WO2018216647A1 - 樹脂組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板、並びに樹脂組成物の製造方法 - Google Patents
樹脂組成物、プリプレグ、レジンシート、金属箔張積層板及びプリント配線板、並びに樹脂組成物の製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- 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
- H05K1/036—Multilayers with layers of different types
-
- 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
-
- 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
- C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- 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
-
- 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
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
Definitions
- the present invention relates to a resin composition, a prepreg, a resin sheet, a metal foil-clad laminate and a printed wiring board, and a method for producing the resin composition.
- the conventional technology described above has insufficient moldability of the printed wiring board. Moreover, there is room for further improvement in the storage stability of the prepreg used as a raw material for the printed wiring board. Therefore, further improvement of them is desired.
- the present invention has been made in view of the above circumstances, a resin composition excellent in moldability of a printed wiring board and storage stability of a prepreg, a prepreg, a resin sheet, a metal foil-clad laminate, a printed wiring board, and a resin composition It aims at providing the manufacturing method of a thing.
- the inventors of the present invention have intensively studied to achieve the above object.
- conventionally there is room for improvement in the moldability of the printed wiring board because the melt viscosity of the prepreg as a raw material is high, and when the prepreg is laminated and cured, the resin composition contained in the prepreg We found out that there was a cause of poor fluidity.
- the prepreg has a high melt viscosity, and there is room for improvement in its storage stability.
- An aromatic ring such as diallyl bisphenol A may be substituted with an allyl group (the same applies in this paragraph). It was found that the aromatic compound having a phenolic hydroxyl group is because the reaction between the allyl group and the maleimide group in the maleimide compound easily proceeds.
- R 1 represents a linear or branched alkyl group having 1 or more carbon atoms or an aryl group which may have a substituent.
- R 1 is a substituent represented by the following formula (5).
- R 2 represents a hydrogen atom or a monovalent organic group.
- R 3 s each independently represent a hydroxyl group or any substituent represented by the following formulas (2), (3) and (4), and at least one of them is And any one of the substituents represented by the following formulas (2), (3) and (4), R 4 represents a single bond, an alkylene group, a phenylene group, a biphenylene group or a naphthylene group, and R 5 Each independently represents a hydrogen atom, an alkyl group, a phenyl group, a biphenyl group, or a naphthyl group.) (In the formulas (2), (3) and (4), R 1 represents a linear or branched alkyl group having 1 or more carbon atoms or an aryl group which may have a substituent.) [6]
- the maleimide compound (B) is bis (4-maleimidophenyl) methane, 2,2-bis ⁇ 4- (4-maleimidophenoxy) -phenyl ⁇ propane, bis (3-ethy
- each R 6 independently represents a hydrogen atom or a methyl group, and n 1 represents an integer of 1 or more.
- the inorganic filler (C) includes at least one selected from the group consisting of silica, alumina, and boehmite.
- a prepreg comprising: a base material; and the resin composition according to any one of [1] to [10] impregnated or coated on the base material.
- a resin sheet comprising a support and the resin composition according to any one of [1] to [10] applied to the support.
- a laminated plate in which at least one selected from the group consisting of the prepreg according to [11] and the resin sheet according to [12] is laminated, and includes the prepreg and the resin sheet.
- a laminate comprising a cured product of a resin composition contained in at least one selected from the group.
- At least one selected from the group consisting of the prepreg according to [11] and the resin sheet according to [12], and at least one single side or both sides selected from the group consisting of the prepreg and the resin sheet A metal foil-clad laminate comprising: a cured product of a resin composition contained in at least one selected from the group consisting of the prepreg and the resin sheet. Board.
- a printed wiring board including an insulating layer and a conductor layer formed on a surface of the insulating layer, wherein the insulating layer is the resin according to any one of [1] to [10]
- a printed wiring board comprising the composition.
- a resin composition excellent in moldability of a printed wiring board and storage stability of a prepreg, a prepreg, a resin sheet, a metal foil-clad laminate, a printed wiring board, and a method for producing the resin composition are provided. Can do.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail, but the present invention is not limited to the present embodiment described below.
- the present invention can be variously modified without departing from the gist thereof.
- the resin composition of the present embodiment has a monovalent substituent represented by the following formula (1a) on the aromatic ring (hereinafter referred to as “substituted allyl group”) and a monovalent represented by the following formula (1b).
- An aromatic compound (A) formed by directly bonding a substituent (hereinafter referred to as “substituted hydroxyl group”) and a maleimide compound (B) are included.
- the aromatic ring include a benzene ring, a naphthalene ring and an anthracene ring, preferably a benzene ring and a naphthalene ring, and more preferably a benzene ring.
- R a represents a hydrogen atom or a monovalent organic group, and the carbon number when having a carbon atom is preferably 1 to 60.
- R a is more preferably a hydrogen atom or an alkyl group or aryl group having 1 to 60 carbon atoms, still more preferably a hydrogen atom or an alkyl group or aryl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom. Or it is a methyl group, Most preferably, it is a hydrogen atom.
- R b represents a monovalent organic group, and the carbon number thereof is preferably 3 to 60.
- R b preferably has 3 to 45 carbon atoms, and more preferably 4 to 43 carbon atoms.
- the aromatic compound (A) has a substituted hydroxyl group that is more sterically hindered than the phenolic hydroxyl group with respect to the substituted allyl group. Therefore, the progress of the reaction between the substituted allyl group and the maleimide group in the maleimide compound is moderately inhibited by the substituted hydroxyl group. Thereby, the melt viscosity of the prepreg using the resin composition of the present embodiment can be made lower than that in the conventional technique. As a result, the flowability of the resin composition is improved when the prepreg is laminated and cured, and the moldability of the laminate, metal foil-clad laminate, and printed wiring board is excellent. Moreover, by moderately inhibiting the progress of the reaction, an increase in the viscosity of the prepreg over time is suppressed, and the storage stability thereof is excellent. However, possible factors are not limited to this.
- the aromatic compound (A) is formed by directly bonding a substituted allyl group and a substituted hydroxyl group to an aromatic ring.
- R b preferably has a hydroxyl group, and R b is more preferably a group represented by the following formula (1c).
- R c represents a linear or branched alkyl group having 1 or more carbon atoms or an aryl group which may have a substituent and may have oxygen in the chain.
- the carbon number of the alkyl group is preferably 4 to 14, and the carbon number of the aryl group is preferably 6 to 12.
- examples of the substituted hydroxyl group include any monovalent substituent represented by the following formulas (2), (3), and (4). From the viewpoint of more effectively and reliably achieving the effects of the present invention, any monovalent substituent represented by the following formulas (2), (3) and (4) is preferable.
- R 1 represents a linear or branched alkyl group having 1 or more carbon atoms or an aryl group which may have a substituent.
- the carbon number of the alkyl group is preferably 4 to 12, and the carbon number of the aryl group is preferably 6 to 12.
- an aryl group which may have a substituent is preferable, and a phenyl group, a biphenyl group or a naphthyl which may have a substituent is preferable from the viewpoint of more effectively and reliably achieving the effects of the present invention.
- Group is more preferable, and a phenyl group which may have a substituent represented by the following formula (5) is more preferable.
- R 2 represents a hydrogen atom or a monovalent organic group, and when it is a monovalent organic group, the carbon number is 1 or more.
- Examples of the substituent in R 1 include a monovalent organic group.
- a monovalent saturated or unsaturated linear group having 1 to 40 carbon atoms which may have a substituent or A branched hydrocarbon group a monovalent saturated or unsaturated alicyclic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, and 1 to carbon atoms which may have a substituent; 40 monovalent aromatic hydrocarbon groups.
- These hydrocarbon groups may have one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom therein.
- Examples of the monovalent saturated or unsaturated linear or branched hydrocarbon group having 1 to 40 carbon atoms which may have a substituent include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl Group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a decyl group represented by an alkyl group having 1 to 40 carbon atoms, a methoxy group, an ethoxy group, and a 3-methylmethoxy group Examples thereof include an alkoxy group having 1 to 40 carbon atoms and a vinyl group.
- Examples of the monovalent saturated or unsaturated alicyclic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent include, for example, a cyclopropyl group, a 2,2-dimethylcyclopropyl group, a cyclopentyl group, Examples include a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, a menthyl group, and a cyclododecyl group.
- Examples of the monovalent aromatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent include, for example, 4- (t-butyl) phenyl group, 2-methylphenyl group, 4-methylphenyl group, And a phenyl group which may have a substituent represented by 4-methoxyphenyl group, and a phenoxy group which may have a substituent represented by phenoxy group.
- the number of carbon atoms in each of the hydrocarbon groups is preferably 3 to 20 from the viewpoint of more effectively and reliably achieving the effects of the present invention.
