WO2013065694A1 - 樹脂組成物、プリプレグ及び積層板 - Google Patents
樹脂組成物、プリプレグ及び積層板 Download PDFInfo
- Publication number
- WO2013065694A1 WO2013065694A1 PCT/JP2012/078062 JP2012078062W WO2013065694A1 WO 2013065694 A1 WO2013065694 A1 WO 2013065694A1 JP 2012078062 W JP2012078062 W JP 2012078062W WO 2013065694 A1 WO2013065694 A1 WO 2013065694A1
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- WIPO (PCT)
- Prior art keywords
- resin composition
- cyanate ester
- ester compound
- epoxy resin
- mixture
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
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- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- 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
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon 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
- C08J5/241—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
- C08L65/02—Polyphenylenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
Definitions
- the present invention relates to a resin composition, a prepreg, and a laminate.
- Printed wiring boards widely used in electronic devices, communication devices, personal computers, and the like have been developed with higher density wiring and higher integration. Along with this, metal foil-clad laminates used for printed wiring boards are required to have excellent properties such as heat resistance, low water absorption, moisture absorption heat resistance, and peel strength.
- FR-4 type laminates in which epoxy resin is cured with dicyandiamide have been widely used as laminates for printed wiring boards.
- the FR-4 type laminate has a limit in meeting the demand for high heat resistance.
- cyanate ester compounds for example, bisphenol A type cyanate ester compounds and novolac type cyanate ester compounds are known (see, for example, Patent Documents 1 to 3).
- Patent Document 4 As a method for imparting water absorption and moisture absorption heat resistance to a laminate, a method of blending a cyanate ester compound having a biphenyl skeleton into the laminate is known (see, for example, Patent Document 4).
- the laminates containing the cyanate ester compounds described in Patent Documents 1 to 3 are excellent in properties such as electrical properties, mechanical properties, chemical resistance, and adhesiveness. However, in terms of water absorption and moisture absorption heat resistance, It may be insufficient.
- the cyanate ester compound having a biphenyl skeleton described in Patent Document 4 has poor solubility in a solvent. Therefore, the cyanate ester compound described in Patent Document 4 gradually precipitates and precipitates even when the melt viscosity increases or dissolves in a solvent depending on the state of take-out during production and storage conditions.
- a laminated board containing such a cyanate ester compound has a problem that the moldability is deteriorated and the appearance after etching is extremely deteriorated.
- a resin composition in which a mixture of positional isomers of a cyanate ester compound having a specific structure is blended with an epoxy resin and an inorganic filler is solvent-soluble.
- the metal foil-clad laminate using the resin composition has been found to be excellent in properties such as adhesion, low water absorption, moisture absorption heat resistance, insulation reliability and appearance, and the present invention. It came to be completed.
- n is each independently an integer of 1 or more, and R 1 and R 2 are each independently a hydrogen atom, an alkyl group, or an aryl group.
- the mixing ratio of the cyanate ester compound (A1) is 30 to 70 mol% with respect to a total of 100 mol% of the mixture (A) of the cyanate ester compound, and the mixing ratio of the cyanate ester compound (A2) is 15
- the resin composition according to [1], in which the content of the cyanate ester compound (A3) is 5 to 35 mol%.
- the resin composition according to [1] or [2], wherein n in the general formulas (1) to (3) are each independently an integer in the range of 1 to 50.
- the aralkyl type epoxy resin is represented by the following general formula (4): a phenol phenyl aralkyl type epoxy resin, a general formula (5): a phenol biphenyl aralkyl type epoxy resin, and the following general formula (6):
- the resin composition according to [4] which is at least one selected from the group consisting of naphthol aralkyl type epoxy resins.
- the content of the inorganic filler (C) is 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the mixture (A) of the cyanate ester compound and the epoxy resin (B) [1] to [ [7]
- 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 the resin composition according to any one of [1] to [8] Board.
- the resin composition of the present invention is excellent in handleability because of its high solvent solubility, and a laminate or a metal foil-clad laminate obtained by curing a prepreg obtained from the resin composition has excellent adhesion and low water absorption. Excellent heat resistance during moisture absorption, insulation reliability and appearance.
- the resin composition of the present embodiment is A cyanate ester compound (A1) having a structural unit represented by the following general formula (1), a cyanate ester compound (A2) having a structural unit represented by the following general formula (2), and the following general formula (3)
- n is each independently an integer of 1 or more, and R 1 and R 2 are each independently a hydrogen atom, an alkyl group, or an aryl group.
- the mixture of cyanate ester compounds (A) used in this embodiment is a mixture of at least two cyanate ester compounds selected from the group consisting of the cyanate ester compounds (A1) to (A3).
- the mixture of the cyanate ester compounds (A1) and (A2), the cyanate ester compounds (A1) and (A3) A mixture, a mixture of the cyanate ester compounds (A2) and (A3), and a mixture of the cyanate ester compounds (A1), (A2) and (A3). It is a mixture of compounds (A1), (A2) and (A3).
- the mixture (A) may contain a prepolymer of the cyanate ester compounds (A1) to (A3).
