WO2019230945A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2019230945A1 WO2019230945A1 PCT/JP2019/021694 JP2019021694W WO2019230945A1 WO 2019230945 A1 WO2019230945 A1 WO 2019230945A1 JP 2019021694 W JP2019021694 W JP 2019021694W WO 2019230945 A1 WO2019230945 A1 WO 2019230945A1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
-
- 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
- C08J2479/00—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 C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- 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
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0275—Fibers and reinforcement materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0275—Fibers and reinforcement materials
- H05K2201/029—Woven fibrous reinforcement or textile
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
Definitions
- the present invention relates to a resin composition, a prepreg using the resin composition, the resin composition, a metal foil-clad laminate and a resin sheet using the prepreg, and a printed wiring board using them.
- Patent Document 1 specifies a composition having excellent varnish storage stability and improved electrical characteristics, copper foil peel strength, and thermal decomposition temperature without reducing multilayer moldability and heat resistance after moisture absorption.
- a combination of a bifunctional vinylbenzyl compound containing a polyphenylene ether skeleton, a specific maleimide compound, a specific cyanate ester resin, and a specific epoxy resin in a predetermined ratio is disclosed. Yes.
- Patent Document 2 a specific vinyl compound, a specific maleimide compound, and a styrene-based thermoplastic resin are obtained as a resin composition that can be cured at a low temperature to obtain a cured product having excellent low dielectric properties, heat resistance, mechanical properties, and chemical resistance.
- a combination of an elastomer and a constituent component at a predetermined ratio is disclosed.
- thermosetting resin composition capable of suppressing a resin residue while obtaining a low dielectric loss tangent, at least selected from the group consisting of polyphenylene ether, a cyanate ester resin, a phenol resin, a maleimide compound, and an epoxy resin.
- a combination of one kind and a filler at a predetermined ratio is disclosed.
- Patent Document 1 examples include a resin composition containing a bifunctional vinylbenzyl compound containing a specific polyphenylene ether skeleton, a specific maleimide compound, a specific cyanate ester resin, and a specific epoxy resin.
- a resin composition containing a bifunctional vinylbenzyl compound containing a specific polyphenylene ether skeleton, a specific maleimide compound, a specific cyanate ester resin, and a specific epoxy resin When used in a copper-clad laminate, it is disclosed that low dielectric loss tangent, metal foil (copper foil) peel strength, and moisture absorption heat resistance are improved.
- examples of Patent Document 2 include examples of films using a resin composition containing a specific vinyl compound, a maleimide compound having a characteristic, and a styrene-based thermoplastic elastomer and combined in a predetermined ratio. It is described, and evaluation is made on low thermal expansion and low dielectric loss tangent.
- Patent Document 3 discloses that a resin residue can be suppressed while obtaining a low dielectric loss tangent property by combining a specific component with polyphenylene ether and controlling the content of polyphenylene ether.
- specific evaluation results for low thermal expansion cannot be confirmed.
- polybutadiene modified with a hydroxy group or an acrylic group is used as an elastomer which gives further low dielectric loss tangent.
- the object of the present invention is to achieve excellent low dielectric constant, low dielectric loss tangent and low thermal expansion at the same time when used for printed wiring board materials (for example, laminates, metal foil-clad laminates) and the like, and uniform
- Another object of the present invention is to provide a resin composition, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board that are cured products.
- the present inventors have found that a maleimide compound (A), a cyanate ester compound (B), a specific polyphenylene ether compound (C), and a block copolymer having a styrene skeleton (D ),
- the resulting resin composition has excellent low dielectric constant, low dielectric loss tangent, and low thermal expansion when used in printed wiring board materials (eg, laminates, metal foil-clad laminates).
- printed wiring board materials eg, laminates, metal foil-clad laminates
- X represents an aryl group
- — (Y—O) n 2 — represents a polyphenylene ether moiety
- R 1 , R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, An alkenyl group or an alkynyl group
- n 2 represents an integer of 1 to 100
- n 1 represents an integer of 1 to 6
- n 3 represents an integer of 1 to 4.
- the block copolymer (D) having a styrene skeleton is a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, a styrene-hydrogenated butadiene block copolymer, a styrene-hydrogenated isoprene block copolymer,
- the resin composition according to [1] containing at least one selected from the group consisting of styrene-hydrogenated (isoprene / butadiene) block copolymers.
- each R 4 independently represents a hydrogen atom or a methyl group, and n 4 represents an integer of 1 or more.
- each R 5 independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n 5 represents an integer of 1 to 10.
- each R 6 independently represents a hydrogen atom, a methyl group or an ethyl group, and each R 7 independently represents a hydrogen atom or a methyl group.
- each R 8 independently represents a hydrogen atom, a methyl group or an ethyl group.
- a metal foil-clad laminate comprising one or more stacked prepregs according to [11] and a metal foil disposed on one or both sides of the prepreg.
- a printed wiring board including an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer is formed from the resin composition according to any one of [1] to [10].
- Printed wiring board including layers.
- the present embodiment an embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.
- the resin composition according to this embodiment includes a maleimide compound (A), a cyanate ester compound (B), a polyphenylene ether compound (C) having a number average molecular weight represented by the formula (1) of 1000 to 7000, and a styrene skeleton.
- a block copolymer (D) having Since the resin composition according to the present embodiment has the above-described configuration, it is excellent in low dielectric constant and low dielectric loss tangent when used for a printed wiring board material (for example, a laminated board or a metal foil-clad laminated board). Property and low thermal expansion are simultaneously achieved, and a uniform cured product is obtained.
- the uniform cured product means that no voids or poor dispersion are observed when the cross section of the cured product is observed with an optical microscope.
- the maleimide compound (A) is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 4,4′-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) Methane, bis (3,5-diethyl-4-maleimidophenyl) methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebis Citraconimide, p-phenylenebiscitraconimide, 2,2-bis (4- (4-maleimidophenoxy) -phenyl
- each R 4 independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
- n 4 represents an integer of 1 or more, and the upper limit value of n 4 is usually 10. From the viewpoint of solubility in organic solvents, the upper limit value of n 4 is preferably 7, more preferably 5.
- the maleimide compound (A) may contain two or more compounds having different n 4 .
- each R 5 is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group). , T-butyl group, n-pentyl group, etc.) or phenyl group.
- a group selected from the group consisting of a hydrogen atom, a methyl group, and a phenyl group is preferable. More preferably, it is one, and it is still more preferable that it is a hydrogen atom.
- n 5 is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less from the viewpoint of further improving solvent solubility.
- the maleimide compound (A) may contain two or more compounds having different n 5 .
- each R 6 independently represents a hydrogen atom, a methyl group or an ethyl group
- each R 7 independently represents a hydrogen atom or a methyl group.
- R 6 is preferably a methyl group or an ethyl group.
- Such compounds include 3,3′-diethyl-5,5′-dimethyl-4,4′-diphenylmethane bismaleimide.
- R ⁇ 8 > shows a hydrogen atom, a methyl group, or an ethyl group each independently. From the viewpoint of more excellent low dielectric constant and low dielectric loss tangent, R 8 is preferably a methyl group.
- An example of such a compound is 2,2-bis (4- (4-maleimidophenoxy) -phenyl) propane.
- the maleimide compound (A) used in the present embodiment a commercially available one may be used.
- the maleimide compound represented by the formula (2) “BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd. ) “MIR-3000” manufactured by Nippon Kayaku Co., Ltd. as the maleimide compound represented by formula (4), and “BMI-70” manufactured by Kay Kasei Co., Ltd. as the formula (4).
- “BMI-80” manufactured by Kay Kasei Co., Ltd. can be preferably used.
- the content of the maleimide compound (A) in the resin composition according to the present embodiment can be appropriately set according to desired properties, and is not particularly limited.
- the content of the maleimide compound (A) is preferably 1 part by mass or more and more preferably 5 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass.
- the upper limit is preferably 90 parts by mass or less, more preferably 60 parts by mass or less, further preferably 40 parts by mass or less, and may be 30 parts by mass or less. By setting it as such a range, it exists in the tendency for high heat resistance and low water absorption to be exhibited more effectively.
- the maleimide compound (A) may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
- resin solid content in the resin composition refers to a component in the resin composition excluding the solvent and filler (F), and the resin solid content is 100 parts by mass.
- the total amount of the components excluding the solvent and the filler (F) in the resin composition is 100 parts by mass.
- the cyanate ester compound (B) is not particularly limited as long as it is a resin having in its molecule an aromatic moiety substituted with at least one cyanate group (cyanate ester group).
- the compound represented by Formula (5) is mentioned, for example.
- Ar ⁇ 1 > represents each independently the phenylene group which may have a substituent, the naphthylene group which may have a substituent, or the biphenylene group which may have a substituent.
- R 81 may independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or a substituent.
- Cyanate ester compound (B) may be a mixture of compounds different in n 8.
- Each Z is independently a single bond or a divalent organic group having 1 to 50 carbon atoms (in which a hydrogen atom is substituted with a heteroatom).
- a divalent organic group having 1 to 10 nitrogen atoms such as —N—R—N—), a carbonyl group (—CO—), a carboxy group (—C ( ⁇ O) O—), a carbonyl dioxide.
- the alkyl group in R 81 of the formula (5) may have a linear structure, a branched structure, or a cyclic structure (such as a cycloalkyl group).
- the hydrogen atom in the alkyl group in formula (5) and the aryl group in R 81 may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group, or the like. Good.
- alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, 2,2-dimethylpropyl group.
- aryl group examples include phenyl group, xylyl group, mesityl group, naphthyl group, phenoxyphenyl group, ethylphenyl group, o-, m- or p-fluorophenyl group, dichlorophenyl group, dicyanophenyl group, trifluorophenyl.
- alkoxy group examples include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group and the like.
- Ar 2 is selected from any one of a phenylene group, a naphthylene group, and a biphenylene group.
- R 9 , R 10 , R 13 , and R 14 are each independently a hydrogen atom, 6 alkyl group, an aryl group having 6 to 12 carbon atoms, and, .R 11, R 12 is selected from any one of at least one optionally substituted aryl group a trifluoromethyl group and a phenolic hydroxy group 0 is .
- n 9 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, selected from any one of the alkoxy groups and hydroxy groups having 1 to 4 carbon atoms An integer of ⁇ 5 is shown, but the cyanate ester compound (B) may be a mixture of compounds having different groups for n 9.
- Ar 3 is selected from any one of a phenylene group, a naphthylene group and a biphenylene group.
