WO2016105051A1 - Composition de résine thermodurcissable destinée à être utilisée à des fréquences élevées, et pré-imprégné, feuille stratifiée et carte de circuit imprimé l'utilisant - Google Patents

Composition de résine thermodurcissable destinée à être utilisée à des fréquences élevées, et pré-imprégné, feuille stratifiée et carte de circuit imprimé l'utilisant Download PDF

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Publication number
WO2016105051A1
WO2016105051A1 PCT/KR2015/014030 KR2015014030W WO2016105051A1 WO 2016105051 A1 WO2016105051 A1 WO 2016105051A1 KR 2015014030 W KR2015014030 W KR 2015014030W WO 2016105051 A1 WO2016105051 A1 WO 2016105051A1
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WIPO (PCT)
Prior art keywords
resin composition
thermosetting resin
group
bisphenol
fiber
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PCT/KR2015/014030
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English (en)
Korean (ko)
Inventor
정동희
권정돈
김무현
홍도웅
Original Assignee
주식회사 두산
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Priority claimed from KR1020150179108A external-priority patent/KR101865649B1/ko
Application filed by 주식회사 두산 filed Critical 주식회사 두산
Priority to CN201580068649.XA priority Critical patent/CN107109049B/zh
Priority to US15/538,488 priority patent/US10590272B2/en
Priority to JP2017551981A priority patent/JP6684822B2/ja
Publication of WO2016105051A1 publication Critical patent/WO2016105051A1/fr
Priority to US16/424,251 priority patent/US10584239B2/en

