WO2010077015A2 - Copolymère de polyester-amide aromatique, film à poids moléculaire élevé, préimprégné, laminé préimprégné, laminé de feuilles métalliques et carte de circuits imprimés - Google Patents

Copolymère de polyester-amide aromatique, film à poids moléculaire élevé, préimprégné, laminé préimprégné, laminé de feuilles métalliques et carte de circuits imprimés Download PDF

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Publication number
WO2010077015A2
WO2010077015A2 PCT/KR2009/007764 KR2009007764W WO2010077015A2 WO 2010077015 A2 WO2010077015 A2 WO 2010077015A2 KR 2009007764 W KR2009007764 W KR 2009007764W WO 2010077015 A2 WO2010077015 A2 WO 2010077015A2
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Prior art keywords
prepreg
repeating unit
aromatic polyester
derived
polyester amide
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Ceased
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PCT/KR2009/007764
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English (en)
Korean (ko)
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WO2010077015A3 (fr
Inventor
크라브주그드미트리
옥태준
박정원
구본혁
오영택
김만종
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Lotte Fine Chemical Co Ltd
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Samsung Fine Chemicals Co Ltd
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Priority to JP2011543430A priority Critical patent/JP2012514067A/ja
Priority to CN2009801532718A priority patent/CN102272195B/zh
Publication of WO2010077015A2 publication Critical patent/WO2010077015A2/fr
Publication of WO2010077015A3 publication Critical patent/WO2010077015A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • 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
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • H05K2201/0137—Materials
    • H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]

Definitions

  • Aromatic polyester amide copolymers polymer films, prepregs, prepreg laminates, metal foil laminates, and printed wiring boards are disclosed. More specifically, aromatic polyester amide copolymer having low thermal expansion coefficient, low dielectric constant and low dielectric loss, and improved transparency, aromatic polyester amide copolymer, polymer film employing the aromatic polyester amide copolymer, prepreg and prepreg A laminate, a metal foil laminate and a printed wiring board employing the prepreg or the prepreg laminate are disclosed.
  • the prepreg used in such a copper clad laminate for a printed wiring board must satisfy the following main characteristics to be suitable for the performance of the semiconductor and the manufacturing conditions of the semiconductor packaging process.
  • the prepreg is prepared by impregnating a resin derived from epoxy or bismaleimide triazine into a glass cloth and then semi-curing it. Next, copper foil is laminated on the prepreg, and the resin is cured to produce a copper foil laminated plate.
  • a copper foil laminate is thinned and subjected to a high temperature process such as a reflow process at 270 ° C. There is a problem that the yield is reduced due to thermal deformation of the copper foil laminate in the form of a thin film.
  • epoxy or bismaleimide triazine resin is required to be improved to low absorbency due to its high hygroscopicity.
  • aromatic liquid crystalline polyester is used for prepreg formation as an alternative to epoxy or bismaleimide triazine resin.
  • prepregs are prepared by impregnating aromatic liquid crystalline polyesters with organic or inorganic woven fabrics.
  • an aromatic liquid crystal polyester prepreg may be manufactured using an aromatic liquid crystal polyester resin and an aromatic liquid crystal polyester woven fabric.
  • the aromatic liquid crystal polyester is dissolved in a solvent containing a halogen element such as chlorine to prepare a solution composition, and the solution composition is impregnated into an aromatic liquid crystal polyester woven fabric and then dried to prepare an aromatic liquid crystal polyester prepreg.
  • this method is difficult to completely remove the solvent containing a halogen element, and since the halogen element can corrode copper foil, the improvement by the use of a non-halogen solvent is calculated
  • One embodiment of the present invention provides an aromatic polyester amide copolymer having low thermal expansion coefficient, low dielectric constant and low dielectric loss.
  • Another embodiment of the present invention provides an aromatic polyester amide copolymer having high transparency.