- R 2 is a monovalent organic group, it preferably has 1 to 9 carbon atoms. Examples of such a monovalent organic group include those having 1 to 9 carbon atoms among the groups exemplified above.
- examples of the aromatic compound (A) include a compound represented by the following formula (6). This compound is preferable from the viewpoint of more effectively and reliably achieving the effects of the present invention.
- An aromatic compound (A) is used individually by 1 type or in combination of 2 or more types.
- two R 3 s each independently represent a hydroxyl group or any of the substituents represented by the above formulas (2), (3) and (4), and at least One represents any substituent represented by the above formulas (2), (3) and (4)
- R 4 represents a single bond, an alkylene group, a phenylene group, a biphenylene group or a naphthylene group
- R 5 each independently represents a hydrogen atom, an alkyl group, a phenyl group, a biphenyl group, or a naphthyl group.
- Examples of the alkyl group for R 5 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, and decyl group.
- Examples of R 4 include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, and bisphenol PH. , Bisphenol TMC, and divalent group that binds two aromatic rings in bisphenol Z.
- R 4 is preferably a divalent group that connects two aromatic rings in bisphenol A, that is, an isopropylidene group (> C (CH 3 ) 2 ).
- the carbon atom in the aromatic ring to which the substituted allyl group is bonded and the carbon atom in the aromatic ring to which the substituted hydroxyl group is bonded are adjacent to each other.
- the resin composition of the present embodiment is further excellent in the moldability of the printed wiring board and the storage stability of the prepreg.
- the aromatic compound (A) may be produced by a conventional method, or a commercially available product may be obtained.
- a manufacturing method of an aromatic compound (A) the process of obtaining the aromatic compound (A) in the manufacturing method of the resin composition of this embodiment mentioned later and the manufacturing method as described in an Example are mentioned, for example.
- the content of the aromatic compound (A) is preferably 5 parts by mass or more and 50 parts by mass or less, and 8 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the resin solid content. The following is more preferable.
- the content of the aromatic compound (A) is within the above range, the moldability of the printed wiring board and the storage stability of the prepreg are further improved.
- “resin solid content” means a component in the resin composition excluding a solvent and a filler unless otherwise specified
- “resin solid content 100 parts by mass” means a resin composition. The sum of the components excluding the solvent and filler in the product is 100 parts by mass.
- the maleimide compound (B) is not particularly limited as long as it is a compound having one or more maleimide groups in the 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, represented by the following formula (7) Maleimide compounds, prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. These can be used alone or in combination of two or more.
- each R 6 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 value of n 1 is preferably 10, more preferably 7.
- the content of the maleimide compound (B) is preferably 5 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the resin solid content. Is more preferable.
- the content of the maleimide compound (B) is within the above range, the moldability of the printed wiring board and the storage stability of the prepreg are further improved, and the thermal expansion coefficient of the obtained cured product is further reduced. The heat resistance tends to be further improved.
- the number of alkenyl groups ( ⁇ ) in the aromatic compound (A) and the maleimide compound (S) is preferably 0.9 to 4.3, and more preferably 1.5 to 4.0.
- this ratio (( ⁇ ) / ( ⁇ )) is within the above range, the moldability of the printed wiring board and the storage stability of the prepreg become better, and the low thermal expansion, thermal elastic modulus, heat resistance, A printed wiring board having further excellent moisture absorption heat resistance, desmear resistance, chemical resistance, and easy curing can be obtained.
- the resin composition of the present embodiment further includes at least one selected from the group consisting of an epoxy resin, a cyanate ester compound, and an alkenyl-substituted nadiimide.
- the resin composition of the present embodiment contains an alkenyl-substituted nadiimide from the viewpoint of more effectively and reliably achieving the effects of the present invention.
- the alkenyl-substituted nadiimide according to the present embodiment is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadiimide groups in the molecule.
- Specific examples thereof include compounds represented by the following formula (8).
- R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- R 8 represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, Or the group represented by following formula (9) or (10) is shown.
- R 9 represents a substituent represented by a methylene group, an isopropylidene group, CO, O, S, or SO 2 .
- R 10 represents an independently selected alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.
- a commercially available alkenyl-substituted nadiimide represented by the formula (8) can also be used. Although it does not specifically limit as what is marketed, For example, it represents with the compound (BANI-M (made by Maruzen Petrochemical Co., Ltd.)) represented by following formula (11), and following formula (12). Compound (BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.)). These may be used alone or in combination of two or more.
- the content of the alkenyl-substituted nadiimide is preferably 10 to 60 parts by mass, more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the resin solid content.
- the moldability is excellent even when the inorganic filler is filled.
- a printed wiring board having excellent curability for example, a thermal elastic modulus such as a flexural modulus at 250 ° C. or a flexural modulus at a solder reflow temperature, desmear resistance, and chemical resistance can be obtained.
- the resin composition preferably does not contain alkenyl-substituted nadiimide.
- the resin composition of this embodiment contains the arbitrary component which has an alkenyl group like an alkenyl substituted nadiimide other than an aromatic compound (A), the sum total of the number of the alkenyl groups of each component in a resin composition.
- the ratio (( ⁇ ) / ( ⁇ t)) of ( ⁇ t) to the number ( ⁇ ) of maleimide groups in the maleimide compound (B) is preferably 0.9 to 4.3, and preferably 1.5 to 4.0. Is more preferable.
- the resin composition of this embodiment may further contain a cyanate ester compound.
- a cyanate ester compound for example, the naphthol aralkyl type cyanate ester shown by following formula (13), the novolak type cyanate ester shown by following formula (14), the biphenyl aralkyl type cyanate ester, Bis (3,5-dimethyl 4-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, , 3,6-tricyanatonaphthalene, 4,4
- each R 11 independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable.
- n 2 represents an integer of 1 or more.
- the upper limit value of n 2 is usually 10, and preferably 6.
- each R 12 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 a 10, preferably a 7.
- the cyanate ester compound is a group consisting of a naphthol aralkyl cyanate ester represented by the formula (13), a novolak cyanate ester represented by the formula (14), and a biphenylaralkyl cyanate ester. 1 type selected from the group consisting of a naphthol aralkyl cyanate ester represented by formula (13) and a novolak cyanate ester represented by formula (14) More preferably, the above is included.
- a cyanate ester compound By using such a cyanate ester compound, a cured product that is superior in flame retardancy, has higher curability, and has a lower thermal expansion coefficient tends to be obtained.
- the production method of these cyanate ester compounds is not particularly limited, and a known method can be used as a synthesis method of the cyanate ester compounds.
- the known method is not particularly limited.
- a method of reacting a phenol resin and cyanogen halide in an inert organic solvent in the presence of a basic compound, a salt of the phenol resin and the basic compound, water examples thereof include a method of forming in a solution to be contained, and then causing the obtained salt and cyanogen halide to undergo a two-phase interface reaction.
- each R 11 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. The upper limit value of n 4 is usually 10 and preferably 6.
- the naphthol aralkyl type phenol resin represented by the formula (15) can be obtained by condensing a naphthol aralkyl resin and cyanic acid.
- the naphthol aralkyl type phenol resin is not particularly limited, and examples thereof include naphthols such as ⁇ -naphthol and ⁇ -naphthol, p-xylylene glycol, ⁇ , ⁇ '-dimethoxy-p-xylene, and 1,4- Examples thereof include those obtained by reaction with benzenes such as di (2-hydroxy-2-propyl) benzene.
- the naphthol aralkyl cyanate ester can be selected from those obtained by condensing the naphthol aralkyl resin obtained as described above and cyanic acid.
- the content of the cyanate ester compound is preferably 0.5 to 45 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the resin solid content.
- the content of the cyanate ester compound is within the above range, the heat resistance and chemical resistance of the obtained cured product tend to be further improved.
- the resin composition of this embodiment may further contain an epoxy resin.
- the epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule.
- a biphenylene glycol type epoxy resin
- the content of the epoxy resin is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the resin solid content.
- the content of the epoxy resin is within the above range, the flexibility, copper foil peel strength, chemical resistance, and desmear resistance of the obtained cured product tend to be further improved.
- the resin composition of this embodiment may further contain an inorganic filler (C).
- the inorganic filler (C) include, but are not limited to, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, Metal oxides such as magnesium oxide and zirconium oxide; metal nitrides such as boron nitride, agglomerated boron nitride, silicon nitride and boehmite; metal sulfates such as barium sulfate; aluminum hydroxide and aluminum hydroxide heat-treated products (aluminum hydroxide) ), Metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate Alumina, clay, ka
- the inorganic filler (C) includes at least one selected from the group consisting of silica, alumina, magnesium oxide, aluminum hydroxide, boehmite, boron nitride, aggregated boron nitride, silicon nitride, and boehmite. Preferably, it contains at least one selected from the group consisting of silica, alumina, and boehmite.
