WO2015046953A1 - Stratifié cuivré utilisant un poly(oxyde de phénylène) modifié - Google Patents

Stratifié cuivré utilisant un poly(oxyde de phénylène) modifié 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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English (en)
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/fr

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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.

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Abstract

La présente invention concerne une composition de résine thermodurcissable, un pré-imprégné comprenant la composition, et un stratifié cuivré, la composition de résine thermodurcissable comprenant : (a) une résine de poly(oxyde de phénylène) modifié, qui est redistribuée en présence d'un composé bisphénol (à l'exception du bisphénol A) et d'un amorceur radicalaire, de telle sorte que la masse moléculaire moyenne en masse (Mw) soit modifiée pour une plage de faibles masses moléculaires, de 1000 à 20 000, et qui possède au moins deux groupes fonctionnels choisis dans un groupe consistant en un groupe hydroxy et un groupe vinyle, aux deux extrémités d'une chaîne moléculaire ; et (b) un agent de durcissement réticulable. La présente invention peut fournir une carte de circuit imprimé pour haute fréquence, présentant simultanément d'excellentes caractéristiques de faible perte diélectrique, ainsi qu'une excellente aptitude à la mise en œuvre, d'excellentes propriétés en tant qu'adhésif sur feuille de cuivre, une excellente stabilité thermique, etc.
PCT/KR2014/009030 2013-09-27 2014-09-26 Stratifié cuivré utilisant un poly(oxyde de phénylène) modifié WO2015046953A1 (fr)

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KR101766014B1 (ko) 2015-06-17 2017-08-07 현대자동차주식회사 파우치 접촉 타입 배터리 셀 및 이를 적용한 배터리 셀 유닛, 배터리 모듈, 배터리 시스템

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CN115232461A (zh) * 2022-08-03 2022-10-25 吉林大学 一种热固性聚苯醚树脂基复合材料、制备方法和应用
CN115232461B (zh) * 2022-08-03 2023-10-24 吉林大学 一种热固性聚苯醚树脂基复合材料、制备方法和应用

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