  • Another embodiment of the present invention by using the aromatic polyester amide copolymer, to provide a prepreg and prepreg laminate having a low thermal expansion coefficient, low dielectric constant and low dielectric loss and improved transparency.
  • Another embodiment of the present invention provides a metal foil laminate and a printed wiring board employing the prepreg or the prepreg laminate.
  • Repeating unit (A) derived from the said aromatic diol provides the aromatic polyester amide copolymer containing the repeating unit (RCN) derived from resorcinol.
  • the repeating unit (A) derived from the aromatic diol may further include a repeating unit (HQ) derived from at least one compound of biphenol and hydroquinone.
  • HQ repeating unit derived from at least one compound of biphenol and hydroquinone.
  • the content of the repeating unit (RCN) and the content of the repeating unit (HQ) may satisfy the following conditions:
  • n (RCN) and n (HQ) are the moles of repeating unit (RCN) and repeating unit (HQ) included in the aromatic polyester amide copolymer, respectively.
  • It provides a prepreg comprising a substrate impregnated with the aromatic polyester amide copolymer.
  • prepreg laminate comprising two or more of the above prepregs.
  • a metal foil laminate in which a metal thin film is formed on at least one surface of the prepreg or the prepreg laminate.
  • the printed wiring board obtained by etching the metal thin film of the said metal foil laminated board is provided.
  • It provides a printed wiring board formed by printing a metal circuit pattern on at least one surface of the polymer film.
  • an aromatic polyester amide copolymer having low thermal expansion coefficient, low dielectric constant and low dielectric loss may be provided.
  • an aromatic polyester amide copolymer having high transparency can be provided.
  • a prepreg and prepreg laminate having a low thermal expansion coefficient, low dielectric constant and low dielectric loss and improved transparency.
  • a metal foil laminate and a printed wiring board employing the prepreg or the prepreg laminate may be provided.
  • the aromatic polyester amide copolymer according to the present embodiment is 20 to 40 mol% of repeating units (A) derived from aromatic diol; 20 to 40 mol% of at least one repeating unit of the repeating unit (B) derived from the aromatic amine which has a phenolic hydroxyl group, and the repeating unit (B ') derived from aromatic diamine; And 20 to 60 mol% of repeating units (C) derived from aromatic dicarboxylic acids, and the repeating units (A) derived from the aromatic diol include repeating units (RCN) derived from resorcinol.
  • RCN repeating units
  • the content of the repeating unit (A) is less than 20 mol%, the solubility in the solvent is lowered, which is not preferable.
  • the content of the repeating unit (A) exceeds 40 mol%, the melting temperature is too high, which is undesirable.
  • the repeating unit (A) derived from the aromatic diol may further include a repeating unit (HQ) derived from at least one compound of biphenol and hydroquinone.
  • HQ repeating unit derived from at least one compound of biphenol and hydroquinone.
  • the number of moles (n (RCN)) of the repeating unit (RCN) and the number of moles (n (HQ)) of the repeating unit (HQ) included in the aromatic polyester amide copolymer may satisfy the following conditions:
  • the molar ratio of the repeating unit (RCN) to the repeating unit (HQ) is appropriately selected in consideration of the transparency of the aromatic polyester amide copolymer to be produced.
  • the repeating unit (B) may include a repeating unit derived from one or more compounds selected from the group consisting of 3-aminophenol, 4-aminophenol and 2-amino-6-naphthol, and the repeating unit (B ') May include repeating units derived from one or more compounds selected from the group consisting of 1,4-phenylene diamine, 1,3-phenylene diamine and 2,6-naphthalene diamine.
  • the content of the repeating unit (C) is less than 20 mol%, the solubility in the solvent is lowered, and if it is more than 60 mol%, the melting temperature is lowered, which is not preferable.
  • the repeating unit (C) may include a repeating unit derived from one or more compounds selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid.