- each n is independently preferably an integer in the range of 1 to 50, more preferably an integer in the range of 1 to 20, more preferably 1 to 10. More preferably, it is an integer in the range.
- the cyanate ester compound (A1) may be a mixture containing a plurality of compounds having different n in the general formula (1). The same applies to the cyanate ester compounds (A2) and (A3).
- R 1 and R 2 in the general formulas (1) to (3) are preferably each independently a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, a phenyl group It is more preferably a group, a naphthyl group or a biphenyl group, and further preferably a hydrogen atom, a methyl group, an ethyl group or a phenyl group.
- a method for producing the mixture of cyanate ester compounds (A) is not particularly limited.
- a method (cyanate synthesis method) in which each phenol compound in the mixture is cyanated using a mixture of the represented phenol compounds as a raw material is preferable.
- n is independently an integer of 1 or more, and R 1 and R 2 are each independently a hydrogen atom, an alkyl group, or an aryl group.
- a method for cyanating a phenol compound is not particularly limited, and a known method can be applied. For example, a method described in IAN HAMERTON, “Chemistry and Technology of Cyanate Ester Resins”, or BLACKIE ACADEMIC & PROFESSIONAL can be used. . By this method, the phenol compounds represented by the general formulas (1) 'to (3)' can be cyanated to obtain a mixture of the cyanate ester compounds (A1) to (A3).
- the method for cyanating other phenol compounds is not particularly limited. For example, in the presence of a base in a solvent, the cyanide halide is always present in excess in excess of the base.
- the mixing ratio of the cyanate ester compounds (A1) to (A3) in the mixture (A) of the cyanate ester compound used in the present embodiment is not particularly limited as long as each component is included.
- the cyanate ester The mixing ratio of the compound (A1) is preferably 30 to 70 mol%, more preferably 40 to 60 mol%, based on the total 100 mol% of the mixture (A).
- the mixing ratio of the cyanate ester compound (A2) is preferably 15 to 45 mol%, more preferably 20 to 40 mol% with respect to the total 100 mol% of the mixture (A).
- the mixing ratio of the cyanate ester compound (A3) is preferably 5 to 35 mol% with respect to the total 100 mol% of the mixture (A), and particularly the viewpoint of solubility of the resin composition in a solvent. More preferably, it is 10 to 30 mol%.
- the content of the mixture (A) of the cyanate ester compound is not particularly limited, but a total of 100 of the mixture (A) of the cyanate ester compound and the epoxy resin (B).
- the amount is preferably 10 to 90 parts by weight, and more preferably 30 to 70 parts by weight with respect to the parts by weight.
- the resin composition containing the mixture (A) of the cyanate ester compound within the above range has improved solvent solubility and curability, and the laminate obtained from the resin composition has improved heat resistance.
- the resin composition containing 30 to 70 parts by mass of the mixture (A) of the cyanate ester compound further improves the solvent solubility, and the laminate obtained from the resin composition has more characteristics such as heat resistance. Further improvement.
- a cyanate ester compound other than the mixture (A) of the cyanate ester compound can be used in combination.
- the cyanate ester compound other than the mixture (A) of the cyanate ester compound is not particularly limited, and known ones can be used.
- bisphenol A type cyanate ester compound bisphenol F type cyanate ester compound, bisphenol M Type cyanate ester compound, bisphenol P type cyanate ester compound, bisphenol E type cyanate ester compound, phenol novolac type cyanate ester compound, cresol novolac type cyanate ester compound, dicyclopentadiene novolac type cyanate ester compound, tetramethyl Bisphenol F type cyanate ester compound, biphenol type cyanate ester compound, phenol aralkyl type cyanate ester compound, xylenol aralkyl type cyanate ester compound, Off tall aralkyl type cyanate ester compound and the like, and include those prepolymers.
- These cyanate ester compounds may be used alone or in combination of two or more.
- Epoxy resin (B) used for this embodiment is not specifically limited, It is preferable that it is an epoxy resin normally used for printed wiring board materials.
- a representative example of the epoxy resin (B) is a non-halogen epoxy resin due to the recent growing interest in environmental problems.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene Type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, glycidylamine, glycidyl ester, butadiene epoxidized compound, hydroxyl group-containing silicone resin and epichlorohydrin
- an aralkyl type epoxy resin is preferable in order to improve flame retardancy.
- aralkyl epoxy resin examples include a phenol phenyl aralkyl epoxy resin represented by the following general formula (4), a phenol biphenyl aralkyl epoxy resin represented by the following general formula (5), and the following general formula (6).
- the naphthol aralkyl type epoxy resin etc. which are represented are mentioned.
- the phenol biphenyl aralkyl type epoxy resin represented by the general formula (5) is preferable from the viewpoint of heat resistance and flame retardancy of the resin composition obtained.
- the said aralkyl type epoxy resin may be used individually by 1 type according to the objective, and can also be used in combination of 2 or more type as appropriate.
- M in the general formulas (4) to (6) are each independently an integer of 1 to 50, and R 3 to R 14 are each independently a hydrogen atom, a methyl group, an ethyl group, or an aryl group. is there.)
