WO2014112464A1 - 樹脂組成物、プリプレグ、積層板、金属箔張積層板及びプリント配線板 - Google Patents
樹脂組成物、プリプレグ、積層板、金属箔張積層板及びプリント配線板 Download PDFInfo
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- WO2014112464A1 WO2014112464A1 PCT/JP2014/050430 JP2014050430W WO2014112464A1 WO 2014112464 A1 WO2014112464 A1 WO 2014112464A1 JP 2014050430 W JP2014050430 W JP 2014050430W WO 2014112464 A1 WO2014112464 A1 WO 2014112464A1
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- BDQNKCYCTYYMAA-UHFFFAOYSA-N O=C=Nc1cccc2c1cccc2 Chemical compound O=C=Nc1cccc2c1cccc2 BDQNKCYCTYYMAA-UHFFFAOYSA-N 0.000 description 2
- 0 CC(*)(*)c1ccccc1 Chemical compound CC(*)(*)c1ccccc1 0.000 description 1
- QBEHLJLSCSIDPE-UHFFFAOYSA-N Cc1c(ccc(Oc2cc(cc(cc3)Oc4ccc(ccc(OCC5OC5)c5)c5c4)c3cc2)c2)c2cc(OCC2OC2)c1 Chemical compound Cc1c(ccc(Oc2cc(cc(cc3)Oc4ccc(ccc(OCC5OC5)c5)c5c4)c3cc2)c2)c2cc(OCC2OC2)c1 QBEHLJLSCSIDPE-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on 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
- 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
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
- C08K2201/011—Nanostructured additives
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0239—Coupling agent for particles
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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]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
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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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
- Y10T442/2992—Coated or impregnated glass fiber fabric
Definitions
- the present invention relates to a resin composition, a prepreg, a laminate, a metal foil-clad laminate, and a printed wiring board.
- the present inventors have found that the following problems occur when a laminate is filled with a high ratio in order to impart characteristics such as low thermal expansion and high thermal conductivity.
- the volume ratio of the resin composition is reduced and the fluidity is lowered.
- the viscosity of the prepreg obtained by impregnating the resin composition into a substrate such as glass cloth and semi-curing is deteriorated.
- Cracks and voids are generated in the metal foil-clad laminate obtained by stacking and curing such a prepreg with a metal foil, and the moldability deteriorates.
- Due to the generation of voids, moisture absorption heat resistance, elastic modulus of the metal foil-clad laminate, and adhesion strength between the copper foil and the insulating layer of the laminate are deteriorated.
- the present invention has been made in view of the above problems, and its purpose is to produce a prepreg whose viscosity is low enough to be convenient for producing a metal foil-clad laminate, and is excellent in moisture absorption heat resistance.
- Another object of the present invention is to provide a resin composition capable of producing a metal foil-clad laminate, and a prepreg, laminate and printed wiring board produced using the resin composition.
- the present invention is as follows.
- [1] Contains alumina and / or boehmite nanoparticles (A) having an average particle size of 1.0 to 100 nm, fine particles (B) having an average particle size of 0.20 to 100 ⁇ m, and a thermosetting resin (C).
- A alumina and / or boehmite nanoparticles
- B fine particles
- C a thermosetting resin
- thermosetting resin (C) is selected from the group consisting of a cyanate ester compound (D), a phenol resin (E), a maleimide compound (F), an epoxy resin (G), and a BT resin (H).
- cyanate ester compound (D) is a compound represented by the following formula (2) and / or the following formula (3).
- each R 5 independently represents a hydrogen atom or a methyl group, and n 1 represents an integer of 1 or more.
- each R 6 independently represents a hydrogen atom or a methyl group, and n 2 represents an integer of 1 or more.
- the maleimide compound (F) is bis (4-maleimidophenyl) methane, 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ propane, bis (3-ethyl-5-methyl-4) -Maleimidophenyl) Any one of the above resin compositions selected from the group consisting of methane and a maleimide compound represented by the following formula (6).
- each R 9 independently represents a hydrogen atom or a methyl group, and n 5 represents an integer of 1 or more.
- the epoxy resin (G) is one or more selected from the group consisting of compounds represented by the following formulas (7), (8), (9), (11) and (12): Any resin composition.
- each R 10 independently represents a hydrogen atom or a methyl group, and n 6 represents an integer of 1 or more.
- each of R 11 independently represents a hydrogen atom or a methyl group, and n 7 represents an integer of 1 or more.
- each R 12 independently represents a hydrogen atom or a methyl group, and n 8 represents an integer of 1 or more.
- each R 13 independently represents a hydrogen atom or a methyl group.
- each R 14 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group having 1 to 4 carbon atoms in the alkyl moiety.
- the phenol resin (E) is a cresol novolac type phenol resin, an aminotriazine novolac type phenol resin, a naphthalene type phenol resin, a naphthol aralkyl type phenol resin represented by the following formula
- Ar independently represents a phenyl group, a naphthyl group, a biphenyl group or an anthracenyl group, or a hydroxyl group-modified product thereof
- R 15 represents a hydrogen atom, an alkyl group, a hydroxyl group-modified product thereof, or an aryl group.
- thermosetting resin (C) contains the cyanate ester compound (D) in an amount of 10 to 60 parts by mass relative to 100 parts by mass of the total amount of the thermosetting resin (C). Resin composition.
- thermosetting resin (C) contains the phenol resin (E) in an amount of 10 to 60 parts by mass with respect to 100 parts by mass of the total amount of the thermosetting resin (C).
- Composition [15] Any of the above, wherein the thermosetting resin (C) contains the maleimide compound (F) in an amount of 3.0 to 50 parts by mass with respect to 100 parts by mass of the total amount of the thermosetting resin (C). Resin composition.
- thermosetting resin (C) contains 10 to 80 parts by mass of the epoxy resin (G) with respect to 100 parts by mass of the total amount of the thermosetting resin (C).
- Composition. Any one of the above resins, wherein the thermosetting resin (C) contains 20 to 80 parts by mass of the BT resin (H) with respect to 100 parts by mass of the total amount of the thermosetting resin (C).
- Composition. [18] The resin composition according to any one of the above, wherein the nanoparticles (A) are alumina nanoparticles.
- a prepreg containing a base material and any one of the resin compositions impregnated or coated on the base material.
- the prepreg wherein the base material is at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers.
- a metal foil-clad laminate comprising any one of the above prepregs and a metal foil laminated on the prepreg.
- a printed wiring board including an insulating layer and a conductor layer formed on a surface of the insulating layer, wherein the insulating layer includes any one of the above resin compositions.
- the present invention it is possible to produce a prepreg whose viscosity is low enough to be convenient for producing a metal foil-clad laminate, and it is possible to produce a metal foil-clad laminate excellent in moisture absorption heat resistance Resin compositions, and prepregs, laminates and printed wiring boards produced using the resin compositions can be provided.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
- the following embodiment is an exemplification for explaining the present invention, and the present invention is not limited to the embodiment, and various modifications can be made without departing from the gist thereof.
- the resin composition of the present embodiment includes alumina and / or boehmite nanoparticles (A) having an average particle size of 1.0 to 100 nm, fine particles (B) having an average particle size of 0.20 to 100 ⁇ m, and a thermosetting resin.
- the nanoparticle (A) containing (C) has its surface treated with a polysiloxane-based modifier.
- alumina is aluminum oxide represented by the chemical formula of Al 2 O 3
- boehmite is alumina. It is a hydrate.
- the nanoparticle (A) is not particularly limited as long as it has a mean particle size (D50) of 1.0 nm to 100 nm.
- Examples of alumina include ⁇ -type alumina, ⁇ -type alumina, ⁇ -type alumina, and ⁇ -type alumina.
- D50 is a median diameter (median diameter), and when the particle size distribution of the measured powder is divided into two, the volume on the large side and the volume on the small side are the total powder
- the particle diameter when occupying 50% of the particle diameter is generally measured by a wet laser diffraction / scattering method.
- Such a nanoparticle (A) is considered to have an effect of entering between a plurality of fine particles (B) (hereinafter also referred to as “filler”), which will be described in detail later, and lubricating the filler in the resin composition. It is done. Therefore, even when the filler content in the resin composition is large, aggregation of the fillers can be prevented, and various problems expected when the filler content is large in the obtained laminate can be solved. From the viewpoint of exhibiting such an effect more effectively and reliably, the nanoparticles (A) preferably include alumina nanoparticles.
- the production method of the nanoparticles (A) used in the present embodiment is not particularly limited, and commercially available products may be used.
- the manufacturing method of an alumina nanoparticle (A) is not specifically limited, Since it is non-porous and small in volume, it is preferable to manufacture by plasma vapor phase synthesis.
- Plasma vapor phase synthesis is a manufacturing method in which a metal or metal oxide is evaporated at high temperature by plasma energy, a reaction gas such as oxygen is added, and then cooled.
- thermosetting resin (C) Since the restraint of the thermosetting resin (C) due to the surface of the alumina nanoparticles, which causes deterioration of the moldability, can be suppressed by the small volume, the effect of improving the moldability by the alumina nanoparticles more effectively and reliably. Can be obtained.
- the nanoparticles (A) used in the present embodiment have a reactive group.
- the reactive group include a hydroxyl group and a group having a halogen atom.
- a hydroxyl group is preferable, and it is preferable that the hydroxyl group is arranged so as to react with a modifier described later.
- the nanoparticles (A) used in the present embodiment are subjected to surface treatment.
- This surface treatment is performed using a polysiloxane-based modifier, that is, a modifier having a polysiloxane skeleton as a main skeleton.
- the modifier is preferably one that adsorbs to the surface of the nanoparticle (A) by chemical interaction, and examples thereof include polysiloxane represented by the following formula (1), which is preferred.
- x is an integer of 0 to 2
- y is an integer of 1 to 10, preferably 2 to 5
- R 1 is 1 It represents a monovalent organic group having ⁇ 18, preferably 1 to 10, more preferably 1 to 3 carbon atoms.
- R 2 represents a monovalent organic group which may have a heteroatom and / or a substituent, preferably represents a hydroxyl group or a hydrolyzable group, and has 1 to 6 hydrolyzable groups, preferably A linear, branched or cyclic alkoxy group having 1 to 2 carbon atoms; preferably a halogen atom which is a chlorine atom; a carboxylic acid group having 1 to 4 and preferably 1 to 2 carbon atoms.
- R 3 represents a divalent organic group which may have a hetero atom or a substituent, preferably an oxygen atom; a linear or branched (preferably linear) alkylene group having 1 to 8 carbon atoms
- R 4 is a monovalent or polyvalent substituent having 4 to 200 siloxane structural units and an alkyl group having 1 to 18 carbon atoms on a silicon atom, wherein the alkyl group having 1 to 18 carbon atoms is a polyether.
- One or more modifying groups selected from a group having a group (G1), a group having a polyester group (G2), a group having an allylalkyl group (G3), and a group having a perfluorinated alkyl group (G4) Partially and independently substituted by (G).
- the surface of the nanoparticles (A) is selectively treated with a modifier, thereby improving the lubricity when the nanoparticles (A) that have entered between the fine particles (B) come into contact with each other. Therefore, it is thought that it can contribute more effectively to the viscosity reduction of the prepreg.
- the said modifier is a thing which is hard to react with a thermosetting resin (C)
- it can prevent that a nanoparticle (A) is restrained by a thermosetting resin (C), and is more effective. Therefore, it becomes possible to improve lubricity.
- the surface treatment may be used in combination with one or more dispersion aids selected from the group consisting of phosphate esters, phosphate ester salts, and alkylbenzene sulfonic acids.
- dispersion aids such as phosphate esters and alkylbenzene sulfonic acids are used as auxiliary agents to prevent steric hindrance on the particle surface. By forming, the dispersion state can be stabilized.
- the group (G1) having a polyether group is represented by the following formula (1A): In which R ′ is preferably a hydrogen atom, a phenyl group or an alkyl group.
- the group (G1) preferably has a molecular weight in the range of 116 to 15,000 daltons.
