WO2015046956A1 - Modified polyphenylene oxide, and copper-clad laminate using same - Google Patents

Modified polyphenylene oxide, and copper-clad laminate using same 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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PCT/KR2014/009034
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French (fr)
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.

Abstract

The present invention relates to a modified polyphenylene oxide which has low dielectric properties while having excellent compatibility and processability with epoxy resin; a thermosetting resin composition which comprises the modified polyphenylene oxide, thereby exhibiting excellent processability and low dielectric properties; a prepreg having excellent processability while implementing low dielectric properties by applying the modified polyphenylene oxide; and a copper-clad laminate comprising the prepreg.

Description

변성 폴리페닐렌 옥사이드 및 이를 이용하는 동박 적층판Modified Polyphenylene Oxide and Copper Clad Laminates Using the Same
본 발명은 에폭시 수지와의 상용성 및 가공성이 우수하면서 유전적 특성이 낮은 변성 폴리페닐렌 옥사이드, 및 상기 변성 폴리페닐렌 옥사이드를 포함하여 가공성 및 낮은 유전 특성을 발휘하는 열경화성 수지 조성물, 그리고 상기 변성 폴리페닐렌 옥사이드를 적용하여 저유전 특성을 구현하면서 가공성이 우수한 프리프레그 및 상기 프리프레그를 포함하는 동박 적층판에 관한 것이다.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.
최근 전자 기기의 고기능화 추세에 따른 고주파화에 대응하기 위해 GHz 영역에서의 유전손실이 적고, 전송 특성이 우수한 저유전 및 저손실계수의 동박적층판(CCL, copper clad laminate) 기판이 요구되고 있다. 이러한 CCL 소재의 주재료인 에폭시 수지는 고주파 신호의 전파속도 및 임피던스 제어에 불리하므로, 이를 개선하기 위한 저유전 특성의 엔지니어링 플라스틱인 폴리페닐렌 옥사이드의 적용 연구가 지속적으로 진행되고 있다. Recently, copper clad laminate (CCL) substrates having low dielectric loss and excellent transmission characteristics with low dielectric loss in the GHz region and excellent transmission characteristics are required to cope with high frequency according to the trend of high functionalization of electronic devices. Epoxy resin, which is the main material of the CCL material, is disadvantageous in the control of the propagation speed and the impedance of the high frequency signal, and thus researches on the application of polyphenylene oxide, which is an engineering plastic having low dielectric properties, to improve this problem are continuously conducted.
열가소성 수지인 폴리페닐렌 옥사이드(polyphenylene oxide, PPO)는 기계적 강도, 열저항성, 흡습성 및 특히 유전적 특성이 우수한 반면, 높은 분자량으로 인하여 녹는점이 높아 가공성이 떨어지고 동박 접착력, 내열성 측면에서 부족하다는 단점이 있다. 또한 CCL의 주재료인 에폭시 등의 극성 고분자와의 비상용성, 및 범용성 용매에 대한 용해성 저하로 인해 일정량 이상 적용이 불가능한 상황이다. 아울러, 에폭시와 반응할 수 있는 알콜기가 1개로 에폭시와의 열경화성에도 문제가 있다. Polyphenylene oxide (PPO), a thermoplastic resin, has excellent mechanical strength, heat resistance, hygroscopicity, and especially dielectric properties.However, due to its high molecular weight, it has a high melting point, resulting in poor workability and lack of copper foil adhesion and heat resistance. have. In addition, due to incompatibility with 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. In addition, there is also a problem in the thermosetting with the epoxy by one alcohol group that can react with the epoxy.
따라서, 전술한 단점을 개선하기 위해서, 중량평균분자량이 34,000 내지 35,000 정도로 높은 폴리페닐렌 옥사이드와 폴리 페놀을 라디칼 개시제 존재 하에서 재분배 반응을 통하여 양 말단에 알코올기가 도입된 저분자 폴리페닐렌 옥사이드를 형성하는 기술이 제시되었다. 실제로 상용화된 재분배 폴리페닐렌 옥사이드의 대표적인 예인 Noryl (Sabic社)는 에폭시 수지와의 상용성이 부족하여 제한적으로 사용되었다. 또한, 상용화된 재분배 폴리페닐렌 옥사이드는 재분배에 사용된 폴리 페놀인 Bisphenol A (4,4'-(propane-2,2-diyl)diphenol)의 구조적인 특성 및 양 말단에 있는 알코올기의 높은 극성으로 인해서 유전 특성을 낮추는 것에 한계가 있었다. Therefore, in order to improve the above-mentioned disadvantage, 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. Technology was presented. In fact, Noryl (Sabic, Inc.), a representative example of commercially available redistributable polyphenylene oxide, has been limited in use due to its lack of compatibility with epoxy resins. In addition, commercially available 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.
본 발명의 목적은 에폭시 수지와의 상용성 및 가공성이 우수하면서 유전적 특성이 낮은 변성 폴리페닐렌 옥사이드를 제공하는 것이다.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.
또, 본 발명의 다른 목적은 상기 변성 폴리페닐렌 옥사이드를 이용하여 제조된 필름을 제공하는 것이다.Another object of the present invention is to provide a film produced using the modified polyphenylene oxide.
또한, 본 발명의 또 다른 목적은 상기 변성 폴리페닐렌 옥사이드를 포함하는 열경화성 수지 조성물, 프리프레그, 기능성 적층 시트, 및 동박 적층판을 제공하는 것이다.In addition, 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.
본 발명은 하기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드를 제공한다.The present invention provides a modified polyphenylene oxide represented by the following formula (1).
화학식 1
Figure PCTKR2014009034-appb-C000001
 Formula 1
Figure PCTKR2014009034-appb-C000001
(상기 화학식 1에서,(In Formula 1,
n은 1 내지 10,000의 정수이고;n is an integer from 1 to 10,000;
a는 0 내지 4의 정수이고, a가 1 내지 4의 정수인 경우, R1은 C1~C12의 알킬기, 및 C1~C12의 알콕시기로 이루어진 군에서 선택되며;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;
m은 0 또는 1이고;m is 0 or 1;
Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 단일결합이거나, 또는 치환 또는 비치환된 C6~C12의 아릴렌기이고, 이때 Y1 및 Y2의 아릴렌기는 수소, C1~C12의 알킬기, C1~C12의 알콕시기 및 C6~C12의 아릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환될 수 있으며;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;
R2 및 R3는 서로 동일하거나 상이하고, 각각 독립적으로 -OH, -CR4=CH2, -C(=O)CR5=CH2, -NH2,
Figure PCTKR2014009034-appb-I000001
, -C(=O)-R6,
Figure PCTKR2014009034-appb-I000002
, -C(=O)-O-R8 및
Figure PCTKR2014009034-appb-I000003
로 이루어진 군에서 선택되며, R 2 and R 3 are the same as or different from each other, and are each independently —OH, —CR 4 ═CH 2 , —C (═O) CR 5 ═CH 2 , —NH 2 ,
Figure PCTKR2014009034-appb-I000001
, -C (= O) -R 6 ,
Figure PCTKR2014009034-appb-I000002
, -C (= O) -OR 8 and
Figure PCTKR2014009034-appb-I000003
Is selected from the group consisting of
R4 내지 R8은 서로 동일하거나 상이하고, 각각 독립적으로 수소, C1~C12의 알킬기, C1~C12의 알콕시기, 및 C1~C12의 아릴렌기로 이루어진 군에서 선택되고,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,
복수의 W는 서로 동일하거나 상이하고, 각각 독립적으로 수소, C1~C12의 알킬기, C1~C12의 알콕시기 및 C6~C12의 아릴기로 이루어진 군에서 선택되고;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;
Ar은 하기 화학식 2 또는 3으로 표시되는 치환체이고,Ar is a substituent represented by the following formula (2) or (3),
화학식 2
Figure PCTKR2014009034-appb-C000002
 Formula 2
Figure PCTKR2014009034-appb-C000002
화학식 3
Figure PCTKR2014009034-appb-C000003
 Formula 3
Figure PCTKR2014009034-appb-C000003
Q1 내지 Q3는 서로 동일하거나 상이하고, 각각 독립적으로 C1~C12의 알킬기, C1~C12의 알콕시기 및 C1~C12의 할로알킬기로 이루어진 군에서 선택되며, 다만 o가 0인 경우, Q1 및 Q2가 모두 알킬기인 경우는 제외되고,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 및 p는 각각 독립적으로 0 내지 3의 정수임).o and p are each independently an integer from 0 to 3).
또, 본 발명은 전술한 변성 폴리페닐렌 옥사이드를 포함하는 필름을 제공한다.In addition, the present invention provides a film containing the modified polyphenylene oxide described above.
또한, 본 발명은 전술한 변성 폴리페닐렌 옥사이드; 및 가교결합성 경화제를 포함하는 열경화성 수지 조성물을 제공한다.In addition, the present invention is a modified polyphenylene oxide described above; And it provides a thermosetting resin composition comprising a crosslinkable curing agent.
게다가, 본 발명은 섬유 기재; 및 상기 섬유 기재에 함침된 전술한 열경화성 수지 조성물을 포함하는 프리프레그를 제공한다.In addition, the present invention is a fiber substrate; And it provides a prepreg comprising the above-mentioned thermosetting resin composition impregnated in the fiber substrate.
아울러, 본 발명은 금속박 또는 고분자 필름 기재; 및 상기 기재의 일면 또는 양면 상에 형성되고, 상기 열경화성 수지 조성물이 경화된 수지층을 포함하는 기능성 적층 시트를 제공한다.In addition, 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.
그리고, 본 발명은 동박; 및 전술한 프리프레그를 포함하되, 이들이 1층 이상 적층하여 성형된 것이 특징인 동박 적층판을 제공한다.And 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.
본 발명에 따른 변성 폴리페닐렌 옥사이드는 종래 변성 폴리페닐렌 옥사이드에 비해 알킬기 및 방향족고리기의 함량이 증가된 비스페놀 모이어티를 주사슬 내에 함유하면서, 양 말단에 비닐기, 에폭시기, 아민기, 에스테르기 등 극성이 낮은 치환기를 가짐으로써, 에폭시 수지와의 상용성 및 가공성이 우수할 뿐만 아니라, 유전적 특성도 낮다. 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. By having 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.
이하, 본 발명에 대해 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.
본 발명에 따른 변성 폴리페닐렌 옥사이드는 비스페놀 A [4,4'-(propane-2,2-diyl)diphenol]를 이용하여 제조된 종래 변성 폴리페닐렌 옥사이드[예컨대, Noryl (Sabic社)]에 비해, 알킬(alkyl) 함량과 방향족(aromatic) 함량이 높은 비스페놀 구조를 주사슬 내에 함유하면서, 양 말단에 알코올기, 비닐기, 에폭시기, 아민기, 에스테르기 등 극성이 낮은 치환기가 도입되어 있는 고분자로서, 상기 화학식 1로 표시되는 것을 특징으로 한다. 이러한 변성 폴리페닐렌 옥사이드는 종래 변성 폴리페닐렌 옥사이드에 비해 에폭시 수지와의 상용성 및 가공성이 우수하면서, 유전적 특성이 낮다.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]. In contrast, 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. As, characterized in that represented by the formula (1). The modified polyphenylene oxide is excellent in compatibility and processability with epoxy resins and lower in dielectric properties than conventional modified polyphenylene oxide.
구체적으로, 상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드는 알킬(alkyl) 함량과 방향족(aromatic) 함량이 증가된 특정 비스페놀(Bisphenol) 유도체에 의해서 폴리페닐렌 옥사이드를 재분배하여 얻은 양 말단이 알코올기인 고분자이거나, 또는 상기 폴리페닐렌 옥사이드를 재분배한 후 양 말단을 극성이 낮은 치환기(예컨대, 비닐기, 에폭시기, 아민기, 에스테르기 등)로 변형시켜 얻은 고분자로서, 주사슬 내에 상기 비스페놀 유도체로부터 유도된 비스페놀 구조를 함유하고 있고, 양 말단에 알코올기, 비닐기, 에폭시기, 아민기, 또는 에스테르기가 도입되어 있다. Specifically, 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.
상기 비스페놀 유도체는 비스페놀 A에 비해 알킬기 및 방향족고리기의 함량이 높다. 이러한 비스페놀 유도체로부터 유도된 비스페놀 구조가 주사슬 내에 함유됨으로써, 본 발명의 변성 폴리페닐렌 옥사이드는 종래 변성 폴리페닐렌 옥사이드에 비해 에폭시 수지와의 상용성 및 가공성이 향상될 수 있다.The bisphenol derivatives have a higher content of alkyl groups and aromatic ring groups than bisphenol A. By containing the bisphenol structure derived from such a bisphenol derivative in the main chain, 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.
