WO2014203511A1 - ポリフェニレンエーテル樹脂組成物、プリプレグ、金属張積層板及びプリント配線板 - Google Patents
ポリフェニレンエーテル樹脂組成物、プリプレグ、金属張積層板及びプリント配線板 Download PDFInfo
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- WO2014203511A1 WO2014203511A1 PCT/JP2014/003177 JP2014003177W WO2014203511A1 WO 2014203511 A1 WO2014203511 A1 WO 2014203511A1 JP 2014003177 W JP2014003177 W JP 2014003177W WO 2014203511 A1 WO2014203511 A1 WO 2014203511A1
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- polyphenylene ether
- resin composition
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- mass
- ether resin
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- 0 CC(*CC1)C1C=C Chemical compound CC(*CC1)C1C=C 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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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
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
-
- 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
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
Definitions
- the present invention relates to a polyphenylene ether resin composition, a prepreg, a metal-clad laminate, and a printed wiring board.
- Polyphenylene ether is known to have excellent dielectric properties such as dielectric constant and dielectric loss tangent, and excellent dielectric properties even in a high frequency band (high frequency region) from the MHz band to the GHz band. For this reason, use of polyphenylene ether as, for example, a molding material for high frequency has been studied. More specifically, it has been studied to be used as a substrate material or the like for constituting a substrate of a printed wiring board provided in an electronic device using a high frequency band.
- polyphenylene ether when used as a molding material such as a substrate material, it is required not only to have excellent dielectric properties but also to have excellent heat resistance and moldability.
- polyphenylene ether is thermoplastic and may not have sufficient heat resistance. For this reason, it is conceivable to use a polyphenylene ether to which a thermosetting resin such as an epoxy resin is added, or to use a polyphenylene ether modified.
- the present applicant has proposed a resin composition using the modified polyphenylene ether compound described in Patent Document 1 as a resin composition containing a modified polyphenylene ether.
- Patent Document 1 has a polyphenylene ether moiety in the molecular structure, a p-ethenylbenzyl group, an m-ethenylbenzyl group, and the like at the molecular end, and a number average molecular weight of 1000 to 7000.
- a polyphenylene ether resin composition containing polyphenylene ether and a cross-linkable curing agent is described.
- TAIC as the cross-linking agent has a slightly reduced reactivity that contributes to the curing reaction, so it is necessary to add a relatively large amount of reaction initiator. This is because when TAIC is included, if the addition amount of the reaction initiator is too small, the reaction becomes slow and Tg (glass transition point) may not be easily increased. However, if a large amount of reaction initiator is added, the life of the varnish or prepreg obtained from the resin composition may be deteriorated.
- the present invention has been made in view of such circumstances, and has excellent heat resistance while maintaining the excellent dielectric properties possessed by the cured product of the resin composition as obtained so far.
- Another object of the present invention is to provide a polyphenylene ether resin composition having properties such as adhesion and Tg.
- Another object of the present invention is to provide a prepreg using the polyphenylene ether resin composition, a metal-clad laminate using the prepreg, and a printed wiring board manufactured using the prepreg.
- the polyphenylene ether resin composition according to one embodiment of the present invention includes (A) a modified polyphenylene ether terminal-modified with a substituent having a carbon-carbon unsaturated double bond, and (B) a carbon-carbon unsaturated double bond.
- the crosslinking agent as component (B) contains 50 to 100% by mass of (B-1) divinylbenzene and (B-2) polybutadiene, and contains component (A) and component (B).
- (B-1): Component (B-2) 1: 100 to 1.5: 1
- a prepreg according to another embodiment of the present invention is produced by impregnating a base material with the polyphenylene ether resin composition.
- the metal-clad laminate according to another embodiment of the present invention is manufactured by laminating the prepreg and metal foil by heat and pressure molding.
- a printed wiring board according to another aspect of the present invention is a printed wiring board manufactured using the prepreg.
- the polyphenylene ether resin composition according to one embodiment of the present invention includes (A) a modified polyphenylene ether terminal-modified with a substituent having a carbon-carbon unsaturated double bond, and (B) a carbon-carbon unsaturated double bond.
- the crosslinking agent as component (B) contains 50 to 100% by mass of (B-1) divinylbenzene and (B-2) polybutadiene, and contains component (A) and component (B).
- (B-1): Component (B-2) 1: 100 to 1.5: 1
- Such a polyphenylene ether resin composition has an excellent dielectric property with a good balance in properties such as high Tg, adhesion and heat resistance in the cured product.
- the modified polyphenylene ether used in the present embodiment is not particularly limited as long as it is a modified polyphenylene ether terminal-modified with a substituent having a carbon-carbon unsaturated double bond.
- the substituent having a carbon-carbon unsaturated double bond is not particularly limited, and examples thereof include a substituent represented by the following formula 1.
- n represents an integer of 0 to 10
- Z represents an arylene group
- R 1 to R 3 independently represent a hydrogen atom or an alkyl group.
- n 0, it indicates that Z is directly bonded to the terminal of polyphenylene ether.
- the arylene group for Z include a monocyclic aromatic group such as a phenylene group and a polycyclic aromatic group such as a naphthalene ring, and a hydrogen atom bonded to the aromatic ring is an alkenyl group, an alkynyl group, a formyl group.
- derivatives substituted with a functional group such as a group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group.
- the functional group represented by the above formula 1 include a functional group containing a vinylbenzyl group, specifically, for example, at least one substituent selected from the following formula 2 or formula 3 and the like. It is done.
- R 4 represents a hydrogen atom or an alkyl group.
- the number average molecular weight of (A) the modified polyphenylene ether used in the present embodiment is not particularly limited, but is preferably 1000 to 7000, more preferably 1000 to 5000, and further preferably 1000 to 3000. preferable.
- the number average molecular weight should just be what was measured by the general molecular weight measuring method here, and the value etc. which were specifically measured using gel permeation chromatography (GPC) are mentioned.
