WO2009119598A1 - エポキシ樹脂組成物、樹脂シート、プリプレグ、多層プリント配線板および半導体装置 - Google Patents
エポキシ樹脂組成物、樹脂シート、プリプレグ、多層プリント配線板および半導体装置 Download PDFInfo
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- WO2009119598A1 WO2009119598A1 PCT/JP2009/055844 JP2009055844W WO2009119598A1 WO 2009119598 A1 WO2009119598 A1 WO 2009119598A1 JP 2009055844 W JP2009055844 W JP 2009055844W WO 2009119598 A1 WO2009119598 A1 WO 2009119598A1
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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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/56—Polyhydroxyethers, e.g. phenoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
- H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
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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
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
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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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31525—Next to glass or quartz
Definitions
- the present invention relates to an epoxy resin composition, a resin sheet, a prepreg, a multilayer printed wiring board, and a semiconductor device.
- the multilayer printed wiring board by the build-up method is usually manufactured by laminating and forming an insulating layer made of a resin composition and having a thickness of 100 ⁇ m or less and a conductor circuit layer.
- an insulating layer made of a resin composition and having a thickness of 100 ⁇ m or less and a conductor circuit layer.
- the formation of a via hole by a laser method, a photo method, or the like can be cited instead of the conventional drilling process.
- the semi-additive method is widely known as a technique for achieving this.
- the substrate is subjected to electroless plating treatment, the circuit formation portion is protected with a plating resist, and then the copper thickness of the circuit formation portion is increased by electroplating,
- a conductor circuit is formed on an insulating layer by performing resist removal and soft etching.
- Japanese Patent Laid-Open No. 07-106767 JP 2003-342350 A Japanese Patent Laid-Open No. 09-1000039 JP 2007-254709 A Table 03/099952 Japanese Patent Laid-Open No. 2005-240019 JP-A-2005-244150 JP 2007-254710 A JP 2008-7575 A JP 2008-74929 A
- An object of the present invention is to produce a multilayer printed wiring board that is excellent in plating adhesion, heat resistance and moisture resistance reliability and capable of forming advanced fine wiring when used in an insulating layer of a multilayer printed wiring board.
- An epoxy resin composition, a resin sheet, a prepreg, a method for producing a multilayer printed wiring board, a multilayer printed wiring board, and a semiconductor device are provided.
- An epoxy resin composition containing (A) an epoxy resin, (B) a phenoxy resin containing a bisphenolacetophenone structure represented by the following general formula (1), and (C) a curing agent, An epoxy resin composition characterized in that the phenoxy resin is contained in an amount of 10 to 30% by weight in the total solid content of the resin composition.
- R 1 may be the same or different from each other and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements
- R 2 is a hydrogen atom, carbon number 1 And a group selected from a hydrocarbon group having 10 to 10 halogen atoms
- R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- m is an integer of 0 to 5
- a novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure (B) a phenoxy resin containing a bisphenolacetophenone structure represented by the general formula (1), (C) a curing agent, (D) [1] to [1] to [10] containing an inorganic filler and (E) a cyanate resin and / or a prepolymer thereof, and (B) the phenoxy resin being contained in an amount of 10 to 30% by weight in the total solid content of the resin composition.
- the epoxy resin composition according to any one of items [6] The epoxy resin composition according to any one of [1] to [5], which contains an imidazole compound as the (C) curing agent.
- the resin composition further contains a poly (meth) acrylic acid ester having a weight average molecular weight of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 5 . 6]
- the epoxy resin composition according to any one of items. [8] Any of the items [1] to [7], wherein the phenoxy resin having the bisphenolacetophenone structure represented by the general formula (1) (B) further has a biphenyl structure.
- the phenoxy resin having the bisphenolacetophenone structure represented by the general formula (1) (B) has a glass transition temperature of 120 ° C. or higher, and any one of the items [1] to [8]
- the content of the (A) epoxy resin is 5 to 80% by weight
- the content of the (B) phenoxy resin is 10 to 30% by weight
- the (C) curing The epoxy resin composition according to any one of items [1] to [11], wherein the content of the agent is 0.01 to 25% by weight.
- the content of the (A) epoxy resin is 5 to 60% by weight
- the content of the (B) phenoxy resin is 10 to 30% by weight
- the (C) curing Item [2] to [9] wherein the content of the agent is 0.01 to 15% by weight
- the content of the (D) inorganic filler is 10 to 75% by weight.
- the content of (A1) novolac epoxy resin having a condensed ring aromatic hydrocarbon structure is 10 to 60% by weight
- the content of (B) phenoxy resin is 10 To 30 wt%
- the content of the (C) curing agent is 0.01 to 5 wt%
- the content of the (D) inorganic filler is 10 to 70 wt%
- (E) cyanate resin and / or its The epoxy resin composition according to any one of items [5] to [13], wherein the content of the prepolymer is 5 to 60% by weight.
- [16] A prepreg obtained by impregnating a glass fiber substrate with the epoxy resin composition according to any one of [1] to [14]. [17] including a step of continuously laminating the resin sheet according to [15] on the surface of the inner layer circuit board on which the inner layer circuit pattern is formed, and a step of forming the conductor circuit layer by a semi-additive method. A method for producing a multilayer printed wiring board. [18] A multilayer printed wiring board obtained by heating and press-molding the resin sheet according to the item [15] or the prepreg according to the item [16] on one or both surfaces of the inner circuit board. [19] A semiconductor device formed by mounting a semiconductor element on the multilayer printed wiring board according to the item [18].
- the specific (A) epoxy resin, (B) a phenoxy resin containing a bisphenolacetophenone structure represented by the general formula (1), and (C) a curing agent are combined, and the specific ( B)
- a resin composition containing a specific amount of phenoxy resin in the total solid content of the resin composition when the resin composition is used for an insulating layer of a multilayer printed wiring board, plating adhesion, heat resistance
- the thermal shock property is high enough not to cause peeling and cracking of the conductor circuit layer, particularly in a thermal shock test such as a thermal cycle.
- the multilayer printed wiring board obtained by using the resin sheet of the present invention for the insulating layer of the multilayer printed wiring board is excellent in fine wiring processability, adhesion between the conductor circuit and the insulating resin layer, and insulation reliability.
- the present invention can be suitably used for a multilayer printed wiring board called a package substrate used for flip chip packages, system-in-package (SiP), package-on-package (PoP), and the like. Since the package substrate acts as an intermediary for signal transmission between the mother board and the semiconductor element between the mother board and the semiconductor element, high-density fine circuit formation and high reliability are particularly required, but the resin sheet of the present invention It is possible to form a high-density fine circuit required for the package substrate by using the above.
- a semiconductor device in which a semiconductor element is mounted on a package substrate manufactured using the resin sheet of the present invention is particularly excellent in reliability.
- the epoxy resin composition of the present invention is an epoxy resin composition containing (A) an epoxy resin, (B) a phenoxy resin containing a bisphenolacetophenone structure represented by the following general formula (1), and (C) a curing agent.
- the (B) phenoxy resin is characterized by containing 10 to 30% by weight in the total solid content of the resin composition.
- R 1 may be the same or different from each other and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements
- R 2 is a hydrogen atom, carbon number 1 And a group selected from a hydrocarbon group having 10 to 10 halogen atoms
- R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- m is an integer of 0 to 5).
- the epoxy resin composition of the present invention combines the specific (A) epoxy resin, (B) a phenoxy resin containing a bisphenolacetophenone structure represented by the general formula (1), and (C) a curing agent,
- a specific (B) phenoxy resin as a resin composition containing a specific amount in the total solid content of the resin composition, when used in an insulating layer of a multilayer printed wiring board, plating adhesion, heat resistance, moisture resistance
- a multilayer printed wiring board that is excellent in reliability and capable of forming advanced fine wiring can be manufactured.
- the epoxy resin composition of the present invention contains (A) an epoxy resin, (B) a phenoxy resin containing a bisphenolacetophenone structure represented by the above general formula (1), and (C) a curing agent as essential components. Other components may be contained. Hereinafter, each component will be described in order.
- the (A) epoxy resin used in the present invention is not particularly limited.
- phenol novolac type epoxy resins alkylphenol novolac type epoxy resins, biphenyl type epoxy resins, and naphthalene type epoxy resins are preferable. Thereby, a flame retardance and moisture absorption solder heat resistance can be improved.
- the epoxy resin used in the present invention is particularly preferably (A1) a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure.
- a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is a novolak type epoxy having a naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, triphenylene, tetraphen, or other condensed ring aromatic hydrocarbon structure.
- Resin. (A1)
- the novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is excellent in low thermal expansion because a plurality of aromatic rings can be regularly arranged.
- the glass transition temperature is also high, it is excellent in heat resistance. Furthermore, since the molecular weight of the repeating structure is large, it is superior in flame retardancy compared to conventional novolak type epoxies, and the weakness of cyanate resin can be improved by combining with cyanate resin. Therefore, when used in combination with the (E) cyanate resin and / or its prepolymer, which will be described later, the glass transition temperature is further increased, so that lead-free mounting reliability is excellent.
- the (A1) novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is obtained by epoxidizing a novolak type phenol resin synthesized from a phenol compound, a formaldehyde compound, and a condensed ring aromatic hydrocarbon compound. is there.
- the phenolic compound is not particularly limited, but examples thereof include cresols such as phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, , 6-xylenol, 3,4-xylenol, xylenols such as 3,5-xylenol, trimethylphenols such as 2,3,5 trimethylphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, etc.
- cresols such as phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, , 6-xylenol, 3,4-xylenol, xylenols such as 3,5-xylenol, trimethylphenols such as
- Alkylphenols such as ethylphenol, isopropylphenol, butylphenol, t-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 Naphthalene diols of 7-dihydroxy naphthalene, resorcinol, catechol, hydroquinone, pyrogallol, polyhydric phenols such as fluoro Guru Singh, alkyl resorcinol, alkyl catechol, alkyl polyhydric phenols such as alkyl hydroquinone. Of these, phenol is preferable from the viewpoint of cost and the effect on the decomposition reaction.
- the aldehyde compound is not particularly limited, and for example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde Benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, 4-hydroxy-3-methoxyaldehyde paraformaldehyde and the like.
- the condensed ring aromatic hydrocarbon compound is not particularly limited, and examples thereof include naphthalene derivatives such as methoxynaphthalene and butoxynaphthalene, anthracene derivatives such as methoxyanthracene, phenanthrene derivatives such as methoxyphenanthrene, other tetracene derivatives, chrysene derivatives, and pyrene derivatives. , Derivatives triphenylene, and tetraphen derivatives.
- the (A1) novolak-type epoxy resin having a condensed ring aromatic hydrocarbon structure is not particularly limited.
- methoxynaphthalene-modified orthocresol novolak epoxy, butoxynaphthalene-modified meta (para) cresol novolak epoxy, and methoxynaphthalene-modified novolak Examples include epoxy.
- the novolak type epoxy resin which has (A1) condensed ring aromatic hydrocarbon structure represented by following formula (2) is preferable.
- Ar represents a condensed ring aromatic hydrocarbon group and is selected from the following formula (3).
- R 4 s may be the same as or different from each other, and may be a hydrogen atom, having 1 to 10 carbon atoms.
- Ar is a structure represented by one or more selected from (Ar @ 1) ⁇ (Ar4), wherein R 5 may be the being the same or different, a hydrogen atom, a carbon (This is a group selected from a hydrocarbon group of formula 1 to 10 or an aryl group such as a halogen element, a phenyl group or a benzyl group, and an organic group including glycidyl ether.)
- the condensed ring aromatic hydrocarbon structure is preferably a naphthalene structure.
- the inorganic filler is excellent in dispersibility, the surface of the insulating layer becomes smooth, and it is preferable from the viewpoint that advanced fine wiring, that is, fine wiring having a narrower conductor width and a narrower inter-conductor width can be formed.
- the (A) epoxy resin used in the present invention preferably has a molecular weight of 5.0 ⁇ 10 3 or less. As a result, heat resistance and low heat decomposability can be imparted, and the film formability when producing a resin sheet with a base material and the adhesion with an inner circuit board when producing a multilayer printed wiring board are improved. Can do.
- the (A) epoxy resin used in the present invention preferably has a molecular weight of 1.0 ⁇ 10 3 or less and 2.0 ⁇ 10 2 or more from the viewpoint of moldability.
- the content of the epoxy resin is not particularly limited, but is preferably 5 to 80% by weight based on the total solid content of the resin composition.
- the content of the epoxy resin is preferably 5 to 60% by weight in the total solid content of the resin composition.
- the content of the epoxy resin is more preferably 10 to 50% by weight, particularly preferably 10 to 30% by weight, based on the total solid content of the resin composition. If the content of the epoxy resin is less than the lower limit, the effect of improving moisture-absorbing solder heat resistance and adhesion may be reduced. Moreover, when the said upper limit is exceeded, since dispersibility may worsen, heat resistance may fall, or the reliability of the product obtained may fall, it is unpreferable. By setting the content of the epoxy resin within the above range, it is possible to achieve an excellent balance of these characteristics.