- the content of the inorganic filler (C) is preferably 30 to 500 parts by weight, more preferably 100 to 400 parts by weight, and further preferably 150 to 300 parts by weight with respect to 100 parts by weight of the resin solid content. It is. When the content of the inorganic filler (C) is within the above range, the obtained cured product tends to have higher rigidity and lower warpage.
- the resin composition of this embodiment may further contain one or more selected from the group consisting of a silane coupling agent and a wetting and dispersing agent.
- a silane coupling agent or a wetting and dispersing agent the dispersibility of the inorganic filler (C), the resin component, the inorganic filler (C), and the adhesive strength of the substrate described later are further improved. Tend to.
- 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.
- ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ Aminosilane compounds such as aminopropyltrimethoxysilane; epoxysilane compounds such as ⁇ -glycidoxypropyltrimethoxysilane; acrylic silane compounds such as ⁇ -acryloxypropyltrimethoxysilane; N- ⁇ - (N— Cationic silane compounds such as vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride; and phenylsilane compounds.
- a silane coupling agent may be used individually by 1 type, or may use 2 or more types together.
- the wetting dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints.
- the resin composition of the present embodiment further contains one or more selected from the group consisting of a phenol resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group, if necessary. May be.
- the resin composition contains such other resins, the copper foil peel strength, bending strength, bending elastic modulus and the like of the obtained cured product tend to be further improved.
- phenol resin As the phenol resin, generally known resins can be used as long as they are phenol resins having two or more hydroxy groups in one molecule, and the kind thereof is not particularly limited. Specific examples thereof include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type.
- the content of the phenol resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content.
- the content of the phenol resin is within the above range, the obtained cured product tends to be more excellent in adhesiveness, flexibility, and the like.
- oxetane resin As the oxetane resin, generally known oxetane resins can be used, and the kind thereof is not particularly limited. Specific examples thereof include alkyloxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3 ′ -Di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name, manufactured by Toagosei), and OXT-121 (Toagosei) Product name). These oxetane resins can be used alone or in combination of two or more. When the resin composition contains such an
- the content of the oxetane resin is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content.
- the content of the oxetane resin is within the above range, the obtained cured product tends to be more excellent in adhesion and flexibility.
- benzoxazine compound As the benzoxazine compound, generally known compounds can be used as long as they have two or more dihydrobenzoxazine rings in one molecule, and the kind thereof is not particularly limited. Specific examples thereof include bisphenol A-type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical) bisphenol F-type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical), and bisphenol S-type benzoxazine BS-BXZ (produced by Konishi Chemical). Product name). These benzoxazine compounds can be used alone or in combination. When the resin composition contains such a benzoxazine compound, the obtained cured product tends to be more excellent in flame retardancy, heat resistance, low water absorption, low dielectric properties and the like.
- the content of the benzoxazine compound is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and further preferably 3 to 80 parts by mass with respect to 100 parts by mass of the resin solid content.
- the content of the benzoxazine compound is within the above range, the resulting cured product tends to be more excellent in heat resistance and the like.
- Compound having a polymerizable unsaturated group As the compound having a polymerizable unsaturated group, generally known compounds can be used, and the kind thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene and divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di ( Mono- or polyhydric alcohol (meth) such as (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Acrylates; Epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type
- the content of the compound having a polymerizable unsaturated group is preferably 0 to 99 parts by mass, more preferably 1 to 90 parts by mass, and still more preferably 3 to 100 parts by mass with respect to 100 parts by mass of the resin solid content. 80 parts by mass.
- the content of the polymerizable unsaturated group-containing compound is within the above range, the cured product obtained tends to be more excellent in heat resistance, toughness, and the like.
- the resin composition of this embodiment may further contain a curing accelerator.
- the curing accelerator is not particularly limited, and examples thereof include imidazoles such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-diperphthalate, and the like.
- Organic peroxides azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethylpyridine, 2-N-ethylanilino Tertiary amines such as ethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenol, xylenol, cresol, resorcin, cateco Phenols such as lead; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts Inorganic metal salts
- the resin composition of this embodiment may further contain a solvent.
- the viscosity at the time of preparing the resin composition is lowered, the handling property is further improved, and the impregnation property to a substrate described later tends to be further improved.
- the solvent is not particularly limited as long as it can dissolve a part or all of the resin component in the resin composition.
- ketones such as acetone, methyl ethyl ketone, and methyl cellosolve
- aromatics such as toluene and xylene Group hydrocarbons
- amides such as dimethylformamide
- propylene glycol monomethyl ether and its acetate A solvent may be used individually by 1 type, or may use 2 or more types together.
- the manufacturing method of the resin composition of this embodiment is not specifically limited,
- bond directly with an aromatic ring reacts with a phenolic hydroxyl group.
- the aromatic compound (A1) is formed by directly bonding a substituted allyl group and a phenolic hydroxyl group to an aromatic ring.
- aromatic compound (A1) is not specifically limited,
- the compound represented by following formula (16) is mentioned.
- R 4 and R 5 have the same meanings as those in formula (6).
- a monofunctional epoxy compound is mentioned, for example.
- the monofunctional epoxy compound include any of the compounds represented by the following formulas (17), (18) and (19), and from the viewpoint of more effectively and reliably achieving the effects of the present invention, Are preferred.
- R 1 has the same meaning as in the above formulas (2), (3) and (4).
- R 1 is preferably an aryl group which may have a substituent from the viewpoint of more effectively and reliably exerting the action and effect of the present invention, and a phenyl group, a biphenyl group or a naphthyl group which may have a substituent. Is more preferable, and a phenyl group which may have a substituent represented by the above formula (5) is preferable.
- the carbon atom in the aromatic ring to which the substituted allyl group is bonded and the carbon atom in the aromatic ring to which the phenolic hydroxyl group is bonded are adjacent to each other.
- the resin composition of the present embodiment is further excellent in the moldability of the printed wiring board and the storage stability of the prepreg.
- a curing accelerator may be appropriately added as necessary.
- the curing accelerator include those described above.
- the addition amount of the curing accelerator is not particularly limited as long as the aromatic compound (A) can be obtained, but 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the obtained aromatic compound (A). It is preferable that it is 0.01 mass part or more and 1 mass part or less.
- the reaction temperature in the step of obtaining the aromatic compound (A) is not particularly limited as long as it is a temperature at which the aromatic compound (A) can be obtained, but is preferably 50 ° C or higher and 160 ° C or lower, and is 100 ° C or higher and 140 ° C or lower. More preferably.
- an aromatic compound (A) and a maleimide compound (B) are blended.
- this step not only the aromatic compound (A) and the maleimide compound (B) but also other components to be contained in the other resin composition are sequentially blended in a solvent and sufficiently stirred to obtain a resin composition. May be.
- known processes such as stirring, mixing, and kneading can be performed.
- the dispersibility of the inorganic filler (C) with respect to the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank provided 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 or a bead mill for mixing, or a revolving or rotating mixing device.
- an organic solvent and / or a curing accelerator can be used as necessary.
- the kind of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. Specific examples thereof are as described above.
- the kind of hardening accelerator will not be specifically limited if it accelerates
- the prepreg of this embodiment is a prepreg comprising a base material and the resin composition impregnated or coated on the base material.
- the manufacturing method of a prepreg can be performed according to a conventional method, and is not specifically limited. For example, after impregnating or applying the resin component in the present embodiment to the substrate, it is semi-cured (B stage) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes, etc.
- the prepreg of this embodiment can be produced.
- the content of the resin composition is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, based on the total mass of the prepreg. More preferably, it is 40 to 80% by mass. When the content of the resin composition is within the above range, the moldability tends to be further improved. From the same viewpoint, the content of the base material is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, and further preferably 20 to 60% by mass with respect to the total mass of the prepreg. is there.
- the substrate is not particularly limited, and known materials used for various printed wiring board materials can be appropriately selected and used depending on the intended use and performance. Specific examples thereof are not particularly limited.
- glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; inorganic fibers other than glass such as quartz; Total fragrance such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technola (registered trademark), manufactured by Teijin Techno Products) Polyamides; Polyesters such as 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.) and Zexion (registered trademark, manufactured by KB Selen); Polyparaphenylene benzoxazole (Zylon (registered Trademark), manufactured by Toyobo Co
- a woven fabric, a nonwoven fabric, roving, a chopped strand mat, and a surfacing mat are mentioned.
- the weaving method of the woven fabric is not particularly limited, and for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones depending on the intended use and performance. .
