WO2015046953A1 - Copper-clad laminate using modified polyphenylene oxide - Google Patents

Copper-clad laminate using modified polyphenylene oxide Download PDF

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Publication number
WO2015046953A1
WO2015046953A1 PCT/KR2014/009030 KR2014009030W WO2015046953A1 WO 2015046953 A1 WO2015046953 A1 WO 2015046953A1 KR 2014009030 W KR2014009030 W KR 2014009030W WO 2015046953 A1 WO2015046953 A1 WO 2015046953A1
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Prior art keywords
bisphenol
resin composition
polyphenylene oxide
group
thermosetting resin
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PCT/KR2014/009030
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French (fr)
Korean (ko)
Inventor
서현진
김인욱
황용재
이혜선
한가영
김한상
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주식회사 두산
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Publication of WO2015046953A1 publication Critical patent/WO2015046953A1/en

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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
    • 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
    • B32B15/20—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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • 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
    • C08L71/126—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • 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 applies a modified polyphenylene oxide resin having a low dielectric loss characteristic to the resin composition for copper foil laminated plate, and relates to a copper foil laminate using prepreg and prepreg excellent in processability while implementing low dielectric properties.
  • 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.
  • the present invention has been made to solve the above problems.
  • a low molecular weight polyphenylene oxide resin is obtained by redistributing a high molecular weight polyphenylene oxide and a specific bisphenol derivative having an increased alkyl content and aromatic content.
  • a resin having excellent dielectric properties and excellent processability and compatibility was obtained.
  • an object of the present invention is to provide a thermosetting resin composition including the above-mentioned modified polyphenylene oxide, which exhibits excellent processability and low dielectric properties, a prepreg and a copper foil laminated plate using the composition.
  • the present invention (a) modified polyphenylene oxide resin; And (b) a crosslinkable curing agent, wherein the modified polyphenylene oxide resin (a) is redistributed in the presence of a bisphenol compound (except bisphenol A) and a radical initiator to obtain a weight-average molecular weight (Mw). It provides a thermosetting resin composition which is modified to a low molecular weight in the range of 1,000 to 20,000, and includes at least two functional groups selected from the group consisting of hydroxy groups and vinyl groups at both ends of the molecular chain.
  • thermosetting resin composition is preferably a thermosetting resin composition for manufacturing a high frequency multilayer printed circuit board.
  • the modified polyphenylene oxide is preferably represented by the following formula (1) or (2).
  • the modified polyphenylene oxide resin (a) is redistribution reaction of a high molecular weight polyphenylene oxide resin having a weight average molecular weight (Mw) in the range of 5,000 to 350,000 in the presence of a specific bisphenol compound and a radical initiator Is preferably modified to low molecular weight.
  • the specific bisphenol compound is a bisphenol-based compound except for bisphenol A (BPA), and is a compound having a higher alkyl group content and aromatic aromatic group content than BPA.
  • crosslinkable curing agent (b) is triallyl isocyanurate (TAIC), di-4-vinylbenzyl oxide, divinylbenzene, divinyl naphthalene, divinylphenyl, 1,7-octadiene, and 1, It is preferable that it is at least one selected from the group consisting of 9-tecadiene.
  • TAIC triallyl isocyanurate
  • thermosetting resin composition preferably further comprises one selected from the group consisting of a flame retardant, an inorganic filler, a rubber, a curing accelerator, and a radical initiator.
  • the present invention is a fiber substrate; And it provides a prepreg comprising the above-mentioned thermosetting resin composition impregnated on the fiber substrate.
  • the fiber base material is glass fiber, glass paper, glass fiber nonwoven fabric (glass web), glass cloth (glass cloth), aramid fiber, aramid paper (aramid paper), polyester fiber, carbon fiber, inorganic fiber and organic fiber It is preferable to include one or more selected from the group consisting of.
  • the present invention provides a copper foil laminate comprising the prepreg and copper foil, and formed by stacking one or more layers thereof, and a printed circuit board including the same.
  • thermosetting resin composition according to the present invention satisfies low dielectric properties and at the same time excellent workability, the laminate using the same may exhibit excellent high frequency characteristics, good moisture absorption heat resistance, and low thermal expansion characteristics.
  • thermosetting resin composition of the present invention is a component of a printed circuit board used in a mobile communication device that handles high frequency signals of 1 GHz or more, 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 use.
  • the present invention seeks to provide a thermosetting resin composition that can be usefully used in printed circuit boards, especially multilayer printed circuit boards for high frequency applications.
  • the dielectric loss of the electrical signal is proportional to the product of the square root of the dielectric constant of the insulating layer forming the circuit, the dielectric tangent and the frequency of the electrical signal, the higher the frequency of the electrical signal, the larger the dielectric loss. Therefore, in order to be used in an insulating layer of a high frequency printed circuit board, it is required to use a material having a low dielectric constant and dielectric loss factor (dielectric loss).
  • the present invention intends to use polyphenylene oxide (PPO) as a constituent of the thermosetting resin composition, but the workability deterioration and copper foil adhesion resulting from the use of PPO having a high molecular weight.
  • PPO polyphenylene oxide
  • a redistribution reaction of a high molecular weight polyphenylene oxide and a specific bisphenol derivative having increased alkyl and aromatic content forms a polyphenylene oxide resin having a low molecular weight.
  • both ends of the redistributed low molecular weight polyphenylene oxide resin are polymers having an alcohol group, or both ends of the redistributed polyphenylene oxide are substituted with a low polarity substituent such as a vinyl group.
  • a resin excellent in dielectric properties and excellent in workability and compatibility can be ensured.
  • the carbon number of the alkyl group in the molecule is increased than the conventionally used Bisphenol A (BPA) to reduce the overall polarity. That is, as the alkyl group content and the aromatic ring group content increase, electron polarization may be reduced and dielectric properties may be improved. Therefore, it was confirmed that a laminate having high heat resistance and dimensional stability may be manufactured by improving low dielectric loss characteristics and improving crosslinking density (see Table 1 below).
  • BPA Bisphenol A
  • unsaturated bonds are possible by modifying both ends of the modified polyphenylene oxide molecular chain having excellent dielectric properties with an unsaturated double bond moiety, for example, a vinyl group. This can cause crosslinking reaction by heat, which contributes to improvement of heat resistance and can suppress deformation and flow of the insulating layer.
  • thermosetting system not only satisfies moisture resistance and dielectric properties due to improved glass transition temperature (Tg), low coefficient of thermal expansion (CTE), and -OH (hydroxy) group, but also can be applied to existing thermosetting system. In addition, it can secure various physical properties and processability at the same time.
  • Tg glass transition temperature
  • CTE low coefficient of thermal expansion
  • -OH hydroxy
  • thermosetting resin composition is a thermosetting resin composition comprising: (a) a modified polyphenylene oxide resin modified at low molecular weight and having at least two hydroxyl groups and / or vinyl groups at both ends of the molecular chain; And (b) a crosslinkable curing agent. At this time, if necessary, it 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 first component constituting the thermosetting resin composition according to the present invention is a modified polyphenylene oxide (PPO) or an oligomer thereof, as long as it contains at least two vinyl groups or hydroxyl groups (-OH) at both ends of the molecular chain. It may be used without particular limitation.
  • PPO polyphenylene oxide
  • oligomer thereof as long as it contains at least two vinyl groups or hydroxyl groups (-OH) at both ends of the molecular chain. It may be used without particular limitation.
  • the modified polyphenylene oxide resin according to the present invention is preferably a modified polyphenylene oxide represented by the following general formula (1) or (2). This is because the side has been modified with two or more vinyl groups, it is possible to satisfy the moisture resistance and dielectric properties due to the glass transition temperature, low thermal expansion coefficient, -OH group reduction.
  • Ar is a bisphenol derivative compound except bisphenol A
  • R is the same as or different from each other, and each independently an alkyl group having 1 to 12 carbon atoms,
  • R 1 and R 2 are the same as or different from each other, and are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aromatic group having 6 to 12 carbon atoms,
  • X is the same as or different from each other, and each independently a hydroxyl group or a vinyl group,
  • n is a natural number between 1 and 10,000, and a is an integer between 0 and 4.
  • Ar means a bisphenol derivative except for bisphenol A (BPA), and is preferably represented by Formula 3 or Formula 4, respectively.
  • R 1 and R 2 are the same as or different from each other, and each independently an alkyl group having 1 to 12 carbon atoms or a haloalkyl group having 1 to 12 carbon atoms, provided that when n is 0, both R 1 and R 2 are alkyl groups Excluded)
  • R 3 is hydrogen or an alkyl group having 1 to 12 carbon atoms
  • n is a natural number between 0 and 3
  • m is a natural number between 1 and 3.
  • the modified polyphenylene oxide resin (a) according to the present invention is more preferably a compound represented by any one of the following formulas (5) to (8).
  • R 1 , R 2 and n are the same as defined in Chemical Formulas 1 and 2,
  • Ar is preferably represented by any one of the following formulas (9) to (14).
  • the one having two or more vinyl groups or hydroxyl groups (-OH) at both ends of the molecular chain is mainly used, but in addition to the vinyl group, conventional unsaturated double bonds known in the art such as allyl groups (allyl)
  • sex moieties is also within the scope of the present invention.
  • the conventional polyphenylene oxide for copper foil laminates was modified by using a high molecular polyphenylene oxide as a low molecular polyphenylene oxide having an alcohol group at both terminals through a redistribution reaction using a polyphenol and a radical initiator as a catalyst. Due to the structural characteristics of Bisphenol A (formula 20), a polyphenol used, and high polarity of alcohol groups at both ends formed after redistribution, there was a limit in implementing low dielectric loss characteristics.
  • the polyphenols used in the redistribution reaction are redistributed using specific bisphenol derivatives (except BPA) having an increased alkyl content and aromatic aromatic content, except for both ends.
  • BPA bisphenol derivatives
  • the polyphenylene oxide having a low dielectric loss can be obtained even after crosslinking by modifying the alcohol group located at the low polar group. Since the modified polyphenylene oxide has a lower molecular weight and a higher alkyl content than the existing polyphenylene derivatives, the modified polyphenylene oxide has excellent compatibility with existing epoxy resins, and improves processability by increasing flowability in manufacturing laminates. The dielectric properties are further improved. Therefore, the printed circuit board manufactured using the resin composition of the present invention has an advantage of improving physical properties such as formability, processability, dielectric properties, heat resistance, and adhesive strength.
  • the specific bisphenol derivative compound having an increased alkyl group content and aromatic aromatic group (aromatic) content can be used without limitation bisphenol-based compounds other than bisphenol A [BPA, 2,2-Bis (4-hydroxyphenyl) propane].