  • each repeating unit included in the aromatic polyester amide copolymer may be represented by any one of the following formulas:
  • R 1 and R 2 are the same as or different from each other, and each represents a halogen atom, a carboxyl group, an amino group, a nitro group, a cyano group, a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group , Substituted or unsubstituted C 2 -C 20 alkenyl group, substituted or unsubstituted C 2 -C 20 alkynyl group, substituted or unsubstituted C 1 -C 20 heteroalkyl group, substituted or unsubstituted C 6 -C 30 An aryl group, a substituted or unsubstituted C 7 -C 30 arylalkyl group, a substituted or unsubstituted C 5 -C 30 heteroaryl group, or a substituted or unsubstituted C 3 -C 30 heteroarylalkyl
  • aromatic polyester amide copolymers include (1) aromatic diols comprising resorcinol and hydroquinone and / or biphenols, or derivatives for ester formation thereof; (2) at least one member selected from the group consisting of an aromatic amine having a phenolic hydroxyl group, or a derivative for forming an amide thereof, and an aromatic diamine or a derivative for forming an amide thereof; And (3) polymerization of aromatic dicarboxylic acids or derivatives for ester formation thereof.
  • the derivative for forming esters of the aromatic diol means that these hydroxyl groups react with carboxylic acids to form ester bonds.
  • the derivative for forming esters of the aromatic hydroxy carboxylic acid or the aromatic dicarboxylic acid may be a derivative having high reactivity such as an acid chloride, an acid anhydride, or forming an ester bond with alcohols, ethylene glycol and the like.
  • the derivative for forming an amide of the aromatic amine or aromatic diamine may be one in which the amine group forms an amide bond with carboxylic acids.
  • the aromatic polyester amide copolymer prepared as described above may be dissolved in a solvent, preferably a thermotropic liquid crystalline polyester amide copolymer capable of forming a melt exhibiting optical anisotropy at 400 ° C. or lower. .
  • the aromatic polyester amide copolymer may have a melting temperature of 250 ° C. to 400 ° C. and a number average molecular weight of 1,000 to 20,000.
  • the aromatic polyester amide copolymer prepared as described above contains a repeating unit (RCN) derived from resorcinol, transparency may be improved, and the prepreg or prepreg laminate employing the same may have high transparency. do.
  • RCN repeating unit
  • the aromatic polyester amide copolymer as described above may be prepared through a general method for producing an aromatic liquid crystal polyester, for example, an aromatic diol corresponding to the repeating unit (RCN) and the repeating unit (HQ), and the Phenolic hydroxyl groups and amine groups of the aromatic amines and / or aromatic diamines corresponding to the repeating units (B) and / or the repeating units (B ') are acylated with an excess of fatty acid anhydride to obtain acylates, and the acylates and aromatics obtained
  • the method of melt-polymerizing by transesterifying dicarboxylic acid is mentioned.
  • the amount of fatty acid anhydride added may be 1.0 to 1.2 times the equivalent, for example, 1.04 to 1.07 times the equivalent of the total equivalent of the phenolic hydroxyl group and the amine group.
  • the addition amount of the fatty acid anhydride is large, the coloring of the aromatic polyester amide copolymer tends to be remarkable, and when the amount is small, the raw material monomer or the like tends to increase in the polymer or the amount of phenol gas generated increases. It is preferable to make such an acylation reaction react at 130-170 degreeC for 30 minutes-8 hours, and it is more preferable to make it react at 140-160 degreeC for 2 to 4 hours.
  • Fatty acid anhydrides used in the acylation reaction include acetic anhydride, propionic anhydride, isobutyric anhydride, gil acetic anhydride, pivalic anhydride, butyric anhydride, and the like, and are not particularly limited thereto. Moreover, these two or more types can be mixed and used. It is preferable to use acetic anhydride in economics and handleability.
  • the transesterification and amide exchange reactions are preferably performed at a temperature increase rate of 0.1 to 2 ° C./min at 130 to 400 ° C., and more preferably at a temperature increase rate of 0.3 to 1 ° C./min at 140 to 350 ° C. .