- the content of the epoxy resin (B) is 10 to 90 masses with respect to a total of 100 mass parts of the mixture (A) of the cyanate ester compound and the epoxy resin (B). Part is preferable, and the range of 30 to 70 parts by weight is particularly preferable.
- the content of the epoxy resin (B) is in the above range, the resulting resin composition is excellent in curability and heat resistance.
- the inorganic filler (C) used in the present embodiment is not particularly limited as long as it is generally used.
- silicas such as natural silica, fused silica, amorphous silica, and hollow silica; aluminum hydroxide, water Aluminum oxide heat-treated products (heat treated with aluminum hydroxide and reduced in part of crystal water), metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; boric acid Examples thereof include zinc, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass fibers (glass fine powders such as E glass and D glass), and hollow glass.
- silica is particularly preferable from the viewpoint of low water absorption of the resin composition.
- the average particle diameter (D50) of the inorganic filler (C) is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m.
- the said inorganic filler (C) can also be used combining suitably what changed the particle size distribution and the average particle diameter.
- D50 is a median diameter (median diameter), and is a diameter in which the volume on the large side is equal to the volume on the small side when the particle size distribution of the measured powder is divided into two. Generally, it is measured by a wet laser diffraction / scattering method.
- the content of the inorganic filler (C) is not particularly limited, but a total of 100 parts by mass of the mixture of cyanate ester compound (A) and the epoxy resin (B). Is preferably 10 to 1000 parts by mass, more preferably 10 to 300 parts by mass, still more preferably 30 to 300 parts by mass, and particularly preferably 30 to 200 parts by mass.
- the inorganic filler (C) used in the present embodiment can be treated with a silane coupling agent or a wetting and dispersing agent.
- the inorganic filler (C) treated with the silane coupling agent has improved wettability to the resin and glass cloth, and the inorganic filler (C) treated with the wet dispersant has improved dispersibility in the resin solution. To do.
- the silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for inorganic surface treatment.
- ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -Aminosilane-based silane coupling agents such as aminopropyltrimethoxysilane
- Epoxysilane-based silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane
- Vinylsilane-based silane couplings such as ⁇ -methacryloxypropyltrimethoxysilane Agents
- cationic silane-based silane coupling agents such as N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride
- phenylsilane-based silane coupling agents may be used individually by 1 type, and can also be used in combination
- the wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer that is usually used for paints.
- a dispersion stabilizer that is usually used for paints.
- acid groups such as Disperbyk-110, 111, 996, and W903 manufactured by Big Chemie Japan are used.
- a copolymer-based wetting and dispersing agent a copolymer-based wetting and dispersing agent.
- the resin composition of the present embodiment may contain a curing accelerator in order to adjust the curing rate as needed.
- the curing accelerator is not particularly limited as long as it is generally used as a curing accelerator for the mixture (A) of the cyanate ester compound and the epoxy resin (B).
- copper, zinc, cobalt And organic metal salts such as nickel; imidazoles and derivatives thereof; tertiary amines and the like.
- the resin composition of this embodiment may contain an organic solvent.
- the organic solvent is not particularly limited as long as it is an organic solvent in which the mixture (A) of the cyanate ester compound and the epoxy resin (B) are dissolved, and examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones; aromatic hydrocarbons such as benzene, toluene, xylene; amides such as dimethylformamide and dimethylacetamide.
- thermosetting resins thermoplastic resins and oligomers thereof, various high molecular compounds such as elastomers, and other flame retardants, as long as desired properties are not impaired.
- These compounds, additives and the like may be included. These are not particularly limited as long as they are generally used.
- a flame retardant compound For example, phosphorus compounds, such as phosphate ester and a melamine phosphate; Nitrogen-containing compounds, such as a melamine and a benzoguanamine; Oxazine ring containing compound; A silicone type compound etc. are mentioned.
- distribution An agent, a leveling agent, a brightening agent, a polymerization inhibitor, etc. can be used in appropriate combination as desired.
- the manufacturing method of the resin composition of this embodiment is a manufacturing method with which the resin composition containing the mixture (A) of the cyanate ester compound mentioned above, an epoxy resin (B), and an inorganic filler (C) is obtained.
- a method of blending the inorganic filler (C) in the epoxy resin (B), dispersing the mixture with a homomixer or the like, and blending the mixture (A) of the cyanate ester compound may be mentioned.
- an organic solvent is added beforehand, viscosity is lowered, handling property is improved, and impregnation property with a substrate such as glass cloth is improved.
- the organic solvent is not particularly limited as long as it is an organic solvent in which the mixture (A) of the cyanate ester compound and the epoxy resin (B) are dissolved, and examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones; aromatic hydrocarbons such as benzene, toluene, xylene; amides such as dimethylformamide and dimethylacetamide.