- the group (G2) having a polyester group is a group having an aliphatic, alicyclic and / or aromatic polyester group, or a group having one of these groups; the following formula (1B) And a group represented by the following formula (1C) It is preferable to have at least one selected from the group consisting of groups represented by The group (G2) preferably has a molecular weight in the range of 344 to 4000 daltons, more preferably in the range of 500 to 2000 daltons, and still more preferably in the range of 500 to 1500 daltons.
- the group (G3) having an allylalkyl group is preferably a phenylpropyl group or a group having this group, and the phenylpropyl group is more preferably a 2-phenylpropyl group.
- the group (G4) having a perfluorinated alkyl group is preferably a perfluorinated alkyl group having 3 to 8 carbon atoms or a group having this group.
- the group (G4) is preferably a tetrahydroperfluorinated alkyl group having 3 to 8 carbon atoms or a group having this group, and the tetrahydroperfluorinated alkyl group is 1,1,2,2 -A tetrahydroperfluorinated alkyl group is more preferred.
- the nanoparticles (A) preferably contain 0.01 to 50% by mass, more preferably 0.05 to 30% by mass of the above modifier with respect to the total amount of the nanoparticles (A). More preferably, the content is 1 to 15% by mass.
- the nanoparticles (A) are preferably dispersed as primary particles in a solvent or resin. As described above, the nanoparticles are stably present as primary particles in the resin composition, so that the nanoparticles (A) can sufficiently exhibit the effect as a lubricant for the fine particles (B). Become. Moreover, although the shape of a nanoparticle (A) is not specifically limited, From a viewpoint of improving the fluidity
- nanoparticles (A) in the present embodiment commercially available products that have been subjected to dispersion treatment can also be used.
- An example of a product of alumina nanoparticles is NANOBYK-3610 (product name) manufactured by Big Chemie.
- An example of a product of boehmite nanoparticles is LP-X-21121 (product name) manufactured by Big Chemie.
- the content of the nanoparticles (A) used in the present embodiment in the resin composition is preferably 0.01 to 10.0% by mass with respect to the total mass (100% by mass) of the fine particles (B). .
- the content of the nanoparticles (A) is more preferably 0.1 to 5.0% by mass with respect to the total mass of the fine particles (B).
- total mass of the fine particles (B) refers to the total mass of various inorganic fillers, organic fillers, and organic / inorganic composite fillers described later.
- Examples of the fine particles (B) having an average particle size of 0.20 ⁇ m to 100 ⁇ m used in the resin composition of the present embodiment include inorganic fillers, organic fillers, and inorganic / organic composite fillers. More specifically, for example, silica such as natural silica, fused silica, amorphous silica, and hollow silica, alumina, aluminum nitride, boron nitride, boehmite, molybdenum oxide, titanium oxide, silicone rubber, silicone composite powder, zinc borate Zinc stannate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass fibers (glass fine powders such as E glass and D glass), hollow glass, and spherical glass.
- silica such as natural silica, fused silica, amorphous silica, and hollow silica
- alumina aluminum nitride, boron n
- These fine particles (B) can be used alone or in combination of two or more.
- silica is preferable from the viewpoint of easily having lower thermal expansibility
- alumina and aluminum nitride are preferable from the viewpoint of easily having higher thermal conductivity.
- the average particle diameter (D50) of the fine particles (B) is required to be 0.20 ⁇ m to 100 ⁇ m from the viewpoint of the nanoparticles (A) entering the gaps and sufficiently fulfilling the role as a lubricant. Further, the average particle diameter is preferably 0.20 ⁇ m to 10 ⁇ m from the viewpoint of forming a finer wiring, and more preferably 0.20 ⁇ m to 5 ⁇ m.
- the shape of the fine particles (B) is not particularly limited, but is preferably spherical from the viewpoint of moldability.
- the content of the fine particles (B) in the present embodiment in the resin composition is 200 parts by mass or more with respect to 100 parts by mass of the thermosetting resin (C) from the viewpoint of the characteristics of the fine particles (B) given to the resin composition. It is preferable that it is 250 mass parts or more.
- fine-particles (B) is not specifically limited, It is preferable that it is 500 mass parts or less, and it is more preferable that it is 400 mass parts or less from a viewpoint of improving a moldability.
- the content of the fine particles (B) may be 1100 parts by mass or less. Preferably, it is 700 parts by mass or less.
- the resin composition of the present embodiment includes a silane coupling agent and / or Or it may contain a wetting and dispersing agent.
- the silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances.
- aminosilanes such as ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, epoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane
- vinylsilanes such as ⁇ -methacryloxypropyltrimethoxysilane
- cationic silanes such as N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride
- phenylsilanes phenylsilanes.
- a silane coupling agent can also be used individually by 1 type or in combination of 2 or more types.
- the wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for coatings.
- examples of the wetting and dispersing agent include a wetting and dispersing agent such as Disperbyk-110, 111, 180, 161, BYK-W996, W9010, and W903 (product names) manufactured by Big Chemie Japan Co., Ltd.
- thermosetting resin (C) in the resin composition of the present embodiment is not particularly limited as long as it is a resin that is cured by heat.
- a thermosetting resin (C) can be used individually by 1 type or in combination of 2 or more types.
- the cyanate ester compound (D) has excellent properties such as chemical resistance and adhesiveness, it can be suitably used as a component of the resin composition in the present embodiment.
- a kind of cyanate ester compound (D) For example, the naphthol aralkyl type cyanate ester compound represented by following formula (2), the novolak type cyanate ester represented by following formula (3) Biphenylaralkyl cyanate, bis (3,5-dimethyl4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1 , 3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2, , 7-dicyanatonaphthalene, 1,
- a naphthol aralkyl cyanate ester compound represented by the following formula (2), a novolac cyanate ester represented by the following formula (3), and a biphenylaralkyl cyanate ester are further excellent in flame retardancy, This is particularly preferable since it has higher curability and has a lower thermal expansion coefficient.
- each R 5 independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
- N 1 represents an integer of 1 or more. The upper limit of n 1 is usually 10, preferably 6.
- each R 6 independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
- N 2 represents an integer of 1 or more. the upper limit value of n 2 is usually 10, preferably 7.
- cyanate ester compounds are not particularly limited, and any method existing as cyanate ester synthesis may be used. Specifically, it can be obtained by reacting a naphthol aralkyl type phenol resin represented by the following formula (4) with cyanogen halide in the presence of a basic compound in an inert organic solvent. Alternatively, a similar salt formed of a naphthol aralkyl type phenolic resin and a basic compound is formed in a solution containing water, and then a two-phase interface reaction with cyanogen halide is performed to obtain a synthetic method. .
- each R 7 independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
- N 3 represents an integer of 1 or more. upper limit of n 3 is usually 10, preferably 6..
- the naphthol aralkyl cyanate ester compounds include naphthols such as ⁇ -naphthol or ⁇ -naphthol, p-xylylene glycol, ⁇ , ⁇ '-dimethoxy-p-xylene, and 1,4-di (2-hydroxy). It can be selected from those obtained by condensing naphthol aralkyl resin obtained by reaction with -2-propyl) benzene and cyanic acid.
- the cyanate group number CN of the cyanate ester compound (D) and the epoxy of the epoxy resin (G) From the viewpoint of heat resistance, flame retardancy, and water absorption, it is preferable to contain them so that the ratio (CN / Ep) to the number Ep is 0.7 to 2.5.
- the content of the cyanate ester compound (D) in the thermosetting resin (C) is determined from the viewpoint of curability and heat resistance. ) Is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass with respect to 100 parts by mass in total.
- the total amount of the thermosetting resin (C) is the heat of the cyanate ester compound (D), phenol resin (E), maleimide compound (F), epoxy resin (G), BT resin (H), etc. This means the total amount of the curable resin, and the total amount does not include the curing accelerator, the wetting dispersant added to the fine particles (B), and the silane coupling agent.
- a phenol resin (E) if it is resin which has two or more phenolic hydroxyl groups in 1 molecule, a well-known thing can be used suitably, The kind is not specifically limited.
- the phenol resin (E) include a cresol novolak type phenol resin, a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A type novolak resin, a dicyclopentadiene type phenol resin, a zylock type phenol resin, a terpene modified phenol resin, and a polyvinyl phenol.
- naphthol aralkyl type phenol resin represented by the above formula (4) biphenyl aralkyl type phenol resin, naphthalene type phenol resin and aminotriazine novolac type phenol resin represented by the following formula (5). These can be used singly or in combination of two or more according to the purpose.
- a cresol novolac type phenol resin an aminotriazine novolac type phenol resin, a naphthalene type phenol resin, a naphthol aralkyl type phenol resin represented by the above formula (4), and the following formula
- the biphenyl aralkyl type phenol resin represented by (5) is preferable, and in particular, a cresol novolac type phenol compound, a naphthol aralkyl type phenol resin represented by the above formula (4), and a biphenyl aralkyl represented by the following formula (5):
- a type phenolic resin is more preferable.
- each R 8 independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
- N 4 represents an integer of 1 or more. upper limit of n 4 is usually 10, preferably 7.
- the content of the phenol resin (E) in the thermosetting resin (C) is that of the thermosetting resin (C) from the viewpoint of curability and heat resistance.
- the total amount is preferably 100 to 60 parts by mass, more preferably 20 to 50 parts by mass.
- the maleimide compound (F) is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ propane, bis (3,5 -Dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, and the following formula (6) And maleimide compounds, prepolymers of these maleimide compounds, and prepolymers of these maleimide compounds and amine compounds.
- each R 9 independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
- N 5 represents an integer of 1 or more. upper limit of n 5 is usually 10, preferably 7.
- the content of the maleimide compound (F) in the thermosetting resin (C) is that of the thermosetting resin (C).
- the amount is preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass with respect to the total amount of 100 parts by mass.
- the epoxy resin (G) is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type Epoxy resin, biphenyl type epoxy resin, aralkyl novolac type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, glycidylamine, glycidyl Examples include compounds obtained by epoxidizing double bonds such as esters and butadiene, and compounds obtained by reaction of hydroxyl-containing silicone resins with epichlorohydrin.
- each R 10 independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
- N 6 represents an integer of 1 or more.
- upper limit of n 6 represents, usually 10, preferably 7.
- each R 11 independently represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
- N 7 represents an integer of 1 or more. The upper limit of n 7 is usually 10, preferably 7.
- R 12 represents a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable.
- N 8 represents an integer of 1 or more. upper limit of n 8 is usually 10, preferably 7.
- each R 13 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group having 1 to 4 carbon atoms in the alkyl moiety.
- each R 14 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group having 1 to 4 carbon atoms in the alkyl moiety.
- the epoxy resin represented by the above formula (11) or (12) a commercially available product can be used. Examples of products include DIC Corporation, EXA-7311, EXA-7311-G3, and EXA-7311-. G4, EXA-7311-G4S, EXA-7311L, HP-6000, and EXA-7311-G5 (product name).
- the content of the epoxy resin (G) in the thermosetting resin (C) is that of the thermosetting resin (C).
- the total amount is preferably 100 to 80 parts by mass, more preferably 20 to 70 parts by mass.
- BT resin (H) is polymerized by dissolving a cyanate ester compound and a maleimide compound in a solvent-free or organic solvent such as methyl ethyl ketone, N-methyl pyrodrine, dimethylformamide, dimethylacetamide, toluene and xylene, and mixing them by heating. It is a thing.
- the cyanate ester compound used for the synthesis of the BT resin (H) is not particularly limited.
- a naphthol aralkyl type cyanate ester compound represented by the above formula (2) a novolak type cyanide represented by the above formula (3)
- Acid ester biphenylaralkyl type cyanate ester, bis (3,5-dimethyl4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis ( 4-cyanatophen
- a naphthol aralkyl cyanate ester compound represented by the above formula (2) a novolac cyanate ester represented by the above formula (3), and a biphenyl aralkyl cyanate ester are obtained. From the viewpoints of flame retardancy, curability, and low thermal expansion, it is preferable. Also, the maleimide compound is not particularly limited.
