WO2015046956A1 - Poly(phénylène oxyde) modifié, et stratifié recouvert de cuivre utilisant celui-ci - Google Patents

Poly(phénylène oxyde) modifié, et stratifié recouvert de cuivre utilisant celui-ci Download PDF

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WO2015046956A1
WO2015046956A1 PCT/KR2014/009034 KR2014009034W WO2015046956A1 WO 2015046956 A1 WO2015046956 A1 WO 2015046956A1 KR 2014009034 W KR2014009034 W KR 2014009034W WO 2015046956 A1 WO2015046956 A1 WO 2015046956A1
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group
formula
polyphenylene oxide
modified polyphenylene
fiber
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Korean (ko)
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서현진
김인욱
한가영
김한상
황용재
이혜선
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주식회사 두산
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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
    • 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
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • 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
    • 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
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • 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
    • 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
    • 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
    • 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
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • 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
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • 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
    • 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
    • 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
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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

Definitions

  • the present invention provides a modified polyphenylene oxide having excellent compatibility and processability with epoxy resins and low dielectric properties, and a thermosetting resin composition exhibiting processability and low dielectric properties, including the modified polyphenylene oxide, and the modified
  • the present invention relates to a prepreg having excellent workability while applying low polyelectricity by applying polyphenylene oxide and a copper foil laminate including the prepreg.
  • CCL copper clad laminate
  • Polyphenylene oxide (PPO) a thermoplastic resin
  • PPO polyphenylene oxide
  • polar polymers such as epoxy, which is the main material of CCL, and solubility deterioration in a general-purpose solvent, application of a certain amount or more is impossible.
  • thermosetting with the epoxy by one alcohol group that can react with the epoxy.
  • polyphenylene oxide and polyphenol having a high weight average molecular weight of about 34,000 to 35,000 are formed to form low molecular polyphenylene oxide having alcohol groups introduced at both ends through redistribution reaction in the presence of a radical initiator.
  • Noryl Sabic, Inc.
  • Noryl a representative example of commercially available redistributable polyphenylene oxide, has been limited in use due to its lack of compatibility with epoxy resins.
  • redistribution polyphenylene oxides are characterized by the structural properties of Bisphenol A (4,4 '-(propane-2,2-diyl) diphenol), a polyphenol used for redistribution, and the high polarity of the alcohol groups at both ends. Because of this, there was a limit to lowering the genetic characteristics.
  • An object of the present invention is to provide a modified polyphenylene oxide having excellent dielectric properties and excellent compatibility with the epoxy resin and processability.
  • Another object of the present invention is to provide a film produced using the modified polyphenylene oxide.
  • Another object of the present invention is to provide a thermosetting resin composition, a prepreg, a functional laminated sheet, and a copper foil laminate comprising the modified polyphenylene oxide.
  • the present invention provides a modified polyphenylene oxide represented by the following formula (1).
  • n is an integer from 1 to 10,000;
  • a is an integer from 0 to 4, when a is an integer of 1 to 4, R 1 is C 1 ⁇ C 12 alkyl, and C 1 ⁇ C 12 alkoxy group is selected from the group consisting of;
  • n 0 or 1
  • Y 1 and Y 2 are the same as or different from each other, and each independently a single bond, or a substituted or unsubstituted C 6 to C 12 arylene group, wherein the arylene groups of Y 1 and Y 2 are hydrogen, C 1 to alkyl group of C 12, C 1 ⁇ C 12 alkoxy group and a C 6 ⁇ C 12 from the group consisting of an aryl group may be substituted with more than one kinds selected substituents, and;
  • R 4 to R 8 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a C 1 to C 12 alkyl group, a C 1 to C 12 alkoxy group, and a C 1 to C 12 arylene group,
  • a plurality of W are the same or different and are each independently hydrogen, C 1 ⁇ C 12 alkyl group, C 1 ⁇ C 12 alkoxy group and a C 6 ⁇ is selected from the group consisting of C 12 aryl group;
  • Ar is a substituent represented by the following formula (2) or (3),
  • Q 1 to Q 3 are the same as or different from each other, and are each independently selected from the group consisting of a C 1 to C 12 alkyl group, a C 1 to C 12 alkoxy group, and a C 1 to C 12 haloalkyl group, provided that o is If 0, except that Q 1 and Q 2 are both alkyl groups,
  • o and p are each independently an integer from 0 to 3).
  • the present invention provides a film containing the modified polyphenylene oxide described above.
  • the present invention is a modified polyphenylene oxide described above; And it provides a thermosetting resin composition comprising a crosslinkable curing agent.
  • the present invention is a fiber substrate; And it provides a prepreg comprising the above-mentioned thermosetting resin composition impregnated in the fiber substrate.
  • the present invention is a metal foil or a polymer film substrate; And a resin layer formed on one or both surfaces of the substrate and including a cured resin layer of the thermosetting resin composition.
  • this invention is copper foil; And it includes the above-mentioned prepreg, it provides a copper foil laminated plate characterized in that they are formed by laminating one or more layers.
  • the modified polyphenylene oxide according to the present invention contains a bisphenol moiety having an increased content of an alkyl group and an aromatic ring group in the main chain, compared to a conventional modified polyphenylene oxide, and has a vinyl group, an epoxy group, an amine group, and an ester at both ends thereof.
  • a low polarity substituent such as a group, not only the compatibility and workability with the epoxy resin are excellent, but also the dielectric properties are low.