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation

Definitions

  • the present invention relates to a novel high-frequency thermosetting resin composition that can simultaneously exhibit excellent low dielectric loss characteristics, good moisture absorption heat resistance, low thermal expansion characteristics, excellent thermal stability, and the like, and prepregs, functional laminated sheets, and copper foil laminates using the same.
  • polyphenylene ether resin having excellent dielectric properties was applied, but it had problems such as high melt viscosity, difficulty in handling, and moldability of prepreg.
  • thermoplastic resin such as polyphenylene ether resin having excellent dielectric properties.
  • the present invention has been made to solve the above-described problems, by using a polyphenylene ether resin in which both sides of the molecular chain is modified with an unsaturated bond substituent and three or more specific crosslinking curing agents, thereby improving heat resistance and low dielectric constant characteristics At the same time, a thermosetting resin composition having excellent overall physical properties was produced.
  • an object of the present invention is to provide a thermosetting resin composition exhibiting excellent heat resistance and low dielectric properties, a prepreg, a laminated sheet and a printed circuit board using the composition.
  • the present invention (a) a polyphenylene ether having two or more unsaturated substituents selected from the group consisting of vinyl and allyl groups at both ends of the molecular chain or oligomers thereof; (b) at least three different crosslinkable curing agents; And (c) provides a high-frequency thermosetting resin composition comprising a flame retardant.
  • the high frequency thermosetting resin composition may further include an inorganic filler surface-treated with a vinyl group-containing silane coupling agent.
  • the crosslinkable curing agent may be a mixture of a hydrocarbon-based crosslinking agent (b1), a crosslinking agent (b2) containing three or more functional groups and a rubber of the block structure (b3).
  • the present invention also provides a fiber substrate surface-treated with a vinyl group-containing silane coupling agent; And it provides a prepreg comprising the above-mentioned thermosetting resin composition impregnated in the fiber substrate.
  • the present invention is a metal foil or a polymer film substrate; And a resin layer formed on one or both surfaces of the substrate and including a cured resin layer of the above-mentioned thermosetting resin composition.
  • the present invention provides a printed circuit board characterized in that the laminate is formed by including one or more layers of the prepreg.
  • thermosetting resin composition according to the present invention simultaneously satisfies the glass transition temperature (Tg) improvement, low coefficient of thermal expansion (CTE), low dielectric properties, low dielectric loss and high heat resistance, excellent processability, the printed circuit board using the high frequency characteristics And good moisture absorption heat resistance and low thermal expansion characteristics can be exhibited.
  • Tg glass transition temperature
  • CTE coefficient of thermal expansion
  • low dielectric properties low dielectric loss and high heat resistance
  • excellent processability the printed circuit board using the high frequency characteristics
  • good moisture absorption heat resistance and low thermal expansion characteristics can be exhibited.
  • thermosetting resin composition of the present invention is a printed circuit board for mobile communication devices that handle high frequency signals of 1 GHz or higher, network-related electronic devices such as base station devices, servers, routers, and various electrical and electronic devices such as large computers. It can be usefully used as a component.
  • 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 relative 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 low dielectric constant and dielectric loss factor (dielectric loss). Due to these demands, high frequency substrate materials have been developed to reduce the hydroxyl groups of epoxy resins, crosslinking methods of thermoplastic resins, application of liquid crystal polymers or polyimide, etc. to realize low dielectric polymer materials. To satisfy the high frequency characteristics, there is insufficient dielectric characteristics or difficulty in forming a substrate.
  • polyphenylene ether (poly (phenylene ether), PPE] was used as a component of the thermosetting resin composition, but low heat resistance caused when using PPE And polyphenylene ethers in which both ends of the molecular chain are modified with a vinyl group or allyl group, in which both ends of the molecular chain are unsaturated bond substituents, and three or more specific crosslinking curing agents in combination with the PPE resin melt. Characterized in that.
  • both ends of the polyphenylene ether are modified with a vinyl group, an allyl group, and the like to enable an unsaturated bond.
  • This can cause crosslinking reaction by heat, which contributes to improvement of heat resistance and can suppress deformation and flow of the insulating layer.
  • the glass transition temperature (Tg), low coefficient of thermal expansion (CTE) and -OH (hydroxy) group not only satisfies the moisture resistance and dielectric properties, but also can be applied in the existing thermal curing system, By studying the dielectric properties according to the crosslinking agent properties, it is possible to secure various physical properties and processability at the same time.
  • both ends are treated with a vinyl group to increase the compatibility of the PPE base resin (base) resin, and by using three or more crosslinkable curing agents having excellent dielectric properties, not only low dielectric properties can be realized through radical polymerization, but also excellent heat resistance and mechanical properties can be realized. (See Table 3 below).
  • the three or more types of crosslinkable curing agents may be mixed with a hydrocarbon-based crosslinking agent, a crosslinking agent containing three or more functional groups, and a block structure rubber.
  • the hydrocarbon-based crosslinking agent since the hydrocarbon-based crosslinking agent has a low polarization property, not only can implement low dielectric properties, but also has excellent molding processability due to flowability.
  • the resin composition of the present invention since the resin composition of the present invention has elastomeric properties due to the hydrocarbon-based crosslinking agent at the time of curing, it is effective for drill wear during drilling.
  • a hydrocarbon-based crosslinking agent is used together with a crosslinking agent containing three or more functional groups (hereinafter, 'three or more functional group-containing crosslinking agents')
  • the volume skeleton of the resin itself increases due to the three or more functional group-containing crosslinking agents.
  • Synergistic effect with the hydrocarbon-based curing agent can be exerted not only to achieve lower dielectric properties than when using a hydrocarbon-based crosslinking agent alone, but also to increase the crosslinking density to improve heat resistance.
  • a block structure rubber such as styrene-butadiene rubber together with the crosslinking agents
  • a rigid structure such as styrene in the polymer chain may act as a domain after curing of the resin composition, and in particular, improve mechanical properties.