- the resin composition of the present embodiment forms a high-quality prepreg because the solvent solubility is improved and the handleability is greatly improved by using the mixture (A) of the specific cyanate compound described above. be able to. Furthermore, by using the high-quality prepreg, a metal foil-clad laminate having excellent heat resistance, flame retardancy, adhesion, low water absorption, heat resistance during moisture absorption, insulation reliability and appearance can be obtained.
- the prepreg of this embodiment is a prepreg formed by impregnating or applying the above-described resin composition to a substrate.
- the manufacturing method of the prepreg of this embodiment combines the base material and the resin composition which contains the said mixture of a cyanate ester compound (A), the said epoxy resin (B), and the said inorganic filler (C) as an essential component. If it is a method of manufacturing a prepreg, it will not specifically limit.
- the resin composition is impregnated or coated on a substrate and then semi-cured by a method of heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes, preferably 1 to 30 minutes. And the like.
- the amount of the resin composition attached to the substrate is preferably in the range of 20 to 95% by mass, more preferably in the range of 30 to 90% by mass in terms of the amount of resin in the prepreg (including the inorganic filler (C)). .
- a base material used for this embodiment it does not specifically limit but the well-known base material used for various printed wiring board materials can be suitably selected and used by the target use and performance.
- glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, T glass
- Inorganic fibers other than glass such as quartz
- Polyparaphenylene Wholly aromatic polyamides such as terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technola (registered trademark), manufactured by Teijin Techno Products)
- Polyesters such as 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), poly
- the said base material is suitably selected according to the intended use and performance, and it may be used individually by 1 type and can also be used in combination of 2 or more type. Although it does not specifically limit as a shape of the said base material, For example, a woven fabric, a nonwoven fabric, roving, a chopped strand mat, a surfacing mat etc. are mentioned.
- the weaving method of the woven fabric is not particularly limited, and examples thereof include plain weave, nanako weave, twill weave and the like.
- the thickness of the substrate is not particularly limited, but is preferably 0.01 to 0.3 mm, for example.
- the base material a base material surface-treated with a silane coupling agent or the like, or a base material that has been physically opened in a woven fabric can be preferably used from the viewpoint of moisture absorption heat resistance.
- 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 more preferably a glass woven fabric made of E-glass glass fibers.
- a film of polyimide, polyamide, polyester or the like can be used as the base material.
- the thickness of the film is not particularly limited, but is preferably 0.002 to 0.05 mm.
- the film is more preferably a film that has been surface-treated by plasma treatment or the like.
- the laminate of this embodiment is a metal foil-clad laminate using the above prepreg.
- the laminated board of this embodiment is excellent in adhesiveness, low water absorption, heat resistance at the time of moisture absorption, insulation reliability, and an external appearance by using the above-mentioned prepreg.
- the laminated board of this embodiment can be manufactured by carrying out lamination molding using the above-mentioned prepreg. Specifically, it can be produced by laminating one or more of the above-described prepregs and laminating and forming a metal foil such as copper or aluminum on one or both sides as desired.
- the metal foil to be used will not be specifically limited if it is used for printed wiring board material, 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.
- As the lamination molding method a usual method for molding a laminated board for a printed wiring board and a multilayer board can be applied.
- the method of using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc. is mentioned.
- the temperature is preferably 100 to 300 ° C.
- the pressure is preferably 2 to 100 kgf / cm 2
- the heating time is preferably in the range of 0.05 to 5 hours.
- post-curing can be performed at a temperature of 150 to 300 ° C., if necessary.
- the laminated board of this embodiment can also be made into a multilayer board by combining the above-mentioned prepreg and a separately prepared wiring board for an inner layer, and carrying out lamination molding.
- the laminated board of the present embodiment can be suitably used as a printed wiring board by forming a predetermined wiring pattern.
- the laminated board of this embodiment has a low thermal expansion coefficient, high flame retardance, good moldability and drilling workability, and particularly as a printed wiring board for semiconductor packages where such performance is required. It can be used effectively.
- 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 described above.
- the printed wiring board of this embodiment can be manufactured by the following method, for example. First, an etching process is performed on the surface of the above-mentioned metal foil-clad laminate to form an inner layer circuit, thereby producing an inner layer substrate. If necessary, surface treatment is performed on the inner layer circuit surface of the inner layer substrate to increase the adhesive strength, then the required number of the prepregs are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is laminated on the outer side. Then, it is integrally molded by heating and pressing. In this way, a multilayer laminate is produced in which an insulating layer made of a cured material of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit.
- 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.
- a printed wiring board is manufactured by performing an etching process on the metal foil for forming an outer layer circuit.
- a resin composition layer (a layer made of the above-mentioned resin composition) in a metal foil-clad laminate using the above-described prepreg (the base material and the above-mentioned resin composition attached thereto). ) Constitutes an insulating layer containing the above-mentioned resin composition.
- Solution 2 was added dropwise to 600 g of 2.43 mol of cyanogen chloride in methylene chloride at ⁇ 10 ° C. over 1.5 hours to obtain Solution 2.
- Solution 2 was stirred for 30 minutes, and then a mixed solution of 0.49 mol of triethylamine and 50 g of methylene chloride was added dropwise to Solution 2 to obtain Solution 3. Further, the solution 3 was stirred for 30 minutes to complete the reaction.
