均粒子径が0.2~3μmの第3無機充填材を含むものである請求の範囲第1項乃至第7項のいずれかに記載の樹脂組成物。
- 前記第3無機充填材の最大粒子径が、10μm以下である請求の範囲第8項に記載の樹脂組成物。
- 前記第2無機充填材の含有量(w2)と、前記第3無機充填材の含有量(w3)との重量比(w2/w3)が、0.02~1.5である請求の範囲第8項又は第9項に記載の樹脂組成物。
- 前記第1無機充填材の含有量(w1)と、前記第2無機充填材の含有量(w2)との重量比(w2/w1)が、0.02~0.5である請求の範囲第1項乃至第10項のいずれかに記載の樹脂組成物。
- さらに、シアネート樹脂を含むものである請求の範囲第1項乃至第11項のいずれかに記載の樹脂組成物。
- 前記エポキシ樹脂は、ビフェニルジメチレン型エポキシ樹脂、ノボラック型エポキシ樹脂、ナフタレン変性クレゾールノボラックエポキシ樹脂、およびアントラセン型エポキシ樹脂よりなる群から選ばれる少なくとも1種である請求の範囲第1項乃至第12項のいずれかに記載の樹脂組成物。
- エポキシ樹脂と、平均粒子径1μm~10μmのシリコーンゴム微粒子と、平均粒子径0.2μm~5μmのベーマイト微粒子と、平均粒子径10nm~100nmのシリカナノ粒子と、を含有することを特徴とする、樹脂組成物。
- 前記シリコーンゴム微粒子は、シリコーンゴムからなるコア部を、シリコーン樹脂で被覆したコアシェル構造粒子である、請求の範囲第14項に記載の樹脂組成物。
- 前記シリカナノ粒子の平均粒子径が40nm以上100nm以下である請求の範囲第14項又は第15項に記載の樹脂組成物。
- さらに、シアネート樹脂を含むものである請求の範囲第14項乃至第16項のいずれかに記載の樹脂組成物。
- さらに、マレイミド樹脂を含むものである請求の範囲第14項乃至第17項のいずれかに記載の樹脂組成物。
- 前記エポキシ樹脂は、ビフェニルアラルキル型エポキシ樹脂、ナフタレン骨格変性エポキシ樹脂、及びクレゾールノボラック型エポキシ樹脂よりなる群から選ばれる少なくとも1種である請求の範囲第14項乃至第18項のいずれかに記載の樹脂組成物。
- 基材上に、請求の範囲第1項乃至第19項のいずれかに記載の樹脂組成物からなる樹脂層が形成されてなることを特徴とする、樹脂シート。
- 請求の範囲第1項乃至第19項のいずれかに記載の樹脂組成物を基材に含浸してなることを特徴とするプリプレグ。
- 基材中に請求の範囲第1項乃至第19項のいずれかに記載の樹脂組成物を含浸してなる樹脂含浸基材層の少なくとも片面に金属箔を有することを特徴とする金属張積層板。
- 請求の範囲第21項に記載のプリプレグ又は当該プリプレグを2枚以上重ね合わせた積層体の少なくとも片面に金属箔を重ね、加熱加圧することにより得られる請求の範囲第22項に記載の金属張積層板。
- 請求の範囲第22項又は第23項に記載の金属張積層板を内層回路基板に用いてなることを特徴とするプリント配線板。
- 内層回路上に、請求の範囲第21項に記載のプリプレグを絶縁層に用いてなるプリント配線板。
- 内層回路上に、請求の範囲第1項乃至第19項のいずれかに記載の樹脂組成物を絶縁層に用いてなるプリント配線板。
- 請求の範囲第24項乃至第26項のいずれかに記載のプリント配線板に半導体素子を搭載してなることを特徴とする半導体装置。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US13/386,135 US20120111621A1 (en) | 2009-07-24 | 2010-07-21 | Resin composition, resin sheet, prepreg, metal-clad laminate, printed wiring board and semiconductor device |
CN201080031042.1A CN102482481B (zh) | 2009-07-24 | 2010-07-21 | 树脂组合物,树脂片材,半固化片,覆金属层叠板,印刷布线板及半导体装置 |
Applications Claiming Priority (10)
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JP2009-172630 | 2009-07-24 | ||
JP2009172630A JP5703547B2 (ja) | 2009-07-24 | 2009-07-24 | 樹脂組成物、プリプレグ、積層板、多層プリント配線および半導体装置 |
JP2009-264857 | 2009-11-20 | ||
JP2009264857A JP5589363B2 (ja) | 2009-11-20 | 2009-11-20 | シリコーンゴム微粒子含有エポキシ樹脂組成物、プリプレグ、金属張積層板、プリント配線板及び半導体装置 |
JP2009265256A JP5589364B2 (ja) | 2009-11-20 | 2009-11-20 | シリコーンゴム微粒子含有エポキシ樹脂組成物、プリプレグ、金属張積層板、プリント配線板及び半導体装置 |