- the polyphenylene ether has more excellent dielectric properties, and the cured product is excellent in balance with high Tg, adhesion and heat resistance. It is thought that the obtained resin composition is obtained.
- the modified polyphenylene ether used in the present embodiment has an average number of substituents having carbon-carbon unsaturated double bonds (terminal substituent numbers) at the molecular end per molecule of the modified polyphenylene ether of 1.5 to The number is preferably 3, more preferably 1.7 to 2.7, and still more preferably 1.8 to 2.5. If the number of substituents is too small, it is considered that a crosslinking point or the like is hardly formed, and there is a tendency that it is difficult to obtain a cured product having sufficient heat resistance.
- the number of terminal substituents of the modified polyphenylene ether includes a numerical value representing an average value of the number of substituents per molecule of all the modified polyphenylene ethers present in 1 mol of the modified polyphenylene ether.
- the number of terminal substituents can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether and calculating the amount of decrease from the number of hydroxyl groups of the polyphenylene ether before modification. The decrease from the number of hydroxyl groups in the polyphenylene ether before modification is the number of terminal functional groups.
- the method for measuring the number of hydroxyl groups remaining in the modified polyphenylene ether is to add a quaternary ammonium salt (tetraethylammonium hydroxide) associated with the hydroxyl group to the modified polyphenylene ether solution and measure the UV absorbance of the mixed solution. Can be obtained.
- a quaternary ammonium salt tetraethylammonium hydroxide
- the intrinsic viscosity of the modified polyphenylene ether used in the present embodiment is preferably 0.03 to 0.12 dl / g, more preferably 0.04 to 0.11 dl / g, and 0.06 to More preferably, it is 0.095 dl / g. If the intrinsic viscosity is too low, the molecular weight tends to be low, and low dielectric properties such as low dielectric constant and low dielectric loss tangent tend to be difficult to obtain. On the other hand, if the intrinsic viscosity is too high, the viscosity is high, sufficient fluidity cannot be obtained, and the moldability of the cured product tends to decrease. Therefore, if the intrinsic viscosity of the modified polyphenylene ether is within the above range, excellent heat resistance and adhesion of the cured product can be realized.
- the intrinsic viscosity here is an intrinsic viscosity measured in methylene chloride at 25 ° C. More specifically, for example, a 0.18 g / 45 ml methylene chloride solution (liquid temperature 25 ° C.) is used as a viscometer. It is the value measured by. Examples of the viscometer include AVS500 Visco System manufactured by Schott.
- the content of a high molecular weight component having a molecular weight of 13,000 or more is desirably 5% by mass or less. That is, the modified polyphenylene ether of this embodiment preferably has a relatively narrow molecular weight distribution.
- the content of a high molecular weight component having a molecular weight of 13,000 or more is small, and the high molecular weight component having a molecular weight of 13,000 or more may be used.
- the lower limit value of the molecular weight component content range may be 0% by mass.
- the content of the high molecular weight component having a molecular weight of 13,000 or more in the modified polyphenylene ether may be 0 to 5% by mass, and more preferably 0 to 3% by mass.
- a modified polyphenylene ether having a low content of high molecular weight components and a narrow molecular weight distribution tends to have a higher reactivity contributing to the curing reaction and a better fluidity.
- the content of the high molecular weight component can be calculated based on the measured molecular weight distribution by measuring the molecular weight distribution using, for example, gel permeation chromatography (GPC). Specifically, it can be calculated from the ratio of the peak area based on the curve showing the molecular weight distribution obtained by GPC.
- GPC gel permeation chromatography
- the modified polyphenylene ether according to the present embodiment has a polyphenylene ether chain in the molecule, and for example, preferably has a repeating unit represented by the following formula 5 in the molecule.
- m represents 1 to 50.
- R 5 , R 6 , R 7 and R 8 are independent from each other. That is, R 5 , R 6 , R 7 and R 8 may be the same group or different groups.
- R 5 , R 6 , R 7 and R 8 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferable.
- R 5 , R 6 , R 7 and R 8 include the following.
- the alkyl group is not particularly limited.
- an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.
- Specific examples include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
- the alkenyl group is not particularly limited, but for example, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Specific examples include a vinyl group, an allyl group, and a 3-butenyl group.
- the alkynyl group is not particularly limited, but for example, an alkynyl group having 2 to 18 carbon atoms is preferable, and an alkynyl group having 2 to 10 carbon atoms is more preferable. Specific examples include an ethynyl group and a prop-2-yn-1-yl group (propargyl group).
- the alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group.
- an alkylcarbonyl group having 2 to 18 carbon atoms is preferable, and an alkylcarbonyl group having 2 to 10 carbon atoms is more preferable.
- Specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, and a cyclohexylcarbonyl group.
- the alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group.
- an alkenylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferable.
- an acryloyl group, a methacryloyl group, a crotonoyl group, etc. are mentioned, for example.
- the alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group.
- an alkynylcarbonyl group having 3 to 18 carbon atoms is preferable, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferable.
- a propioyl group etc. are mentioned, for example.
- m is a numerical value such that the number average molecular weight of the modified polyphenylene ether falls within the range as described above. Is preferred. Specifically, it is preferably 1 to 50.
- the method for synthesizing the (A) modified polyphenylene ether used in the present embodiment is not particularly limited as long as it can synthesize modified polyphenylene ether terminal-modified with a substituent having a carbon-carbon unsaturated double bond.
- Specific examples include a method of reacting a polyphenylene ether in which a hydrogen atom of a terminal phenolic hydroxyl group is substituted with an alkali metal atom such as sodium or potassium with a compound represented by the following formula 6.
- n represents an integer of 0 to 10
- Z represents an arylene group
- R 1 to R 3 independently represent a hydrogen atom or an alkyl group.
- X represents a halogen atom, and specific examples include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Among these, a chlorine atom is preferable.