- the phenoxy resin containing the bisphenolacetophenone structure represented by the following general formula (1) used in the present invention is contained in a specific amount of 10 to 30% by weight in the total solid content of the epoxy resin composition.
- the combined (A) epoxy resin and (C) curing agent it has excellent heat resistance and moisture resistance reliability, and the surface roughness (Ra) is reduced, making it possible to form advanced fine wiring. It becomes.
- R 1 may be the same or different from each other, and is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a group selected from halogen elements, and R 2 is a hydrogen atom, And a group selected from a hydrocarbon group having 1 to 10 or a halogen element, R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and m is an integer of 0 to 5.
- the phenoxy resin containing the bisphenol acetophenone structure represented by the general formula (1) used in the present invention is a conventional bisphenol A or bisphenol F. Or since it has a bulky structure compared with the phenoxy resin containing a bisphenol S structure, it is excellent in solvent solubility and compatibility with thermosetting resin components, such as an epoxy resin to mix
- the (B) phenoxy resin used in the present invention has a property of being strong in thermal shock and easy to relieve stress.
- the (B) phenoxy resin is combined in a specific amount of 10 to 30% by weight in the total solid content of the epoxy resin composition, so that the combined (A) epoxy resin and (C) Estimated that, in combination with a curing agent, a uniform rough surface can be formed with low roughness, and advanced fine wiring can be formed while being excellent in plating adhesion, heat resistance and moisture resistance reliability. Is done.
- examples of the hydrocarbon group having 1 to 10 carbon atoms include linear, branched, or cyclic alkyl groups and aryl groups.
- examples of the hydrocarbon group having 1 to 10 carbon atoms include linear, branched, or cyclic alkyl groups and aryl groups.
- examples of the halogen element include fluorine, chlorine, bromine and the like.
- the (B) phenoxy resin can be synthesized by a known method such as a method of increasing the molecular weight of a phenol resin containing an epoxy resin and bisphenolacetophenone as essential components using a catalyst.
- a bisphenol acetophenone having an appropriate substituent that induces the bisphenol acetophenone structure represented by the general formula (1) is used.
- the epoxy resin is not particularly limited.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z Type epoxy resin, bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac epoxy resin, etc.
- novolac type epoxy resin novolac type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, arylalkylene type epoxy resin, naphthalene type epoxy resin, anthracene Type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin , And epoxy resins such as a fluorene epoxy resin.
- One of these can be used alone, or two or more can be used in combination.
- the phenol resin that may be contained in addition to bisphenol acetophenone is not particularly limited.
- a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak resin, a novolak type phenol resin such as an arylalkylene type novolak resin, and an unmodified resole phenol examples thereof include resol type phenol resins such as oil-modified resol phenol resins modified with resin, tung oil, linseed oil, walnut oil and the like.
- One of these may be used alone, or two or more having different weight average molecular weights may be used in combination, or one or more of the above-described resins may be used in combination with their prepolymer. You can also.
- arylalkylene type phenol resins are particularly preferable. Thereby, moisture absorption solder heat resistance can be improved further.
- the catalyst is not particularly limited as long as it is a compound having a catalytic ability to promote a reaction between an epoxy resin and a phenol resin or a reaction with an alcoholic hydroxyl group or a carboxyl group generated by a reaction between an epoxy group and a phenolic hydroxyl group.
- examples thereof include alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like.
- Specific examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride.
- Alkali metal alkoxides such as sodium methoxide and sodium ethoxide, alkali metal phenoxides, sodium hydride, lithium hydride and the like, and alkali metal salts of organic acids such as sodium acetate and sodium stearate.
- alkali metal salts of organic acids such as sodium acetate and sodium stearate.
- quaternary ammonium salts are preferable, and among quaternary ammonium salts, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetramethylammonium-paratoluenesulfonic acid are preferable.
- quaternary ammonium salts are preferable, and among quaternary ammonium salts, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammoni
- the catalyst is used in an amount of 0.001 to 1% by weight based on the solid content of the reaction.
- the alkali metal content remains in the phenoxy resin, and the insulating properties of the printed wiring board using the alkali metal component deteriorate, so the total content of Li, Na and K in the phenoxy resin Is preferably 5 ppm or less, more preferably 4 ppm or less, and even more preferably 3 ppm or less. If it exceeds 5 ppm, the insulating properties deteriorate, which is not preferable.
- the phosphorus content in the phenoxy resin is preferably 150 ppm or less, More preferably, it is 140 ppm or less, More preferably, it is 100 ppm or less. If it exceeds 150 ppm, the insulating properties deteriorate, which is not preferable.
- a solvent may be used in the step of the synthesis reaction at the time of production, and any solvent may be used as long as it dissolves the phenoxy resin and does not adversely affect the reaction.
- the solvent is not particularly limited, and examples thereof include aromatic hydrocarbons, ketones, amide solvents, glycol ethers, and the like. Specific examples of the aromatic hydrocarbon include toluene and xylene. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, cyclohexanone, acetylacetone, and dioxane.
- amide solvent examples include formamide, N, N-dimethylformamide, acetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like.
- glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol Examples thereof include monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether.
- the amount of the solvent to be used can be appropriately selected according to the reaction conditions. For example, in the case of the two-stage production, it is preferable that the solid content concentration is 35% to 95%.
- the reaction temperature is in a temperature range that does not cause decomposition of the catalyst used.
- the reaction temperature is preferably 50 to 230 ° C, more preferably 120 to 200 ° C.
- a low boiling point solvent such as acetone or methyl ethyl ketone
- the reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave.
- the (B) phenoxy resin may contain a structure other than the bisphenolacetophenone structure of the general formula (1), and the structure is not particularly limited, but is bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type. , Phenol novolac type, cresol novolac type structure and the like. Among them, those containing a biphenyl type structure are preferable from the viewpoint of a high glass transition temperature and a low coefficient of linear thermal expansion.
- the glass transition temperature of the (B) phenoxy resin is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, from the viewpoint of heat resistance.
- the glass transition temperature here can be measured by differential scanning calorimetry (DSC).
- DSC differential scanning calorimeter
- TA Instruments, DSC2920 a value obtained by performing a soot measurement under a nitrogen atmosphere (30 ml / min) with a temperature increase rate of 10 ° C./min can be used.
- a tangent line is drawn on the DSC curve before and after the glass transition temperature, and the glass transition temperature (Tg) is determined from the intersection of the tangent lines.
- the content of the bisphenolacetophenone structure of the general formula (1) in the (B) phenoxy resin is not particularly limited, but is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 85 mol or less. More preferably, it is 15 mol% or more and 75 mol% or less. If the content is less than the lower limit, the effect of improving heat resistance and moisture resistance reliability may not be obtained. Moreover, since solvent solubility will worsen when content exceeds an upper limit, it is unpreferable.
- the weight average molecular weight of the (B) phenoxy resin is not particularly limited, but is preferably 5.0 ⁇ 10 3 to 1.0 ⁇ 10 5 , more preferably 1.0 ⁇ 10 4 to 7.0 ⁇ 10 4 , Most preferred is 2.0 ⁇ 10 4 to 5.0 ⁇ 10 4 . If the weight average molecular weight exceeds the upper limit, the compatibility with other resins and the solubility in solvents are extremely poor, and if not less than the lower limit, the film-forming property is deteriorated, and the multilayer printed wiring board This is not preferable because it causes problems when used for manufacturing. In addition, the weight average molecular weight in this invention says here the polystyrene conversion value by a gel permeation chromatography measurement.
- the content of the (B) phenoxy resin is 10 to 30% by weight, preferably 10 to 25% by weight, more preferably 10 to 20% by weight, based on the total solid content of the resin composition. It is. In such a case, the balance of the mechanical strength of the insulating resin layer, the plating adhesion with the conductor circuit, the thermal expansion coefficient, and the heat resistance is improved, and the moisture resistance reliability is also improved.
- the content of the (B) phenoxy resin is particularly preferably 10 to 15% by weight based on the total solid content of the resin composition.
- any curing agent or curing accelerator that can be used as an epoxy resin can be used.
- curing agent (C) used for this invention a phenol type hardening
- curing agent for example, well-known and usual things, such as a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a terpene modified phenol resin, polyvinylphenol, are used alone. Or it can use in combination of 2 or more types. Use of a phenolic curing agent improves flame retardancy and adhesion.
- the hardening accelerator of epoxy resins such as an imidazole compound, a triphenylphosphine, and a triphenylphosphine derivative
- Zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bis Cyanate curing catalysts such as organometallic salts such as acetylacetonate cobalt (II) and trisacetylacetonate cobalt (III); tertiary amines such as triethylamine, tributylamine, diazabicyclo [2,2,2] octane; phenol, Examples thereof include phenol compounds such as bisphenol A and nonylphenol, organic acids such as acetic acid, benzoic acid, salicylic acid, and paratoluenesulfonic acid, and mixtures thereof. One of these can be used alone, including derivatives
- an imidazole compound More preferably, it is an imidazole compound compatible with the resin component contained in the resin composition.
- an imidazole compound compatible with the resin component contained in the resin composition.
- the reaction of the epoxy resin can be effectively promoted, and equivalent characteristics can be imparted even if the amount of the imidazole compound is reduced.
- a resin composition using such an imidazole compound can be cured with high uniformity from a minute matrix unit with a resin component. Thereby, the insulation of the insulating layer formed in the multilayer printed wiring board and heat resistance can be improved.
- imidazole compound examples include 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2,4-diamino-6.
- an imidazole compound selected from 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 2-ethyl-4-methylimidazole is preferable.
- These imidazole compounds have a particularly excellent compatibility, so that a highly uniform cured product can be obtained and a fine and uniform roughened surface can be formed on the surface of the insulating layer.
- a fine conductor circuit can be easily formed, and high heat resistance can be imparted to the multilayer printed wiring board.
- the content of the curing agent (C) is not particularly limited, but is preferably 0.01 to 25% by weight based on the total solid content of the resin composition.
- curing agent is suitably selected by the component to be used.
- the phenolic curing agent is not necessarily used, for example, when it contains (E) a cyanate resin and / or a prepolymer thereof described later. Accordingly, the curing agent such as the above-mentioned phenol-based curing agent is preferably 0 to 25% by weight, more preferably 0 to 15% by weight, based on the total solid content of the resin composition.
- the curing accelerator is effective when added in a small amount as compared with a curing agent such as the above-mentioned phenol-based curing agent.
- a curing accelerator such as an imidazole compound
- the curing accelerator is preferably 0.01 to 5.00% by weight, more preferably 0.05 to 3.% in the total solid content of the resin composition. 00% by weight is preferred.
- the curing accelerator such as an imidazole compound is preferably 0.01 to 0.5% by weight, more preferably 0.05 to 0.3% by weight, based on the total solid content of the resin composition. More preferably, it is 0.05 to 0.25% by weight.
- the epoxy resin composition according to the present invention preferably further contains (D) an inorganic filler from the viewpoint of low thermal expansion and mechanical strength.
- the inorganic filler is not particularly limited, but for example, silicates such as talc, fired clay, unfired clay, mica, glass, oxides such as titanium oxide, alumina, silica, fused silica, calcium carbonate, carbonic acid Carbonates such as magnesium and hydrotalcite, metal hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, zinc borate and metaboric acid Examples include borates such as barium, aluminum borate, calcium borate and sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride, titanates such as strontium titanate and barium titanate.
- silica is particularly preferable from the viewpoint of low thermal expansion and insulation reliability, and spherical fused silica is more preferable.
- aluminum hydroxide is preferable in terms of flame resistance.
- the particle diameter of the (D) inorganic filler is not particularly limited, but an inorganic filler having a monodispersed average particle diameter can be used, or an inorganic filler having a polydispersed average particle diameter can be used. Furthermore, one or two or more inorganic fillers having an average particle size of monodisperse and / or polydisperse can be used in combination. Among these, when the conductor circuit width of the multilayer printed wiring board and the width (L / S) between the conductor circuits are less than 15/15 ⁇ m, the average particle size is 1.2 ⁇ m or less and 0.1 ⁇ m or more in terms of insulation reliability. And the thing by which the coarse grain of 5 micrometers or more was cut is preferable.
- the average particle size is 5 ⁇ m or less and 0.2 ⁇ m or more, and the coarse particles of 20 ⁇ m or more are 0.1% or less. If the average particle size is less than the lower limit, the fluidity is remarkably deteriorated and the moldability is lowered. Moreover, when the said upper limit is exceeded, the insulation of a conductor circuit may fall.
- the average particle size can be measured using a laser diffraction / scattering particle size distribution measuring device (a general device such as Shimadzu SALD-7000).