- the triethylamine hydrochloride was filtered from the solution 3 to obtain a filtrate. The obtained filtrate was washed with 1000 mL of 0.1N hydrochloric acid, and then washed with 1000 mL of water four times.
- n is an integer of 1 to 50
- n is an integer of 1 to 50
- the obtained crystals were washed with diethyl ether and hexane and then dried under reduced pressure to obtain a brown solid.
- the obtained brown solid was analyzed by infrared absorption spectrum, and as a result, 4,4′-biphenylaralkyl type cyanate compound represented by the following formula (16) (in the infrared absorption spectrum, around 2264 cm ⁇ 1) (The absorption of cyanate groups was confirmed).
- n is an integer of 1 to 50.
- Example 1 50 parts by mass of a mixture of biphenyl aralkyl type cyanate compound synthesized in Synthesis Example 1, 50 parts by mass of biphenyl aralkyl type epoxy resin (NC3000-H, manufactured by Nippon Kayaku Co., Ltd.), zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) 0.04 parts by mass and 100 parts by mass of synthetic silica (SC-2050MR, manufactured by Admatex, average particle size: 0.8 ⁇ m) were mixed to obtain a resin composition. Methyl ethyl ketone was added to this resin composition to obtain a varnish.
- NC3000-H manufactured by Nippon Kayaku Co., Ltd.
- zinc octylate manufactured by Nippon Chemical Industry Co., Ltd.
- SC-2050MR synthetic silica
- This varnish was further diluted with methyl ethyl ketone, impregnated with E glass cloth (thickness 0.1 mm), and dried by heating at 160 ° C. for 4 minutes to obtain a prepreg having a resin content of 48% by mass.
- 4 sheets of this prepreg were stacked and 18 ⁇ m electrolytic copper foils were placed one above the other and pressed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper-clad laminate having a thickness of 0.4 mm. .
- the 4,4′-biphenylaralkyl cyanate compound obtained in Synthesis Example 2 was insoluble in methyl ethyl ketone. Therefore, the obtained varnish was impregnated and coated on E glass cloth (thickness 0.1 mm) in a state where the mixture of the cyanate ester compound was dispersed in a solvent (methyl ethyl ketone) and dried at 160 ° C. for 4 minutes. Thus, a prepreg having a resin content of 48% by weight was obtained. Next, 4 sheets of this prepreg were stacked and 18 ⁇ m electrolytic copper foils were placed one above the other and pressed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper-clad laminate having a thickness of 0.4 mm. .
- the resin composition of the present invention has high solvent solubility and excellent handling properties, and can realize a metal foil-clad laminate having excellent adhesion, low water absorption, moisture absorption heat resistance, insulation reliability and appearance, It is suitable as a printed wiring board material for high density and has industrial applicability.