- R 15 and R 16 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, carbon Selected from the group consisting of an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, and an aryl group substituted with at least one of a hydroxy group, a trifluoromethyl group and a cyanato group.
- N 10 represents an integer of 0 to 5, but the cyanate ester compound (B) may be a mixture of compounds having different groups for n 10.
- Examples of the cyanate ester compound represented by the formula (5) include phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, biphenyl aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, and xylene.
- Examples thereof include a resin type cyanate ester compound, an adamantane skeleton type cyanate ester compound, a bisphenol A type cyanate ester compound, a diallyl bisphenol A type cyanate ester compound, and a naphthol aralkyl type cyanate ester compound.
- cyanate ester compound represented by the formula (5) examples include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, 1-cyanato-4-methylbenzene, 1-cyanato- 2-, 1-Cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1-cyanato -2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2- (4- Cianaphenyl) -2-phenylpropane (cyanate of 4- ⁇ -cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanate Nato-2- or 1-cyan
- phenol novolac type cyanate ester compound naphthol aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, bisphenol A type cyanate ester compound, bisphenol M type cyanate ester compound, diallyl bisphenol type cyanate ester Naphthol aralkyl cyanate compounds are particularly preferred.
- the cured product of the resin composition using these cyanate ester compounds has excellent properties such as heat resistance and low dielectric properties (low dielectric constant, low dielectric loss tangent).
- the content of the cyanate ester compound (B) in the resin composition according to the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited.
- the content of the cyanate ester compound (B) is preferably 1 part by mass or more and more preferably 5 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass. More preferably, it is 10 mass parts or more, and may be 12 mass parts or more, 15 mass parts or more, and 20 mass parts or more.
- the upper limit of the content is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, still more preferably less than 70 parts by mass, still more preferably 60 parts by mass or less, and 50 parts by mass. Hereinafter, it may be 40 parts by mass or less.
- the cyanate ester compound (B) may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the number average molecular weight of the polyphenylene ether compound (C) represented by the formula (1) used in the present embodiment is 1000 or more and 7000 or less. By setting the number average molecular weight to 7000 or less, fluidity during molding can be secured. In addition, when the number average molecular weight is 1000 or more, the inherent excellent dielectric properties (low dielectric constant, low dielectric loss tangent) and heat resistance of the polyphenylene ether resin can be obtained. Among these, in order to obtain more excellent fluidity, heat resistance, and dielectric properties, the number average molecular weight of the polyphenylene ether compound (C) is preferably 1100 or more and 5000 or less.
- the number average molecular weight of the polyphenylene ether compound (C) is 4500 or less, and more preferably, the number average molecular weight of the polyphenylene ether compound (C) is 3000 or less.
- the number average molecular weight is measured using gel permeation chromatography according to a standard method.
- the polyphenylene ether compound (C) represented by the formula (1) used in the present embodiment preferably has a minimum melt viscosity of 50000 Pa ⁇ s or less. By setting the minimum melt viscosity to 50000 Pa ⁇ s or less, fluidity can be ensured and multilayer molding becomes possible.
- the lower limit of the minimum melt viscosity is not particularly defined, but may be, for example, 1000 Pa ⁇ s or more.
- the polyphenylene ether compound (C) represented by the formula (1) preferably contains a polymer of a structural unit represented by the following formula (8).
- R 18 , R 19 , R 20 , and R 21 each independently represents an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom.
- the polymer may further include at least one structural unit selected from the group consisting of structural units represented by formula (9) and formula (10).
- R 22 , R 23 , R 24 , R 28 and R 29 each independently represents an alkyl group or phenyl group having 6 or less carbon atoms.
- R 25 , R 26 and R 27 are each Independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
- R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
- -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
- the above formulas (8), (9), and (10) are preferably — (YO) — in the formula (1).
- -(YO)- has n2 number of repeating units (1 to 100).
- X represents an aryl group (aromatic group), — (Y—O) n 2 — represents a polyphenylene ether moiety, R 1 , R 2 and R 3 each independently represents a hydrogen atom, An alkyl group, an alkenyl group or an alkynyl group; n 2 represents an integer of 1 to 100; n 1 represents an integer of 1 to 6; and n 3 represents an integer of 1 to 4.
- n 1 is an integer of 1 or more and 4 or less, more preferably n 1 is 1 or 2, and ideally n 1 is 1.
- n 3 is an integer of 1 or more and 3 or less, more preferably n 3 is 1 or 2, and ideally n 3 is 2.
- an aromatic hydrocarbon group can be used as the aryl group in X of the formula (1).
- a group in which n 3 hydrogen atoms are removed from one ring structure selected from a benzene ring structure, a biphenyl structure, an indenyl ring structure, and a naphthalene ring structure (for example, a phenyl group, a biphenyl group, Indenyl group and naphthyl group) can be used, and a biphenyl group is preferably used.
- the aryl group includes a diphenyl ether group in which the above aryl group is bonded by an oxygen atom, a benzophenone group bonded by a carbonyl group, and the like, a 2,2-diphenylpropane group bonded by an alkylene group, and the like.
- the aryl group may be substituted with a general substituent such as an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, particularly a methyl group), an alkenyl group, an alkynyl group, or a halogen atom.
- the “aryl group” is substituted on the polyphenylene ether moiety via an oxygen atom, the number of general substituents depends on the number of polyphenylene ether moieties.
- the polyphenylene ether compound (C) particularly preferably includes a polyphenylene ether represented by the structure of the following formula (11).
- X represents an aryl group (aromatic group)
- — ( YO ) n2 — represents a polyphenylene ether moiety
- n2 represents an integer of 1 to 100, respectively.
- — (Y—O) n2 — and n2 have the same meanings as in formula (1).
- a plurality of compounds different in n2 may be contained.
- X in Formula (1) and Formula (11) is preferably Formula (12), Formula (13), or Formula (14), and — (YO) in Formula (1) and Formula (11) n2 ⁇ is more preferably a structure in which the formula (15) or the formula (16) is arranged, or a structure in which the formula (15) and the formula (16) are arranged at random.
- R 38 , R 39 , R 40 and R 41 each independently represents a hydrogen atom or a methyl group.
- —B— is a straight, branched or cyclic group having 20 or less carbon atoms.
- It is a divalent hydrocarbon group.
- -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms
- the method for producing the modified polyphenylene ether having the structure represented by the formula (11) is not particularly limited.
- a bifunctional phenylene ether obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound. It can be produced by converting the terminal phenolic hydroxyl group of the oligomer to vinyl benzyl ether.
- Such modified polyphenylene ether may be a commercially available product.
- OPE-2St1200 and OPE-2st2200 manufactured by Mitsubishi Gas Chemical Co., Ltd. can be preferably used.
- the content of the polyphenylene ether compound (C) in the resin composition according to this embodiment is preferably 1 part by mass or more, and preferably 5 parts by mass or more with respect to 100 parts by mass of the resin solid content of the resin composition. Is more preferable, and more preferably 8 parts by mass or more. Moreover, as an upper limit of the said content, it is preferable that it is 40 mass parts or less, it is more preferable that it is 30 mass parts or less, and 25 mass parts or less may be sufficient. By making such a range. It tends to more effectively achieve low dielectric constant, low dielectric loss tangent and good moldability.
- the resin composition may contain only one type of polyphenylene ether compound (C), or may contain two or more types. When 2 or more types are included, the total amount is preferably within the above range.
- Block copolymer having styrene skeleton (D) The “block copolymer (D) having a styrene skeleton” according to the present embodiment refers to an elastomer that is a block copolymer having a polystyrene block structure, and does not include a random copolymer. Further, a compound composed only of an aromatic vinyl compound is represented as “styrene oligomer (E)”, and is not included in “block copolymer (D) having a styrene skeleton”.
- styrene-isoprene block copolymers In particular, styrene-isoprene block copolymers, styrene-hydrogenated butadiene block copolymers, styrene-hydrogenated isoprene block copolymers, and styrene-hydrogenated (butadiene / isoprene) block copolymers have better low dielectric loss tangents. From the viewpoint of imparting sex.
- styrene having a substituent may be used.
- styrene derivatives such as ⁇ -methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used.
- the styrene content (hereinafter also referred to as “styrene ratio”) in the block copolymer (D) having a styrene skeleton is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more. It is.
- the upper limit of the styrene content is not particularly limited as long as it is less than 100% by mass, but for example, it is preferably less than 99% by mass, and more preferably 70% by mass or less. By setting it as such a range, it exists in the tendency which solvent solubility and compatibility with another compound improve more.
- the styrene content is the mass of the styrene unit contained in the block copolymer (D) having a styrene skeleton (a) g, and the mass of the entire block copolymer (D) having a styrene skeleton (b) )
- g it is a value represented by (a) / (b) ⁇ 100 (unit:%).
- the content of the block copolymer (D) having a styrene skeleton in the resin composition according to this embodiment is preferably 1 part by mass or more with respect to 100 parts by mass of the resin solid content of the resin composition.
- the amount is preferably at least 8 parts by mass.
- the upper limit of the content is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 22 parts by mass or less. By setting it as such a range, it exists in the tendency which is more excellent in low dielectric constant property, low dielectric loss tangent property, and moldability.
- 2 or more types of block copolymers (D) may be included. When 2 or more types are included, the total amount is preferably within the above range.
- the resin composition may contain only one type of block copolymer (D) having a styrene skeleton, or may contain two or more types. When 2 or more types are included, the total amount is preferably within the above range.
- block copolymer (D) having a styrene skeleton in the present embodiment, commercially available products may be used. For example, TR2630 (manufactured by JSR Corporation), TR2003 (JSR) as styrene-butadiene-styrene block copolymers. Product).
- examples of the styrene-isoprene-styrene block copolymer include SIS5250 (manufactured by JSR Corporation).
- examples of the styrene-hydrogenated isoprene-styrene block copolymer include SEPTON 2104 (manufactured by Kuraray Co., Ltd.).
- the resin composition according to this embodiment desirably contains a styrene oligomer (E) in order to improve low dielectric constant and low dielectric loss tangent.
- the “styrene oligomer (E)” used in the present embodiment is distinguished from the above-described “block copolymer (D) having a styrene skeleton”.
- the styrene oligomer (E) is obtained by polymerizing at least one selected from the group consisting of styrene, the above styrene derivative, and vinyl toluene, and has a number average molecular weight of 178 to 1600 and an average number of aromatic rings. Is a compound having no branched structure in which the total amount of 2 to 14, the number of aromatic rings 2 to 14 is 50% by mass or more, and the boiling point is 300 ° C. or more.