또한, 상기 비스페놀 구조의 알킬(alkyl) 함량 및 방향족(aromatic) 함량이 클수록, 상기 화학식 1의 변성 폴리페닐렌 옥사이드는 전자 분극 현상이 감소하여 유전 특성이 더 감소될 수 있다.In addition, as the alkyl content and aromatic content of the bisphenol structure are larger, the modified polyphenylene oxide of Chemical Formula 1 may further reduce electron polarization, thereby further decreasing dielectric properties.
게다가, 상기 화학식 1의 변성 폴리페닐렌 옥사이드는 분자쇄의 양쪽 말단이 극성이 낮은 치환기, 즉 비닐기, 에폭시기, 아민기, 또는 에스테르기로 개질되어 있다. 따라서, 종래 변성 폴리페닐렉 옥사이드와 달리, 본 발명의 변성 폴리페닐렌 옥사이드는 양 말단의 낮은 극성의 치환기로 인해 에폭시 수지와의 상용성이 향상될 뿐만 아니라, 저유전 특성을 갖는다. In addition, 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.
<변성 폴리페닐렌 옥사이드 및 이의 제조방법><Modified polyphenylene oxide and preparation method thereof>
상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드에서, n은 1 내지 10,000의 정수이고, 바람직하게는 1 내지 1,000의 정수이며, 더욱 바람직하게는 1 내지 100일 수 있다.In the modified polyphenylene oxide represented by Formula 1, n is an integer of 1 to 10,000, preferably an integer of 1 to 1,000, more preferably 1 to 100.
또, 상기 a는 0 내지 4의 정수로, 상기 a가 0이면, 수소가 치환기 R1으로 치환되지 않는 것을 의미하며, 상기 a가 1 내지 4의 정수인 경우, R1은 C1~C12의 알킬기, 및 C1~C12의 알콕시기로 이루어진 군에서 선택되며, 바람직하게는 메틸기, 에틸기, 프로필기, 및 tert-부틸기로 이루어진 군에서 선택될 수 있다.In addition, 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.
또, 상기 m은 0 또는 1이고, 바람직하게는 1일 수 있다.In addition, m is 0 or 1, preferably 1 may be.
또, 상기 Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 단일결합이거나, 또는 치환 또는 비치환된 C6~C12의 아릴렌기이고, 바람직하게는 단일결합 또는 페닐렌기일 수 있다. In addition, 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.
이때, 상기 Y1 및 Y2의 아릴렌기는 수소, C1~C12의 알킬기, C1~C12의 알콕시기 및 C6~C12의 아릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환될 수 있고, 바람직하게는 메틸기, 프로필기 및 tert-부틸기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환될 수 있다.At this time, 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.
또, 상기 R2 및 R3는 서로 동일하거나 상이하고, 각각 독립적으로 -OH, -CR4=CH2, -C(=O)CR5=CH2, -NH2,
Figure PCTKR2014009034-appb-I000004
, -C(=O)-R6,
Figure PCTKR2014009034-appb-I000005
, -C(=O)-O-R8 및
Figure PCTKR2014009034-appb-I000006
로 이루어진 군에서 선택되며, In addition, R 2 and R 3 are the same as or different from each other, and each independently -OH, -CR 4 = CH 2 , -C (= O) CR 5 = CH 2 , -NH 2 ,
Figure PCTKR2014009034-appb-I000004
, -C (= O) -R 6 ,
Figure PCTKR2014009034-appb-I000005
, -C (= O) -OR 8 and
Figure PCTKR2014009034-appb-I000006
Is selected from the group consisting of
상기 R4 내지 R8은 서로 동일하거나 상이하고, 각각 독립적으로 수소, C1~C12의 알킬기, C1~C12의 알콕시기, 및 C1~C12의 아릴렌기로 이루어진 군에서 선택되고,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; ,
복수의 W는 서로 동일하거나 상이하고, 각각 독립적으로 수소, C1~C12의 알킬기, C1~C12의 알콕시기 및 C6~C12의 아릴기로 이루어진 군에서 선택된다.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.
바람직하게는 상기 R2 및 R3는 -OH, -CH=CH2, -C(-CH3)=CH2, -C(=O)CH=CH2, -C(=O)-C(-CH3)=CH2, -NH2,
Figure PCTKR2014009034-appb-I000007
, -C(=O)-CH3,
Figure PCTKR2014009034-appb-I000008
, -C(=O)-O-CH3, 및
Figure PCTKR2014009034-appb-I000009
로 이루어진 군에서 선택될 수 있다.Preferably, the R 2 and R 3 is -OH, -CH = CH 2, -C (-CH 3) = CH 2, -C (= O) CH = CH 2, -C (= O) -C ( -CH 3 ) = CH 2 , -NH 2 ,
Figure PCTKR2014009034-appb-I000007
, -C (= O) -CH 3 ,
Figure PCTKR2014009034-appb-I000008
, -C (= 0) -O-CH 3 , and
Figure PCTKR2014009034-appb-I000009
It may be selected from the group consisting of.
또, 상기 Ar은 비스페놀 A(BPA)를 제외한 비스페놀 유도체로부터 유도된 치환체로서, 상기 화학식 2 또는 3으로 표시되는 치환체이고, 바람직하게는 하기 화학식 2a 내지 화학식 2e, 및 화학식 3a 중 어느 하나로 표시되는 치환체일 수 있으며, 더 바람직하게는 하기 화학식 2aa, 화학식 2ab, 화학식 2ba 및 화학식 3aa 중 어느 하나로 표시되는 치환체일 수 있다. In addition, 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).
[화학식 2a][Formula 2a]
Figure PCTKR2014009034-appb-I000010
(o = 1~3)
Figure PCTKR2014009034-appb-I000010
(o = 1 to 3)
[화학식 2b][Formula 2b]
Figure PCTKR2014009034-appb-I000011
(o=0~3)
Figure PCTKR2014009034-appb-I000011
(o = 0-3)
[화학식 2c][Formula 2c]
Figure PCTKR2014009034-appb-I000012
(o=0~3)
Figure PCTKR2014009034-appb-I000012
(o = 0-3)
[화학식 2d][Formula 2d]
Figure PCTKR2014009034-appb-I000013
(o=0~3)
Figure PCTKR2014009034-appb-I000013
(o = 0-3)
[화학식 2e][Formula 2e]
Figure PCTKR2014009034-appb-I000014
(o=0~3)
Figure PCTKR2014009034-appb-I000014
(o = 0-3)
[화학식 3a][Formula 3a]
Figure PCTKR2014009034-appb-I000015
(p=1~3)
Figure PCTKR2014009034-appb-I000015
(p = 1 to 3)
[화학식 2aa][Formula 2aa]
Figure PCTKR2014009034-appb-I000016
Figure PCTKR2014009034-appb-I000016
[화학식 2ab][Formula 2ab]
Figure PCTKR2014009034-appb-I000017
Figure PCTKR2014009034-appb-I000017
[화학식 2ba][Formula 2ba]
Figure PCTKR2014009034-appb-I000018
Figure PCTKR2014009034-appb-I000018
[화학식 3aa]Formula 3aa]
Figure PCTKR2014009034-appb-I000019
Figure PCTKR2014009034-appb-I000019
상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드의 예로는 하기 화학식 4로 표시되는 변성 폴리페닐렌 옥사이드이 있는데, 이에 한정되지 않는다.Examples of the modified polyphenylene oxide represented by Chemical Formula 1 include a modified polyphenylene oxide represented by the following Chemical Formula 4, but are not limited thereto.
화학식 4
Figure PCTKR2014009034-appb-C000004
 Formula 4
Figure PCTKR2014009034-appb-C000004
상기 화학식 4에서,In Chemical Formula 4,
n, m, Ar, Y1, Y2, R2, 및 R3는 각각 화학식 1에서 정의한 바와 같다.n, m, Ar, Y 1 , Y 2 , R 2 , and R 3 are the same as defined in Chemical Formula 1.
상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드의 구체적인 예로는 하기 화학식 5로 표시되는 변성 폴리페닐렌 옥사이드 내지 화학식 13으로 표시되는 변성 폴리페닐렌 옥사이드 등이 있는데, 이에 한정되지 않는다.Specific examples of the 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.
화학식 5
Figure PCTKR2014009034-appb-C000005
 Formula 5
Figure PCTKR2014009034-appb-C000005
화학식 6
Figure PCTKR2014009034-appb-C000006
 Formula 6
Figure PCTKR2014009034-appb-C000006
화학식 7
Figure PCTKR2014009034-appb-C000007
 Formula 7
Figure PCTKR2014009034-appb-C000007
화학식 8
Figure PCTKR2014009034-appb-C000008
 Formula 8
Figure PCTKR2014009034-appb-C000008
화학식 9
Figure PCTKR2014009034-appb-C000009
 Formula 9
Figure PCTKR2014009034-appb-C000009
화학식 10
Figure PCTKR2014009034-appb-C000010
 Formula 10
Figure PCTKR2014009034-appb-C000010
화학식 11
Figure PCTKR2014009034-appb-C000011
 Formula 11
Figure PCTKR2014009034-appb-C000011
화학식 12
Figure PCTKR2014009034-appb-C000012
 Formula 12
Figure PCTKR2014009034-appb-C000012
화학식 13
Figure PCTKR2014009034-appb-C000013
 Formula 13
Figure PCTKR2014009034-appb-C000013
상기 화학식 5 내지 13에서,In Chemical Formulas 5 to 13,
n, Ar, R6, R7 및 W은 각각 화학식 1에서 정의한 바와 같고,n, Ar, R 6, R 7 and W are the same as defined in Chemical Formula 1,
W1 및 W2는 서로 동일하거나 상이하며, 각각 독립적으로 수소, C1~C12의 알킬기, C1~C12의 알콕시기 및 C6~C12의 아릴기로 이루어진 군에서 선택되고, 바람직하게는 수소, 메틸기, 프로필기, 및 tert-부틸기로 이루어진 군에서 선택될 수 있고, 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 및 b는 각각 0 또는 1이다.a and b are 0 or 1, respectively.
상기 화학식 1의 변성 폴리페닐렌 옥사이드의 대표적인 예로는 다음과 같은 화합물 등이 있는데, 이에 한정되지 않는다.Representative examples of the modified polyphenylene oxide of Chemical Formula 1 include the following compounds, but are not limited thereto.
Figure PCTKR2014009034-appb-I000020
Figure PCTKR2014009034-appb-I000020
Figure PCTKR2014009034-appb-I000021
Figure PCTKR2014009034-appb-I000021
Figure PCTKR2014009034-appb-I000022
Figure PCTKR2014009034-appb-I000022
Figure PCTKR2014009034-appb-I000023
Figure PCTKR2014009034-appb-I000023
Figure PCTKR2014009034-appb-I000024
Figure PCTKR2014009034-appb-I000024
상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드의 중량평균분자량(Mw)은 특별히 한정되지 않으며, 예를 들어 5,000 ~ 100,000 범위, 바람직하게는 3,000 ~ 60,000일 수 있다.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.
본 발명은 전술한 화학식 1의 변성 폴리페닐렌 옥사이드를 제조하는 방법을 제공한다.The present invention provides a method for preparing the modified polyphenylene oxide of the formula (1).
상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드는 알킬(alkyl) 함량과 방향족(aromatic) 함량이 높은 특정 비스페놀(Bisphenol) 유도체를 이용하여 폴리페닐렌 옥사이드를 재분배 반응시켜 제조될 수 있다.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.
일례로, 상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드의 제조방법은 비스페놀 A(BPA)를 제외한 특정 비스페놀 유도체를 이용하여 폴리페닐렌 옥사이드를 재분배 반응시켜 알코올-말단 변성 폴리페닐렌 옥사이드를 형성하는 단계를 포함할 수 있다.In one example, 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.
또는, 상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드는 알킬(alkyl) 함량과 방향족(aromatic) 함량이 높은 특정 비스페놀(Bisphenol) 유도체를 이용하여 폴리페닐렌 옥사이드를 재분배 반응시킨 후, 양쪽 말단에 위치하는 알코올기를 극성이 낮은 치환기(예컨대, 비닐기, 에폭시기, 아민기, 에스테르기 등)로 개질시켜 제조될 수 있다.Alternatively, 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.).
일례로, 상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드의 제조방법은 비스페놀 A(BPA)를 제외한 특정 비스페놀 유도체를 이용하여 폴리페닐렌 옥사이드를 재분배 반응시켜 알코올-말단 변성 폴리페닐렌 옥사이드를 형성하는 단계; 및 상기 알코올-말단 변성 폴리페닐렌 옥사이드의 말단기를 비닐기, 에폭시기, 아민기 또는 에스테르기로 개질시키는 단계를 포함하는데, 이에 한정되지 않는다.In one example, 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.