- the content of the inorganic filler (D) is not particularly limited, but is preferably 10% to 75% by weight, more preferably 10 to 70% by weight, and further 30% by weight based on the total solid content of the resin composition. % To 70% by weight is preferred.
- the content of the inorganic filler is 35 to 60% by weight in the total solid content of the resin composition. preferable. If the inorganic filler content exceeds the above upper limit, the fluidity of the resin composition may be extremely poor, which may be undesirable, and if it is less than the lower limit, the strength of the insulating layer made of the resin composition is not sufficient, It may not be preferable.
- the epoxy resin composition according to the present invention preferably further contains (E) a cyanate resin and / or a prepolymer thereof from the viewpoint of improving the heat resistance and flame retardancy of the epoxy resin composition.
- (E) a cyanate resin and / or a prepolymer thereof is contained in combination with the above (B) phenoxy resin containing a bisphenolacetophenone structure, the resins are excellent in compatibility, excellent in heat resistance, and linear. Since the expansion coefficient is low, it is preferable in that the surface smoothness of the insulating layer is excellent and the desmear property is excellent.
- the method for obtaining the cyanate resin and / or its prepolymer is not particularly limited.
- the cyanate resin can be obtained by reacting a cyanogen halide with a phenol and prepolymerizing it by a method such as heating as necessary. it can.
- the commercial item prepared in this way can also be used.
- the type of cyanate resin is not particularly limited, and examples thereof include novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, and bisphenol type cyanate resin such as tetramethylbisphenol F type cyanate resin.
- the (E) cyanate resin and / or prepolymer thereof preferably has two or more cyanate groups (—O—CN) in the molecule.
- cyanate groups —O—CN
- phenol novolac-type cyanate ester resins are excellent in flame retardancy and low thermal expansion, and 2,2′-bis (4-cyanatophenyl) isopropylidene and dicyclopentadiene-type cyanate esters have a crosslinking density. Excellent control and moisture resistance reliability.
- a phenol novolac type cyanate ester resin is preferred from the viewpoint of low thermal expansion.
- other cyanate ester resins may be used alone or in combination of two or more, and are not particularly limited.
- (E) cyanate resin may be used alone, (E) cyanate resin having a different weight average molecular weight is used in combination, or (E) cyanate resin and its prepolymer are used in combination.
- the prepolymer is usually obtained by, for example, trimerizing the (E) cyanate resin by a heat reaction or the like, and is preferably used for adjusting the moldability and fluidity of the resin composition. It is.
- the prepolymer is not particularly limited. For example, when a prepolymer having a trimerization ratio of 20 to 50% by weight is used, good moldability and fluidity can be exhibited.
- the content when the above (E) cyanate resin and / or prepolymer thereof is used is not particularly limited, but it is preferably 5 to 60% by weight in the total solid content of the resin composition. More preferably, it is 10 to 50% by weight. Thereby, the heat resistance which a cyanate resin has, and the flame retardance improvement effect
- the content of (E) cyanate resin and / or its prepolymer is particularly preferably 10 to 20% by weight in the total solid content of the resin composition.
- (A1) a novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure
- (B) a phenoxy resin containing a bisphenolacetophenone structure represented by the above general formula (1)
- the (B) phenoxy resin is contained in an amount of 10 to 30 in the total solid content of the resin composition.
- the content by weight is particularly preferred from the viewpoint of excellent fine wiring processability and excellent insulation reliability between lines.
- the dispersibility of the inorganic filler in the resin is excellent, there is no stripe unevenness derived from the inorganic filler that usually appears, it is uniform, and the planar smoothness of the surface of the insulating layer is excellent. Further, it is presumed that by being excellent in heat resistance, low thermal expansion, and further excellent in desmear properties, it is particularly excellent in fine wiring processability and excellent insulation reliability between lines.
- the epoxy resin composition of the present invention preferably further contains a poly (meth) acrylic acid ester having a weight average molecular weight of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 5 .
- a poly (meth) acrylic acid ester having a weight average molecular weight of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 5 .
- the surface smoothness is improved and the fine wiring processability is more preferable.
- poly (meth) acrylic acid ester by using poly (meth) acrylic acid ester, the defoaming property and defoaming property can be improved, and the wettability between the film or metal foil and the insulating resin layer can be controlled.
- the poly (meth) acrylate a polymer obtained by polymerizing (meth) acrylate is preferably used.
- the (meth) acrylic acid ester is not particularly limited.
- Examples include butyl, cyclohexyl methacrylate, octadecyl methacrylate, 2-ethy
- These monomers can be used as a homopolymer, a copolymer obtained by polymerizing two or more of the above monomers, a mixture obtained by mixing two or more of the above polymerized polymers, or a mixture of a polymer and a monomer.
- the poly (meth) acrylic acid ester has a weight average molecular weight of 1.0 ⁇ 10 3 to 1.0 ⁇ 10 5 , more preferably 3.0 ⁇ 10 3 to 1.5 ⁇ 10 4. It is preferable from the point of the addition effect of poly (meth) acrylic acid ester.
- the poly (meth) acrylic acid ester used in the present invention is preferably an alkyl ester polymer of (meth) acrylic acid, and the alkyl carbon number is particularly preferably about 3 to 10.
- butyl acrylate, polybutyl acrylate, a copolymer of butyl acrylate and 2-ethyl-hexyl acrylate, 2-ethyl-hexyl acrylate, and 2-ethyl-hexyl acrylate are preferable.
- the poly (meth) acrylic acid ester used for this invention contains 50.0 weight% or more of repeating units derived from butyl acrylate in the said poly (meth) acrylic acid ester.
- the content of the acrylic surfactant is preferably 0.1 to 10.0% by weight, more preferably 0.3 to 5.0% by weight of the resin composition.
- the preferable amount of the acrylic surfactant is within the above range. If the upper limit is exceeded, the acrylic surfactant is segregated on the surface of the coating film, resulting in poor insulation and poor adhesion to the conductor circuit. If the lower limit is not reached, defects such as repellency and unevenness occur in the coating film, which makes it difficult to process fine circuit wiring and may reduce productivity.
- the epoxy resin composition of the present invention preferably further uses a coupling agent.
- the coupling agent is not particularly limited, and examples thereof include silane-based, titanate-based, and aluminum-based coupling agents.
- silane-based, titanate-based, and aluminum-based coupling agents include silane-based, titanate-based, and aluminum-based coupling agents.
- One of these can be used alone, or two or more can be used in combination.
- a coupling agent By using a coupling agent, the wettability of the interface of the said epoxy resin and cyanate resin, and an inorganic filler can be improved. As a result, heat resistance, particularly moisture-absorbing solder heat resistance can be improved.
- the content of the coupling agent is not particularly limited, but is preferably 0.05 to 5.00 parts by weight with respect to 100 parts by weight of the inorganic filler. In particular, 0.01 to 2.50 parts by weight are more preferable. If the content of the coupling agent is less than the lower limit, the effect of covering the inorganic filler and improving the heat resistance may not be sufficient. On the other hand, if the upper limit is exceeded, the bending strength of the insulating resin layer may decrease. By setting the content of the coupling agent within the above range, it is possible to achieve an excellent balance of these characteristics.
- the epoxy resin composition of the present invention includes, as necessary, organic particles such as core-shell rubber particles and acrylic rubber particles, silicone-based, fluorine-based, polymer-based antifoaming agents, and An additive such as a colorant such as a leveling agent, titanium oxide, or carbon black can be contained.
- the resin composition has various additives such as an ion scavenger, a non-reactive diluent, a reactive diluent, a thixotropic agent for improving various properties such as resin compatibility, stability, and workability. Agents, thickeners and the like may be added as appropriate.
- the resin sheet of this invention forms the resin layer which consists of an epoxy resin composition which concerns on the said this invention on a base material.
- the resin layer made of the epoxy resin composition according to the present invention is excellent in circuit step embedding property, flatness after embedding, and laser processability.
- the resin sheet is laminated on a substrate such as a film or a metal foil. Therefore, the handling property of the resin layer and the adaptability to various processing processes are excellent.
- the method for producing the resin sheet is not particularly limited.
- the resin composition is dissolved in a solvent using various mixers such as an ultrasonic dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation and revolution dispersion method.
- a solvent for example, alcohols, ethers, acetals, ketones, esters, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, ketone esters, and ester ethers
- An organic solvent such as can be used.
- the solid content in the resin varnish is not particularly limited, but is preferably 30 to 80% by weight, particularly preferably 40 to 70% by weight.
- the resin varnish is coated on a substrate using various coating apparatuses, and then dried.
- the resin varnish is spray-coated on a substrate with a spray device and then dried.
- a resin sheet can be produced by these methods.
- the coating apparatus is not particularly limited, and for example, a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a comma coater, a curtain coater, or the like can be used. Among these, a method using a die coater, a knife coater, and a comma coater is preferable. As a result, a resin sheet with a substrate having a uniform resin layer thickness without voids can be efficiently produced.
- the substrate is not particularly limited, but a film or a metal foil is preferably used.
- a film is not specifically limited,
- the thermoplastic resin film which has heat resistance such as polyester resins, such as a polyethylene terephthalate and a polybutylene terephthalate, a fluorine resin, and a polyimide resin, can be used.
- the metal foil is not particularly limited.
- Metal foils such as zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys can be used.
- the thickness of the substrate is not particularly limited, but it is preferable to use a substrate 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, the plating adhesion between the resin layer and the circuit becomes good, and the fine wiring processing becomes easy.
- the thickness of the resin layer of the resin sheet is not particularly limited, but when the thickness of the multilayer printed wiring board is 1.6 mm, it is preferably 10 to 100 ⁇ m, more preferably 20 to 80 ⁇ m. Further, when the thickness of the multilayer printed wiring board is 1.8 mm, the thickness of the resin layer of the resin sheet is preferably 1 to 60 ⁇ m, particularly preferably 5 to 40 ⁇ m. The thickness of the resin layer is preferably equal to or greater than the lower limit for improving insulation reliability, and is preferably equal to or less than the upper limit for achieving thinning of the multilayer printed wiring board. Thereby, when manufacturing a printed wiring board, while being able to fill with the unevenness
- the prepreg of the present invention is obtained by impregnating a glass fiber base material with the epoxy resin composition according to the present invention. Thereby, the prepreg suitable for manufacturing the multilayer printed wiring board excellent in heat resistance and mechanical strength can be obtained.
- Examples of the glass fiber substrate used in the present invention include glass woven fabric and glass nonwoven fabric. Thereby, the intensity
- Examples of the method for impregnating the glass fiber base material with the epoxy resin composition of the present invention include, for example, preparing a resin varnish as described above, immersing the fiber base material in the resin varnish, and applying with various coater devices, For example, a spraying method may be used. Among these, the method of immersing the glass fiber substrate in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a glass fiber base material can be improved. In addition, when a glass fiber base material is immersed in a resin varnish, a normal impregnation coating equipment can be used.
- the solvent used in the resin varnish desirably has good solubility in the resin component in the epoxy resin composition, but a poor solvent may be used as long as it does not have an adverse effect.
- the nonvolatile content concentration in the resin varnish is not particularly limited, but is preferably 40 to 80% by weight, and particularly preferably 50 to 65% by weight. Thereby, the viscosity of a resin varnish can be made into a suitable level, and the impregnation property to a glass fiber base material can further be improved.
- a prepreg can be obtained by impregnating the glass fiber substrate with the epoxy resin composition and drying at a predetermined temperature, for example, 80 to 200 ° C.
- the multilayer printed wiring board of the present invention is formed by heating and press-molding the resin sheet according to the present invention or the prepreg according to the present invention on one side or both sides of an inner layer circuit board. Specifically, the resin sheet or prepreg of the present invention is combined with the resin layer side and the inner circuit board, and vacuum-heated and pressure-molded using a vacuum-pressure laminator device, and then heat-cured with a hot-air dryer or the like. By doing so, a multilayer printed wiring board can be obtained.
- the conditions for heat and pressure molding are not particularly limited, but as an example, it can be carried out at a temperature of 60 to 160 ° C.
- the conditions for heat curing are not particularly limited, but it can be carried out at a temperature of 140 to 240 ° C. for a time of 30 to 120 minutes.
- a multilayer printed wiring board can be obtained by overlaying the resin layer side of the resin sheet or prepreg of the present invention on an inner layer circuit board and heat-pressing it using a flat plate press or the like.
- the conditions for heat and pressure molding are not particularly limited, but as an example, it can be carried out at a temperature of 140 to 240 ° C. and a pressure of 1 to 4 MPa.
- the inner layer circuit board used for obtaining the multilayer printed wiring board is preferably, for example, one in which a predetermined conductor circuit is formed by etching or the like on both sides of a copper clad laminate and the conductor circuit portion is blackened. Can be used.