- Examples of the styrene oligomer (E) used in the present embodiment include a styrene polymer, vinyl toluene polymer, ⁇ -methyl styrene polymer, vinyl toluene- ⁇ -methyl styrene polymer, styrene- ⁇ -styrene polymer, and the like. Is mentioned. As the styrene polymer, commercially available products may be used.
- Picolastic A5 manufactured by Eastman Chemical
- Picolastic A-75 manufactured by Eastman Chemical
- Picotex 75 manufactured by Eastman Chemical
- FTR-8100 manufactured by Mitsui Chemicals, Inc.
- FTR-8120 manufactured by Mitsui Chemicals, Inc.
- An example of the vinyltoluene- ⁇ -methylstyrene polymer is Picotex LC (manufactured by Eastman Chemical Co.).
- content of the styrene oligomer (E) in the resin composition which concerns on this embodiment shall be 1 mass part or more and 30 mass parts or less with respect to 100 mass parts of resin solid content of a resin composition.
- the resin composition may contain only one type of styrene oligomer (E), or may contain two or more types. When 2 or more types are included, the total amount is preferably within the above range.
- the resin composition according to the present embodiment desirably contains a filler (F) in order to improve low dielectric constant, low dielectric loss tangent, flame resistance, and low thermal expansion.
- a filler (F) used by this embodiment a well-known thing can be used suitably, The kind is not specifically limited, What is generally used in this industry can be used suitably. .
- silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, aggregated boron nitride, silicon nitride , Aluminum nitride, Barium sulfate, Aluminum hydroxide, Aluminum hydroxide heat-treated product (Aluminum hydroxide is heat-treated and part of crystal water is reduced), Boehmite, Magnesium hydroxide and other metal hydrates, Oxidation Molybdenum compounds such as molybdenum and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C -Glass, L-glass, D-glass, S
- These fillers may be used alone or in combination of two or more. Among these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide, and magnesium hydroxide is preferable. By using these fillers, characteristics such as thermal expansion characteristics, dimensional stability, and flame retardancy of the resin composition are improved.
- the content of the filler (F) in the resin composition according to the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited, but the resin solid content in the resin composition is 100 parts by mass. In this case, the amount is preferably 50 parts by mass or more. As an upper limit, 1600 mass parts or less are preferable, 500 mass parts or less are more preferable, and 300 mass parts or less are especially preferable. Alternatively, the filler (F) may be 75 to 250 parts by mass, or 100 to 200 parts by mass. By making content of a filler (F) into this range, the moldability of a resin composition becomes favorable.
- the resin composition may contain only 1 type of filler (F), and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
- the filler (F) it is preferable to use at least one selected from the group consisting of a silane coupling agent and a wetting and dispersing agent.
- a silane coupling agent those generally used for inorganic surface treatment can be suitably used, and the type thereof is not particularly limited.
- aminosilanes such as ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxylane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4 Epoxy silanes such as epoxycyclohexyl) ethyltrimethoxysilane, vinylsilanes such as ⁇ -methacryloxypropyltrimethoxysilane, vinyl-tri ( ⁇ -methoxyethoxy) silane, N- ⁇ - (N-vinylbenzylaminoethyl)- Cationic silanes such as ⁇ -aminopropyltrimethoxysilane hydrochloride, phenylsilanes and the like can be mentioned.
- a silane coupling agent may be used independently or may use 2 or more types together.
- a wet dispersing agent what is generally used for coating materials can be used suitably, The kind is not specifically limited.
- a copolymer-based wetting and dispersing agent is used, and specific examples thereof include Disperbyk-110, 111, 161, 180, 2009, 2152, BYK-W996, BYK-W9010 manufactured by Big Chemie Japan Co., Ltd. , BYK-W903, BYK-W940 and the like.
- the wetting and dispersing agent may be used alone or in combination of two or more.
- the content of the silane coupling agent is not particularly limited, and may be about 1 to 5 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
- the content of the dispersant (particularly the wet dispersant) is not particularly limited, and may be, for example, about 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
- the resin composition which concerns on this embodiment contains a flame retardant (G) for the improvement of a flame resistance.
- a flame retardant (G) used in the present embodiment known ones can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, Halogen flame retardants such as pentabromobenzyl (meth) acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin, red Phosphorus, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate,
- the flame retardants may be used alone or in combination of two or more.
- phosphorus-based flame retardants are preferable, and 1,3-phenylenebis (2,6-dixylenyl phosphate) is particularly preferable because low dielectric properties are not easily impaired.
- the phosphorus content in the resin composition is preferably 0.1 to 5% by mass.
- the content of the flame retardant (G) is preferably 1 part by mass or more and more preferably 5 parts by mass or more with respect to 100 parts by mass of the resin solid content in the resin composition.
- the upper limit of the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and may be 15 parts by mass or less. Only one type of flame retardant (G) may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the block copolymer (D) having a styrene skeleton] may contain a thermoplastic elastomer (hereinafter referred to as “other thermoplastic elastomer”), a curing accelerator, an organic solvent, and the like that are not described in the block copolymer.
- the total amount of the polyphenylene ether compound other than the polyphenylene ether compound (C) and the other thermoplastic elastomer is preferably 3% by mass or less based on the resin solid content. % Or less is more preferable.
- the epoxy resin is not particularly limited as long as it is a compound or resin having two or more epoxy groups in one molecule.
- the epoxy resin is not particularly limited as long as it is a compound or resin having two or more epoxy groups in one molecule.
- epoxy resins may be used alone or in combination of two or more.
- biphenylaralkyl type epoxy resins naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable.
- the phenol resin is not particularly limited as long as it is a compound or resin having two or more phenolic hydroxy groups in one molecule.
- the phenol resin is not particularly limited as long as it is a compound or resin having two or more phenolic hydroxy groups in one molecule.
- bisphenol A type phenol resin bisphenol E type phenol resin, bisphenol F type phenol resin, Bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolak type phenol resin, glycidyl ester type phenol resin, aralkyl novolac phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak Resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol Le resin, naphthol aralkyl type phenol resins,
- phenolic resins may be used alone or in combination of two or more.
- it should be at least one selected from the group consisting of biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins. preferable.
- the oxetane resin is not particularly limited.
- oxetane, alkyl oxetane for example, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxatan, etc.
- 3-methyl- 3-methoxymethyloxetane 3,3-di (trifluoromethyl) perfluoxetane
- 2-chloromethyloxetane 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (Toagosei Co., Ltd.) Product), OXT-121 (product of Toagosei Co., Ltd.) and the like.
- These oxetane resins may be used alone or in combination of two or more.
- the benzoxazine compound is not particularly limited as long as it has two or more dihydrobenzoxazine rings in one molecule.
- bisphenol A type benzoxazine BA-BXZ product of Konishi Chemical Co., Ltd.
- bisphenol F Type benzoxazine BF-BXZ product of Konishi Chemical Co., Ltd.
- bisphenol S type benzoxazine BS-BXZ product of Konishi Chemical Co., Ltd.
- “Other thermoplastic elastomers” “Other thermoplastic elastomers” is distinguished from “block copolymer (D) having a styrene skeleton”.
- the “block copolymer (D) having a styrene skeleton” refers to an elastomer that has a polystyrene block structure and is a block copolymer, and the “other thermoplastic elastomer” refers to any other elastomer. That is, a random copolymer, a block copolymer having no styrene skeleton, and the like are applicable.
- the other thermoplastic elastomer is, for example, at least selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene random copolymer, butyl rubber, ethylene propylene rubber, fluorine rubber, silicone rubber, hydrogenated compounds thereof, and alkyl compounds thereof.
- One type is mentioned. Among these, it is at least one selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene random copolymer, butyl rubber, and ethylene propylene rubber from the viewpoint of better compatibility with the polyphenylene ether compound (C). Is more preferable.
- the resin composition according to the present embodiment may contain a curing accelerator for appropriately adjusting the curing rate.
- the curing accelerator include those usually used as a curing accelerator such as a maleimide compound, a cyanate ester compound, and an epoxy resin, and organic metal salts (for example, zinc octylate, zinc naphthenate, cobalt naphthenate, Copper naphthenate, iron acetylacetone, nickel octylate, manganese octylate, etc.), phenol compounds (eg, phenol, xylenol, cresol, resorcin, catechol, octylphenol, nonylphenol, etc.), alcohols (eg, 1-butanol, 2-ethyl) Hexanol, etc.), imidazoles (eg 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2
- the content of the curing accelerator may be usually about 0.005 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.
- the resin composition according to the present embodiment may contain various polymer compounds such as thermosetting resins, thermoplastic resins, and oligomers other than the above components, and various additives.
- Additives include UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, antifoaming agents, dispersants, and leveling. Agents, brighteners, polymerization inhibitors and the like. These additives may be used alone or in combination of two or more.
- the resin composition according to this embodiment may contain an organic solvent.
- the resin composition according to the present embodiment is in a form (solution or varnish) in which at least a part, preferably all, of the various resin components described above are dissolved or compatible with an organic solvent.
- the organic solvent is not particularly limited as long as it is a polar organic solvent or a nonpolar organic solvent capable of dissolving or compatibilizing at least some, preferably all of the above-described various resin components.
- Examples of the polar organic solvent include ketones.
- acetone methyl ethyl ketone, methyl isobutyl ketone, etc.
- cellosolves eg, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.
- esters eg, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, acetic acid
- Amides eg, dimethoxyacetamide, dimethylformamide, etc.
- nonpolar organic solvents include aromatic hydrocarbons (eg, toluene, xylene). etc And the like. These organic solvents may be used alone or in combination of two or more.
- the resin composition according to this embodiment can be prepared according to a conventional method, and is represented by maleimide compound (A), cyanate ester compound (B), and formula (1), and has a number average molecular weight of 1000 or more and 7000.
- the preparation method is not particularly limited as long as it is a method capable of obtaining a polyphenylene ether compound (C), a block copolymer (D) having a styrene skeleton, and a resin composition uniformly containing the other optional components described above.
- a maleimide compound (A), a cyanate ester compound (B), a polyphenylene ether compound (C) represented by the formula (1) and having a number average molecular weight of 1000 or more and 7000, and a block copolymer having a styrene skeleton (D ) are sequentially blended in a solvent and sufficiently stirred, the resin composition according to this embodiment can be easily prepared.
- the resin composition according to this embodiment includes a maleimide compound (A), a cyanate ester compound (B), a polyphenylene ether compound (C) having a number average molecular weight represented by the formula (1) of 1000 or more and 7000 or less, and
- the sum of the mass of the block copolymer (D) having a styrene skeleton preferably occupies 90% by mass or more, more preferably 95% by mass or more, and 98% by mass of the resin solid content contained in the resin composition. % May be occupied.