먼저, 알킬 함량 및 방향족 함량이 높은 특정 비스페놀 유도체(단, 비스페놀 A (BPA) 제외됨)를 이용하여 폴리페닐렌 옥사이드를 재분배 반응시켜 알코올-말단 변성 폴리페닐렌 옥사이드를 형성한다(이하, 'S100 단계'라 함). 상기 S100 단계를 통해 고분자량의 폴리페닐렌 옥사이드가 재분배되어 양 말단에 알코올기를 갖는 저분자량의 폴리페닐렌 옥사이드로 개질될 수 있다.First, 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.
본 발명에서 사용 가능한 비스페놀 유도체는 양 말단에 알코올기(-OH)를 함유하되, 비스페놀 A (BPA)보다 분자 내 알킬 함량 및 방향족 함량이 높은 비스페놀 유도체라면 특별히 한정되지 않는다. 예를 들면, 하기 화학식 14으로 표시되는 비스페놀 유도체, 화학식 15로 표시되는 비스페놀 유도체 등이 있는데, 이에 한정되지 않는다. 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). For example, bisphenol derivatives represented by the following formula (14), bisphenol derivatives represented by the formula (15) and the like, but are not limited thereto.
화학식 14
Figure PCTKR2014009034-appb-C000014
 Formula 14
Figure PCTKR2014009034-appb-C000014
화학식 15
Figure PCTKR2014009034-appb-C000015
 Formula 15
Figure PCTKR2014009034-appb-C000015
상기 화학식 14 및 15에서,In Chemical Formulas 14 and 15,
Q1 내지 Q3는 서로 동일하거나 상이하고, 각각 독립적으로 C1~C12의 알킬기, C1~C12의 알콕시기 및 C1~C12의 할로알킬기로 이루어진 군에서 선택되며, 다만 o가 0인 경우, Q1 및 Q2가 모두 알킬기인 경우는 제외되고,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 및 p는 각각 독립적으로 0 내지 3의 정수이다.o and p are each independently an integer of 0-3.
상기 화학식 14 또는 15로 표시되는 비스페놀 유도체의 예로는 하기 화학식 14a의 비스페놀 유도체 내지 화학식 14e의 비스페놀 유도체, 및 화학식 15a의 비스페놀 유도체 등이 있고, 더 구체적인 예로는 하기 화학식 14aa의 비스페놀 유도체, 화학식 14ab의 비스페놀 유도체, 화학식 14ba의 비스페놀 유도체, 화학식 15aa의 비스페놀 유도체 등이 있는데, 이에 한정되지 않는다. 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.
[화학식 14a][Formula 14a]
Figure PCTKR2014009034-appb-I000025
(o = 1~3)
Figure PCTKR2014009034-appb-I000025
(o = 1 to 3)
[화학식 14b][Formula 14b]
Figure PCTKR2014009034-appb-I000026
(o=0~3)
Figure PCTKR2014009034-appb-I000026
(o = 0-3)
[화학식 14c][Formula 14c]
Figure PCTKR2014009034-appb-I000027
(o=0~3)
Figure PCTKR2014009034-appb-I000027
(o = 0-3)
[화학식 14d][Formula 14d]
Figure PCTKR2014009034-appb-I000028
(o=0~3)
Figure PCTKR2014009034-appb-I000028
(o = 0-3)
[화학식 14e][Formula 14e]
Figure PCTKR2014009034-appb-I000029
(o=0~3)
Figure PCTKR2014009034-appb-I000029
(o = 0-3)
[화학식 15a][Formula 15a]
Figure PCTKR2014009034-appb-I000030
(p=1~3)
Figure PCTKR2014009034-appb-I000030
(p = 1 to 3)
[화학식 14aa][Formula 14aa]
Figure PCTKR2014009034-appb-I000031
Figure PCTKR2014009034-appb-I000031
[화학식 14ab][Formula 14ab]
Figure PCTKR2014009034-appb-I000032
Figure PCTKR2014009034-appb-I000032
[화학식 14ba][Formula 14ba]
Figure PCTKR2014009034-appb-I000033
Figure PCTKR2014009034-appb-I000033
[화학식 15aa][Formula 15aa]
Figure PCTKR2014009034-appb-I000034
Figure PCTKR2014009034-appb-I000034
상기와 같은 비스페놀 유도체의 함량은 특별히 한정되지 않으며, 사용되는 폴리페닐렌 옥사이드의 중량평균분자량이나 재분배시킨 폴리페닐렌 옥사이드의 Target 분자량에 따라 조절하는 것이 바람직하며, 예컨대 폴리페닐렌 옥사이드의 100 중량부를 기준으로 약 10 내지 50 중량부일 수 있다.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.
본 발명에서 사용 가능한 폴리페닐렌 옥사이드는 당 업계에 알려진 폴리페닐렌 옥사이드라면 특별히 제한되지 않으며, 예를 들어 하기 화학식 16으로 표시되는 폴리페닐렌 옥사이드 등일 수 있고, 구체적인 예로는 하기 화학식 16a로 표시되는 폴리페닐렌 옥사이드 등이 있으며, 더 구체적인 예로는 Sabic社의 Noryl, SA-120 등이 있는데, 이에 한정되지 않는다.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.
화학식 16
Figure PCTKR2014009034-appb-C000016
 Formula 16
Figure PCTKR2014009034-appb-C000016
상기 화학식 16에서,In Chemical Formula 16,
a는 0 내지 4의 정수이고, a가 1 내지 4의 정수인 경우, R1은 C1~C12의 알킬기 및 C1~C12의 알콕시기로 이루어진 군에서 선택되고, 바람직하게는 메틸기, 에틸기, 프로필기 및 tert-부틸기로 이루어진 군에서 선택될 수 있으며,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,
n은 1 ~ 3,000의 정수이다.n is an integer of 1 to 3,000.
[화학식 16a][Formula 16a]
Figure PCTKR2014009034-appb-I000035
Figure PCTKR2014009034-appb-I000035
상기 화학식 16a에서, In Chemical Formula 16a,
n은 1 ~ 3,000의 정수이다. n is an integer of 1 to 3,000.
상기 폴리페닐렌 옥사이드의 중량평균분자량(Mw)은 특별히 한정되지 않으며, 예컨대 2,000 ~ 350,000일 수 있다. The weight average molecular weight (Mw) of the polyphenylene oxide is not particularly limited, and may be, for example, 2,000 to 350,000.
상기 폴리페닐렌 옥사이드의 함량은 특별히 한정되지 않으며, 반응 혼합물(폴리페닐렌 옥사이드, 비스페놀 유도체, 라디칼 개시제 및 용매 포함) 100 중량부를 기준으로 약 1 내지 75 중량부, 바람직하게는 10 내지 40 중량부일 수 있다.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.
상기 S100 단계의 재분배 반응은 라디칼 개시제 및/또는 용매의 존재하에서 이루어질 수 있다. 상기 라디칼 개시제를 이용할 경우, 상기 폴리페닐렌 옥사이드와 비스페놀 유도체 간의 재분배 반응이 개시됨과 동시에 촉진되어 반응 속도를 향상시킬 수 있다.The redistribution reaction of step S100 may be performed in the presence of a radical initiator and / or a solvent. When the radical initiator is used, the redistribution reaction between the polyphenylene oxide and the bisphenol derivative is initiated and promoted to improve the reaction rate.
본 발명에서 사용 가능한 라디칼 개시제로는 당 업계에 알려진 라디칼 개시제라면 특별히 한정되지 않으며, 예컨대 벤조일 퍼옥시드 등과 같은 과산화물; 3,3',5,5'-테트라메틸-1,4-디페노퀴논 등과 같은 퀴논 화합물; 전이 금속 및 아민을 함유하는 착체 등이 있는데, 이에 한정되지 않는다.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.
이러한 라디칼 개시제의 함량은 특별히 한정되지 않으나, 반응물의 함량, 재분배 반응 속도 등을 고려하여 조절하는 것이 적절하며, 예컨대 폴리페닐렌 옥사이드 100 중량부를 기준으로 0 내지 10 중량부일 수 있고, 바람직하게는 1 내지 10 중량부일 수 있다.Although 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.
또, 본 발명에서 사용 가능한 용매는 당 업계에서 통상적으로 사용하고 있는 용매이면 특별히 제한하지 않는다. 상기 용매의 비제한적인 예로는 메탄올, 에탄올, 프로판올, 이소프로판올, 부탄올, 이소부탄올, 펜탄올, 헥산올 등의 알코올계 용매; 벤젠, 에틸벤젠, 클로로벤젠, 톨루엔, 자일렌 등의 방향족 탄화수소 용매 등이 있으며, 이들은 단독으로 또는 2종 이상이 혼합되어 사용될 수 있다. 바람직하게는 톨루엔, 또는 톨루엔과 메탄올의 혼합 등일 수 있다. 일례에 따르면, 톨루엔과 메탄올을 혼합하여 사용할 경우, 톨루엔과 메탄올의 혼합 비율은 톨루엔 : 메탄올 = 1 : 0.01 ~ 1 : 0.5 부피 비율일 수 있다.In addition, the solvent which can be used by this invention will not be restrict | limited especially if it is a solvent normally used in the art. 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. Preferably, it may be toluene or a mixture of toluene and methanol. According to an example, when toluene and methanol are mixed and used, the mixing ratio of toluene and methanol may be a volume ratio of toluene: methanol = 1: 0.01 to 1: 0.5.
상기 재분배 반응의 온도는 특별히 한정되지 않으나, 약 20 내지 150 ℃, 바람직하게는 60 내지 80 ℃일 경우, 반응속도가 향상될 수 있다.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.
일례에 따르면, 전술한 반응물, 라디칼 개시제 및 용매를 이용하여 S100 단계를 수행하면, 양 말단이 알코올기인 상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드, 즉 하기 화학식 17로 표시되는 알코올-말단 변성 폴리페닐렌 옥사이드를 얻을 수 있다.According to one embodiment, when performing the step S100 using the above-described reactant, radical initiator and solvent, the modified polyphenylene oxide represented by the formula (1), both ends of the alcohol group, that is, the alcohol-terminal modified poly represented by the following formula (17) Phenylene oxide can be obtained.
화학식 17
Figure PCTKR2014009034-appb-C000017
 Formula 17
Figure PCTKR2014009034-appb-C000017
상기 화학식 17에서,In Chemical Formula 17,
a, R1, Ar, n은 각각 화학식 1에서 정의한 바와 같다.a, R 1 , Ar, n are as defined in the formula (1), respectively.
상기 화학식 17로 표시되는 알코올-말단 변성 폴리페닐렌 옥사이드의 중량평균분자량은 사용된 폴리페닐렌 옥사이드의 중량평균분자량 등에 따라 달라지며, 예를 들어 2,000 내지 20,000 범위일 수 있다. 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.
이후, 상기 S100 단계에서 얻은 알코올-말단 변성 폴리페닐렌 옥사이드의 양 말단기를 비닐기, 에폭시기, 아민기 또는 에스테르기로 개질시킨다(이하, 'S200 단계'). 상기 S200 단계를 통해 상기 알코올-말단 변성 폴리페닐렌 옥사이드의 양 말단에 위치하는 알코올기 대신에 극성이 낮은 치환기, 예컨대 비닐기, 에폭시기, 아민기 또는 에스테르기가 도입됨으로써, 상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드를 얻을 수 있다.Thereafter, 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'). Through the 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.
상기 S200 단계는 당 업계에서 알코올기 대신 비닐기, 에폭시기, 아민기 또는 에스테르기를 도입하는 다양한 반응을 통해 행해질 수 있다.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.
일례에 따르면, 상기 S200 단계는 상기 S100 단계에서 얻은 알코올-말단 변성 폴리페닐렌 옥사이드를 방향족 탄화수소 용매에서 염기성 촉매의 존재하에 산무수물과 반응시켜 알코올-말단 변성 폴리페닐렌 옥사이드의 양 말단기를 비닐기로 개질시키는 단계를 포함한다. According to an example, 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.
상기 방향족 탄화수소 용매의 예로는 톨루엔, 벤젠, 에틸벤젠, 클로로벤젠, 자일렌 등이 있는데, 이에 한정되지 않는다.Examples of the aromatic hydrocarbon solvent include toluene, benzene, ethylbenzene, chlorobenzene, xylene, and the like, but are not limited thereto.
상기 염기성 촉매의 예로는 디메틸아미노피리딘, 트리페닐포스핀, 트리페닐안티몬 등이 있는데, 이에 한정되지 않는다.Examples of the basic catalyst include, but are not limited to, dimethylaminopyridine, triphenylphosphine, triphenylantimony, and the like.
이러한 염기성 촉매의 함량은 특별히 한정되지 않으나, 알코올-말단 변성 폴리페닐렌 옥사이드 100 중량부)를 기준으로 1 ~ 20 중량부일 수 있다.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).
상기 산무수물의 예로는 메타크릴산 무수물(methacrylic anhydride), 아크릴산 무수물 등이 있는데, 이에 한정되지 않는다.Examples of the acid anhydride include methacrylic anhydride, acrylic anhydride, and the like, but is not limited thereto.