- the method for producing a multilayer printed wiring board according to the present invention includes a step of continuously laminating the resin sheet according to the present invention on a surface on which an inner layer circuit pattern of the inner layer circuit board is formed, and a conductor circuit layer. A step of forming by a semi-additive method.
- the multilayer printed wiring board obtained above further hardens the resin layer, peels and removes the film or metal foil, and roughens the resin layer surface with an oxidizing agent such as permanganate or dichromate.
- an oxidizing agent such as permanganate or dichromate.
- a conductive wiring circuit can be formed by metal plating.
- the insulating layer formed from the resin sheet of the present invention can form a large number of fine irregularities on its surface in the roughening treatment step, and the insulating resin layer surface has high smoothness. Therefore, a fine wiring circuit can be formed with high accuracy.
- the semiconductor device is manufactured by mounting a semiconductor element on a multilayer printed wiring board having a high-density, fine wiring circuit manufactured by the same method as the above-mentioned multilayer printed wiring board and sealing with a sealing resin. To do.
- the mounting method and the sealing method of the semiconductor element are not particularly limited. For example, after aligning a semiconductor element and a multilayer printed wiring board with a connection electrode portion on the multilayer printed wiring board and a metal bump of the semiconductor element with a flip chip bonder, etc., an IR reflow device, a heat plate, etc.
- a semiconductor device can be obtained by curing. Since the multilayer printed wiring board of the present invention can be easily processed into fine wiring during production, a semiconductor device having excellent mounting reliability and thermal shock resistance can be manufactured by using it as a package substrate.
- Example I series The Examples and Comparative Examples were evaluated using the phenoxy resins A to C obtained above and the following raw materials.
- Epoxy resin A / tetramethylbiphenyl type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd. “YX-4000”, epoxy equivalent 185 g / eq
- Epoxy resin B / bisphenol A type epoxy resin Japan Epoxy Resin Co., Ltd. “jER828”, epoxy equivalent 186 g / eq
- Epoxy resin C / bisphenol F type epoxy resin “JER806” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of 168 g / eq
- Epoxy resin D / biphenyl dimethylene type epoxy resin Nippon Kayaku Co., Ltd.
- Phenol curing agent / biphenylalkylene type novolak resin “MEH-7851-3H” manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent: 220 g / eq (11) Curing accelerator / imidazole compound: manufactured by Shikoku Kasei Kogyo Co., Ltd.
- Example I-1 (1) Preparation of resin varnish 30.0 parts by weight of epoxy resin D, 15 parts by weight of phenoxy resin A, 19.8 parts by weight of cyanate resin, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Furthermore, 35.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 60% by weight.
- a via hole of ⁇ 60 ⁇ m for interlayer connection was formed in a predetermined position with the carbon dioxide gas laser in the laminate. Thereafter, the laminate is immersed in a swelling liquid at 70 ° C. (Atotech Japan Co., Swelling Dip Securigant P) for 5 minutes, and further in an aqueous potassium permanganate solution (Atotech Japan Co., Concentrate Compact CP) at 80 ° C. After immersion for 20 minutes, neutralization and desmear treatment in the via hole were performed.
- a swelling liquid at 70 ° C. (Atotech Japan Co., Swelling Dip Securigant P) for 5 minutes, and further in an aqueous potassium permanganate solution (Atotech Japan Co., Concentrate Compact CP) at 80 ° C.
- the laminate was subjected to degreasing, catalyst application, and activation steps, and then an electroless copper plating film was formed to a thickness of about 1 ⁇ m. Thereafter, a resist layer for electrolytic copper plating was formed to a thickness of 20 ⁇ m, exposed according to the circuit pattern, and unexposed portions were removed. Next, the copper plating part not covered with the resist layer was etched to form a circuit pattern. Furthermore, electrolytic copper plating was performed to increase the thickness of the circuit pattern. Thereafter, the resin was post-cured by heating at a temperature of 200 ° C. for 60 minutes to cure the insulating resin layer.
- solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) is formed to a thickness of 20 ⁇ m on the circuit surface, and the connection electrode part is exposed so that a semiconductor element can be mounted by exposure and development, and heated at 180 ° C. for 60 minutes.
- the solder resist was cured, nickel gold plating treatment was performed, and the resultant was cut into a size of 50 mm ⁇ 50 mm to obtain a multilayer printed wiring board.
- a semiconductor element (TEG chip, size 15 mm ⁇ 15 mm, thickness 0.8 mm) has a solder bump formed of an eutectic of Sn / Pb composition, and a circuit protective film formed of a positive photosensitive resin (Sumitomo). Bakelite CRC-8300) was used.
- a flux material was uniformly applied to the solder bumps by a transfer method, and then mounted on the multilayer printed wiring board by thermocompression bonding using a flip chip bonder device.
- a liquid sealing resin manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S
- CRP-4152S Sumitomo Bakelite Co., Ltd.
- Example I-2 > 25.0 parts by weight of epoxy resin D, 25.0 parts by weight of phenoxy resin A, 19.9 parts by weight of phenol curing agent and 0.1 part by weight of curing accelerator were dissolved and dispersed in methyl ethyl ketone. Further, 30.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirring device to prepare a resin varnish having a solid content of 50% by weight. Using this resin varnish, a resin sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example I-1.
- Example I-3 8.0 parts by weight of epoxy resin A, 10.0 parts by weight of epoxy resin D, 12.0 parts by weight of phenoxy resin A, 9.9 parts by weight of phenol curing agent, and 0.1 part by weight of curing accelerator were dissolved and dispersed in methyl ethyl ketone. Further, 60.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirring device to prepare a resin varnish having a solid content of 50% by weight. Using this resin varnish, a resin sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example I-1.
- Example I-4 15.0 parts by weight of epoxy resin B, 15.0 parts by weight of epoxy resin D, 15.0 parts by weight of phenoxy resin B, 19.8 parts by weight of cyanate resin, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Furthermore, 35.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight. Using this resin varnish, a resin sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example I-1.
- Example I-5 14.0 parts by weight of epoxy resin C, 14.0 parts by weight of epoxy resin D, 15.0 parts by weight of phenoxy resin C, 17.8 parts by weight of cyanate resin, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Further, 35.0 parts by weight of an inorganic filler and 4.0 parts by weight of acrylic rubber particles were added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight. Using this resin varnish, a resin sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example I-1.
- ⁇ Comparative Example I-6> 6.0 parts by weight of phenoxy resin A, 20 parts by weight of epoxy resin E, 34.0 parts by weight of cyanate resin, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Furthermore, 40 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight. Using this resin varnish, a resin sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example I-1.
- the evaluation method is as follows. (1) Plating peel strength After the desmear treatment, the laminate was subjected to degreasing, catalyst application, and activation steps, and then an electroless copper plating film was formed to a thickness of about 1 ⁇ m. Thereafter, a resist layer for electrolytic copper plating was formed to a thickness of 25 ⁇ m, and the peel strength (90 ° peel strength) of the copper plating film was measured according to JIS C-6648. (2) Reflow heat resistance test Using the multilayer printed wiring board before mounting the semiconductor element of the semiconductor device, it was passed through a 260 ° C. reflow furnace, and the presence or absence of swelling of the multilayer printed wiring board was visually confirmed.
- the multilayer printed wiring board was passed through a reflow furnace 30 times. As reflow conditions, the temperature is gradually raised from room temperature (25 ° C.) to 160 ° C. (50 to 60 seconds). Next, the temperature is raised to 160 ° C. to 200 ° C. over 50 to 60 seconds. Thereafter, the temperature is raised from 200 ° C. to 260 ° C. in 65 to 75 seconds, and further heated (reflowed) at a temperature of 260 to 262 ° C. for 5 to 10 seconds. Then, it is the conditions (cooling) to cool to 30 degreeC over 15 minutes.
- Each code is as follows.
- Examples I-1 to I-5 a resin composition containing 10 to 30% by weight of a phenoxy resin containing a bisphenolacetophenone structure represented by the general formula (1) of the present invention, and the resin composition were used.
- a semiconductor device having high plating peel strength and excellent moisture resistance reliability could be obtained.
- the semiconductor device of the present invention is excellent in thermal shock resistance.
- Comparative Example I-1 uses a phenoxy resin that does not contain the bisphenolacetophenone structure represented by the above general formula (1), so it is inferior in heat resistance and defective in the moisture resistance reliability test and the thermal shock test. did.
- Comparative Examples I-2 and I-3 since the content of the phenoxy resin containing the bisphenolacetophenone structure represented by the general formula (1) is insufficient, the heat resistance is inferior, and the reflow heat resistance test is expanded. As a result, the insulation resistance value decreased in the moisture resistance reliability test.
- Comparative Examples I-4 and I-5 an appropriate desmear surface was not obtained because the content of the phenoxy resin containing the bisphenolacetophenone structure represented by the general formula (1) was excessive. For this reason, plating peeling easily occurs, and a sample that can withstand the reliability test cannot be manufactured.
- Example I-6> Dissolve and disperse 30.0 parts by weight of epoxy resin D, 15.0 parts by weight of phenoxy resin A, 19.2 parts by weight of cyanate resin, 0.2 parts by weight of curing accelerator, and 0.6 parts by weight of polyacrylate in methyl ethyl ketone. It was. Furthermore, 35.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight. Using this resin varnish, a resin sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example I-1.
- Example I-7 30.0 parts by weight of epoxy resin F, 15.0 parts by weight of phenoxy resin A, 19.2 parts by weight of cyanate resin, 0.2 parts by weight of curing accelerator, and 0.6 parts by weight of polyacrylate are dissolved and dispersed in methyl ethyl ketone. It was. Furthermore, 35.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight. Using this resin varnish, a resin sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example I-1.
- Example I-6 and I-7 and Comparative Example I-2 the coated sheet surface roughness and fine wiring formation were evaluated. The results are shown in Table 2. Moreover, the evaluation method is as follows.
- Ten-point average roughness (Rz) was measured with a non-contact type three-dimensional optical interference type surface roughness meter (manufactured by Nippon Beco, WYKO NT1100). Here, Rz is defined by JIS-B0601.
- the evaluation sample was obtained by laminating a resin sheet on both sides of a copper clad laminate, peeling off the PET base material, anti-curing at 170 ° C. for 60 minutes, and roughening as described above.
- A Good (the circuit shape is normal with no short circuit, disconnection, peeling, etc.)
- ⁇ Virtually no problem
- ⁇ Virtually unusable (when there is a problem such as short circuit, disconnection, or peeling)
- ⁇ Unusable (There are defects such as short circuit, disconnection, or peeling.)
- Example II series Examples and Comparative Examples were evaluated using the phenoxy resins A to C obtained in the above synthesis examples and the following raw materials.
- the weight part to be added represents the amount of resin excluding solvent.
- Epoxy resin A ′ novolak type having naphthalene structure (“HP-5000” manufactured by DIC Corporation, epoxy equivalent 250 g / eq)
- Epoxy resin B ′ Cresol novolak type having naphthalene structure (“EXA-9900” manufactured by DIC Corporation, epoxy equivalent 270 g / eq)
- Epoxy resin C ′ bis A type (Japan Epoxy Resin “jER828EL”, epoxy equivalent 190 g / eq)
- Epoxy resin D ' naphthalene type (DIC Corporation "HP-4032”, epoxy equivalent 151 g / eq)
- Epoxy resin E ′ Naphthalene type (“HP-4700” manufactured by DIC Corporation, epoxy equivalent 165 g / eq)
- Epoxy resin F ′ Phosphophenanthrene-modified bisphenol A type epoxy resin (“FX305” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 504 g / eq
- Phenol curing agent B ′ cresol novolak compound having a triazine ring (Phenolite “LA-7054” 60% solution manufactured by DIC)
- Curing accelerator A ′ imidazole compound (“Cureazole 1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.)
- Curing accelerator B ′ Imidazole compound (“Cureazole 2E4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.)
- Curing accelerator C ′ Cyanoethylimidazole: “2E4MZ-CN” manufactured by Shikoku Kasei Kogyo Co., Ltd.
- Inorganic filler Spherical silica (“SO-25H” manufactured by Admatechs Co., Ltd., coarse particle cut having an average particle size of 0.5 ⁇ m, 5 ⁇ m or more)
- Inorganic filler Aluminum hydroxide (Showa Denko “HP-360”, average particle size 3.0 ⁇ m, 0.1 ⁇ m or less fine powder cut)
- Cyanate resin A ′ Novolak type (“Primaset PT-30” manufactured by Lonza Japan Co., Ltd.)
- Cyanate resin B ′ Bis A-type prepolymer (“Primaset BA230” manufactured by Lonza Japan Co., Ltd.) (19) Vinyl acetal (“KS-1” manufactured by Sekisui Chemical Co., Ltd.)
- Coupling agent Epoxy silane (“KBM-403E” manufactured by Shin-Etsu Chemical Co., Ltd.)