- the resin composition according to the present embodiment can be suitably used as an insulating layer of a printed wiring board and a semiconductor package material.
- the resin composition according to the present embodiment can be suitably used as a material for constituting a prepreg, a metal foil-clad laminate using the prepreg, a resin sheet, and a printed wiring board.
- the prepreg according to the present embodiment is formed from a base material and the resin composition according to the present embodiment.
- the prepreg according to the present embodiment is obtained, for example, by impregnating or applying the resin composition according to the present embodiment to a base material and then semi-curing it by a method of drying at 120 to 220 ° C. for about 2 to 15 minutes. It is done.
- the amount of the resin composition (including the cured product of the resin composition) attached to the substrate that is, the amount of the resin composition (including the filler (F)) relative to the total amount of the prepreg after semi-curing is 20 to 99. It is preferably in the range of mass%.
- the substrate is not particularly limited as long as it is a substrate used for various printed wiring board materials.
- the material of the substrate include glass fiber (for example, E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.)
- examples include inorganic fibers other than glass (for example, quartz) and organic fibers (for example, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, and the like).
- the form of the substrate is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. These base materials may be used independently or may use 2 or more types together.
- a woven fabric subjected to ultra-opening treatment and plugging treatment is preferable from the viewpoint of dimensional stability, and from the viewpoint of moisture absorption heat resistance, silane coupling agents such as epoxy silane treatment and aminosilane treatment, etc.
- a glass woven fabric surface-treated with is preferable.
- a low dielectric glass cloth made of glass fibers exhibiting low dielectric constant and low dielectric loss tangent such as L-glass, NE-glass, and Q-glass is more preferable.
- the metal foil-clad laminate according to the present embodiment includes one or more prepregs according to the present embodiment, and a metal foil disposed on one or both sides of the prepreg.
- the metal foil-clad laminate according to the present embodiment includes, for example, a method in which one or more prepregs according to the present embodiment are stacked, and a metal foil is disposed on one or both surfaces of the laminate, and more specifically, It can be produced by arranging and molding a metal foil such as copper or aluminum on one side or both sides.
- metal foil such as rolled copper foil and electrolytic copper foil, is mentioned.
- the thickness of the metal foil is not particularly limited, and may be about 1.5 to 70 ⁇ m.
- the molding method include methods usually used for molding laminated boards for printed wiring boards and multilayer boards. More specifically, a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc. are used. Examples of the method include laminate molding at a temperature of about 180 to 350 ° C., a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg / cm 2 . Moreover, it can also be set as a multilayer board by carrying out lamination molding combining the prepreg which concerns on this embodiment, and the wiring board for inner layers produced separately.
- a metal foil (copper foil) of about 35 ⁇ m is disposed on both surfaces of one prepreg according to the present embodiment, and after forming and laminating by the above molding method, an inner layer circuit is formed. Then, this circuit is blackened to form an inner layer circuit board, and then this inner layer circuit board and the prepreg according to the present embodiment are alternately arranged one by one, and a metal foil (copper) is further formed on the outermost layer.
- a multi-layer board can be produced by arranging and foil-molding under the above conditions, preferably under vacuum.
- the metal foil-clad laminate according to this embodiment can be suitably used as a printed wiring board.
- the printed wiring board according to the present embodiment includes an insulating layer and a conductor layer disposed on the surface of the insulating layer, and the insulating layer includes a layer formed from the resin composition according to the present embodiment.
- a printed wiring board can be manufactured according to a conventional method, and the manufacturing method is not particularly limited.
- an example of the manufacturing method of a printed wiring board is shown. First, a metal foil clad laminate such as the copper clad laminate described above is prepared. Next, an etching process is performed on the surface of the metal foil-clad laminate to form an inner layer circuit, thereby producing an inner layer substrate.
- the inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as necessary, then the required number of the prepregs are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is stacked 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. Next, after drilling for through holes and via holes in the multilayer laminate, 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.
- the printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer is a resin composition according to the present embodiment described above and a cured product thereof. At least one of them is included. That is, the prepreg according to the present embodiment described above (including at least one of the base material and the resin composition according to the present embodiment impregnated or coated thereon and the cured product thereof), the metal foil according to the present embodiment described above.
- An insulating layer in which the layer of the resin composition of the tension laminate includes at least one of the resin composition and its cured product according to the present embodiment. It will consist of
- the resin sheet which concerns on this embodiment contains a support body and the layer formed from the resin composition which concerns on this embodiment arrange
- the resin sheet can be used as a build-up film or a dry film solder resist.
- a resin sheet is obtained by apply
- Examples of the support used here include a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylenetetrafluoroethylene copolymer film, a release film in which a release agent is applied to the surface of these films, and a polyimide.
- Examples thereof include organic film base materials such as films, conductor foils such as copper foil and aluminum foil, and plate-like materials such as glass plates, SUS plates, and FRP, but are not particularly limited.
- Examples of the coating method include a method in which a solution obtained by dissolving the resin composition according to the present embodiment in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like. Can be mentioned. Moreover, it can also be set as a single layer sheet (resin sheet) by peeling or etching a support body from the resin sheet on which the support body and the resin composition were laminated
- the drying conditions for removing the solvent are not particularly limited, but the solvent in the resin composition is easily removed, and curing during drying is performed. From the viewpoint of suppressing the progress of the above, the temperature is preferably 20 to 200 ° C. for 1 to 90 minutes. Moreover, in a single layer sheet or a resin sheet, the resin composition can be used in an uncured state by simply drying the solvent, or used in a semi-cured (B-stage) state as necessary. You can also. Furthermore, the thickness of the resin layer of the single layer or the resin sheet according to this embodiment can be adjusted by the concentration of the solution of the resin composition according to this embodiment and the coating thickness, and is not particularly limited. From the viewpoint of easy removal, the thickness is preferably 0.1 to 500 ⁇ m.
- the reaction was completed by stirring at the same temperature for 30 minutes. Thereafter, the reaction solution was allowed to stand to separate an organic phase and an 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 was concentrated under reduced pressure, and finally concentrated to dryness at 90 ° C. for 1 hour to obtain 331 g of the desired naphthol aralkyl-type cyanate ester compound (SNCN) (orange viscous product).
- the obtained SNCN had a weight average molecular weight Mw of 600. Further, the IR spectrum of SNCN showed absorption of 2250 cm ⁇ 1 (cyanate group) and did not show absorption of a hydroxy group.
- Example 1 In formula (2), 24 parts by mass of maleimide compound (A) (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), wherein R 4 is all hydrogen atoms and n 4 is 1 to 3, obtained from Synthesis Example 1.
- A maleimide compound (A) (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), wherein R 4 is all hydrogen atoms and n 4 is 1 to 3, obtained from Synthesis Example 1.
- Example 2 In formula (2), 15 parts by mass of maleimide compound (A) (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), wherein R 4 is all hydrogen atoms and n 4 is 1 to 3, obtained from Synthesis Example 1.
- A maleimide compound (A) (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), wherein R 4 is all hydrogen atoms and n 4 is 1 to 3, obtained from Synthesis Example 1.
- Rephenylene ether compound (C) (OPE-2St2200, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 2200, vinyl group equivalent: 1100 g / eq.) 10 parts by mass, styrene-hydrogenated isoprene block copolymer (D) (SEPTON 2104, manufactured by Kuraray Co., Ltd., styrene ratio 65%) 10 parts by mass, ⁇ -methylstyrene polymer (E) (Crystalx 3085, manufactured by Eastman Chemical, number average molecular weight: 664) 20 parts by mass, spherical silica ( F) 150 parts by mass (SC2050-MB, manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m), 1,3-phenylenebis (2,6-di-xylenyl phosphate as a phosphorus flame retardant (G) ) (PX-200, manufactured by Daihachi Chemical Industry Co.,
- Dielectric constant (Dk) and dielectric loss tangent (Df) Perturbation cavity resonator (Agilent Technology Co., Ltd., Agilent8722ES) using a sample obtained by removing the copper foil of the metal foil-clad laminate of 0.4 mm thickness obtained in each Example and each Comparative Example by etching. The dielectric constant and dielectric loss tangent of 10 GHz were measured.
- Linear thermal expansion coefficient (CTE) Using the sample obtained by removing the copper foil of the metal foil-clad laminate of 0.1 mm thickness obtained in each Example and each Comparative Example by etching, the TMA method (Thermo-mechanical specified in JLSC 6481: 1996) was used.
- the thermal expansion coefficient of the glass cloth in the longitudinal direction was measured for the insulating layer of the laminate by analysis, and the value was determined. Specifically, after removing the copper foils on both sides of the metal foil-clad laminate obtained above by etching, a 4.5 mm ⁇ 16 mm evaluation board was produced, and a thermomechanical analyzer (TA Instruments) The temperature was raised from 40 ° C. to 340 ° C. at 10 ° C. per minute, and the linear thermal expansion coefficient (CTE) (ppm / ° C.) at 60 ° C. to 120 ° C. was measured.
- CTE linear thermal expansion coefficient
- the resin composition of the present invention is used in various applications such as electrical / electronic materials, machine tool materials, aviation materials, etc., for example, electrical insulating materials, semiconductor plastic packages, sealing materials, adhesives, laminated materials, Widely and effectively usable as resist, build-up laminated board material, etc. Especially, it can be used particularly effectively as printed wiring board material for high integration and high density in recent information terminal equipment and communication equipment. It is.
- excellent low dielectric constant, low dielectric loss tangent, and low thermal expansion are achieved at the same time, and a uniform cured product is obtained. The practicality is extremely high.