  • the modified polyphenylene oxide according to the present invention is prepared in conventional modified polyphenylene oxide [eg Noryl (Sabic)] prepared using bisphenol A [4,4 '-(propane-2,2-diyl) diphenol].
  • the polymer contains a bisphenol structure having a high alkyl content and an aromatic content in the main chain, and a substituent having low polarity such as an alcohol group, a vinyl group, an epoxy group, an amine group, or an ester group is introduced at both ends thereof.
  • a substituent having low polarity such as an alcohol group, a vinyl group, an epoxy group, an amine group, or an ester group is introduced at both ends thereof.
  • the modified polyphenylene oxide is excellent in compatibility and processability with epoxy resins and lower in dielectric properties than conventional modified polyphenylene oxide.
  • the modified polyphenylene oxide represented by Formula 1 is an alcohol group at both ends obtained by redistributing the polyphenylene oxide by a specific bisphenol derivative having an increased alkyl content and aromatic content. It is a polymer or a polymer obtained by redistributing the polyphenylene oxide and modifying both ends with low polar substituents (for example, vinyl group, epoxy group, amine group, ester group, etc.) and derived from the bisphenol derivative in the main chain.
  • the bisphenol structure is contained, and an alcohol group, a vinyl group, an epoxy group, an amine group, or an ester group is introduced at both terminals.
  • the bisphenol derivatives have a higher content of alkyl groups and aromatic ring groups than bisphenol A.
  • the modified polyphenylene oxide of the present invention can be improved compatibility and processability with the epoxy resin compared to the conventional modified polyphenylene oxide.
  • the modified polyphenylene oxide of Chemical Formula 1 may further reduce electron polarization, thereby further decreasing dielectric properties.
  • the modified polyphenylene oxide of Chemical Formula 1 is modified at both ends of the molecular chain with a low polarity substituent, that is, a vinyl group, an epoxy group, an amine group, or an ester group. Therefore, unlike the conventional modified polyphenylene oxide, the modified polyphenylene oxide of the present invention not only improves compatibility with the epoxy resin due to low polar substituents at both ends, but also has low dielectric properties.
  • n is an integer of 1 to 10,000, preferably an integer of 1 to 1,000, more preferably 1 to 100.
  • a is an integer of 0 to 4, and when a is 0, it means that hydrogen is not substituted with a substituent R 1 , and when a is an integer of 1 to 4, R 1 represents C 1 to C 12 . It is selected from the group consisting of an alkyl group and a C 1 to C 12 alkoxy group, preferably from the group consisting of a methyl group, an ethyl group, a propyl group, and a tert-butyl group.
  • n is 0 or 1, preferably 1 may be.
  • Y 1 and Y 2 are the same as or different from each other, and each independently represent a single bond or a substituted or unsubstituted C 6 to C 12 arylene group, preferably a single bond or a phenylene group.
  • the arylene group of Y 1 and Y 2 may be substituted with one or more substituents selected from the group consisting of hydrogen, C 1 ⁇ C 12 alkyl group, C 1 ⁇ C 12 alkoxy group and C 6 ⁇ C 12 aryl group It may be preferably substituted with one or more substituents selected from the group consisting of methyl, propyl and tert-butyl groups.
  • R 4 to R 8 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a C 1 to C 12 alkyl group, a C 1 to C 12 alkoxy group, and a C 1 to C 12 arylene group; ,
  • the plurality of Ws are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a C 1 to C 12 alkyl group, a C 1 to C 12 alkoxy group, and a C 6 to C 12 aryl group.
  • Ar is a substituent derived from a bisphenol derivative except for bisphenol A (BPA), and is a substituent represented by Formula 2 or 3, and preferably a substituent represented by any one of Formulas 2a to 2e and 3a. It may be, and more preferably may be a substituent represented by any one of the following formula (2aa), (2ab), (2ba) and (3aa).
  • modified polyphenylene oxide represented by Chemical Formula 1 examples include a modified polyphenylene oxide represented by the following Chemical Formula 4, but are not limited thereto.
  • n, m, Ar, Y 1 , Y 2 , R 2 , and R 3 are the same as defined in Chemical Formula 1.
  • modified polyphenylene oxide represented by Formula 1 include modified polyphenylene oxide represented by Formula 5 to modified polyphenylene oxide represented by Formula 13, but are not limited thereto.
  • W 1 and W 2 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a C 1 to C 12 alkyl group, a C 1 to C 12 alkoxy group and a C 6 to C 12 aryl group, preferably May be selected from the group consisting of hydrogen, methyl, propyl, and tert-butyl groups,
  • a and b are 0 or 1, respectively.
  • modified polyphenylene oxide of Chemical Formula 1 include the following compounds, but are not limited thereto.
  • the weight average molecular weight (Mw) of the modified polyphenylene oxide represented by Formula 1 is not particularly limited, and may be, for example, in the range of 5,000 to 100,000, preferably 3,000 to 60,000.
  • the present invention provides a method for preparing the modified polyphenylene oxide of the formula (1).
  • the modified polyphenylene oxide represented by Chemical Formula 1 may be prepared by redistributing the polyphenylene oxide using a specific bisphenol (Bisphenol) derivative having a high alkyl content and an aromatic content.
  • the method for producing a modified polyphenylene oxide represented by Formula 1 is to redistribute the polyphenylene oxide using a specific bisphenol derivative except for bisphenol A (BPA) to form an alcohol-terminated modified polyphenylene oxide It may include a step.