  • bisphenol derivatives that can be used include bisphenol AP (1,1-Bis (4-hydroxyphenyl) -1-phenyl-ethane), bisphenol AF (2,2-Bis (4-hydroxyphenyl) hexafluoropropane), bisphenol B ( 2,2-Bis (4-hydroxyphenyl) butane), bisphenol BP (Bis- (4-hydroxyphenyl) diphenylmethane), bisphenol C (2,2-Bis (3-methyl-4-hydroxyphenyl) propane), bisphenol C (Bis (4-hydroxyphenyl) -2,2-dichlorethylene), bisphenol G (2,2-Bis (4-hydroxy-3-isopropyl-phenyl) propane), bisphenol M (1,3-Bis (2-hydroxy-4-hydroxyphenyl) propane), bisphenol
  • the modified polyphenylene oxide resin (a) has a specific bisphenol compound and a radical represented by any one of the following Chemical Formulas 9 to 14 for the high molecular weight polyphenylene oxide resin having a weight average molecular weight (Mw) in the range of 5,000 to 350,000. It is preferred that the redistribution reaction in the presence of an initiator modify the weight average molecular weight (Mw) to a low molecular weight in the range of 1000 to 20,000. More preferably from 1000 to 10,000. However, it is not particularly limited thereto.
  • the bisphenol compound may be any one or more of the following formula (16) to formula (19).
  • the second component constituting the thermosetting resin composition according to the present invention is a crosslinkable curing agent.
  • cross-linking curing agents are used to crosslink the polyphenylene oxide in three dimensions to form a network structure. Even if low molecular weight modified polyphenylene oxide is used to increase the flowability of the resin composition, the use of a crosslinking curing agent contributes to the improvement of heat resistance of the 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 according to the present invention has excellent miscibility with polyphenylene oxide whose side is modified with a vinyl group.
  • crosslinkable curing agents that can be used 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 heat resistance and reliability.
  • 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 (c) 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.
  • Additive bromine flame retardants that are not reactive with poly (phenylene oxide) and do not degrade heat and dielectric properties are suitable 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.
  • 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 (d) known in the art used for lamination, if necessary.
  • inorganic fillers 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.
  • 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 and mechanical properties. 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 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 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 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, silicone resin, and the like. It may also include additives commonly used in thermosetting resin compositions used in the production of electronic devices (especially printed wiring boards).
  • the thermosetting resin composition comprises (a) a modified polyphenylene oxide resin containing at least two hydroxyl groups / vinyl groups at both ends of the molecular chain, modified to a low molecular weight; Based on 100 parts by weight of the 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, and may be optionally mixed with various organic solvents such as acetone, cyclohexanone, methyl ethyl ketone, toluene, xylene, tetrahydrofuran and the like.
  • 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 of this invention contains the 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; And it is provided on one or both surfaces of the metal foil, and provides a metal foil with a resin comprising a resin layer cured the thermosetting resin composition.
  • the metal foil can be used without limitation those made of a common metal or alloy 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.
  • the copper foil that can be used include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, ILSIN, and the like.
  • the present invention includes a 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 resin composition described above can be sufficiently stirred at room temperature using a stirrer, impregnated with a glass substrate, dried, laminated with copper foil, and applied with heat and pressure to obtain a desired laminate.
  • the heating pressure conditions may be appropriately adjusted according to the thickness of the laminate to be manufactured or the type 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 1 below). Therefore, the prepreg and printed circuit board of the present invention are used for a mobile communication device that handles 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 of a printed circuit board.
  • Alcohol terminal polymer polyphenylene oxide used in the present invention used commercially available SA-120 (SABIC Co., Ltd.), in order to secure the properties of the other copper foil laminate plate, cyanate resin, epoxy resin, curing agent, curing accelerator, inorganic filler, As a solvent, commercially available products were used without purification.
  • the cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of 0.85 Kg of light brown powder having a weight average molecular weight (Mw) of 6,500 was obtained.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the polyphenylene oxide before redistribution reaction was 9000.
  • the cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of 0.85 Kg of light brown powder having a weight average molecular weight (Mw) of 3,500 was obtained.
  • the cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of 0.8 Kg of light brown powder having a weight average molecular weight (Mw) of 6,300 was obtained.
  • the cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of 0.75 Kg of light brown powder having a weight average molecular weight (Mw) of 7,200 was obtained.
  • the cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of 0.82 Kg of light brown powder having a weight average molecular weight (Mw) of 6,600 was obtained.
  • the resin composition having the composition as shown in Table 1 was impregnated into the glass fiber substrate, and then dried at 150 ° C. for 5 minutes to obtain a prepreg having a resin content of 50% by weight. Eight sheets of the above prepregs were stacked and 18 ⁇ m copper foils were laminated on both outer surfaces, and then pressed at 210 ° C. under 25 kg / cm 2 for 150 minutes to prepare a copper foil laminate.
  • a copper foil laminate was manufactured in the same manner as in Example 1, except that polyphenylene oxide of Synthesis Example 2 was used instead of polyphenylene oxide of Synthesis Example 6.
  • a copper foil laminate was manufactured through the same process as in Example 1, except that the resin composition having the composition shown in Table 1 was applied.
  • 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 simultaneously exhibited improved adhesion to copper foil, excellent heat resistance, thermal stability, and the like (see Table 1 above).
  • Example 1 and Example 2 exhibited a lower dielectric constant and excellent low dielectric loss characteristics, compared to Comparative Example 1 and Comparative Example 2 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 provides a thermosetting resin composition, a prepreg comprising the composition, and a copper-clad laminate, the thermosetting resin composition comprising: (a) a modified polyphenylene oxide resin which is redistributed in the presence of a bisphenol compound (except for bisphenol A) and a radical initiator, so that the weight-average molecular weight (Mw) is modified to a low molecular weight range of 1,000 to 20,000, and which has at least two functional groups selected from a group consisting of a hydroxy group and a vinyl group, at both ends of a molecular chain; and (b) a crosslinkable curing agent. The present invention can provide a printed circuit board for high frequency simultaneously exhibiting excellent low dielectric loss characteristics as well as excellent processability, copper foil adhesive property, thermal stability, etc.

Description

변성 폴리페닐렌 옥사이드를 이용한 동박적층판Copper Clad Laminated Plate Using Modified Polyphenylene Oxide
본 발명은 동박 적층판용 수지 조성물에 저유전 손실의 특성을 가지는 변성 폴리페닐렌 옥사이드 수지를 적용하여, 저유전 특성을 구현하면서도 가공성이 우수한 프리프레그 및 프리프레그를 이용한 동박 적층판에 관한 것이다. The present invention applies a modified polyphenylene oxide resin having a low dielectric loss characteristic to the resin composition for copper foil laminated plate, and relates to a copper foil laminate using prepreg and prepreg excellent in processability while implementing low dielectric properties.
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 분자량이 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 옥사이드인 SA-90 (SABIC 社)는 우수한 에폭시 수지와의 상용성과 높은 녹는점이 개선이 되었으나, 재분배에 사용된 폴리 페놀인 Bisphenol A (4,4'-(propane-2,2-diyl)diphenol)의 구조적인 특성 및 양 말단에 있는 알코올기의 높은 극성으로 인해 유전 특성을 낮추는 것에 한계가 있었다. Therefore, in order to improve the above-mentioned disadvantages, a technique of forming a low molecular weight polyphenylene oxide having alcohol groups introduced at both terminals through a redistribution reaction of high molecular weight polyphenylene oxide and polyphenol in the presence of a radical initiator has been proposed. In fact, commercially available redistribution polyphenylene oxide SA-90 (SABIC) has improved the compatibility with high epoxy resins and high melting point, but Bisphenol A (4,4 '-(propane-2), a polyphenol used for redistribution Due to the structural properties of (2-diyl) diphenol) and the high polarity of the alcohol groups at both ends, there was a limit to lowering the dielectric properties.
본 발명은 전술한 문제점을 해결하기 위해서 안출된 것이다.The present invention has been made to solve the above problems.
본 발명에서는 유전적 특성을 개선하기 위해서, 분자량이 높은 폴리페닐렌 옥사이드와 알킬(alkyl) 함량과 방향족(aromatic) 함량이 증가된 특정 비스페놀 유도체를 재분배 반응하여 저분자량 폴리페닐렌 옥사이드 수지를 확보하고, 상기 저분자량 폴리페닐렌 옥사이드의 양 말단을 알코올기나 극성이 낮은 비닐기(Vinyl group)로 변성함으로써 유전특성이 우수하고, 가공성 및 상용성이 우수한 수지를 확보하였다. In the present invention, in order to improve the dielectric properties, a low molecular weight polyphenylene oxide resin is obtained by redistributing a high molecular weight polyphenylene oxide and a specific bisphenol derivative having an increased alkyl content and aromatic content. By modifying both ends of the low molecular weight polyphenylene oxide with an alcohol group or a low polar vinyl group, a resin having excellent dielectric properties and excellent processability and compatibility was obtained.
이에, 본 발명은 전술한 변성 폴리페닐렌 옥사이드를 포함하여 우수한 가공성과 낮은 유전특성을 발휘하는 열경화성 수지 조성물, 상기 조성물을 이용하는 프리프레그 및 동박적층판을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a thermosetting resin composition including the above-mentioned modified polyphenylene oxide, which exhibits excellent processability and low dielectric properties, a prepreg and a copper foil laminated plate using the composition.
본 발명은 (a) 변성 폴리페닐렌 옥사이드 수지; 및 (b) 가교결합성 경화제를 포함하며, 상기 변성 폴리페닐렌 옥사이드 수지(a)는 비스페놀 화합물 (비스페놀A는 제외)과 라디칼 개시제 존재 하에서 재분배되어 중량 평균 분자량 (Mw, Weight-average molecular weight)이 1,000 내지 20,000 범위의 저분자량으로 개질되고, 분자쇄의 양 말단에 히드록시기 및 비닐기로 구성된 군으로부터 선택되는 관능기를 2개 이상 포함하는 것을 특징으로 하는 열경화성 수지 조성물을 제공한다. The present invention (a) modified polyphenylene oxide resin; And (b) a crosslinkable curing agent, wherein the modified polyphenylene oxide resin (a) is redistributed in the presence of a bisphenol compound (except bisphenol A) and a radical initiator to obtain a weight-average molecular weight (Mw). It provides a thermosetting resin composition which is modified to a low molecular weight in the range of 1,000 to 20,000, and includes at least two functional groups selected from the group consisting of hydroxy groups and vinyl groups at both ends of the molecular chain.
이때 상기 열경화성 수지 조성물은 고주파용 다층 인쇄회로기판 제조용 열경화성 수지 조성물인 것이 바람직하다. At this time, the thermosetting resin composition is preferably a thermosetting resin composition for manufacturing a high frequency multilayer printed circuit board.
본 발명에서, 상기 변성 폴리페닐렌 옥사이드는 하기 화학식 1 또는 화학식 2로 표시되는 것이 바람직하다. In the present invention, the modified polyphenylene oxide is preferably represented by the following formula (1) or (2).