- a glass woven fabric whose surface is treated with a fiber-opening treatment or a silane compound such as a silane coupling agent is preferably used.
- the thickness and mass of the substrate are not particularly limited, but usually a substrate having a thickness of 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 (weight) of 250 g / m 2 or less, and glass of E glass, S glass, T glass, and Q glass.
- a woven fabric (cloth) of at least one fiber selected from the group consisting of fibers and organic fibers is more preferable.
- the prepreg of the present embodiment has excellent storage stability by including the resin composition described above. This is because the progress of the reaction between the substituted allyl group in the aromatic compound (A) and the maleimide group in the maleimide compound is appropriately inhibited by the substituent in the aromatic compound (A). This is thought to be because the increase in viscosity is suppressed.
- the resin sheet of the present embodiment includes a support (sheet base) and the resin composition applied to the sheet base, and the resin composition is laminated on one or both sides of the sheet base. It is a thing.
- the resin sheet is used as one means of thinning, for example, by directly applying a thermosetting resin (including an inorganic filler) used for a prepreg or the like to a support such as a metal foil or a film. It can be produced by drying.
- the sheet base material include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, aluminum foil, copper foil and Gold leaf is mentioned. Of these, electrolytic copper foil and PET film are preferred.
- Examples of the coating method include a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is coated on a sheet substrate with a bar coater, a die coater, a doctor blade, a baker applicator, or the like.
- the resin sheet is preferably obtained by applying the resin composition to a support (sheet base material) and then semi-curing (B-stage).
- a method for obtaining such a resin sheet specifically, a method in which the resin composition is applied to a sheet substrate such as a copper foil and then heated in a dryer at 100 to 200 ° C. for 1 to 60 minutes. And a method of producing a resin sheet by semi-curing the resin.
- the amount of the resin composition attached to the support is preferably in the range of 1 to 300 ⁇ m in terms of the resin thickness of the resin sheet.
- the resin sheet of this embodiment can be used as a build-up material for a printed wiring board.
- the laminate of the present embodiment is formed by stacking at least one selected from the group consisting of the above prepreg and resin sheet, and is at least one selected from the group consisting of the above prepreg and resin sheet.
- the cured product of the resin composition contained in This laminated board can be obtained, for example, by stacking and curing at least one selected from the group consisting of the above-mentioned prepreg and resin sheet.
- the metal foil-clad laminate of the present embodiment has at least one selected from the group consisting of the above prepreg and resin sheet, and at least one type selected from the group consisting of the above prepreg and resin sheet.
- This metal foil-clad laminate can be obtained by laminating at least one selected from the group consisting of the above-mentioned prepreg and resin sheet, and laminating and forming a metal foil on one or both sides thereof. . More specifically, one or a plurality of the above-described prepregs and / or resin sheets are stacked, and if desired, a metal foil such as copper or aluminum is disposed on one or both sides thereof, and this is laminated as necessary. By doing so, a metal foil-clad laminate can be manufactured.
- 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 1 to 70 ⁇ m, more preferably 1.5 to 35 ⁇ m.
- a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used when 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.
- the printed wiring board of the present 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 conductor layer serving as a circuit can be formed from the metal foil in the metal foil-clad laminate. Alternatively, the conductor layer can be formed on the surface of the insulating layer by electroless plating.
- This printed wiring board is excellent in chemical resistance, desmear resistance, and insulation reliability, and can be used particularly effectively as a printed wiring board for semiconductor packages that require such performance.
- the printed wiring board of the present embodiment can be manufactured by the following method, for example.
- the metal foil-clad laminate such as a copper-clad laminate
- An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to produce an inner layer substrate.
- a surface treatment is performed on the inner layer circuit surface of the inner layer substrate to increase the adhesive strength as necessary.
- a required number of the above-mentioned prepregs are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is stacked on the outer side, and is integrally formed by heating and pressing.
- 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 drilling process for through holes and via holes is performed on the multilayer laminate.
- desmear treatment is performed to remove smear, which is a resin residue derived from the resin component contained in the cured product layer.
- a plated metal film is formed on the wall surface of the hole to conduct 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.
- a board is manufactured.
- the above-described prepreg (the base material and the above-described resin composition attached thereto) and the metal foil-clad laminate resin composition layer (the layer made of the above-described resin composition) include the above-described resin composition.
- An insulating layer is formed.
- a printed wiring board may be produced by forming a conductor layer serving as a circuit on the prepreg or the resin sheet. At this time, a method of electroless plating can be used for forming the conductor layer.
- the progress of the reaction between the substituted allyl group in the aromatic compound (A) and the maleimide group in the maleimide compound is moderately inhibited by the substituent in the aromatic compound (A).
- the melt viscosity of the prepreg is lower than that in the prior art, the fluidity of the resin composition is improved when the prepreg is laminated and cured, and the moldability of the printed wiring board is excellent.
- solution 2 in which 65 g of triethylamine (0.64 mol; 0.5 mol with respect to 1 mol of hydroxy group) was dissolved in 65 g of dichloromethane was added for 10 minutes. Over time. After completion of the pouring of the solution 2, the reaction was completed by stirring at the same temperature for 30 minutes. Thereafter, the reaction solution was allowed to stand to separate the organic phase and the aqueous phase. The organic phase obtained was washed 5 times with 1300 g of water.
- the electric conductivity of the waste water in the fifth washing with water was 5 ⁇ S / cm, and it was confirmed that the ionic compounds that could be removed were sufficiently removed by washing with water.
- the organic phase after washing with water is concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain a naphthol aralkyl-type cyanate ester compound represented by the above formula (13) (wherein R 11 is all SN 495V-CN, cyanate ester group equivalent: 261 g / eq., Orange viscous product) 331 g.
- the infrared absorption spectrum of the obtained SN495V-CN showed an absorption of 2250 cm ⁇ 1 (cyanate group) and no absorption of a hydroxy group.
- Example 1 10.0 parts by mass of ⁇ -naphthol aralkyl cyanate ester resin obtained in Synthesis Example 1, novolac maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd., functional group equivalent: 186 g / eq.) 0 parts by mass, 25.0 parts by mass of bisallylnadiimide (BANI-M, manufactured by Maruzen Petrochemical Co., Ltd., functional group equivalent: 286 g / eq.), Represented by the above formula (21) obtained in Synthesis Example 2 12.5 parts by mass of the compound, 7.0 parts by mass of biphenylaralkyl type epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290 g / eq.), Silane coupling agent (Z-6040) 6.9 parts by mass, manufactured by Toray Dow Corning Co., Ltd., 1.0 part by mass of a wetting and dispersing
- This varnish was impregnated and coated on E glass woven fabric (thickness: 95 ⁇ m, mass (weight): 108 g / m 2, the same applies hereinafter), dried by heating at 130 ° C. for 3 minutes, and a resin composition content of 45 mass. % Prepreg was obtained.
- Example 2 10.0 parts by mass of ⁇ -naphthol aralkyl cyanate ester resin obtained in Synthesis Example 1, novolac maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd., functional group equivalent: 186 g / eq.) 0 parts by mass, bisallylnadiimide (BANI-M, manufactured by Maruzen Petrochemical Co., Ltd., functional group equivalent: 286 g / eq.) 25.0 parts by mass, represented by the above formula (22) obtained in Synthesis Example 3 13.0 parts by mass of the compound, 7.0 parts by mass of biphenyl aralkyl type epoxy compound (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., functional group equivalent: 290 g / eq.), Silane coupling agent (Z-6040) 6.9 parts by mass, manufactured by Toray Dow Corning Co., Ltd., 1.0 part by mass of a wetting and dispers
- (Comparative Example 2) 10. 10.0 parts by mass of ⁇ -naphthol aralkyl cyanate ester resin obtained in Synthesis Example 1, novolac maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd., functional group equivalent: 186 g / eq.) 0 parts by mass, bisallylnadiimide (BANI-M, manufactured by Maruzen Petrochemical Co., Ltd., functional group equivalent: 286 g / eq.) 36.0 parts by mass, biphenylaralkyl type epoxy compound (NC-3000H, Nippon Kayaku ( Co., Ltd., functional group equivalent: 290 g / eq.) 7.0 parts by mass, silane coupling agent (Z-6040, manufactured by Toray Dow Corning Co., Ltd.), 6.9 parts by mass, wetting and dispersing agent (DISPERBYK-111) , Manufactured by Big Chemie Japan Co., Ltd.) and
- Glass transition temperature (Tg) After obtaining a copper clad laminate as described above, a copper foil on both sides was removed therefrom by etching to obtain a sample. About the sample, in accordance with JIS K7244-3 (JIS C6481), using a dynamic viscoelasticity measuring device (manufactured by TA Instruments Japan Co., Ltd.), the start temperature is 50 ° C., the end temperature is 350 ° C. Dynamic viscoelasticity was measured at a temperature rate of 10 ° C./min. The maximum value of the loss elastic modulus (E ′′) obtained at that time was defined as the glass transition temperature. The glass transition temperature is an index of heat resistance. In Table 1, the glass transition temperature is in the region of 350 ° C. or lower. In some cases, the value was indicated, and when there was no glass transition temperature in the region of 350 ° C. or lower, “> 350 ° C.” was indicated. The results are shown in Table 1.