  • BPA bisphenol A
  • the modified polyphenylene oxide represented by Chemical Formula 1 may be redistributed to a polyphenylene oxide using a specific bisphenol derivative having high alkyl content and aromatic content, and then positioned at both ends.
  • the alcohol group can be prepared by modifying a low polar substituent (eg, vinyl group, epoxy group, amine group, ester group, etc.).
  • the method for producing a modified polyphenylene oxide represented by Formula 1 is to redistribute the polyphenylene oxide using a specific bisphenol derivative except for bisphenol A (BPA) to form an alcohol-terminated modified polyphenylene oxide step; And modifying the end group of the alcohol-terminal modified polyphenylene oxide with a vinyl group, an epoxy group, an amine group or an ester group, but is not limited thereto.
  • BPA bisphenol A
  • the polyphenylene oxide is redistributed using a specific bisphenol derivative having high alkyl content and aromatic content (except bisphenol A (BPA)) to form an alcohol-terminated modified polyphenylene oxide (hereinafter, referred to as' S100 step) ').
  • the high molecular weight polyphenylene oxide may be redistributed through the step S100 to be modified with low molecular weight polyphenylene oxide having alcohol groups at both ends.
  • the bisphenol derivative usable in the present invention contains an alcohol group (-OH) at both ends, and is not particularly limited as long as it is a bisphenol derivative having higher alkyl content and aromatic content than bisphenol A (BPA).
  • BPA bisphenol A
  • bisphenol derivatives represented by the following formula (14), bisphenol derivatives represented by the formula (15) and the like but are not limited thereto.
  • Q 1 to Q 3 are the same as or different from each other, and are each independently selected from the group consisting of a C 1 to C 12 alkyl group, a C 1 to C 12 alkoxy group, and a C 1 to C 12 haloalkyl group, provided that o is If 0, except that Q 1 and Q 2 are both alkyl groups,
  • o and p are each independently an integer of 0-3.
  • Examples of the bisphenol derivative represented by Formula 14 or 15 include bisphenol derivatives of Formula 14a to bisphenol derivatives of Formula 14e, bisphenol derivatives of Formula 15a, and the like, and more specific examples of bisphenol derivatives of Formula 14aa and Formula 14ab Bisphenol derivatives, bisphenol derivatives of formula 14ba, bisphenol derivatives of formula 15aa, and the like, but are not limited thereto.
  • the content of the bisphenol derivative as described above is not particularly limited, and is preferably adjusted according to the weight average molecular weight of the polyphenylene oxide used or the target molecular weight of the redistributed polyphenylene oxide, for example, 100 parts by weight of the polyphenylene oxide. It may be about 10 to 50 parts by weight on a basis.
  • the polyphenylene oxide that can be used in the present invention is not particularly limited as long as it is a polyphenylene oxide known in the art, and may be, for example, polyphenylene oxide represented by the following Chemical Formula 16, and specific examples thereof may be represented by the following Chemical Formula 16a.
  • Polyphenylene oxide and the like, and more specific examples thereof include Saryl's Noryl and SA-120, but are not limited thereto.
  • a is an integer from 0 to 4, when a is an integer of 1 to 4, R 1 is selected from the group consisting of alkoxy group of C 1 ⁇ C 12 alkyl group and a C 1 ⁇ C 12, preferably a methyl group, an ethyl group, It may be selected from the group consisting of propyl group and tert-butyl group,
  • n is an integer of 1 to 3,000.
  • n is an integer of 1 to 3,000.
  • the weight average molecular weight (Mw) of the polyphenylene oxide is not particularly limited, and may be, for example, 2,000 to 350,000.
  • the content of the polyphenylene oxide is not particularly limited, about 1 to 75 parts by weight, preferably 10 to 40 parts by weight based on 100 parts by weight of the reaction mixture (including polyphenylene oxide, bisphenol derivative, radical initiator and solvent). Can be.
  • the redistribution reaction of step S100 may be performed in the presence of a radical initiator and / or a solvent.
  • a radical initiator When used, the redistribution reaction between the polyphenylene oxide and the bisphenol derivative is initiated and promoted to improve the reaction rate.
  • the radical initiator usable in the present invention is not particularly limited as long as it is a radical initiator known in the art, and includes, for example, peroxides such as benzoyl peroxide and the like; Quinone compounds such as 3,3 ', 5,5'-tetramethyl-1,4-diphenoquinone and the like; And complexes containing a transition metal and an amine, but are not limited thereto.
  • the content of such radical initiator is not particularly limited, it is appropriate to adjust in consideration of the content of the reactants, redistribution reaction rate, etc., for example, may be 0 to 10 parts by weight based on 100 parts by weight of polyphenylene oxide, preferably 1 To 10 parts by weight.
  • the solvent which can be used by this invention will not be restrict
  • Non-limiting examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol; Aromatic hydrocarbon solvents such as benzene, ethylbenzene, chlorobenzene, toluene, xylene, and the like, and these may be used alone or in combination of two or more thereof.
  • it may be toluene or a mixture of toluene and methanol.
  • the temperature of the redistribution reaction is not particularly limited, but when the temperature is about 20 to 150 ° C., preferably 60 to 80 ° C., the reaction rate may be improved.
  • R 1 , Ar, n are as defined in the formula (1), respectively.