- Cyanate catalyst Cobalt acetylacetonate ("Narsem second cobalt"
- Example II-1 Production of resin sheet 30 parts by weight of cyanate resin A ′, 50 parts by weight of epoxy resin A ′ as a novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure, and the bisphenolacetophenone structure obtained in the above synthesis example 20 parts by weight of the phenoxy resin A contained, 70 parts by weight of spherical silica as an inorganic filler, 0.5 part by weight of the curing accelerator A ′, and 1 part by weight of the coupling agent were mixed and dissolved in methyl ethyl ketone and cyclohexanone. Subsequently, it stirred for 60 minutes using the high-speed stirring apparatus, and prepared the resin varnish of 60% of solid content weight. In addition, the ratio of the inorganic filler in a resin composition was about 41 weight%.
- the resin varnish obtained above was coated on a polyethylene terephthalate (hereinafter referred to as PET) film using a comma coater so that the thickness of the resin layer after drying was 40 ⁇ m, and this was applied at 150 ° C.
- the substrate was dried for 5 minutes with a drying apparatus to produce a resin sheet with a substrate.
- a multilayer printed wiring board and a semiconductor device were obtained in the same manner as in Example I-1.
- Example II-2 A resin varnish having a solid content of 60% was prepared in the same manner as in Example II-1, except that 20 parts by weight of phenoxy resin B was used instead of phenoxy resin A. Using this resin varnish, a resin sheet, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example II-1.
- Example II-3> A resin varnish having a solid content of 60% was prepared in the same manner as in Example II-1, except that 20 parts by weight of phenoxy resin C was used instead of phenoxy resin A. Using this resin varnish, a resin sheet, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example II-1.
- Example II-4> The solid content was the same as in Example II-3 except that 50 parts by weight of epoxy resin B ′ was used in place of epoxy resin A ′ and 70 parts by weight of aluminum hydroxide was used in place of spherical silica as the inorganic filler. A resin varnish having a weight of 60% was prepared. Using this resin varnish, a resin sheet, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example II-1.
- Example II-5 A resin varnish having a solid content of 60% was prepared in the same manner as in Example II-3 except that 70 parts by weight of aluminum hydroxide was used in place of the spherical silica as the inorganic filler. Using this resin varnish, a resin sheet, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example II-1.
- Example 2 As disclosed in Table No. 03/099952 (Example 1), 45 parts by weight of cyanate resin B ′, 30 parts by weight of epoxy resin C ′, 12 parts by weight of phenoxy resin D ′, and methyl ethyl ketone and cyclohexanone. Mixed and dissolved. Furthermore, 30 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 60% by weight. In addition, the ratio of the inorganic filler in a resin composition was about 26 weight%. Using this resin varnish, a resin sheet, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example II-1.
- phenol curing agent B ′ triazine-containing cresol novolak compound: DIC Phenolite “LA-7054” 60% solution product, hydroxyl group equivalent 125 g / eq
- a curing accelerator C ′ (“CUREZOL 2E4MZ-CN” manufactured by Shikoku Kasei Kogyo Co., Ltd.) was dissolved and dispersed in methyl ethyl ketone.
- an inorganic filler was added, and the mixture was stirred for 10 minutes using a high-speed stirring device to prepare a resin varnish having a solid content of 60% by weight.
- the ratio of the inorganic filler in a resin composition was about 23 weight%.
- a resin sheet, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example II-1.
- Example II-1 was repeated except that 20 parts by weight of phenoxy E ′ was used. In addition, the ratio of the inorganic filler in a resin composition was 41 weight%. Using this resin varnish, a resin sheet, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example II-1.
- the evaluation method will be described below.
- the coefficient of thermal expansion was defined as an average linear thermal expansion coefficient at a temperature of 25 to 150 ° C. in the second cycle.
- the evaluation sample was measured by using a resin plate obtained by laminating two insulating resin layers of the resin sheet obtained above and then heat-curing at 200 ° C. for 1 hour with a drier in a nitrogen atmosphere. .
- Ra surface roughness
- the surface roughness (Ra) was measured with a non-contact type three-dimensional optical interference type surface roughness meter (manufactured by Nippon Beco, WYKO NT1100). Ra here is defined by JIS-B0601.
- the evaluation sample was obtained by laminating a resin sheet on both sides of a copper clad laminate, peeling off the PET base material, anti-curing at 170 ° C. for 60 minutes, and roughening as described above.
- the evaluation was performed by using an ultrasonic deep defect inspection apparatus to evaluate the presence or absence of abnormality such as peeling of the insulating resin layer of the semiconductor device, peeling of the back surface of the semiconductor element, and chipping of the solder bumps.
- Each code is as follows. ⁇ : Passed under Level 2a condition ⁇ : Passed under Level 3 condition ⁇ : Abnormality occurred under Level 3 condition
- Examples II-1 to II-5 had excellent values of thermal expansion coefficient of about 30 ppm and excellent mounting reliability.
- the surface roughness (Ra) of the insulating resin layer was a good value of less than 0.3 ⁇ m. As a result, it is considered that the result was excellent in the fine wiring formability.
- the resin sheet of this invention has the small surface roughness of a conductor circuit, when using it for a printed wiring board, it can be anticipated that it is excellent also in a high frequency characteristic.
- Examples II-1 to II-5 have a plating peel strength of 0.6 km / m or more while having a low roughness (Ra).
- the resin sheet of the present invention was a result of having very high insulation reliability between lines even in a fine wiring circuit. Therefore, it is suitable for a package substrate for a semiconductor device that is thinned and densified. Examples II-1 and II-5 were particularly excellent in line insulation reliability, and Examples II-1 and II-5 were particularly excellent in mounting reliability.
- Comparative Example II-1 and Comparative Example II-5 which do not use a phenoxy resin having a bisphenolacetophenone structure, are excellent in plating peel strength but have high surface roughness. Therefore, it is inferior to fine wiring formability.
- Comparative Example II-2 using no phenoxy resin is excellent in low thermal expansibility, but is inferior in fine wiring formability due to high surface roughness. In addition, the plating peel strength is low and the mounting reliability is poor.
- Comparative Example II-3 and Comparative Example II-4, which do not use phenoxy resin and cyanate resin are inferior in all of low thermal expansion, fine circuit formation, and line insulation reliability.