- the compound represented by the above formula 6 is not particularly limited, but for example, p-chloromethylstyrene and m-chloromethylstyrene are preferable.
- the raw material polyphenylene ether is not particularly limited as long as it can finally synthesize a predetermined modified polyphenylene ether.
- those containing polyphenylene ether as a main component More specifically, examples of such polyphenylene ether include polyphenylene ether having a structure represented by Formula 7.
- Equation 7 for s and t, for example, the total value of s and t is preferably 1 to 30. Further, s is preferably from 0 to 20, and t is preferably from 0 to 20. That is, s represents 0 to 20, t represents 0 to 20, and the sum of s and t preferably represents 1 to 30.
- examples of the method for synthesizing the modified polyphenylene ether include the methods described above. Specifically, the polyphenylene ether as described above and the compound represented by Formula 6 are dissolved in a solvent and stirred. By doing so, the polyphenylene ether and the compound represented by Formula 6 react to obtain the modified polyphenylene ether used in the present embodiment.
- the alkali metal hydroxide is not particularly limited as long as it can function as a dehalogenating agent, and examples thereof include sodium hydroxide. Moreover, alkali metal hydroxide is normally used in the state of aqueous solution, and specifically, it is used as sodium hydroxide aqueous solution.
- reaction conditions such as reaction time and reaction temperature vary depending on the compound represented by Formula 6, and are not particularly limited as long as the above reaction proceeds favorably.
- the reaction temperature is preferably room temperature to 100 ° C., more preferably 30 to 100 ° C.
- the reaction time is preferably 0.5 to 20 hours, more preferably 0.5 to 10 hours.
- the solvent used at the time of reaction is not particularly limited as long as it can dissolve polyphenylene ether and the compound represented by Formula 6 and does not inhibit the reaction between the polyphenylene ether and the compound represented by Formula 6. It is not limited. Specifically, toluene etc. are mentioned.
- the above reaction is preferably performed in the state where not only the alkali metal hydroxide but also the phase transfer catalyst is present. That is, the above reaction is preferably performed in the presence of an alkali metal hydroxide and a phase transfer catalyst. By doing so, it is considered that the above reaction proceeds more suitably.
- phase transfer catalyst is not particularly limited, and examples thereof include quaternary ammonium salts such as tetra-n-butylammonium bromide.
- the polyphenylene ether resin composition according to the present embodiment preferably contains the modified polyphenylene ether obtained as described above as the modified polyphenylene ether.
- the crosslinking agent (B) having a carbon-carbon unsaturated double bond of the present embodiment contains 50 to 100% by mass of (B-1) divinylbenzene and (B-2) polybutadiene.
- dibenylbenzene used in the present embodiment for example, commercially available ones can be used. From the viewpoint of improvement in Tg and reactivity, dibenylbenzene having high purity can be used. preferable. Specifically, preferably, diphenylbenzene having a purity of 60% or more, more preferably diphenylbenzene having a purity of 80% or more can be used.
- the (B-2) polybutadiene used in the present embodiment is not particularly limited, and examples thereof include 1,4-polybutadiene, 1,2-polybutadiene, terminal acrylate-modified polybutadiene, terminal urethane methacrylate-modified polybutadiene, and the like.
- polybutadiene having a number average molecular weight of about 100 to 4000 is preferably used, and a number average molecular weight of 500 to 3000 is more preferable. Since polybutadiene having a number average molecular weight within the above range is excellent in compatibility with polyphenylene ether, improvement in adhesion and heat resistance can be expected.
- each of the components described above has a mass ratio of these components, a mass ratio of the component (A) and the component (B), and the component (A).
- Component (B) 65: 35 to 95: 5
- the content ratio of Component (B-1) to Component (B-2) is mass ratio
- Component (B-1): Component (B- 2) 1: 100 to 1.5: 1.
- the polyphenylene ether resin composition contains each component in such a ratio, so that the properties necessary for a printed wiring board such as high Tg, adhesion, and heat resistance are excellent in balance and have excellent dielectric properties. A cured product can be obtained.
- each component 65 to 95% by mass of the (A) modified polyphenylene ether, (B), with respect to the total amount of the components (A) and (B) in the cured product.
- B modified polyphenylene ether
- the “content ratio” described above in the present embodiment is not a blending ratio when blending each component when adjusting the resin composition or a component ratio in a varnish state, but the resin composition is semi-cured. This is the component ratio in the so-called “B stage state”.
- the content ratio of each component in the B stage state can be measured by combining, for example, NMR, GC-MS, DI-MS and the like.
- the polyphenylene ether resin composition according to the present embodiment may be composed of the (A) modified polyphenylene ether, the (B-1) dibenenylbenzene, and the (B-2) polybutadiene. As long as it contains an essential component, it may further contain other components.
- the polyphenylene ether resin composition according to the present embodiment may further contain another crosslinking agent (B-3) having a carbon-carbon unsaturated double bond as the crosslinking agent (B).
- B-3 another crosslinking agent having a carbon-carbon unsaturated double bond as the crosslinking agent (B).
- the amount of the other crosslinking agent (B-3) used is preferably 40% by mass or less, and at most 50% by mass or less in the crosslinking agent (B). This is because the addition of another crosslinking agent (B-3) can be expected to improve the adhesion and glass transition point (Tg), but if the amount used is too large, the dielectric properties may be lowered.
- any crosslinking agent having a carbon-carbon unsaturated double bond other than the above-mentioned (B-1) divinylbenzene and (B-2) polybutadiene may be used without any particular limitation. it can.
- a crosslinking agent containing a (meth) acrylate group is used.
- a cross-linking agent containing a (meth) acrylate group it can be expected to improve the adhesion (adhesive force).
- it is a polyfunctional crosslinking agent which has two or more (meth) acrylate groups, it can anticipate improving a glass transition point (Tg).
- crosslinking agent containing a (meth) acrylate group examples include alkyl (meth) acrylate, tricyclodecanol (meth) acrylate, fluorene (meth) acrylate, isocyanurate (meth) acrylate, trimethylolpropane (meta ) Acrylate and the like.