  • thermosetting resin composition according to the present invention is a non-epoxy clock thermosetting resin composition, (a) a polyphenylene ether having two or more unsaturated substituents selected from the group consisting of vinyl groups and allyl groups at both ends of the molecular chain, or a Oligomers; (b) three or more crosslinkable curing agents; And (c) flame retardants.
  • the thermosetting resin composition may further include an inorganic filler surface-treated with a vinyl group-containing silane coupling agent.
  • a curing accelerator, an initiator eg, a radical initiator
  • thermosetting resin composition according to the present invention comprises polyphenylene ether (PPE) or an oligomer thereof.
  • PPE polyphenylene ether
  • the PPE or oligomer thereof has two or more vinyl groups, allyl groups, or both at both ends of the molecular chain, and may be used without particular limitation on its structure.
  • the allylated polyphenylene ether represented by following General formula (1) is preferable. 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.
  • Y is bisphenol A type, bisphenol F type, bisphenol S type, naphthalene type, anthracene type, biphenyl type, tetramethyl biphenyl type, phenol novolak type, cresol novolak type, bisphenol A novolak type, and bisphenol S no. At least one compound selected from the group consisting of
  • n are each independently a natural number of 3 to 20.
  • the present invention mainly uses two or more vinyl groups at both ends of the molecular chain, it is also possible to use conventional unsaturated double-bonding moieties known in the art in addition to the vinyl groups. Belongs to the category.
  • polyphenylene ether is inherently high in melting point, and therefore, high in melt viscosity of the resin composition, making it difficult to produce a multilayer sheet.
  • polyphenylene ether instead of using the conventional high molecular weight polyphenylene ether as it is, it is preferable to use a modified form with a low molecular weight through a redistribution reaction.
  • a compound such as a phenol-derived compound or bisphenol A is generally used.
  • the dielectric constant decreases due to the rotation of the molecular structure. Is generated.
  • a conventional high molecular weight polyphenylene ether (PPE) resin instead of using a conventional high molecular weight polyphenylene ether (PPE) resin as it is, redistribution reaction using specific bisphenol compounds having increased alkyl group (Akyl) content and aromatic ring group (Aromatic) content As a low-molecular weight modified form, a vinyl group (Vinyl group) is introduced at both ends of the resin through redistribution.
  • the redistribution reaction is carried out in the presence of a radical initiator, a catalyst, or a radical initiator and a catalyst.
  • the conventional polyphenylene ether for copper foil laminates was used by reforming the polymer polyphenylene ether into a low molecular polyphenylene ether 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, a polyphenol used for, and the high polarity of alcohol groups at both ends formed after redistribution, there was a limit to low dielectric loss characteristics.
  • the modified polyphenylene ether has a lower molecular weight and higher alkyl group content than the existing polyphenylene-derived compounds, the modified polyphenylene ether has excellent compatibility with existing epoxy resins and the like, and improves processability by increasing flowability in manufacturing laminates. And 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 compound having an increased alkyl content and aromatic ring content may be used without limitation bisphenol-based compounds other than bisphenol A [BPA, 2,2-Bis (4-hydroxyphenyl) propane].
  • bisphenol compounds 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-dichloroethylene), bisphenol G (2,2-Bis (4-hydroxy-3-isopropyl-phenyl) propane), bisphenol M (1,3-Bis (2-hydroxyphenyl ) -2-
  • the polyphenylene ether resin (a) is redistributed to a high molecular weight polyphenylene ether resin having a number average molecular weight ranging from 10,000 to 30,000 in the presence of a bisphenol-based compound (except for bisphenol A), thereby obtaining a number average molecular weight (Mn).
  • Mn number average molecular weight
  • This may be modified to a low molecular weight in the range of 1,000 to 10,000, preferably the number average molecular weight (Mn) is in the range of 1000 to 5,000, more preferably may be in the range of 1000 to 3000.
  • the molecular weight distribution of the polyphenylene ether is preferably 3 or less (Mw / Mn ⁇ 3), preferably in the range of 1.5 to 2.5.
  • the content of the polyphenylene ether resin or oligomer thereof may be about 20 to 50% by weight based on the total weight of the resin composition.
  • thermosetting resin composition according to the present invention includes three or more different crosslinkable curing agents.
  • the crosslinkable curing agent crosslinks the polyphenylene ether in three dimensions to form a network structure, and uses a low molecular weight modified polyphenylene ether to increase the fluidity of the resin composition. Even with the use of three or more crosslinking curing agents, the heat resistance of the polyphenylene ether can be improved.
  • the crosslinkable curing agent may not only realize low dielectric constant and dielectric loss characteristics by crosslinking PPE, but also increase flowability of the curable resin composition and improve peel strength with other substrates (eg, copper foil). You can.
  • the crosslinkable curing agent may be selected from the group consisting of a hydrocarbon-based crosslinking agent (b1), a crosslinking agent (b2) containing three or more functional groups, and a rubber of a block structure (b3).
  • a hydrocarbon-based crosslinking agent (b1), a crosslinking agent (b2) containing three or more functional groups, and a block structure rubber (b3) may be used as the crosslinkable curing agent.
  • the hydrocarbon-based crosslinking agent usable in the present invention is not particularly limited as long as it is a hydrocarbon-based crosslinking agent having a double bond or a triple bond, and may preferably be a diene crosslinking agent.
  • Specific examples include butadiene (eg, 1,2-butadiene, 1,3-butadiene, etc.) or polymers thereof, decadiene (eg, 1,9-decadiene, etc.) or polymers thereof, octadiene (eg, 1,7- Octadiene, etc.) or polymers thereof, vinylcarbazole, and the like, which may be used alone or in combination of two or more thereof.
  • polybutadiene represented by the following Chemical Formula 2 may be used as the hydrocarbon-based crosslinking agent.
  • n is an integer of 10 to 30
  • the molecular weight (Mw) of the hydrocarbon-based crosslinking agent may be in the range of 500 to 3,000, preferably in the range of 1,000 to 3,000.
  • Non-limiting examples of crosslinking agents containing three or more (preferably three to four) functional groups usable in the present invention include triallyl isocyanurate (TAIC), 1,2,4-trivinyl cyclo Hexane (1,2,4-trivinyl cyclohexane, TVCH) and the like, these may be used alone or in combination of two or more.
  • TAIC triallyl isocyanurate
  • 1,2,4-trivinyl cyclo Hexane 1,2,4-trivinyl cyclo Hexane
  • TVCH 1,2,4-trivinyl cyclohexane
  • triallyl isocyanurate represented by the following formula (3) may be used as a crosslinking agent containing three or more functional groups.