본 발명에 따른 바람직한 일례에 따르면, 상기 변성 폴리페닐렌 옥사이드 수지(a)는 중량 평균 분자량(Mw)이 5,000 ~ 350,000 범위의 고분자량 폴리페닐렌옥사이드 수지를 특정 비스페놀 화합물과 라디칼 개시제 존재 하에서 재분배반응하여 저분자량으로 개질된 것이 바람직하다. 여기서, 상기 특정 비스페놀 화합물은 비스페놀A(BPA)를 제외한 비스페놀 계열 화합물로서, BPA 보다 분자 내 알킬기(alkyl) 함량과 방향족 고리기(aromatic) 함량이 높은 화합물이다. According to a preferred embodiment of the present invention, the modified polyphenylene oxide resin (a) is redistribution reaction of a high molecular weight polyphenylene oxide resin having a weight average molecular weight (Mw) in the range of 5,000 to 350,000 in the presence of a specific bisphenol compound and a radical initiator Is preferably modified to low molecular weight. Herein, the specific bisphenol compound is a bisphenol-based compound except for bisphenol A (BPA), and is a compound having a higher alkyl group content and aromatic aromatic group content than BPA.
또한 상기 가교결합성 경화제(b)는 트리알릴이소시아누레이트 (TAIC), 다이-4-바이닐벤질 옥사이드, 디비닐벤젠, 디비닐나프탈렌, 디비닐페닐, 1,7-옥타디엔, 및 1,9-테카디엔으로 구성된 군으로부터 선택된 1종 이상인 것이 바람직하다. In addition, the crosslinkable curing agent (b) is triallyl isocyanurate (TAIC), di-4-vinylbenzyl oxide, divinylbenzene, divinyl naphthalene, divinylphenyl, 1,7-octadiene, and 1, It is preferable that it is at least one selected from the group consisting of 9-tecadiene.
본 발명의 바람직한 다른 일례에 따르면, 상기 열경화성 수지 조성물은 난연제, 무기 필러, 러버, 경화 촉진제, 및 라디칼 개시제로 구성된 군으로부터 선택되는 것을 더 포함하는 것이 바람직하다. According to another preferred embodiment of the present invention, the thermosetting resin composition preferably further comprises one selected from the group consisting of a flame retardant, an inorganic filler, a rubber, a curing accelerator, and a radical initiator.
아울러, 본 발명은 섬유 기재; 및 상기 섬유 기재에 함침된 전술한 열경화성 수지 조성물을 포함하는 프리프레그(prepreg)를 제공한다.In addition, the present invention is a fiber substrate; And it provides a prepreg comprising the above-mentioned thermosetting resin composition impregnated on the fiber substrate.
여기서, 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 것이 바람직하다. Here, the fiber base material is glass fiber, glass paper, glass fiber nonwoven fabric (glass web), glass cloth (glass cloth), aramid fiber, aramid paper (aramid paper), polyester fiber, carbon fiber, inorganic fiber and organic fiber It is preferable to include one or more selected from the group consisting of.
나아가, 본 발명은 상기 프리프레그(prepreg) 및 동박을 포함하며, 이들을 1층 이상 적층하여 성형된 동박 적층판 및 이를 포함하는 인쇄회로기판을 제공한다.Furthermore, the present invention provides a copper foil laminate comprising the prepreg and copper foil, and formed by stacking one or more layers thereof, and a printed circuit board including the same.
본 발명에 따른 열경화성 수지 조성물은 저유전 특성을 만족하면서 이와 동시에 우수한 가공성을 나타내므로, 이를 이용한 적층판은 우수한 고주파 특성과 양호한 흡습 내열성, 저열팽창 특성을 나타낼 수 있다. Since the thermosetting resin composition according to the present invention satisfies low dielectric properties and at the same time excellent workability, the laminate using the same may exhibit excellent high frequency characteristics, good moisture absorption heat resistance, and low thermal expansion characteristics.
따라서 본 발명의 열경화성 수지 조성물은 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 인쇄회로기판의 부품 용도로서 유용하게 사용될 수 있다. Therefore, the thermosetting resin composition of the present invention is a component of a printed circuit board used in a mobile communication device that handles high frequency signals of 1 GHz or more, 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 use.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 인쇄회로기판, 특히 고주파수 용도의 다층 인쇄회로기판에 유용하게 사용될 수 있는 열경화성 수지 조성물을 제공하고자 한다.The present invention seeks to provide a thermosetting resin composition that can be usefully used in printed circuit boards, especially multilayer printed circuit boards for high frequency applications.
전기신호의 유전손실은 회로를 형성하는 절연층의 비유전율의 평방근, 유전 정접 및 전기신호의 주파수의 곱에 비례하기 때문에, 전기신호의 주파수가 높을수록 유전 손실이 커진다. 따라서 고주파수 인쇄회로기판의 절연층에 사용되기 위해서는, 유전율과 유전 손실인자(유전손실)이 낮은 물질을 사용하는 것이 요구된다. Since the dielectric loss of the electrical signal is proportional to the product of the square root of the dielectric constant of the insulating layer forming the circuit, the dielectric tangent and the frequency of the electrical signal, the higher the frequency of the electrical signal, the larger the dielectric loss. Therefore, in order to be used in an insulating layer of a high frequency printed circuit board, it is required to use a material having a low dielectric constant and dielectric loss factor (dielectric loss).
전술한 낮은 유전 특성 및 유전손실 특성을 만족시키기 위해, 본 발명에서는 열경화성 수지 조성물의 구성 성분으로 폴리페닐렌 옥사이드 (PPO)를 사용하고자 하나, 높은 분자량을 갖는 PPO를 사용시 초래되는 가공성 저하, 동박 접착력 저하, 내열성 부족 등을 고려하여, 분자량이 높은 폴리페닐렌 옥사이드와 알킬(alkyl) 함량과 방향족(aromatic) 함량이 증가된 특정 비스페놀 유도체를 재분배 반응하여 저분자량을 갖는 폴리페닐렌 옥사이드 수지를 형성한다. 한편 본 발명에서는 상기 재분배된 저분자량의 폴리페닐렌 옥사이드 수지의 양쪽 말단이 알코올기인 고분자이거나, 또는 상기 폴리페닐렌 옥사이드를 재분배한 후 양 말단을 극성이 낮은 치환기, 예컨대 비닐기(Vinyl group)로 변성시켜 얻은 고분자를 사용함으로써, 유전특성이 우수하고, 가공성 및 상용성이 우수한 수지를 확보할 수 있다.In order to satisfy the low dielectric and dielectric loss characteristics described above, the present invention intends to use polyphenylene oxide (PPO) as a constituent of the thermosetting resin composition, but the workability deterioration and copper foil adhesion resulting from the use of PPO having a high molecular weight. In consideration of degradation, lack of heat resistance, and the like, a redistribution reaction of a high molecular weight polyphenylene oxide and a specific bisphenol derivative having increased alkyl and aromatic content forms a polyphenylene oxide resin having a low molecular weight. . Meanwhile, in the present invention, both ends of the redistributed low molecular weight polyphenylene oxide resin are polymers having an alcohol group, or both ends of the redistributed polyphenylene oxide are substituted with a low polarity substituent such as a vinyl group. By using the polymer obtained by denaturation, a resin excellent in dielectric properties and excellent in workability and compatibility can be ensured.
특히, 본 발명에서 폴리페닐렌 옥사이드의 재분배 반응에 사용되는 비스페놀 유도체들은, 종래 사용되는 Bisphenol A (BPA) 보다 분자 내에 알킬 그룹의 탄소수가 증가하여 전체적인 극성을 감소시킨다. 즉, 알킬기(alkyl) 함량과 방향족 고리기(aromatic) 함량이 증가함에 따라 전자 분극 현상을 줄이고 유전특성을 개선할 수 있다. 따라서 저유전 손실 특성 구현과 가교 밀도를 향상시켜 내열 및 치수 안정성이 높은 적층판을 제조할 수 있음을 확인하였다(하기 표 1 참조).In particular, the bisphenol derivatives used in the redistribution reaction of the polyphenylene oxide in the present invention, the carbon number of the alkyl group in the molecule is increased than the conventionally used Bisphenol A (BPA) to reduce the overall polarity. That is, as the alkyl group content and the aromatic ring group content increase, electron polarization may be reduced and dielectric properties may be improved. Therefore, it was confirmed that a laminate having high heat resistance and dimensional stability may be manufactured by improving low dielectric loss characteristics and improving crosslinking density (see Table 1 below).
또한 본 발명에서는 유전 특성이 우수한 변성 폴리페닐렌 옥사이드 분자쇄의 양 말단을 불포화 이중결합성 모이어티, 일례로 비닐기(vinyl)로 개질함으로써, 불포화 결합이 가능하다. 이는 열에 의해 가교 반응이 일어나, 내열 향상에 기여하고 절연층의 변형, 유동을 억제시킬 수 있다. In addition, in the present invention, unsaturated bonds are possible by modifying both ends of the modified polyphenylene oxide molecular chain having excellent dielectric properties with an unsaturated double bond moiety, for example, a vinyl group. This can cause crosslinking reaction by heat, which contributes to improvement of heat resistance and can suppress deformation and flow of the insulating layer.
아울러, 유리 전이온도(Tg) 향상, 낮은 열팽창계수(CTE), 및 -OH (하이드록시)기의 감소로 인한 내습성 및 유전특성을 만족시킬 뿐만 아니라, 기존 열경화 시스템에서 적용이 가능하도록 하였으며, 다양한 물성 확보와 가공성을 동시에 확보할 수 있다. In addition, it not only satisfies moisture resistance and dielectric properties due to improved glass transition temperature (Tg), low coefficient of thermal expansion (CTE), and -OH (hydroxy) group, but also can be applied to existing thermosetting system. In addition, it can secure various physical properties and processability at the same time.
<열경화성 수지 조성물><Thermosetting resin composition>
본 발명에 따른 열경화성 수지 조성물은 열경화성 수지 조성물로서, (a) 저분자량으로 개질되고, 분자쇄의 양쪽 말단에 2개 이상의 히드록시기 및/또는 비닐기를 갖는 변성 폴리페닐렌 옥사이드 수지; 및 (b) 가교결합성 경화제를 포함하여 구성될 수 있다. 이때 필요에 따라 시아네이트 수지, 에폭시 수지, 난연제, 무기 필러, 경화촉진제, 라디칼 개시제, 용매 등을 더 포함할 수 있다. The thermosetting resin composition according to the present invention is a thermosetting resin composition comprising: (a) a modified polyphenylene oxide resin modified at low molecular weight and having at least two hydroxyl groups and / or vinyl groups at both ends of the molecular chain; And (b) a crosslinkable curing agent. At this time, if necessary, it 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.
(a) 변성 폴리페닐렌 옥사이드 수지(a) Modified Polyphenylene Oxide Resin
본 발명에 따른 열경화성 수지 조성물을 구성하는 첫번째 성분은 변성 폴리페닐렌 옥사이드(PPO) 또는 이의 올리고머로서, 분자쇄의 양 말단에 2개 이상의 비닐기나 히드록시기(-OH)를 포함하는 것이면, 그 구조에 특별히 한정되지 않고 사용될 수 있다.The first component constituting the thermosetting resin composition according to the present invention is a modified polyphenylene oxide (PPO) or an oligomer thereof, as long as it contains at least two vinyl groups or hydroxyl groups (-OH) at both ends of the molecular chain. It may be used without particular limitation.