- examples of other components include flame retardants, inorganic fillers, additives, and reaction initiators.
- the total content of the components (A) to (B) is preferably 30% by mass or more based on the total amount of the polyphenylene ether resin composition. It is more preferably 90% by mass, and further preferably 40 to 80% by mass. If it is such a range, the effect which the polyphenylene ether resin composition concerning this embodiment shows can fully be exhibited, without inhibiting other ingredients.
- the polyphenylene ether resin composition according to this embodiment preferably contains a flame retardant.
- a flame retardant is not particularly limited. Specific examples include halogen-based flame retardants such as brominated flame retardants and phosphorus-based flame retardants.
- halogen-based flame retardant examples include, for example, brominated flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, and chlorinated flame retardants such as chlorinated paraffin. Etc.
- chlorinated flame retardants such as chlorinated paraffin.
- phosphorus-based flame retardant include, for example, phosphate esters such as condensed phosphate esters and cyclic phosphate esters, phosphazene compounds such as cyclic phosphazene compounds, and phosphinic acid metal salts such as aluminum dialkylphosphinates. Examples include phosphinate flame retardants, melamine phosphates such as melamine phosphate, and melamine polyphosphate. As a flame retardant, each illustrated flame retardant may be used independently and may be
- an incompatible bromine-containing compound as a brominated flame retardant from the viewpoint that a sufficient amount of flame retardancy can be exhibited with a small amount and that the Tg is hardly lowered.
- the bromine-containing compound When a bromine-containing compound is used as the flame retardant, the bromine-containing compound is blended so that the bromine content is 8 to 20% by mass with respect to the total amount of the resin component in the polyphenylene ether resin composition according to the present embodiment. It is preferable. By setting it as such content, while showing favorable flame retardance, it does not have a bad influence on heat resistance or fluidity
- Examples of the inorganic filler that can be contained in the polyphenylene ether resin composition according to the present embodiment include those added to increase the heat resistance and flame retardancy of the cured product of the resin composition, and are not particularly limited. By containing an inorganic filler, heat resistance, flame retardancy and the like can be enhanced.
- a resin composition containing polyphenylene ether has a lower crosslink density than a general epoxy resin composition for an insulating substrate, and the thermal expansion coefficient of the cured product, in particular, heat at a temperature exceeding Tg. The expansion coefficient ⁇ 2 tends to increase.
- an inorganic filler By including an inorganic filler, it has excellent dielectric properties and heat resistance and flame retardancy of the cured product, and the thermal expansion coefficient of the cured product, especially the glass transition temperature, has been exceeded while the viscosity when made into a varnish is low. It is possible to reduce the thermal expansion coefficient ⁇ 2 at temperature and toughen the cured product.
- the inorganic filler include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, and calcium carbonate.
- an inorganic filler although you may use as it is, what was surface-treated with the silane coupling agent of a vinyl silane type, a styryl silane type, a methacryl silane type, or an acryl silane type is especially preferable.
- a metal-clad laminate obtained by using a resin composition in which an inorganic filler surface-treated with such a silane coupling agent is blended has high heat resistance during moisture absorption, and tends to have high interlayer peel strength. There is.
- the content thereof is preferably 10 to 150% by mass, more preferably 10 to 100% by mass, and more preferably 20 to 100% with respect to the polyphenylene ether resin composition. More preferably, it is mass%.
- the polyphenylene ether resin composition according to the present embodiment may contain other additives.
- additives for example, antifoaming agents such as silicone antifoaming agents and acrylic ester antifoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, wetting and dispersing agents, etc. A dispersing agent etc. are mentioned.
- the polyphenylene ether resin composition according to this embodiment may contain a reaction initiator. Even if the polyphenylene ether resin composition comprises a modified polyphenylene ether and a thermosetting curing agent, the curing reaction can proceed at a high temperature. However, depending on the process conditions, it may be difficult to increase the temperature until curing proceeds, so a reaction initiator may be added.
- the reaction initiator is not particularly limited as long as it can accelerate the curing reaction between the modified polyphenylene ether and the thermosetting curing agent.
- An oxidizing agent such as ronitrile can be used.
- a carboxylic acid metal salt etc. can be used together as needed. By doing so, the curing reaction can be further accelerated.
- ⁇ , ⁇ '-bis (t-butylperoxy-m-isopropyl) benzene is preferably used. Since ⁇ , ⁇ '-bis (t-butylperoxy-m-isopropyl) benzene has a relatively high reaction start temperature, it suppresses the acceleration of the curing reaction when it is not necessary to cure such as during prepreg drying. And a decrease in storage stability of the polyphenylene ether resin composition can be suppressed. Furthermore, ⁇ , ⁇ '-bis (t-butylperoxy-m-isopropyl) benzene has low volatility, and therefore does not volatilize during prepreg drying or storage and has good stability. Moreover, a reaction initiator may be used independently or may be used in combination of 2 or more type.
- the polyphenylene ether resin composition according to the present embodiment is often prepared and used in the form of a varnish for the purpose of impregnating the substrate (fibrous substrate) for forming the prepreg. . That is, the polyphenylene ether resin composition is usually a varnish (resin varnish) in many cases.
- a resin varnish is prepared as follows, for example.
- each component that can be dissolved in an organic solvent such as a modified polyphenylene ether and a thermosetting curing agent
- an organic solvent such as a modified polyphenylene ether and a thermosetting curing agent
- heating may be performed as necessary.
- a component that is used as necessary and does not dissolve in an organic solvent such as an inorganic filler, is added and dispersed using a ball mill, a bead mill, a planetary mixer, a roll mill or the like until a predetermined dispersion state is obtained.
- a varnish-like resin composition is prepared.
- the organic solvent used here is not particularly limited as long as it dissolves the modified polyphenylene ether and the thermosetting curing agent and does not inhibit the curing reaction. Specifically, toluene etc. are mentioned, for example.