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Abstract
Description
[1]
マレイミド化合物(A)、シアン酸エステル化合物(B)、下記式(1)で表される数平均分子量が1000以上7000以下であるポリフェニレンエーテル化合物(C)及びスチレン骨格を有するブロック共重合体(D)を含有する、樹脂組成物。
前記スチレン骨格を有するブロック共重合体(D)が、スチレン-ブタジエンブロック共重合体、スチレン-イソプレンブロック共重合体、スチレン-水添ブタジエンブロック共重合体、スチレン-水添イソプレンブロック共重合体、スチレン-水添(イソプレン/ブタジエン)ブロック共重合体からなる群より選ばれる、少なくとも1種を含有する、[1]に記載の樹脂組成物。
前記マレイミド化合物(A)が、下記式(2)、(3)、(4)及び(17)からなる群より選ばれる、少なくとも1種を含有する、[1]又は[2]に記載の樹脂組成物。
さらに、スチレンオリゴマー(E)を含有する、[1]~[3]のいずれか一つに記載の樹脂組成物。
さらに、充填材(F)を含有する、[1]~[4]のいずれか一つに記載の樹脂組成物。
樹脂固形分100質量部に対する前記充填材(F)の含有量が、50~300質量部である、[5]に記載の樹脂組成物。
さらに、難燃剤(G)を含有する、[1]~[6]のいずれか1つに記載の樹脂組成物。
樹脂固形分100質量部に対する前記式(1)で示されるポリフェニレンエーテル化合物(C)の含有量が、1~90質量部である、[1]~[7]のいずれか一つに記載の樹脂組成物。
樹脂固形分100質量部に対する前記スチレン骨格を有するブロック共重合体(D)の含有量が、1~50質量部である、[1]~[8]のいずれか一つに記載の樹脂組成物。
前記式(1)で示されるポリフェニレンエーテル化合物(C)が式(11)で表される、[1]~[9]のいずれか一つに記載の樹脂組成物。
基材、及び、[1]~[10]のいずれか一つに記載の樹脂組成物から形成されたプリプレグ。
1枚以上重ねた[11]に記載のプリプレグと、前記プリプレグの片面又は両面に配置した金属箔とを含む金属箔張積層板。
支持体と、前記支持体の表面に配置した[1]~[10]のいずれか一つに記載の樹脂組成物から形成された層とを含む、樹脂シート。
絶縁層と、前記絶縁層の表面に配置し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から形成された層を含む、プリント配線板。
本実施形態に係る樹脂組成物は、マレイミド化合物(A)、シアン酸エステル化合物(B)、式(1)で表される数平均分子量が1000以上7000であるポリフェニレンエーテル化合物(C)及びスチレン骨格を有するブロック共重合体(D)を含有する。本実施形態に係る樹脂組成物は、上記の構成を備えることにより、プリント配線板用材料(例えば、積層板、金属箔張積層板)等に用いると、優れた低誘電率性、低誘電正接性、低熱膨張性を同時に達成し、かつ均一な硬化物となる。
本実施形態に係るマレイミド化合物(A)は、分子中に一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、例えば、N-フェニルマレイミド、N-ヒドロキシフェニルマレイミド、ビス(4-マレイミドフェニル)メタン、4,4’-ジフェニルメタンビスマレイミド、ビス(3,5-ジメチル-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、フェニルメタンマレイミド、o-フェニレンビスマレイミド、m-フェニレンビスマレイミド、p-フェニレンビスマレイミド、o-フェニレンビスシトラコンイミド、m-フェニレンビスシトラコンイミド、p-フェニレンビスシトラコンイミド、2,2-ビス(4-(4-マレイミドフェノキシ)-フェニル)プロパン、3,3’-ジエチル-5,5’-ジメチル-4,4’-ジフェニルメタンビスマレイミド、4-メチル-1,3-フェニレンビスマレイミド、1,6-ビスマレイミド-(2,2,4-トリメチル)ヘキサン、4,4’-ジフェニルエーテルビスマレイミド、4,4’-ジフェニルスルフォンビスマレイミド、1,3-ビス(3-マレイミドフェノキシ)ベンゼン、1,3-ビス(4-マレイミドフェノキシ)ベンゼン、4,4’-ジフェニルメタンビスシトラコンイミド、2,2-ビス[4-(4-シトラコンイミドフェノキシ)フェニル]プロパン、ビス(3,5-ジメチル-4-シトラコンイミドフェニル)メタン、ビス(3-エチル-5-メチル-4-シトラコンイミドフェニル)メタン、ビス(3,5-ジエチル-4-シトラコンイミドフェニル)メタン、前記式(2)、(3)、(4)及び(17)で表されるマレイミド化合物等が挙げられる。
これらの中でも、前記式(2)、(3)、(4)及び(17)で表されるマレイミド化合物が低熱膨張性及び耐熱性向上の面で特に好ましい。これらのマレイミド化合物は、単独で用いても、2種以上を併用してもよい。
マレイミド化合物(A)は1種のみ用いてもよいし、2種以上用いてもよい。2種以上用いる場合は、合計量が上記範囲となることが好ましい。
本実施形態に係るシアン酸エステル化合物(B)は、少なくとも1つのシアナト基(シアン酸エステル基)により置換された芳香族部分を分子内に有する樹脂であれば特に限定されない。
アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、n-ペンチル基、1-エチルプロピル基、2,2-ジメチルプロピル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、トリフルオロメチル基等が挙げられる。
アリール基の具体例としては、フェニル基、キシリル基、メシチル基、ナフチル基、フェノキシフェニル基、エチルフェニル基、o-,m-又はp-フルオロフェニル基、ジクロロフェニル基、ジシアノフェニル基、トリフルオロフェニル基、メトキシフェニル基、o-,m-又はp-トリル基等が挙げられる。
アルコキシ基の具体例としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、tert-ブトキシ基等が挙げられる。
式(5)のZにおける2価の有機基の具体例としては、メチレン基、エチレン基、トリメチレン基、シクロペンチレン基、シクロヘキシレン基、トリメチルシクロヘキシレン基、ビフェニルイルメチレン基、ジメチルメチレン-フェニレン-ジメチルメチレン基、フルオレンジイル基、フタリドジイル基等が挙げられる。前記2価の有機基中の水素原子は、フッ素原子、塩素原子等のハロゲン原子、メトキシ基、フェノキシ基等のアルコキシ基、シアノ基等で置換されていてもよい。式(5)のZにおける窒素数1~10の2価の有機基としては、イミノ基、ポリイミド基等が挙げられる。
式(6)のAr2及び式(7)のAr3の具体例としては、1,4-フェニレン基、1,3-フェニレン基、4,4’-ビフェニレン基、2,4’-ビフェニレン基、2,2’-ビフェニレン基、2,3’-ビフェニレン基、3,3’-ビフェニレン基、3,4’-ビフェニレン基、2,6-ナフチレン基、1,5-ナフチレン基、1,6-ナフチレン基、1,8-ナフチレン基、1,3-ナフチレン基、1,4-ナフチレン基等が挙げられる。式(6)のR9~R14及び式(7)のR15、R16におけるアルキル基及びアリール基は式(5)で記載したものと同様である。
シアン酸エステル化合物(B)は1種のみ用いてもよいし、2種以上用いてもよい。2種以上用いる場合は、合計量が上記範囲となることが好ましい。
本実施形態に係るポリフェニレンエーテル化合物(C)は、式(1)で表される化合物である。本実施形態に係る樹脂組成物は、このような構造を有するポリフェニレンエーテル化合物を含有することにより、プリント配線板用材料(例えば、積層板、金属箔張積層板)等に用いると、優れた低誘電正接性及び均一な硬化物を与える。
式(1)との関係でいうと、上記式(8)、(9)、(10)は式(1)の-(Y-O)-であることが好ましい。-(Y-O)-はn2の数(1~100)の繰り返し単位を有する。
-(Y-O)n2-及びn2は、式(1)におけるものと同義である。n2の異なる化合物を複数種含んでいてもよい。
また、このような変性ポリフェニレンエーテルは市販品を用いることができ、例えば、三菱ガス化学(株)製OPE-2St1200、OPE-2st2200を好適に使用することができる。
樹脂組成物は、ポリフェニレンエーテル化合物(C)を、1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
本実施形態に係る「スチレン骨格を有するブロック共重合体(D)」とは、ポリスチレンブロック構造を有するブロック共重合体であるエラストマーを指し、ランダム共重合体は含まない。また、芳香族ビニル化合物のみからなる化合物は、これらとは区別して「スチレンオリゴマー(E)」と表し、「スチレン骨格を有するブロック共重合体(D)」には含まない。
樹脂組成物は、スチレン骨格を有するブロック共重合体(D)を、1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
本実施形態におけるスチレン骨格を有するブロック共重合体(D)としては、市販品を用いてもよく、例えばスチレン-ブタジエン-スチレンブロック共重合体としてはTR2630(JSR(株)製)、TR2003(JSR(株)製)が挙げられる。またスチレン-イソプレン-スチレンブロック共重合体としては、SIS5250(JSR(株)製)が挙げられる。スチレン-水添イソプレン-スチレンブロック共重合体としては、SEPTON2104((株)クラレ製)が挙げられる。
本実施形態に係る樹脂組成物は、低誘電率性及び低誘電正接性向上のために、スチレンオリゴマー(E)を含むことが望ましい。本実施形態で用いられる「スチレンオリゴマー(E)」は、上述した「スチレン骨格を有するブロック共重合体(D)」とは区別される。
樹脂組成物は、スチレンオリゴマー(E)を、1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
本実施形態に係る樹脂組成物は、低誘電率性、低誘電正接性、耐燃性及び低熱膨張性の向上のため、充填材(F)を含むことが望ましい。本実施形態で使用される充填材(F)としては、公知のものを適宜使用することができ、その種類は特に限定されず、当業界において一般に使用されているものを好適に用いることができる。具体的には、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、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、窒化ホウ素、凝集窒化ホウ素、窒化ケイ素、窒化アルミニウム、硫酸バリウム、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、酸化モリブデンや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、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、球状ガラスなど無機系の充填材の他、スチレン型、ブタジエン型、アクリル型などのゴムパウダー、コアシェル型のゴムパウダー、シリコーンレジンパウダー、シリコーンゴムパウダー、シリコーン複合パウダーなど有機系の充填材などが挙げられる。これらの充填材は、単独で用いても、2種以上を併用してもよい。
これらの中でも、シリカ、水酸化アルミニウム、ベーマイト、酸化マグネシウム及び水酸化マグネシウムからなる群から選択される1種又は2種以上が好適である。これらの充填材を使用することで、樹脂組成物の熱膨張特性、寸法安定性、難燃性などの特性が向上する。
樹脂組成物は、充填材(F)を、1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