본 발명에 따른 변성 폴리페닐렌 옥사이드 수지는 하기 화학식 1 또는 화학식 2로 표시되는 변성 폴리페닐렌 옥사이드가 바람직하다. 이는 사이드가 2개 이상의 비닐기로 개질되었으므로, 유리전이온도 향상, 낮은 열팽창계수, -OH기 감소로 인한 내습 특성 및 유전특성을 만족시킬 수 있기 때문이다. The modified polyphenylene oxide resin according to the present invention is preferably a modified polyphenylene oxide represented by the following general formula (1) or (2). This is because the side has been modified with two or more vinyl groups, it is possible to satisfy the moisture resistance and dielectric properties due to the glass transition temperature, low thermal expansion coefficient, -OH group reduction.
화학식 1
Figure PCTKR2014009030-appb-C000001
 Formula 1
Figure PCTKR2014009030-appb-C000001
화학식 2
Figure PCTKR2014009030-appb-C000002
 Formula 2
Figure PCTKR2014009030-appb-C000002
상기 화학식 1 또는 화학식 2에서, In Chemical Formula 1 or Chemical Formula 2,
Ar 은 비스페놀A를 제외한 비스페놀 유도체 화합물이고, Ar is a bisphenol derivative compound except bisphenol A,
R은 서로 동일하거나 또는 상이하며, 각각 독립적으로 탄소수 1~12의 알킬기이며, R is the same as or different from each other, and each independently an alkyl group having 1 to 12 carbon atoms,
R1과 R2는 서로 동일하거나 또는 상이하며, 각각 독립적으로 수소, 탄소수 1~12의 알킬기, 탄소수 1~12의 알콕시기 및 탄소수 6~12의 방향족기이며, R 1 and R 2 are the same as or different from each other, and are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aromatic group having 6 to 12 carbon atoms,
X는 서로 동일하거나 또는 상이하며, 각각 독립적으로 히드록시기 또는 비닐기이며, X is the same as or different from each other, and each independently a hydroxyl group or a vinyl group,
n은 1 내지 10,000 사이의 자연수이며, a는 0 내지 4 사이의 정수이다. n is a natural number between 1 and 10,000, and a is an integer between 0 and 4.
상기 화학식 1~2에서, Ar은 비스페놀A (BPA)를 제외한 비스페놀 유도체를 의미하며, 각각 화학식 3 또는 화학식 4로 표시되는 것이 바람직하다. In Formulas 1 to 2, Ar means a bisphenol derivative except for bisphenol A (BPA), and is preferably represented by Formula 3 or Formula 4, respectively.
화학식 3
Figure PCTKR2014009030-appb-C000003
 Formula 3
Figure PCTKR2014009030-appb-C000003
화학식 4
Figure PCTKR2014009030-appb-C000004
 Formula 4
Figure PCTKR2014009030-appb-C000004
상기 화학식 3 또는 4에서, In Chemical Formula 3 or 4,
R1 과 R2는 서로 동일하거나 또는 상이하며, 각각 독립적으로 탄소수 1 내지 12의 알킬기 또는 탄소수 1 내지 12의 할로알킬기이며, (단, n이 0인 경우 R1 및 R2 모두가 알킬기인 경우는 제외됨) R 1 and R 2 are the same as or different from each other, and each independently an alkyl group having 1 to 12 carbon atoms or a haloalkyl group having 1 to 12 carbon atoms, provided that when n is 0, both R 1 and R 2 are alkyl groups Excluded)
R3는 수소, 또는 탄소수 1~12의 알킬기이며, R 3 is hydrogen or an alkyl group having 1 to 12 carbon atoms,
n은 0 내지 3 사이의 자연수이며, m은 1 내지 3 사이의 자연수이다. n is a natural number between 0 and 3, and m is a natural number between 1 and 3.
본 발명에 따른 변성 폴리페닐렌 옥사이드 수지(a)는 하기 화학식 5 내지 화학식 8 중 어느 하나로 표시되는 화합물인 것이 보다 바람직하다. The modified polyphenylene oxide resin (a) according to the present invention is more preferably a compound represented by any one of the following formulas (5) to (8).
화학식 5
Figure PCTKR2014009030-appb-C000005
 Formula 5
Figure PCTKR2014009030-appb-C000005
화학식 6
Figure PCTKR2014009030-appb-C000006
 Formula 6
Figure PCTKR2014009030-appb-C000006
화학식 7
Figure PCTKR2014009030-appb-C000007
 Formula 7
Figure PCTKR2014009030-appb-C000007
화학식 8
Figure PCTKR2014009030-appb-C000008
 Formula 8
Figure PCTKR2014009030-appb-C000008
상기 화학식 5~8에서, In Chemical Formulas 5 to 8,
R1, R2 및 n은 각각 화학식 1~2에서 정의된 바와 같으며, R 1 , R 2 and n are the same as defined in Chemical Formulas 1 and 2,
Ar은 하기 화학식 9 내지 화학식 14 중 어느 하나로 표시되는 것이 바람직하다. Ar is preferably represented by any one of the following formulas (9) to (14).
[화학식 9][Formula 9]
Figure PCTKR2014009030-appb-I000001
(n = 1~3)
Figure PCTKR2014009030-appb-I000001
(n = 1 to 3)
[화학식 10][Formula 10]
Figure PCTKR2014009030-appb-I000002
(n=1~3)
Figure PCTKR2014009030-appb-I000002
(n = 1 to 3)
[화학식 11][Formula 11]
Figure PCTKR2014009030-appb-I000003
(n=0~3)
Figure PCTKR2014009030-appb-I000003
(n = 0-3)
[화학식 12][Formula 12]
Figure PCTKR2014009030-appb-I000004
(n=0~3)
Figure PCTKR2014009030-appb-I000004
(n = 0-3)
[화학식 13][Formula 13]
Figure PCTKR2014009030-appb-I000005
(n=0~3)
Figure PCTKR2014009030-appb-I000005
(n = 0-3)
[화학식 14][Formula 14]
Figure PCTKR2014009030-appb-I000006
(n=0~3)
Figure PCTKR2014009030-appb-I000006
(n = 0-3)
본 발명에서는 분자쇄의 양 말단에 2개 이상의 비닐(vinyl)기나 히드록시기(-OH)를 가진 것을 주로 사용하고 있으나, 상기 비닐기 이외에 알릴기(allyl) 등의 당 업계에 알려진 통상적인 불포화 이중결합성 모이어티(moiety)를 사용하는 것도 본 발명의 범주에 속한다. In the present invention, the one having two or more vinyl groups or hydroxyl groups (-OH) at both ends of the molecular chain is mainly used, but in addition to the vinyl group, conventional unsaturated double bonds known in the art such as allyl groups (allyl) The use of sex moieties is also within the scope of the present invention.
한편 본 발명에서는 종래 고분자량의 폴리페닐렌 옥사이드(PPO) 수지를 그대로 사용하는 대신, 알킬기(Alkyl) 함량과 방향족 고리기(Aromatic) 함량이 증가된 특정 비스페놀(Bisphenol) 유도체들을 이용하여 재분배반응을 통해 상기 고분자량의 PPO 보다 저분자량을 갖도록 개질된 형태로서, 재분배를 통한 수지의 양 말단에 비닐기(Vinyl group)가 도입된 형태를 사용하는 것이 바람직하다. Meanwhile, in the present invention, instead of using a conventional high molecular weight polyphenylene oxide (PPO) resin as it is, redistribution reaction using specific bisphenol (Bisphenol) derivatives having increased alkyl group (Akyl) content and aromatic ring group (Aromatic) content As the modified form to have a lower molecular weight than the high molecular weight PPO, it is preferable to use a form in which vinyl groups are introduced at both ends of the resin through redistribution.
즉, 종래 동박 적층판용 폴리페닐렌 옥사이드는 고분자 폴리페닐렌 옥사이드를 폴리페놀과 라디칼 개시제를 촉매로 사용한 재분배 반응을 통하여 양 말단에 알코올기를 가지는 저분자 폴리페닐렌 옥사이드로 개질하여 사용하였으나, 종래 재분배에 사용되는 폴리페놀인 Bisphenol A (하기 화학식 20)의 구조적 특성과 재분배 후 생성되는 양 말단의 알코올기의 높은 극성으로 인하여 낮은 유전손실 특성 구현에 한계가 있었다.That is, the conventional polyphenylene oxide for copper foil laminates was modified by using a high molecular polyphenylene oxide as a low molecular polyphenylene oxide having an alcohol group at both terminals through a redistribution reaction using a polyphenol and a radical initiator as a catalyst. Due to the structural characteristics of Bisphenol A (formula 20), a polyphenol used, and high polarity of alcohol groups at both ends formed after redistribution, there was a limit in implementing low dielectric loss characteristics.
이에 비해, 본 발명에서는 재분배 반응에 사용되는 폴리페놀을 알킬기(Alkyl) 함량과 방향족 고리기(Aromatic) 함량이 증가된 특정 비스페놀(Bisphenol) 유도체들(BPA 제외)을 사용하여 재분배한 후, 양 말단에 위치하는 알코올기를 극성이 낮은 비닐기(Vinyl group)로 변형함으로써 가교 후에도 유전손실이 적은 폴리페닐렌 옥사이드를 얻을 수 있다. 이러한 변성 폴리페닐렌 옥사이드는, 기존 폴리 페닐렌 유도체들보다 분자량이 작고, 또한 알킬기(alkyl) 함량이 높기 때문에 기존 에폭시 수지 등과 상용성이 우수하고, 적층판 제조시 흐름성이 증가하여 공정성이 개선되고, 유전특성이 추가로 개선된다. 따라서, 본 발명의 수지 조성물을 사용하여 제조된 인쇄회로기판은 성형성, 가공성, 유전특성, 내열성, 접착강도 등의 물성이 향상되는 장점이 있다.In contrast, in the present invention, the polyphenols used in the redistribution reaction are redistributed using specific bisphenol derivatives (except BPA) having an increased alkyl content and aromatic aromatic content, except for both ends. The polyphenylene oxide having a low dielectric loss can be obtained even after crosslinking by modifying the alcohol group located at the low polar group. Since the modified polyphenylene oxide has a lower molecular weight and a higher alkyl content than the existing polyphenylene derivatives, the modified polyphenylene oxide has excellent compatibility with existing epoxy resins, and improves processability by increasing flowability in manufacturing laminates. The dielectric properties are further improved. Therefore, the printed circuit board manufactured using the resin composition of the present invention has an advantage of improving physical properties such as formability, processability, dielectric properties, heat resistance, and adhesive strength.