  • the weight average molecular weight of the alcohol-terminated modified polyphenylene oxide represented by Chemical Formula 17 depends on the weight average molecular weight of the polyphenylene oxide used and the like, and may be, for example, in the range of 2,000 to 20,000.
  • both terminal groups of the alcohol-terminated modified polyphenylene oxide obtained in step S100 are modified with a vinyl group, an epoxy group, an amine group, or an ester group (hereinafter, 'S200 step').
  • a low polarity substituent such as a vinyl group, an epoxy group, an amine group, or an ester group is introduced instead of an alcohol group positioned at both ends of the alcohol-terminated modified polyphenylene oxide, thereby modifying the compound represented by Chemical Formula 1 Polyphenylene oxide can be obtained.
  • the S200 step may be performed through various reactions in the art to introduce a vinyl group, an epoxy group, an amine group or an ester group instead of an alcohol group.
  • the step S200 is the reaction of the alcohol-terminal modified polyphenylene oxide obtained in the step S100 with an acid anhydride in the presence of a basic catalyst in an aromatic hydrocarbon solvent to form both end groups of the alcohol-terminal modified polyphenylene oxide Modifying with a group.
  • aromatic hydrocarbon solvent examples include toluene, benzene, ethylbenzene, chlorobenzene, xylene, and the like, but are not limited thereto.
  • Examples of the basic catalyst include, but are not limited to, dimethylaminopyridine, triphenylphosphine, triphenylantimony, and the like.
  • the content of the basic catalyst is not particularly limited, but may be 1 to 20 parts by weight based on 100 parts by weight of the alcohol-terminated modified polyphenylene oxide).
  • acid anhydride examples include methacrylic anhydride, acrylic anhydride, and the like, but is not limited thereto.
  • the step S200 is the alcohol-terminal modified polyphenylene oxide and epichlorohydrin obtained in the step S100 is dissolved by heating and then reacted in the presence of alkali metal hydroxide alcohol-terminal modified polyphenyls Modifying both end groups of the ethylene oxide with an epoxy group.
  • Non-limiting examples of the alkali metal hydroxide is sodium hydroxide, potassium hydroxide and the like.
  • the content of the alkali metal hydroxide is not particularly limited, and may be, for example, 1 to 10 parts by weight based on 100 parts by weight of the alcohol-terminated modified polyphenylene oxide.
  • step S200 the alcohol-terminated modified polyphenylene oxide obtained in step S100 is reacted with 1,3-dinitrobenzene in the presence of potassium carbonate in a dimethylformamide solution to form a first reactant. Doing; Precipitating the first reactant with methanol; And reacting the precipitate in 2-methoxyethanol with Pt / C and triethylamine under a hydrogen atmosphere, through which steps both groups of the alcohol-terminated modified polyphenylene oxide are modified with an amine group. Can be.
  • the alcohol-terminated modified polyphenylene oxide obtained in step S100 by heating with methyl 4-chlorocarbonylbenzoate to dissolve to form a reaction solution; And reacting the reaction solution by adding triethylamine to modify both terminal groups of the alcohol-terminated modified polyphenylene oxide with an ester group.
  • the present invention provides a film containing the modified polyphenylene oxide represented by the above formula (1).
  • the film may be used as an insulating layer of a copper foil laminate.
  • the film may further include an epoxy resin in addition to the modified polyphenylene oxide of Chemical Formula 1.
  • an epoxy resin in addition to the modified polyphenylene oxide of Chemical Formula 1.
  • the present invention is a modified polyphenylene oxide represented by the above formula (1); And it provides a thermosetting resin composition comprising a crosslinkable curing agent.
  • thermosetting resin composition may further include a cyanate resin, an epoxy resin, a flame retardant, an inorganic filler, a curing accelerator, a radical initiator, a solvent, and the like.
  • the cross-linking curing agent is used to form a network structure by cross-linking the modified polyphenylene oxide of Formula 1 three-dimensionally. Even if a modified low molecular weight modified polyphenylene oxide is used to increase the fluidity of the resin composition, the use of a crosslinkable curing agent contributes to improving the heat resistance of the modified polyphenylene oxide. It also has the effect of increasing the flowability of the resin composition and improving the peel strength with other substrates (eg copper foil).
  • the crosslinkable curing agent usable in the present invention preferably has excellent miscibility with the modified polyphenylene oxide whose terminal is an alcohol group, a vinyl group, an epoxy group, an amine group or an ester group.
  • Non-limiting examples include allyl oxide compounds prepared by the reaction of divinylbenzene, divinyl naphthalene, divinyldiphenyl, styrene monomer, phenol and allyl chloride of the vinyl benzyl oxide compound series; Diene series such as triallyl isocyanurate (TAIC), triallyanurate (TAC), 1,2,4-trivinyl cyclohexane, 1,7-octadiene, 1,9-decadiene, di-4 Vinylbenzyl oxide, and the like.
  • curing agent may be used individually or it may mix 2 or more types. Not only are they excellent in compatibility, they are also excellent in formability and have a small dielectric constant value, excellent
  • the content of the crosslinkable curing agent may be in the range of 5 to 50 parts by weight, and preferably in the range of 10 to 40 parts by weight, based on 100 parts by weight of the modified polyphenylene oxide resin. Can be.
  • the content of the crosslinkable curing agent falls within the above-mentioned range, the curability, molding processability and adhesive strength of the resin composition are good.