JP2009-265256 | 2009-11-20 | ||
JP2010038652A JP2011173985A (ja) | 2010-02-24 | 2010-02-24 | 硫酸バリウム粒子含有エポキシ樹脂組成物、プリプレグ、金属張積層板、プリント配線板及び半導体装置 |
JP2010-038652 | 2010-02-24 | ||
JP2010044145A JP5703570B2 (ja) | 2010-03-01 | 2010-03-01 | プリプレグ、積層板、多層プリント配線板、及び、半導体装置 |
JP2010-044145 | 2010-03-01 |
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US (1) | US20120111621A1 (ja) |
KR (1) | KR20120050433A (ja) |
CN (1) | CN102482481B (ja) |
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US9944787B2 (en) | 2012-03-30 | 2018-04-17 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg and laminate |
US20130316180A1 (en) * | 2012-05-07 | 2013-11-28 | Case Western Reserve University | Biocompatible Packaging Suitable for Long-term Implantation and Method of Formation |
JPWO2014112464A1 (ja) * | 2013-01-15 | 2017-01-19 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、積層板、金属箔張積層板及びプリント配線板 |
US10138393B2 (en) | 2013-01-15 | 2018-11-27 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, laminate, metal foil-clad laminate, and printed-wiring board |
WO2014112464A1 (ja) * | 2013-01-15 | 2014-07-24 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、積層板、金属箔張積層板及びプリント配線板 |
JPWO2016088743A1 (ja) * | 2014-12-01 | 2017-09-07 | 三菱瓦斯化学株式会社 | 樹脂シート及びプリント配線板 |
WO2016088743A1 (ja) * | 2014-12-01 | 2016-06-09 | 三菱瓦斯化学株式会社 | 樹脂シート及びプリント配線板 |
JP2017052884A (ja) * | 2015-09-10 | 2017-03-16 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板 |
WO2019142747A1 (ja) * | 2018-01-19 | 2019-07-25 | Agc株式会社 | 樹脂付金属箔の製造方法 |
CN111601666A (zh) * | 2018-01-19 | 2020-08-28 | Agc株式会社 | 带树脂的金属箔的制造方法 |
JPWO2019142747A1 (ja) * | 2018-01-19 | 2021-01-28 | Agc株式会社 | 樹脂付金属箔の製造方法 |
JP7176533B2 (ja) | 2018-01-19 | 2022-11-22 | Agc株式会社 | 樹脂付金属箔の製造方法 |
JP2019155666A (ja) * | 2018-03-09 | 2019-09-19 | Tdk株式会社 | 樹脂基板 |
JP7124355B2 (ja) | 2018-03-09 | 2022-08-24 | Tdk株式会社 | 樹脂基板 |
CN111253855A (zh) * | 2018-12-03 | 2020-06-09 | 味之素株式会社 | 树脂组合物 |
Also Published As
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CN102482481A (zh) | 2012-05-30 |
CN102482481B (zh) | 2014-12-17 |
US20120111621A1 (en) | 2012-05-10 |
KR20120050433A (ko) | 2012-05-18 |
TW201109359A (en) | 2011-03-16 |
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