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Abstract
Description
[1]芳香環に下記式(1a)で表される1価の置換基と下記式(1b)で表される1価の置換基とが直接結合してなる芳香族化合物(A)と、マレイミド化合物(B)と、を含む樹脂組成物。
CH2=CRaCH2- (1a)
RbO- (1b)
(式(1a)中、Raは水素原子又は1価の有機基を示し、式(1b)中、Rbは1価の有機基を示す。)
[2]前記芳香族化合物(A)において、前記式(1a)で表される1価の置換基が結合する前記芳香環における炭素原子と、前記式(1b)で表される1価の置換基が結合する前記芳香環における炭素原子が互いに隣接する、[1]に記載の樹脂組成物。
[3]前記式(1b)で表される1価の置換基は、下記式(2)、(3)及び(4)で表されるいずれかの1価の置換基である、[1]又は[2]に記載の樹脂組成物。
[4]前記R1は、下記式(5)で表される置換基である、[3]に記載の樹脂組成物。
[5]前記芳香族化合物(A)が、下記式(6)で表される化合物を含む、[1]~[4]のいずれか一つに記載の樹脂組成物。
[6]前記マレイミド化合物(B)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、ポリテトラメチレンオキシド-ビス(4-マレイミドベンゾエート)及び下記式(7)で表されるマレイミド化合物からなる群より選ばれる少なくとも1種である、[1]~[5]のいずれか一つに記載の樹脂組成物。
[7]エポキシ樹脂、シアン酸エステル化合物及びアルケニル置換ナジイミドからなる群より選ばれる少なくとも1種をさらに含む、[1]~[6]のいずれか一つに記載の樹脂組成物。
[8]無機充填材(C)をさらに含む、[1]~[7]のいずれか一つに記載の樹脂組成物。
[9]前記無機充填材(C)が、シリカ、アルミナ及びベーマイトからなる群より選ばれる少なくとも1種を含む、[8]に記載の樹脂組成物。
[10]前記無機充填材(C)の含有量が、樹脂固形分100質量部に対して30~500質量部である、[8]又は[9]に記載の樹脂組成物。
[11]基材と、当該基材に含浸又は塗布された[1]~[10]のいずれか一つに記載の樹脂組成物と、を備える、プリプレグ。
[12]支持体と、当該支持体に塗布された[1]~[10]のいずれか一つに記載の樹脂組成物と、を備える、レジンシート。
[13][11]に記載のプリプレグ、及び[12]に記載のレジンシートからなる群より選ばれる少なくとも1種を1枚以上重ねてなる積層板であって、前記プリプレグ及び前記レジンシートからなる群より選ばれる少なくとも1種に含まれる樹脂組成物の硬化物を含む、積層板。
[14][11]に記載のプリプレグ、及び[12]に記載のレジンシートからなる群より選ばれる少なくとも1種と、前記プリプレグ及び前記レジンシートからなる群より選ばれる少なくとも1種の片面又は両面に配された金属箔と、を有する金属箔張積層板であって、前記プリプレグ及び前記レジンシートからなる群より選ばれる少なくとも1種に含まれる樹脂組成物の硬化物を含む、金属箔張積層板。
[15]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、[1]~[10]のいずれか一つに記載の樹脂組成物を含むプリント配線板。
[16]芳香環に下記式(1a)で表される1価の置換基とフェノール性水酸基とが直接結合してなる芳香族化合物(A1)と、フェノール性水酸基と反応する化合物とを反応させて、芳香環に下記式(1a)で表される1価の置換基と下記式(1b)で表される1価の置換基とが直接結合してなる芳香族化合物(A)を得る工程と、前記芳香族化合物(A)とマレイミド化合物(B)とを配合する工程と、を有する、樹脂組成物の製造方法。
CH2=CRaCH2- (1a)
RbO- (1b)
(式(1a)中、Raは水素原子又は1価の有機基を示し、式(1b)中、Rbは1価の有機基を示す。)
本実施形態の樹脂組成物は、芳香環に下記式(1a)で表される1価の置換基(以下、「置換アリル基」という。)と下記式(1b)で表される1価の置換基(以下、「置換水酸基」という。)とが直接結合してなる芳香族化合物(A)と、マレイミド化合物(B)とを含むものである。ここで芳香環としては、例えば、ベンゼン環、ナフタレン環及びアントラセン環が挙げられるが、好ましくはベンゼン環及びナフタレン環であり、より好ましくはベンゼン環である。
CH2=CRaCH2- (1a)
RbO- (1b)
ここで、式(1a)中、Raは水素原子又は1価の有機基を示し、炭素原子を有する場合の炭素数は、好ましくは1~60である。Raはより好ましくは、水素原子あるいは炭素数1~60のアルキル基又はアリール基であり、さらに好ましくは、水素原子又は炭素数1~6のアルキル基又はアリール基であり、特に好ましくは水素原子又はメチル基であり、極めて好ましくは水素原子である。一方、式(1b)中、Rbは1価の有機基を示し、その炭素数は好ましくは3~60である。Rbの炭素数はより好ましくは3~45であり、更に好ましくは4~43である。
本実施形態に係る芳香族化合物(A)は、芳香環に置換アリル基と置換水酸基とが直接結合してなるものである。置換水酸基としては、Rbが水酸基を有するものであると好ましく、Rbが下記式(1c)で表される基であるとより好ましい。
Rc-CH(OH)-CH2- (1c)
ここで、Rcは、置換基を有していてもよく鎖内に酸素を有していてもよい、直鎖状若しくは分岐状の炭素数1以上のアルキル基又はアリール基を示す。アルキル基の炭素数は、好ましくは4~14であり、アリール基の炭素数は、好ましくは6~12である。
本実施形態に係るマレイミド化合物(B)は、分子中に1個以上のマレイミド基を有する化合物であれば、特に限定されるものではない。その具体例としては、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、下記式(7)で表されるマレイミド化合物、これらマレイミド化合物のプレポリマー、若しくはマレイミド化合物とアミン化合物のプレポリマーが挙げられる。これらは1種若しくは2種以上を適宜混合して用いることができる。
本実施形態の樹脂組成物は、エポキシ樹脂、シアン酸エステル化合物及びアルケニル置換ナジイミドからなる群より選ばれる少なくとも1種をさらに含むと好ましい。これらの中では、本発明による作用効果をより有効かつ確実に奏する観点から、本実施形態の樹脂組成物がアルケニル置換ナジイミドを含むことがより好ましい。
本実施形態の樹脂組成物は、シアン酸エステル化合物を更に含有してもよい。シアン酸エステル化合物としては、特に限定されないが、例えば、下記式(13)で示されるナフトールアラルキル型シアン酸エステル、下記式(14)で示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;これらシアン酸エステルのプレポリマーが挙げられる。これらのシアン酸エステル化合物は、1種単独で、又は2種以上を組み合わせて使用してもよい。
本実施形態の樹脂組成物は、エポキシ樹脂を更に含有してもよい。かかるエポキシ樹脂としては、1分子中に2つ以上のエポキシ基を有する樹脂であれば特に限定されないが、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E型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノ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、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセン型エポキシ樹脂、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、グリシジルエステル型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、アラルキルノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ポリオール型エポキシ樹脂、イソシアヌレート環含有エポキシ樹脂、あるいはこれらのハロゲン化物が挙げられる。これらの中では、ビフェニルアラルキル型エポキシ樹脂が好ましい。