- the epoxy resin composition and resin sheet of the present invention can be suitably used for the production of printed wiring boards and the like that require fine processing for densification.
- printed circuit boards for electronic devices that require miniaturization of parts, high-speed signal transmission, and high reliability can be obtained, making semiconductor devices with high density, thinness, and excellent reliability. Applicable.
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Abstract
Description
例えば、ビスフェノールアセトフェノン構造を含むフェノキシ樹脂を絶縁層に用いた(例えば、特許文献2)場合や、シアネートエステル樹脂を絶縁層に用いた(特許文献3)場合には、めっき密着性に問題があり、セミアディティブ法に適用することはできなかった。
しかしながら、いずれも全ての問題を解決するものはない。特に、今後、回路導体幅、回路導体間幅がより狭くなることから、微細回路の絶縁信頼性に大きな問題がある。また、プリプレグを絶縁樹脂層に用いて低熱膨張性にする例(特許文献9、及び10)も開示されているが、低熱膨張性と微細配線形成、および微細回路の絶縁信頼性を満足するものはなかった。
[1] (A)エポキシ樹脂、(B)下記一般式(1)で表されるビスフェノールアセトフェノン構造を含むフェノキシ樹脂、及び(C)硬化剤を含有するエポキシ樹脂組成物であって、前記(B)フェノキシ樹脂が樹脂組成物の全固形分中に10~30重量%含有することを特徴とする、エポキシ樹脂組成物。
[2] 前記樹脂組成物は、更に(D)無機充填材を含有することを特徴とする、[1]項に記載のエポキシ樹脂組成物。
[3] 前記樹脂組成物は、更に(E)シアネート樹脂、及び/又はそのプレポリマーを含有することを特徴とする、[1]項又は[2]項に記載のエポキシ樹脂組成物。
[4] 前記(A)エポキシ樹脂が、縮合環芳香族炭化水素構造を有するノボラック型エポキシ樹脂であることを特徴とする、[1]~[3]項のいずれかに記載のエポキシ樹脂組成物。
[5] (A1)縮合環芳香族炭化水素構造を有するノボラック型エポキシ樹脂、(B)上記一般式(1)で表されるビスフェノールアセトフェノン構造を含むフェノキシ樹脂、(C)硬化剤、(D)無機充填材、及び(E)シアネート樹脂、及び/又はそのプレポリマーを含有し、前記(B)フェノキシ樹脂が樹脂組成物の全固形分中に10~30重量%含有する、[1]~[4]項のいずれかに記載のエポキシ樹脂組成物。
[6] 前記(C)硬化剤として、イミダゾール化合物を含有することを特徴とする、[1]~[5]項のいずれかに記載のエポキシ樹脂組成物。
[7] 前記樹脂組成物は、更に、重量平均分子量が1.0×103~1.0×105のポリ(メタ)アクリル酸エステルを含有することを特徴とする、[1]~[6]項のいずれかに記載のエポキシ樹脂組成物。
[8] 前記(B)一般式(1)で表されるビスフェノールアセトフェノン構造を有するフェノキシ樹脂が、更にビフェニル構造を有するものであることを特徴とする、[1]~[7]項のいずれかに記載のエポキシ樹脂組成物。
[9] 前記(B)一般式(1)で表されるビスフェノールアセトフェノン構造を有するフェノキシ樹脂が、ガラス転移温度が120℃以上であることを特徴とする、[1]~[8]項のいずれかに記載のエポキシ樹脂組成物。
[10] 前記(D)無機充填材の粒径は、0.2μm~5μmであることを特徴とする、[2]~[9]項のいずれかに記載のエポキシ樹脂組成物。
[11] 前記(D)無機充填材は、シリカ、及び/または水酸化アルミニウムであることを特徴とする、[2]~[10]項のいずれかに記載のエポキシ樹脂組成物。
[12] 樹脂組成物の全固形分中に、前記(A)エポキシ樹脂の含有量が5~80重量%、前記(B)フェノキシ樹脂の含有量が10~30重量%、前記(C)硬化剤の含有量が0.01~25重量%であることを特徴とする、[1]~[11]項のいずれかに記載のエポキシ樹脂組成物。
[13] 樹脂組成物の全固形分中に、前記(A)エポキシ樹脂の含有量が5~60重量%、前記(B)フェノキシ樹脂の含有量が10~30重量%、前記(C)硬化剤の含有量が0.01~15重量%、前記(D)無機充填材の含有量が10~75重量%であることを特徴とする、[2]~[9]項のいずれかに記載のエポキシ樹脂組成物。
[14] 樹脂組成物の全固形分中に、(A1)縮合環芳香族炭化水素構造を有するノボラック型エポキシ樹脂の含有量が10~60重量%、前記(B)フェノキシ樹脂の含有量が10~30重量%、前記(C)硬化剤の含有量が0.01~5重量%、前記(D)無機充填材の含有量が10~70重量%、及び(E)シアネート樹脂及び/又はそのプレポリマーの含有量が5~60重量%であることを特徴とする、[5]~[13]項のいずれかに記載のエポキシ樹脂組成物。
[15] 前記[1]~[14]項のいずれかに記載のエポキシ樹脂組成物からなる樹脂層を基材上に形成してなる樹脂シート。
[16] 前記[1]~[14]項のいずれかに記載のエポキシ樹脂組成物をガラス繊維基材に含浸させてなるプリプレグ。
[17] 前記[15]項に記載の樹脂シートを、内層回路基板の内層回路パターンが形成された面に重ね合わせて連続積層する工程、及び導体回路層をセミアディティブ法で形成する工程を含む多層プリント配線板の製造方法。
[18] 前記[15]項に記載の樹脂シート、または前記[16]項に記載のプリプレグを、内層回路板の片面または両面に重ね合わせて加熱加圧成形してなる多層プリント配線板。
[19] 前記[18]項に記載の多層プリント配線板に半導体素子を実装してなる半導体装置。
さらに、内層回路基板の内層回路パターンが形成された面に重ね合わせて連続積層する工程、及び導体回路層をセミアディティブ法で形成する工程を有する製造方法で製造することにより歩留まりよく製造できる。
本発明の樹脂シートを用い製造されたパッケージ基板に半導体素子を搭載してなる半導体装置は特に信頼性に優れる。
このような場合は、無機充填材の分散性に優れ、絶縁層表面が平滑になり、高度な微細配線すなわち、より狭導体幅、狭導体間幅の微細配線を形成できる点から好ましい。
上記エポキシ樹脂の含有量は、さらに好ましくは樹脂組成物の全固形分中に10~50重量%であり、特に好ましくは10~30重量%である。
エポキシ樹脂の含有量が上記下限値未満であると、吸湿半田耐熱性、密着性を向上させる効果が低下する場合がある。また、上記上限値を超えると、分散性が悪くなることがあったり、耐熱性が低下したり、得られる製品の信頼性が低下したりする場合があるため好ましくない。エポキシ樹脂の含有量を上記範囲内とすることにより、これらの特性のバランスに優れたものとすることができる。
なぜなら、絶縁層の凹凸が大きいと無電解メッキ等により絶縁層表面に導体を形成した際に導体の高さの差が大きくなり、エッチングにより回路を形成する際に、エッチング量の調整が難しく、エッチング量の過不足により、所望の導体回路幅、導体回路間幅にできない場合があるからである。
また、耐熱性を向上するには、用いられるフェノキシ樹脂のガラス転移温度(Tg)を高くする必要がある。しかしながら、フェノキシ樹脂のTgを高くすると、その剛直な構造のため、エポキシ樹脂との相溶性が低下して大きな海島構造となり、デスミア処理において酸化粗化されるフェノキシ樹脂のドメインが大きくなるため、表面凹凸(Ra)が大きくなってしまい微細配線形成には不適切となっていた。このように、従来は、フェノキシ樹脂の高Tg化と相溶性の両立に課題があった。
その点、本発明で用いられる上記一般式(1)で表されるビスフェノールアセトフェノン構造を含むフェノキシ樹脂(以下、単に「(B)フェノキシ樹脂」と記載する。)は、従来のビスフェノールA又はビスフェノールF又はビスフェノールS構造を含むフェノキシ樹脂に比べて、嵩高い構造を持っているため、溶剤溶解性や、配合するエポキシ樹脂等の熱硬化性樹脂成分との相溶性に優れる。また、本発明に用いられる(B)フェノキシ樹脂は、熱衝撃性に強く、応力緩和がしやすい性質を有する。従って、本発明においては、特に前記(B)フェノキシ樹脂がエポキシ樹脂組成物の全固形分中に10~30重量%と特定量で含まれることにより、組み合わされる(A)エポキシ樹脂と(C)硬化剤と相俟って、低粗度で均一な粗面を形成することができるようになり、めっき密着性、耐熱性、耐湿信頼性に優れながら、高度な微細配線を形成可能になると推定される。(B)フェノキシ樹脂の含有量が上限値を超えると、樹脂組成物中の高分子量成分が多くなるため、絶縁樹脂層の熱膨張率が高くなったり、架橋密度が下がり、信頼性上の不具合を起こす恐れがある。また、下限値未満であると、硬化性が十分でなく、絶縁樹脂層の機械強度が低下したり、デスミア処理時にめっき密着性が著しく低下するため好ましくない。
また、R1及びR2において、ハロゲン元素としては、フッ素、塩素、臭素等が挙げられる。
エポキシ樹脂とフェノール樹脂の交互重合をおこなう際の仕込み比は、エポキシ当量/フェノール性水酸基=1.1~1.5/0.9~0.5とすることが好ましく、更に1.2~1.3/0.8~0.7とすることが好ましい。
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。
上記フェノール系硬化剤は、例えば後述する(E)シアネート樹脂及び/又はそのプレポリマーを含有する場合には、必ずしも用いる必要はない。従って、上記フェノール系硬化剤のような硬化剤は、樹脂組成物の全固形分中に0~25重量%であることが好ましく、更に0~15重量%であることが好ましい。
中でも、イミダゾール化合物のような硬化促進剤は、樹脂組成物の全固形分中に0.01~0.5重量%であることが好ましく、更に0.05~0.3重量%であることが好ましく、より更に0.05~0.25重量%であることが好ましい。
前記プレポリマーは、通常、前記(E)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。
このような特定の組み合わせの場合には、無機充填材の樹脂中での分散性が優れ、通常現れる無機充填材に由来するスジムラがなく、均一であり、絶縁層表面の平面平滑性に優れる。また、耐熱性にも優れ、低熱膨張であり、さらにデスミア性にも優れることにより、特に微細配線加工性に優れ、線間絶縁信頼性にも優れるようになると推定される。
本発明の樹脂シートは、前記本発明に係るエポキシ樹脂組成物からなる樹脂層を基材上に形成してなるものである。
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、樹脂層と回路とのメッキ密着性が良好となり、また微細配線加工が容易となる。
本発明のプリプレグは、前記本発明に係るエポキシ樹脂組成物をガラス繊維基材に含浸させてなる。
これにより、耐熱性、機械強度に優れた多層プリント配線板を製造するのに好適なプリプレグを得ることができる。
本発明の多層プリント配線板は、前記本発明に係る樹脂シート又は前記本発明に係るプリプレグを、内層回路板の片面又は両面に重ね合わせて加熱加圧成形してなるものである。
具体的には、上記本発明の樹脂シート又はプリプレグの樹脂側と内層回路板とを合わせて、真空加圧式ラミネーター装置などを用いて真空加熱加圧成形させ、その後、熱風乾燥装置等で加熱硬化させることにより多層プリント配線板を得ることができる。
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60~160℃、圧力0.2~3MPaで実施することができる。また、加熱硬化させる条件としては特に限定されないが、温度140~240℃、時間30~120分間で実施することができる。
あるいは、上記本発明の樹脂シート又はプリプレグの樹脂層側を内層回路板に重ね合わせ、これを平板プレス装置などを用いて加熱加圧成形することにより、多層プリント配線板を得ることができる。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。
なお、上記多層プリント配線板を得る際に用いられる内層回路板は、例えば、銅張積層版の両面に、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。
上記半導体装置は、上記多層プリント配線板を得た同様の方法で製造した、高密度な、微細配線回路を有する多層プリント配線板に半導体素子を実装し、封止樹脂によって封止することによって製造する。半導体素子の実装方法、封止方法は特に限定されない。例えば、半導体素子と多層プリント配線板とを、フリップチップボンダーなどで多層プリント配線板上の接続用電極部と半導体素子の金属バンプとの位置合わせを行ったあと、IRリフロー装置、熱板、その他加熱装置を用いて半田バンプを融点以上に加熱し、多層プリント配線板と半田バンプとを溶融接合することにより接続し、多層プリント配線板と半導体素子との間に液状封止樹脂を充填し、硬化させることで半導体装置を得ることができる。
本発明の多層プリント配線板は、製造時、微細配線加工が容易なためパッケージ用基板として使用することにより、実装信頼性に優れ、且つ熱衝撃性に優れた半導体装置を製造することができる。
<フェノキシ樹脂の合成例>
上記一般式(1)で表されるビスフェノールアセトフェノン構造を含むフェノキシ樹脂の合成は、特許文献2に準じ合成した。以下に合成例を示すが、必ずしも当該文献の方法、反応温度、反応時間に限定されるものではない。
容量1Lの反応容器に、テトラメチルビフェニル型エポキシ樹脂(ジャパンエポキシレジン株式会社製「YX-4000」、エポキシ当量185g/eq)100g、ビスフェノールアセトフェノン80g、およびシクロヘキサノン70gを入れ攪拌して溶解させた。次に、50wt%テトラメチルアンモニウムクロライド溶液0.4gを滴下し、窒素雰囲気下、180℃で5時間反応させた。反応終了後、析出物をろ過し、真空乾燥機にて、95℃で8時間真空乾燥し、構造式(4)で表される重量平均分子量38000、ガラス転移温度130℃のビスフェノールアセトフェノン構造を含むフェノキシ樹脂Aを得た。
容量1Lの反応容器に、ビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製「jER828」、エポキシ当量186g/eq)100g、ビスフェノールアセトフェノン70g、およびシクロヘキサノン70gを入れ攪拌して溶解させた。次に、50wt%テトラメチルアンモニウムクロライド溶液0.4gを滴下し、窒素雰囲気下、180℃で5時間反応させた。反応終了後、析出物をろ過し、真空乾燥機にて、95℃で8時間真空乾燥し、構造式(5)で表される重量平均分子量46000、ガラス転移温度110℃のビスフェノールアセトフェノン構造を含むフェノキシ樹脂Bを得た。
容量1Lの反応容器に、ビスフェノールF型エポキシ樹脂(ジャパンエポキシレジン株式会社製・「jER806」、エポキシ当量168g/eq)100g、ビスフェノールアセトフェノン90g、およびシクロヘキサノン70gを入れ攪拌して溶解させた。次に、50wt%テトラメチルアンモニウムクロライド溶液0.4gを滴下し、窒素雰囲気下、180℃で5時間反応させた。反応終了後、析出物をろ過し、真空乾燥機にて、95℃で8時間真空乾燥し、構造式(6)で表される重量平均分子量21000、ガラス転移温度110℃のビスフェノールアセトフェノン構造を含むフェノキシ樹脂Cを得た。
上記で得られたフェノキシ樹脂A~C、及び、以下の原料を用い、実施例及び比較例の評価を行った。
(2)エポキシ樹脂B/ビスフェノールA型エポキシ樹脂:ジャパンエポキシレジン株式会社製・「jER828」、エポキシ当量186g/eq
(3)エポキシ樹脂C/ビスフェノールF型エポキシ樹脂:ジャパンエポキシレジン株式会社製・「jER806」、エポキシ当量168g/eq