- divarnbenzene contained in the polyphenylene ether resin composition according to the present embodiment is volatilized when the varnish is cured through a heat drying process as described later (prepreg)
- the blending of each component in the varnish is The content ratio in the obtained prepreg is different. Therefore, it is necessary to adjust the composition of each component in the varnish so that the content ratio of each component in the obtained B-staged semi-cured product (prepreg) is in the range as described above.
- the amount of divinylbenzene volatilized in the course of the heat-drying process for converting the resin composition into a B-stage is previously grasped so that the content ratio of each component of the resin composition in the B-stage state becomes a desired amount.
- the amount of each component in the varnish adjustment stage may be set by reverse calculation.
- dibenylbenzene is a step (heat drying step) in which a varnish-like resin composition is generally used, for example, a substrate having a thickness of 0.1 mm is impregnated, and then at 130 ° C. for about 3 minutes. About 80% is volatilized by the heat drying process. Therefore, when going through the heating and drying step, it is preferable to prepare divinylbenzene and adjust the varnish formulation so that the content ratio in the B-stage state is about 5 times.
- Examples of a method for producing a prepreg using the obtained resin varnish include a method in which a fibrous base material is impregnated with the obtained resin varnish and then dried.
- the fibrous base material used when producing the prepreg include glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper. .
- a glass cloth is used, a laminate having excellent mechanical strength can be obtained, and a flat glass processed glass cloth is particularly preferable.
- the flattening processing can be performed, for example, by continuously pressing a glass cloth with a press roll at an appropriate pressure and compressing the yarn flatly.
- the thickness of the fibrous base material for example, a thickness of 0.04 to 0.3 mm can be generally used.
- the impregnation of the resin base material with the resin varnish is performed by dipping or coating. This impregnation can be repeated a plurality of times as necessary. At this time, it is also possible to repeat the impregnation using a plurality of resin varnishes having different compositions and concentrations, and finally adjust to a desired composition and resin amount.
- a semi-cured (B stage) prepreg is obtained by removing the solvent by heating the fibrous base material impregnated with the resin varnish at a desired heating condition, for example, 80 to 170 ° C. for 1 to 10 minutes.
- a method for producing a metal-clad laminate using the prepreg thus obtained one or a plurality of prepregs are stacked, and a metal foil such as a copper foil is stacked on both upper and lower sides or one side thereof.
- a laminated body of double-sided metal foil tension or single-sided metal foil tension can be produced by heat and pressure forming and laminating and integrating.
- the heating and pressing conditions can be appropriately set depending on the thickness of the laminate to be produced, the type of the resin composition of the prepreg, etc. For example, the temperature is 170 to 210 ° C., the pressure is 1.5 to 4.0 MPa, and the time For 60 to 150 minutes.
- the polyphenylene ether resin composition according to this embodiment is a polyphenylene ether resin composition having excellent balance of dielectric properties, high Tg, adhesion, and heat resistance. Therefore, metal-clad laminates using prepregs obtained using polyphenylene ether resin compositions produce printed wiring boards that have excellent dielectric properties and heat resistance, have high Tg, and suppress the occurrence of molding defects. can do.
- the polyphenylene ether resin composition according to one embodiment of the present invention includes (A) a modified polyphenylene ether terminal-modified with a substituent having a carbon-carbon unsaturated double bond, and (B) a carbon-carbon unsaturated double bond.
- the crosslinking agent as component (B) contains 50 to 100% by mass of (B-1) divinylbenzene and (B-2) polybutadiene, and contains component (A) and component (B).
- the polyphenylene ether resin composition contains 70 to 95% by mass of the (A) modified polyphenylene ether and 0 to (B-1) divinylbenzene with respect to the total amount of the components (A) and (B). It is preferable to contain 1 to 15% by mass and 4 to 25% by mass of the (B-2) polybutadiene. Thereby, it is thought that the outstanding polyphenylene ether resin composition as mentioned above can be obtained more reliably.
- the crosslinking agent as component (B) may further contain other crosslinking agent (B-3) having a carbon-carbon unsaturated double bond at 50% by mass or less. it can.
- the other crosslinking agent (B-3) preferably contains a compound containing a (meth) acrylate group. Thereby, the adhesiveness (adhesive force) of the cured product of the resin composition can be improved.
- polyphenylene ether resin composition 70 to 95% by mass of the (A) modified polyphenylene ether and (B-1) divinylbenzene are added to the total amount of the components (A) and (B). It is preferable to contain 0.1 to 15% by mass, 4 to 25% by mass of the (B-2) polybutadiene, and 17.5% by mass or less of the (B-3) other crosslinking agent. Thereby, it is thought that the outstanding polyphenylene ether resin composition as mentioned above can be obtained more reliably.
- the substituent at the terminal of the (A) modified polyphenylene ether is a substituent represented by the following formula 1.
- n represents an integer of 0 to 10
- Z represents an arylene group
- R 1 to R 3 independently represent a hydrogen atom or an alkyl group.
- the substituent at the terminal of the (A) modified polyphenylene ether is a substituent selected from the following formula 2 or formula 3.
- the substituent at the terminal of the (A) modified polyphenylene ether is a substituent having a (meth) acrylate group.
- the same effect as when polyphenylene ether is modified with the functional groups represented by the above formulas 1 to 3 can be expected.
- the number average molecular weight of the (A) modified polyphenylene ether is preferably 1000 to 7000.
- the polyphenylene ether resin composition preferably further contains a flame retardant. Thereby, a flame retardance can be provided more reliably.
- the flame retardant is a bromine-containing compound
- the bromine-containing compound is blended so that the bromine content with respect to the total amount of resin components in the resin composition is 8 to 20% by mass. It is preferable. Thereby, there is an advantage that heat resistance and fluidity are not adversely affected while exhibiting good flame retardancy.