- maleimide compounds represented by formula (6) prepolymers of these maleimide compounds, and prepolymers of these maleimide compounds and amine compounds. These may be used alone or in combination of two or more.
- the ratio of the maleimide compound in the BT resin (H) is not particularly limited, but is preferably in the range of 5 to 75% by mass with respect to the total amount of the BT resin (H) from the viewpoint of glass transition temperature, flame retardancy, and curability. A range of 10 to 70% by mass is more preferable. Further, the range of the molecular weight of the prepolymer BT resin (H) is not particularly limited, but from the viewpoint of handling properties, glass transition temperature, and curability, the number average molecular weight is in the range of about 100 to 100,000. Preferably there is.
- thermosetting resin (C) When BT resin (H) is used in this embodiment, from the viewpoint of curability and heat resistance, the content of BT resin (H) in thermosetting resin (C) is the same as that of thermosetting resin (C).
- the amount is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass with respect to the total amount of 100 parts by mass.
- the resin composition of this embodiment further contains an imidazole compound represented by the following formula (13).
- This imidazole compound has an effect of accelerating curing and has an effect of further increasing the glass transition temperature of the cured product.
- Ar independently represents a phenyl group, a naphthyl group, a biphenyl group or an anthracenyl group, or a hydroxyl group-modified product thereof, and a phenyl group is preferable.
- R 15 represents a hydrogen atom, an alkyl group, a hydroxyl group-modified product thereof, or an aryl group, and the aryl group is preferably a phenyl group. More preferably, both Ar and R 15 are phenyl groups.
- the content of the imidazole compound in the thermosetting resin (C) is based on 100 parts by mass of the total amount of the thermosetting resin (C).
- the content is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass.
- curing accelerators can be used in combination with the imidazole compound as long as the desired characteristics are not impaired.
- examples of such a curing accelerator include organic peroxides exemplified by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide and di-tert-butyl-di-perphthalate; Azo compounds such as bisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N- Tertiary amines such as methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin and
- the resin composition of the present embodiment may contain a solvent as necessary.
- a solvent for example, when an organic solvent is used, the viscosity at the time of preparing the resin composition can be further reduced, handling properties are improved, and impregnation properties into a glass cloth are further enhanced.
- the kind of solvent will not be specifically limited if it can melt
- Specific examples thereof include, for example, ketones such as acetone, methyl ethyl ketone and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; and propylene glycol methyl ether and its acetate.
- a solvent can be used individually by 1 type or in combination of 2 or more types.
- the resin composition in the present embodiment can be prepared according to a conventional method. Nanoparticles (A) having an average particle size of 1.0 nm to 100 nm, fine particles (B) having an average particle size of 0.20 ⁇ m to 100 ⁇ m, and
- the preparation method is not particularly limited as long as it is a method by which a thermosetting resin (C) and a resin composition containing the other optional components described above can be obtained uniformly.
- the resin composition of this embodiment can be easily prepared by sequentially blending the nanoparticles (A), the fine particles (B), and the thermosetting resin (C) in a solvent and stirring them sufficiently. .
- the nanoparticles (A) are preferably preliminarily surface-treated with a polysiloxane-based modifier and then stirred, mixed and kneaded with other components from the viewpoint of further reducing the viscosity of the prepreg.
- an organic solvent can be used as necessary.
- the kind of the organic solvent is not particularly limited as long as it can dissolve the thermosetting resin (C). Specific examples thereof are as described above.
- the dispersibility of the fine particles (B) with respect to the resin composition can be further improved by subjecting the fine particles (B) to a stirring dispersion treatment using a stirrer equipped with a stirrer having an appropriate stirring ability.
- the above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill, a bead mill or the like, or a revolution / spinning type mixing device.
- the prepreg of the present embodiment contains a base material and the above resin composition impregnated or coated on the base material.
- This prepreg can be obtained by impregnating or applying the above resin composition to a substrate.
- the preparation of the prepreg can be performed according to a conventional method, and is not particularly limited. For example, after impregnating or applying the resin composition of the present embodiment to a base material, it is semi-cured (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes.
- the prepreg of this embodiment can be produced.
- the prepreg of the present embodiment is not particularly limited, but the amount of the resin composition with respect to the total amount of prepreg is preferably in the range of 30 to 90% by mass.
- the substrate used in the present embodiment is not particularly limited, and known materials used for various printed wiring board materials may be appropriately selected and used depending on the intended use and performance. it can. Specific examples thereof include glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass and T glass, inorganic fibers other than glass such as quartz, polyparaphenylene terephthalamide (Kevlar), and the like.
- glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass and T glass
- inorganic fibers other than glass such as quartz, polyparaphenylene terephthalamide (Kevlar), and the like.
- E glass, T glass, S glass, Q glass, and organic fiber are preferable from the viewpoint of low thermal expansion.
- These base materials can be used individually by 1 type or in combination of 2 or more types.
- shape of the base material for example, woven fabric, non-woven fabric, roving, chopped strand mat, and surfacing mat are known.
- weaving method of the woven fabric plain weave, nanako weave, twill weave, etc. are known. It can be appropriately selected according to the intended use and performance. Those obtained by fiber-opening and glass woven fabrics surface-treated with a silane coupling agent or the like are preferably used.
- the thickness and mass of the base material are not particularly limited, but usually about 0.01 to 0.3 mm is preferably used.
- the base material is preferably a glass woven fabric having a thickness of 200 ⁇ m or less and a mass of 250 g / m 2 or less, and a glass woven fabric made of glass fibers of E glass, S glass, and T glass. More preferred.
- the laminate of this embodiment contains one or more of the above prepregs.
- the laminate is not particularly limited as long as it includes one or more prepregs, and may have any other layer.
- a manufacturing method of a laminated board a well-known method can be applied suitably, and it is not specifically limited. For example, it is obtained by laminating one prepreg or two or more prepregs and then curing, and more specifically, laminating the above prepregs by laminating them and heating and press-molding them. Can be obtained.
- the heating temperature is not particularly limited, but is preferably 65 to 300 ° C, more preferably 120 to 270 ° C.
- the pressure to be applied is not particularly limited, but is preferably 2 to 5 MPa, more preferably 2.5 to 4 MPa.
- the laminated board of this embodiment can be used suitably as a metal foil tension laminated board mentioned later by providing the layer which consists of metal foil.
- the metal foil tension laminate sheet of this embodiment contains the above-mentioned prepreg and metal foil laminated on the prepreg.
- one or more of the prepregs may be stacked, or the metal foil may be provided on one side or both sides of the prepreg.
- one or a plurality of the prepregs described above are stacked, and a metal foil such as copper or aluminum is arranged on one or both sides as desired, and this is laminated and formed as necessary.
- the metal foil-clad laminate of this embodiment can be produced.
- the metal foil used here will not be specifically limited if it is used for printed wiring board material, Well-known copper foils, such as a rolled copper foil and an electrolytic copper foil, are preferable.
- the thickness of the metal foil is not particularly limited, but is preferably 2 to 70 ⁇ m, more preferably 2 to 35 ⁇ m.
- a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of forming a metal foil-clad laminate.
- the temperature is generally 100 to 300 ° C.
- the pressure is 2 to 100 kgf / cm 2
- the heating time is generally 0.05 to 5 hours.
- post-curing can be performed at a temperature of 150 to 300 ° C., if necessary.
- a multilayer board can be formed by combining and molding the prepreg of the present embodiment and a separately prepared wiring board for an inner layer.
- the metal foil-clad laminate of the present embodiment described above can be suitably used as a printed wiring board by forming a predetermined wiring pattern.
- the metal foil-clad laminate of this embodiment has a low coefficient of thermal expansion, good moldability, and chemical resistance, and is used particularly effectively as a printed wiring board for semiconductor packages that require such performance. Can do.
- the printed wiring board of this embodiment is a printed wiring board including an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the resin composition.
- a printed wiring board can be manufactured, for example, by the following method. First, a metal foil clad laminate such as a copper clad laminate is prepared. An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to produce an inner layer substrate. The inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, then the required number of prepregs of the present invention are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is formed on the outer side. Laminate and heat and press to form one piece.
- a multilayer metal foil-clad laminate in which an insulating layer made of a cured material of the base material and the resin composition is formed between the inner layer circuit and the outer layer circuit metal foil is produced.
- the multilayer metal foil-clad laminate is subjected to drilling for through holes and via holes, and then desmear treatment is performed to remove smears, which are resin residues derived from the resin component contained in the insulating layer. Done.
- a plated metal film is formed on the wall surface of the hole to connect the inner layer circuit and the metal foil for the outer layer circuit, and further, the outer layer circuit is formed by etching the metal foil for the outer layer circuit.
- the prepreg of the present embodiment (the base material and the resin composition of the present embodiment impregnated or coated thereon), the resin composition layer of the metal foil-clad laminate (the resin composition of the present embodiment).
- Layer constitutes an insulating layer containing the resin composition.
- Disperbyk-180 product name, manufactured by Big Chemie Japan Co., Ltd.
- Softening point 86) with stirring while keeping the temperature in the reactor at ⁇ 5 to + 5 ° C. and the pH at 1 or less.
- C., Nippon Steel Chemical Co., Ltd. (20 g, 0.0935 mol) and triethylamine (14.16 g, 0.14 mol) dissolved in 92 mL of methylene chloride were added dropwise over 1 hour using a dropping funnel. After completion of the dropwise addition, 4.72 g (0.047 mol) of triethylamine was further added dropwise over 15 minutes. After completion of dropping, the mixture was stirred at the same temperature for 15 minutes, and then the reaction solution was separated to separate the organic layer.
- Example 1 1 part by weight of alumina nanoparticles (product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan Co., Ltd.), surface-treated with a polysiloxane-based modifier, spherical fused silica (product) Name “FB-3SDC”, average particle size: 3.0 ⁇ m, 300 parts by mass, spherical fused silica (product name “SFP-120MC”, average particle size: 0.30 ⁇ m, Denki Kagaku Kogyo) 100 parts by mass of the product, 40 parts by mass of the ⁇ -naphthol aralkyl cyanate ester resin (cyanate equivalent: 261 g / eq.) Obtained in Synthesis Example 3, and a polyoxynaphthylene type epoxy resin (product name “HP- 6000 ", epoxy equivalent: 250 g / eq., Manufactured by DIC Corporation), 60 parts by mass, wetting and dis
- This varnish was mixed to obtain a varnish.
- This varnish was diluted with methyl ethyl ketone, impregnated on a 0.1 mm thick E glass woven fabric, and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 63 mass%.
- Example 2 40 parts by mass of 2,2-bis (4-cyanatephenyl) propane prepolymer (product name “CA210”, cyanate equivalent weight 139, manufactured by Mitsubishi Gas Chemical Co., Ltd.) instead of ⁇ -naphthol aralkyl type cyanate resin A prepreg was obtained in the same manner as in Example 1 except that it was used.
- Example 3 In place of the ⁇ -naphthol aralkyl type cyanate ester resin, a novolak type cyanate ester resin in which R 6 in the above formula (3) is all hydrogen atoms (product name “Primerset PT-30”, manufactured by Lonza Japan Ltd., A prepreg was obtained in the same manner as in Example 1 except that 40 parts by mass of cyanate equivalent: 124 g / eq.) was used.
- Example 4 1 part by weight of alumina nanoparticles (product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan Co., Ltd.), surface-treated with a polysiloxane-based modifier, spherical fused silica (product) Name “FB-3SDC”, average particle size: 3.0 ⁇ m, 300 parts by mass, spherical fused silica (SFP-120MC, average particle size: 0.3 ⁇ m, manufactured by Denki Kagaku) 100 36 parts by mass of the ⁇ -naphthol aralkyl-type cyanate ester resin (cyanate equivalent: 261 g / eq.) Obtained in Synthesis Example 3 and the maleimide compound used in Synthesis Example 4 (product name “BMI-2300”) 26 parts by mass of polyoxynaphthylene type epoxy resin (product name “HP-6000”, epoxy equivalent: 250 g / eq., Manufactured by DIC Corporation)
- This varnish was diluted with methyl ethyl ketone, impregnated on a 0.1 mm thick E glass woven fabric, and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 63 mass%.