이때, 상기 알킬기(alkyl) 함량과 방향족 고리기(aromatic) 함량이 증가된 특정 비스페놀 유도체 화합물은 비스페놀A [BPA, 2,2-Bis(4-hydroxyphenyl)propane]를 제외한 비스페놀 계열 화합물을 제한 없이 사용할 수 있다. 사용 가능한 비스페놀 유도체의 비제한적인 예로는 비스페놀 AP(1,1-Bis(4-hydroxyphenyl)-1-phenyl-ethane), 비스페놀 AF(2,2-Bis(4-hydroxyphenyl)hexafluoropropane), 비스페놀 B(2,2-Bis(4-hydroxyphenyl)butane), 비스페놀 BP(Bis-(4-hydroxyphenyl)diphenylmethane), 비스페놀C (2,2-Bis(3-methyl-4-hydroxyphenyl)propane), 비스페놀 C(Bis(4-hydroxyphenyl)-2,2-dichlorethylene), 비스페놀 G(2,2-Bis(4-hydroxy-3-isopropyl-phenyl)propane), 비스페놀 M(1,3-Bis(2-(4-hydroxyphenyl)-2-propyl)benzene), 비스페놀 P(Bis(4-hydroxyphenyl)sulfone), 비스페놀 PH(5,5'-(1-Methylethyliden)-bis[1,1'-(bisphenyl)-2-ol]propane), 비스페놀 TMC(1,1-Bis(4-hydroyphenyl)-3,3,5-trimethyl-cyclohexane), 비스페놀 Z(1,1-Bis(4-hydroxyphenyl)-cyclohexane) 또는 이들의 1종 이상 혼합물 등이 있다. 바람직하게는, 화학식 9 내지 화학식 14로 이루어진 비스페놀 계열 화합물 군에서 선택되는 1종 이상을 사용할 수 있으며, 일례로 하기 화학식 16 내지 화학식 19 중 어느 하나 이상의 비스페놀 계열 화합물일 수 있다.In this case, the specific bisphenol derivative compound having an increased alkyl group content and aromatic aromatic group (aromatic) content can be used without limitation bisphenol-based compounds other than bisphenol A [BPA, 2,2-Bis (4-hydroxyphenyl) propane]. Can be. Non-limiting examples of bisphenol derivatives that can be used include bisphenol AP (1,1-Bis (4-hydroxyphenyl) -1-phenyl-ethane), bisphenol AF (2,2-Bis (4-hydroxyphenyl) hexafluoropropane), bisphenol B ( 2,2-Bis (4-hydroxyphenyl) butane), bisphenol BP (Bis- (4-hydroxyphenyl) diphenylmethane), bisphenol C (2,2-Bis (3-methyl-4-hydroxyphenyl) propane), bisphenol C (Bis (4-hydroxyphenyl) -2,2-dichlorethylene), bisphenol G (2,2-Bis (4-hydroxy-3-isopropyl-phenyl) propane), bisphenol M (1,3-Bis (2- (4-hydroxyphenyl) ) -2-propyl) benzene), bisphenol P (Bis (4-hydroxyphenyl) sulfone), bisphenol PH (5,5 '-(1-Methylethyliden) -bis [1,1'-(bisphenyl) -2-ol] propane), bisphenol TMC (1,1-Bis (4-hydroyphenyl) -3,3,5-trimethyl-cyclohexane), bisphenol Z (1,1-Bis (4-hydroxyphenyl) -cyclohexane) or one or more thereof Mixtures and the like. Preferably, at least one selected from the group of bisphenol-based compounds consisting of Formulas 9 to 14 may be used, and for example, at least one bisphenol-based compound of Formulas 16 to 19 may be used.
본 발명에 따른 변성 폴리페닐렌 옥사이드 수지(a)는 중량 평균 분자량(Mw)이 5,000~350,000 범위의 고분자량 폴리페닐렌 옥사이드 수지를 하기 화학식 9 내지 화학식 14 중 어느 하나로 표시되는 특정 비스페놀 화합물과 라디칼 개시제 존재 하에서 재분배 반응하여 중량 평균 분자량(Mw)이 1000 내지 20,000 범위의 저분자량으로 개질된 것이 바람직하다. 보다 바람직하게는 1000 내지 10,000 범위일 수 있다. 그러나 이에 특별히 제한되는 것은 아니다. The modified polyphenylene oxide resin (a) according to the present invention has a specific bisphenol compound and a radical represented by any one of the following Chemical Formulas 9 to 14 for the high molecular weight polyphenylene oxide resin having a weight average molecular weight (Mw) in the range of 5,000 to 350,000. It is preferred that the redistribution reaction in the presence of an initiator modify the weight average molecular weight (Mw) to a low molecular weight in the range of 1000 to 20,000. More preferably from 1000 to 10,000. However, it is not particularly limited thereto.
이때 상기 비스페놀 화합물은 하기 화학식 16 내지 화학식 19 중 어느 하나 이상의 비스페놀 계열 화합물을 사용할 수 있다.In this case, the bisphenol compound may be any one or more of the following formula (16) to formula (19).
(b) 가교결합성 경화제(b) crosslinkable curing agents
본 발명에 따른 열경화성 수지 조성물을 구성하는 두번째 성분은 가교결합성 경화제이다. The second component constituting the thermosetting resin composition according to the present invention is a crosslinkable curing agent.
이러한 가교결합(cross-linking)성 경화제는 상기 폴리페닐렌 옥사이드를 3차원 적으로 가교결합시켜 망상구조를 형성하기 위해 사용되는 것이다. 레진 조성물의 유동성을 증가시키기 위해 저분자량으로 개질된 폴리페닐렌 옥사이드를 사용하더라도, 가교결합성 경화제 사용으로 인해 폴리페닐렌 옥사이드의 내열성 개선에 기여하게 된다. 또한 수지 조성물의 유동성을 증가시키며 다른 기재(예, 구리 호일)와의 박리 강도를 향상시키는 효과를 갖는다.Such cross-linking curing agents are used to crosslink the polyphenylene oxide in three dimensions to form a network structure. Even if low molecular weight modified polyphenylene oxide is used to increase the flowability of the resin composition, the use of a crosslinking curing agent contributes to the improvement of heat resistance of the 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 발명에 따른 가교결합성 경화제는 사이드가 비닐기로 개질된 폴리페닐렌 옥사이드와 우수한 혼화성을 갖는 것이 바람직하다. 사용 가능한 가교결합성 경화제의 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.It is preferable that the crosslinkable curing agent according to the present invention has excellent miscibility with polyphenylene oxide whose side is modified with a vinyl group. Non-limiting examples of crosslinkable curing agents that can be used 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 특성 뿐만 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.
(c) 난연제(c) flame retardants
본 발명에 따른 열경화성 수지 조성물은, 필요에 따라 난연제(c)를 더 포함할 수 있다. The thermosetting resin composition which concerns on this invention can further contain a flame retardant (c) 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 폴레(페닐렌 옥사이드)와 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. Additive bromine flame retardants that are not reactive with poly (phenylene oxide) and do not degrade heat and dielectric properties are suitable in the present invention.
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.
(d) 무기 필러(d) weapon filler
본 발명에 따른 열경화성 수지 조성물은, 필요에 따라 라미네이트에 사용되는 당 업계에 알려진 통상적인 무기 필러(d)를 더 포함할 수 있다. The thermosetting resin composition according to the present invention may further include a conventional inorganic filler (d) known in the art used for lamination, if necessary.
이러한 무기 필러는 수지층과 다른 층간의 열팽창계수(CTE) 차이를 감소시켜 최종 제품의 휨 특성, 저팽창화, 기계적 강도(toughness), 저응력화를 효과적으로 향상시킬 수 있다. These inorganic fillers 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. 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.
상기 무기 필러 중에서는 낮은 열팽창계수를 나타내는 용융 실리카가 가장 바람직하다. Among the 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 and mechanical properties. 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.
본 발명에 따른 열경화성 수지 조성물은, 가교 결합성 경화제의 유리한 효과를 강화하기 위해 반응 개시제를 더 포함할 수 있다. 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 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 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 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 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 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 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 응력완화제 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, silicone resin, and the like. It may also include additives commonly 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) 분자쇄의 양 말단에 히드록시기/비닐기를 2개 이상 포함하고, 저분자량으로 개질된 변성 폴리페닐렌 옥사이드 수지; 상기 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 comprises (a) a modified polyphenylene oxide resin containing at least two hydroxyl groups / vinyl groups at both ends of the molecular chain, modified to a low molecular weight; Based on 100 parts by weight of the 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 혼용할 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, and may be optionally mixed with various organic solvents such as acetone, cyclohexanone, methyl ethyl ketone, toluene, xylene, tetrahydrofuran and the like. 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 발명의 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 of this invention contains the 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.
<수지 부착 동박><Copper foil with resin>
본 발명은 금속박; 및 상기 금속박의 일면 또는 양면 상에 형성되고, 상기 열경화성 수지 조성물이 경화된 수지층을 포함하는 수지 부착 금속박을 제공한다.The present invention is a metal foil; And it is provided on one or both surfaces of the metal foil, and provides a metal foil with a resin comprising a resin layer cured the thermosetting resin composition.
본 발명의 수지 부착 금속박에서, 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. In the metal foil with a resin of the present invention, the metal foil can be used without limitation those made of a common metal or alloy 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 the copper foil that can be used include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, ILSIN, and the like.
<적층판 및 인쇄회로기판><Laminated board and printed circuit board>
본 발명은 전술한 프리프레그(prepreg) 2개 이상을 서로 겹친 후, 이를 통상의 조건으로 가열, 가압하여 형성되는 적층판을 포함한다. The present invention includes a 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 적층판을 얻을 수 있다. 이때 적층판 성형시, 가열가압 조건은 제조하는 적층판의 두께나 본 발명에 따른 열경화성 수지 조성물의 종류 등에 따라 적절히 조절될 수 있다.In one example, the resin composition described above can be sufficiently stirred at room temperature using a stirrer, impregnated with a glass substrate, dried, laminated with copper foil, and applied with heat and pressure to obtain a desired laminate. At this time, when forming the laminate, the heating pressure conditions may be appropriately adjusted according to the thickness of the laminate to be manufactured or the type 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 1 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 1 below). Therefore, the prepreg and printed circuit board of the present invention are used for a mobile communication device that handles 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 of a printed circuit board.
이하 본 발명을 실시예를 통해 구체적으로 설명하나, 하기 실시예 및 실험예는 본 발명의 한 형태를 예시하는 것에 불과할 뿐이며, 본 발명의 범위가 하기 실시예 및 실험예에 의해 제한되는 것은 아니다. 또한, 이하의 기재에 있어서, 「부」는 「질량부」를 의미한다.Hereinafter, the present invention will be described in detail with reference to Examples, but the following Examples and Experimental Examples are merely illustrative of one embodiment of the present invention, and the scope of the present invention is not limited to the following Examples and Experimental Examples. In addition, in the following description, "part" means a "mass part."