- a prepreg according to another embodiment of the present invention is produced by impregnating a base material with the polyphenylene ether resin composition.
- the prepreg thus obtained has a high Tg and is excellent in balance with respect to dielectric properties, adhesion, heat resistance, and the like.
- the metal-clad laminate according to another embodiment of the present invention is manufactured by laminating the prepreg and metal foil by heat and pressure molding.
- the metal-clad laminate thus obtained has a high Tg and is excellent in balance with respect to dielectric properties, adhesion, heat resistance, and the like.
- a printed wiring board according to another aspect of the present invention is a printed wiring board manufactured using the prepreg.
- the printed wiring board obtained in this way has a high Tg and is excellent in balance in dielectric properties, adhesion, heat resistance, and the like.
- a modified polyphenylene ether was synthesized.
- the intrinsic viscosity measured in methylene chloride at 25 ° C. is indicated as intrinsic viscosity (IV).
- the average number of phenolic hydroxyl groups at the molecular end per molecule of polyphenylene ether is shown as the number of terminal hydroxyl groups.
- Modified Polyphenylene Ether 1 (Modified PPE1)
- Polyphenylene ether and chloromethylstyrene were reacted to obtain modified polyphenylene ether 1 (modified PPE1).
- a 1 liter three-necked flask equipped with a temperature controller, a stirrer, a cooling facility, and a dropping funnel was charged with polyphenylene ether (polyphenylene ether having the structure shown in the above formula (5), SABIC Innovative).
- the mixture was stirred until polyphenylene ether, chloromethylstyrene, and tetra-n-butylammonium bromide were dissolved in toluene. At that time, it was gradually heated and finally heated until the liquid temperature reached 75 ° C. And the sodium hydroxide aqueous solution (sodium hydroxide 20g / water 20g) was dripped at the solution over 20 minutes as an alkali metal hydroxide. Thereafter, the mixture was further stirred at 75 ° C. for 4 hours. Next, after neutralizing the contents of the flask with 10% by mass hydrochloric acid, a large amount of methanol was added. By doing so, a precipitate was produced in the liquid in the flask.
- sodium hydroxide aqueous solution sodium hydroxide 20g / water 20g
- the product contained in the reaction solution in the flask was reprecipitated. Then, the precipitate was taken out by filtration, washed three times with a mixed solution having a mass ratio of methanol and water of 80:20, and then dried at 80 ° C. under reduced pressure for 3 hours.
- the obtained solid was analyzed by 1H-NMR (400 MHz, CDCl 3, TMS). As a result of NMR measurement, a peak derived from ethenylbenzyl was confirmed at 5 to 7 ppm. Thereby, it was confirmed that the obtained solid was a modified polyphenylene ether having a group represented by the formula (1) at the molecular end. Specifically, it was confirmed that the polyphenylene ether was ethenylbenzylated.
- Mn number average molecular weight
- the number of terminal functionalities of the modified polyphenylene ether was measured as follows.
- TEAH tetraethylammonium hydroxide
- Residual OH amount ( ⁇ mol / g) [(25 ⁇ Abs) / ( ⁇ ⁇ OPL ⁇ X)] ⁇ 106
- ⁇ represents an extinction coefficient and is 4700 L / mol ⁇ cm.
- OPL is the cell optical path length, which is 1 cm.
- the calculated residual OH amount (number of terminal hydroxyl groups) of the modified polyphenylene ether was almost zero, indicating that the hydroxyl groups of the polyphenylene ether before modification were almost modified. From this, it was found that the decrease from the number of terminal hydroxyl groups of polyphenylene ether before modification was the number of terminal hydroxyl groups of polyphenylene ether before modification. That is, it was found that the number of terminal hydroxyl groups of the polyphenylene ether before modification was the number of terminal functional groups of the modified polyphenylene ether. That is, the terminal functional number was 1.9.
- the intrinsic viscosity (IV) of the modified polyphenylene ether was measured in methylene chloride at 25 ° C. Specifically, the intrinsic viscosity (IV) of the modified polyphenylene ether was measured using a 0.18 g / 45 ml methylene chloride solution (liquid temperature 25 ° C.) of the modified polyphenylene ether, using a viscometer (AVS500 Visco System manufactured by Schott). It was measured. As a result, the intrinsic viscosity (IV) of the modified polyphenylene ether was 0.086 dl / g.
- the molecular weight distribution of the modified polyphenylene ether was measured using GPC. Then, from the obtained molecular weight distribution, the content of a high molecular weight component having a number average molecular weight (Mn) and a molecular weight of 13,000 or more was calculated. Further, the content of the high molecular weight component was specifically calculated from the ratio of the peak area based on the curve showing the molecular weight distribution obtained by GPC. As a result, Mn was 2300. Moreover, content of the high molecular weight component was 0.1 mass%.
- Modified PPE1 Modified polyphenylene ether obtained by the above synthesis method
- Modified PPE2 SA9000 manufactured by SABIC Innovative Plastics (modified polyphenylene ether in which the terminal hydroxyl group of the polyphenylene ether of Formula 7 is modified with a methacryl group)
- reaction initiator 1,3-bis (butylperoxyisopropyl) benzene (Perbutyl P manufactured by NOF Corporation)
- SAYTEX 8010 Ethylene bis (pentabromophenyl) (manufactured by Albemarle Japan)
- each component other than the initiator is added to toluene at a blending ratio shown in Table 1 (in the table, “part” indicates part by mass) and added to toluene so that the solid content concentration is 50% by mass. It was.
- the mixture was heated to 80 ° C. and stirred at 80 ° C. for 30 minutes. Thereafter, the stirred mixture was cooled to 40 ° C., and 1,3-bis (butylperoxyisopropyl) benzene as an initiator (perbutyl P manufactured by NOF Corporation) was added at a blending ratio shown in Table 1. By doing so, a varnish-like resin composition (resin varnish) was obtained.