  • By-product fatty acids and unreacted anhydrides may be discharged out of the reaction system by evaporation or distillation in order to shift the equilibrium in the transesterification reaction and the amide exchange reaction of the fatty acid ester and the carboxylic acid obtained by acylation.
  • the acylation reaction, transesterification reaction and amide exchange reaction can be carried out in the presence of a catalyst.
  • the catalyst is conventionally known as a catalyst for polyester, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, N, N-dimethylaminopyridine, N-methyl Midazoles and the like.
  • the catalyst is usually introduced simultaneously with the monomer upon the addition of the monomer, and acylation and transesterification reactions occur in the presence of the catalyst.
  • the polycondensation by the transesterification reaction and the amide exchange reaction is usually carried out by melt polymerization, but it is possible to use melt polymerization and solid phase polymerization together.
  • the polymerizer used for the melt polymerization is not particularly limited, and may be a reactor equipped with a stirring apparatus generally used for high viscosity reactions. At this time, the same reactor may be used as the reactor of the acylation process and the polymerizer of the melt polymerization process or different reactors may be used for each process.
  • the solid phase polymerization may be performed by pulverizing the prepolymer discharged from the melt polymerization process into a flake or powder phase and then proceeding with the polymerization.
  • Such solid phase polymerization can be carried out by, for example, heat treatment in a solid state for 1 to 30 hours at 200 to 350 ° C. in an inert atmosphere such as nitrogen.
  • the solid phase polymerization may be carried out under stirring or may be carried out in an unstirred state.
  • the reactor equipped with the suitable stirring apparatus can also be used together with a melt polymerization tank and a solid state polymerization tank.
  • the aromatic polyester amide copolymer prepared as described above may have a thermal expansion rate of 3 ppm / K or less.
  • the obtained aromatic polyester amide copolymer may be pelletized by a known method and then molded or fiberized according to a known method.
  • such an aromatic polyester amide copolymer may be dissolved in a solvent and then applied to a metal thin film, then dried and heat treated to form a polymer film, and may also be used in the manufacture of a woven or nonwoven fabric.
  • the prepreg according to this embodiment comprises a substrate impregnated with the aromatic polyester amide copolymer.
  • the prepreg may be, for example, impregnating a solution of a composition in which the aromatic polyester amide copolymer is dissolved in a solvent to an organic or inorganic fabric and / or non-fabrics substrate, or the composition solution It can be produced by forming a by applying to the woven fabric and / or nonwoven substrate and then removing the solvent.
  • the solvent for dissolving the aromatic polyester amide copolymer may be used in an amount of 100 to 100,000 parts by weight based on 100 parts by weight of the aromatic polyester amide copolymer, and when the content of the solvent is less than 100 parts by weight, the solution viscosity may increase. There is a problem at the time of processing, and when it exceeds 100,000 weight part, since the quantity of an aromatic polyester amide copolymer is small and there exists a tendency for productivity to fall, it is unpreferable.
  • a non-halogen solvent is used as a solvent which melt
  • the present invention is not limited thereto, and in addition, polar aprotic compounds, halogenated phenols, o-dichlorobenzene, chloroform, methylene chloride, tetrachloroethane and the like may be used alone or in combination of two or more thereof.
  • the aromatic polyester amide copolymer is well dissolved in a non-halogen solvent and does not have to use a solvent containing a halogen element
  • the metal foil of the metal foil laminate or printed wiring board containing the same uses a solvent containing a halogen element. It is possible to prevent problems such as corrosion due to.
  • woven and / or nonwoven fabrics comprising aromatic polyester fibers, glass fibers, carbon fibers and paper or a mixture of two or more thereof may be used.
  • the impregnation method in the said prepreg manufacturing process as for the time to impregnate the said base material with the composition solution which melt
  • the temperature at which the base material is impregnated with the composition solution in which the aromatic polyester amide copolymer is dissolved in a solvent can be in the range of 20 to 190 ° C, and is preferably performed at room temperature.