이러한 산무수물(a)과 상기 알코올-말단 변성 폴리페닐렌 옥사이드(b)의 혼합 비율은 특별히 한정되지 않으나, 산무수물의 종류 등을 고려하여 조절하는 것이 바람직하며, 예를 들어 a : b = 10 ~ 40 : 100 중량 비율일 수 있다.The mixing ratio of the acid anhydride (a) and the alcohol-terminal modified polyphenylene oxide (b) is not particularly limited, but is preferably adjusted in consideration of the type of acid anhydride, for example, a: b = 10 40 to 100 weight ratio.
다른 일례에 따르면, 상기 S200 단계는 상기 S100 단계에서 얻은 알코올-말단 변성 폴리페닐렌 옥사이드 및 에피클로로하이드린(epichlorohydrin)을 가열하여 용해시킨 다음 알칼리금속수산화물의 존재하에서 반응시켜 알코올-말단 변성 폴리페닐렌 옥사이드의 양 말단기를 에폭시기로 개질시키는 단계를 포함한다.According to another example, 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.
상기 알코올-말단 변성 폴리페닐렌 옥사이드(a) 및 에피클로로하이드린(b)의 혼합 비율은 특별히 한정되지 않으며, 예를 들어 a : b = 100 : 10 ~ 40 중량 비율일 수 있다.The mixing ratio of the alcohol-terminated modified polyphenylene oxide (a) and epichlorohydrin (b) is not particularly limited, and may be, for example, a: b = 100: 10 to 40 weight ratio.
상기 알칼리금속수산화물의 비제한적인 예로는 수산화나트륨, 수산화칼륨 등이 있다.Non-limiting examples of the alkali metal hydroxide is sodium hydroxide, potassium hydroxide and the like.
이러한 알칼리금속수산화물의 함량은 특별히 한정되지 않으며, 예컨대 알코올-말단 변성 폴리페닐렌 옥사이드 100 중량부를 기준으로 1 ~ 10 중량부일 수 있다.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.
또 다른 일례에 따르면, 상기 S200 단계는 상기 S100 단계에서 얻은 알코올-말단 변성 폴리페닐렌 옥사이드를 디메틸포름아마이드 용액에서 탄산칼륨의 존재하에 1,3-디나이트로벤젠과 반응시켜 제1 반응물을 형성하는 단계; 상기 제1 반응물을 메탄올로 침전시키는 단계; 및 2-메톡시에탄올에서 상기 침전물을 수소 분위기하에서 Pt/C 및 트리에틸아민과 반응시키는 단계를 포함하며, 이러한 단계들을 통해 상기 알코올-말단 변성 폴리페닐렌 옥사이드의 양 말단기를 아민기로 개질시킬 수 있다.According to another example, in 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.
또 다른 일례에 따르면, 상기 S100 단계에서 얻은 알코올-말단 변성 폴리페닐렌 옥사이드를 메틸 4-클로로카보닐벤조에이트와 함께 가열하여 용해시켜 반응 용액을 형성하는 단계; 및 상기 반응 용액에 트라이에틸아민을 첨가하여 반응시켜 알코올-말단 변성 폴리페닐렌 옥사이드의 양 말단기를 에스테르기로 개질시키는 단계를 포함할 수 있다.According to another example, 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.
<변성 폴리페닐렌 옥사이드 필름><Modified polyphenylene oxide film>
한편, 본 발명은 전술한 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드를 포함하는 필름을 제공한다. On the other hand, the present invention provides a film containing the modified polyphenylene oxide represented by the above formula (1).
상기 화학식 1의 변성 폴리페닐렌 옥사이드의 유전 특성이 낮기 때문에, 상기 필름은 동박 적층판의 절연층 등으로 이용될 수 있다.Since the dielectric properties of the modified polyphenylene oxide of Formula 1 are low, the film may be used as an insulating layer of a copper foil laminate.
또, 상기 필름은 상기 화학식 1의 변성 폴리페닐렌 옥사이드 이외, 에폭시 수지를 더 포함할 수 있다. 이때, 상기 화학식 1의 변성 폴리페닐렌 옥사이드가 에폭시 수지와의 상용성이 우수하기 때문에, 다양한 용도로 사용될 수 있다.In addition, the film may further include an epoxy resin in addition to the modified polyphenylene oxide of Chemical Formula 1. At this time, since the modified polyphenylene oxide of Formula 1 is excellent in compatibility with the epoxy resin, it can be used in various applications.
<열경화성 수지 조성물><Thermosetting resin composition>
한편, 본 발명은 전술한 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드; 및 가교결합성 경화제를 포함하는 열경화성 수지 조성물을 제공한다.On the other hand, 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.
필요에 따라, 상기 열경화성 수지 조성물은 시아네이트 수지, 에폭시 수지, 난연제, 무기 필러, 경화촉진제, 라디칼 개시제, 용매 등을 더 포함할 수 있다. If necessary, the 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.
상기 가교결합성(cross-linking) 경화제는 상기 화학식 1의 변성 폴리페닐렌 옥사이드를 3차원적으로 가교결합시켜 망상구조를 형성하기 위해 사용되는 것이다. 레진 조성물의 유동성을 증가시키기 위해 저분자량으로 개질된 변성 폴리페닐렌 옥사이드를 사용하더라도, 가교결합성 경화제 사용으로 인해 변성 폴리페닐렌 옥사이드의 내열성 개선에 기여하게 된다. 또한, 수지 조성물의 유동성을 증가시키며 다른 기재(예, 구리 호일)와의 박리 강도를 향상시키는 효과를 갖는다.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).
본 발명에서 사용 가능한 가교결합성 경화제는 말단이 알코올기, 비닐기기, 에폭시기, 아민기 또는 에스테르기인 변성 폴리페닐렌 옥사이드와 우수한 혼화성을 갖는 것이 바람직하다. 비제한적인 예로는 비닐벤질옥사이드 화합물 계열의 디비닐벤젠(Divinylbenzene), 디비닐나프탈렌, 디비닐디페닐, 스티렌모노머, 페놀 및 알릴클로라이드의 반응으로 제조된 알릴옥사이드 화합물; 트리알릴이소시아누레이트 (TAIC), 트리알리시아누레이트 (TAC), 1,2,4-트리바이닐 사이클로헥산, 1,7-옥타디엔, 1,9-데카디엔 등의 디엔계열, 다이-4-바이닐벤질 옥사이드 등이 있다. 이때 전술한 경화제를 단독 사용하거나 또는 2종 이상 혼용할 수도 있다. 이들은 융합성(compatibility)이 뛰어날 뿐만 아니라, 성형성이 우수하고 작은 유전 상수값과 뛰어난 내열성 및 신뢰성을 갖도록 해 주기 때문에 바람직하다.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. At this time, the above-mentioned hardening | 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 heat resistance and reliability.
본 발명에서는 전술한 가교결합성 경화제의 적절한 혼용 및 최적화된 함량 조절을 통해 저유전 특성뿐만 아니라 다양한 물성과 가공성을 극대화할 수 있다. In the present invention, it is possible to maximize various physical properties and processability as well as low dielectric properties through appropriate mixing and optimized content control of the aforementioned crosslinkable curing agent.
본 발명에 따른 열경화성 수지 조성물에서, 상기 가교결합성 경화제의 함량은 변성 폴리페닐렌옥사이드 수지 100 중량부 기준으로 하여, 5 내지 50 중량부 범위일 수 있으며, 바람직하게는 10 내지 40 중량부 범위일 수 있다. 상기 가교 결합성 경화제의 함량이 전술한 범위에 해당되는 경우, 수지 조성물의 경화성, 성형 가공성 및 접착력이 양호하다.In the thermosetting resin composition according to the present invention, 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. When 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.
또, 본 발명에 따른 열경화성 수지 조성물은, 필요에 따라 난연제를 더 포함할 수 있다. Moreover, the thermosetting resin composition which concerns on this invention can further contain a flame retardant as needed.
상기 난연제는 당업계에 알려진 통상적인 난연제를 제한 없이 사용할 수 있으며, 일례로 브롬이나 염소를 함유하는 할로겐 난연제, 트리페닐포스페이트, 트리케실포스페이트, 트리스디크로로프로필로스페이트, 포스파젠 등의 인계 난연제, 삼산화안티몬 등의 안티몬계 난연제, 수산화알루니늄, 수산화마그네슘 등의 무기물의 난연제 등을 들 수 있다. 본 발명에서는 변성 폴리페닐렌 옥사이드와 반응성이 없으며 내열 특성 및 유전 특성에 저하를 주지 않는 첨가형 브롬 난연제가 적합하다. 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. In the present invention, an additive bromine flame retardant which is not reactive with modified polyphenylene oxide and does not degrade heat resistance and dielectric properties is suitable.
본 발명에서 브롬화 난연제는 브로모프탈이미드(Bromophthalimide), 브로모페닐(Bromophenyl) 첨가형 브롬 난연제나 혹은 Allyl terminated 되어진 형태의 테트라브로모비스페놀 A (Tetrabromo bisphenol A) Allyl ether, 디바이닐페놀 (Divinylphenol) 형태의 난연성 경화제를 사용하여 경화제의 특성과 난연 특성을 동시에 얻을 수 있다. 또한 브롬화 유기화합물도 사용할 수 있는데, 이의 구체예로는, 디카브로모디페닐(decabromodiphenyl) 에탄(ethane), 4,4-디브로모비페닐, 에틸렌 비스테트라브로모프탈리미드(ethylenbistetrabromophthalimide) 등이 있다. In the present invention, 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.
본 발명에 따른 열경화성 수지 조성물에서, 상기 난연제의 함량은 변성 폴리페닐렌옥사이드 수지 100 중량부 기준으로 하여, 5 내지 50 중량부 범위일 수 있으며, 바람직하게는 10 내지 40 중량부 범위일 수 있다. 상기 난연제가 상기 범위로 포함되면 난연 94V-0 수준의 화염 저항성을 충분히 가질 수 있으며, 우수한 열저항성과 전기적 특성을 나타낼 수 있다. 상기 난연제는 브롬화 유기화합물인 것이 바람직하다. In the thermosetting resin composition according to the present invention, 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. When the flame retardant is included in the above range, it 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.
또, 본 발명에 따른 열경화성 수지 조성물은, 필요에 따라 라미네이트에 사용되는 당 업계에 알려진 통상적인 무기 필러를 더 포함할 수 있다. In addition, the thermosetting resin composition according to the present invention may further include a conventional inorganic filler known in the art used for lamination, if necessary.
상기 무기 필러는 수지층과 다른 층간의 열팽창계수(CTE) 차이를 감소시켜 최종 제품의 휨 특성, 저팽창화, 기계적 강도(toughness), 저응력화를 효과적으로 향상시킬 수 있다. 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.
본 발명에서 사용 가능한 무기 필러의 비제한적인 예로는, 천연 실리카(natural silica), 용융 실리카(Fused silica), 비결정질 실리카(amorphous silica), 결정 실리카(crystalline silica) 등과 같은 실리카류; 보에마이트(boehmite), 알루미나, 탈크(Talc), 구형 유리, 탄산칼슘, 탄산마그네슘, 마그네시아, 클레이, 규산칼슘, 산화티탄, 산화안티몬, 유리섬유, 붕산알루미늄, 티탄산바륨, 티탄산스트론튬, 티탄산칼슘, 티탄산마그네슘, 티탄산비스무스, 산화티탄, 지르콘산바륨, 지르콘산칼슘, 질화붕소, 질화규소, 활석(talc), 운모(mica) 등이 포함된다. 이러한 무기 필러는 단독 또는 2개 이상으로 혼용하여 사용될 수 있다. 이러한 무기 필러 중에서, 낮은 열팽창계수를 나타내는 용융 실리카가 가장 바람직하다. 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.
본 발명에서 무기 필러의 크기는 특별히 제한되지 않으나, 평균 입경이 0.5~5 ㎛ 범위가 분산성에서 유리하다. 또한, 상기 무기 필러의 함량은 특별한 제한이 없으며, 전술한 휨특성, 기계적 물성 등을 고려하여 적절히 조절할 수 있다. 일례로, 변성 폴리페닐렌옥사이드 수지 100 중량부를 기준으로 하여, 5 내지 90 중량부 범위일 수 있으며, 바람직하게는 30 내지 80 중량부 범위일 수 있다. 상기 무기 필러의 함량이 과도하게 되면 성형성에 불리할 수 있다.In the present invention, the size of the inorganic filler is not particularly limited, but an average particle diameter in the range of 0.5 to 5 μm is advantageous in dispersibility. In addition, 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.
또, 본 발명에 따른 열경화성 수지 조성물은, 가교 결합성 경화제의 유리한 효과를 강화하기 위해 반응 개시제를 더 포함할 수 있다. In addition, the 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.
이러한 반응 개시제는 변성 폴리페닐렌 옥사이드와 가교결합성 경화제의 경화를 더 가속시킬 수 있으며, 레진의 내열성 등의 특성을 증가시킬 수 있다. 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.