<재료><Material>
본 발명에서 사용되는 알코올 말단 고분자 폴리페닐렌 옥사이드는 상용화되어 있는 SA-120 (SABIC 社)를 사용하였고, 기타 동박 적층판의 특성 확보를 위해 시아네이트 수지, 에폭시 수지, 경화제, 경화 촉진제, 무기 충진제, 용매 등은 상용화 되어 있는 제품을 정제 없이 사용하였다. Alcohol terminal polymer polyphenylene oxide used in the present invention used commercially available SA-120 (SABIC Co., Ltd.), in order to secure the properties of the other copper foil laminate plate, cyanate resin, epoxy resin, curing agent, curing accelerator, inorganic filler, As a solvent, commercially available products were used without purification.
[합성예 1]Synthesis Example 1
화학식 16을 사용한 알코올 말단 변성 폴리페닐렌 옥사이드 제조Preparation of Alcohol Terminal Modified Polyphenylene Oxide Using Formula 16
온도계, 교반기 및 냉각기를 구비한 20L 둥근바닥 플라스크에 1.0 Kg 의 화학식 15와 화학식 16 0.1 Kg과 Toluene 10 Kg을 투입한 후 60℃로 가열하며 질소 분위기 하에서 충분히 용해시켰다. 촉매로서 Benzoyl peroxide 75% 10g을 Toluene 90g 녹인 후 반응기로 천천히 적하시켰다. 적하가 끝난 후 반응기의 온도를 90℃로 승온시켜 8시간 30분 반응 후에 상온으로 냉각시켰다. 냉각된 반응액을 Toluene에 약 50%까지 농축시킨 후, 농축액을 과량의 메탄올에 침전시켜 침전물을 진공오븐에 80℃에서 24시간 건조 시켰다. 건조 후 중량 평균 분자량(Mw)이 6,500인 0.85 Kg 의 연한 갈색 분말 형태의 재분배 폴리페닐렌 옥사이드 수지를 수득하였다. 여기서, 재분배 반응 이전의 폴리페닐렌 옥사이드의 중량 평균 분자량(Mw)은 9000 이었다. Into a 20 L round bottom flask equipped with a thermometer, a stirrer, and a cooler, 1.0 Kg of Formula 15, 16 Kg of Formula 16, and 10 Kg of Toluene were added thereto, and then heated to 60 ° C. and sufficiently dissolved in a nitrogen atmosphere. As a catalyst, 10 g of Benzoyl peroxide 75% was dissolved in 90 g of toluene and slowly added dropwise into the reactor. After the dropping was completed, the temperature of the reactor was raised to 90 ° C., and then cooled to room temperature after the reaction for 8 hours and 30 minutes. The cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of 0.85 Kg of light brown powder having a weight average molecular weight (Mw) of 6,500 was obtained. Here, the weight average molecular weight (Mw) of the polyphenylene oxide before redistribution reaction was 9000.
[화학식 15][Formula 15]
Figure PCTKR2014009030-appb-I000007
Figure PCTKR2014009030-appb-I000007
[화학식 16][Formula 16]
Figure PCTKR2014009030-appb-I000008
Figure PCTKR2014009030-appb-I000008
[합성예 2]Synthesis Example 2
화학식 16을 사용한 알코올 말단 변성 폴리페닐렌 옥사이드 제조Preparation of Alcohol Terminal Modified Polyphenylene Oxide Using Formula 16
온도계, 교반기 및 냉각기를 구비한 20L 둥근바닥 플라스크에 1.0 Kg의 화학식 15와 화학식 16 0.5Kg과 Toluene 10 Kg을 투입한 후 60℃로 가열하며 질소 분위기 하에서 충분히 용해시켰다. 촉매로서 벤조일 페록사이드(Benzoyl peroxide) 75% 10g을 Toluene 90g 녹인 후 반응기로 천천히 적하시켰다. 적하가 끝난 후 반응기의 온도를 90℃로 승온시켜 8시간 30분 반응 후에 상온으로 냉각시켰다. 냉각된 반응액을 Toluene에 약 50%까지 농축시킨 후, 농축액을 과량의 메탄올에 침전시켜 침전물을 진공오븐에 80℃에서 24시간 건조시켰다. 건조 후 중량 평균 분자량(Mw)이 3,500인 0.85 Kg 의 연한 갈색 분말 형태의 재분배 폴리페닐렌 옥사이드 수지를 수득하였다.Into a 20 L round bottom flask equipped with a thermometer, a stirrer, and a cooler, 1.0 Kg of Formula 15, 0.5 Kg of Formula 16, and 10 Kg of Toluene were added thereto, and then heated to 60 ° C. and sufficiently dissolved in a nitrogen atmosphere. As a catalyst, 10 g of 75% of benzoyl peroxide (Benzoyl peroxide) was dissolved in 90 g of toluene and slowly added dropwise into the reactor. After the dropping was completed, the temperature of the reactor was raised to 90 ° C., and then cooled to room temperature after the reaction for 8 hours and 30 minutes. The cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of 0.85 Kg of light brown powder having a weight average molecular weight (Mw) of 3,500 was obtained.
[합성예 3]Synthesis Example 3
화학식 17을 사용한 알코올 말단 변성 폴리페닐렌 옥사이드 제조Preparation of Alcohol Terminal Modified Polyphenylene Oxide Using Formula 17
온도계, 교반기 및 냉각기를 구비한 20L 둥근바닥 플라스크에 1.0 Kg의 화학식 15와 화학식 17 0.1Kg과 Toluene 10 Kg을 투입한 후 60℃로 가열하며 질소 분위기 하에서 충분히 용해시켰다. 촉매로서 Benzoyl peroxide 75% 10g을 Toluene 90g 녹인 후 반응기로 천천히 적하시켰다. 적하가 끝난 후 반응기의 온도를 90℃로 승온시켜 8시간 30분 반응 후에 상온으로 냉각시켰다. 냉각된 반응액을 Toluene에 약 50%까지 농축시킨 후, 농축액을 과량의 메탄올에 침전시켜 침전물을 진공오븐에 80℃에서 24시간 건조시켰다. 건조 후 중량 평균 분자량(Mw)이 6,300인 0.8 Kg 의 연한 갈색 분말 형태의 재분배 폴리페닐렌 옥사이드 수지를 수득하였다.Into a 20 L round bottom flask equipped with a thermometer, a stirrer, and a cooler, 1.0 Kg of Formula 15, 0.1 Kg of Formula 17, and 10 Kg of Toluene were added thereto, and then heated to 60 ° C. and sufficiently dissolved in a nitrogen atmosphere. As a catalyst, 10 g of Benzoyl peroxide 75% was dissolved in 90 g of toluene and slowly added dropwise into the reactor. After the dropping was completed, the temperature of the reactor was raised to 90 ° C., and then cooled to room temperature after the reaction for 8 hours and 30 minutes. The cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of 0.8 Kg of light brown powder having a weight average molecular weight (Mw) of 6,300 was obtained.
[화학식 17][Formula 17]
Figure PCTKR2014009030-appb-I000009
Figure PCTKR2014009030-appb-I000009
[합성예 4]Synthesis Example 4
화학식 18을 사용한 알코올 말단 변성 폴리페닐렌 옥사이드 제조Preparation of Alcohol Terminal Modified Polyphenylene Oxide Using Formula 18
온도계, 교반기 및 냉각기를 구비한 20L 둥근바닥 플라스크에 1.0 Kg 의 화학식 15와 화학식 18 0.1 Kg과 Toluene 10 Kg을 투입한 후 60℃로 가열하며 질소 분위기 하에서 충분히 용해시켰다. 촉매로서 Benzoyl peroxide 75% 10g을 Toluene 90g 녹인 후 반응기로 천천히 적하시켰다. 적하가 끝난 후 반응기의 온도를 90℃로 승온시켜 8시간 30분 반응 후에 상온으로 냉각시켰다. 냉각된 반응액을 Toluene에 약 50%까지 농축시킨 후, 농축액을 과량의 메탄올에 침전시켜 침전물을 진공오븐에 80℃에서 24시간 건조시켰다. 건조 후 중량 평균 분자량(Mw)이 7,200인 0.75 Kg 의 연한 갈색 분말 형태의 재분배 폴리페닐렌 옥사이드 수지를 수득하였다.1.0 Kg of Formula 15, 0.1 Kg of Formula 18, and 10 Kg of Toluene were added to a 20 L round bottom flask equipped with a thermometer, a stirrer, and a cooler, and heated to 60 ° C., and sufficiently dissolved in a nitrogen atmosphere. As a catalyst, 10 g of Benzoyl peroxide 75% was dissolved in 90 g of toluene and slowly added dropwise into the reactor. After the dropping was completed, the temperature of the reactor was raised to 90 ° C., and then cooled to room temperature after the reaction for 8 hours and 30 minutes. The cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of 0.75 Kg of light brown powder having a weight average molecular weight (Mw) of 7,200 was obtained.
[화학식 18][Formula 18]
Figure PCTKR2014009030-appb-I000010
Figure PCTKR2014009030-appb-I000010
[합성예 5]Synthesis Example 5
화학식 19를 사용한 알코올 말단 변성 폴리페닐렌 옥사이드 제조Preparation of Alcohol Terminal Modified Polyphenylene Oxide Using Formula 19
온도계, 교반기 및 냉각기를 구비한 20L 둥근바닥 플라스크에 1.0 Kg 의 화학식 15와 화학식 19 0.1Kg과 Toluene 10 Kg을 투입한 후 60℃로 가열하며 질소 분위기 하에서 충분히 용해시켰다. 촉매로서 Benzoyl peroxide 75% 10g을 Toluene 90g 녹인 후 반응기로 천천히 적하시켰다. 적하가 끝난 후 반응기의 온도를 90℃로 승온시켜 8시간 30분 반응 후에 상온으로 냉각시켰다. 냉각된 반응액을 Toluene에 약 50%까지 농축시킨 후, 농축액을 과량의 메탄올에 침전시켜 침전물을 진공오븐에 80℃에서 24시간 건조시켰다. 건조 후 중량 평균 분자량(Mw)이 6,600인 0.82 Kg 의 연한 갈색 분말 형태의 재분배 폴리페닐렌 옥사이드 수지를 수득하였다.1.0 Kg of Formula 15, 0.1 Kg of Formula 19, and 10 Kg of Toluene were added to a 20 L round bottom flask equipped with a thermometer, a stirrer, and a cooler, and then heated to 60 ° C. and sufficiently dissolved in a nitrogen atmosphere. As a catalyst, 10 g of Benzoyl peroxide 75% was dissolved in 90 g of toluene and slowly added dropwise into the reactor. After the dropping was completed, the temperature of the reactor was raised to 90 ° C., and then cooled to room temperature after the reaction for 8 hours and 30 minutes. The cooled reaction solution was concentrated to about 50% in Toluene, and then the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, a redistributed polyphenylene oxide resin in the form of 0.82 Kg of light brown powder having a weight average molecular weight (Mw) of 6,600 was obtained.