  • thermosetting resin composition which concerns on this invention can further contain a flame retardant as needed.
  • the flame retardant may be used without limitation, conventional flame retardants known in the art, for example, phosphorus-based flame retardants such as halogen flame retardant containing bromine or chlorine, triphenyl phosphate, trikeyl phosphate, trisdichloropropyl phosphate, phosphazene And antimony flame retardants such as antimony trioxide, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.
  • phosphorus-based flame retardants such as halogen flame retardant containing bromine or chlorine, triphenyl phosphate, trikeyl phosphate, trisdichloropropyl phosphate, phosphazene
  • antimony flame retardants such as antimony trioxide
  • inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.
  • an additive bromine flame retardant which is not reactive with modified polyphenylene oxide and does not degrade heat resistance and dielectric properties is suitable.
  • the brominated flame retardant is bromophthalimide, bromophenyl-added bromine flame retardant, or tetrabromo bisphenol A in allyl terminated form, allyl ether, divinylphenol.
  • Flame retardant curing agents in the form can be used to obtain the properties of the curing agent and flame retardant properties simultaneously.
  • Brominated organic compounds may also be used, and specific examples thereof include dicabromodiphenyl ethane, 4,4-dibromobiphenyl, and ethylene bistetrabromophthalimide.
  • the content of the flame retardant may be in the range of 5 to 50 parts by weight, preferably in the range of 10 to 40 parts by weight based on 100 parts by weight of the modified polyphenylene oxide resin.
  • the flame retardant may have a flame resistance of flame retardant 94V-0, and may exhibit excellent thermal resistance and electrical characteristics.
  • the flame retardant is preferably a brominated organic compound.
  • thermosetting resin composition according to the present invention may further include a conventional inorganic filler known in the art used for lamination, if necessary.
  • the inorganic filler can effectively improve the warpage characteristics, low expansion, mechanical toughness and low stress of the final product by reducing the difference in the coefficient of thermal expansion (CTE) between the resin layer and other layers.
  • CTE coefficient of thermal expansion
  • Non-limiting examples of the inorganic fillers usable in the present invention include silicas such as natural silica, fused silica, amorphous silica, crystalline silica, and the like; Boehmite, alumina, talc, spherical glass, calcium carbonate, magnesium carbonate, magnesia, clay, calcium silicate, titanium oxide, antimony oxide, glass fiber, aluminum borate, barium titanate, strontium titanate, calcium titanate , Magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, boron nitride, silicon nitride, talc, mica and the like. These inorganic fillers may be used alone or in combination of two or more. Of these inorganic fillers, fused silica having a low coefficient of thermal expansion is most preferred.
  • the size of the inorganic filler is not particularly limited, but an average particle diameter in the range of 0.5 to 5 ⁇ m is advantageous in dispersibility.
  • the content of the inorganic filler is not particularly limited, and may be appropriately adjusted in consideration of the aforementioned bending characteristics, mechanical properties, and the like. For example, based on 100 parts by weight of the modified polyphenylene oxide resin, it may be in the range of 5 to 90 parts by weight, preferably 30 to 80 parts by weight. Excessive content of the inorganic filler may be detrimental to moldability.
  • thermosetting resin composition according to the present invention may further include a reaction initiator in order to enhance the advantageous effect of the crosslinkable curing agent.
  • Such a reaction initiator may further accelerate the curing of the modified polyphenylene oxide and the crosslinkable curing agent, and may increase properties such as heat resistance of the resin.
  • reaction initiators include ⁇ , ⁇ ′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butyl peroxy) -3 Hexyne, benzoyl peroxide, 3,3 ′, 5,5′-tetramethyl-1,4-diphenoxyquinone, chloranyl, 2,4,6-tri-t-butylphenoxyl, t -Butyl peroxyisopropyl monocarbonate, azobisisisobutylonitrile and the like.
  • metal carboxylate salts may be further used.
  • the reaction initiator may be included in 2 to 5 parts by weight based on 100 parts by weight of the modified polyphenylene oxide, but is not limited thereto.
  • thermosetting resin composition of the present invention may further include a curing accelerator.
  • the curing accelerator may use an organometallic salt or organometallic complex including at least one metal selected from the group consisting of iron, copper, zinc, cobalt, lead, nickel, manganese, and tin.
  • organometallic salts or organometallic complexes examples include iron naphthenates, copper naphthenates, zinc naphthenates, cobalt naphthenates, nickel naphthenates, manganese naphthenates, tin naphthenates, zinc Octanoate, tin octanoate, iron octanoate, copper octanoate, zinc 2-ethylhexanate, lead acetylacetonate, cobalt acetylacetonate, or dibutyltin malate. It is not limited. In addition, these can be used 1 type or in mixture of 2 or more types.
  • the curing accelerator may be included in an amount of 0.01 to 1 part by weight based on 10 to 60 parts by weight of the modified polyphenylene oxide, but is not limited thereto.
  • thermosetting resin composition of the present invention may further include a conventional rubber (rubber) known in the art.
  • thermosetting resin composition of the present invention is a flame retardant generally known in the art as needed, other thermosetting resins or thermoplastic resins and oligomers thereof not described above, as long as they do not impair the intrinsic properties of the resin composition.
  • Various polymers such as, solid rubber particles or other additives such as ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents and the like may be further included.