사용 가능한 반응개시제의 비제한적인 예로는 α,α′-비스(t-부틸퍼옥시-m-이소프로필)벤젠, 2,5-디메틸-2,5-디(t-부틸 퍼옥시)-3-헥신(hexyne), 벤조일퍼옥사이드, 3,3′,5,5′-테트라메틸-1,4-디페녹시퀴논, 클로라닐, 2,4,6-트리-t -부틸페녹실, t-부틸퍼옥시이소프로필 모노카르보네이트, 아조비시스이소부틸로니트릴 (azobisisobutylonitrile) 등이 있다. 추가로 금속 카르복실레이트 염을 더 사용할 수도 있다. 상기 반응 개시제는 변성 폴리페닐렌옥사이드 100 중량부에 대해 2 ~ 5 중량부로 포함될 수 있으나, 이에 제한되는 것은 아니다. Non-limiting examples of reaction initiators that can be used include α, α′-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. In addition, 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.
또한, 본 발명의 열경화성 수지 조성물은 경화촉진제를 추가로 포함할 수 있다. 상기 경화촉진제는 철, 구리, 아연, 코발트, 납, 니켈, 망간 및 주석으로 이루어진 군에서 선택된 1종 이상의 금속을 포함하는 유기 금속 염 또는 유기 금속 착물을 사용할 수 있다. In addition, the 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.
상기 유기 금속 염 또는 유기 금속 착물의 예로는 철 나프테네이트(napthenates), 구리 나프테네이트, 아연 나프테네이트, 코발트 나프테네이트, 니켈 나프테네이트, 망간 나프테네이트, 주석 나프테네이트, 아연 옥타노에이트(octanoate), 주석 옥타노에이트, 철 옥타노에이트, 구리 옥타노에이트, 아연 2-에틸헥사네이트, 납 아세틸아세토네이트, 코발트 아세틸아세토네이트, 또는 디부틸주석 말레이트 등이 있으나, 이에 한정되는 것은 아니다. 또한, 이들은 1종 또는 2종 이상 혼합하여 사용할 수 있다. 상기 경화 촉진제는 변성 폴리페닐렌옥사이드 10~60 중량부에 대해 0.01~1 중량부로 포함될 수 있으나, 이에 제한되는 것은 아니다. Examples of such organometallic salts or organometallic complexes 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.
또한, 본 발명의 열경화성 수지 조성물은 당 업계에 알려진 통상적인 러버(rubber)를 추가로 포함할 수 있다.In addition, the thermosetting resin composition of the present invention may further include a conventional rubber (rubber) known in the art.
전술한 성분 이외에, 본 발명의 열경화성 수지 조성물은 상기 수지 조성물의 고유 특성을 해하지 않는 한, 필요에 따라 당 업계에 일반적으로 알려진 난연제나, 상기에서 기재되지 않은 다른 열경화성 수지나 열가소성 수지 및 이들의 올리고머와 같은 다양한 고분자, 고체상 고무 입자 또는 자외선 흡수제, 항산화제, 중합개시제, 염료, 안료, 분산제, 증점제, 레벨링제 등과 같은 기타 첨가제 등을 추가로 포함할 수 있다. 일례로, 실리콘계 파우더, 나일론 파우더, 불소수지 파우더 등의 유기충전제, 오르벤, 벤톤 등의 증점제; 실리콘계, 불소수지계 등의 고분자계 소포제 또는 레벨링제; 이미다졸계, 티아졸계, 트리아졸계, 실란계 커플링제 등의 밀착성 부여제; 프탈로시아닌, 카본 블랙 등이 착색제 등을 들 수 있다. In addition to the above-mentioned components, the 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. For example, 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.
상기 열 경화성 수지 조성물에는 경화 후의 수지 조성물에 적당한 가요성을 부여하는 것 등을 목적으로 하여, 열가소성 수지를 배합할 수 있다. 이러한 열가소성 수지의 예를 들면, 시아네이트 수지, 에폭시 수지, 페녹시 수지, 폴리비닐아세탈 수지, 폴리이미드, 폴리아미드이미드, 폴리옥사이드설폰, 폴리설폰 등을 들 수 있다. 이들의 열가소성 수지는 어느 1종만을 단독으로 사용하여도 좋고, 2종 이상을 병용하여도 좋다.A thermoplastic resin can be mix | blended with the said thermosetting resin composition for the purpose of providing suitable flexibility to the resin composition after hardening, etc. Examples of such a 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.
상기 수지 첨가제로는, 실리콘 파우더, 나일론 파우더, 불소 파우더 등의 유기 충전제; 올벤, 벤톤 등의 증점제; 실리콘계, 불소계, 고분자계의 소포제 또는 레벨링제; 이미다졸계, 티아졸계, 트리아졸계, 실란 커플링제, 에폭시실란, 아미노실란, 알킬실란, 머캡토실란 등의 밀착성 부여제; 프탈로시아닌ㆍ블루, 프탈로시아닌ㆍ그린, 아이오딘ㆍ그린, 디스아조 옐로우, 카본 블랙 등의 착색제; 고급 지방산, 고급 지방산 금속염, 에스테르계 왁스 등의 이형제; 변성 실리콘 오일, 실리콘 파우더, 실리콘 레진 등의 응력 완화제 등이 있다. 또한, 전자 기기(특히, 인쇄 배선 기판)의 생산에 사용되는 열경화성 수지 조성물에 통상적으로 사용되는 첨가제들을 포함할 수 있다.As said resin additive, 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).
본 발명의 바람직한 일례에 따르면, 상기 열경화성 수지 조성물은 (a) 상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드 수지; 상기 변성 폴리페닐렌 옥사이드 수지 100 중량부를 기준으로 (b) 가교결합성 경화제 5~50 중량부 (c) 난연제 5~50 중량부; 및 (d) 무기필러 5~90 중량부 범위로 포함하여 구성될 수 있다. 이때, 상기 구성성분의 기준은 조성물 전체 중량일 수 있으며, 또는 유기용제가 포함된 바니쉬 전체 중량일수도 있다. According to a preferred embodiment of the present invention, 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.
상기 유기용제는 당 업계에 알려진 통상적인 유기용제를 제한 없이 사용할 수 있으며, 일례로 아세톤, 사이클로헥사논, 메틸에틸케톤, 톨루엔, 크실렌, 테트라히드로푸란 등 등 다양한 유기 용제를 임의로 혼용 사용할 수 있다. 여기서, 유기용제의 함량은 전술한 조성물의 조성비를 이용하여 바니쉬 전체 100 중량부를 만족시키는 잔량의 범위일 수 있으며, 특별히 제한되지 않는다. 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. Here, 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.
<프리프레그><Prepreg>
본 발명에 따른 프리프레그는, 섬유 기재 및 상기 섬유 기재에 함침된 전술한 열경화성 수지 조성물을 포함한다. 여기서, 상기 열경화성 수지 조성물은 용매에 용해되거나 분산된 형태의 수지 바니쉬일 수도 있다.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. Here, the thermosetting resin composition may be a resin varnish dissolved or dispersed in a solvent.
상기 섬유 기재는 임의로 절곡 가능한, 가요성을 갖는 당 업계의 통상적인 무기물 섬유기재, 유기물 섬유기재, 또는 이들의 혼합 형태 등을 사용할 수 있다. 사용하는 용도 또는 성능을 기준으로, 전술한 섬유기재를 선택하면 된다.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.
본 발명에서 사용 기재의 예로는 E-glass, D-glass, S-glass, NE-glass, T-glass 및 Q-glass 등의 무기물 섬유, 폴리이미드, 폴리아미드, 폴리에스테르 등의 유기물의 섬유 및 혼합물등이 있으며, 사용하는 용도 또는 성능을 기준으로 선택하면 된다.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.
사용 가능한 섬유 기재의 비제한적인 예를 들면, E-glass, D-glass, S-glass, NE-glass, T-glass, Q-glass 등과 같은 유리 섬유 (무기물 섬유); 유리 페이퍼, 유리 섬유 부직포 (glass web), 유리 직물(glass cloth), 아라미드 섬유, 아라미드 페이퍼(aramid paper), 폴리이미드, 폴리아미드, 폴리에스터, 방향족 폴리에스테르, 불소 수지 등과 같은 유기 섬유; 탄소 섬유, 종이, 무기 섬유 또는 이들의 1종 이상의 혼합 형태 등이 있다. 상기 섬유 기재의 형태는 전술한 섬유 등으로 이루어진 직포나 부직포; 로빙(roving), 촙프트 스트랜드 매트(choPPOd strand mat), 서페이싱 매트(surfacing mat), 금속 섬유, 카본 섬유, 광물 섬유 등으로 이루어진 직포, 부직포, 매트류 등을 들 수 있다. 이들 기재는 단독 또는 2종 이상 혼용할 수 있다. 강화된 섬유기재를 혼용하는 경우 프리프레그의 강성, 치수 안정성을 향상시킬 수 있다. 이러한 섬유 기재의 두께는 특별히 한정되지 않으며, 예를 들어 약 0.01 ㎜ 내지 0.3 ㎜ 범위일 수 있다.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. which consist of roving, a choPPOd strand mat, a surfacing mat, metal fiber, carbon fiber, mineral fiber, etc. are mentioned. These base materials can be used individually or in mixture of 2 or more types. When the reinforced fiber base is mixed, the stiffness and dimensional stability of the prepreg can be improved. The thickness of this fibrous substrate is not particularly limited and may be, for example, in the range of about 0.01 mm to 0.3 mm.
상기 수지 조성물은 프리프레그 형성에 사용되는 것으로서, 전술한 본 발명의 열경화성 수지 조성물을 사용할 수 있다.The said resin composition is used for prepreg formation, The thermosetting resin composition of this invention mentioned above can be used.
일반적으로 프리프레그는, 섬유 기재에 열경화성 수지 조성물을 코팅 또는 함침시킨 후, 가열에 의해 B-stage(반경화 상태)까지 경화시켜 얻은 시트 형상의 재료를 지칭한다. 전술한 방법 이외에, 본 발명의 프리프레그는 당 업계에 알려진 공지의 핫멜트법, 솔벤트법 등에 의해 제조될 수 있다. In general, 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. In addition to the above-described method, 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.
솔벤트법은 프리프레그 형성용 열경화성 수지 조성물을 유기 용매에 용해시켜 형성된 수지 조성물 바니쉬에 섬유 기재를 함침시킨 후 건조하는 방법이다. 이러한 솔벤트법을 채용하는 경우 일반적으로 수지 바니쉬를 이용한다. 상기 수지 조성물을 섬유 기재에 함침시키는 방법의 일례를 들면, 기재를 수지 바니시에 침지하는 방법, 수지 바니시를 각종 코터에 의해 기재에 도포하는 방법, 수지 바니시를 스프레이에 의해 기재에 분사하는 방법 등을 들 수 있다. 이때, 섬유 기재를 수지 바니시에 침지하는 경우 섬유 기재에 대한 수지 조성물의 함침성을 향상시킬 수 있어 바람직하다. 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. In the case of employing such a solvent method, a resin varnish is generally used. Examples of 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. At this time, when 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.
상기 수지 조성물 바니쉬를 조제하는 경우 유기 용제의 예를 들면, 아세톤, 메틸에틸케톤, 시클로헥사논 등의 케톤류, 아세트산에틸, 아세트산부틸, 셀로솔브아세테이트, 프로필렌글리콜모노메틸옥사이드아세테이트, 카비톨아세테이트 등의 아세트산 에스테르류, 셀로솔브, 부틸카비톨 등의 카비톨류, 톨루엔, 크실렌 등의 방향족 탄화수소류, 디메틸포름아미드, 디메틸아세트아미드, N-메틸피롤리돈, 테트라히드로푸란 등을 들 수 있다. 유기 용제는 1종을 사용하거나 2종 이상을 조합하여 사용하여도 좋다.When preparing the said resin composition varnish, For example, 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.
또한 핫멜트법은 수지 조성물을 유기 용매에 용해하지 않고, 수지 조성물과 박리성이 우수한 이형지에 코팅한 후 이를 시트상 섬유 기재에 라미네이트하거나, 또는 다이 코터에 의해 직접 도공하는 방법일 수 있다. 또한, 지지체 위에 적층된 열 경화성 수지 조성물로 이루어지는 접착 필름을 시트상 보강 기재의 양면으로부터 가열, 가압 조건 하에서 연속적으로 열라미네이트함으로써 제조될 수도 있다.In addition, 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. Moreover, 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.
본 발명의 수지 조성물은, 섬유로 이루어지는 시트상 섬유 기재나 글라스 기재에 당해 수지 조성물을 코팅 또는 함침시키고, 가열에 의해 반경화시킴으로써 프리프레그로 제조될 수 있다. 바람직하게는 인쇄회로기판용 프리프레그이다. 이때 상기 수지 조성물은 수지 바니쉬로 조제된 것일 수 있다. 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. Preferably it is a prepreg for printed circuit boards. At this time, the resin composition may be prepared by a resin varnish.