  • the block structure rubbers usable in the present invention are in the form of block copolymers, preferably in the form of block copolymers containing butadiene units, more preferably styrene units, acrylonitrile units, acrylate units together with butadiene units. Rubber in the form of block copolymers containing units such as the like. Non-limiting examples include styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber, acrylate-butadiene rubber, acrylonitrile-butadiene-styrene rubber, and these may be used alone or in combination of two or more thereof. have.
  • SBR styrene-butadiene rubber
  • acrylonitrile-butadiene rubber acrylate-butadiene rubber
  • acrylonitrile-butadiene-styrene rubber acrylonitrile-butadiene-styrene rubber
  • styrene-butadiene rubber represented by the following formula (4) may be used as the rubber of the block structure.
  • n is an integer of 5 to 20
  • m is an integer of 5 to 20.
  • the content of the crosslinkable curing agent (b) is not particularly limited, but may be in the range of about 5 to 45% by weight based on the total weight of the resin composition, preferably about 10 to 30% by weight Can range from%.
  • the content of the crosslinkable curing agent falls within the above-described range, the low dielectric properties, curability, molding processability and adhesive strength of the resin composition are good.
  • the hydrocarbon-based crosslinking agent (b1), the crosslinking agent (b2) containing three or more functional groups, and the block structure rubber are used as the three or more crosslinkable curing agents
  • the content of the crosslinking agent (b2) and the block structure rubber (b3) containing at least two functional groups are each in the range of about 1.65 to 15% by weight, preferably in the range of about 3.33 to 10% by weight, more preferably based on the total weight of the resin composition. Such as about 5 to 10% by weight.
  • the hydrocarbon-based crosslinking agent (b1), the crosslinking agent (b2) containing three or more functional groups and the rubber of the block structure as a mixture of the three or more crosslinkable curing agents
  • the present invention may further include conventional crosslinkable curing agents known in the art, in addition to the above-described hydrocarbon-based curing agent, at least three functional group-containing crosslinking agents and rubbers of block structure.
  • the crosslinkable curing agent has excellent miscibility with the polyphenylene ether whose side is modified with vinyl group, allyl group or the like.
  • Non-limiting examples of crosslinkable curing agents that can be used include divinylnaphthalene, divinyldiphenyl, styrene monomer, phenol, triallyl cyanurate (TAC), di-4-vinylbenzyl ether [di- (4-vinylbenzyl) ether] (Formula 5) and the like.
  • TAC triallyl cyanurate
  • di-4-vinylbenzyl ether di- (4-vinylbenzyl) ether
  • a di-4-vinylbenzyl ether [di- (4-Vinylbenzyl) ether] (formula 5), which exhibits an initiation delaying reaction as a crosslinking agent, is used as another crosslinkable curing agent (hydrocarbon-based curing agent, three or more).
  • Functional groups-containing hardeners and block-structured rubbers in an optimized amount to facilitate viscosity control.
  • di-4-vinylbenzyl ether when di-4-vinylbenzyl ether is mixed with a hydrocarbon-based curing agent, three or more functional group-containing curing agents, and a block-type rubber as a crosslinking curing agent, low dielectric properties and flow characteristics due to content control are simultaneously secured. can do.
  • the hydrocarbon-based curing agent, the at least three functional group-containing curing agent and the rubber of the block structure are each in the range of about 1.65 to 15% by weight, preferably in the range of about 3.33 to 10% by weight, more preferably about It may be used in the range of 5 to 10% by weight, and di-4-vinylbenzyl ether may be used in the range of about 1 to 10% by weight, preferably about 2 to 5% by weight, based on the total weight of the resin composition.
  • thermosetting resin composition according to the present invention includes a flame retardant (c).
  • the flame retardant may be used without limitation conventional flame retardant known in the art, for example, halogen flame retardant containing bromine or chlorine; Phosphorus flame retardants such as triphenyl phosphate, tricesyl phosphate, trisdichloropropyl phosphate and phosphazene; Antimony flame retardants such as antimony trioxide; Flame retardants of inorganic substances such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide. Additive bromine flame retardants that are not reactive with polyphenylene ether and do not degrade heat and dielectric properties are suitable in the present invention.
  • the brominated flame retardant in the present invention is bromophthalimide, bromophenyl-added bromine flame retardant, or tetrabromo bisphenol A Allyl ether in the allyl terminated form.
  • a flame retardant curing agent in the form of divinylphenol, the characteristics of the curing agent and the flame retardant properties can be simultaneously obtained.
  • a brominated organic compound may also be used, and specific examples thereof include dicabromodiphenylethane, 4,4-dibromobiphenyl, and ethylene bistetrabromophthalimide.
  • the content of the flame retardant may be included in about 10 to 30% by weight based on the total weight of the resin composition, preferably in the range of about 10 to 20% by weight.
  • the flame retardant may have a flame resistance of flame retardant 94V-0 level, it may exhibit excellent thermal resistance and electrical properties.
  • thermosetting resin composition according to the present invention may further include an inorganic filler surface-treated with a vinyl group-containing silane coupling agent.
  • the inorganic filler is a surface-treated with a vinyl group-containing silane coupling agent, which is excellent in compatibility with polyphenylene ethers containing vinyl and / or allyl groups at both ends, thereby lowering dielectric properties, Hygroscopic heat resistance and workability can be improved further.
  • the inorganic filler can effectively improve the warpage characteristics, low expansion, mechanical toughness, 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
  • the inorganic filler (d) usable in the present invention is not particularly limited as long as the surface is treated with a vinyl group-containing silane coupling agent as the inorganic filler known in the art.
  • 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, whose surfaces are treated with a vinyl group-containing silane coupling agent. will be.
  • These inorganic fillers may be used alone or in combination of two or more. Of these
  • the method for producing the inorganic filler surface-treated with the vinyl group-containing silane coupling agent is not particularly limited and may be prepared according to conventional methods known in the art.
  • the inorganic filler may be added to a solution containing a vinyl group-containing silane coupling agent and then dried.
  • the size of the inorganic filler (d) is not particularly limited, but is advantageous in dispersibility when the average particle diameter is in the range of about 0.5 to 5 ⁇ m.
  • the content of the inorganic filler is not particularly limited, and may be appropriately adjusted in consideration of the aforementioned bending characteristics, mechanical properties, and the like. In one example, the range of about 10 to 50% by weight based on the total weight of the thermosetting resin composition is preferred. If the content of the inorganic filler is excessively large, moldability may decrease.