  • the amount of the aromatic polyester amide copolymer impregnated per unit area of the substrate is in the range of 0.1 to 1,000 g / m 2 .
  • the said impregnation amount is less than 0.1 g / m ⁇ 2> , productivity falls and it is unpreferable, and when it exceeds 1,000 g / m ⁇ 2> , since the viscosity of a solution is high and processing becomes difficult, it is unpreferable.
  • an inorganic filler such as silica, aluminum hydroxide, calcium carbonate, hardened epoxy, crosslinked acryl, etc., in order to control the dielectric constant and thermal expansion rate within a range that does not impair the object of the invention.
  • Organic fillers may be added.
  • an inorganic filler having a high dielectric constant may be added.
  • a titanate such as barium titanate or strontium titanate, a part of titanium or barium of barium titanate, or the like may be used.
  • content of such an inorganic filler and / or an organic filler is the ratio of 0.0001-100 weight part with respect to 100 weight part of aromatic polyester amide copolymers. If the amount of the inorganic filler and / or the organic filler is less than 0.0001 parts by weight, it is difficult to sufficiently increase the dielectric constant of the prepreg or lower the thermal expansion coefficient, and if it exceeds 100 parts by weight, the effect of the aromatic polyester amide copolymer as a binder is increased. There is a tendency to be less.
  • the prepreg according to the present embodiment uses an aromatic liquid crystalline polyester amide copolymer having low hygroscopicity and low dielectric properties and an organic or inorganic woven fabric and / or nonwoven fabric having excellent mechanical strength, and thus has excellent dimensional stability, low thermal deformation, and rigidity. It is advantageous for drilling and additive manufacturing.
  • the prepreg according to the present embodiment includes an aromatic polyester amide copolymer containing a repeating unit (RCN) derived from resorcinol, high transparency can be obtained by appropriately adjusting the content of the repeating unit (RCN).
  • RCN repeating unit
  • the composition solution in which the aromatic polyester amide copolymer is dissolved in a solvent is impregnated into the substrate, or after applying the composition solution to the substrate, the solvent is removed.
  • a method is not specifically limited, It is preferable by solvent evaporation.
  • evaporation by methods such as a heating, reduced pressure, and ventilation, is mentioned.
  • solvent heating evaporation is preferred from the viewpoint of applicability to existing prepreg manufacturing processes, production efficiency, and handling, and more preferably evaporation by ventilation heating.
  • the heating temperature is pre-dried for 1 minute to 2 hours in the range of 20 to 190 °C with respect to the composition solution of the aromatic polyester amide copolymer obtained in the production method of the present invention, 190 to 350 °C It is preferable to carry out the heat treatment from 1 minute to 10 hours at.
  • the prepreg according to the present embodiment thus obtained preferably has a thickness of about 5 to 200 ⁇ m, preferably about 30 to 150 ⁇ m.
  • the prepreg has a thermal expansion coefficient of 10 ppm / K or less in one direction, a dielectric constant of 3.5 or less, and a dielectric loss of 0.01 or less.
  • the dielectric loss means an energy loss lost by heat in the dielectric when an alternating electric field is applied to the dielectric.
  • the thermal expansion rate exceeds 10 ppm / K, peeling of the prepreg occurs, which is not preferable.
  • the dielectric constant exceeds 3.5 or the dielectric loss exceeds 0.01, the dielectric constant is unsuitable as an insulating substrate in the high frequency region.
  • a prepreg laminated body can be manufactured by laminating
  • a metal foil laminated board can be manufactured by arrange
  • each prepreg or a prepreg laminated body, and a metal thin film is not specifically limited, It is preferable that it is 0.1-300 micrometers. If the thickness of the prepreg or the prepreg laminate is less than 0.1 ⁇ m, cracks are easily generated during the winding process, and if it exceeds 300 ⁇ m, the number of layers of the multilayer stack having a limited thickness is not preferable. When the thickness of the metal thin film is less than 0.1 ⁇ m, cracks are easily generated when the metal thin film is laminated.