- the obtained resin varnish was impregnated with glass cloth (# 2116 type, WEA116E, E glass, thickness 0.1 mm manufactured by Nitto Boseki Co., Ltd.), and then dried by heating at 130 ° C. for about 3 minutes.
- a prepreg of 100 ⁇ m was obtained. In that case, it adjusted so that content (resin content) of resin components, such as polyphenylene ether and a heat-crosslinking-type hardening
- the content ratio of each component in the obtained B-stage state was as shown in Table 2 unlike the blending ratio in the varnish because a part of dibenenylbenzene was volatilized by the heat drying process (in the table) , “Part” means part by mass).
- the content ratio of each component in a B stage state was performed as follows. First, the prepreg obtained as described above was heated at 163 ° C. for 15 minutes, and the weight loss ⁇ M before and after heating was measured. Furthermore, when the prepreg after this measurement was heated at 200 ° C. for 25 minutes, the weight loss before heating and after overheating was zero.
- the volatile component in the resin composition in the prepreg was measured using GC-MS under the same condition as above, which was heated at 163 ° C. for 15 minutes, but a very small amount of toluene was detected. It was confirmed that nearly all of the volatile components were divinylbenzene. Therefore, it was found that the weight loss ⁇ M corresponds to divinylbenzene remaining in the prepreg.
- the virtual residual amount M of divinylbenzene in the prepreg is calculated from the blending ratio of each component in the varnish stage. Can be calculated.
- the amount of divinylbenzene volatilized in the course of the prepreg production process is M- ⁇ M.
- the compounding amount of divinylbenzene at the varnish stage was 15 parts by mass, but when ⁇ M was measured by the above method, it was equivalent to 2.625 parts by mass. This means that the volatile content of divinylbenzene is equivalent to 82.5% of the initial blending amount.
- the dielectric constant and dielectric loss tangent of the evaluation substrate at 10 GHz were measured by a cavity resonator perturbation method. Specifically, the dielectric constant and dielectric loss tangent of the evaluation substrate at 10 GHz were measured using a network analyzer (N5230A manufactured by Agilent Technologies).
- Tg of the prepreg was measured using a viscoelastic spectrometer “DMS100” manufactured by Seiko Instruments Inc. At this time, dynamic viscoelasticity measurement (DMA) was performed with a bending module at a frequency of 10 Hz, and the temperature at which tan ⁇ was maximized when the temperature was increased from room temperature to 280 ° C. at a temperature increase rate of 5 ° C./min was Tg. did.
- DMA dynamic viscoelasticity measurement
- PCT solder heat resistance The solder heat resistance after moisture absorption was measured by the following method. First, the obtained 50 mm ⁇ 50 mm copper-clad laminate was etched, 121 ° C., 2 atm (0.2 MPa), and 5 hours pressure cooker test (PCT) were performed on each sample. Was immersed in a solder bath for 20 seconds, and the presence or absence of occurrence of measling or swelling was visually observed.
- the examples of the polyphenylene ether resin compositions according to the present invention have a high Tg of 200 ° C. or higher in their cured products, and have good adhesion and heat resistance. It was found that the characteristics were excellent in balance and had excellent dielectric characteristics.
- Comparative Example 2 dibenzylbenzene and polybutadiene were used in combination as a crosslinking agent. However, when the amount of polybutadiene was excessively increased, the heat resistance and flame retardancy were lowered. This was the same tendency in Comparative Example 8 in which a crosslinking agent containing a (meth) acrylate group was further blended as a crosslinking agent.