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Abstract
Description
すなわち、本発明は、以下に関する。
[1]
下記一般式(1)で表される構造単位を有するシアン酸エステル化合物(A1)、下記一般式(2)で表される構造単位を有するシアン酸エステル化合物(A2)、及び下記一般式(3)で表される構造単位を有するシアン酸エステル化合物(A3)からなる群より選択される少なくとも2種のシアン酸エステル化合物の混合物(A)と、
エポキシ樹脂(B)と、
無機充填材(C)と、を含む樹脂組成物。
[2]
前記シアン酸エステル化合物の混合物(A)の合計100mol%に対して、前記シアン酸エステル化合物(A1)の混合比率が30~70mol%であり、前記シアン酸エステル化合物(A2)の混合比率が15~45mol%であり、前記シアン酸エステル化合物(A3)の混合比率が5~35mol%である[1]に記載の樹脂組成物。
[3]
前記一般式(1)~(3)中のnがそれぞれ独立して1~50の範囲の整数である[1]又は[2]に記載の樹脂組成物。
[4]
前記エポキシ樹脂(B)が、アラルキル型エポキシ樹脂である[1]~[3]のいずれかに記載の樹脂組成物。
[5]
前記アラルキル型エポキシ樹脂が、下記一般式(4)で表されるフェノールフェニルアラルキル型エポキシ樹脂、下記一般式(5)で表されるフェノールビフェニルアラルキル型エポキシ樹脂、及び下記一般式(6)で表されるナフトールアラルキル型エポキシ樹脂からなる群より選択される少なくとも1種である[4]に記載の樹脂組成物。
[6]
前記無機充填材(C)がシリカである[1]~[5]のいずれかに記載の樹脂組成物。
[7]
前記シアン酸エステル化合物の混合物(A)の含有量が、前記シアン酸エステル化合物の混合物(A)と前記エポキシ樹脂(B)との合計100質量部に対して10~90質量部である[1]~[6]のいずれかに記載の樹脂組成物。
[8]
前記無機充填材(C)の含有量が、前記シアン酸エステル化合物の混合物(A)と前記エポキシ樹脂(B)の合計量100質量部に対して10~1000質量部である[1]~[7]のいずれかに記載の樹脂組成物。
[9]
[1]~[8]のいずれかに記載の樹脂組成物を基材に含浸又は塗布してなるプリプレグ。
[10]
[9]に記載のプリプレグを用いた金属箔張リ積層板。
[11]
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卜配線板であって、前記絶縁層が[1]~[8]のいずれかに記載の樹脂組成物を含むプリント配線板。
本実施形態の樹脂組成物は、
下記一般式(1)で表される構造単位を有するシアン酸エステル化合物(A1)、下記一般式(2)で表される構造単位を有するシアン酸エステル化合物(A2)、及び下記一般式(3)で表される構造単位を有するシアン酸エステル化合物(A3)からなる群より選択される少なくとも2種のシアン酸エステル化合物の混合物(A)と、
エポキシ樹脂(B)と、
無機充填材(C)と、を含む。
本実施形態に用いるシアン酸エステル化合物の混合物(A)は、前記シアン酸エステル化合物(A1)~(A3)からなる群より選択される少なくとも2種のシアン酸エステル化合物の混合物である。
本実施形態に用いるエポキシ樹脂(B)は、特に限定されないが、プリント配線板材料用に通常使用されるエポキシ樹脂であることが好ましい。エポキシ樹脂(B)の代表的な例としては近年の環境問題への関心の高まりから、非ハロゲン系エポキシ樹脂が挙げられる。その中でも、例えばビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、3官能フェノール型エポキシ樹脂、4官能フェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、アラルキル型エポキシ樹脂、脂環式エポキシ樹脂、ポリオール型エポキシ樹脂、グリシジルアミン、グリシジルエステル、ブタジエンなどの2重結合をエポキシ化した化合物、水酸基含有シリコーン樹脂類とエピクロルヒドリンとの反応により得られる化合物等が挙げられ、特に難燃性を向上させるためにはアラルキル型エポキシ樹脂が好ましい。
本実施形態に用いる無機充填材(C)は、一般に使用されるものであれば、特に限定されないが、例えば、天然シリカ、溶融シリカ、アモルファスシリカ、中空シリカ等のシリカ類;水酸化アルミニウム、水酸化アルミニウム加熱処理品(水酸化アルミニウムを加熱処理し、結晶水の一部を減じたもの)、ベーマイト、水酸化マグネシウム等の金属水和物;酸化モリブデン、モリブデン酸亜鉛等のモリブデン化合物;ホウ酸亜鉛、錫酸亜鉛、アルミナ、クレー、カオリン、タルク、焼成クレー、焼成カオリン、焼成タルク、マイカ、ガラス短繊維(EガラスやDガラスなどのガラス微粉末類)、中空ガラスなどが挙げられる。その中でも特にシリカが樹脂組成物の低吸水性などの観点から好ましい。
本実施形態の樹脂組成物には、必要に応じ、硬化速度を適宜調節するために硬化促進剤を含有させてもよい。前記硬化促進剤としては、前記シアン酸エステル化合物の混合物(A)や前記エポキシ樹脂(B)の硬化促進剤として一般に使用されるものであれば、特に限定されず、例えば、銅、亜鉛、コバルト、ニッケル等の有機金属塩類;イミダゾール類及びその誘導体;第3級アミン等が挙げられる。