本実施形態の樹脂組成物は、無機充填材(C)を更に含有してもよい。無機充填材(C)としては、特に限定されないが、例えば、天然シリカ、溶融シリカ、合成シリカ、アモルファスシリカ、アエロジル、中空シリカ等のシリカ類;ホワイトカーボン等のケイ素化合物;チタンホワイト、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム等の金属酸化物;窒化ホウ素、凝集窒化ホウ素、窒化ケイ素、ベーマイト等の金属窒化物;硫酸バリウム等の金属硫酸化物;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、錫酸亜鉛等の亜鉛化合物;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、E-ガラス、A-ガラス、NE-ガラス、C-ガラス、L-ガラス、D-ガラス、S-ガラス、M-ガラスG20、ガラス短繊維(Eガラス、Tガラス、Dガラス、Sガラス、Qガラス等のガラス微粉末類を含む。)、中空ガラス、並びに球状ガラスが挙げられる。無機充填材(C)は、1種を単独で用いても、2種以上を併用してもよい。
本実施形態の樹脂組成物は、シランカップリング剤及び湿潤分散剤からなる群より選ばれる1種以上を更に含有してもよい。樹脂組成物が、シランカップリング剤や湿潤分散剤を含むことにより、上記無機充填材(C)の分散性、樹脂成分、無機充填材(C)、及び後述する基材の接着強度がより向上する傾向にある。
本実施形態の樹脂組成物は、必要に応じて、フェノール樹脂、オキセタン樹脂、ベンゾオキサジン化合物、及び重合可能な不飽和基を有する化合物からなる群より選択される1種又は2種以上を更に含有してもよい。樹脂組成物がこのようなその他の樹脂等を含むことにより、得られる硬化物の銅箔ピール強度、曲げ強度、及び曲げ弾性率等がより向上する傾向にある。
フェノール樹脂としては、1分子中に2個以上のヒドロキシ基を有するフェノール樹脂であれば、一般に公知のものを使用でき、その種類は特に限定されない。その具体例としては、ビスフェノールA型フェノール樹脂、ビスフェノールE型フェノール樹脂、ビスフェノールF型フェノール樹脂、ビスフェノールS型フェノール樹脂、フェノールノボラック樹脂、ビスフェノールAノボラック型フェノール樹脂、グリシジルエステル型フェノール樹脂、アラルキルノボラック型フェノール樹脂、ビフェニルアラルキル型フェノール樹脂、クレゾールノボラック型フェノール樹脂、多官能フェノール樹脂、ナフトール樹脂、ナフトールノボラック樹脂、多官能ナフトール樹脂、アントラセン型フェノール樹脂、ナフタレン骨格変性ノボラック型フェノール樹脂、フェノールアラルキル型フェノール樹脂、ナフトールアラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、ビフェニル型フェノール樹脂、脂環式フェノール樹脂、ポリオール型フェノール樹脂、リン含有フェノール樹脂、及び水酸基含有シリコーン樹脂類が挙げられるが、特に制限されるものではない。これらのフェノール樹脂は、1種を単独で又は2種以上を組み合わせて用いることができる。樹脂組成物がこのようなフェノール樹脂を含むことにより、得られる硬化物の接着性や可撓性等により優れる傾向にある。
オキセタン樹脂としては、一般に公知のものを使用でき、その種類は特に限定されない。その具体例としては、オキセタン、2-メチルオキセタン、2,2-ジメチルオキセタン、3-メチルオキセタン、3,3-ジメチルオキセタン等のアルキルオキセタン、3-メチル-3-メトキシメチルオキセタン、3,3'-ジ(トリフルオロメチル)パーフルオキセタン、2-クロロメチルオキセタン、3,3-ビス(クロロメチル)オキセタン、ビフェニル型オキセタン、OXT-101(東亞合成製商品名)、及びOXT-121(東亞合成製商品名)が挙げられる。これらのオキセタン樹脂は、1種又は2種以上を組み合わせて用いることができる。樹脂組成物がこのようなオキセタン樹脂を含むことにより、得られる硬化物の接着性や可撓性等により優れる傾向にある。
ベンゾオキサジン化合物としては、1分子中に2個以上のジヒドロベンゾオキサジン環を有する化合物であれば、一般に公知のものを用いることができ、その種類は特に限定されない。その具体例としては、ビスフェノールA型ベンゾオキサジンBA-BXZ(小西化学製商品名)ビスフェノールF型ベンゾオキサジンBF-BXZ(小西化学製商品名)、及びビスフェノールS型ベンゾオキサジンBS-BXZ(小西化学製商品名)が挙げられる。これらのベンゾオキサジン化合物は、1種又は2種以上混合して用いることができる。樹脂組成物がこのようなベンゾオキサジン化合物を含むことにより、得られる硬化物の難燃性、耐熱性、低吸水性、低誘電特性等により優れる傾向にある。
重合可能な不飽和基を有する化合物としては、一般に公知のものを使用でき、その種類は特に限定されない。その具体例としては、エチレン、プロピレン、スチレン、ジビニルベンゼン、ジビニルビフェニル等のビニル化合物;メチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の1価又は多価アルコールの(メタ)アクリレート類;ビスフェノールA型エポキシ(メタ)アクリレート、ビスフェノールF型エポキシ(メタ)アクリレート等のエポキシ(メタ)アクリレート類;及びベンゾシクロブテン樹脂が挙げられる。これらの不飽和基を有する化合物は、1種又は2種以上混合して用いることができる。樹脂組成物がこのような重合可能な不飽和基を有する化合物を含むことにより、得られる硬化物の耐熱性や靱性等により優れる傾向にある。
本実施形態の樹脂組成物は、硬化促進剤を更に含有してもよい。硬化促進剤としては、特に限定されないが、例えば、トリフェニルイミダゾール等のイミダゾール類;過酸化ベンゾイル、ラウロイルパーオキサイド、アセチルパーオキサイド、パラクロロベンゾイルパーオキサイド、ジ-tert-ブチル-ジ-パーフタレート等の有機過酸化物;アゾビスニトリル等のアゾ化合物;N,N-ジメチルベンジルアミン、N,N-ジメチルアニリン、N,N-ジメチルトルイジン、N,N-ジメチルピリジン、2-N-エチルアニリノエタノール、トリ-n-ブチルアミン、ピリジン、キノリン、N-メチルモルホリン、トリエタノールアミン、トリエチレンジアミン、テトラメチルブタンジアミン、N-メチルピペリジン等の第3級アミン類;フェノール、キシレノール、クレゾール、レゾルシン、カテコール等のフェノール類;ナフテン酸鉛、ステアリン酸鉛、ナフテン酸亜鉛、オクチル酸亜鉛、オレイン酸錫、ジブチル錫マレート、ナフテン酸マンガン、ナフテン酸コバルト、アセチルアセトン鉄等の有機金属塩;これら有機金属塩をフェノール、ビスフェノール等の水酸基含有化合物に溶解してなるもの;塩化錫、塩化亜鉛、塩化アルミニウム等の無機金属塩;ジオクチル錫オキサイド、その他のアルキル錫、並びにアルキル錫オキサイド等の有機錫化合物が挙げられる。これらのなかでも、トリフェニルイミダゾールが硬化反応を促進し、ガラス転移温度、熱膨張率が優れる傾向にあるため、特に好ましい。
本実施形態の樹脂組成物は、溶剤を更に含有してもよい。樹脂組成物が溶剤を含むことにより、樹脂組成物の調製時における粘度が低下し、ハンドリング性がより向上するとともに後述する基材への含浸性がより向上する傾向にある。
本実施形態の樹脂組成物の製造方法は、特に限定されないが、例えば、芳香環に置換アリル基とフェノール性水酸基とが直接結合してなる芳香族化合物(A1)と、フェノール性水酸基と反応する化合物とを反応させて、芳香環に置換アリル基と置換水酸基とが直接結合してなる芳香族化合物(A)を得る工程と、芳香族化合物(A)とマレイミド化合物(B)とを配合する工程とを有するものである。
(プリプレグ)
本実施形態のプリプレグは、基材と、該基材に含浸又は塗布された上記の樹脂組成物とを備えるプリプレグである。プリプレグの製造方法は、常法にしたがって行うことができ、特に限定されない。例えば、本実施形態における樹脂成分を基材に含浸又は塗布させた後、100~200℃の乾燥機中で1~30分加熱するなどして半硬化(Bステ-ジ化)させることで、本実施形態のプリプレグを作製することができる。
本実施形態のレジンシートは、支持体(シート基材)と、該シート基材に塗布された上記樹脂組成物とを備え、上記樹脂組成物は、該シート基材の片面又は両面に積層されたものである。レジンシートとは、薄葉化の1つの手段として用いられるもので、例えば、金属箔やフィルムなどの支持体に、直接、プリプレグ等に用いられる熱硬化性樹脂(無機充填材を含む)を塗布及び乾燥して製造することができる。