본 발명의 프리프레그는 상기 기재에 코팅 또는 함침한 후, 추가적으로 건조 과정을 거쳐 형성될 수 있고, 이때 상기 건조는 20 내지 200℃에서 이루어질 수 있다. 일례로, 본 발명의 프리프레그는 상기 열경화성 수지 조성물 바니쉬에 기재를 함침시키고 70~170℃, 1~10 분 동안 가열 건조함으로써, 반경화 (B-Stage) 상태의 프리프레그를 제조할 수 있다.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. As an example, 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 ℃, 1 to 10 minutes.
<기능성 적층 시트><Functional laminated sheet>
본 발명은 금속박 또는 고분자 필름 기재; 및 상기 기재의 일면 또는 양면 상에 형성되고, 상기 열경화성 수지 조성물이 경화된 수지층을 포함하는 기능성 적층 시트를 제공한다.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.
일례로, 금속박; 및 상기 금속박의 일면 또는 양면 상에 형성되고, 상기 열경화성 수지 조성물이 경화된 수지층을 포함하는 수지 부착 동박이 있다.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.
상기 금속박은 당업계에 알려진 통상의 금속 또는 합금으로 이루어진 것을 제한 없이 사용할 수 있다. 이때 상기 금속박이 동박인 경우, 본 발명에 따른 열경화성 수지 조성물을 코팅하고 건조하여 형성된 적층판을 동박 적층판으로 사용할 수 있다. 바람직하게는 동박이다. The metal foil can be used without limitation those made of conventional metals or alloys known in the art. At this time, when 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. Preferably it is copper foil.
상기 동박은 압연법 및 전해법으로 제조되는 모든 동박을 포함한다. 여기서, 동박은 표면이 산화 부식되는 것을 방지하기 위해서, 녹방지 처리되어 있을 수 있다. The said copper foil includes all the copper foils manufactured by the rolling method and the electrolytic method. Here, the copper foil may be subjected to rust prevention treatment in order to prevent oxidative corrosion of the surface.
상기 금속박은 상기 열경화성 수지 조성물이 경화된 수지층과 접하는 일면 상에 소정의 표면 조도(Rz)가 형성될 수도 있다. 이때 표면조도(Rz)는 특별히 제한되지 않으나, 일례로 0.6 ㎛ 내지 3.0 ㎛ 범위일 수 있다.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. In this case, the surface roughness Rz is not particularly limited, but may be, for example, in a range of 0.6 μm to 3.0 μm.
또한 상기 금속박의 두께는 특별히 제한되지 않으나, 최종물의 두께와 기계적 특성을 고려하여 5 ㎛ 미만인 것을 사용할 수 있으며, 바람직하게는 1 내지 3 ㎛ 범위일 수 있다. 사용 가능한 동박의 예로는, CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, ILSIN 등이 있다. In addition, the thickness of the metal foil is not particularly limited, but may be used less than 5 ㎛ in consideration of the thickness and mechanical properties of the final product, preferably may be in the range of 1 to 3 ㎛. Examples of copper foil that can be used include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, ILSIN and the like.
또, 본 발명에서 사용 가능한 고분자 필름으로는 당 업계에서 절연필름으로 알려진 것이라면, 특별히 한정되지 않는다. 예를 들어, 폴리이미드 필름, 에폭시수지 필름 등이 있는데, 이에 한정되지 않는다.In addition, 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. For example, there are a polyimide film, an epoxy resin film, and the like, but is not limited thereto.
<동박 적층판 및 인쇄회로기판>Copper Clad Laminates and Printed Circuit Boards
본 발명은 전술한 프리프레그(prepreg) 2개 이상을 서로 겹친 후, 이를 통상의 조건으로 가열, 가압하여 형성되는 동박 적층판을 포함한다. 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.
또한, 본 발명은 상기 프리프레그 및 동박을 적층하고, 통상의 조건으로 가열가압 성형하여 형성되는 동박 적층판을 포함한다. In addition, 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.
일례로, 전술한 수지 조성물을 상온에서 교반기를 이용하여 충분히 교반한 후에 유리 기재에 함침시켜 건조한 후, 동박 등과 함께 적층하여 열과 압력을 가한 후 원하는 동박 적층판을 얻을 수 있다. 이때, 동박 적층판 성형시, 가열가압 조건은 제조하는 동박 적층판의 두께나 본 발명에 따른 열경화성 수지 조성물의 종류 등에 따라 적절히 조절될 수 있다.For example, 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. At this time, when forming the 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.
아울러, 본 발명은 상기 프리프레그(prepreg), 절연 수지 시트, 및 수지 부착 동박으로 구성된 군으로부터 선택되는 1종 이상을 포함하여 적층 성형된 인쇄회로기판, 바람직하게는 다층 인쇄회로기판을 포함한다. In addition, 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.
본 발명에서 인쇄회로기판이란, 도금 스루홀법이나 빌드업법 등에 의해 1층 이상 적층한 인쇄회로기판을 지칭하며, 내층 배선판에 전술한 프리프레그나 또는 절연 수지 시트를 포개어 맞추고 가열 가압 성형함으로써 얻을 수 있다. In the present invention, 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.
상기 인쇄회로기판은 당 업계에 알려진 통상의 방법에 의해 제조될 수 있다. 이의 바람직한 일례를 들면, 본 발명에 따른 프리프레그의 일면 또는 양면에 동박을 적층하고 가열 가압하여 동박 적층판을 제작한 후, 동박 적층판에 구멍을 개구하여 스루홀도금을 행한 후, 도금막을 포함하는 동박을 에칭 처리하여 회로를 형성함으로써 제조될 수 있다.The printed circuit board may be manufactured by conventional methods known in the art. As a preferable example of this, after laminating | stacking and heat-pressing copper foil on the one or both surfaces of the prepreg which concerns on this invention, 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.
이상에서 설명한 바와 같이, 프리프레그 및 인쇄회로기판은 본 발명에 따른 열경화성 수지 조성물로부터 제조될 수 있다. 이들 프리프레그 및 동박 적층판은 낮은 유전율과 유전 손실을 가질 뿐만 아니라, 우수한 내열성을 동시에 가짐을 알 수 있었다(하기 표 2 참고). 따라서, 본 발명의 프리프레그 및 인쇄회로기판은 1 GHz 이상의 고주파 신호를 취급하는 이동체 통신기기나 그 기지국 장치, 서버, 라우터 등의 네트워크 관련 전자기기 및 대형 컴퓨터 등의 각종 전기전자 기기에 사용되는 네트워크용 인쇄회로기판의 부품 용도로서 유용하게 사용될 수 있다. As described above, 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). Accordingly, 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.
이하, 실시예를 통하여 본 발명을 더욱 상세하게 설명한다. 단, 실시예는 본 발명을 예시하기 위한 것이지 이들만으로 한정하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, an Example is for illustrating this invention and is not limited only to these.
[합성예 1] 알코올-말단 변성 폴리페닐렌 옥사이드(alcohol-MPPO-1) 제조Synthesis Example 1 Preparation of Alcohol-Terminal Modified Polyphenylene Oxide (alcohol-MPPO-1)
Figure PCTKR2014009034-appb-I000036
Figure PCTKR2014009034-appb-I000036
온도계, 교반기 및 냉각기를 구비한 20 L의 둥근 바닥 플라스크에 화합물 1 (1.0 Kg, 이때, n= 약 60), 화합물 2 (0.1 Kg) 및 Toluene (10 Kg)을 투입한 후 60 ℃로 가열하고, 질소 분위기 하에서 충분히 용해시켰다. 이후, 75 %의 Benzoyl peroxide (10 g)을 Toluene (90 g)에 녹인 후 이를 상기 플라스크에 천천히 적하시켰다. 적하가 끝난 후, 플라스크의 온도를 90 ℃로 승온시킨 다음, 8시간 30분 후에 상온으로 냉각시켰다. 이후, 냉각된 반응액을 Toluene에 약 50 %까지 농축한 후, 농축액을 과량의 메탄올에 침전시켜 침전물을 얻은 다음, 상기 침전물을 80 ℃의 진공 오븐에서 24 시간 동안 건조시켜 연한 갈색 분말의 alchol-MPPO-1 (0.85 kg, 중량 평균분자량: 6500)을 수득하였다.Into a 20 L round bottom flask equipped with a thermometer, a stirrer and a cooler, Compound 1 (1.0 Kg, n = about 60), Compound 2 (0.1 Kg) and Toluene (10 Kg) were added thereto, followed by heating to 60 ° C. It fully dissolved in nitrogen atmosphere. Thereafter, 75% of Benzoyl peroxide (10 g) was dissolved in Toluene (90 g) and then slowly added to the flask. After the dropping was completed, the flask was heated to 90 ° C., and then cooled to room temperature after 8 hours and 30 minutes. Thereafter, the cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol to obtain a precipitate. The precipitate was dried in a vacuum oven at 80 ° C. for 24 hours to give a light brown powder of alchol-. MPPO-1 (0.85 kg, weight average molecular weight: 6500) was obtained.
[합성예 2] 알코올-말단 변성 폴리페닐렌 옥사이드(alchol-MPPO-2) 제조Synthesis Example 2 Preparation of Alcohol-Terminal Modified Polyphenylene Oxide (alchol-MPPO-2)
Figure PCTKR2014009034-appb-I000037
Figure PCTKR2014009034-appb-I000037
합성예 1에서 사용된 화합물 2 (0.1 kg) 대신 화합물 2 (0.5 kg)을 사용하는 것을 제외하고는 합성예 1과 동일하게 수행하여 연한 갈색 분말의 alchol-MPPO-2 (0.85 kg, 중량 평균분자량: 3500)을 수득하였다.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.
[합성예 3] 알코올-말단 변성 폴리페닐렌 옥사이드(alchol-MPPO-3) 제조Synthesis Example 3 Preparation of Alcohol-Terminal Modified Polyphenylene Oxide (alchol-MPPO-3)
Figure PCTKR2014009034-appb-I000038
Figure PCTKR2014009034-appb-I000038
합성예 1에서 사용된 화합물 2 (0.1 kg) 대신 화합물 3 (0.1 kg)을 사용하는 것을 제외하고는 준비예 1과 동일하게 수행하여 연한 갈색 분말의 alchol-MPPO-3 (0.8 kg, 중량 평균분자량: 6300)을 수득하였다.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.
[합성예 4] 알코올-말단 변성 폴리페닐렌 옥사이드(alchol-MPPO-4) 제조Synthesis Example 4 Preparation of Alcohol-Terminal Modified Polyphenylene Oxide (alchol-MPPO-4)
Figure PCTKR2014009034-appb-I000039
Figure PCTKR2014009034-appb-I000039
합성예 1에서 사용된 화합물 2 (0.1 kg) 대신 화합물 4 (0.1 kg)을 사용하는 것을 제외하고는 준비예 1과 동일하게 수행하여 연한 갈색 분말의 alchol-MPPO-4 (0.75 kg, 중량 평균분자량: 7200)을 수득하였다.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.
[합성예 5] 알코올-말단 변성 폴리페닐렌 옥사이드(alchol-MPPO-5) 제조Synthesis Example 5 Preparation of Alcohol-Terminal Modified Polyphenylene Oxide (alchol-MPPO-5)
Figure PCTKR2014009034-appb-I000040
Figure PCTKR2014009034-appb-I000040
합성예 1에서 사용된 화합물 2 (0.1 kg) 대신 화합물 5 (0.1 kg)을 사용하는 것을 제외하고는 준비예 1과 동일하게 수행하여 연한 갈색 분말의 alchol-MPPO-5 (0.82 kg, 중량 평균분자량: 6600)을 수득하였다.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.
[합성예 6] 비닐-말단 변성 폴리페닐렌 옥사이드(vinyl-MPPO-1) 제조Synthesis Example 6 Preparation of vinyl-terminated modified polyphenylene oxide (vinyl-MPPO-1)
온도계, 교반기 및 냉각기를 구비한 5 L의 둥근 바닥 플라스크에 합성예 1에서 얻은 alchol-MPPO-1 (700 g), Methacrylic anhydride (127 g), 및 4-Dimethylaminopyridine (100 g)을 Toluene (1400 g)에 용해시킨 후, Reflux 온도까지 승온시킨 다음, 6 시간 동안 반응시킨 후, 상온까지 반응액을 냉각시켰다. 이후, 냉각된 반응액을 과량의 메탄올에 침전을 시켜 침전물을 얻은 후, 상기 침전물을 메탄올로 충분히 세척하였다. 이어서, 세척된 침전물을 80 ℃의 진공오븐에서 24 시간 동안 건조시켜 연한 갈색의 분말인 하기 vinyl-MPPO-1 (700 g, 중량 평균분자량: 6,375)을 수득하였다.In a 5 L round bottom flask equipped with thermometer, stirrer and cooler, alchol-MPPO-1 (700 g), Methacrylic anhydride (127 g), and 4-Dimethylaminopyridine (100 g) obtained in Synthesis Example 1 were added to Toluene (1400 g). After dissolving in), 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.