(4)エポキシ樹脂D/ビフェニルジメチレン型エポキシ樹脂:日本化薬株式会社製・「NC-3000」、エポキシ当量275g/eq
(5)エポキシ樹脂E/アントラセン型エポキシ樹脂:ジャパンエポキシレジン株式会社製・「YX-8800」、エポキシ当量180g/eq
(6)エポキシ樹脂F/ナフタレン構造を有するノボラック型:DIC株式会社製、「HP-5000」、エポキシ当量250g/eq
(7)フェノキシ樹脂D/ビスフェノールA型エポキシ樹脂とビスフェノールF型エポキシ樹脂との共重合体であり、末端部はエポキシ基を有している:ジャパンエポキシレジン株式会社製・「jER4275」重量平均分子量60000
(8)フェノキシ樹脂E/ビフェニル型エポキシ樹脂とビスフェノールS型エポキシ樹脂との共重合体であり、末端部はエポキシ基を有している:ジャパンエポキシレジン株式会社製・「YX8100」重量平均分子量25000
(9)シアネート樹脂/ノボラック型シアネート樹脂:ロンザジャパン株式会社製・「プリマセットPT-30」、重量平均分子量700
(10)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:明和化成株式会社製「MEH-7851-3H」、水酸基当量220g/eq
(11)硬化促進剤/イミダゾール化合物:四国化成工業株式会社製・「キュアゾール1B2PZ(1-ベンジル-2-フェニルイミダゾール)」
(12)無機充填材:アドマテックス社製・「SO-25H」、平均粒子径0.5μm
(13)アクリルゴム粒子:三菱レイヨン株式会社製「W450A」、平均粒子径0.5μm
(14)ポリアクリル酸エステル:ビックケミー・ジャパン株式会社「BYK350」(重量平均分子量8000~15000)
(1)樹脂ワニスの調製
エポキシ樹脂D30.0重量部、フェノキシ樹脂A15重量部、シアネート樹脂19.8重量部、硬化促進剤0.2重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材35.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分60重量%の樹脂ワニスを調製した。
基材としてポリエチレンテレフタレートフィルム(三菱ポリエステルフィルム社製SFB38)に、上記で得られた樹脂ワニスを、コンマコーター装置を用いて乾燥後の絶縁フィルム(樹脂層)の厚さが40μmとなるように塗工し、これを150℃の乾燥装置で5分間乾燥して、基材付き樹脂シートを製造した。
所定の内層回路が両面に形成された内層回路基板の表裏に、上記で得られた基材付き樹脂シートの樹脂シート面を内側にして重ね合わせ、これを、真空加圧式ラミネーター装置を用いて、温度100℃、圧力1MPaにて真空加熱加圧成形させた。そして、基材付き樹脂シートから基材を剥離し、熱風乾燥装置にて170℃で60分間加熱し硬化させ、積層体を得た。
なお、内層回路基板としては、下記のものを使用した。
絶縁層:ハロゲンフリー FR-4材、厚さ0.4mm
導体層:銅箔厚み18μm、L/S=120/180μm、クリアランスホール1mmφ、3mmφ、スリット2mm
その後、積層体を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20分浸漬後、中和してビアホール内のデスミア処理を行った。
半導体素子(TEGチップ、サイズ15mm×15mm、厚み0.8mm)は、半田バンプはSn/Pb組成の共晶で形成され、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、上記多層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、液状封止樹脂は、温度150℃、120分の条件で硬化させた。
エポキシ樹脂D25.0重量部、フェノキシ樹脂A25.0重量部、フェノール硬化剤19.9重量部、硬化促進剤0.1重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材30.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
エポキシ樹脂A8.0重量部、エポキシ樹脂D10.0重量部、フェノキシ樹脂A12.0重量部、フェノール硬化剤9.9重量部、硬化促進剤0.1重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材60.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
エポキシ樹脂B15.0重量部、エポキシ樹脂D15.0重量部、フェノキシ樹脂B15.0重量部、シアネート樹脂19.8重量部、硬化促進剤0.2重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材35.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
エポキシ樹脂C14.0重量部、エポキシ樹脂D14.0重量部、フェノキシ樹脂C15.0重量部、シアネート樹脂17.8重量部、硬化促進剤0.2重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材35.0重量部とアクリルゴム粒子4.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
エポキシ樹脂D30.0重量部、フェノキシ樹脂D15.0重量部、シアネート樹脂19.8重量部、硬化促進剤0.2重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材35.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
エポキシ樹脂D40.0重量部、フェノキシ樹脂A5.0重量部、シアネート樹脂19.8重量部、硬化促進剤0.2重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材35.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
エポキシ樹脂B15.0重量部、エポキシ樹脂D15.0重量部、フェノキシ樹脂A4.0重量部、フェノール硬化剤24.4重量部、硬化促進剤0.1重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材37.5重量部とアクリルゴム粒子4.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
フェノキシ樹脂A45.0重量部、エポキシ樹脂D10.0重量部、シアネート樹脂9.8重量部、硬化促進剤0.2重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材35.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
フェノキシ樹脂A36.0重量部、エポキシ樹脂B16.0重量部、エポキシ樹脂D18.0重量部、フェノール硬化剤29.9重量部、硬化促進剤0.1重量部をメチルエチルケトンに溶解、分散させ、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
フェノキシ樹脂A6.0重量部、エポキシ樹脂E20重量部、シアネート樹脂34.0重量部、硬化促進剤0.2重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材40重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
フェノキシ樹脂E6.0重量部、エポキシ樹脂E20重量部、シアネート樹脂34.0重量部、硬化促進剤0.2重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材40重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
(1)めっき剥離強度
デスミア処理後の積層体について脱脂、触媒付与、活性化の工程を経た後、無電解銅メッキ皮膜を約1μmの厚みで形成した。その後、電解銅メッキ用レジスト層を厚さ25μmになるように形成し、前記銅メッキ皮膜の引き剥がし強度(90°ピール強度)をJIS C-6481にもとづいて測定した。
(2)リフロー耐熱性試験
上記半導体装置の半導体素子を実装する前の多層プリント配線板を用い、260℃リフロー炉に通し、多層プリント配線板の膨れの有無を目視にて確認した。多層プリント配線板は、リフロー炉に30回通した。
リフロー条件は、室温(25℃)から160℃まで徐々に昇温する(50~60秒)。次に、160℃~200℃まで、50~60秒かけて昇温する。その後、200℃から260℃まで65~75秒で昇温し、さらに、260~262℃の温度で5~10秒加熱(リフロー)する。その後、15分かけて30℃まで冷却する(放冷)条件である。
各符号は以下の通りである。
◎:30回繰り返しても膨れなし
○:10~29回目で膨れ発生
△:4~9回目で膨れ発生
×:3回目までに膨れ発生
(3)耐湿信頼性試験
耐湿信頼性は、上記半導体装置の半導体素子を実装する前のパッケージ用基板を用い、温度135℃、湿度85%の雰囲気下において、Line/Space=50μm/50μm配線の168時間経過後の絶縁抵抗値を評価した。試験はESPEC社製
各符号は以下の通りである。
◎:良好 抵抗値108Ω以上
△:実質上使用不可 抵抗値106Ω以上108Ω未満
×:使用不可 抵抗値106Ω未満
(4)熱衝撃性試験
上記半導体装置をフロリナート中で-55℃10分、125℃10分、-55℃10分を1サイクルとして、1000サイクル処理し、テストピースにクラックが発生していないか目視で確認した。
各符号は以下の通りである。
○:クラック発生なし
×:クラック発生
実施例I-1~I-5はいずれも、めっき剥離強度が高く、耐湿信頼性にも優れる半導体装置を得ることができた。特に本発明の半導体装置は、熱衝撃性に優れていることが明らかになった。
一方、比較例I-1は上記一般式(1)で表されるビスフェノールアセトフェノン構造を含まないフェノキシ樹脂を用いているため、耐熱性に劣り、耐湿信頼性試験および熱衝撃性試験で不良が発生した。比較例I-2およびI-3は、上記一般式(1)で表されるビスフェノールアセトフェノン構造を含むフェノキシ樹脂の含有量が不足しているため、耐熱性が劣り、リフロー耐熱性試験において脹れが発生し、耐湿信頼性試験において絶縁抵抗値が低下した。比較例I-4およびI-5は、上記一般式(1)で表されるビスフェノールアセトフェノン構造を含むフェノキシ樹脂の含有量が過剰であるため、適切なデスミア粗面が得られなかった。そのため、めっき剥離が起こりやすく、信頼性試験に耐えうるサンプルの作製ができなかった。比較例I-6およびI-7は、上記一般式(1)で表されるビスフェノールアセトフェノン構造を含むフェノキシ樹脂の含有量が不足しているため、耐熱性が劣り、耐湿信頼性試験および熱衝撃性試験で不良が発生した。
エポキシ樹脂D30.0重量部、フェノキシ樹脂A15.0重量部、シアネート樹脂19.2重量部、硬化促進剤0.2重量部、及びポリアクリル酸エステル0.6重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材35.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
エポキシ樹脂F30.0重量部、フェノキシ樹脂A15.0重量部、シアネート樹脂19.2重量部、硬化促進剤0.2重量部、及びポリアクリル酸エステル0.6重量部をメチルエチルケトンに溶解、分散させた。さらに、無機充填材35.0重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分50重量%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例I-1と同様にして、基材付き樹脂シート、多層プリント配線板及び半導体装置を得た。
十点平均粗さ(Rz)を非接触型三次元光干渉式表面粗さ計で測定した(日本ビーコ社製、WYKO NT1100)。
ここでのRzはJIS-B0601により定義されるものである。尚、評価サンプルは樹脂シートを銅張積層板の両面にラミネートし、PET基材を剥離後、170℃で60分反硬化、前述の粗化したものを用いた。
外層回路パターンの短絡、および断線の有無を金属顕微鏡で観察、および導通テストで判定した。また、断面から、配線形状の観察し評価を行った。尚、評価サンプルは、レーザー加工および外層回路において、L/S=20/20μmパターン形成したもの、L/S=10/10μmパターン形成したもの、L/S=8/8μmパターン形成したものを用いて測定を行った。
各符号は、以下の通りである。
◎:良好 (短絡、断線、剥離等なく、回路形状が正常である。)
○:実質上問題なし
△:実質上使用不可 (短絡、断線、又は剥離等の不具合がある場合)
×:使用不可 (短絡、断線、又は剥離等の不具合がある。)
上記合成例で得られたフェノキシ樹脂A~C、及び、以下の原料を用い、実施例及び比較例の評価を行った。尚、投入する重量部は、溶剤等を除く樹脂量を表す。
(2)エポキシ樹脂B’:ナフタレン構造を有するクレゾールノボラック型(DIC株式会社製「EXA-9900」、エポキシ当量270g/eq)
(3)エポキシ樹脂C’:ビスA型(ジャパンエポキシレジン株式会社製「jER828EL」、エポキシ当量190g/eq)
(4)エポキシ樹脂D’:ナフタレン型(DIC株式会社製「HP-4032」、エポキシ当量151g/eq)
(5)エポキシ樹脂E’:ナフタレン型(DIC株式会社製「 HP-4700」、エポキシ当量165g/eq)
(6)エポキシ樹脂F’:ホスフォフェナントレン変性ビスフェノールA型エポキシ樹脂(東都化成(株)製「FX305」、エポキシ当量504g/eq)
(7)エポキシ樹脂G’:ホスフォフェナントレン変性フェノールノボラックエポキシ樹脂(東都化成(株)製「FX289ZA」、エポキシ当量310g/eq)
(8)フェノキシ樹脂D’:ビフェニル型エポキシ樹脂とビスフェノールS型エポキシ樹脂との共重合体:ジャパンエポキシレジン株式会社製「YX-8100」重量平均分子量40000、ガラス転移温度150℃)
(9)フェノキシ樹脂E’:ビスフェノールA型エポキシ樹脂とビスフェノールF型エポキシ樹脂との共重合体:ジャパンエポキシレジン株式会社製「jER4275」重量平均分子量60000、ガラス転移温度75℃)
(10)フェノール硬化剤A’:日本化薬社製「GPH103」
(11)フェノール硬化剤B’:トリアジン環を有するクレゾールノボラック化合物(DIC社製フェノライト「LA-7054」60%溶液品)
(12)硬化促進剤A’:イミダゾール化合物(四国化成工業株式会社製「キュアゾール1B2PZ」)
(13)硬化促進剤B’:イミダゾール化合物(四国化成工業株式会社製「キュアゾール2E4MZ」)
(14)硬化促進剤C’:シアノエチルイミダゾール:四国化成工業社製「2E4MZ-CN」
(15)無機充填材:球状シリカ(アドマテックス社製「SO-25H」、平均粒子径0.5μm、5μm以上の粗粒カット)
(16)無機充填材:水酸化アルミニウム(昭和電工社製「HP-360」、平均粒子径3.0μm、0.1μm以下微粉カット)
(17)シアネート樹脂A’:ノボラック型(ロンザジャパン株式会社製「プリマセットPT-30」)
(18)シアネート樹脂B’:ビスA型プレポリマー(ロンザジャパン株式会社製「プリマセットBA230」)
(19)ビニルアセタール(積水化学工業社製「KS-1」)
(20)カップリング剤:エポキシシラン(信越化学工業社製「KBM-403E」)
(21)シアネート触媒:コバルトアセチルアセトナート(日本化学産業社製「ナーセム第二コバルト」)
(1)樹脂シートの製造
シアネート樹脂A’を30重量部、縮合環芳香族炭化水素構造を有するノボラック型エポキシ樹脂としてエポキシ樹脂A’を50重量部、前記合成例で得られたビスフェノールアセトフェノン構造を含むフェノキシ樹脂Aを20重量部、無機充填材として球状シリカを70重量部、硬化促進剤A’0.5重量部、カップリング剤を1重量部とを、メチルエチルケトンおよびシクロヘキサノンに混合溶解させた。次いで、高速攪拌装置を用いて60分間攪拌して、固形分重量60%の樹脂ワニスを調製した。尚、樹脂組成物中の無機充填材の割合は、約41重量%であった。