  • thermosetting resin composition according to the present invention may further comprise a reaction initiator to enhance the advantageous effect of the crosslinkable curing agent.
  • Such a reaction initiator may further accelerate the curing of the polyphenylene ether 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-butylperoxyisopropyl monocarbonate, azobisisisobutylonitrile, and the like, and further metal carboxylate salts may be further used.
  • the content of the reaction initiator may be about 2 to 5 parts by weight based on 100 parts by weight of polyphenylene ether, but is not limited thereto.
  • thermosetting resin composition of the present invention may further include a curing accelerator.
  • curing accelerator examples include an organometallic salt or an 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 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 to this. In addition, these can be used 1 type or in mixture of 2 or more types.
  • the amount of the curing accelerator may range from about 0.01 to 1 part by weight based on 10 to 60 parts by weight of polyphenylene ether, but is not limited thereto.
  • 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 resins include phenoxy resins, polyvinyl acetal resins, polyimides, polyamideimides, polyethersulfones, polysulfones and the like. These may be used individually by any 1 type, and may use 2 or more types together.
  • 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 conventionally used in thermosetting resin compositions used in the production of electronic devices (especially printed wiring boards).
  • the thermosetting resin composition is based on 100 parts by weight of the composition: (a) about 20 to 50 parts by weight of a polyphenylene ether resin having two or more unsaturated substituents at both ends of the molecular chain; (b) about 5 to 45 parts by weight of three or more crosslinkable curing agents; And (c) may include a flame retardant in the range of about 10 to 30 parts by weight, and may further include a total of 100 parts by weight of an organic solvent or other components.
  • 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 thermosetting resin composition is based on 100 parts by weight of the composition (a) about 20 to 50 parts by weight of a polyphenylene ether resin having two or more unsaturated substituents at both ends of the molecular chain; (b) about 5 to 45 parts by weight of three or more crosslinkable curing agents; (c) about 10 to 30 parts by weight of a flame retardant; And (d) about 10 to about 50 parts by weight of the inorganic filler surface-treated with the vinyl group-containing silane coupling agent, and may further include 100 parts by weight of organic solvent or other components.
  • 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.
  • Organic solvents usable in the present invention can be used without limitation to conventional organic solvents known in the art, for example acetone, cyclohexanone, methyl ethyl ketone, toluene, xylene, tetrahydrofuran, these alone or Two or more kinds may be mixed and used.
  • 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 the present invention includes a fiber substrate surface treated with a vinyl group-containing silane coupling agent; And the above-mentioned thermosetting resin composition impregnated in the fiber base material.
  • the thermosetting resin composition may be a resin varnish dissolved or dispersed in a solvent.
  • thermosetting resin composition when the thermosetting resin composition is impregnated into the fibrous substrate surface-treated with the vinyl group-containing silane coupling agent, the fiber substrate and all the components constituting the composition (ie, resin and optionally inorganic filler) Since it contains this vinyl group, it is excellent in compatibility between these, dielectric property improves, moisture absorption heat resistance, and workability are also improved, and a high frequency material can be developed.
  • the fibrous substrate usable in the present invention is known in the art as a substrate of prepreg and is not particularly limited as long as the surface is treated with a vinyl group-containing silane coupling agent.
  • a vinyl group-containing silane coupling agent for example, there are arbitrarily bendable flexible inorganic fiber substrates, organic fiber substrates, or mixed forms thereof, and the like, whose surfaces are treated with vinyl group-containing silane coupling agents.
  • the above-mentioned fiber base material can be selected based on the use or performance to be used.
  • the fiber substrate include inorganic fibers such as glass fibers, carbon fibers, and the like, such as E-glass, D-glass, S-glass, NE-glass, T-glass, and Q-glass; Organic fibers such as polyimide, polyamide, polyester, aramid fiber, aromatic polyester, and fluororesin; And mixtures of the inorganic and organic fibers; Papers, nonwovens, fabrics, papers, etc., made of the inorganic fibers and / or organic fibers, and mats such as roving, chopped strand mats, and surfacing mats. As described above, the surface is treated with a vinyl group-containing silane coupling agent, and may be used alone or in combination of two or more thereof. In addition, when the reinforced fiber substrate is mixed, the stiffness and dimensional stability of the prepreg can be improved.
  • inorganic fibers such as glass fibers, carbon fibers, and the like, such as E-glass, D-glass, S-glass, NE-glass, T-glass, and Q-glass
  • the fiber base material is glass fiber, glass paper, glass fiber nonwoven fabric (glass fiber), glass cloth (glass cloth), aramid fiber, aramid paper (aramid paper), polyester fiber, carbon fiber, inorganic Fibers, organic fibers and mixtures thereof can be used.
  • the thickness of the fibrous substrate is not particularly limited and may be, for example, in the range of about 0.01 to 0.3 mm.
  • the method for treating the surface of the fibrous base with the vinyl group-containing silane coupling agent may be prepared by conventional methods known in the art, and for example, the inorganic filler surface-treated with the vinyl group-containing silane coupling agent described above. It may be prepared as in the preparation method.
  • the method for producing the prepreg of the present invention is not particularly limited and may be prepared according to a production method known in the art.
  • the prepreg is a sheet-like material obtained by coating or impregnating the above-mentioned thermosetting resin composition on a fiber substrate surface-treated with a vinyl group-containing silane coupling agent, and then curing it to B-stage (semi-cured state) by heating.
  • the heating temperature and time is not particularly limited, for example, the heating temperature may be in the range of about 20 ⁇ 200 °C, preferably in the range of about 70 ⁇ 170 °C, heating time may be in the range of about 1 to 10 minutes.
  • the prepreg of the present invention may 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 the 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
  • Acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate
  • Carbitols such as cellosolve and butyl carbitol
  • Aromatic hydrocarbons such as toluene and xylene
  • the said organic solvent may be used 1 type, or may be used in combination of 2 or more type.
  • 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 fiber base material or coating it directly by a die coater.
  • it may be produced by continuously laminating an adhesive film made of a thermosetting resin composition laminated on a support under both heating and pressurization conditions from both sides of a sheet-like reinforcing base material.