  • organic fillers such as silicon-based powder, nylon powder, and fluororesin powder, thickeners such as orbene and benton; Polymeric antifoaming agents or leveling agents such as silicone-based and fluorine-based resins; Adhesion imparting agents such as imidazole series, thiazole series, triazole series, and silane coupling agents; Phthalocyanine, carbon black, etc. can be mentioned a coloring agent.
  • thermoplastic resin can be mix
  • thermoplastic resin include cyanate resin, epoxy resin, phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyoxide sulfone, polysulfone and the like. Any one of these thermoplastic resins may be used alone, or two or more thereof may be used in combination.
  • Organic fillers such as a silicone powder, nylon powder, a fluorine powder; Thickeners such as olben and benton; Antifoaming agents or leveling agents based on silicon, fluorine and polymers; Adhesion imparting agents such as imidazole series, thiazole series, triazole series, silane coupling agents, epoxy silanes, aminosilanes, alkylsilanes and mercaptosilanes; Coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow and carbon black; Mold release agents such as higher fatty acids, higher fatty acid metal salts, and ester waxes; Stress relieving agents such as modified silicone oil, silicone powder, and silicone resin. It may also include additives conventionally used in thermosetting resin compositions used in the production of electronic devices (especially printed wiring boards).
  • the thermosetting resin composition is (a) a modified polyphenylene oxide resin represented by the formula (1); Based on 100 parts by weight of the modified polyphenylene oxide resin (b) 5 to 50 parts by weight of a crosslinkable curing agent (c) 5 to 50 parts by weight of a flame retardant; And (d) 5 to 90 parts by weight of inorganic filler It can be configured to include a range. At this time, the basis of the component may be the total weight of the composition, or may be the total weight of the varnish containing the organic solvent.
  • the organic solvent may be a conventional organic solvent known in the art without limitation, for example, a variety of organic solvents such as acetone, cyclohexanone, methyl ethyl ketone, toluene, xylene, tetrahydrofuran and the like can be used arbitrarily.
  • the content of the organic solvent may be in the range of the remaining amount to satisfy the total 100 parts by weight of the varnish using the composition ratio of the above-described composition, it is not particularly limited.
  • the prepreg which concerns on this invention contains a fiber base material and the above-mentioned thermosetting resin composition impregnated to the said fiber base material.
  • the thermosetting resin composition may be a resin varnish dissolved or dispersed in a solvent.
  • the fibrous substrate may be arbitrarily bent, and may be used in the art of a conventional inorganic fiber substrate, organic fiber substrate, or a mixed form thereof. What is necessary is just to select the above-mentioned fiber base material based on the use or performance to be used.
  • Examples of the substrate used in the present invention include inorganic fibers such as E-glass, D-glass, S-glass, NE-glass, T-glass, and Q-glass, and organic fibers such as polyimide, polyamide, polyester, and the like. Mixtures, etc. are selected based on the intended use or performance.
  • Non-limiting examples of fiber substrates that can be used include glass fibers (inorganic fibers) such as E-glass, D-glass, S-glass, NE-glass, T-glass, Q-glass, and the like; Organic fibers such as glass paper, glass fiber nonwoven fabric, glass cloth, aramid fiber, aramid paper, polyimide, polyamide, polyester, aromatic polyester, fluororesin, and the like; Carbon fibers, paper, inorganic fibers, or a mixture of one or more thereof.
  • the fiber base may be in the form of a woven or nonwoven fabric made of the above fibers; A woven fabric, a nonwoven fabric, a mat, etc.
  • this fibrous substrate is not particularly limited and may be, for example, in the range of about 0.01 mm to 0.3 mm.
  • the said resin composition is used for prepreg formation,
  • the thermosetting resin composition of this invention mentioned above can be used.
  • prepreg refers to a sheet-like material obtained by coating or impregnating a thermosetting resin composition on a fibrous substrate and then curing the resin to a B-stage (semi-cured state) by heating.
  • the prepreg of the present invention can be prepared by a known hot melt method, a solvent method and the like known in the art.
  • the solvent method is a method in which the resin composition varnish formed by dissolving the thermosetting resin composition for prepreg formation in an organic solvent is impregnated with a fiber base and dried.
  • a resin varnish is generally used.
  • the method of impregnating the resin composition into the fiber substrate include a method of immersing the substrate in a resin varnish, a method of applying the resin varnish to the substrate by various coaters, a method of spraying the resin varnish onto the substrate by spraying, and the like. Can be mentioned.
  • the fiber base material is immersed in a resin varnish, since the impregnation property of the resin composition with respect to a fiber base material can be improved, it is preferable.
  • ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, a cellosolve acetate, a propylene glycol monomethyl oxide acetate, a cavitol acetate, etc.
  • Carboxitols such as acetic acid esters, cellosolves and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran and the like.
  • You may use an organic solvent 1 type or in combination of 2 or more types.
  • the hot-melt method may be a method of coating a resin composition and a release paper having excellent peelability without dissolving the resin composition in an organic solvent and then laminating it on a sheet-like fibrous substrate, or coating directly by a die coater.
  • it may be manufactured by continuously laminating an adhesive film made of a thermosetting resin composition laminated on a support under heating and pressing conditions from both sides of a sheet-like reinforcing base material.
  • the resin composition of this invention can be manufactured as a prepreg by coating or impregnating the said resin composition in the sheet-like fiber base material or glass base material which consists of fibers, and semi-hardening by heating.
  • the resin composition may be prepared by a resin varnish.