- Example 5 Except that the amount of alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier was changed from 1 part by mass to 3 parts by mass, the same as in Example 4, A prepreg was obtained.
- alumina nanoparticles product name “NANOBYK-3610”
- Example 6 Except that the amount of alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier was changed from 1 part by mass to 5 parts by mass, the same as in Example 4, A prepreg was obtained.
- alumina nanoparticles product name “NANOBYK-3610”
- Example 7 A prepreg was obtained in the same manner as in Example 4 except that 26 parts by mass of the maleimide compound (product name “BMI-70”) used in Synthesis Example 5 was used instead of the maleimide compound (product name “BMI-2300”). It was.
- Example 8 Instead of a polyoxynaphthylene type epoxy resin (product name “HP-6000”), a phenol biphenyl aralkyl type epoxy resin (product name “NC-3000-FH”) in which R 11 in the above formula (8) is all hydrogen atoms, A prepreg was obtained in the same manner as in Example 4 except that 38 parts by mass of epoxy equivalent: 320 g / eq., Manufactured by Nippon Kayaku Co., Ltd. was used.
- Example 9 Naphthol aralkyl epoxy resin (product name “ESN-175V”, epoxy equivalent: 255 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.) instead of polyoxynaphthylene type epoxy resin (product name “HP-6000”) A prepreg was obtained in the same manner as in Example 4 except that 38 parts by mass of was used.
- ESN-175V epoxy equivalent: 255 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.
- HP-6000 polyoxynaphthylene type epoxy resin
- Example 10 Instead of a polyoxynaphthylene type epoxy resin (product name “HP-6000”), a phenol phenylaralkyl type epoxy resin (product name “NC-2000-L”) in which R 10 in the above formula (7) is all hydrogen atoms, A prepreg was obtained in the same manner as in Example 4 except that 38 parts by mass of epoxy equivalent: 226 g / eq., Manufactured by Nippon Kayaku Co., Ltd. was used.
- Example 11 A prepreg was obtained in the same manner as in Example 4 except that 0.01 parts by mass of 2-ethyl-4-methylimidazole (product name “2E4MZ”, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was further added to obtain the varnish. Obtained.
- Example 12 When obtaining the varnish, the ⁇ -naphthol aralkyl cyanate ester resin obtained in Synthesis Example 3 and the maleimide compound used in Synthesis Example 4 were not used, and 62 parts by mass of BT resin 1 obtained in Synthesis Example 4 were used. A prepreg was obtained in the same manner as Example 4 except for the addition.
- Example 13 When obtaining the varnish, the ⁇ -naphthol aralkyl cyanate ester resin obtained in Synthesis Example 3 and the maleimide compound used in Synthesis Example 4 were not used, and 62 parts by mass of BT resin 2 obtained in Synthesis Example 5 were used. A prepreg was obtained in the same manner as Example 4 except for the addition.
- Example 14 When obtaining the varnish, the ⁇ -naphthol aralkyl cyanate ester resin obtained in Synthesis Example 3 and the maleimide compound used in Synthesis Example 4 were not used, and 59 parts by mass of the BT resin 1 obtained in Synthesis Example 4 were used. 3 parts by mass of naphthol aralkyl type phenol resin (product “SN-495”, manufactured by Nippon Steel Chemical Co., Ltd., hydroxyl equivalent: 236 g / eq.) In which R 7 in the above formula (4) is all hydrogen atoms are added. A prepreg was obtained in the same manner as in Example 4 except that.
- Example 15 When obtaining the varnish, the amount of spherical fused silica (product name “FB-3SDC”) used was changed from 300 parts by mass to 150 parts by mass, and the amount of spherical fused silica (product name “SFP-120MC”) used was changed to 100. The mass was changed from 150 parts by mass to 2 parts by mass of the wetting dispersant 3 (product name “disperbyk-w903”, manufactured by BYK Japan Japan Co., Ltd.) instead of the wetting and dispersing agent 2 (product name “disperbyk-111”).
- the wetting dispersant 3 product name “disperbyk-w903”, manufactured by BYK Japan Japan Co., Ltd.
- Example 4 In the same manner as in Example 4 except that 200 parts by mass of alumina fine particles (product name “AX3-15”, average particle size: 3.0 ⁇ m, manufactured by Nippon Steel & Sumikin Materials Co., Ltd., Micron) was further added. A prepreg having a resin content of 64% by mass was obtained.
- alumina fine particles product name “AX3-15”, average particle size: 3.0 ⁇ m, manufactured by Nippon Steel & Sumikin Materials Co., Ltd., Micron
- Example 16 When obtaining the varnish, we do not use spherical fused silica (product name “FB-3SDC”) and spherical fused silica (product name “SFP-120MC”), wetting and dispersing agent 1 (product name “disperbyk-161”), And 5 parts by weight of the wetting dispersant 3 (product name “disperbyk-w903”) instead of the wetting dispersant 2 (product name “disperbyk-111”), and further alumina fine particles (product name “AX3-15”, average particle)
- a prepreg having a resin content of 69% by mass was obtained in the same manner as in Example 4 except that 400 parts by mass of diameter: 3.0 ⁇ m, manufactured by Nippon Steel & Sumikin Materials Co., Ltd., Micron) was added.
- Example 17 When obtaining the varnish, we do not use spherical fused silica (product name “FB-3SDC”) and spherical fused silica (product name “SFP-120MC”), wetting and dispersing agent 1 (product name “disperbyk-161”), And 5 parts by weight of a wetting dispersant 3 (product name “disperbyk-w903”) instead of the wetting dispersant 2 (product name “disperbyk-111”), and further alumina fine particles (product name “ASEP-20”, average particle) Other than adding 100 parts by mass of diameter: 0.3 ⁇ m, manufactured by Denki Kagaku Kogyo Co., Ltd., and 300 parts by mass of boehmite fine particles (product name “BM5009”, average particle size: 3.0 ⁇ m, manufactured by Admatex Co., Ltd.) Obtained a prepreg having a resin content of 66% by mass in the same manner as in Example 4.
- spherical fused silica product name “
- Example 18 Example 4 except that 10 parts by mass of silicone rubber powder (silicone composite powder, product name “KMP-600”, manufactured by Shin-Etsu Chemical Co., Ltd.) whose surface was coated with a silicone resin was further added to obtain the varnish. Similarly, a prepreg having a resin content of 60% by mass was obtained.
- silicone rubber powder silicone composite powder, product name “KMP-600”, manufactured by Shin-Etsu Chemical Co., Ltd.
- Example 19 1 part by mass of alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with the polysiloxane-based modifier used in Example 1, spherical fused silica (product name “FB-3SDC”, average) 300 parts by mass of particle size: 3.0 ⁇ m, manufactured by Denki Kagaku Kogyo), 100 parts by mass of spherical fused silica (product name “SFP-120MC”, average particle size: 0.3 ⁇ m, manufactured by Denki Kagaku Kogyo) 49 parts by mass of the phenol biphenyl aralkyl type epoxy resin (product name “NC-3000-FH”) used in Example 8 and 36 parts by mass of the naphthol aralkyl type epoxy resin (product name “SN-495”) used in Example 14 Parts, 15 parts by mass of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (product name “BMI-70”), wetting and dispersing
- Example 20 1 part by mass of alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with the polysiloxane-based modifier used in Example 1, spherical fused silica (product name “FB-3SDC”, average) 300 parts by mass of particle size: 3.0 ⁇ m, manufactured by Denki Kagaku Kogyo), 100 parts by mass of spherical fused silica (product name “SFP-120MC”, average particle size: 0.3 ⁇ m, manufactured by Denki Kagaku Kogyo) 44 parts by mass of oxynaphthylene type epoxy resin (product name “HP-6000”) and biphenylaralkyl type phenol resin (product name “KAYAHARD GPH-103”, Japan) in which R 8 in formula (5) is all hydrogen atoms 18 parts by mass of hydroxyl group equivalent: 231 g / eq., Manufactured by Kayaku Co., Ltd., naphthalene type phenolic resin
- This varnish was diluted with methyl ethyl ketone, impregnated on a 0.1 mm thick E glass woven fabric, and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 63 mass%.
- Example 21 Example except that 17 parts by mass of the maleimide compound (product name “BMI-2300”) used in Synthesis Example 4 was used instead of bis (3-ethyl-5-methyl-4maleimidophenyl) methane (BMI-70) In the same manner as in No. 20, a prepreg was obtained.
- Example 22 The varnish produced in Example 1 was impregnated and coated on an S glass woven fabric having a thickness of 0.1 mm and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 61% by mass.
- Example 23 The varnish produced in Example 4 was impregnated and applied to an S glass woven fabric having a thickness of 0.1 mm and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 61% by mass.
- Example 24 The varnish produced in Example 7 was impregnated and applied to an S glass woven fabric having a thickness of 0.1 mm and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 61% by mass.
- Example 25 The varnish produced in Example 12 was impregnated and applied to an S glass woven fabric having a thickness of 0.1 mm and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 61% by mass.
- Example 26 Surface prepared in Synthesis Example 2 instead of alumina nanoparticles (product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan Co., Ltd.) surface-treated with a polysiloxane-based modifier A prepreg was obtained in the same manner as in Example 1 except that the treated nanoparticles were used.
- alumina nanoparticles product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan Co., Ltd.
- Example 27 Surface prepared in Synthesis Example 2 instead of alumina nanoparticles (product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan Co., Ltd.) surface-treated with a polysiloxane-based modifier A prepreg was obtained in the same manner as in Example 4 except that the treated nanoparticles were used.
- alumina nanoparticles product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan Co., Ltd.
- Example 28 Surface prepared in Synthesis Example 2 instead of alumina nanoparticles (product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan Co., Ltd.) surface-treated with a polysiloxane-based modifier A prepreg was obtained in the same manner as in Example 12 except that the treated nanoparticles were used.
- alumina nanoparticles product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan Co., Ltd.
- Example 29 Surface prepared in Synthesis Example 2 instead of alumina nanoparticles (product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan Co., Ltd.) surface-treated with a polysiloxane-based modifier A prepreg was obtained in the same manner as in Example 19 except that the treated nanoparticles were used.
- alumina nanoparticles product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan Co., Ltd.
- Example 30 Polysiloxane-based modifier instead of alumina nanoparticles (product name “NANOBYK-3610”, average particle size: 20 nm, manufactured by Big Chemie Japan) surface-treated with a polysiloxane-based modifier A prepreg was prepared in the same manner as in Example 4 except that boehmite nanoparticles (product name “LP-X-21121”, average particle size: 10 nm, manufactured by Big Chemie Japan Co., Ltd.) were used. Obtained.
- Example 1 A prepreg was obtained in the same manner as in Example 1 except that alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier were not used.
- alumina nanoparticles product name “NANOBYK-3610”
- Example 2 A prepreg was obtained in the same manner as in Example 4 except that alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier were not used.
- alumina nanoparticles product name “NANOBYK-3610”
- Example 3 A prepreg was obtained in the same manner as in Example 8 except that alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier were not used.
- alumina nanoparticles product name “NANOBYK-3610”
- Example 4 A prepreg was obtained in the same manner as in Example 12 except that alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier were not used.
- alumina nanoparticles product name “NANOBYK-3610”
- Example 5 A prepreg was obtained in the same manner as in Example 15 except that alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier were not used.
- alumina nanoparticles product name “NANOBYK-3610”
- Example 6 A prepreg was obtained in the same manner as in Example 16 except that alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier were not used.
- alumina nanoparticles product name “NANOBYK-3610”
- Example 7 A prepreg was obtained in the same manner as in Example 17 except that alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier were not used.
- alumina nanoparticles product name “NANOBYK-3610”
- Example 8 A prepreg was obtained in the same manner as in Example 20 except that alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier were not used.