本実施形態の積層板は、上述のプリプレグ及びレジンシートからなる群より選ばれる少なくとも1種を1枚以上重ねてなるものであって、上述のプリプレグ及びレジンシートからなる群より選ばれる少なくとも1種に含まれる樹脂組成物の硬化物を含む。この積層板は、例えば、上述のプリプレグ及びレジンシートからなる群より選ばれる少なくとも1種を1枚以上重ねて硬化して得ることができる。また、本実施形態の金属箔張積層板は、上述のプリプレグ及びレジンシートからなる群より選ばれる少なくとも1種と、上述のプリプレグ及びレジンシートからなる群より選ばれる少なくとも1種の片面又は両面に配された金属箔とを有する金属箔張積層板であって、上記プリプレグ及びレジンシートからなる群より選ばれる少なくとも1種に含まれる樹脂組成物の硬化物を含むものである。この金属箔張積層板は、上述のプリプレグ及びレジンシートからなる群より選ばれる少なくとも1種を1枚以上重ね、その片面若しくは両面に金属箔を配して積層成形することにより、得ることができる。より具体的には、前述のプリプレグ及び/又はレジンシートを1枚あるいは複数枚重ね、所望によりその片面若しくは両面に銅やアルミニウムなどの金属箔を配置した構成とし、これを必要に応じて積層成形することにより、金属箔張積層板を製造することができる。ここで使用する金属箔は、プリント配線板材料に用いられるものであれば、特に限定されないが、圧延銅箔や電解銅箔などの公知の銅箔が好ましい。また、金属箔の厚さは、特に限定されないが、1~70μmが好ましく、より好ましくは1.5~35μmである。金属箔張積層板の成形方法及びその成形条件についても、特に限定されず、一般的なプリント配線板用積層板及び多層板の手法及び条件を適用することができる。例えば、金属箔張積層板の成形時には多段プレス機、多段真空プレス機、連続成形機、及びオートクレーブ成形機などを用いることができる。また、金属箔張積層板の成形において、温度は100~300℃、圧力は面圧2~100kgf/cm2、加熱時間は0.05~5時間の範囲が一般的である。さらに、必要に応じて、150~300℃の温度で後硬化を行うこともできる。また、上述のプリプレグと、別途作製した内層用の配線板とを組み合わせて積層成形することにより、多層板とすることも可能である。
本実施形態のプリント配線板は、絶縁層と、その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、上記絶縁層が、上述の樹脂組成物を含むものである。回路となる導体層は、上記の金属箔張積層板における金属箔から形成することができる。あるいは、導体層は、絶縁層の表面に無電解めっきにより形成することもできる。このプリント配線板は、耐薬品性、耐デスミア性及び絶縁信頼性に優れるものであり、そのような性能が要求される半導体パッケージ用プリント配線板として、殊に有効に用いることができる。
α-ナフトールアラルキル型フェノール樹脂(SN495V、OH基当量:236g/eq.、新日鐵化学(株)製)300g(OH基換算1.28mol)及びトリエチルアミン194.6g(1.92mol;ヒドロキシ基1molに対して1.5mol)をジクロロメタン1800gに溶解させ、これを溶液1とした。塩化シアン125.9g(2.05mol;ヒドロキシ基1molに対して1.6mol)、ジクロロメタン293.8g、36%塩酸194.5g(1.92mol;ヒドロキシ基1molに対して1.5mol)、水1205.9gを、撹拌下、液温-2~-0.5℃に保ちながら、溶液1を30分かけて注下した。溶液1の注下終了後、同温度にて30分撹拌した後、トリエチルアミン65g(0.64mol;ヒドロキシ基1molに対して0.5mol)をジクロロメタン65gに溶解させた溶液(溶液2)を10分かけて注下した。溶液2の注下終了後、同温度にて30分撹拌して反応を完結させた。その後、反応液を静置して有機相と水相とを分離した。得られた有機相を水1300gで5回洗浄した。水洗5回目の廃水の電気伝導度は5μS/cmであり、水による洗浄により、除けるイオン性化合物は十分に除けられてことを確認した。水洗後の有機相を減圧下で濃縮し、最終的に90℃で1時間濃縮乾固させて、上記式(13)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(式中のR11は全て水素原子である。SN495V-CN,シアン酸エステル基当量:261g/eq.、橙色粘性物)331gを得た。得られたSN495V-CNの赤外吸収スペクトルは2250cm-1(シアン酸エステル基)の吸収を示し、且つ、ヒドロキシ基の吸収は示さなかった。
反応器内で、芳香族化合物(A1)に該当するジアリルビスフェノールA(DABPA、大和化成工業(株)製、水酸基当量:154g/eq.)5.0質量部と、フェノール性水酸基と反応する化合物に該当する単官能エポキシ化合物(製品名「ED-509E」、ADEKA社製)7.5質量部と、イミダゾール系硬化促進剤(2,4,5-トリフェニルイミダゾール(東京化成工業(株)製))0.05質量部とを混合した。その混合物を、反応が完結するまで135℃で1時間以上加熱し、芳香族化合物(A)に該当する下記式(21)で表される化合物を得た。反応の完結はGPC(ゲルパーミエーションクロマトグラフィー)にて確認した。
反応器内で、芳香族化合物(A1)に該当するジアリルビスフェノールA(DABPA、大和化成工業(株)製、水酸基当量:154g/eq.)5.3質量部と、単官能エポキシ化合物(製品名「YED-188」、三菱化学社製)7.1質量部と、イミダゾール系硬化促進剤(2,4,5-トリフェニルイミダゾール(東京化成工業(株)製))0.05質量部とを混合した。その混合物を、反応が完結するまで135℃で1時間以上加熱し、芳香族化合物(A)に該当する下記式(22)で表される化合物を得た。反応の完結はGPC(ゲルパーミエーションクロマトグラフィー)にて確認した。
合成例1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10.0質量部、ノボラック型マレイミド化合物(BMI-2300、大和化成工業(株)製、官能基当量:186g/eq.)45.0質量部、ビスアリルナジイミド(BANI-M、丸善石油化学(株)製、官能基当量:286g/eq.)25.0質量部、合成例2で得られた上記式(21)で表される化合物12.5質量部、ビフェニルアラルキル型エポキシ化合物(NC-3000H、日本化薬(株)製、官能基当量:290g/eq.)7.0質量部、シランカップリング剤(Z-6040、東レ・ダウコーニング(株)製)6.9質量部、湿潤分散剤(DISPERBYK-111、ビッグケミー・ジャパン(株)製)1.0質量部及び同(DISPERBYK-161、ビッグケミー・ジャパン(株)製)1.0質量部、イミダゾール系硬化促進剤(2,4,5-トリフェニルイミダゾール(東京化成工業(株)製))0.5質量部、並びに溶融シリカ(SC-4053SQ、アドマテックス(株)製)200質量部を混合し、メチルエチルケトンで希釈することでワニスを得た。このワニスをEガラス織布(厚さ:95μm、質量(目付け):108g/m2。以下同様。)に含浸塗工し、130℃で3分間加熱乾燥して、樹脂組成物含有量45質量%のプリプレグを得た。
合成例1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10.0質量部、ノボラック型マレイミド化合物(BMI-2300、大和化成工業(株)製、官能基当量:186g/eq.)45.0質量部、ビスアリルナジイミド(BANI-M、丸善石油化学(株)製、官能基当量:286g/eq.)25.0質量部、合成例3で得られた上記式(22)で表される化合物13.0質量部、ビフェニルアラルキル型エポキシ化合物(NC-3000H、日本化薬(株)製、官能基当量:290g/eq.)7.0質量部、シランカップリング剤(Z-6040、東レ・ダウコーニング(株)製)6.9質量部、湿潤分散剤(DISPERBYK-111、ビッグケミー・ジャパン(株)製)1.0質量部及び同(DISPERBYK-161、ビッグケミー・ジャパン(株)製)1.0質量部、イミダゾール系硬化促進剤(2,4,5-トリフェニルイミダゾール(東京化成工業(株)製))0.5質量部、並びに溶融シリカ(SC-4053SQ、アドマテックス(株)製)200質量部を混合し、メチルエチルケトンで希釈することでワニスを得た。このワニスをEガラス織布に含浸塗工し、130℃で3分間加熱乾燥して、樹脂組成物含有量45質量%のプリプレグを得た。
合成例1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10.0質量部、ノボラック型マレイミド化合物(BMI-2300、大和化成工業(株)製、官能基当量:186g/eq.)45.0質量部、ビスアリルナジイミド(BANI-M、丸善石油化学(株)製、官能基当量:286g/eq.)25.0質量部、芳香族化合物(A1)に該当するジアリルビスフェノールA(DABPA、大和化成工業(株)製、水酸基当量:154g/eq.)5.0質量部、Rで示される1価の有機基を有する化合物に該当する単官能エポキシ化合物(製品名「ED-509E」、ADEKA社製)7.5質量部、ビフェニルアラルキル型エポキシ化合物(NC-3000H、日本化薬(株)製、官能基当量:290g/eq.)7.0質量部、シランカップリング剤(Z-6040、東レ・ダウコーニング(株)製)6.9質量部、湿潤分散剤(DISPERBYK-111、ビッグケミー・ジャパン(株)製)1.0質量部及び同(DISPERBYK-161、ビッグケミー・ジャパン(株)製)1.0質量部、イミダゾール系硬化促進剤(2,4,5-トリフェニルイミダゾール(東京化成工業(株)製))0.5質量部、並びに溶融シリカ(SC-4053SQ、アドマテックス(株)製)200質量部を混合し、メチルエチルケトンで希釈することでワニスを得た。このワニスをEガラス織布に含浸塗工し、130℃で3分間加熱乾燥して、樹脂組成物含有量45質量%のプリプレグを得た。