Figure PCTKR2014009034-appb-I000041
Figure PCTKR2014009034-appb-I000041
[합성예 7] 에폭시-말단 변성 폴리페닐렌 옥사이드(epoxy-MPPO-1) 제조Synthesis Example 7 Preparation of Epoxy-terminated Modified Polyphenylene Oxide (epoxy-MPPO-1)
온도계, 교반기 및 냉각기를 구비한 5 L의 둥근 바닥 플라스크에 합성예 1에서 얻은 alchol-MPPO-1 (1 kg) 및 에피클로로하이드린 (2.5 kg)을 투입한 후 가열하여 용해시켰다. 이후, 상기 반응액에 수산화나트륨 (50 g)을 천천히 분할 투입한 후, 100 ℃에서 12 시간 동안 교반시킨 다음, 상온으로 냉각시켜 반응물을 얻었다. 이어서, 상기 반응물을 과량의 메탄올에 침전시켜 침전물을 얻고, 이 침전물을 충분히 메탄올로 세척한 다음, 80 ℃의 진공오븐에서 24 시간 동안 건조시켜 epoxy-MPPO-1 (900 g, 중량평균분자량: 6,400)를 수득하였다. Into a 5 L round bottom flask equipped with a thermometer, a stirrer and a cooler, 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.
Figure PCTKR2014009034-appb-I000042
Figure PCTKR2014009034-appb-I000042
[합성예 8] 아민-말단 변성 폴리페닐렌 옥사이드(amine-MPPO-1) 제조Synthesis Example 8 Preparation of Amine-Ended Modified Polyphenylene Oxide (amine-MPPO-1)
온도계, 교반기 및 냉각기를 구비한 5 L의 둥근 바닥 플라스크에 합성예 1에서 얻은 alchol-MPPO-1 (1kg) 및 디메틸포름아마이드 용매 (2 L)를 함께 투입한 후, 80 ℃로 승온시킨 다음 30 분간 교반하였다. 이후, 상기 반응물에 1,3-디나이트로벤젠 (150 g) 및 탄산칼륨 (300 g)을 투입한 다음, 150 ℃에서 8시간 동안 교반하였다. 이후, 상기 반응물을 과량의 메탄올에 침전시켜 여과한 후 침전물을 얻은 다음, 얻은 침전물을 2-메톡시에탄올 (3 L)과 함께 5 L의 둥근 바닥 플라스크에 투입하였다. 이후, 수소 분위기하에서 Pt/C (30 g) 및 트리에틸아민(100 g)을 상기 플라스크에 첨가하고, 20 시간 동안 반응시킨 후, 필터링을 통해 촉매와 분리된 생성물을 메탄올에 침전시켜 amine-MPPO-1 (1.1 kg, 중량평균분자량: 6,350)를 수득하였다.Into a 5 L round bottom flask equipped with a thermometer, a stirrer and a cooler, alchol-MPPO-1 (1 kg) and dimethylformamide solvent (2 L) obtained in Synthesis Example 1 were added together, and the temperature was raised to 80 ° C., followed by 30 Stirred for a minute. Thereafter, 1,3-dinitrobenzene (150 g) and potassium carbonate (300 g) were added to the reaction, followed by stirring at 150 ° C. for 8 hours. The reaction was then precipitated in excess methanol and filtered to yield a precipitate which was then poured into a 5 L round bottom flask with 2-methoxyethanol (3 L). Subsequently, Pt / C (30 g) and triethylamine (100 g) were added to the flask under a hydrogen atmosphere, reacted for 20 hours, and the catalyst and the separated product were precipitated in methanol by filtration through amine-MPPO. -1 (1.1 kg, weight average molecular weight: 6,350) was obtained.
Figure PCTKR2014009034-appb-I000043
Figure PCTKR2014009034-appb-I000043
[합성예 9] 에스테르-말단 변성 폴리페닐렌 옥사이드(ester-MPPO-1) 제조Synthesis Example 9 Preparation of Ester-terminated Modified Polyphenylene Oxide (ester-MPPO-1)
온도계, 교반기 및 냉각기를 구비한 5 L의 둥근 바닥 플라스크에 합성예 1에서 얻은 alchol-MPPO-1 (700 g) 및 메틸 4-크로로카보닐 벤조에이트 (Methyl 4--(chlorocarbonyl)-benzoate, MCCB) (150 g)을 투입한 후 가열하여 용해시켰다. 이후, 상기 반응액에 트라이에틸아민 (120 g)을 천천히 투입한 다음, 70 ℃에서 5시간 동안 교반하였다. 이어서, 상기 반응물을 과량의 메탄올에 침전시켜 침전물을 얻고, 얻은 침전물을 충분히 메탄올로 세척한 다음, 80 ℃의 진공오븐에서 24 시간 동안 건조시켜 ester-MPPO-1 (600 g, 중량평균분자량: 6,200)를 수득하였다.In a 5 L round bottom flask equipped with thermometer, stirrer and cooler, alchol-MPPO-1 (700 g) and 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.
Figure PCTKR2014009034-appb-I000044
Figure PCTKR2014009034-appb-I000044
[비교 합성예 1] 알코올-말단 변성 폴리페닐렌 옥사이드(alchol-MPPO-com) 제조Comparative Synthesis Example 1 Alcohol-terminated modified polyphenylene oxide (alchol-MPPO-com)
Figure PCTKR2014009034-appb-I000045
Figure PCTKR2014009034-appb-I000045
합성예 1에서 사용된 화합물 2 (0.1 kg) 대신 화합물 6 (0.5 kg)을 사용하는 것을 제외하고는 합성예 1과 동일하게 수행하여 연한 갈색 분말의 alchol-MPPO-com (0.80 kg, 중량 평균분자량: 3800)을 수득하였다.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.
[비교 합성예 2] 비닐-말단 변성 폴리페닐렌 옥사이드 (vinyl-MPPO-com) 제조Comparative Synthesis Example 2 Preparation of vinyl-terminated modified polyphenylene oxide (vinyl-MPPO-com)
합성예 6에서 사용된 합성예 1에서 얻은 alchol-MPPO-1 (700 g) 대신에 비교 합성예 1에서 얻은 alchol-MPPO-com (700 g)을 사용하는 것을 제외하고는, 합성예 6과 동일하게 수행하여 연한 갈색 분말의 vinyl-MPPO-com (700 g, 중량평균분자량: 3,700)을 수득하였다. Same as Synthesis Example 6, except that alchol-MPPO-com (700 g) obtained in Comparative Synthesis Example 1 was used instead of alchol-MPPO-1 (700 g) obtained in Synthesis Example 1 used in Synthesis Example 6. To give a light brown powder of vinyl-MPPO-com (700 g, weight average molecular weight: 3,700).
Figure PCTKR2014009034-appb-I000046
Figure PCTKR2014009034-appb-I000046
[실시예 1]Example 1
합성예 6에서 얻은 비닐-말단 변성 폴리페닐렌 옥사이드(vinyl-MPPO-1)를 이형지에 코팅한 후 150 ℃에서 5 분간 건조한 다음 박리하고, 210 ℃ 및 25 kg/cm2의 조건으로 150 분간 경화하여 폴리페닐렌 옥사이드 필름을 제조하였다. 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.
[실시예 2] Example 2
실시예 1에서 사용된 변성 폴리페닐렌 옥사이드 대신 합성예 1에서 얻은 알코올-말단 변성 폴리페닐렌 옥사이드(alchol-MPPO-1)를 사용하는 것을 제외하고는, 실시예 1과 동일하게 수행하여 변성 폴리페닐렌 옥사이드 필름을 제조하였다.Except for using the alcohol-terminal modified polyphenylene oxide (alchol-MPPO-1) obtained in Synthesis Example 1 instead of the modified polyphenylene oxide used in Example 1, the modified poly A phenylene oxide film was prepared.
[실시예 3]Example 3
실시예 1에서 사용된 변성 폴리페닐렌 옥사이드 대신 합성예 8에서 얻은 아민-말단 변성 폴리페닐렌 옥사이드(amine-MPPO-1)를 사용하는 것을 제외하고는, 실시예 1과 동일하게 수행하여 변성 폴리페닐렌 옥사이드 필름을 제조하였다.Except for using the amine-terminated modified polyphenylene oxide (amine-MPPO-1) obtained in Synthesis Example 8 instead of the modified polyphenylene oxide used in Example 1, the modified poly A phenylene oxide film was prepared.
[실시예 4]Example 4
실시예 1에서 사용된 변성 폴리페닐렌 옥사이드 대신 합성예 9에서 얻은 에스테르-말단 변성 폴리페닐렌 옥사이드(ester-MPPO-1)를 사용하는 것을 제외하고는, 실시예 1과 동일하게 수행하여 변성 폴리페닐렌 옥사이드 필름을 제조하였다.Except for using the 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.
[비교예 1]Comparative Example 1
실시예 1에서 사용된 변성 폴리페닐렌 옥사이드 대신 비교 합성예 2에서 얻은 비닐-말단 변성 폴리페닐렌 옥사이드(Vinyl-MPPO-com)를 사용하는 것을 제외하고는, 실시예 1과 동일하게 수행하여 변성 폴리페닐렌 옥사이드 필름을 제조하였다.Modification was carried out in the same manner as in Example 1, except that the vinyl-terminated modified polyphenylene oxide (Vinyl-MPPO-com) obtained in Comparative Synthesis Example 2 was used instead of the modified polyphenylene oxide used in Example 1. Polyphenylene oxide film was prepared.
[비교예 2]Comparative Example 2
실시예 1에서 사용된 변성 폴리페닐렌 옥사이드 대신 비교 합성예 1에서 얻은 알코올-말단 변성 폴리페닐렌 옥사이드(Alcohol-MPPO-com)를 사용하는 것을 제외하고는, 실시예 1과 동일하게 수행하여 변성 폴리페닐렌 옥사이드 필름을 제조하였다.Modification was carried out in the same manner as in Example 1 except that the alcohol-terminated modified polyphenylene oxide (Alcohol-MPPO-com) obtained in Comparative Synthesis Example 1 was used instead of the modified polyphenylene oxide used in Example 1. Polyphenylene oxide film was prepared.
[실시예 5]Example 5
하기 표 2와 같은 조성의 수지 조성물을 유리섬유 기재에 함침시킨 후, 150 ℃에서 5분 건조하여 수지 함량 50 중량%의 프리프레그를 얻었다. 상기 프리프레그를 8장 겹치고 바깥쪽 양면에 18 ㎛ 동박을 적층한 후, 210 ℃, 25 kg/cm2의 조건으로 150 분간 프레스하여 동박 적층판을 제조하였다. After impregnating the resin composition of the composition shown in Table 2 to the glass fiber substrate, and dried for 5 minutes at 150 ℃ to obtain a prepreg of the resin content 50% by weight. Eight sheets of the above prepregs were stacked and 18 µm copper foils were laminated on both outer surfaces, and then pressed at 210 ° C. for 25 minutes at 25 kg / cm 2 to prepare a copper foil laminate.
[실시예 6]Example 6
실시예 5에서 사용된 합성예 6의 변성 폴리페닐렌 옥사이드 대신 합성예 1의 변성 폴리페닐렌 옥사이드를 사용하는 것을 제외하고는, 실시예 5와 동일하게 수행하여 프리프레그 및 동박 적층판을 제조하였다.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.
[비교예 3] ~ [비교예 5][Comparative Example 3] ~ [Comparative Example 5]
하기 표 2와 같은 조성의 수지 조성물을 적용한 것을 제외하고는, 상기 실시예 5와 동일하게 수행하여 프리프레그 및 동박 적층판을 제조하였다. 표 2에 기재된 화합물 1은 상기 화학식 16a로 표시되는 폴리페닐렌 옥사이드(n=60)이다.Except that the resin composition of the composition shown in Table 2 was applied, it was carried out in the same manner as in Example 5 to prepare a prepreg and a copper foil laminate. Compound 1 shown in Table 2 is a polyphenylene oxide represented by the formula (16a) (n = 60).
[실험예 1]Experimental Example 1
본 발명에 따른 변성 폴리페닐렌 옥사이드의 유전 특성 및 가공 특성을 확인하기 위해서, 실시예 1 내지 4, 및 비교예 1 내지 2에서 얻은 변성 폴리페닐렌 옥사이드 필름에 대하여 하기 실험을 수행하였다. 실험 결과를 하기 표 1에 나타내었다.In order to confirm the dielectric and processing properties of the modified polyphenylene oxide according to the present invention, the following experiments were performed on the modified polyphenylene oxide films obtained in Examples 1 to 4 and Comparative Examples 1 and 2. The experimental results are shown in Table 1 below.