- alumina nanoparticles product name “NANOBYK-3610”
- Example 10 Alumina nanoparticles (product name “NANOBYK-3610”) surface-treated with a polysiloxane-based modifier are not used, and spherical fused silica (product name “FB-3SDC”, average particle size: 3.0 ⁇ m)
- a prepreg was obtained in the same manner as in Example 22 except that the amount used was from 300 parts by mass to 200 parts by mass.
- Alumina nanoparticles product name “NANOBYK-3610” surface-treated with a polysiloxane-based modifier are not used, and spherical fused silica (product name “FB-3SDC”, average particle size: 3.0 ⁇ m)
- a prepreg was obtained in the same manner as in Example 23 except that the amount used was from 300 parts by mass to 200 parts by mass.
- Alumina nanoparticles product name “NANOBYK-3610” surface-treated with a polysiloxane-based modifier are not used, and spherical fused silica (product name “FB-3SDC”, average particle size: 3.0 ⁇ m)
- a prepreg was obtained in the same manner as in Example 24 except that the amount used was from 300 parts by mass to 200 parts by mass.
- Alumina nanoparticles product name “NANOBYK-3610” surface-treated with a polysiloxane-based modifier are not used, and spherical fused silica (product name “FB-3SDC”, average particle size: 3.0 ⁇ m)
- a prepreg was obtained in the same manner as in Example 25 except that the amount used was from 300 parts by mass to 200 parts by mass.
- alumina nanoparticles product name “NANOBYK-3610”
- an ultrasonic disperser product name “UP200S”, manufactured by hielscher, as a 5% by mass methyl ethyl ketone slurry.
- the prepreg was obtained in the same manner as in Example 1 except that untreated alumina nanoparticles having an average particle diameter (D50) of 20 nm were added.
- Tables 1 and 2 show the measurement results of the melt viscosity of the obtained prepreg and the results of evaluation of formability, heat resistance and moisture absorption heat resistance using the obtained copper-clad laminate.
- melt viscosity prepreg viscosity: unit: x16 Pa ⁇ s
- moldability heat resistance
- moisture absorption heat resistance thermal expansion coefficient
- thermal conductivity thermal conductivity of the prepreg were evaluated by the following methods.
- -Prepreg viscosity The melt viscosity at 120 ° C was measured using a flow tester (manufactured by Shimadzu Corporation).
- Formability After removing the copper foil of the copper clad laminate by etching, the exposed surface was visually observed to evaluate the presence or absence of voids. The case where a void was not recognized was evaluated as ⁇ , and the case where a void was observed was evaluated as ⁇ .
- Heat resistance A 50 ⁇ 50 mm sample was floated on 280 ° C. solder for 30 minutes, the presence or absence of delamination was visually confirmed, and the following criteria were evaluated. ⁇ : No abnormality at all ⁇ : Generation of delamination while floating for 0 to 30 minutes / Hygroscopic heat resistance: Specimens obtained by etching away copper foil other than half of one side of a 50 mm ⁇ 50 mm sample (ie, half of one side) The test piece with the copper foil remaining only on the surface was treated for 3 hours at 121 ° C. and 2 atm using a pressure cooker tester (PC-3 type, manufactured by Hirayama Seisakusho), and then soldered at 260 ° C. The appearance change after immersion for 30 seconds was visually observed.
- PC-3 type manufactured by Hirayama Seisakusho
- the test was performed 4 times, and the evaluation was performed based on the number of times that occurrence of swelling was observed (number of occurrences of swelling / number of tests).
- -Thermal expansion coefficient After removing the copper foil of the copper foil-clad laminate by etching, place it at a predetermined position of a thermomechanical analyzer (TA Instruments), and raise the temperature from 40 ° C to 340 ° C at 10 ° C per minute Then, the linear expansion coefficient in the plane direction from 60 ° C. to 120 ° C. was measured. The measurement direction was the longitudinal direction (Warp) of the glass cloth of the laminate.
- Thermal conductivity (W / m ⁇ K) density (kg / m 3 ) ⁇ specific heat (kJ / kg ⁇ K) ⁇ thermal diffusivity (m 2 / S) ⁇ 1000
- the present invention provides a resin capable of producing a prepreg having a viscosity that is low enough to be convenient for producing a metal foil-clad laminate and capable of producing a metal foil-clad laminate excellent in moisture absorption heat resistance.
- a composition, and a prepreg, a laminate and a printed wiring board produced using the resin composition are provided. Therefore, there is industrial applicability in such a field.
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Abstract
Description
(1)樹脂組成物の体積比率が小さくなって流動性が低下し、その結果、樹脂組成物をガラスクロス等の基材に含浸させて半硬化して得られるプリプレグの粘度が悪化する。
(2)そのようなプリプレグを金属箔と重ねて硬化させた金属箔張積層板にクラックやボイドが発生し、成型性が悪化する。
(3)ボイドの発生により、金属箔張積層板の吸湿耐熱性、弾性率、及び、銅箔と積層板の絶縁層との密着強度が悪化する。
すなわち、本発明は、下記のとおりである。
[1]平均粒子径が1.0nm~100nmのアルミナ及び/又はベーマイトのナノ粒子(A)、平均粒子径が0.20μm~100μmの微粒子(B)及び熱硬化性樹脂(C)を含有する樹脂組成物であって、前記ナノ粒子(A)は、その表面がポリシロキサンベースの改質剤によって処理されたものである、樹脂組成物。
[2]前記ナノ粒子(A)が、リン酸エステル、リン酸エステル塩、及びアルキルベンゼンスルホン酸からなる群より選ばれる1種以上の分散助剤によって処理されたものである、上記樹脂組成物。
[3]前記微粒子(B)を、前記熱硬化性樹脂(C)100質量部に対して、200質量部以上含有する、上記いずれかの樹脂組成物。
[4]前記微粒子(B)が、シリカ、アルミナ、窒化アルミニウム、窒化ホウ素、ベーマイト、酸化チタン、シリコーンゴム及びシリコーン複合パウダーからなる群より選ばれる1種以上である、上記いずれかの樹脂組成物。
[5]前記ナノ粒子(A)が、溶剤又は樹脂中に1次粒子として分散されたものである、上記いずれかの樹脂組成物。
[6]前記熱硬化性樹脂(C)が、シアン酸エステル化合物(D)、フェノール樹脂(E)、マレイミド化合物(F)、エポキシ樹脂(G)及びBT樹脂(H)からなる群より選ばれる1種以上である、上記いずれかの樹脂組成物。
[7]前記シアン酸エステル化合物(D)が、下記式(2)及び/又は下記式(3)で表される化合物である、上記いずれかの樹脂組成物。
[8]前記マレイミド化合物(F)が、ビス(4-マレイミドフェニル)メタン、2,2-ビス{4-(4-マレイミドフェノキシ)-フェニル}プロパン、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン及び下記式(6)で表されるマレイミド化合物からなる群より選ばれる1種以上である、上記いずれかの樹脂組成物。
[9]前記エポキシ樹脂(G)が、下記式(7)、(8)、(9)、(11)及び(12)で表される化合物からなる群より選ばれる1種以上である、上記いずれかの樹脂組成物。
[10]前記フェノール樹脂(E)が、クレゾールノボラック型フェノール樹脂、アミノトリアジンノボラック型フェノール樹脂、ナフタレン型フェノール樹脂、下記式(4)で表されるナフトールアラルキル型フェノール樹脂、及び下記式(5)で表されるビフェニルアラルキル型フェノール樹脂からなる群より選ばれる1種以上である、上記いずれかの樹脂組成物。
[11]下記式(13)で表されるイミダゾール化合物を更に含有する、上記いずれかの樹脂組成物。
[12]前記アルミナナノ粒子(A)を、前記微粒子(B)の総質量に対して0.010~5質量%含有する、上記いずれかの樹脂組成物。
[13]前記熱硬化性樹脂(C)が、シアン酸エステル化合物(D)を、前記熱硬化性樹脂(C)の総量100質量部に対して、10~60質量部含有する、上記いずれかの樹脂組成物。