本実施形態に係る樹脂組成物は、耐燃性の向上のため難燃剤(G)を含むことが好ましい。本実施形態で使用される難燃剤(G)としては、公知のものが使用でき、例えば、臭素化エポキシ樹脂、臭素化ポリカーボネート、臭素化ポリスチレン、臭素化スチレン、臭素化フタルイミド、テトラブロモビスフェノールA、ペンタブロモベンジル(メタ)アクリレート、ペンタブロモトルエン、トリブロモフェノール、ヘキサブロモベンゼン、デカブロモジフェニルエーテル、ビス-1,2-ペンタブロモフェニルエタン、塩素化ポリスチレン、塩素化パラフィン等のハロゲン系難燃剤、赤リン、トリクレジルホスフェート、トリフェニルホスフェート、クレジルジフェニルホスフェート、トリキシレニルホスフェート、トリアルキルホスフェート、ジアルキルホスフェート、トリス(クロロエチル)ホスフェート、ホスファゼン、1,3-フェニレンビス(2,6-ジキシレニルホスフェート)、10-(2,5-ジヒドロキシフェニル)-10H-9-オキサ-10-ホスファフェナントレン-10-オキサイド、等のリン系難燃剤、水酸化アルミニウム、水酸化マグネシウム、部分ベーマイト、ベーマイト、ほう酸亜鉛、三酸化アンチモン等の無機系難燃剤、シリコーンゴム、シリコーンレジン等のシリコーン系難燃剤が挙げられる。これらの難燃剤は単独で用いても、2種以上を併用してもよい。これらの中でも、リン系難燃剤が好ましく、特に、1,3-フェニレンビス(2,6-ジキシレニルホスフェート)が低誘電特性を損ないにくいことから好ましい。樹脂組成物中のリン含有量は0.1~5質量%が好ましい。
難燃剤(G)の含有量は、含有する場合、樹脂組成物中の樹脂固形分100質量部に対して、1質量部以上であることが好ましく、5質量部以上であることがより好ましい。また、前記含有量の上限値は、30質量部以下であることが好ましく、20質量部以下であることがより好ましく、15質量部以下であってもよい。
難燃剤(G)は、1種のみ用いてもよいし、2種以上用いてもよい。2種以上用いる場合、合計量が上記範囲となることが好ましい。
さらに、本実施形態に係る樹脂組成物においては、所期の特性が得られる範囲において、上記ポリフェニレンエーテル化合物(C)以外のポリフェニレンエーテル化合物、エポキシ樹脂、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、[4.スチレン骨格を有するブロック共重合体(D)]に記載されていない熱可塑性エラストマー(以下、「その他熱可塑性エラストマー」という)、硬化促進剤、有機溶剤等を含有していてもよい。これらを併用することで、樹脂組成物を硬化した硬化物の難燃性、低誘電性など所望する特性を向上させることができる。
本実施形態に係る樹脂組成物は、上記ポリフェニレンエーテル化合物(C)以外のポリフェニレンエーテル化合物、及び、上記その他熱可塑性エラストマーの総量が、樹脂固形分の3質量%以下であることが好ましく、1質量%以下であることがより好ましい。このような構成とすることにより、本発明の効果がより効果的に発揮される。
エポキシ樹脂としては、1分子中に2個以上のエポキシ基を有する化合物又は樹脂であれば特に限定されず、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、グリシジルエステル型エポキシ樹脂、アラルキルノボラック型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、多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、アントラセン型エポキシ樹脂、ナフタレン骨格変性ノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、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、ビフェニル型エポキシ樹脂、脂環式エポキシ樹脂、ポリオール型エポキシ樹脂、リン含有エポキシ樹脂、グリシジルアミン、グリシジルエステル、ブタジエン等の二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ロヒドリンとの反応により得られる化合物等が挙げられる。これらのエポキシ樹脂は、単独で用いても、2種以上を併用してもよい。これらの中でも、難燃性及び耐熱性をより一層向上する観点から、ビフェニルアラルキル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、多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であることが好ましい。
フェノール樹脂としては、1分子中に2個以上のフェノール性ヒドロキシ基を有する化合物又は樹脂であれば特に限定されず、例えば、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、水酸基含有シリコーン樹脂類等が挙げられる。これらのフェノール樹脂は、単独で用いても、2種以上を併用してもよい。これらの中でも、耐燃性をより一層向上する観点から、ビフェニ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、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からなる群より選択される少なくとも1種であることが好ましい。
オキセタン樹脂としては、特に限定されず、例えば、オキセタン、アルキルオキセタン(例えば、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-ジメチルオキサタン等)、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(株)製品)、OXT-121(東亞合成(株)製品)等が挙げられる。これらのオキセタン樹脂は、単独で用いても、2種以上を併用してもよい。
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特に限定されず、例えば、ビスフェノールA型ベンゾオキサジンBA-BXZ(小西化学(株)製品)、ビスフェノールF型ベンゾオキサジンBF-BXZ(小西化学(株)製品)、ビスフェノールS型ベンゾオキサジンBS-BXZ(小西化学(株)製品)等が挙げられる。これらのベンゾオキサジン化合物は、単独で用いても、2種以上を併用してもよい。
「その他熱可塑性エラストマー」は、「スチレン骨格を有するブロック共重合体(D)」とは区別される。「スチレン骨格を有するブロック共重合体(D)」とは、ポリスチレンブロック構造を有し、かつブロック共重合体であるエラストマーを示し、「その他熱可塑性エラストマー」とは、それ以外のエラストマーを示す。すなわち、ランダム共重合体、スチレン骨格を有しないブロック共重合体等が該当する。その他熱可塑性エラストマーとしては、例えばポリイソプレン、ポリブタジエン、スチレンブタジエンランダム共重合体、ブチルゴム、エチレンプロピレンゴム、フッ素ゴム、シリコーンゴム、それらの水添化合物、それらのアルキル化合物からなる群より選択される少なくとも1種が挙げられる。これらの中でも、ポリフェニレンエーテル化合物(C)との相溶性により優れる観点から、ポリイソプレン、ポリブタジエン、スチレンブタジエンランダム共重合体、ブチルゴム、及びエチレンプロピレンゴムからなる群より選択される少なくとも1種であることがより好ましい。
本実施形態に係る樹脂組成物は、硬化速度を適宜調節するための硬化促進剤を含有してもよい。硬化促進剤としては、マレイミド化合物、シアン酸エステル化合物、エポキシ樹脂などの硬化促進剤として通常用いられているものが挙げられ、有機金属塩類(例えば、オクチル酸亜鉛、ナフテン酸亜鉛、ナフテン酸コバルト、ナフテン酸銅、アセチルアセトン鉄、オクチル酸ニッケル、オクチル酸マンガン等)、フェノール化合物(例えば、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、オクチルフェノール、ノニルフェノール等)、アルコール類(例えば、1-ブタノール、2-エチルヘキサノール等)、イミダゾール類(例えば、2-メチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾール、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール等)、及びこれらのイミダゾール類のカルボン酸若しくはその酸無水類の付加体等の誘導体、アミン類(例えば、ジシアンジアミド、ベンジルジメチルアミン、4-メチル-N,N-ジメチルベンジルアミン等)、リン化合物(例えば、ホスフィン系化合物、ホスフィンオキサイド系化合物、ホスホニウム塩系化合物、ダイホスフィン系化合物等)、エポキシ-イミダゾールアダクト系化合物、過酸化物(例えば、ベンゾイルパーオキサイド、p-クロロベンゾイルパーオキサイド、ジ-t-ブチルパーオキサイド、ジイソプロピルパーオキシカーボネート、ジ-2-エチルヘキシルパーオキシカーボネート等)、アゾ化合物(例えば、アゾビスイソブチロニトリル等)が挙げられる。硬化促進剤は、単独で用いても、2種以上を併用してもよい。
本実施形態に係る樹脂組成物は、有機溶剤を含有してもよい。この場合、本実施形態に係る樹脂組成物は、上述した各種樹脂成分の少なくとも一部、好ましくは全部が有機溶剤に溶解又は相溶した形態(溶液又はワニス)である。有機溶剤としては、上述した各種樹脂成分の少なくとも一部、好ましくは全部を溶解又は相溶可能な極性有機溶剤又は無極性有機溶剤であれば特に限定されず、極性有機溶剤としては、例えば、ケトン類(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等)、セロソルブ類(例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等)、エステル類(例えば、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソアミル、乳酸エチル、メトキシプロピオン酸メチル、ヒドロキシイソ酪酸メチル等)アミド類(例えば、ジメトキシアセトアミド、ジメチルホルムアミド類等)が挙げられ、無極性有機溶剤としては、芳香族炭化水素(例えば、トルエン、キシレン等)が挙げられる。これらの有機溶剤は、単独で用いても、2種以上を併用してもよい。
本実施形態に係る樹脂組成物は、常法にしたがって調製することができ、マレイミド化合物(A)、シアン酸エステル化合物(B)、式(1)で表され数平均分子量が1000以上7000であるポリフェニレンエーテル化合物(C)、スチレン骨格を有するブロック共重合体(D)、及び上述したその他の任意成分を均一に含有する樹脂組成物が得られる方法であれば、その調製方法は特に限定されない。例えば、マレイミド化合物(A)、シアン酸エステル化合物(B)、式(1)で表され数平均分子量が1000以上7000であるポリフェニレンエーテル化合物(C)、及びスチレン骨格を有するブロック共重合体(D)を順次溶剤に配合し、十分に撹拌することで本実施形態に係る樹脂組成物を容易に調製することができる。
本実施形態に係る樹脂組成物は、マレイミド化合物(A)、シアン酸エステル化合物(B)、式(1)で表される数平均分子量が1000以上7000以下であるポリフェニレンエーテル化合物(C)、及び、スチレン骨格を有するブロック共重合体(D)の質量の和が樹脂組成物に含まれる樹脂固形分の90質量%以上を占めることが好ましく、95質量%以上を占めることがより好ましく、98質量%以上を占めてもよい。
本実施形態に係る樹脂組成物は、プリント配線板の絶縁層、半導体パッケージ用材料として好適に用いることができる。本実施形態に係る樹脂組成物は、プリプレグ、プリプレグを用いた金属箔張積層板、樹脂シート、及びプリント配線板を構成する材料として好適に用いることができる。
本実施形態に係るプリプレグは、基材と、本実施形態に係る樹脂組成物から形成される。本実施形態に係るプリプレグは、例えば、本実施形態に係る樹脂組成物を基材に含浸又は塗布させた後、120~220℃で2~15分程度乾燥させる方法等によって半硬化させることにより得られる。この場合、基材に対する樹脂組成物(樹脂組成物の硬化物も含む)の付着量、すなわち半硬化後のプリプレグの総量に対する樹脂組成物量(充填材(F)を含む。)は、20~99質量%の範囲であることが好ましい。