合成例1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10.0質量部、ノボラック型マレイミド化合物(BMI-2300、大和化成工業(株)製、官能基当量:186g/eq.)47.0質量部、ビスアリルナジイミド(BANI-M、丸善石油化学(株)製、官能基当量:286g/eq.)36.0質量部、ビフェニルアラルキル型エポキシ化合物(NC-3000H、日本化薬(株)製、官能基当量:290g/eq.)7.0質量部、シランカップリング剤(Z-6040、東レ・ダウコーニング(株)製)6.9質量部、湿潤分散剤(DISPERBYK-111、ビッグケミー・ジャパン(株)製)1.0質量部及び同(DISPERBYK-161、ビッグケミー・ジャパン(株)製)1.0質量部、イミダゾール系硬化促進剤(2,4,5-トリフェニルイミダゾール(東京化成工業(株)製))0.5質量部及び溶融シリカ(SC-4053SQ、アドマテックス(株)製)200質量部を混合し、メチルエチルケトンで希釈することでワニスを得た。このワニスをEガラス織布に含浸塗工し、130℃で3分間加熱乾燥して、樹脂組成物含有量45質量%のプリプレグを得た。
上記で得られたプリプレグ1枚に対して12μm厚の電解銅箔(3EC-III、三井金属鉱業(株)製)を上下に配置し、圧力30kgf/cm2、温度220℃で120分間の積層成型を行い、絶縁層厚さ0.1mmの銅張積層板を得た。
上述のようにして銅張積層板を得た後、そこから両面の銅箔をエッチングにより除去して試料を得た。その試料について、JIS K7244-3(JIS C6481)に準拠し、動的粘弾性測定装置(ティー・エイ・インスツルメント・ジャパン株式会社製)を用い、開始温度50℃、終了温度350℃、昇温速度10℃/分の条件にて、動的粘弾性を測定した。その際に得られた損失弾性率(E")の最大値をガラス転移温度とした。ガラス転移温度は耐熱性の指標である。なお、表1において、350℃以下の領域でガラス転移温度がある場合はその値を表記し、350℃以下の領域でガラス転移温度がない場合は「>350℃」と表記した。結果を表1に示す。
上述のようにして銅張積層板を得た後、そこから両面の銅箔をエッチングにより除去して試料を得た。その試料について、目視にて表面を観察してボイドの有無を評価した。ボイドの存在が多く確認された場合は、成形ができないものとして「C」と評価し、ボイドの存在が確認されたものの、その数が少ない場合は、成形可能であるとして「B」と評価し、ボイドの存在が確認されない場合は、良好に成形可能であるとして「A」と評価した。結果を表1に示す。
上記実施例及び比較例で得られたプリプレグの最低溶融粘度を、レオメータ(ティー・エイ・インスツルメント・ジャパン株式会社製)を用い、開始温度80℃、終了温度180℃、昇温速度3℃/min、周波数10pts/s、歪0.1%の条件にて測定した。この最低溶融粘度が低いほど、積層板作製時の流れ特性(樹脂フロー性)が良好であり、成形性に優れていることを意味する。結果を表1に示す。
上述のようにして得られたプリプレグを恒温槽に収容し、40℃で1週間保管した。その保管前後の粘度の変化を、フローテスターを用いて測定した。詳細には、フローテスター(株式会社島津製作所製)を用い、測定温度120℃、引張荷重10kg、ダイ穴径φ1mm、ダイ長さ10mmにて測定した。この粘度の変化が少ない程、積層板作製時の流れ特性(樹脂フロー性)が良好のまま、保管可能な期間が長いことを示し、プリプレグが保存安定性に優れていることを意味する。結果を表1に示す。
Claims (16)
- 芳香環に下記式(1a)で表される1価の置換基と下記式(1b)で表される1価の置換基とが直接結合してなる芳香族化合物(A)と、マレイミド化合物(B)と、を含む樹脂組成物。
CH2=CRaCH2- (1a)
RbO- (1b)
(式(1a)中、Raは水素原子又は1価の有機基を示し、式(1b)中、Rbは1価の有機基を示す。) - 前記芳香族化合物(A)において、前記式(1a)で表される1価の置換基が結合する前記芳香環における炭素原子と、前記式(1b)で表される1価の置換基が結合する前記芳香環における炭素原子が互いに隣接する、請求項1に記載の樹脂組成物。
- 前記芳香族化合物(A)が、下記式(6)で表される化合物を含む、請求項1~4のいずれか一項に記載の樹脂組成物。
- エポキシ樹脂、シアン酸エステル化合物及びアルケニル置換ナジイミドからなる群より選ばれる少なくとも1種をさらに含む、請求項1~6のいずれか一項に記載の樹脂組成物。
- 無機充填材(C)をさらに含む、請求項1~7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、アルミナ及びベーマイトからなる群より選ばれる少なくとも1種を含む、請求項8に記載の樹脂組成物。
- 前記無機充填材(C)の含有量が、樹脂固形分100質量部に対して30~500質量部である、請求項8又は9に記載の樹脂組成物。
- 基材と、当該基材に含浸又は塗布された請求項1~10のいずれか一項に記載の樹脂組成物と、を備える、プリプレグ。
- 支持体と、当該支持体に塗布された請求項1~10のいずれか一項に記載の樹脂組成物と、を備える、レジンシート。
- 請求項11に記載のプリプレグ、及び請求項12に記載のレジンシートからなる群より選ばれる少なくとも1種を1枚以上重ねてなる積層板であって、前記プリプレグ及び前記レジンシートからなる群より選ばれる少なくとも1種に含まれる樹脂組成物の硬化物を含む、積層板。
- 請求項11に記載のプリプレグ、及び請求項12に記載のレジンシートからなる群より選ばれる少なくとも1種と、前記プリプレグ及び前記レジンシートからなる群より選ばれる少なくとも1種の片面又は両面に配された金属箔と、を有する金属箔張積層板であって、前記プリプレグ及び前記レジンシートからなる群より選ばれる少なくとも1種に含まれる樹脂組成物の硬化物を含む、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1~10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。
- 芳香環に下記式(1a)で表される1価の置換基とフェノール性水酸基とが直接結合してなる芳香族化合物(A1)と、フェノール性水酸基と反応する化合物とを反応させて、芳香環に下記式(1a)で表される1価の置換基と下記式(1b)で表される1価の置換基とが直接結合してなる芳香族化合物(A)を得る工程と、
前記芳香族化合物(A)とマレイミド化合物(B)とを配合する工程と、を有する、樹脂組成物の製造方法。
CH2=CRaCH2- (1a)
RbO- (1b)
(式(1a)中、Raは水素原子又は1価の有機基を示し、式(1b)中、Rbは1価の有機基を示す。)
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CN113490715A (zh) * | 2019-02-28 | 2021-10-08 | 三菱瓦斯化学株式会社 | 树脂组合物、预浸料、覆金属箔层叠板、树脂复合片及印刷电路板 |
CN114127180A (zh) * | 2019-06-28 | 2022-03-01 | 三菱瓦斯化学株式会社 | 薄膜、层叠体、带薄膜层的半导体晶圆、带薄膜层的半导体搭载用基板和半导体装置 |
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CN113490715A (zh) * | 2019-02-28 | 2021-10-08 | 三菱瓦斯化学株式会社 | 树脂组合物、预浸料、覆金属箔层叠板、树脂复合片及印刷电路板 |
CN114127180A (zh) * | 2019-06-28 | 2022-03-01 | 三菱瓦斯化学株式会社 | 薄膜、层叠体、带薄膜层的半导体晶圆、带薄膜层的半导体搭载用基板和半导体装置 |
CN114127180B (zh) * | 2019-06-28 | 2023-06-09 | 三菱瓦斯化学株式会社 | 薄膜、层叠体、带薄膜层的半导体晶圆、带薄膜层的半导体搭载用基板和半导体装置 |
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KR20200013632A (ko) | 2020-02-07 |
CN110546188A (zh) | 2019-12-06 |
JPWO2018216647A1 (ja) | 2020-03-26 |
JP7116927B2 (ja) | 2022-08-12 |
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