[14]前記熱硬化性樹脂(C)が、フェノール樹脂(E)を、前記熱硬化性樹脂(C)の総量100質量部に対して、10~60質量部含有する、上記いずれかの樹脂組成物。
[15]前記熱硬化性樹脂(C)が、マレイミド化合物(F)を、前記熱硬化性樹脂(C)の総量100質量部に対して、3.0~50質量部含有する、上記いずれかの樹脂組成物。
[16]前記熱硬化性樹脂(C)が、エポキシ樹脂(G)を、前記熱硬化性樹脂(C)の総量100質量部に対して、10~80質量部含有する、上記いずれかの樹脂組成物。
[17]前記熱硬化性樹脂(C)が、BT樹脂(H)を、前記熱硬化性樹脂(C)の総量100質量部に対して、20~80質量部含有する、上記いずれかの樹脂組成物。
[18]前記ナノ粒子(A)が、アルミナナノ粒子である、上記いずれかの樹脂組成物。
[19]基材と、その基材に含浸又は塗布した上記いずれかの樹脂組成物と、を含有するプリプレグ。
[20]前記基材が、Eガラスクロス、Tガラスクロス、Sガラスクロス、Qガラスクロス及び有機繊維からなる群より選ばれる1種以上である、上記プリプレグ。
[21]上記いずれかのプリプレグを1枚以上含有する積層板。
[22]上記いずれかのプリプレグと、そのプリプレグに積層した金属箔と、を含有する金属箔張積層板。
[23]絶縁層と、前記絶縁層の表面に形成された導体層とを含むプリント配線板であって、前記絶縁層が、上記いずれかの樹脂組成物を含むプリント配線板。
このようなナノ粒子(A)は、樹脂組成物において、後に詳述する複数の微粒子(B)(以下、「フィラー」ともいう。)の間に入り込み、そのフィラーを潤滑させる効果を有すると考えられる。よって、樹脂組成物におけるフィラー含有量が多い場合にも、フィラー同士の凝集を防ぎ、得られた積層板においてフィラー含有量が多い場合に予想される種々の不具合を解決することができる。このような効果をより有効且つ確実に奏する観点から、ナノ粒子(A)はアルミナナノ粒子を含むことが好ましい。
この表面処理はポリシロキサンベースの改質剤、すなわち、ポリシロキサン骨格を主骨格として有する改質剤を用いて施される。改質剤は、ナノ粒子(A)の表面に化学的な相互作用により吸着するものが好ましく、例えば、下記式(1)で表されるポリシロキサンが挙げられ、これが好ましい。ここで、下記式(1)において,xは0~2の整数を示し、好ましくは0であり、yは1~10の整数を示し、好ましくは2~5の整数であり、R1は1~18個、好ましくは1~10個、より好ましくは1~3個の炭素原子を有する1価の有機基を示す。R2はヘテロ原子及び/又は置換基を有していてもよい1価の有機基を示し、好ましくは、水酸基又は加水分解性基を示し、加水分解性基は、1~6個、好ましくは1~2個の炭素原子を有する直鎖、分岐又は環状のアルコキシ基;好ましくは塩素原子であるハロゲン原子;1~4個、好ましくは1~2個の炭素原子を有するカルボン酸基を示す。R3はヘテロ原子や置換基を有してもよい2価の有機基を示し、好ましくは、酸素原子;1~8個の炭素原子を有する直鎖又は分岐(好ましくは直鎖)のアルキレン基;アルキレンエーテル基;アルキレンチオエーテル基;好ましくは酸化エチレン、酸化プロピレン、酸化ブチレン若しくは酸化スチレン又は酸化物の混合物に基づく、又はスタティスティク若しくはブロックポリエーテルに基づくアルキレンポリエーテル基;アリーレンポリエーテル基;アルキレンポリエステル基;あるいは、エステル及び/若しくはエーテル基に加えて、ウレタン及び/若しくは尿素基を有する有機脂肪族、芳香族又はアリル脂肪族基である。R4は4~200個のシロキサン構造単位及び珪素原子上に炭素数1~18のアルキル基を有する1価又は多価の置換基であって、炭素数1~18のアルキル基が、ポリエーテル基を有する基(G1)、ポリエステル基を有する基(G2)、アリルアルキル基を有する基(G3)及び過フッ素化アルキル基を有する基(G4)から選択される1つ又は複数の改質基(G)によって、部分的且つ独立して置換されたものである。
ポリシロキサンベースの改質剤によって粒子の表面張力を低下させることで効果的に凝集を防ぎ、更に、リン酸エステル及びアルキルベンゼンスルホン酸等の分散助剤を補助的に使用し、粒子表面に立体障害を形成することで、分散状態を安定化させることができる。
また、ナノ粒子(A)の形状は特に限定されないが、樹脂組成物中での流動性を高める観点から、球状が好ましい。
これらの中でも、より低い熱膨張性を有しやすい観点から、シリカが好ましく、また、より高い熱伝導性を有しやすい観点から、アルミナ及び窒化アルミニウムが好ましい。
微粒子(B)の平均粒子径(D50)は、ナノ粒子(A)がその隙間に入り込み、潤滑材としての役目を十分果たす観点から0.20μm~100μmであることを要する。さらに、その平均粒子径は0.20μm~10μmであることが、より微細な配線を形成できる観点から好ましく、0.20μm~5μmであることがより好ましい。
また、微粒子(B)の粒子の形状は特に限定されないが、成形性の観点から、球状であることが好ましい。
また、微粒子(B)の樹脂組成物における含有量の上限は特に限定されないが、500質量部以下であることが好ましく、成形性を高める観点から、400質量部以下であることがより好ましい。また、より優れた熱伝導性を求められる場合、高熱伝導性のフィラーは、一般的に比重が大きくなるケースが多いことから、微粒子(B)の含有量は、1100質量部以下であることが好ましく、700質量部以下であることがより好ましい。
シアン酸エステル化合物(D)の種類としては、特に限定されないが、例えば、下記式(2)で表されるナフトールアラルキル型シアン酸エステル化合物、下記式(3)で表されるノボラック型シアン酸エステル、ビフェニルアラルキル型シアン酸エステル、ビス(3,5-ジメチル4-シアナトフェニル)メタン、ビス(4-シアナトフェニル)メタン、1,3-ジシアナトベンゼン、1,4-ジシアナトベンゼン、1,3,5-トリシアナトベンゼン、1,3-ジシアナトナフタレン、1,4-ジシアナトナフタレン、1,6-ジシアナトナフタレン、1,8-ジシアナトナフタレン、2,6-ジシアナトナフタレン、2,7-ジシアナトナフタレン、1,3,6-トリシアナトナフタレン、4、4’-ジシアナトビフェニル、ビス(4-シアナトフェニル)エーテル、ビス(4-シアナトフェニル)チオエーテル、ビス(4-シアナトフェニル)スルホン、及び、2、2-ビス(4-シアナトフェニル)プロパンが挙げられる。
この中でも、下記式(2)で表されるナフトールアラルキル型シアン酸エステル化合物、下記式(3)で表されるノボラック型シアン酸エステル、及びビフェニルアラルキル型シアン酸エステルが難燃性に更に優れ、硬化性がより高く、かつ硬化物の熱膨張係数が一層低いことから特に好ましい。
ここで、熱硬化性樹脂(C)の総量とは、上記シアン酸エステル化合物(D)、フェノール樹脂(E)、マレイミド化合物(F)、エポキシ樹脂(G)及びBT樹脂(H)等の熱硬化性樹脂の合計量を意味し、その合計量には、硬化促進剤、微粒子(B)に加える湿潤分散剤及びシランカップリング剤は含まない。
これらの中でも、吸水性及び耐熱性の観点からは、クレゾールノボラック型フェノール樹脂、アミノトリアジンノボラック型フェノール樹脂、ナフタレン型フェノール樹脂、上記式(4)で表されるナフトールアラルキル型フェノール樹脂、及び下記式(5)で表されるビフェニルアラルキル型フェノール樹脂が好ましく、とりわけ、クレゾールノボラック型フェノール化合物、上記式(4)で表されるナフトールアラルキル型フェノール樹脂、及び下記式(5)で表されるビフェニルアラルキル型フェノール樹脂がより好ましい。
その中でも、ビス(4-マレイミドフェニル)メタン、2,2-ビス{4-(4-マレイミドフェノキシ)-フェニル}プロパン、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン、及び下記式(6)で表されるマレイミド化合物が好ましく、とりわけ、下記式(6)で表されるマレイミド化合物が好ましい。
上記式(11)又は(12)出表されるエポキシ樹脂としては、市販品を用いることができ、製品例としては、DIC株式会社製、EXA-7311、EXA-7311-G3、EXA-7311-G4、EXA-7311-G4S、EXA-7311L,HP-6000、及びEXA-7311-G5(以上、製品名)が挙げられる。
この中でも、上記式(2)で表されるナフトールアラルキル型シアン酸エステル化合物、上記式(3)で表されるノボラック型シアン酸エステル、及びビフェニルアラルキル型シアン酸エステルが、得られるプリント配線板の難燃性、硬化性、及び低熱膨張率の観点から好ましい。
また、マレイミド化合物も特に限定されず、例えば、N-フェニルマレイミド、N-ヒドロキシフェニルマレイミド、ビス(4-マレイミドフェニル)メタン、2,2-ビス{4-(4-マレイミドフェノキシ)-フェニル}プロパン、ビス(3,5-ジメチル-4-マレイミドフェニル)メタン、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン、ビス(3,5-ジエチル-4-マレイミドフェニル)メタン、及び上記式(6)で表されるマレイミド化合物、並びに、これらマレイミド化合物のプレポリマー、及びこれらのマレイミド化合物とアミン化合物とのプレポリマーが挙げられ。これらは、1種又は2種以上を混合して使用することも可能である。
その中でも、ビス(4-マレイミドフェニル)メタン、2,2-ビス{4-(4-マレイミドフェノキシ)-フェニル}プロパン、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン、及び上記式(6)で表されるマレイミド化合物が好ましく、とりわけ、上記式(6)で表されるマレイミド化合物が好ましい。
また、プレポリマーであるBT樹脂(H)の分子量の範囲は特に限定されるものではないが、ハンドリング性、ガラス転移温度、及び硬化性の観点から、数平均分子量で約100~100000の範囲であることが好ましい。
本実施形態の樹脂組成物は、下記式(13)で表されるイミダゾール化合物を更に含有することが好ましい。このイミダゾール化合物は、硬化促進の作用を有し、硬化物のガラス転移温度を更に高める作用を有する。
これらの中でも低熱膨張性の観点から、Eガラス、Tガラス、Sガラス、Qガラス及び有機繊維が好ましい。
これらの基材は、1種を単独で又は2種以上を組み合わせて使用することができる。
基材の形状としては、例えば、織布、不織布、ロービング、チョップドストランドマット及びサーフェシングマットなど、織布の織り方としては、平織り、ななこ織り及び綾織り等が知られており、これら公知のものから目的とする用途や性能により適宜選択して使用することができる。これらを開繊処理したもの及びシランカップリング剤などで表面処理したガラス織布が好適に使用される。基材の厚さ及び質量は、特に限定されないが、通常は0.01~0.3mm程度のものが好適に用いられる。とりわけ、強度と吸水性の観点から、基材は、厚さ200μm以下、質量250g/m2以下のガラス織布が好ましく、Eガラス、Sガラス、及びTガラスのガラス繊維からなるガラス織布がより好ましい。
この態様においては、本実施形態のプリプレグ(基材及びこれに含浸又は塗布された本実施形態の樹脂組成物)、金属箔張積層板の樹脂組成物層(本実施形態の樹脂組成物からなる層)が、樹脂組成物を含む絶縁層を構成することになる。
本実施形態によると、硬化物を簡易かつ再現性良く作製可能な、低熱膨張及び高熱伝導性等の特性が高度に付与されたプリプレグ用樹脂組成物を提供することができる。また、本実施形態によると、金属箔張積層板の成型性が良好で、かつ耐熱性や吸湿耐熱性が良好なプリプレグ、積層板及びプリント配線板等を得ることができる。
〔表面改質に用いられるポリシロキサンの合成〕
ヒータ、内部温度計、攪拌機及び窒素ガス接続を取り付けた反応器に、下記式(14)で表されるSiH官能基を有するポリシロキサンを加え、窒素ガス雰囲気下、70℃まで加熱し、そこに触媒として10ppmのヘキサクロロ白金(IV)酸を加えた。更に、その反応器に下記式(15)で表されるアリルエーテル251gとビニルトリエトキシシラン73gを加えた。この際に反応温度が80℃を超えないように注意した。これらの反応溶液を80℃で1時間撹拌した後、真空下で未反応のビニルトリメトキシシラン、及び未反応ポリシロキサンを除くことで、琥珀色のポリシロキサンを得た。
〔表面処理ナノ粒子の調整〕
プラズマ気相合成にて製造されたデルタ型:ガンマ型=70:30(質量比)の組成を有し、平均粒子径(D50)が20nmである球状ナノアルミナ40gに合成例1で合成したポリシロキサンを4g加え、ミキサーにて1分間撹拌した後、80℃で1時間加熱した。ここにメトキシプロピルアセテート56.8g、及び、リン酸エステル及びアルキルベンゼンスルホン酸類からなる湿潤分散剤であるDisperbyk-180(製品名、ビックケミー・ジャパン(株)製)3.2gの混合溶液を加え、撹拌した後、超音波によって分散し、表面処理ナノ粒子を得た。
〔α-ナフトールアラルキル型シアン酸エステル樹脂の合成〕
温度計、攪拌器、滴下漏斗及び還流冷却器を取りつけた反応器を予めブラインにより0~5℃に冷却しておき、そこへ塩化シアン7.47g(0.122mol)、35%塩酸9.75g(0.0935mol)、水76ml、及び塩化メチレン44mlを仕込んだ。
この反応器内の温度を-5~+5℃、pHを1以下に保ちながら、撹拌下、α-ナフトールアラルキル型フェノール樹脂(製品名「SN485」、OH基当量:214g/eq.軟化点:86℃、新日鐵化学(株)製)20g(0.0935mol)、及びトリエチルアミン14.16g(0.14mol)を塩化メチレン92mLに溶解した溶液を、滴下漏斗により1時間かけて滴下した。滴下終了後、更にトリエチルアミン4.72g(0.047mol)を15分間かけて滴下した。
滴下終了後、同温度で15分間撹拌した後、反応液を分液し、有機層を分取した。得られた有機層を水100mLで2回洗浄した後、エバポレーターにより減圧下で塩化メチレンを留去し、最終的に80℃で1時間濃縮乾固させて、上記式(2)におけるR5が全て水素原子であるα-ナフトールアラルキル型フェノール樹脂のシアン酸エステル化物(α-ナフトールアラルキル型シアン酸エステル樹脂)23.5gを得た。