本実施形態に係る金属箔張積層板は、1枚以上重ねた本実施形態に係るプリプレグと、プリプレグの片面又は両面に配置した金属箔とを有する。本実施形態に係る金属箔張積層板は、例えば、本実施形態に係るプリプレグを1枚以上重ね、その片面又は両面に金属箔を配置して積層成形する方法が挙げられ、より詳細にはその片面又は両面に銅、アルミニウム等の金属箔を配置して積層成形することにより作製できる。金属箔としては、プリント配線板用材料に用いられるものであれば特に限定されないが、例えば、圧延銅箔、電解銅箔等の銅箔が挙げられる。金属箔(銅箔)の厚さは、特に限定されず、1.5~70μm程度であってもよい。成形方法としては、プリント配線板用積層板及び多層板を成形する際に通常用いられる方法が挙げられ、より詳細には多段プレス機、多段真空プレス機、連続成形機、オートクレーブ成形機等を使用して、温度180~350℃程度、加熱時間100~300分程度、面圧20~100kg/cm2程度で積層成形する方法が挙げられる。また、本実施形態に係るプリプレグと、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できる。多層板の製造方法としては、例えば、本実施形態に係るプリプレグ1枚の両面に35μm程度の金属箔(銅箔)を配置し、上記の成形方法にて積層形成した後、内層回路を形成し、この回路に黒化処理を実施して内層回路板を形成し、この後、この内層回路板と本実施形態に係るプリプレグとを交互に1枚ずつ配置し、さらに最外層に金属箔(銅箔)を配置して、上記条件にて好ましくは真空下で積層成形することにより、多層板を作製することができる。本実施形態に係る金属箔張積層板は、プリント配線板として好適に使用することができる。
本実施形態に係るプリント配線板は、絶縁層と、絶縁層の表面に配置した導体層と、を含み、絶縁層が、本実施形態に係る樹脂組成物から形成された層を含む。このようなプリント配線板は、常法に従って製造でき、その製造方法は特に限定されない。以下、プリント配線板の製造方法の一例を示す。まず上述した銅張積層板等の金属箔張積層板を用意する。次に、金属箔張積層板の表面にエッチング処理を施して内層回路の形成を行い、内層基板を作製する。この内層基板の内層回路表面に、必要に応じて接着強度を高めるための表面処理を行い、次いでその内層回路表面に上述したプリプレグを所要枚数重ね、さらにその外側に外層回路用の金属箔を積層し、加熱加圧して一体成形する。このようにして、内層回路と外層回路用の金属箔との間に、基材及び熱硬化性樹脂組成物の硬化物からなる絶縁層が形成された多層の積層板が製造される。次いで、この多層の積層板にスルーホールやバイアホール用の穴あけ加工を施した後、この穴の壁面に内層回路と外層回路用の金属箔とを導通させるめっき金属皮膜を形成し、さらに外層回路用の金属箔にエッチング処理を施して外層回路を形成することで、プリント配線板が製造される。
本実施形態に係る樹脂シートは、支持体と、前記支持体の表面に配置した本実施形態に係る樹脂組成物から形成された層とを含む。樹脂シートは、ビルドアップ用フィルム又はドライフィルムソルダーレジストとして使用することができる。樹脂シートの製造方法としては、特に限定されないが、例えば、上記の本実施形態に係る樹脂組成物を溶剤に溶解させた溶液を支持体に塗布(塗工)し乾燥することで樹脂シートを得る方法が挙げられる。
1-ナフトールアラルキル樹脂(新日鉄住金化学株式会社製)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1モルに対して1.5モル)、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たことを確認した。
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目的とするナフトールアラルキル型のシアン酸エステル化合物(SNCN)(橙色粘性物)を331g得た。得られたSNCNの重量平均分子量Mwは600であった。また、SNCNのIR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。
式(2)において、R4が全て水素原子であり、n4が1~3であるマレイミド化合物(A)(BMI-2300、大和化成工業(株)製)24質量部、合成例1より得られたSNCN(B)56質量部、式(11)において、Xが式(12)であり-(Y-O)n2-が式(15)の構造単位が重合したものであるポリフェニレンエーテル化合物(C)(OPE-2St1200、三菱ガス化学(株)製、数平均分子量1187、ビニル基当量:590g/eq.)10質量部、スチレン-ブタジエンブロック共重合体(D)(TR2630、JSR(株)製、スチレン率32%)10質量部、球状シリカ(F)(SC2050-MB、(株)アドマテックス製、平均粒子径0.5μm)150質量部を混合し、メチルエチルケトンで固形分を65質量%に希釈しワニスを得た。
式(2)において、R4が全て水素原子であり、n4が1~3であるマレイミド化合物(A)(BMI-2300、大和化成工業(株)製)15質量部、合成例1より得られたSNCN(B)35質量部、式(11)において、Xが式(12)であり、-(Y-O)n2-が式(15)の構造単位が重合したものであるポリフェニレンエーテル化合物(C)(OPE-2St1200、三菱ガス化学(株)製、数平均分子量1187、ビニル基当量:590g/eq.)10質量部、及び(C)の二つ目の成分として、式(11)において、Xが式(12)であり、-(Y-O)n2-が式(15)の構造単位が重合したものであるポリフェニレンエーテル化合物(C)(OPE-2St2200、三菱ガス化学(株)製、数平均分子量2200、ビニル基当量:1100g/eq.)10質量部、スチレン-ブタジエンブロック共重合体(D)(TR2630、JSR(株)製、スチレン率32%)10質量部、α-メチルスチレン重合体(E)(クリスタレックス3085、イーストマンケミカル社製、数平均分子量:664)20質量部、球状シリカ(F)(SC2050-MB、(株)アドマテックス製、平均粒子径0.5μm)150質量部を混合し、メチルエチルケトンで固形分を65質量%に希釈しワニスを得た。以降、実施例1と同様にして厚さ0.1mm及び0.4mmの金属張積層板を得た。得られた金属張積層板の評価結果を表1に示す。
式(2)において、R4が全て水素原子であり、n4が1~3であるマレイミド化合物(A)を用いる代わりに、式(3)において、R5が全て水素原子であり、n5の平均値が1.4であるマレイミド化合物(A)(MIR-3000、日本化薬(株)製)を15質量部用いた以外は、実施例2と同様にして厚さ0.1mm及び0.4mmの金属張積層板を得た。得られた金属張積層板の評価結果を表1に示す。
式(2)において、R4が全て水素原子であり、n4が1~3であるマレイミド化合物(A)を用いる代わりに、式(17)において、R8が全てメチル基であるマレイミド化合物(A)(BMI-80、ケイ・アイ化成(株)製)を15質量部用いた以外は、実施例2と同様にして厚さ0.1mm及び0.4mmの金属張積層板を得た。得られた金属張積層板の評価結果を表1に示す。
式(2)において、R4が全て水素原子であり、n4が1~3であるマレイミド化合物(A)(BMI-2300、大和化成工業(株)製)12質量部、合成例1より得られたナフトールアラルキル型シアン酸エステルSNCN(B)28質量部、式(11)において、Xが式(12)であり、-(Y-O)n2-が式(15)の構造単位が重合したものであるポリフェニレンエーテル化合物(C)(OPE-2St1200、三菱ガス化学(株)製、数平均分子量1187、ビニル基当量:590g/eq.)10質量部、及び(C)の二つ目の成分として、式(11)において、Xが式(12)であり-(Y-O)n2-が式(11)において、Xが式(12)であり、-(Y-O)n2-が式(15)の構造単位が重合したものであるポリフェニレンエーテル化合物(C)(OPE-2St2200、三菱ガス化学(株)製、数平均分子量2200、ビニル基当量:1100g/eq.)10質量部、スチレン-水添イソプレンブロック共重合体(D)(SEPTON2104、(株)クラレ製、スチレン率65%)10質量部、α-メチルスチレン重合体(E)(クリスタレックス3085、イーストマンケミカル製、数平均分子量:664)20質量部、球状シリカ(F)(SC2050-MB、(株)アドマテックス製、平均粒子径0.5μm)150質量部、リン系難燃剤(G)として1,3-フェニレンビス(2,6-ジ-キシレニルホスフェート)(PX-200、大八化学工業(株)製)10質量部を混合し、メチルエチルケトンで固形分を65質量%に希釈しワニスを得た。以降、実施例1と同様にして厚さ0.1mm及び0.4mmの金属張積層板を得た。得られた金属張積層板の評価結果を表1に示す。
式(2)において、R4が全て水素原子であり、n4が1~3であるマレイミド化合物(A)(BMI-2300、大和化成工業(株)製)30質量部、合成例1より得られたナフトールアラルキル型シアン酸エステルSNCN(B)70質量部、球状シリカ(F)(SC2050-MB、(株)アドマテックス製、平均粒子径0.5μm)150質量部を混合し、メチルエチルケトンで固形分を65質量%に希釈しワニスを得た。以降、実施例1と同様にして厚さ0.1mm及び0.4mmの金属張積層板を得た。得られた金属張積層板の評価結果を表2に示す。
スチレン-ブタジエンブロック共重合体(D)(TR2630)10質量部を用いず、式(11)において、Xが式(12)であり、-(Y-O)n2-が式(15)の構造単位が重合したものであるポリフェニレンエーテル化合物(C)(OPE-2St1200、三菱ガス化学(株)製、数平均分子量1187、ビニル基当量:590g/eq.)20質量部を用いた以外は、実施例1と同様にして厚さ0.1mm及び0.4mmの金属張積層板を得た。得られた金属張積層板の評価結果を表2に示す。
式(2)において、R4が全て水素原子であり、n4が1~3であるマレイミド化合物(A)(BMI-2300、大和化成工業(株)製)27質量部、合成例1より得られたナフトールアラルキル型シアン酸エステルSNCN(B)63質量部、スチレン-ブタジエンブロック共重合体(D)(TR2630)10質量部、球状シリカ(F)(SC2050-MB、(株)アドマテックス製、平均粒子径0.5μm)150質量部を混合し、メチルエチルケトンで固形分を65質量%に希釈しワニスを得た。以降、実施例1と同様にして厚さ0.1mm及び0.4mmの金属張積層板を得た。得られた金属張積層板の評価結果を表2に示す。
式(2)において、R4が全て水素原子であり、n4が1~3であるマレイミド化合物(A)(BMI-2300、大和化成工業(株)製)21質量部、合成例1より得られたナフトールアラルキル型シアン酸エステル(B)49質量部、スチレン-ブタジエンブロック共重合体(D)(TR2630)10質量部、α-メチルスチレン重合体(E)(クリスタレックス3085、イーストマンケミカル社製、数平均分子量:664)20質量部、球状シリカ(F)(SC2050-MB、(株)アドマテックス製、平均粒子径0.5μm)150質量部を混合し、メチルエチルケトンで固形分を65質量%に希釈しワニスを得た。以降、実施例1と同様にして厚さ0.1mm及び0.4mmの金属張積層板を得た。得られた金属張積層板の評価結果を表2に示す。
実施例3において、式(11)において、Xが式(12)であり、-(Y-O)n2-が式(15)の構造単位が重合したものであるポリフェニレンエーテル化合物(C)(OPE-2St1200)10質量部、及び(C)の二つ目の成分として、式(11)において、Xが式(12)であり、-(Y-O)n2-が式(15)の構造単位が重合したものであるポリフェニレンエーテル化合物(C)(OPE-2St2200)10質量部を用いず、代わりに式(1)の構造を満たさないポリフェニレンエーテル化合物(SA9000、SABIC製)20質量部を用いた以外は、実施例3と同様にして厚さ0.1mm及び0.4mmの金属張積層板を得た。得られた金属張積層板の評価結果を表2に示す。