  • the heating and pressurization process applied in the production of the metal foil laminate is preferably performed at a temperature of 150 to 180 ° C. and a pressure of 9 to 20 MPa, but the prepreg characteristics, the reactivity of the aromatic polyester amide copolymer composition, the ability of the press machine, Since it can determine suitably in consideration of the thickness of a metal foil laminated board, etc., it is not specifically limited.
  • the metal foil laminate according to the present embodiment may further include an adhesive layer interposed therebetween to increase the bonding strength between the prepreg laminate and the metal thin film.
  • an adhesive layer a thermoplastic resin composition or a thermosetting resin composition may be used.
  • the adhesive layer preferably has a thickness of 0.1 ⁇ 100 ⁇ m. If the thickness is less than 0.1 mu m, the adhesive strength is low, which is not preferable. If the thickness exceeds 100 mu m, the thickness becomes too thick, which is not preferable.
  • a printed wiring board can be manufactured by etching the metal thin film of the said metal foil laminated board, and forming a circuit.
  • a printed wiring board may be manufactured by printing a metal circuit pattern on at least one surface of the polymer film.
  • a through hole etc. can also be formed in the said printed wiring board as needed.
  • the multilayer printed wiring board according to the present embodiment can be manufactured by, for example, arranging a predetermined number of the prepregs between components such as an inner substrate or a metal thin film, and molding under heating and pressurization, in accordance with the thickness of the insulating layer of interest. Can be. Heating and pressurization conditions at this time can be suitably determined similarly to the conditions at the time of manufacture of the said metal foil laminated board.
  • the prepreg laminated body, metal foil laminated board, printed wiring board, etc. which are used for an electrical insulation material can be mentioned, You can use these together two or more types.
  • the temperature was raised to 150 ° C. over 30 minutes under a nitrogen gas stream and refluxed for 3 hours while maintaining the temperature.
  • An aromatic polyester amide copolymer was prepared in the same manner as in Example 1, except that only 220.2 g (2.0 mol) of resorcinol was used without using any hydroquinone as the aromatic diol.
  • an aromatic polyester amide copolymer composition solution and a prepreg were prepared in the same manner as in Example 1.
  • An aromatic polyester amide copolymer was prepared in the same manner as in Example 1, except that only 220.2 g (2.0 mol) of hydroquinone was used without using any resorcinol as the aromatic diol.
  • an aromatic polyester amide copolymer composition solution and a prepreg were prepared in the same manner as in Example 1.
  • the prepregs prepared in Examples 1 and 2 and the prepregs prepared in Comparative Example 1 were each immersed in a soldering bath having a soldering temperature of 290 ° C. for 1 minute, and the surface state was observed. No deformation or blister occurred in all of the prepregs prepared in Examples 1 and 2 and Comparative Example 1.
  • the dielectric constant and the dielectric loss were measured using an impedance analyzer and are shown in Table 1 below.
  • each thermal expansion coefficient was measured using TMA (TMA company, Q400), and it is shown in following Table 1.

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  • Polyamides (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un copolymère de polyester-amide aromatique, un film à poids moléculaire élevé, un préimprégné, un laminé préimprégné, un laminé de feuilles métalliques et une carte de circuits imprimés. Le copolymère de polyester-amide aromatique décrit dans l'invention comprend: de 20 à 40 % en moles d'un motif récurrent aromatique obtenu à partir de diol (A); de 20 à 40 % en moles d'au moins un motif récurrent choisi parmi un motif récurrent (B) obtenu à partir d'une amine aromatique comprenant un groupe hydroxyle phénolique et un motif récurrent (B') obtenu à partir d'une diamine aromatique; et de 20 à 60 % en moles d'un motif récurrent (C) obtenu à partir d'un acide dicarboxylique aromatique, le motif récurrent aromatique obtenu à partir de diol (A) contenant un motif récurrent obtenu à partir de résorcinol (RCN).