  • the prepreg of the present invention may be formed by coating or impregnating the substrate, and then additionally drying, wherein the drying may be performed at 20 to 200 ° C.
  • the prepreg of the present invention may be prepared by semi-curing (B-Stage) by impregnating the substrate in the thermosetting resin composition varnish and heat-dried for 70 to 170 °C, 1 to 10 minutes.
  • the present invention is a metal foil or a polymer film substrate; And a resin layer formed on one or both surfaces of the substrate and including a cured resin layer of the thermosetting resin composition.
  • metal foil For example, metal foil; And copper foil with resin which is formed on one or both surfaces of the metal foil, and includes a resin layer in which the thermosetting resin composition is cured.
  • the metal foil can be used without limitation those made of conventional metals or alloys known in the art.
  • the metal foil is a copper foil
  • the laminate formed by coating and drying the thermosetting resin composition according to the present invention can be used as a copper foil laminate.
  • it is copper foil.
  • the said copper foil includes all the copper foils manufactured by the rolling method and the electrolytic method.
  • the copper foil may be subjected to rust prevention treatment in order to prevent oxidative corrosion of the surface.
  • the metal foil may have a predetermined surface roughness Rz formed on one surface of the thermosetting resin composition in contact with the cured resin layer.
  • the surface roughness Rz is not particularly limited, but may be, for example, in a range of 0.6 ⁇ m to 3.0 ⁇ m.
  • the thickness of the metal foil is not particularly limited, but may be used less than 5 ⁇ m in consideration of the thickness and mechanical properties of the final product, preferably may be in the range of 1 to 3 ⁇ m.
  • copper foil that can be used include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, ILSIN and the like.
  • the polymer film usable in the present invention is not particularly limited as long as it is known as an insulating film in the art.
  • an insulating film in the art there are a polyimide film, an epoxy resin film, and the like, but is not limited thereto.
  • the present invention includes a copper foil laminate formed by overlapping two or more prepregs described above with each other, and then heating and pressing them under normal conditions.
  • the present invention includes a copper foil laminate formed by laminating the prepreg and the copper foil, and being formed by heat press molding under ordinary conditions.
  • the above-mentioned resin composition is sufficiently stirred at room temperature using a stirrer, impregnated with a glass substrate, dried, laminated with copper foil, etc., and then applied with heat and pressure to obtain a desired copper foil laminate.
  • the heating pressure conditions may be appropriately adjusted according to the thickness of the copper foil laminate to be manufactured or the kind of the thermosetting resin composition according to the present invention.
  • the present invention includes a printed circuit board, preferably a multilayer printed circuit board, laminated and molded, including at least one selected from the group consisting of the prepreg, the insulating resin sheet, and the copper foil with resin.
  • a printed circuit board refers to a printed circuit board laminated by one or more layers by a plating through-hole method, a build-up method, etc., and can be obtained by overlaying the above-described prepreg or insulating resin sheet on an inner wiring board and heating and pressing.
  • the printed circuit board may be manufactured by conventional methods known in the art.
  • a copper foil laminated board is produced, opening a hole in a copper foil laminated board, through-hole plating, and then copper foil containing a plating film It can be produced by etching to form a circuit.
  • the prepreg and the printed circuit board may be prepared from the thermosetting resin composition according to the present invention.
  • These prepregs and copper foil laminates not only have low dielectric constant and dielectric loss, but also have excellent heat resistance at the same time (see Table 2 below).
  • the prepregs and printed circuit boards of the present invention are networks used for mobile communication devices that handle high frequency signals of 1 GHz or higher, network-related electronic devices such as base station devices, servers, routers, and various electrical and electronic devices such as large computers. It can be usefully used as a component part of a printed circuit board.
  • Alchol-MPPO-2 (0.85 kg, weight average molecular weight) of light brown powder, similar to Synthesis Example 1, except that Compound 2 (0.5 kg) was used instead of Compound 2 (0.1 kg) used in Synthesis Example 1. : 3500) was obtained.
  • Alchol-MPPO-3 (0.8 kg, weight average molecular weight) of light brown powder, which was prepared in the same manner as in Preparation Example 1, except that Compound 3 (0.1 kg) was used instead of Compound 2 (0.1 kg) used in Synthesis Example 1. 6300) was obtained.
  • Alchol-MPPO-4 (0.75 kg, weight average molecular weight) of light brown powder, similar to Preparation Example 1, except that Compound 4 (0.1 kg) was used instead of Compound 2 (0.1 kg) used in Synthesis Example 1. : 7200) was obtained.
  • Alchol-MPPO-5 (0.82 kg, weight average molecular weight) of light brown powder, similar to Preparation 1, except that Compound 5 (0.1 kg) was used instead of Compound 2 (0.1 kg) used in Synthesis Example 1. 6600) was obtained.
  • alchol-MPPO-1 700 g
  • Methacrylic anhydride 127 g
  • 4-Dimethylaminopyridine 100 g obtained in Synthesis Example 1
  • Toluene 1400 g
  • the reaction mixture was heated up to Reflux temperature, reacted for 6 hours, and then cooled to room temperature. Thereafter, the cooled reaction solution was precipitated in excess methanol to obtain a precipitate, and then the precipitate was sufficiently washed with methanol.
  • the washed precipitate was then dried in a vacuum oven at 80 ° C. for 24 hours to afford the following vinyl-MPPO-1 (700 g, weight average molecular weight: 6,375) which is a light brown powder.