- the present invention has wide industrial applicability in technical fields such as a resin composition and a printed wiring board using the resin composition.
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Abstract
Description
ポリフェニレンエーテルと、クロロメチルスチレンとを反応させて変性ポリフェニレンエーテル1(変性PPE1)を得た。具体的には、まず、温度調節器、攪拌装置、冷却設備、及び滴下ロートを備えた1リットルの3つ口フラスコに、ポリフェニレンエーテル(上記式(5)に示す構造を有するポリフェニレンエーテル、SABICイノベーティブプラスチックス社製のSA90、固有粘度(IV)0.083dl/g、末端水酸基数1.9個、数平均分子量Mn2000)200g、p-クロロメチルスチレンとm-クロロメチルスチレンとの質量比が50:50の混合物(東京化成工業株式会社製のクロロメチルスチレン:CMS)30g、相間移動触媒として、テトラ-n-ブチルアンモニウムブロマイド1.227g、及びトルエン400gを仕込み、攪拌した。そして、ポリフェニレンエーテル、クロロメチルスチレン、及びテトラ-n-ブチルアンモニウムブロマイドが、トルエンに溶解するまで攪拌した。その際、徐々に加熱し、最終的に液温が75℃になるまで加熱した。そして、その溶液に、アルカリ金属水酸化物として、水酸化ナトリウム水溶液(水酸化ナトリウム20g/水20g)を20分間かけて、滴下した。その後、さらに、75℃で4時間攪拌した。次に、10質量%の塩酸でフラスコの内容物を中和した後、多量のメタノールを投入した。そうすることによって、フラスコ内の液体に沈殿物を生じさせた。すなわち、フラスコ内の反応液に含まれる生成物を再沈させた。そして、この沈殿物をろ過によって取り出し、メタノールと水との質量比が80:20の混合液で3回洗浄した後、減圧下、80℃で3時間乾燥させた。
ここで、εは、吸光係数を示し、4700L/mol・cmである。また、OPLは、セル光路長であり、1cmである。
本実施例において、ポリフェニレンエーテル樹脂組成物を調製する際に用いる成分について説明する。
変性PPE1:上記の合成方法により得られた変性ポリフェニレンエーテル
変性PPE2:SABICイノベーティブプラスチックス社製のSA9000(式7のポリフェニレンエーテルの末端水酸基をメタクリル基で変性した変性ポリフェニレンエーテル)
DVB810:ジビニルベンゼン 純度約81%(新日鐵住金化学社製)
B-1000:ポリブタジエン(日本曹達社製)
DCP:トリシクロデカンジメタノールジメタクリレート(新中村化学、分子量332のモノマー)
TAIC:トリアリルイソシアヌレート(日本化成株式会社製)
開始剤:1,3-ビス(ブチルパーオキシイソプロピル)ベンゼン(日油株式会社製のパーブチルP)
SAYTEX 8010:エチレンビス(ペンタブロモフェニル)(アルベマール日本社製)
まず、開始剤以外の各成分を表1に記載の配合割合で(表中、「部」は質量部を示す)、固形分濃度が50質量%となるように、トルエンに添加し、混合させた。その混合物を、80℃になるまで加熱し、80℃のままで30分間攪拌した。その後、その攪拌した混合物を40℃まで冷却した後、開始剤である1,3-ビス(ブチルパーオキシイソプロピル)ベンゼン(日油株式会社製のパーブチルP)を表1に記載の配合割合で添加することによって、ワニス状の樹脂組成物(樹脂ワニス)が得られた。
10GHzにおける評価基板の誘電率及び誘電正接を、空洞共振器摂動法で測定した。具体的には、ネットワーク・アナライザ(アジレント・テクノロジー株式会社製のN5230A)を用い、10GHzにおける評価基板の誘電率及び誘電正接を測定した。
銅張り積層板の1枚目と2枚目のガラスクロス間の引き剥がし強さをJIS C 6481に準拠して測定した。幅10mm、長さ100mmのパターンを形成し、引っ張り試験機により50mm/分の速度で引き剥がし、その時の引き剥がし強さを測定した。測定単位はkN/mである。
セイコーインスツルメンツ株式会社製の粘弾性スペクトロメータ「DMS100」を用いて、プリプレグのTgを測定した。このとき、曲げモジュールで周波数を10Hzとして動的粘弾性測定(DMA)を行い、昇温速度5℃/分の条件で室温から280℃まで昇温した際のtanδが極大を示す温度をTgとした。
吸湿後はんだ耐熱性は、以下の方法により測定した。まず得られた50mm×50mmの銅張積層板をエッチングし、121℃、2気圧(0.2MPa)、5時間のプレッシャークッカーテスト(PCT)を各サンプルで行い、サンプル数5個で、288℃の半田槽中に20秒間浸漬し、ミーズリングやフクレの発生の有無を目視で観察した。
難燃性は得られた銅張積層板をエッチングし、127×12.7mmにカットした後、UL94に準拠して評価した。
Claims (14)
- (A)炭素-炭素不飽和二重結合を有する置換基により末端変性された変性ポリフェニレンエーテル、(B)炭素-炭素不飽和二重結合を有する架橋剤を含有し、
成分(B)である架橋剤が、(B-1)ジビニルベンゼン及び(B-2)ポリブタジエンを50~100質量%含み、
成分(A)と成分(B)の含有比が質量比で、成分(A):成分(B)=65:35~95:5であり、かつ
成分(B-1)と成分(B-2)の含有比が質量比で、成分(B-1):成分(B-2)=1:100~1.5:1であることを特徴とする、ポリフェニレンエーテル樹脂組成物。 - 前記成分(A)及び(B)の合計量に対して、
前記(A)変性ポリフェニレンエーテルを70~95質量%、
前記(B-1)ジビニルベンゼンを0.1~15質量%、および
前記(B-2)ポリブタジエンを4~25質量%
含有する、請求項1に記載のポリフェニレンエーテル樹脂組成物。 - 成分(B)である架橋剤が、炭素-炭素不飽和二重結合を有する他の架橋剤(B-3)を50質量%以下で更に含む、請求項1に記載のポリフェニレンエーテル樹脂組成物。
- 他の架橋剤(B-3)が(メタ)アクリレート基を含有する化合物を含む、請求項3に記載のポリフェニレンエーテル樹脂組成物。
- 前記成分(A)及び(B)の合計量に対して、
前記(A)変性ポリフェニレンエーテルを70~95質量%、
前記(B-1)ジビニルベンゼンを0.1~15質量%、
前記(B-2)ポリブタジエンを4~25質量%、及び
前記(B-3)他の架橋剤を17.5質量%以下で含有する、請求項2または3に記載のポリフェニレンエーテル樹脂組成物。 - 前記(A)変性ポリフェニレンエーテルの末端における前記置換基が、(メタ)アクリレート基を有する置換基である、請求項1~5のいずれかに記載のポリフェニレンエーテル樹脂組成物。
- 前記(A)変性ポリフェニレンエーテルの数平均分子量が1000~7000である、請求項1~8のいずれかに記載のポリフェニレンエーテル樹脂組成物。
- 更に難燃剤を含有する、請求項1~9のいずれかに記載のポリフェニレンエーテル樹脂組成物。
- 前記難燃剤が臭素含有化合物であり、前記臭素含有化合物が、樹脂組成物における樹脂成分の全量に対する臭素含有量が8~20質量%となるように配合されている、請求項10に記載のポリフェニレンエーテル樹脂組成物。
- 請求項1~11のいずれかに記載のポリフェニレンエーテル樹脂組成物が基材に含浸されたプリプレグ。
- 請求項12に記載のプリプレグと金属箔とを加熱加圧成形することにより積層して製造される金属張積層板。
- 請求項12に記載のプリプレグを用いて製造されたことを特徴とするプリント配線板。
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US16/448,191 Continuation US10870721B2 (en) | 2013-06-18 | 2019-06-21 | Polyphenylene ether resin composition, prepreg, metal-clad laminate and printed wiring board |
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US20190300639A1 (en) | 2019-10-03 |
US20160145370A1 (en) | 2016-05-26 |
US10870721B2 (en) | 2020-12-22 |
JP6455728B2 (ja) | 2019-01-23 |
US10590223B2 (en) | 2020-03-17 |
CN105358595B (zh) | 2017-12-22 |
CN105358595A (zh) | 2016-02-24 |
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