(1)誘電率(Dk)及び誘電正接(Df):
各実施例及び各比較例で得られた厚さ0.4mmの金属箔張積層板の銅箔をエッチングにより除去したサンプルを用いて、摂動法空洞共振器(アジレントテクノロジー(株)製品、Agilent8722ES)により、10GHzの誘電率及び誘電正接を測定した。
(2)線熱膨張係数(CTE):
各実施例及び各比較例で得られた厚さ0.1mmの金属箔張積層板の銅箔をエッチングにより除去したサンプルを用いて、JlS C 6481:1996に規定されるTMA法(Thermo-mechanical analysis)により積層板の絶縁層についてガラスクロスの縦方向の熱膨張係数を測定し、その値を求めた。具体的には、上記で得られた金属箔張積層板の両面の銅箔をエッチングにより除去した後に、4.5mm×16mmの評価基板を作製し、熱機械分析装置(TAインスツルメント製)で40℃から340℃まで毎分10℃で昇温し、60℃から120℃における線熱膨張係数(CTE)(ppm/℃)を測定した。
(3)硬化物の均一性(分散不良):
各実施例及び各比較例で得られた厚さ0.4mmの金属張積層板の断面をBUEHLER製MetaServ3000により研磨し、Nikon製EPIPHOTを用いて断面の状態を観察した。ボイド及び分散不良の見られたものをNG、見られなかったものをそれぞれOKとしている。
Claims (14)
- 前記スチレン骨格を有するブロック共重合体(D)が、スチレン-ブタジエンブロック共重合体、スチレン-イソプレンブロック共重合体、スチレン-水添ブタジエンブロック共重合体、スチレン-水添イソプレンブロック共重合体及びスチレン-水添(イソプレン/ブタジエン)ブロック共重合体からなる群より選ばれる、少なくとも1種を含有する、請求項1に記載の樹脂組成物。
- さらに、スチレンオリゴマー(E)を含有する、請求項1~3のいずれか一項に記載の樹脂組成物。
- さらに、充填材(F)を含有する、請求項1~4のいずれか一項に記載の樹脂組成物。
- 樹脂固形分100質量部に対する前記充填材(F)の含有量が、50~300質量部である、請求項5に記載の樹脂組成物。
- さらに、難燃剤(G)を含有する、請求項1~6のいずれかに記載の樹脂組成物。
- 樹脂固形分100質量部に対する前記式(1)で示されるポリフェニレンエーテル化合物(C)の含有量が、1~90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。
- 樹脂固形分100質量部に対する前記スチレン骨格を有するブロック共重合体(D)の含有量が、1~50質量部である、請求項1~8のいずれか一項に記載の樹脂組成物。
- 基材、及び、請求項1~10のいずれか一項に記載の樹脂組成物から形成されたプリプレグ。
- 1枚以上重ねた請求項11に記載のプリプレグと、前記プリプレグの片面又は両面に配置した金属箔とを含む金属箔張積層板。
- 支持体と、前記支持体の表面に配置した請求項1~10のいずれか一項に記載の樹脂組成物から形成された層とを含む、樹脂シート。
- 絶縁層と、前記絶縁層の表面に配置し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から形成された層を含む、プリント配線板。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5233710B2 (ja) | 1974-08-05 | 1977-08-30 | ||
JPS5649773B2 (ja) | 1976-04-07 | 1981-11-25 | ||
JP2003138132A (ja) * | 2001-10-31 | 2003-05-14 | Hitachi Chem Co Ltd | 変性シアネートエステル系樹脂組成物、難燃性樹脂フィルム、難燃性多層プリント配線板およびそれらの製造方法 |
JP2009161725A (ja) * | 2007-05-31 | 2009-07-23 | Mitsubishi Gas Chem Co Inc | 硬化性樹脂組成物および硬化性フィルムならびにそれらの硬化物 |
JP2010138364A (ja) * | 2008-02-12 | 2010-06-24 | Mitsubishi Gas Chemical Co Inc | 樹脂組成物、プリプレグおよび金属箔張り積層板 |
JP2010275527A (ja) * | 2009-04-28 | 2010-12-09 | Hitachi Chem Co Ltd | 樹脂組成物、樹脂ワニス、複合材料及びその製造方法、プリプレグ並びに樹脂フィルム |
JP2011208150A (ja) * | 2011-05-27 | 2011-10-20 | Hitachi Chem Co Ltd | 変性シアネートエステル系樹脂組成物、それを用いる樹脂フィルム、多層プリント配線板およびそれらの製造方法 |
JP2017206578A (ja) | 2016-05-16 | 2017-11-24 | 住友ベークライト株式会社 | 熱硬化性樹脂組成物、キャリア付樹脂膜、プリプレグ、金属張積層板、樹脂基板、プリント配線基板、及び半導体装置 |
JP2018131519A (ja) * | 2017-02-15 | 2018-08-23 | 三菱瓦斯化学株式会社 | 樹脂組成物、樹脂シート及びプリント配線板 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0290860B1 (en) * | 1987-04-27 | 1995-01-25 | Mitsubishi Gas Chemical Company, Inc. | Thermosetting resin composition |
JPH05233710A (ja) | 1992-02-24 | 1993-09-10 | Nec Corp | 文字列照合方法 |
JP5021208B2 (ja) * | 2004-01-30 | 2012-09-05 | 新日鐵化学株式会社 | 硬化性樹脂組成物 |
US20060074151A1 (en) * | 2004-09-28 | 2006-04-06 | Polyclad Laminates, Inc. | Low expansion dielectric compositions |
JP5040092B2 (ja) * | 2005-10-04 | 2012-10-03 | 日立化成工業株式会社 | 安定性の優れた低誘電正接樹脂ワニスおよびそれを用いた配線板材料 |
CN103965606A (zh) * | 2013-02-04 | 2014-08-06 | 联茂电子股份有限公司 | 一种低介电材料 |
TWI491671B (zh) * | 2013-05-21 | 2015-07-11 | Elite Material Co Ltd | Low dielectric halogen-free resin compositions and circuit boards for which they are used |
CN104341766B (zh) * | 2013-08-09 | 2017-03-01 | 台光电子材料(昆山)有限公司 | 低介电树脂组合物及应用其的铜箔基板及印刷电路板 |
CN103709717B (zh) * | 2013-12-17 | 2017-10-20 | 中山台光电子材料有限公司 | 乙烯苄基醚化‑dopo化合物树脂组合物及制备和应用 |
JP2015172144A (ja) * | 2014-03-12 | 2015-10-01 | パナソニックIpマネジメント株式会社 | プリプレグ、金属張積層板、プリント配線板 |
JP6910590B2 (ja) * | 2016-10-12 | 2021-07-28 | 三菱瓦斯化学株式会社 | プリント配線板用樹脂組成物、プリプレグ、金属箔張積層板、積層樹脂シート、樹脂シート、及びプリント配線板 |
CN111491968B (zh) * | 2017-12-28 | 2023-11-28 | 松下知识产权经营株式会社 | 聚苯醚树脂组合物、预浸料、带树脂的膜、带树脂的金属箔、覆金属箔层压板及布线板 |
CN111886263A (zh) * | 2018-03-28 | 2020-11-03 | 松下知识产权经营株式会社 | 树脂组合物、和使用其的预浸料、带树脂的膜、带树脂的金属箔、覆金属箔层压板及布线板 |
-
2019
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Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5233710B2 (ja) | 1974-08-05 | 1977-08-30 | ||
JPS5649773B2 (ja) | 1976-04-07 | 1981-11-25 | ||
JP2003138132A (ja) * | 2001-10-31 | 2003-05-14 | Hitachi Chem Co Ltd | 変性シアネートエステル系樹脂組成物、難燃性樹脂フィルム、難燃性多層プリント配線板およびそれらの製造方法 |
JP2009161725A (ja) * | 2007-05-31 | 2009-07-23 | Mitsubishi Gas Chem Co Inc | 硬化性樹脂組成物および硬化性フィルムならびにそれらの硬化物 |
JP2010138364A (ja) * | 2008-02-12 | 2010-06-24 | Mitsubishi Gas Chemical Co Inc | 樹脂組成物、プリプレグおよび金属箔張り積層板 |
JP2010275527A (ja) * | 2009-04-28 | 2010-12-09 | Hitachi Chem Co Ltd | 樹脂組成物、樹脂ワニス、複合材料及びその製造方法、プリプレグ並びに樹脂フィルム |
JP2011208150A (ja) * | 2011-05-27 | 2011-10-20 | Hitachi Chem Co Ltd | 変性シアネートエステル系樹脂組成物、それを用いる樹脂フィルム、多層プリント配線板およびそれらの製造方法 |
JP2017206578A (ja) | 2016-05-16 | 2017-11-24 | 住友ベークライト株式会社 | 熱硬化性樹脂組成物、キャリア付樹脂膜、プリプレグ、金属張積層板、樹脂基板、プリント配線基板、及び半導体装置 |
JP2018131519A (ja) * | 2017-02-15 | 2018-08-23 | 三菱瓦斯化学株式会社 | 樹脂組成物、樹脂シート及びプリント配線板 |
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JPWO2019230945A1 (ja) | 2020-06-25 |
EP3805316A1 (en) | 2021-04-14 |
EP3805316A4 (en) | 2022-04-06 |
KR20200139837A (ko) | 2020-12-14 |
US20210214547A1 (en) | 2021-07-15 |
TWI814832B (zh) | 2023-09-11 |
TW202003691A (zh) | 2020-01-16 |
CN112204105B (zh) | 2023-04-14 |
KR102329650B1 (ko) | 2021-11-19 |
CN112204105A (zh) | 2021-01-08 |
JP6680405B1 (ja) | 2020-04-15 |
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