〔BT樹脂1の合成〕
合成例3で作製したα-ナフトールアラルキル型シアン酸エステル樹脂(シアネート当量:261g/eq.)36質量部と、上記式(6)におけるR9が全て水素原子であり、n5が1~3であるマレイミド化合物(製品名「BMI-2300」、大和化成工業(株)製)24質量部をジメチルアセトアミドに溶解し、150℃で攪拌しながら反応させ、BT樹脂1を得た。
〔BT樹脂2の合成〕
合成例3で作製したα-ナフトールアラルキル型シアン酸エステル樹脂(シアネート当量:261g/eq.)36質量部とビス(3-エチル-5-メチル-マレイミドフェニル)メタン(製品名「BMI-70」、大和化成工業(株)製)26質量部とをジメチルアセトアミドに溶解し、150℃で攪拌しながら反応させ、BT樹脂2を得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」、平均粒子径:20nm、ビックケミー・ジャパン(株)製)を1質量部、球状溶融シリカ(製品名「FB-3SDC」、平均粒子径:3.0μm、電気化学工業社製)を300質量部、球状溶融シリカ(製品名「SFP-120MC」、平均粒子径:0.30μm、電気化学工業社製)を100質量部、合成例3で得られたα-ナフトールアラルキル型シアン酸エステル樹脂(シアネート当量:261g/eq.)を40質量部、ポリオキシナフチレン型エポキシ樹脂(製品名「HP-6000」、エポキシ当量:250g/eq.、DIC(株)製)を60質量部、湿潤分散剤1(製品名「disperbyk-161」、ビックケミー・ジャパン(株)製)を1質量部、湿潤分散剤2(製品名「disperbyk-111」、ビックケミー・ジャパン(株)製)を2質量部、及びシランカップリング剤(製品名「Z6040」、東レ・ダウコーティング(株)製)を5質量部混合してワニスを得た。このワニスをメチルエチルケトンで希釈し、厚さ0.1mmのEガラス織布に含浸塗工し、140℃で3分間加熱乾燥して、樹脂含有量63質量%のプリプレグを得た。
α-ナフトールアラルキル型シアン酸エステル樹脂の代わりに2,2-ビス(4-シアネートフェニル)プロパンのプレポリマー(製品名「CA210」、シアネート当量139、三菱ガス化学(株)製)を40質量部使用した以外は実施例1と同様にして、プリプレグを得た。
α-ナフトールアラルキル型シアン酸エステル樹脂の代わりに上記式(3)におけるR6が全て水素原子であるノボラック型シアン酸エステル樹脂(製品名「プリマセットPT-30」、ロンザジャパン(株)製、シアネート当量:124g/eq.)を40質量部使用した以外は実施例1と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」、平均粒子径:20nm、ビックケミー・ジャパン(株)製)を1質量部、球状溶融シリカ(製品名「FB-3SDC」、平均粒子径:3.0μm、電気化学工業社製)を300質量部、球状溶融シリカ(SFP-120MC、平均粒子径:0.3μm、電気化学工業社製)を100質量部、合成例3で得られたα-ナフトールアラルキル型シアン酸エステル樹脂(シアネート当量:261g/eq.)を36質量部、合成例4で使用したマレイミド化合物(製品名「BMI-2300」)を26質量部、ポリオキシナフチレン型エポキシ樹脂(製品名「HP-6000」、エポキシ当量:250g/eq.、DIC(株)製)を38質量部、湿潤分散剤1(製品名「disperbyk-161」、ビックケミー・ジャパン(株)製)を1質量部、湿潤分散剤2(製品名「disperbyk-111」、ビックケミー・ジャパン(株)製)を2質量部、シランカップリング剤(製品名「Z6040」、東レ・ダウコーティング(株)製)を5質量部、及び2,4,5-トリフェニルイミダゾール(和光純薬社製)を1質量部混合してワニスを得た。このワニスをメチルエチルケトンで希釈し、厚さ0.1mmのEガラス織布に含浸塗工し、140℃で3分間加熱乾燥して、樹脂含有量63質量%のプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)の使用量を1質量部から3質量部に変更した以外は実施例4と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)の使用量を1質量部から5質量部に変更した以外は実施例4と同様にして、プリプレグを得た。
マレイミド化合物(製品名「BMI-2300」)の代わりに合成例5で使用したマレイミド化合物(製品名「BMI-70」)を26質量部使用した以外は実施例4と同様にして、プリプレグを得た。
ポリオキシナフチレン型エポキシ樹脂(製品名「HP-6000」)の代わりに上記式(8)におけるR11が全て水素原子であるフェノールビフェニルアラルキル型エポキシ樹脂(製品名「NC-3000-FH」、エポキシ当量:320g/eq.、日本化薬(株)製)を38質量部使用した以外は実施例4と同様にして、プリプレグを得た。
ポリオキシナフチレン型エポキシ樹脂(製品名「HP-6000」)の代わりにナフトールアラルキル型エポキシ樹脂(製品名「ESN-175V」、エポキシ当量:255g/eq.、新日鐵化学(株)製)を38質量部使用した以外は実施例4と同様にして、プリプレグを得た。
ポリオキシナフチレン型エポキシ樹脂(製品名「HP-6000」)の代わりに上記式(7)におけるR10が全て水素原子であるフェノールフェニルアラルキル型エポキシ樹脂(製品名「NC-2000-L」、エポキシ当量:226g/eq.、日本化薬(株)製)を38質量部使用した以外は実施例4と同様にして、プリプレグを得た。
ワニスを得る際に、更に2-エチル-4-メチルイミダゾール(製品名「2E4MZ」、四国化成工業(株)製)を0.01質量部加えた以外は実施例4と同様にして、プリプレグを得た。
ワニスを得る際に、合成例3で得られたα-ナフトールアラルキル型シアン酸エステル樹脂及び合成例4で使用したマレイミド化合物を使用せず、合成例4で得られたBT樹脂1を62質量部加えた以外は実施例4と同様にして、プリプレグを得た。
ワニスを得る際に、合成例3で得られたα-ナフトールアラルキル型シアン酸エステル樹脂及び合成例4で使用したマレイミド化合物を使用せず、合成例5で得られたBT樹脂2を62質量部加えた以外は実施例4と同様にして、プリプレグを得た。
ワニスを得る際に、合成例3で得られたα-ナフトールアラルキル型シアン酸エステル樹脂及び合成例4で使用したマレイミド化合物を使用せず、合成例4で得られたBT樹脂1を59質量部、上記式(4)におけるR7が全て水素原子であるナフトールアラルキル型フェノール樹脂(製品「SN-495」、新日鐵化学(株)製、水酸基当量:236g/eq.)を3質量部加えた以外は実施例4と同様にして、プリプレグを得た。
ワニスを得る際に、球状溶融シリカ(製品名「FB-3SDC」)の使用量を300質量部から150質量部に変更し、球状溶融シリカ(製品名「SFP-120MC」)の使用量を100質量部から150質量部に変更し、湿潤分散剤2(製品名「disperbyk-111」)の代わりに湿潤分散剤3(製品名「disperbyk-w903」、ビックケミー・ジャパン(株)製)を2質量部加え、更にアルミナ微粒子(製品名「AX3-15」、平均粒子径:3.0μm、新日鉄住金マテリアルズ(株)マイクロン社製)を200質量部加えた以外は実施例4と同様にして、樹脂含有量64質量%のプリプレグを得た。
ワニスを得る際に、球状溶融シリカ(製品名「FB-3SDC」)及び球状溶融シリカ(製品名「SFP-120MC」)を使用せず、湿潤分散剤1(製品名「disperbyk-161」)、及び湿潤分散剤2(製品名「disperbyk-111」)の代わりに湿潤分散剤3(製品名「disperbyk-w903」)を5質量部加え、更にアルミナ微粒子(製品名「AX3-15」、平均粒子径:3.0μm、新日鉄住金マテリアルズ(株)マイクロン社製)を400質量部加えた以外は実施例4と同様にして、樹脂含有量69質量%のプリプレグを得た。
ワニスを得る際に、球状溶融シリカ(製品名「FB-3SDC」)及び球状溶融シリカ(製品名「SFP-120MC」)を使用せず、湿潤分散剤1(製品名「disperbyk-161」)、及び湿潤分散剤2(製品名「disperbyk-111」)の代わりに湿潤分散剤3(製品名「disperbyk-w903」)を5質量部加え、更にアルミナ微粒子(製品名「ASEP-20」、平均粒子径:0.3μm、電気化学工業(株)製)を100質量部、ベーマイト微粒子(製品名「BM5009」、平均粒子径:3.0μm、アドマテックス(株)製)を300質量部加えた以外は実施例4と同様にして、樹脂含有量66質量%のプリプレグを得た。
ワニスを得る際に、更にシリコーンレジンで表面を被覆したシリコーンゴムパウダー(シリコーン複合パウダー、製品名「KMP-600」、信越化学工業(株)製)を10質量部加えた以外は実施例4と同様にして、樹脂含有量60質量%のプリプレグを得た。
実施例1で使用したポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を1質量部、球状溶融シリカ(製品名「FB-3SDC」、平均粒子径:3.0μm、電気化学工業社製)を300質量部、球状溶融シリカ(製品名「SFP-120MC」、平均粒子径:0.3μm、電気化学工業社製)を100質量部、実施例8で用いたフェノールビフェニルアラルキル型エポキシ樹脂(製品名「NC-3000-FH」)を49質量部、実施例14で使用したナフトールアラルキル型フェノール樹脂(製品名「SN-495」)を36質量部、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン(製品名「BMI-70」)を15質量部、湿潤分散剤1(製品名「disperbyk-161」、ビックケミー・ジャパン(株)製)を1質量部、湿潤分散剤2(製品名「disperbyk-111」、ビックケミー・ジャパン(株)製)を2質量部、シランカップリング剤(製品名「Z6040」、東レ・ダウコーティング(株)製)を5質量部、2-エチル-4-メチルイミダゾール(製品名「2E4MZ」、四国化成工業(株)製)を0.02質量部混合してワニスを得た。このワニスをメチルエチルケトンで希釈し、厚さ0.1mmのEガラス織布に含浸塗工し、140℃で3分間加熱乾燥して、樹脂含有量63質量%のプリプレグを得た。
実施例1で使用したポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を1質量部、球状溶融シリカ(製品名「FB-3SDC」、平均粒子径:3.0μm、電気化学工業社製)を300質量部、球状溶融シリカ(製品名「SFP-120MC」、平均粒子径:0.3μm、電気化学工業社製)を100質量部、ポリオキシナフチレン型エポキシ樹脂(製品名「HP-6000」)を44質量部、上記式(5)におけるR8が全て水素原子であるビフェニルアラルキル型フェノール樹脂(製品名「KAYAHARD GPH-103」、日本化薬(株)製、水酸基当量:231g/eq.)を18質量部、ナフタレン型フェノール樹脂(製品名「EPICLON EXB-9500」、DIC(株)製、水酸基当量:153g/eq.)を18質量部、アミノトリアジンノボラック樹脂(製品名「PHENOLITE LA-3018-50P」、水酸基当量:151g/eq.、DIC(株)製)を3質量部、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン(製品名「BMI-70」)を17質量部、湿潤分散剤1(製品名「disperbyk-161」)を1質量部、湿潤分散剤2(製品名「disperbyk-111」)を2質量部、シランカップリング剤(製品名「Z6040」、東レ・ダウコーティング(株)製)を5質量部、2-エチル-4-メチルイミダゾール(製品名「2E4MZ」、四国化成工業(株)製)を0.02質量部混合してワニスを得た。このワニスをメチルエチルケトンで希釈し、厚さ0.1mmのEガラス織布に含浸塗工し、140℃で3分間加熱乾燥して、樹脂含有量63質量%のプリプレグを得た。
ビス(3-エチル-5-メチル-4マレイミドフェニル)メタン(BMI-70)の代わりに合成例4で使用したマレイミド化合物(製品名「BMI-2300」)を17質量部使用した以外は実施例20と同様にして、プリプレグを得た。
実施例1で作製したワニスを、厚さ0.1mmのSガラス織布に含浸塗工し、140℃で3分間加熱乾燥して、樹脂含有量61質量%のプリプレグを得た。
実施例4で作製したワニスを、厚さ0.1mmのSガラス織布に含浸塗工し、140℃で3分間加熱乾燥して、樹脂含有量61質量%のプリプレグを得た。
実施例7で作製したワニスを、厚さ0.1mmのSガラス織布に含浸塗工し、140℃で3分間加熱乾燥して、樹脂含有量61質量%のプリプレグを得た。