  • the surface is surface-treated with a vinyl group-containing silane coupling agent, and the above-mentioned thermosetting resin composition is coated on a sheet-like fibrous substrate or glass substrate made of fibers, or the substrate is impregnated with the thermosetting resin composition.
  • a prepreg preferably a prepreg for a printed circuit board, may be manufactured.
  • the thermosetting resin composition may be prepared by a resin varnish.
  • Laminated sheet according to the present invention is a metal foil or a polymer film substrate; And a resin layer formed on one or both surfaces of the substrate, and the thermosetting resin composition cured.
  • metal foil For example, metal foil; And copper foil with resin which is formed on one or both surfaces of the metal foil, and includes a resin layer in which the thermosetting resin composition is cured.
  • the metal foil can be used without limitation those made of conventional metals or alloys known in the art.
  • the metal foil is a copper foil
  • the laminate formed by coating and drying the thermosetting resin composition according to the present invention can be used as a copper foil laminate.
  • it is copper foil.
  • copper foil examples include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, ILSIN and the like.
  • 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 the surface from being oxidized and corroded.
  • 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 in the range of 0.6 to 3.0 ⁇ m for example.
  • 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 in the range of 1 to 3 ⁇ m.
  • the polymer film usable in the present invention is not particularly limited as long as it is known as an insulating film in the art.
  • an insulating film in the art there are a polyimide film, an epoxy resin film, and the like, but is not limited thereto.
  • the present invention includes a 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.
  • thermosetting resin composition is sufficiently stirred at room temperature using a stirrer, impregnated with a glass substrate, dried, laminated with copper foil and the like, and then subjected to heat and pressure to obtain a desired copper foil laminate.
  • the heating pressure conditions may be appropriately adjusted according to the thickness of the copper foil laminate to be manufactured or the kind of the thermosetting resin composition according to the present invention.
  • the present invention includes a printed circuit board, preferably a multilayer printed circuit board, laminated and molded, including at least one selected from the group consisting of the prepreg, the insulating resin sheet, and the copper foil with resin.
  • a printed circuit board refers to a printed circuit board laminated by one or more layers by a plating through-hole method, a build-up method, etc., and can be obtained by overlaying the above-described prepreg or insulating resin sheet on an inner wiring board and heating and pressing.
  • the printed circuit board may be manufactured by conventional methods known in the art.
  • a copper foil laminated board is produced, opening a hole in a copper foil laminated board, through-hole plating, and then copper foil containing a plating film It can be produced by etching to form a circuit.
  • the prepreg and the printed circuit board may be prepared from the thermosetting resin composition according to the present invention.
  • These prepregs and printed circuit boards not only have low dielectric constant and dielectric loss, but also have a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), and excellent heat resistance (see Table 1 below).
  • CTE coefficient of thermal expansion
  • Tg high glass transition temperature
  • Table 1 excellent heat resistance
  • the prepregs and printed circuit boards of the present invention are networks used for mobile communication devices that handle high frequency signals of 1 GHz or higher, network-related electronic devices such as base station devices, servers, routers, and various electrical and electronic devices such as large computers. It can be usefully used as a component part of a printed circuit board.
  • thermosetting resin composition After dissolving the polyphenylene ether in toluene according to the composition shown in Table 1, two or more crosslinkable curing agents, flame retardants and inorganic fillers were mixed, stirred for 3 hours, then an initiator was added, and further 1 hour While stirring to prepare a thermosetting resin composition.
  • the amount of each composition is used in parts by weight.
  • the resin composition prepared above was impregnated into a glass fiber surface-treated with a vinyl group-containing silane coupling agent, and then dried at 165 ° C. for about 3 to 10 minutes to prepare a prepreg. Thereafter, 1 ply of the prepreg was laminated and pressed to prepare a laminated thin plate having a thickness of 0.1 mm.
  • a resin composition, a prepreg, and a printed circuit board were manufactured in the same manner as in the above example, except that the compositions described in Table 2 were followed.
  • Table 2 the amount of each unit used is in parts by weight.
  • Example 1 Example 2 Example 3 Alirate PPE 40 40 40 40 TAIC 8 10 5 1,2-butadiene 8 5 10 1,9-Decadiene - - - Di- (4-vinylbenzyl) ether 2 2 2 SBR 3 2 2 Flame retardant 9 9 9 Initiator 2 2 2 Inorganic fillers surface-treated with Amino Sliane - - - Inorganic fillers surface-treated with vinyl silane 30 30 30 30 30 Epoxy Silane G / F - - - Vinyl Silane G / F ⁇ ⁇ ⁇ 1) Allylate PPE: MX-9000 (Number average molecular weight: 2000 ⁇ 3000) 2) 1,2-Butadiene: B-1000 (NIPPON SODA) 3) 1,9-decadiene: 1,9-decadiene (EVONIC) 4) Styrene -Butadiene: P-1500 (Asahi Kasei Chemical) 5) TAIC: TAIC (NIPPON KASEI CHEM
  • TMA glass transition temperature measurement The evaluation board
  • the printed circuit board was floated in Solder 288 to measure the time until the separation phenomenon between the insulating layer and the copper foil, the insulating layer and the metal core or the insulating layer occurred. .
  • the copper foil laminated sheet was impregnated with copper etching solution, and the evaluation board
  • the substrates were evaluated by dipping at intervals of 10 seconds and measuring the time until the separation phenomenon between the insulating layer and the copper foil, the insulating layer and the metal core, or the insulating layer occurred.
  • the dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured with a dielectric constant measuring instrument (RF Impedence / Material Analyzer; Agilent) using a substrate obtained by impregnating the copper foil laminate with copper liquid and removing the copper foil.
  • RF Impedence / Material Analyzer Agilent
  • substrate was produced by 127 mm in length and 12.7 mm in width
  • the circuit pattern formed on the printed circuit board was pulled up in the 90 'direction, and the time when a circuit pattern (copper foil) peels was measured and evaluated.
  • Example Comparative example One 2 3
  • One 2 3 4 5 6 DSC Tg (°C) 195 207 185 205 200 190 193 217 170 CTE (%) 2.0 1.9 2.1 2.6 2.5 2.4 2.2 1.8 2.8
  • Dielectric Loss Df @ 1 GHz) 0.0017 0.0019 0.0020 0.0026 0.0026 0.0025 0.0025 0.0027 0.0025 Flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
  • thermosetting resin composition of the present invention not only had excellent low lubrication loss characteristics and low dielectric constant, but also exhibited high glass transition temperature (Tg), excellent heat resistance, low thermal expansion characteristics, high thermal stability, and the like. (See Table 3 above).