本実施形態の樹脂組成物の製造方法は、上述したシアン酸エステル化合物の混合物(A)、エポキシ樹脂(B)及び無機充填材(C)を含む樹脂組成物が得られる製造方法であれば、特に限定されない。例えば前記エポキシ樹脂(B)に前記無機充填材(C)を配合し、ホモミキサー等で分散させ、さらに前記シアン酸エステル化合物の混合物(A)を配合する方法などが挙げられる。また、本実施形態の樹脂組成物は、後述するプリプレグに使用する場合、予め有機溶剤を添加して、粘度を下げ、ハンドリング性を向上させると共にガラスクロス等の基材との含浸性を高めることが好ましい。前記有機溶剤としては、前記シアン酸エステル化合物の混合物(A)及び前記エポキシ樹脂(B)が溶解する有機溶剤であれば、特に限定されず、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類;ベンゼン、トルエン、キシレンなどの芳香族炭化水素類;ジメチルホルムアミドやジメチルアセトアミドなどのアミド類等が挙げられる。
本実施形態のプリプレグは、上述の樹脂組成物を基材に含浸又は塗布してなるプリプレグである。
本実施形態の積層板は、上述のプリプレグを用いた金属箔張り積層板である。本実施形態の積層板は、上述のプリプレグを用いることにより、密着性、低吸水性、吸湿時の耐熱性、絶縁信頼性及び外観に優れる。
≪プリント配線板≫
本実施形態のプリント配線板は、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、前記絶縁層が上述の樹脂組成物を含む。
原料として、ビフェニルアラルキル型フェノール化合物(MEH-7852、OH基当量:183g/eq、明和化成(株)製)を用いた。該ビフェニルアラルキル型フェノール化合物は、1H-NMR測定により分析した結果、下記式(10)~(12)で表される成分を表1-Aに示した割合で含有していた。
該ビフェニルアラルキル型フェノール化合物1.22mol(OH基換算)及びトリエチルアミン1.82molをクロロホルム475mLに溶解させて溶液1を得た。2.43molの塩化シアンの塩化メチレン溶液600gに-10℃で溶液1を1.5時間かけて滴下して溶液2を得た。溶液2を30分撹拌した後、0.49molのトリエチルアミンと塩化メチレン50gとの混合溶液を溶液2に滴下して溶液3を得た。さらに溶液3を30分撹拌して反応を完結させた。溶液3からトリエチルアミンの塩酸塩をろ別してろ液を得た。得られたろ液を0.1N塩酸1000mLにより洗浄した後、水1000mLによる洗浄を4回繰り返した。洗浄後のろ液を、硫酸ナトリウムにより乾燥した後、75℃でエバポレートし、黄色固体の結晶を得た。得られた結晶をジエチルエーテル及びヘキサンにて洗浄した後、減圧乾燥することにより、褐色固形物を得た。得られた褐色固形物は、赤外吸収スペクトルで分析した結果、下記式(13)~(15)で表されるビフェニルアラルキル型のシアン酸エステル化合物の混合物(赤外吸収スペクトルにおいて、2264cm-1付近にシアネート基の吸収を確認)であった。該混合物中の下記式(13)~(15)で表されるシアン酸エステル化合物の組成割合は、1H-NMRで測定した結果、表1-Bに示すとおりであった。
4,4’-ビフェニルアラルキル型フェノール樹脂(KAYAHARD GPH-65、OH基当量:204g/eq、日本化薬株式会社製)1.1mol(OH基換算)及びトリエチルアミン1.6molを3-メチルテトラヒドロフラン900mLに溶解させて溶液1-2を得た。2.2molの塩化シアンの塩化メチレン溶液2500gに-10℃で溶液1-2を1.5時間かけて滴下して溶液2-2を得た。溶液2-2を30分撹拌した後、0.4molのトリエチルアミンと塩化メチレン100gとの混合溶液を溶液2-2に滴下して溶液3-2を得た。さらに溶液3-2を30分撹拌して反応を完結させた。溶液3-2からトリエチルアミンの塩酸塩をろ別してろ液を得た。得られたろ液を0.1N塩酸 1000mLにより洗浄した後、水1000mLによる洗浄を4回繰り返した。洗浄後のろ液を、硫酸ナトリウムにより乾燥した後、75℃でエバポレートし、黄色固体の結晶を得た。得られた結晶をジエチルエーテル及びヘキサンにて洗浄した後、減圧乾燥することにより、褐色固形物を得た。得られた褐色固形物は、赤外吸収スペクトルにより分析した結果、下記式(16)で表される4,4’-ビフェニルアラルキル型のシアン酸エステル化合物(赤外吸収スペクトルにおいて、2264cm-1付近にシアネート基の吸収を確認)であった。
合成例1で合成したビフェニルアラルキル型シアン酸エステル化合物の混合物50質量部、ビフェニルアラルキル型エポキシ樹脂(NC3000-H、日本化薬製)50質量部、オクチル酸亜鉛(日本化学産業(株)製)0.04質量部、及び合成シリカ100質量部(SC-2050MR、アドマテックス製、平均粒子径:0.8μm)を混合して樹脂組成物を得た。この樹脂組成物にメチルエチルケトンを加えてワニスを得た。このワニスをさらにメチルエチルケトンで希釈し、Eガラスクロス(厚さ0.1mm)に含浸塗工し、160℃で4分間加熱乾燥して、樹脂含有量48質量%のプリプレグを得た。次に、このプリプレグを4枚重ね、18μmの電解銅箔を上下に配置し、圧力30kgf/cm2、温度220℃で120分間プレスを行い、厚さ0.4mmの銅張り積層板を得た。
合成例2で得た4,4’-ビフェニルアラルキル型シアン酸エステル化合物50質量部、ビフェニルアラルキル型エポキシ樹脂(NC3000-H、日本化薬製)50質量部、オクチル酸亜鉛(日本化学産業(株)製)0.04質量部をメチルエチルケトンで溶解混合し、さらに合成シリカ(SC-2050MR、アドマテックス製、平均粒子径:0.8μm)100質量部を混合してワニスを得た。しかし、得られたワニスにおいて、合成例2で得た4,4’-ビフェニルアラルキル型シアン酸エステル化合物はメチルエチルケトンには不溶であった。そのため、得られたワニスを、該シアン酸エステル化合物の混合物を溶剤(メチルエチルケトン)に分散させた状態で、Eガラスクロス(厚さ0.1mm)に含浸塗工し、160℃で4分間加熱乾燥して、樹脂含有量48重量%のプリプレグを得た。次に、このプリプレグを4枚重ね、18μmの電解銅箔を上下に配置し、圧力30kgf/cm2、温度220℃で120分間プレスを行い、厚さ0.4mmの銅張り積層板を得た。
合成例1で合成したビフェニルアラルキル型シアン酸エステル化合物の混合物の代わりにビスフェノールA型シアン酸エステル化合物(CA210、三菱ガス化学製)を50質量部用いた以外は実施例1と同様にして銅張り積層板を得た。