[화학식 19][Formula 19]
Figure PCTKR2014009030-appb-I000011
Figure PCTKR2014009030-appb-I000011
[합성예 6]Synthesis Example 6
1-1. 비닐 말단 변성 폴리페닐렌 옥사이드 제조1-1. Vinyl Terminal Modified Polyphenylene Oxide Preparation
온도계, 교반기 및 냉각기를 구비한 5L 둥근바닥 플라스크에 합성예 2에서 얻은 폴리페닐렌 옥사이드 700 g과 Methacrylic anhydride 127 g, 4-Dimethylaminopyridine 100 g을 Toluene 1400g에 용해시킨 후 Reflux 온도까지 승온하여 6시간 반응을 진행한 후 상온까지 반응액을 냉각시켰다. 냉각된 반응액을 과량의 메탄올에 침전을 시키고, 수득된 침전물을 충분한 메탄올로 세척하였다. 얻어진 침전물을 진공 오븐에서 80℃로 24시간 건조시켰다. 건조 후 중량 평균 분자량(Mw)이 3,650인 연한 갈색의 분말 형태의 비닐기가 도입된 폴리페닐렌 옥사이드 수지 700g을 수득하였다. In a 5L round bottom flask equipped with a thermometer, a stirrer and a cooler, 700 g of polyphenylene oxide obtained in Synthesis Example 2, 127 g of Methacrylic anhydride, and 100 g of 4-Dimethylaminopyridine were dissolved in 1400 g of toluene, and the temperature was raised to Reflux temperature for 6 hours. After proceeding to cool the reaction solution to room temperature. The cooled reaction solution was precipitated in excess methanol and the precipitate obtained was washed with sufficient methanol. The precipitate obtained was dried at 80 ° C. for 24 hours in a vacuum oven. After drying, 700 g of a polyphenylene oxide resin having a vinyl group in the form of a light brown powder having a weight average molecular weight (Mw) of 3,650 was obtained.
[합성예 7]Synthesis Example 7
화학식 20을 사용한 알코올 말단 변성 폴리페닐렌 옥사이드 제조Preparation of Alcohol Terminal Modified Polyphenylene Oxide Using Formula 20
온도계, 교반기 및 냉각기를 구비한 20L 둥근 바닥 플라스크에 화학식 15 1.0 Kg과 화학식 20의 화합물 (BPA) 0.5 Kg과 Toluene 10 Kg을 투입 후 60℃로 가열하며 질소 분위기 하에서 충분히 용해시켰다. 촉매로서 Benzoyl peroxide 75% 10g을 Toluene 90g 녹인 후 반응기로 천천히 적하시켰다. 적하가 끝난 후 반응기의 온도를 90℃로 승온시켜 8시간 30분 반응 후에 상온으로 냉각시켰다. 냉각된 반응액을 Toluene에 약 50%까지 농축 후, 농축액을 과량의 메탄올에 침전시켜 침전물을 진공오븐에 80℃에서 24시간 건조 시켰다. 건조 후 중량 평균 분자량(Mw)이 3,800인 0.80 Kg 의 연한 갈색 분말 형태의 알코올 말단 변성 폴리페닐렌 옥사이드 수지를 수득하였다.Into a 20 L round bottom flask equipped with a thermometer, a stirrer, and a cooler, 1.0 Kg of Formula 15, 0.5 Kg of Compound (BPA) and 10 Kg of Toluene were added thereto, and the resulting mixture was heated to 60 ° C and sufficiently dissolved in a nitrogen atmosphere. As a catalyst, 10 g of Benzoyl peroxide 75% was dissolved in 90 g of toluene and slowly added dropwise into the reactor. After the dropping was completed, the temperature of the reactor was raised to 90 ° C., and then cooled to room temperature after the reaction for 8 hours and 30 minutes. After the cooled reaction solution was concentrated to about 50% in Toluene, the concentrate was precipitated in excess methanol, and the precipitate was dried in a vacuum oven at 80 ° C. for 24 hours. After drying, an alcohol terminal modified polyphenylene oxide resin in the form of 0.80 Kg of light brown powder having a weight average molecular weight (Mw) of 3,800 was obtained.
[화학식 20][Formula 20]
Figure PCTKR2014009030-appb-I000012
Figure PCTKR2014009030-appb-I000012
[합성예 8]Synthesis Example 8
비닐 말단 변성 폴리페닐렌 옥사이드 제조Vinyl Terminal Modified Polyphenylene Oxide Preparation
온도계, 교반기 및 냉각기를 구비한 5L 둥근바닥 플라스크에 합성예 7에서 얻은 폴리페닐렌 옥사이드 700g과 Methacrylic anhydride 127g와 4-Dimethylaminopyridine 100 g을 Toluene 1400g에 용해한 후 Reflux 온도까지 승온하여 6시간 반응을 진행한 후 상온까지 반응액을 냉각시켰다. 냉각된 반응액을 과량의 메탄올에 침전시키고 수득된 침전물을 충분한 메탄올로 세척하였다. 얻어진 침전물을 진공오븐에서 80℃로 24시간 건조시켰다. 건조 후 중량 평균 분자량(Mw)이 3,900인 700 g의 연한 갈색의 분말 형태의 비닐기가 도입된 폴리페닐렌 옥사이드 수지를 수득하였다.In a 5L round bottom flask equipped with a thermometer, a stirrer, and a cooler, 700 g of polyphenylene oxide, 127 g of methacrylic anhydride, and 100 g of 4-dimethylaminopyridine obtained in Synthesis Example 7 were dissolved in 1400 g of toluene, and then heated to Reflux temperature for 6 hours. After cooling the reaction solution to room temperature. The cooled reaction solution was precipitated in excess methanol and the precipitate obtained was washed with sufficient methanol. The precipitate obtained was dried at 80 ° C. for 24 hours in a vacuum oven. After drying, a polyphenylene oxide resin having a vinyl group introduced in the form of 700 g of a light brown powder having a weight average molecular weight (Mw) of 3,900 was obtained.
[실시예 1. 수지 조성물, 프리프레그 및 동박 적층판의 제조][Example 1. Production of Resin Composition, Prepreg and Copper Foil Laminate]
하기 표 1과 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℃, 25kg/cm2 의 조건으로 150분간 프레스하여 동박 적층판을 제조하였다. The resin composition having the composition as shown in Table 1 was impregnated into the glass fiber substrate, and then dried at 150 ° C. for 5 minutes to obtain a prepreg having a resin content of 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. under 25 kg / cm 2 for 150 minutes to prepare a copper foil laminate.
[실시예 2] Example 2
합성예 6의 폴리페닐렌 옥사이드 대신 합성예 2의 폴리페닐렌 옥사이드를 사용한 것을 제외하고는, 상기 실시예 1과 동일한 과정을 거쳐 동박 적층판을 제조하였다. A copper foil laminate was manufactured in the same manner as in Example 1, except that polyphenylene oxide of Synthesis Example 2 was used instead of polyphenylene oxide of Synthesis Example 6.
[비교예 1 ~ 3] [Comparative Examples 1 to 3]
하기 표 1과 같은 조성의 수지 조성물을 적용한 것을 제외하고는, 상기 실시예 1과 동일한 과정을 거쳐 동박 적층판을 제조하였다.A copper foil laminate was manufactured through the same process as in Example 1, except that the resin composition having the composition shown in Table 1 was applied.
실험예 1. 동박 적층판의 물성 Experimental Example 1. Physical Properties of Copper Clad Laminates
실시예 1~2 및 비교예 1~3에서 제조된 동박 적층판에 대하여 하기 실험을 수행하였으며, 그 결과를 하기 표 1에 나타내었다.The following experiment was performed on the copper foil laminates prepared in Examples 1 and 2 and Comparative Examples 1 to 3, and the results are shown in Table 1 below.
[측정 조건][Measuring conditions]
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 5cmㅧ5cm의 크기로 절단한 적층체를 넣은 후, 10분간 외관 변화를 육안으로 확인하였다.4. Heat resistance: After putting the laminated body cut | disconnected in the size of 5 cm x 5 cm in the lead bath of 288 degreeC, 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 1
　 실시예 1 실시예 2 비교예1 비교예2 비교예 3
폴리페닐렌 옥사이드 (PPO 수지) 합성예 6 100
합성예 2 100
합성예 8 100
합성예 7 100
화학식 15 100
경화제 TAC 40 40 40 40 40
난연제 Saytex 8010 40 40 40 40 40
무기필러 SC-5200SQ 77 77 77 77 77
동박적층판 적용 특성 1GHz Dk 3.63 3.70 3.75 3.82 3.90
Df 0.0025 0.004 0.0045 0.0051 0.0053
P/S (@1/2Oz-gf/cm) 1.0 0.9 0.8 0.8 0.6
내열성(S/F @288) > 600 sec > 300 sec > 300 sec > 300 sec >300sec
Tg 170 160 160 150 130
Table 1
Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3
Polyphenylene Oxide (PPO Resin) Synthesis Example 6 100
Synthesis Example 2 100
Synthesis Example 8 100
Synthesis Example 7 100
Formula 15 100
Hardener TAC 40 40 40 40 40
Flame retardant Saytex 8010 40 40 40 40 40
Inorganic filler SC-5200SQ 77 77 77 77 77
Copper Clad Laminate Application Characteristics 1 GHz Dk 3.63 3.70 3.75 3.82 3.90
Df 0.0025 0.004 0.0045 0.0051 0.0053
P / S (@ 1 / 2Oz-gf / cm) 1.0 0.9 0.8 0.8 0.6
Heat resistance (S / F @ 288) > 600 sec > 300 sec > 300 sec > 300 sec > 300sec
Tg 170 160 160 150 130
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 (상기 표 1 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 simultaneously exhibited improved adhesion to copper foil, excellent heat resistance, thermal stability, and the like (see Table 1 above).
특히, 실시예 1과 실시예 2는 각각 이들의 구성에 대응되는 비교예 1과 비교예 2에 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 1 and Example 2 exhibited a lower dielectric constant and excellent low dielectric loss characteristics, compared to Comparative Example 1 and Comparative Example 2 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 (13)

  1. (a) 변성 폴리페닐렌 옥사이드 수지; 및(a) modified polyphenylene oxide resins; And
    (b) 가교결합성 경화제를 포함하는 열경화성 수지 조성물로서, (b) a thermosetting resin composition comprising a crosslinkable curing agent,
    상기 변성 폴리페닐렌 옥사이드 수지(a)는 비스페놀 화합물 (비스페놀A는 제외)과 라디칼 개시제 존재 하에서 폴리페닐렌 옥사이드를 재분배하여 중량 평균 분자량(Mw)이 1000 내지 20,000 범위의 저분자량으로 개질되고, The modified polyphenylene oxide resin (a) is redistributed to the polyphenylene oxide in the presence of a bisphenol compound (except bisphenol A) and a radical initiator to be modified to a low molecular weight in the range of 1000 to 20,000 by weight average molecular weight (Mw),
    분자쇄의 양 말단에 히드록시기 및 비닐기로 구성된 군으로부터 선택되는 관능기를 2개 이상 포함하는 것을 특징으로 하는 열경화성 수지 조성물. A thermosetting resin composition comprising at least two functional groups selected from the group consisting of hydroxyl groups and vinyl groups at both ends of the molecular chain.