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une composition de résine thermodurcissable destinée à être utilisée à des fréquences élevées, la composition comprenant : (a) un polyéther de phénylène ayant deux groupes substituants insaturés ou plus choisis dans le groupe constitué par le groupe vinyle et le groupe allyle aux deux extrémités de la chaîne moléculaire de ce dernier, ou un oligomère dudit polyéther de phénylène ; (b) trois types différents ou plus d'agents de durcissement par réticulation ; et (c) un agent ignifuge. La présente invention permet de fournir une carte de circuit imprimé destinée à être utilisée à des fréquences élevées, qui présente simultanément entre autres, une exceptionnelle caractéristique de perte diélectrique faible et une bonne résistance à la chaleur et à l'absorption d'humidité, des caractéristiques de faible dilatation thermique, une stabilité thermique et d'excellentes propriétés de travail.
PCT/KR2015/014030 2014-12-22 2015-12-21 Composition de résine thermodurcissable destinée à être utilisée à des fréquences élevées, et pré-imprégné, feuille stratifiée et carte de circuit imprimé l'utilisant WO2016105051A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201580068649.XA CN107109049B (zh) 2014-12-22 2015-12-21 高频用热固性树脂组合物、利用其的预浸料、层叠片和印刷电路基板
US15/538,488 US10590272B2 (en) 2014-12-22 2015-12-21 Thermosetting resin composition for frequency, and prepreg, laminated sheet and printed circuit board using same
JP2017551981A JP6684822B2 (ja) 2014-12-22 2015-12-21 高周波用熱硬化性樹脂組成物及びこれを用いたプリプレグ、積層シート、並びに印刷回路基板
US16/424,251 US10584239B2 (en) 2014-12-22 2019-05-28 Thermosetting resin composition for frequency, and prepreg, laminated sheet and printed circuit board using same