この基材付き樹脂シートを用い、実施例I-1と同様にして、多層プリント配線板及び半導体装置を得た。
フェノキシ樹脂Aの代わりに、フェノキシ樹脂Bを20量部用いた以外は、実施例II-1と同様にして、固形分重量60%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例II-1と同様にして、樹脂シート、多層プリント配線板、及び半導体装置を得た。
フェノキシ樹脂Aの代わりにフェノキシ樹脂Cを20重量部用いた以外は、実施例II-1と同様にして、固形分重量60%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例II-1と同様にして、樹脂シート、多層プリント配線板、及び半導体装置を得た。
エポキシ樹脂A’の代わりにエポキシ樹脂B’を50重量部用い、無機充填材として球状シリカの代わりに水酸化アルミニウムを70重量部用いた以外は、実施例II-3と同様にして、固形分重量60%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例II-1と同様にして、樹脂シート、多層プリント配線板及び半導体装置を得た。
無機充填材として球状シリカの代わりに水酸化アルミニウムを70重量部用いた以外は、実施例II-3と同様にして、固形分重量60%の樹脂ワニスを調製した。
この樹脂ワニスを用い、実施例II-1と同様にして、樹脂シート、多層プリント配線板及び半導体装置を得た。
再表03/099952号公報(実施例1)に開示のとおり、シアネート樹脂B’を45重量部、エポキシ樹脂C’を30重量部、フェノキシ樹脂D’を12重量部とを、メチルエチルケトンおよびシクロヘキサノンに混合溶解させた。さらに、無機充填材を30重量部添加して、高速攪拌装置を用いて10分間攪拌して、固形分60重量%の樹脂ワニスを調製した。尚、樹脂組成物中の無機充填材の割合は、約26重量%であった。
この樹脂ワニスを用い、実施例II-1と同様にして、樹脂シート、多層プリント配線板、及び半導体装置を得た。
特許3104589号公報に開示のとおり、シアネートB’を50重量部、エポキシD’を50重量部、フェノキシ樹脂なし、コバルトアセチルアセトナートを0.01重量部とを、メチルエチルケトンおよびシクロヘキサノンに混合溶解させた。さらに、無機充填材70重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分60重量%の樹脂ワニスを調製した。尚、樹脂組成物中の無機充填材の割合は、約41重量%であった。
この樹脂ワニスを用い、実施例II-1と同様にして、樹脂シート、多層プリント配線板、及び半導体装置を得た。
特開2007-254710号公報(実施例5)に開示のとおり、シアネート樹脂を含まず、エポキシC’を28重量部、エポキシE’を28重量部、フェノキシなし、フェノール硬化剤A’(ビフェニルジメチレン型:日本化薬工業株式会社製「GPH-103」、水酸基当量231/eq)を60重量部、硬化促進剤(四国化成工業株式会社製「キュアゾール2E4MZ」)を0.1重量部とを、メチルエチルケトンおよびシクロヘキサノンに溶解、分散させた。さらに、無機充填材を75重量部とビニルアセタールを5重量部添加して、高速攪拌装置を用いて10分間攪拌して、固形分60重量%の樹脂ワニスを調製した。尚、樹脂組成物中の無機充填材の割合は、約38重量%であった。
この樹脂ワニスを用い、実施例II-1と同様にして、樹脂シート、多層プリント配線板、及び半導体装置を得た。
特開2008-074929号公報(実施例5)に開示の通り、シアネート樹脂、およびフェノキシ樹脂を含まず、エポキシ樹脂F’及びG’(リン含有エポキシ、東都化成株式会社製「FX305」「FX289ZA」)を80(各40重量部)重量部、フェノール硬化剤B’(トリアジン含有クレゾールノボラック化合物:DIC社製フェノライト「LA-7054」60%溶液品、水酸基当量125g/eq)を20重量部、硬化促進剤C’(四国化成工業株式会社製「キュアゾール2E4MZ-CN」)を0.06重量部とを、メチルエチルケトンに溶解、分散させた。さらに、無機充填材30重量部を添加して、高速攪拌装置を用いて10分間攪拌して、固形分60重量%の樹脂ワニスを調製した。尚、樹脂組成物中の無機充填材の割合は、約23重量%であった。
この樹脂ワニスを用い、実施例II-1と同様にして、樹脂シート、多層プリント配線板、及び半導体装置を得た。
フェノキシE’を20重量部用いた以外は、実施例II-1と同じにした。尚、樹脂組成物中の無機充填材の割合は、41重量%であった。
この樹脂ワニスを用い、実施例II-1と同様にして、樹脂シート、多層プリント配線板、及び半導体装置を得た。
(1)熱膨張率
熱機械測定装置(TAインスツルメント社製)を用い、窒素雰囲気下、引っ張りモードで昇温速度10℃/min、温度25~300℃、荷重5g、2サイクル測定を行った。熱膨張率は、2サイクル目の温度25~150℃における平均線熱膨張係数とした。
尚、評価サンプルは、前記で得られた樹脂シートの絶縁樹脂層を2枚ラミネートし、続いて窒素雰囲気下の乾燥機により200℃で1時間、加熱硬化した樹脂板を用いて測定を行った。
表面粗度(Ra)を非接触型三次元光干渉式表面粗さ計(日本ビーコ社製、WYKO NT1100)で測定した。ここでのRaはJIS-B0601により定義されるものである。尚、評価サンプルは樹脂シートを銅張積層板の両面にラミネートし、PET基材を剥離後、170℃で60分反硬化、前述の粗化したものを用いた。
デスミア処理後の積層体について脱脂、触媒付与、活性化の工程を経た後、無電解銅メッキ皮膜を約1μmの厚みで形成した。その後、電解銅メッキ用レジスト層を厚さ25μmになるように形成し、前記銅メッキ皮膜の引き剥がし強度(90°ピール強度)をJIS C-6481にもとづいて測定した。
外層回路パターンの短絡、および断線の有無を金属顕微鏡で観察、および導通テストで判定。また、断面から、配線形状の観察し評価を行った。尚、評価サンプルは、レーザー加工および外層回路において、L/S=10/10μmパターン形成したものを用いて測定を行った。
各符号は、以下の通りである。
◎:良好 (短絡、断線、剥離等なく、回路形状が正常な場合)
○:実質上問題なし
×:使用不可 (短絡、断線、又は剥離等の不具合がある場合)
印加電圧3.3VDC、温度130℃、湿度85%の条件で、線間絶縁信頼性試験を行った。尚、評価サンプルは、前記L/S=10/10μmパターンで作製した基板上に、更に樹脂シートを積層したプリント配線板を用いた。
絶縁抵抗値が、1x108Ω未満になった時点で終了とした。
各符号は、以下の通りである。
◎:良好 500時間以上
○:実質上問題なし 200時間以上500時間未満
×:使用不可 200時間未満
前記で得られた半導体装置を、IPC/JEDECのJ-STD-20に準拠して、リフロー260℃リフローを3回行った。
リフロー条件は、室温(25℃)から160℃まで徐々に昇温する(50~60秒)。次に、160℃~200℃まで、50~60秒かけて昇温する。その後、200℃から260℃まで65~75秒で昇温し、さらに、260~262℃の温度で5~10秒加熱(リフロー)する。その後、15分かけて30℃まで冷却する(放冷)条件である。
評価は、超音波深傷検査装置で半導体装置の絶縁樹脂層の剥離、半導体素子裏面の剥離、および半田バンプの欠損等の異常の有無を評価した。
各符号は以下の通りである。
◎:Level2aの条件下で合格
○:Level3の条件下で合格
×:Level3の条件下で異常発生
また、本発明の樹脂シートは、導体回路の表面粗度が小さいので、プリント配線板に用いた際に、高周波特性にも優れることが期待できる。さらに、実施例II-1~II-5は、低粗度(Ra)でありながら、0.6km/m以上のめっきピール強度を有する。
本発明の樹脂シートは、実施例II-1~II-5でも明らかなように、微細配線回路でも非常に高い線間絶縁信頼性を有する結果であった。よって、薄型化、高密度化の半導体装置用のパッケージ基板に好適である。尚、実施例II-1およびII-5は、特に線間絶縁信頼性に優れ、実施例II-1およびII-5は、特に実装信頼性に優れる結果であった。
Claims (19)
- 前記樹脂組成物は、更に(D)無機充填材を含有することを特徴とする、請求の範囲第1項に記載のエポキシ樹脂組成物。
- 前記樹脂組成物は、更に(E)シアネート樹脂及び/又はそのプレポリマーを含有することを特徴とする、請求の範囲第1項又は第2項に記載のエポキシ樹脂組成物。
- 前記(A)エポキシ樹脂が、縮合環芳香族炭化水素構造を有するノボラック型エポキシ樹脂であることを特徴とする、請求の範囲第1項~第3項のいずれかに記載のエポキシ樹脂組成物。
- (A1)縮合環芳香族炭化水素構造を有するノボラック型エポキシ樹脂、(B)下記一般式(1)で表されるビスフェノールアセトフェノン構造を含むフェノキシ樹脂、(C)硬化剤、(D)無機充填材、及び(E)シアネート樹脂及び/又はそのプレポリマーを含有し、前記(B)フェノキシ樹脂が樹脂組成物の全固形分中に10~30重量%含有する、請求の範囲第1項~第4項のいずれかに記載のエポキシ樹脂組成物。
- 前記(C)硬化剤として、イミダゾール化合物を含有することを特徴とする、請求の範囲第1項~第5項のいずれかに記載のエポキシ樹脂組成物。
- 前記樹脂組成物は、更に、重量平均分子量が1.0×103~1.0×105のポリ(メタ)アクリル酸エステルを含有することを特徴とする、請求の範囲第1項~第6項のいずれかに記載のエポキシ樹脂組成物。
- 前記(B)一般式(1)で表されるビスフェノールアセトフェノン構造を有するフェノキシ樹脂が、更にビフェニル構造を有するものであることを特徴とする、請求の範囲第1項~第7項のいずれかに記載のエポキシ樹脂組成物。
- 前記(B)一般式(1)で表されるビスフェノールアセトフェノン構造を有するフェノキシ樹脂が、ガラス転移温度が120℃以上であることを特徴とする、請求の範囲第1項~第8項のいずれかに記載のエポキシ樹脂組成物。
- 前記(D)無機充填材の粒径は、0.2μm~5μmであることを特徴とする、請求の範囲第2項~第9項のいずれかに記載のエポキシ樹脂組成物。
- 前記(D)無機充填材は、シリカ、及び/または水酸化アルミニウムであることを特徴とする、請求の範囲第2項~第10項のいずれかに記載のエポキシ樹脂組成物。
- 樹脂組成物の全固形分中に、前記(A)エポキシ樹脂の含有量が5~80重量%、前記(B)フェノキシ樹脂の含有量が10~30重量%、前記(C)硬化剤の含有量が0.01~25重量%であることを特徴とする、請求の範囲第1項~第11項のいずれかに記載のエポキシ樹脂組成物。
- 樹脂組成物の全固形分中に、前記(A)エポキシ樹脂の含有量が5~60重量%、前記(B)フェノキシ樹脂の含有量が10~30重量%、前記(C)硬化剤の含有量が0.01~15重量%、前記(D)無機充填材の含有量が10~75重量%であることを特徴とする、請求の範囲第2項~第12項のいずれかに記載のエポキシ樹脂組成物。
- 樹脂組成物の全固形分中に、(A1)縮合環芳香族炭化水素構造を有するノボラック型エポキシ樹脂の含有量が10~60重量%、前記(B)フェノキシ樹脂の含有量が10~30重量%、前記(C)硬化剤の含有量が0.01~5重量%、前記(D)無機充填材の含有量が10~70重量%、及び(E)シアネート樹脂及び/又はそのプレポリマーの含有量が5~60重量%であることを特徴とする、請求の範囲第5項~第13項のいずれかに記載のエポキシ樹脂組成物。
- 請求の範囲第1項~第14項のいずれかに記載のエポキシ樹脂組成物からなる樹脂層を基材上に形成してなる樹脂シート。
- 請求の範囲第1項~第14項のいずれかに記載のエポキシ樹脂組成物をガラス繊維基材に含浸させてなるプリプレグ。
- 請求の範囲第15項に記載の樹脂シートを、内層回路基板の内層回路パターンが形成された面に重ね合わせて連続積層する工程、及び導体回路層をセミアディティブ法で形成する工程を含む多層プリント配線板の製造方法。
- 請求の範囲第15項に記載の樹脂シート、または請求の範囲第16項に記載のプリプレグを、内層回路板の片面または両面に重ね合わせて加熱加圧成形してなる多層プリント配線板。
- 請求の範囲第18項に記載の多層プリント配線板に半導体素子を実装してなる半導体装置。
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US12/921,401 US8969490B2 (en) | 2008-03-25 | 2009-03-24 | Epoxy resin composition, resin sheet, prepreg, multilayer printed wiring board and semiconductor device |
KR1020107021309A KR101524898B1 (ko) | 2008-03-25 | 2009-03-24 | 에폭시 수지 조성물, 수지 시트, 프리프레그, 다층 프린트 배선판 및 반도체 장치 |
CN200980110301.7A CN101977984B (zh) | 2008-03-25 | 2009-03-24 | 环氧树脂组合物、树脂片、半固化片、多层印刷布线板及半导体装置 |
JP2010505684A JP5510314B2 (ja) | 2008-03-25 | 2009-03-24 | エポキシ樹脂組成物、樹脂シート、プリプレグ、多層プリント配線板および半導体装置 |
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WO2007129662A1 (ja) * | 2006-05-08 | 2007-11-15 | Sekisui Chemical Co., Ltd. | 絶縁材料、電子部品装置の製造方法及び電子部品装置 |
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JP2014028905A (ja) * | 2012-07-31 | 2014-02-13 | Arisawa Manufacturing Co Ltd | エポキシ樹脂組成物 |
JP2016020473A (ja) * | 2014-06-17 | 2016-02-04 | 大阪ガスケミカル株式会社 | フルオレン骨格を有するフェノキシ樹脂及びその製造方法並びに成形体 |
WO2016047682A1 (ja) * | 2014-09-25 | 2016-03-31 | 積水化学工業株式会社 | 樹脂フィルム及び積層フィルム |
JP2015010232A (ja) * | 2014-10-16 | 2015-01-19 | 太陽インキ製造株式会社 | 熱硬化性組成物、ドライフィルムおよびプリント配線板 |
JP2017031311A (ja) * | 2015-07-31 | 2017-02-09 | 大阪ガスケミカル株式会社 | フルオレン骨格を有するフェノキシ樹脂及びその製造方法並びに成形体 |
JP2018100327A (ja) * | 2016-12-19 | 2018-06-28 | パナソニックIpマネジメント株式会社 | プリプレグ、金属張積層板及びプリント配線板 |
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US8969490B2 (en) | 2015-03-03 |
KR20110002838A (ko) | 2011-01-10 |
JP5510314B2 (ja) | 2014-06-04 |
KR101524898B1 (ko) | 2015-06-01 |
JPWO2009119598A1 (ja) | 2011-07-28 |
TW200944549A (en) | 2009-11-01 |
TWI444398B (zh) | 2014-07-11 |
US20110007489A1 (en) | 2011-01-13 |
CN101977984A (zh) | 2011-02-16 |
CN101977984B (zh) | 2014-03-26 |
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