  2. 제1항에 있어서, 상기 변성 폴리페닐렌 옥사이드 수지(a)는 하기 화학식 1 또는 화학식 2로 표시되는 것을 특징으로 하는 열경화성 수지 조성물. The thermosetting resin composition according to claim 1, wherein the modified polyphenylene oxide resin (a) is represented by the following general formula (1) or (2).
    [화학식 1][Formula 1]
    Figure PCTKR2014009030-appb-I000013
    Figure PCTKR2014009030-appb-I000013
    [화학식 2][Formula 2]
    Figure PCTKR2014009030-appb-I000014
    Figure PCTKR2014009030-appb-I000014
    상기 식에서, Where
    Ar 은 비스페놀A를 제외한 비스페놀 계열 화합물이고, Ar is a bisphenol-based compound except for bisphenol A,
    R은 서로 동일하거나 또는 상이하며, 각각 독립적으로 탄소수 1~12의 알킬기이며, R is the same as or different from each other, and each independently an alkyl group having 1 to 12 carbon atoms,
    R1과 R2는 서로 동일하거나 또는 상이하며, 각각 독립적으로 수소, 탄소수 1~12의 알킬기, 탄소수 1~12의 알콕시기 및 탄소수 6~12의 방향족기이며,R 1 and R 2 are the same as or different from each other, and are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aromatic group having 6 to 12 carbon atoms,
    X는 서로 동일하거나 또는 상이하며, 각각 독립적으로 히드록시기 또는 비닐기이며, X is the same as or different from each other, and each independently a hydroxyl group or a vinyl group,
    n은 1 내지 10,000 사이의 자연수이며, a는 0 내지 4 사이의 정수이다.n is a natural number between 1 and 10,000, and a is an integer between 0 and 4.
  3. 제2항에 있어서, 상기 Ar은 하기 화학식 3 또는 화학식 4로 표시되는 것을 특징으로 하는 열경화성 수지 조성물:The thermosetting resin composition according to claim 2, wherein Ar is represented by the following Chemical Formula 3 or Chemical Formula:
    [화학식 3][Formula 3]
    Figure PCTKR2014009030-appb-I000015
    Figure PCTKR2014009030-appb-I000015
    [화학식 4][Formula 4]
    Figure PCTKR2014009030-appb-I000016
    Figure PCTKR2014009030-appb-I000016
    상기 화학식 3 또는 4에서, In Chemical Formula 3 or 4,
    R1 과 R2는 서로 동일하거나 또는 상이하며, 각각 독립적으로 탄소수 1 내지 12의 알킬기 또는 탄소수 1 내지 12의 할로알킬기이며, (단, n이 0인 경우 R1 및 R2 모두가 알킬기인 경우는 제외됨) R 1 and R 2 are the same as or different from each other, and each independently an alkyl group having 1 to 12 carbon atoms or a haloalkyl group having 1 to 12 carbon atoms, provided that when n is 0, both R 1 and R 2 are alkyl groups Excluded)
    R3는 수소, 또는 탄소수 1~12의 알킬기이며, R 3 is hydrogen or an alkyl group having 1 to 12 carbon atoms,
    n은 0 내지 3 사이의 자연수이며, m은 1 내지 3 사이의 자연수이다. n is a natural number between 0 and 3, and m is a natural number between 1 and 3.
  4. 제1항에 있어서, 상기 비스페놀 화합물(비스페놀A는 제외)은 비스페놀 AP(1,1-Bis(4-hydroxyphenyl)-1-phenyl-ethane), 비스페놀 AF(2,2-Bis(4-hydroxyphenyl)hexafluoropropane), 비스페놀 B(2,2-Bis(4-hydroxyphenyl)butane), 비스페놀 BP(Bis-(4-hydroxyphenyl)diphenylmethane), 비스페놀C (2,2-Bis(3-methyl-4-hydroxyphenyl)propane), 비스페놀 C(Bis(4-hydroxyphenyl)-2,2-dichlorethylene), 비스페놀 G(2,2-Bis(4-hydroxy-3-isopropyl-phenyl)propane), 비스페놀 M(1,3-Bis(2-(4-hydroxyphenyl)-2-propyl)benzene), 비스페놀 P(Bis(4-hydroxyphenyl)sulfone), 비스페놀 PH(5,5'-(1-Methylethyliden)-bis[1,1'-(bisphenyl)-2-ol]propane), 비스페놀 TMC(1,1-Bis(4-hydroyphenyl)-3,3,5-trimethyl-cyclohexane), 및 비스페놀 Z(1,1-Bis(4-hydroxyphenyl)-cyclohexane)로 구성된 군으로부터 선택되는 것을 특징으로 하는 열경화성 수지 조성물. The method of claim 1, wherein the bisphenol compound (excluding bisphenol A) is bisphenol AP (1,1-Bis (4-hydroxyphenyl) -1-phenyl-ethane), bisphenol AF (2,2-Bis (4-hydroxyphenyl) hexafluoropropane), bisphenol B (2,2-Bis (4-hydroxyphenyl) butane), bisphenol BP (Bis- (4-hydroxyphenyl) diphenylmethane), bisphenol C (2,2-Bis (3-methyl-4-hydroxyphenyl) propane ), Bisphenol C (Bis (4-hydroxyphenyl) -2,2-dichlorethylene), bisphenol G (2,2-Bis (4-hydroxy-3-isopropyl-phenyl) propane), bisphenol M (1,3-Bis ( 2- (4-hydroxyphenyl) -2-propyl) benzene), bisphenol P (Bis (4-hydroxyphenyl) sulfone), bisphenol PH (5,5 '-(1-Methylethyliden) -bis [1,1'-(bisphenyl ) -2-ol] propane), bisphenol TMC (1,1-Bis (4-hydroyphenyl) -3,3,5-trimethyl-cyclohexane), and bisphenol Z (1,1-Bis (4-hydroxyphenyl) -cyclohexane Thermosetting resin composition, characterized in that it is selected from the group consisting of.
  5. 제1항에 있어서, 상기 변성 폴리페닐렌옥사이드 수지(a)는 중량평균 분자량(Mw)이 5,000 ~ 350,000 범위의 고분자량 폴리페닐렌옥사이드 수지를 비스페놀 화합물 (단, 비스페놀A는 제외)과 라디칼 개시제 존재 하에서 재분배 반응하여 상기 고분자량 폴리페닐렌옥사이드 수지보다 저분자량으로 개질된 것을 특징으로 하는 열경화성 수지 조성물.The method of claim 1, wherein the modified polyphenylene oxide resin (a) is a high molecular weight polyphenylene oxide resin having a weight average molecular weight (Mw) in the range of 5,000 to 350,000 bisphenol compound (except bisphenol A) and a radical initiator The redistribution reaction in the presence of the thermosetting resin composition, characterized in that the modified to a lower molecular weight than the high molecular weight polyphenylene oxide resin.
  6. 제1항에 있어서, 상기 가교결합성 경화제(b)는 트리알릴이소시아누레이트 (TAIC), 다이-4-바이닐벤질 옥사이드, 디비닐벤젠, 디비닐나프탈렌, 디비닐페닐, 1,7-옥타디엔, 및 1,9-테카디엔으로 구성된 군으로부터 선택된 1종 이상인 것을 특징으로 하는 열경화성 수지 조성물. The method of claim 1, wherein the crosslinkable curing agent (b) is triallyl isocyanurate (TAIC), di-4-vinylbenzyl oxide, divinylbenzene, divinyl naphthalene, divinylphenyl, 1,7-octa Thermoene resin composition, characterized in that at least one member selected from the group consisting of dienes, and 1,9- tetadiene.
  7. 제1항에 있어서, 상기 조성물은 난연제를 더 포함하는 것을 특징으로 하는 열경화성 수지 조성물. The thermosetting resin composition of claim 1, wherein the composition further comprises a flame retardant.
  8. 제7항에 있어서, 상기 난연제는 할로겐 함유 난연제, 인계 난연제, 안티몬계 난연제 및 금속 수산화물로 이루어진 군에서 선택되는 1종 이상인 것을 특징으로 하는 열경화성 수지 조성물.The thermosetting resin composition according to claim 7, wherein the flame retardant is at least one selected from the group consisting of halogen-containing flame retardants, phosphorus flame retardants, antimony flame retardants, and metal hydroxides.
  9. 제1항에 있어서, 상기 조성물은 러버 및 무기 필러로 구성된 군으로부터 선택되는 것을 더 포함하는 것을 특징으로 하는 열경화성 수지 조성물.The thermosetting resin composition according to claim 1, wherein the composition further comprises one selected from the group consisting of rubber and inorganic filler.
  10. 섬유 기재; 및 Fiber substrates; And
    상기 섬유 기재에 함침된 제1항 내지 제9항 중 어느 한 항에 기재된 열경화성 수지 조성물을 포함하는 프리프레그.A prepreg comprising the thermosetting resin composition according to any one of claims 1 to 9 impregnated in the fiber base material.
  11. 제10항에 있어서, 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 substrate of claim 10, wherein the fiber substrate is glass fiber, glass paper, glass fiber nonwoven fabric, glass cloth, aramid fiber, aramid paper, polyester fiber, carbon fiber, inorganic fiber And one or more selected from the group consisting of organic fibers.
  12. 금속박 또는 고분자 필름 기재; 및 Metal foil or polymer film base material; And
    상기 기재의 일면 또는 양면 상에 형성되고, 제1항 내지 제9항 중 어느 한 항에 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 in any one of Claims 1-9 hardened | cured.
    을 포함하는 기능성 적층 시트.Functional laminated sheet comprising a.
  13. 제10항의 프리프레그 및 동박을 포함하며, 이들을 1층 이상 적층하여 성형된 것을 특징으로 하는 동박 적층판. The copper foil laminated sheet containing the prepreg and copper foil of Claim 10, These were laminated | stacked and shape | molded one or more layers.
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CN112020523B (en) * 2018-04-27 2023-10-24 松下知识产权经营株式会社 Resin composition, prepreg, resin-coated film, resin-coated metal foil, metal foil-clad laminate, and wiring board
CN114891202A (en) * 2022-03-31 2022-08-12 国科广化(南雄)新材料研究院有限公司 High-temperature-resistant thermosetting polyphenyl ether resin and preparation and application thereof
CN115232461A (en) * 2022-08-03 2022-10-25 吉林大学 Thermosetting polyphenyl ether resin-based composite material, preparation method and application
CN115232461B (en) * 2022-08-03 2023-10-24 吉林大学 Thermosetting polyphenyl ether resin matrix composite material, preparation method and application

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