Applications Claiming Priority (4)

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KR20140186496 2014-12-22
KR10-2014-0186496 2014-12-22
KR10-2015-0179108 2015-12-15
KR1020150179108A KR101865649B1 (ko) 2014-12-22 2015-12-15 고주파용 열경화성 수지 조성물, 이를 이용한 프리프레그, 적층 시트 및 인쇄회로기판

Related Child Applications (2)

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US15/538,488 A-371-Of-International US10590272B2 (en) 2014-12-22 2015-12-21 Thermosetting resin composition for frequency, and prepreg, laminated sheet and printed circuit board using same
US16/424,251 Continuation US10584239B2 (en) 2014-12-22 2019-05-28 Thermosetting resin composition for frequency, and prepreg, laminated sheet and printed circuit board using same

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WO2019012953A1 (fr) * 2017-07-12 2019-01-17 パナソニックＩｐマネジメント株式会社 Stratifié plaqué de métal, feuille métallique contenant de la résine et carte de câblage

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US20020077447A1 (en) * 2000-12-19 2002-06-20 Industrial Technology Research Institute Curable polyphenylene ether resin, composition made therefrom, and process for preparing the resin
US20120315814A1 (en) * 2011-06-13 2012-12-13 Nan Ya Plastics Corporation High-frequency copper foil covered substrate and compound material used therein
EP2595460A1 (fr) * 2010-07-14 2013-05-22 Guangdong Shengyi Sci. Tech Co., Ltd Matériau composite et substrat de circuit à haute fréquence fabriqué à l'aide du matériau composite et procédé de fabrication associé
CN103467967A (zh) * 2013-09-16 2013-12-25 广东生益科技股份有限公司 一种热固性树脂组合物及其用途
US20140044918A1 (en) * 2012-08-09 2014-02-13 Guangdong Shengyi Sci.Tech Co., Ltd Polyphenylene ether resin composition, and a prepreg and a copper clad laminate made therefrom

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US20020077447A1 (en) * 2000-12-19 2002-06-20 Industrial Technology Research Institute Curable polyphenylene ether resin, composition made therefrom, and process for preparing the resin
EP2595460A1 (fr) * 2010-07-14 2013-05-22 Guangdong Shengyi Sci. Tech Co., Ltd Matériau composite et substrat de circuit à haute fréquence fabriqué à l'aide du matériau composite et procédé de fabrication associé
US20120315814A1 (en) * 2011-06-13 2012-12-13 Nan Ya Plastics Corporation High-frequency copper foil covered substrate and compound material used therein
US20140044918A1 (en) * 2012-08-09 2014-02-13 Guangdong Shengyi Sci.Tech Co., Ltd Polyphenylene ether resin composition, and a prepreg and a copper clad laminate made therefrom
CN103467967A (zh) * 2013-09-16 2013-12-25 广东生益科技股份有限公司 一种热固性树脂组合物及其用途

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019012953A1 (fr) * 2017-07-12 2019-01-17 パナソニックＩｐマネジメント株式会社 Stratifié plaqué de métal, feuille métallique contenant de la résine et carte de câblage

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