  • alchol-MPPO-1 (1 kg) and epichlorohydrin (2.5 kg) obtained in Synthesis Example 1 were added and heated to dissolve. Thereafter, sodium hydroxide (50 g) was slowly added to the reaction solution, and stirred at 100 ° C for 12 hours, and then cooled to room temperature to obtain a reaction product. Subsequently, the reaction was precipitated in excess methanol to obtain a precipitate. The precipitate was sufficiently washed with methanol and then dried in a vacuum oven at 80 ° C. for 24 hours to obtain epoxy-MPPO-1 (900 g, weight average molecular weight: 6,400). ) was obtained.
  • alchol-MPPO-1 700 g
  • methyl 4-chlorocarbonyl benzoate (Methyl 4-(chlorocarbonyl) -benzoate, obtained in Synthesis Example 1, MCCB) (150 g) was added and then heated to dissolve. Then, triethylamine (120 g) was slowly added to the reaction solution, followed by stirring at 70 ° C. for 5 hours. Subsequently, the reactant was precipitated in excess methanol to obtain a precipitate, and the obtained precipitate was washed with methanol sufficiently and then dried in a vacuum oven at 80 ° C. for 24 hours to obtain ester-MPPO-1 (600 g, weight average molecular weight: 6,200). ) was obtained.
  • Alchol-MPPO-com (0.80 kg, weight average molecular weight) of light brown powder, similar to Synthesis Example 1, except that Compound 6 (0.5 kg) was used instead of Compound 2 (0.1 kg) used in Synthesis Example 1. 3800) was obtained.
  • the vinyl-terminated modified polyphenylene oxide (vinyl-MPPO-1) obtained in Synthesis Example 6 was coated on a release paper, dried at 150 ° C. for 5 minutes, and then peeled off, and cured at 210 ° C. and 25 kg / cm 2 for 150 minutes. To prepare a polyphenylene oxide film.
  • ester-terminated modified polyphenylene oxide (ester-MPPO-1) obtained in Synthesis Example 9 instead of the modified polyphenylene oxide used in Example 1, the modified poly A phenylene oxide film was prepared.
  • a prepreg and a copper foil laminate were prepared in the same manner as in Example 5 except that the modified polyphenylene oxide of Synthesis Example 1 was used instead of the modified polyphenylene oxide of Synthesis Example 6 used in Example 5.
  • Dielectric constant (Dk) measured using a material analyzer in accordance with the test standard of IPC TM-650.2.5.5.1.
  • Dielectric loss (Df) measured using a material analyzer in accordance with the test standard of IPC TM-650.2.5.5.1.
  • the modified polyphenylene oxides of Examples 1 to 4 not only have a low dielectric constant, but also had a significantly lower dielectric loss than the modified polyphenylene oxides of Comparative Examples 1 and 2.
  • Dielectric constant (Dk) measured using a material analyzer in accordance with the test standard of IPC TM-650.2.5.5.1.
  • Dielectric loss (Df) measured using a material analyzer in accordance with the test standard of IPC TM-650.2.5.5.1.
  • Glass transition temperature (Tg) After etching the copper foil layer of a copper foil laminated body, it measured using DSC (Differential Scanning Calorimeter).
  • thermosetting resin composition of the present invention not only had excellent low dielectric loss characteristics and low dielectric constant, but also exhibited improved adhesion to copper foil, excellent heat resistance, thermal stability, and the like (see Table 2).
  • Example 5 and Example 6 exhibited a lower dielectric constant and excellent low dielectric loss characteristics compared to Comparative Example 3 and Comparative Example 4 corresponding to their configurations, respectively.
  • Example 1 using the modified polyphenylene oxide modified at both ends of the vinyl group exhibits a more synergistic effect in terms of heat resistance and adhesion to copper foil.

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Abstract

La présente invention concerne un poly(phénylène oxyde) modifié présentant de faibles propriétés diélectriques tout en présentant d'excellentes propriétés de compatibilité et d'usinabilité avec une résine époxy ; une composition de résine thermodurcissable comprenant le poly(phénylène oxyde) modifié, présentant ainsi une excellente usinabilité et de faibles propriétés diélectriques ; un préimprégné présentant une excellente usinabilité tout en présentant de faibles propriétés diélectriques par application du poly(phénylène oxyde) modifié ; et un stratifié recouvert de cuivre comprenant le préimprégné.
PCT/KR2014/009034 2013-09-27 2014-09-26 Poly(phénylène oxyde) modifié, et stratifié recouvert de cuivre utilisant celui-ci WO2015046956A1 (fr)

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CN114891202A (zh) * 2022-03-31 2022-08-12 国科广化(南雄)新材料研究院有限公司 一种耐高温热固性聚苯醚树脂及其制备与应用
CN115339174A (zh) * 2022-08-15 2022-11-15 黄河三角洲京博化工研究院有限公司 一种低介电固化片及其制备方法

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TW201833095A (zh) * 2016-11-30 2018-09-16 日商三菱瓦斯化學股份有限公司 化合物、樹脂、組成物以及光阻圖型形成方法及迴路圖型形成方法
KR102257969B1 (ko) 2018-04-06 2021-05-28 주식회사 엘지화학 열가소성 수지 조성물
KR102642936B1 (ko) * 2020-12-14 2024-03-05 한국전자기술연구원 고방열 고분자 조성물 및 이를 포함하는 고방열 성형품

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