実施例12で作製したワニスを、厚さ0.1mmのSガラス織布に含浸塗工し、140℃で3分間加熱乾燥して、樹脂含有量61質量%のプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」、平均粒子径:20nm、ビックケミー・ジャパン(株)製)の代わりに合成例2で作製した表面処理ナノ粒子を使用した以外は、実施例1と同様にしてプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」、平均粒子径:20nm、ビックケミー・ジャパン(株)製)の代わりに合成例2で作製した表面処理ナノ粒子を使用した以外は、実施例4と同様にしてプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」、平均粒子径:20nm、ビックケミー・ジャパン(株)製)の代わりに合成例2で作製した表面処理ナノ粒子を使用した以外は、実施例12と同様にしてプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」、平均粒子径:20nm、ビックケミー・ジャパン(株)製)の代わりに合成例2で作製した表面処理ナノ粒子を使用した以外は、実施例19と同様にしてプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」、平均粒子径:20nm、ビックケミー・ジャパン(株)製)の代わりにポリシロキサンベースの改質剤で表面処理を施されたベーマイトナノ粒子(製品名「LP-X-21121」、平均粒子径:10nm、ビックケミー・ジャパン(株)製)を使用した以外は、実施例4と同様にしてプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用しない以外は実施例1と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用しない以外は実施例4と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用しない以外は実施例8と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用しない以外は実施例12と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用しない以外は実施例15と同様にしてプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用しない以外は実施例16と同様にしてプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用しない以外は実施例17と同様にしてプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用しない以外は実施例20と同様にしてプリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)の代わりにシリカナノ粒子(製品名「NANOBYK-3652」、平均粒子径:20nm、ビックケミー・ジャパン(株)製)を1質量部使用した以外は実施例4と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用せず、球状溶融シリカ(製品名「FB-3SDC」、平均粒子径:3.0μm、電気化学工業社製)の使用量を300質量部から200質量部に変更した以外は実施例22と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用せず、球状溶融シリカ(製品名「FB-3SDC」、平均粒子径:3.0μm、電気化学工業社製)の使用量を300質量部から200質量部に変更した以外は実施例23と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用せず、球状溶融シリカ(製品名「FB-3SDC」、平均粒子径:3.0μm、電気化学工業社製)の使用量を300質量部から200質量部に変更した以外は実施例24と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)を使用せず、球状溶融シリカ(製品名「FB-3SDC」、平均粒子径:3.0μm、電気化学工業社製)の使用量を300質量部から200質量部に変更した以外は実施例25と同様にして、プリプレグを得た。
ポリシロキサンベースの改質剤で表面処理を施されたアルミナナノ粒子(製品名「NANOBYK-3610」)の代わりに、5質量%のメチルエチルケトンスラリーとして超音波分散器(製品名「UP200S」、hielscher製)にて5分間分散処理した、平均粒子径(D50)が20nmの未処理アルミナナノ粒子を添加した以外は、実施例1と同様にしてプリプレグを得た。
実施例1~30及び比較例1~14で得られたプリプレグ1枚を挟むように、12μm厚の電解銅箔(3EC-III、三井金属鉱業(株)製)をそのプリプレグの上下に配置し、圧力30kgf/cm2、温度220℃で120分間の積層成型を行い、絶縁層厚さ0.14mmの銅張積層板を得た。
プリプレグの溶融粘度(プリプレグ粘度:単位:×16Pa・s)、成形性、耐熱性、吸湿耐熱性、熱膨張率及び熱伝導率は、下記方法にて評価した。
・プリプレグ粘度:フローテスター(島津製作所製)を用い、120℃における溶融粘度の測定を行った。
・成形性:銅張積層板の銅箔をエッチングにより除去した後に、露出した表面を目視にて観察して、ボイドの有無を評価した。ボイドが認められなかった場合を○、認められた場合を×と評価した。
・耐熱性:50×50mmのサンプルを、280℃半田に30分間フロートさせて、デラミネーションの有無を目視により確認し、下記基準により評価した。
○:全く異常なし ×:0~30分間フロートさせている間にデラミネーション発生
・吸湿耐熱性:50mm×50mmのサンプルの片面の半分以外の銅箔をエッチング除去した試験片(すなわち、片面の半分のみに銅箔が残存した試験片)を、プレッシャークッカー試験機(平山製作所社製、PC-3型)を用いて、121℃、2気圧の条件で3時間処理してから、260℃の半田の中に30秒間浸漬した後の外観変化を目視で観察した。4回試験を行いフクレの発生が認めれた回数(フクレ発生回数/試験回数)により評価した。
・熱膨張率:銅箔張積層板の銅箔をエッチングにより除去した後に、熱機械分析装置(TAインスツルメント製)の所定位置に置き、40℃から340℃まで毎分10℃で昇温し、60℃から120℃での面方向の線膨張係数を測定した。測定方向は積層板のガラスクロスの縦方向(Warp)とした。
・熱伝導率:得られた銅箔張積層板の密度を測定し、また、比熱をDSC(TA Instrumen社製、Q100型)により測定し、さらに、キセノンフラッシュアナライザ(Bruker社製、製品名「LFA447Nanoflash」)により熱拡散率を測定した。そして、熱伝導率を以下の式から算出した。
・熱伝導率(W/m・K)=密度(kg/m3)×比熱(kJ/kg・K)×熱拡散率(m2/S)×1000
Claims (23)
- 平均粒子径が1.0nm~100nmのアルミナ及び/又はベーマイトのナノ粒子(A)、平均粒子径が0.20μm~100μmの微粒子(B)及び熱硬化性樹脂(C)を含有する樹脂組成物であって、前記ナノ粒子(A)は、その表面がポリシロキサンベースの改質剤によって処理されたものである、樹脂組成物。
- 前記ナノ粒子(A)が、リン酸エステル、リン酸エステル塩、及びアルキルベンゼンスルホン酸からなる群より選ばれる1種以上の分散助剤によって処理されたものである、請求項1に記載の樹脂組成物。
- 前記微粒子(B)を、前記熱硬化性樹脂(C)100質量部に対して、200質量部以上含有する、請求項1又は2に記載の樹脂組成物。
- 前記微粒子(B)が、シリカ、アルミナ、窒化アルミニウム、窒化ホウ素、ベーマイト、酸化チタン、シリコーンゴム及びシリコーン複合パウダーからなる群より選ばれる1種以上である、請求項1~3のいずれか一項に記載の樹脂組成物。
- 前記ナノ粒子(A)が、溶剤又は樹脂中に1次粒子として分散されたものである、請求項1~4のいずれか一項に記載の樹脂組成物。
- 前記熱硬化性樹脂(C)が、シアン酸エステル化合物(D)、フェノール樹脂(E)、マレイミド化合物(F)、エポキシ樹脂(G)及びBT樹脂(H)からなる群より選ばれる1種以上である、請求項1~5のいずれか一項に記載の樹脂組成物。
- 前記エポキシ樹脂(G)が、下記式(7)、(8)、(9)、(11)及び(12)で表される化合物からなる群より選ばれる1種以上である、請求項6~8のいずれか一項に記載の樹脂組成物。
- 前記アルミナナノ粒子(A)を、前記微粒子(B)の総質量に対して0.010~5質量%含有する、請求項1~11のいずれか一項に記載の樹脂組成物。
- 前記熱硬化性樹脂(C)が、シアン酸エステル化合物(D)を、前記熱硬化性樹脂(C)の総量100質量部に対して、10~60質量部含有する、請求項6~12のいずれか一項に記載の樹脂組成物。
- 前記熱硬化性樹脂(C)が、フェノール樹脂(E)を、前記熱硬化性樹脂(C)の総量100質量部に対して、10~60質量部含有する、請求項6~13のいずれか一項に記載の樹脂組成物。
- 前記熱硬化性樹脂(C)が、マレイミド化合物(F)を、前記熱硬化性樹脂(C)の総量100質量部に対して、3.0~50質量部含有する、請求項6~14のいずれか一項に記載の樹脂組成物。
- 前記熱硬化性樹脂(C)が、エポキシ樹脂(G)を、前記熱硬化性樹脂(C)の総量100質量部に対して、10~80質量部含有する、請求項6~15のいずれか一項に記載の樹脂組成物。
- 前記熱硬化性樹脂(C)が、BT樹脂(H)を、前記熱硬化性樹脂(C)の総量100質量部に対して、20~80質量部含有する、請求項6~16のいずれか一項に記載の樹脂組成物。
- 前記ナノ粒子(A)が、アルミナナノ粒子である、請求項1~17のいずれか一項に記載の樹脂組成物。
- 基材と、その基材に含浸又は塗布した請求項1~18のいずれか一項に記載の樹脂組成物と、を含有するプリプレグ。
- 前記基材が、Eガラスクロス、Tガラスクロス、Sガラスクロス、Qガラスクロス及び有機繊維からなる群より選ばれる1種以上である、請求項19に記載のプリプレグ。
- 請求項19又は20に記載のプリプレグを1枚以上含有する積層板。
- 請求項19又は20に記載のプリプレグと、そのプリプレグに積層した金属箔と、を含有する金属箔張積層板。
- 絶縁層と、前記絶縁層の表面に形成された導体層とを含むプリント配線板であって、前記絶縁層が、請求項1~18のいずれか一項に記載の樹脂組成物を含むプリント配線板。
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EP14740816.5A EP2947122B1 (en) | 2013-01-15 | 2014-01-14 | Resin composition, prepreg, laminate, metal foil-clad laminate, and printed wiring board |
CN201480004959.0A CN105073899B (zh) | 2013-01-15 | 2014-01-14 | 树脂组合物、预浸料、层叠板、覆金属箔层叠板和印刷电路板 |
JP2014557455A JP6414799B2 (ja) | 2013-01-15 | 2014-01-14 | 樹脂組成物、プリプレグ、積層板、金属箔張積層板及びプリント配線板 |
US14/654,911 US10138393B2 (en) | 2013-01-15 | 2014-01-14 | Resin composition, prepreg, laminate, metal foil-clad laminate, and printed-wiring board |
SG11201505058PA SG11201505058PA (en) | 2013-01-15 | 2014-01-14 | Resin composition, prepreg, laminate, metal foil-clad laminate, and printed-wiring board |
KR1020157021331A KR102280840B1 (ko) | 2013-01-15 | 2014-01-14 | 수지 조성물, 프리프레그, 적층판, 금속박 피복 적층판 및 프린트 배선판 |
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JP2017193691A (ja) * | 2016-04-22 | 2017-10-26 | 日立化成株式会社 | 多層プリント配線板用の接着フィルム |
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JP7352406B2 (ja) | 2019-08-06 | 2023-09-28 | 関東電化工業株式会社 | 熱伝導性粒子充填ファイバー |
JP7314837B2 (ja) | 2020-02-28 | 2023-07-26 | 味の素株式会社 | 樹脂組成物 |
JP2021134337A (ja) * | 2020-02-28 | 2021-09-13 | 味の素株式会社 | 樹脂組成物 |
WO2021200871A1 (ja) * | 2020-03-31 | 2021-10-07 | デンカ株式会社 | 半硬化物複合体及びその製造方法、硬化物複合体及びその製造方法、並びに多孔質体に含浸させて用いられる熱硬化性組成物 |
JP7287580B1 (ja) * | 2021-08-27 | 2023-06-06 | 株式会社レゾナック | 熱伝導性組成物 |
WO2023026615A1 (ja) * | 2021-08-27 | 2023-03-02 | 昭和電工株式会社 | 熱伝導性組成物 |
WO2024122651A1 (ja) * | 2022-12-09 | 2024-06-13 | 株式会社アドマテックス | アルミナ粒子材料及びその製造方法、有機物組成物 |
Also Published As
Publication number | Publication date |
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CN105073899A (zh) | 2015-11-18 |
TW201437273A (zh) | 2014-10-01 |
US20150344733A1 (en) | 2015-12-03 |
KR102280840B1 (ko) | 2021-07-22 |
JPWO2014112464A1 (ja) | 2017-01-19 |
EP2947122A1 (en) | 2015-11-25 |
CN105073899B (zh) | 2017-08-01 |
JP6414799B2 (ja) | 2018-10-31 |
EP2947122B1 (en) | 2017-08-30 |
US10138393B2 (en) | 2018-11-27 |
SG11201505058PA (en) | 2015-08-28 |
KR20150105417A (ko) | 2015-09-16 |
EP2947122A4 (en) | 2016-08-31 |
TWI604005B (zh) | 2017-11-01 |
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