PCT/KR2009/007764 2008-12-31 2009-12-24 Copolymère de polyester-amide aromatique, film à poids moléculaire élevé, préimprégné, laminé préimprégné, laminé de feuilles métalliques et carte de circuits imprimés Ceased WO2010077015A2 (fr)

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JP2011543430A JP2012514067A (ja) 2008-12-31 2009-12-24 芳香族ポリエステルアミド共重合体、高分子フィルム、プリプレグ、プリプレグ積層体、金属箔積層板及びプリント配線板
CN2009801532718A CN102272195B (zh) 2008-12-31 2009-12-24 芳香族聚酯酰胺共聚物、高分子膜、预浸料坯、预浸料坯层叠体、金属箔层叠板和印刷线路板

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KR1020080138704A KR101054271B1 (ko) 2008-12-31 2008-12-31 방향족 폴리에스테르 아미드 공중합체, 상기 방향족 폴리에스테르 아미드 공중합체를 채용한 프리프레그와 프리프레그 적층체, 및 상기 프리프레그 또는 프리프레그 적층체를 채용한 금속박 적층판과 프린트 배선판
KR10-2008-0138704 2008-12-31

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JP2014518915A (ja) * 2011-05-06 2014-08-07 三星精密化学株式会社 全芳香族ポリエステルアミド共重合体樹脂、該全芳香族ポリエステルアミド共重合体樹脂を含む高分子フィルム、該高分子フィルムを含む軟性金属箔積層板、及び該軟性金属箔積層板を具備する軟性印刷回路基板
JP2014521801A (ja) * 2011-08-04 2014-08-28 サムスン ファイン ケミカルズ カンパニー リミテッド 熱硬化性樹脂製造用組成物及びその硬化物、該硬化物を含むプリプレグ、及び該プリプレグを採用した金属箔積層板並びにプリント配線板

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KR20120100306A (ko) * 2011-03-03 2012-09-12 삼성정밀화학 주식회사 전방향족 폴리에스테르 아미드 공중합체 수지, 상기 수지를 포함하는 필름, 상기 필름을 포함하는 연성 금속박 적층판, 및 상기 연성 금속박 적층판을 구비하는 연성 인쇄 회로기판
CN106480735B (zh) * 2015-08-28 2019-06-14 广东生益科技股份有限公司 电路基板及其制备方法
CN106810690B (zh) * 2017-01-12 2019-09-10 苏州大学 一种芳香族聚酯酰胺及其制备方法

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JPH0723446B2 (ja) * 1985-12-06 1995-03-15 ポリプラスチックス株式会社 安定化ポリエステル樹脂組成物
JPH0726011B2 (ja) * 1986-10-17 1995-03-22 ポリプラスチックス株式会社 ポリエステル樹脂組成物
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014518915A (ja) * 2011-05-06 2014-08-07 三星精密化学株式会社 全芳香族ポリエステルアミド共重合体樹脂、該全芳香族ポリエステルアミド共重合体樹脂を含む高分子フィルム、該高分子フィルムを含む軟性金属箔積層板、及び該軟性金属箔積層板を具備する軟性印刷回路基板
JP2014521801A (ja) * 2011-08-04 2014-08-28 サムスン ファイン ケミカルズ カンパニー リミテッド 熱硬化性樹脂製造用組成物及びその硬化物、該硬化物を含むプリプレグ、及び該プリプレグを採用した金属箔積層板並びにプリント配線板

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CN102272195A (zh) 2011-12-07
KR20100080082A (ko) 2010-07-08
KR101054271B1 (ko) 2011-08-08
WO2010077015A3 (fr) 2010-10-07
CN102272195B (zh) 2013-06-05
JP2012514067A (ja) 2012-06-21
TW201035169A (en) 2010-10-01

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