合成例1で合成したビフェニルアラルキル型シアン酸エステル化合物の混合物の代わりにフェノールノボラック型シアン酸エステル化合物(PT-30、ロンザジャパン製)を50質量部用いた以外は実施例1と同様にして銅張り積層板を得た。
実施例1及び比較例1~3により得られた銅張り積層板の物性を以下の方法により測定した。当該測定結果を表2に示す。
実施例1及び比較例1~3により得られた銅張り積層板について、JIS C6481に準拠して、銅箔ピール強度(単位:kgf/cm)を測定した。銅箔ピール強度が高いほど、得られた銅張り積層板は密着性に優れると評価した。
実施例1及び比較例1~3により得られた銅張り積層板を用いて、50mm×50mmのサンプルを作成した。該サンプルの片面の半分以外の全銅箔をエッチング除去して試験片を得た。該試験片を、プレッシャークッカー試験機(PC-3型)により、121℃、2気圧の条件で3時間処理後、260℃のハンダ中に30秒浸漬した。浸漬後の試験片の外観変化を目視で観察し、下記基準により吸湿耐熱性を評価した。また、プレッシャークッカー試験機による処理時間を4時間及び5時間に変更した以外は上記と同様にして吸湿耐熱性を評価した。
(評価基準)
○(良):浸漬後の試験片においてフクレ発生が無かった。
×(不良):浸漬後の試験片においてフクレ発生が有った。
実施例1及び比較例1~3により得られた銅張り積層板をエッチングし、銅箔を除去した後、ボイドの有無を確認した。
実施例1及び比較例1~3により得られた銅張り積層板をエッチングし、銅箔を除去した後、板の外観(ムラの有無)を目視で確認した。
実施例1及び比較例1~3により得られた銅張り積層板をエッチングし、銅箔を除去した。該銅箔を除去した後の積層板について、JIS C6481に準拠して、プレッシャークッカー試験機(PC-3型)により、121℃、2気圧で5時間処理後の吸水率を測定した。
Claims (11)
- 前記シアン酸エステル化合物の混合物(A)の合計100mol%に対して、前記シアン酸エステル化合物(A1)の混合比率が30~70mol%であり、前記シアン酸エステル化合物(A2)の混合比率が15~45mol%であり、前記シアン酸エステル化合物(A3)の混合比率が5~35mol%である請求項1に記載の樹脂組成物。
- 前記一般式(1)~(3)中のnがそれぞれ独立して1~50の範囲の整数である請求項1又は2に記載の樹脂組成物。
- 前記エポキシ樹脂(B)が、アラルキル型エポキシ樹脂である請求項1~3のいずれか一項に記載の樹脂組成物。
- 前記無機充填材(C)がシリカである請求項1~5のいずれか一項に記載の樹脂組成物。
- 前記シアン酸エステル化合物の混合物(A)の含有量が、前記シアン酸エステル化合物の混合物(A)と前記エポキシ樹脂(B)との合計100質量部に対して10~90質量部である請求項1~6のいずれか一項に記載の樹脂組成物。
- 前記無機充填材(C)の含有量が、前記シアン酸エステル化合物の混合物(A)と前記エポキシ樹脂(B)の合計量100質量部に対して10~1000質量部である請求項1~7のいずれか一項に記載の樹脂組成物。
- 請求項1~8のいずれか一項に記載の樹脂組成物を基材に含浸又は塗布してなるプリプレグ。
- 請求項9に記載のプリプレグを用いた金属箔張り積層板。
- [規則91に基づく訂正 21.01.2013]
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1~8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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KR1020147011791A KR101958046B1 (ko) | 2011-11-02 | 2012-10-30 | 수지 조성물, 프리프레그 및 적층판 |
CN201280053929.XA CN103917571B (zh) | 2011-11-02 | 2012-10-30 | 树脂组合物、预浸料和层压板 |
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KR (1) | KR101958046B1 (ja) |
CN (1) | CN103917571B (ja) |
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WO2018047724A1 (ja) | 2016-09-12 | 2018-03-15 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板 |
WO2018139368A1 (ja) | 2017-01-26 | 2018-08-02 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板 |
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TWI565752B (zh) | 2017-01-11 |
CN103917571B (zh) | 2016-01-20 |
SG11201401958TA (en) | 2014-09-26 |
EP2774938A1 (en) | 2014-09-10 |
JP5988176B2 (ja) | 2016-09-07 |
US20140377565A1 (en) | 2014-12-25 |
KR101958046B1 (ko) | 2019-03-13 |
JPWO2013065694A1 (ja) | 2015-04-02 |
EP2774938A4 (en) | 2015-07-15 |
US9527979B2 (en) | 2016-12-27 |
CN103917571A (zh) | 2014-07-09 |
KR20140097146A (ko) | 2014-08-06 |
TW201326297A (zh) | 2013-07-01 |
EP2774938B1 (en) | 2016-02-03 |
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