(1) 유전율(Dk): IPC TM-650.2.5.5.1의 시험 규격에 준하여 물질 분석기(Material Analyzer)를 이용하여 측정하였다.(1) Dielectric constant (Dk): measured using a material analyzer in accordance with the test standard of IPC TM-650.2.5.5.1.
(2) 유전손실(Df): IPC TM-650.2.5.5.1의 시험 규격에 준하여 물질 분석기(Material Analyzer)를 이용하여 측정하였다.(2) Dielectric loss (Df): measured using a material analyzer in accordance with the test standard of IPC TM-650.2.5.5.1.
표 1
　 실시예 1 실시예 2 실시예 3 실시예 4 비교예 1 비교예 2
Dk (@ 1MHz) 2.45 2.52 2.52 2.5 2.54 2.59
Df (@ 1MHz) 0.004 0.005 0.005 0.004 0.006 0.007
Table 1
Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2
Dk (@ 1 MHz) 2.45 2.52 2.52 2.5 2.54 2.59
Df (@ 1 MHz) 0.004 0.005 0.005 0.004 0.006 0.007
상기 표 1에서 알 수 있는 바와 같이, 실시예 1 ~ 4의 변성 폴리페닐렌 옥사이드는 유전율이 낮을 뿐만 아니라, 비교예 1 및 2의 변성 폴리페닐렌 옥사이드에 비해 유전 손실이 현저하게 낮았다.As can be seen in Table 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.
[실험예 2] Experimental Example 2
실시예 5 ~ 6 및 비교예 3 ~ 5에서 제조된 동박 적층판에 대하여 하기 실험을 실시하였고, 그 결과를 하기 표 2에 나타내었다.The following experiments were carried out for the copper foil laminates prepared in Examples 5 to 6 and Comparative Examples 3 to 5, and the results are shown in Table 2 below.
(1) 유전율(Dk): IPC TM-650.2.5.5.1의 시험 규격에 준하여 물질 분석기(Material Analyzer)를 이용하여 측정하였다.(1) Dielectric constant (Dk): measured using a material analyzer in accordance with the test standard of IPC TM-650.2.5.5.1.
(2) 유전손실(Df): IPC TM-650.2.5.5.1의 시험 규격에 준하여 물질 분석기(Material Analyzer)를 이용하여 측정하였다.(2) Dielectric loss (Df): measured using a material analyzer in accordance with the test standard of IPC TM-650.2.5.5.1.
(3) 접착성(P/S): IPC-TM-650.2.4.8의 시험 규격에 준하여 측정하였다.(3) Adhesiveness (P / S): Measured according to the test standard of IPC-TM-650.2.4.8.
(4) 내열성: 288℃의 납조에서 5cm×5cm의 크기로 절단한 적층체를 넣은 후, 10분간 외관 변화를 육안으로 확인하였다.(4) Heat resistance: After putting the laminated body cut | disconnected in the magnitude | size of 5 cm x 5 cm in the 288 degreeC lead bath, the external appearance change was visually confirmed for 10 minutes.
(5) 유리전이온도(Tg): 동박 적층체의 동박층을 에칭한 후 DSC (Differential Scanning Calorimeter)를 이용하여 측정하였다.(5) Glass transition temperature (Tg): After etching the copper foil layer of a copper foil laminated body, it measured using DSC (Differential Scanning Calorimeter).
표 2
Figure PCTKR2014009034-appb-T000001
 TABLE 2
Figure PCTKR2014009034-appb-T000001
실험 결과, 본 발명의 열경화성 수지 조성물은 우수한 저유전 손실 특성과 낮은 유전율을 가질 뿐만 아니라, 동박과의 접착력 향상, 우수한 내열성, 열적 안정성 등을 동시에 나타낸다는 것을 알 수 있었다(표 2 참조). As a result of the experiment, it was found that the 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).
특히, 실시예 5와 실시예 6은 각각 이들의 구성에 대응되는 비교예 3과 비교예 4에 비하여, 보다 낮은 유전율과 우수한 저유전 손실 특성을 나타낸다는 것을 확인할 수 있었다. 추가로, 비닐기로 양 말단이 개질된 변성 폴리페닐렌 옥사이드를 사용하는 실시예 1은 내열성 및 동박과의 접착력 면에서 보다 상승효과가 발휘된다는 것을 알 수 있었다. In particular, it was confirmed that 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. In addition, it was found that 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.

Claims (9)

  1. 하기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드:Modified polyphenylene oxide represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2014009034-appb-I000047
    Figure PCTKR2014009034-appb-I000047
    (상기 화학식 1에서,(In Formula 1,
    n은 1 내지 10,000의 정수이고;n is an integer from 1 to 10,000;
    a는 0 내지 4의 정수이고, a가 1 내지 4의 정수인 경우, R1은 C1~C12의 알킬기, 및 C1~C12의 알콕시기로 이루어진 군에서 선택되며;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;
    m은 0 또는 1이고;m is 0 or 1;
    Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 직접결합이거나, 또는 치환 또는 비치환된 C6~C12의 아릴렌기이고, 이때 Y1 및 Y2의 아릴렌기는 수소, C1~C12의 알킬기, C1~C12의 알콕시기 및 C6~C12의 아릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환될 수 있으며;Y 1 and Y 2 are the same as or different from each other, and each independently a direct 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;
    R2 및 R3는 서로 동일하거나 상이하고, 각각 독립적으로 -OH, -CR4=CH2, -C(=O)CR5=CH2, -NH2,
    Figure PCTKR2014009034-appb-I000048
    , -C(=O)-R6,
    Figure PCTKR2014009034-appb-I000049
    , -C(=O)-O-R8 및
    Figure PCTKR2014009034-appb-I000050
    로 이루어진 군에서 선택되며,     R 2 and R 3 are the same as or different from each other, and are each independently —OH, —CR 4 ═CH 2 , —C (═O) CR 5 ═CH 2 , —NH 2 ,
    Figure PCTKR2014009034-appb-I000048
    , -C (= O) -R 6 ,
    Figure PCTKR2014009034-appb-I000049
    , -C (= O) -OR 8 and
    Figure PCTKR2014009034-appb-I000050
    Is selected from the group consisting of
    R4 내지 R8은 서로 동일하거나 상이하고, 각각 독립적으로 수소, C1~C12의 알킬기, C1~C12의 알콕시기, 및 C1~C12의 아릴렌기로 이루어진 군에서 선택되고,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,
    복수의 W는 서로 동일하거나 상이하고, 각각 독립적으로 수소, C1~C12의 알킬기, C1~C12의 알콕시기 및 C6~C12의 아릴기로 이루어진 군에서 선택되고;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;
    Ar은 하기 화학식 2 또는 3으로 표시되는 치환체이고,Ar is a substituent represented by the following formula (2) or (3),
    [화학식 2][Formula 2]
    Figure PCTKR2014009034-appb-I000051
    Figure PCTKR2014009034-appb-I000051
    [화학식 3][Formula 3]
    Figure PCTKR2014009034-appb-I000052
    Figure PCTKR2014009034-appb-I000052
    Q1 내지 Q3는 서로 동일하거나 상이하고, 각각 독립적으로 C1~C12의 알킬기, C1~C12의 알콕시기 및 C1~C12의 할로알킬기로 이루어진 군에서 선택되며, 다만 o가 0인 경우, Q1 및 Q2가 모두 알킬기인 경우는 제외되고,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 및 p는 각각 독립적으로 0 내지 3의 정수임).o and p are each independently an integer from 0 to 3).
  2. 제1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드는 하기 화학식 4로 표시되는 변성 폴리페닐렌 옥사이드인 것이 특징인 변성 폴리페닐렌 옥사이드:The modified polyphenylene oxide represented by Formula 1 is a modified polyphenylene oxide, characterized in that the modified polyphenylene oxide represented by the following formula (4):
    [화학식 4][Formula 4]
    Figure PCTKR2014009034-appb-I000053
    Figure PCTKR2014009034-appb-I000053
    (상기 식에서,(Wherein
    n, m, Ar, Y1, Y2, R2, 및 R3는 각각 제1항에서 정의한 바와 같음).n, m, Ar, Y 1 , Y 2 , R 2 , and R 3 are each as defined in claim 1).
  3. 제1항에 있어서, The method of claim 1,
    상기 화학식 1로 표시되는 변성 폴리페닐렌 옥사이드는 하기 화학식 5 내지 13으로 이루어진 군에서 선택된 화학식으로 표시되는 변성 폴리페닐렌 옥사이드인 것이 특징인 변성 폴리페닐렌 옥사이드:The modified polyphenylene oxide represented by Formula 1 is a modified polyphenylene oxide, characterized in that the modified polyphenylene oxide represented by the formula selected from the group consisting of the following formulas 5 to 13.
    [화학식 5][Formula 5]
    Figure PCTKR2014009034-appb-I000054
    Figure PCTKR2014009034-appb-I000054
    [화학식 6][Formula 6]
    Figure PCTKR2014009034-appb-I000055
    Figure PCTKR2014009034-appb-I000055
    [화학식 7][Formula 7]
    Figure PCTKR2014009034-appb-I000056
    Figure PCTKR2014009034-appb-I000056
    [화학식 8][Formula 8]
    Figure PCTKR2014009034-appb-I000057
    Figure PCTKR2014009034-appb-I000057
    [화학식 9][Formula 9]
    Figure PCTKR2014009034-appb-I000058
    Figure PCTKR2014009034-appb-I000058
    [화학식 10][Formula 10]
    Figure PCTKR2014009034-appb-I000059
    Figure PCTKR2014009034-appb-I000059
    [화학식 11][Formula 11]
    Figure PCTKR2014009034-appb-I000060
    Figure PCTKR2014009034-appb-I000060
    [화학식 12][Formula 12]
    Figure PCTKR2014009034-appb-I000061
    Figure PCTKR2014009034-appb-I000061
    [화학식 13][Formula 13]
    Figure PCTKR2014009034-appb-I000062
    Figure PCTKR2014009034-appb-I000062
    (상기 식에서,(Wherein
    n, Ar, R6 및 R7은 각각 제1항에서 정의한 바와 같고,n, Ar, R 6 and R 7 are each as defined in claim 1,
    W1 및 W2는 서로 동일하거나 상이하며, 각각 독립적으로 수소, C1~C12의 알킬기, C1~C12의 알콕시기 및 C6~C12의 아릴기로 이루어진 군에서 선택되고,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,
    a 및 b는 각각 0 또는 1임).a and b are each 0 or 1).
  4. 제1항 내지 제3항 중 어느 한 항에 기재된 변성 폴리페닐렌 옥사이드를 포함하는 필름.The film containing the modified polyphenylene oxide as described in any one of Claims 1-3.
  5. 제1항 내지 제3항 중 어느 한 항에 기재된 변성 폴리페닐렌 옥사이드; 및 가교결합성 경화제를 포함하는 열경화성 수지 조성물.Modified polyphenylene oxide as described in any one of Claims 1-3; And a crosslinkable curing agent.
  6. 섬유 기재; 및 Fiber substrates; And
    상기 섬유 기재에 함침된 제5항에 기재된 열경화성 수지 조성물The thermosetting resin composition of Claim 5 impregnated in the said fiber base material
    을 포함하는 프리프레그.Prepreg comprising a.
  7. 제6항에 있어서, The method of claim 6,
    상기 섬유 기재는 유리 섬유, 유리 페이퍼, 유리 섬유 부직포 (glass web), 유리 직물(glass cloth), 아라미드 섬유, 아라미드 페이퍼(aramid paper), 폴리에스테르 섬유, 탄소 섬유, 무기섬유 및 유기섬유로 구성된 군에서 선택되는 1종 이상을 포함하는 것을 특징으로 하는 프리프레그.The fiber base is a group consisting of glass fiber, glass paper, glass fiber nonwoven fabric (glass web), glass cloth, aramid fiber, aramid paper, polyester fiber, carbon fiber, inorganic fiber and organic fiber Prepreg comprising at least one selected from.
  8. 금속박 또는 고분자 필름 기재; 및 Metal foil or polymer film base material; And
    상기 기재의 일면 또는 양면 상에 형성되고, 제5항에 기재된 열경화성 수지 조성물이 경화된 수지층The resin layer formed on one side or both sides of the said base material, and the thermosetting resin composition of Claim 5 hardened | cured.
    을 포함하는 기능성 적층 시트.Functional laminated sheet comprising a.
  9. 동박; 및 제6항에 기재된 프리프레그를 포함하되, 이들이 1층 이상 적층하여 성형된 것이 특징인 동박 적층판.Copper foil; And the prepreg according to claim 6, wherein they are molded by laminating one or more layers.
PCT/KR2014/009034 2013-09-27 2014-09-26 Modified polyphenylene oxide, and copper-clad laminate using same WO2015046956A1 (en)

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