WO2013019085A2 - Composition servant à préparer une résine thermodurcissable et article durci préparé à partir de cette résine, préimprégné contenant un article durci et plaque stratifiée en feuilles de métal et carte de câblage imprimé utilisant un préimprégné - Google Patents

Composition servant à préparer une résine thermodurcissable et article durci préparé à partir de cette résine, préimprégné contenant un article durci et plaque stratifiée en feuilles de métal et carte de câblage imprimé utilisant un préimprégné Download PDF

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Publication number
WO2013019085A2
WO2013019085A2 PCT/KR2012/006180 KR2012006180W WO2013019085A2 WO 2013019085 A2 WO2013019085 A2 WO 2013019085A2 KR 2012006180 W KR2012006180 W KR 2012006180W WO 2013019085 A2 WO2013019085 A2 WO 2013019085A2
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WO
WIPO (PCT)
Prior art keywords
prepreg
repeating unit
thermosetting resin
composition
derived
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2012/006180
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English (en)
Korean (ko)
Other versions
WO2013019085A3 (fr
Inventor
김미정
김양섭
구본혁
김만종
윤종화
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lotte Fine Chemical Co Ltd
Original Assignee
Samsung Fine Chemicals Co Ltd
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Publication date
Priority claimed from KR1020120084187A external-priority patent/KR101767691B1/ko
Application filed by Samsung Fine Chemicals Co Ltd filed Critical Samsung Fine Chemicals Co Ltd
Priority to JP2014523850A priority Critical patent/JP6111247B2/ja
Priority to CN201280038714.0A priority patent/CN103732687B/zh
Publication of WO2013019085A2 publication Critical patent/WO2013019085A2/fr
Publication of WO2013019085A3 publication Critical patent/WO2013019085A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—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
    • C08J5/241—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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/12—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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/12—Polyester-amides

Definitions

  • thermosetting resin manufacture its hardened
  • Copper foil laminates are widely used as printed circuit board substrates of electronic devices due to their excellent stamping processability and drill processability and low cost. have.
  • the prepregs applied to the copper foil laminates for printed circuit boards must satisfy excellent heat resistance, dimensional stability, chemical resistance, and excellent electrical characteristics to be suitable for semiconductor performance and semiconductor packaging manufacturing process conditions.
  • the prepreg is prepared by impregnating a resin derived from epoxy or bismaletriazine into a glass cloth, followed by drying and semi-curing. Next, copper foil is laminated
  • a copper foil laminate is thinned and subjected to a high temperature process such as a reflow process at 260 ° C. A problem such as a decrease in yield due to thermal deformation of the thin film copper foil laminate through such a high temperature process occurs.
  • epoxy or bismaleimide triazine resins are required to be improved to low absorbency due to their high hygroscopicity, and in particular, semiconductor packaging requiring high frequency and high speed processing due to poor dielectric properties in the high frequency region of 1 GHz or more.
  • semiconductor packaging requiring high frequency and high speed processing due to poor dielectric properties in the high frequency region of 1 GHz or more.
  • a low dielectric prepreg that does not cause such a problem is desired.
  • aromatic polyester is used to form prepreg as an alternative to epoxy or bismaleimide triazine resin.
  • prepregs are prepared by impregnating aromatic polyesters with organic or inorganic woven fabrics.
  • an aromatic polyester prepreg may be produced using an aromatic polyester resin and an aromatic polyester woven fabric.
  • the aromatic polyester is dissolved in a solvent containing a halogen element such as chlorine to prepare a solution composition.
  • the solution composition is impregnated with an aromatic polyester woven fabric and then dried to prepare an aromatic 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 a composition for preparing a thermosetting resin comprising an aromatic polyester amide copolymer having excellent flame retardancy having at least one of an amine end group and a hydroxy end group, an epoxy resin, and optionally bismaleimide.
  • thermosetting resin film including a cured product of the composition for preparing a thermosetting resin.
  • Another embodiment of the present invention provides a prepreg comprising a cured product of the composition for preparing a thermosetting resin.
  • Another embodiment of the present invention provides a metal foil laminate and a printed wiring board employing the prepreg.
  • the repeating unit (C) derived from the aromatic diol provides a composition for preparing a thermosetting resin including a repeating unit (DOPO-HQ) derived from a compound represented by Formula 1 below:
  • the repeating unit (C) derived from the aromatic diol may further include a repeating unit (HQ) derived from at least one compound of 4,4′-biphenol and hydroquinone.
  • HQ repeating unit
  • the content of the repeating unit (DOPO-HQ) and the content of the repeating unit (HQ) may satisfy the following conditions:
  • the repeating unit (A) is para hydroxy benzoic acid, meta hydroxy benzoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid and 2-hydroxy It is derived from at least one compound selected from the group consisting of oxy-1-naphthoic acid, and the repeating unit (B) is 3-aminophenol, 4-aminophenol, 5-amino-1-naphthol, 8-amino- It is derived from at least one compound selected from the group consisting of 2-naphthol and 3-amino-2-naphthol, and the repeating unit (B ′) is 1,4-phenylene diamine, 1,3-phenylene diamine, It is derived from at least one compound selected from the group consisting of 1,5-diaminonaphthalene, 2,3-diaminonaphthalene and 1,8-diaminonaphthalene,
  • repeating unit (B), repeating unit (B '), repeating unit (C) and repeating unit (D) may satisfy the following conditions:
  • n (B), n (B '), n (C) and n (D) are the repeating units (B), repeating units (B') and repeating units (B) contained in the aromatic polyester amide copolymer, respectively. C) and the number of moles of the repeating unit (D).
  • composition for preparing a thermosetting resin may further include 5 to 30 parts by weight of bismaleimide based on 100 parts by weight of the aromatic polyester amide copolymer.
  • cured material of the said composition for thermosetting resin manufacture.
  • It provides a prepreg comprising a cured product of the composition for producing a thermosetting resin contained in the substrate.
  • the total content of the composition for preparing a thermosetting resin and the cured product thereof contained per unit area of the substrate may range from 0.1 to 1,000 g / m 2 .
  • the substrate may include at least one selected from the group consisting of aromatic polyester fibers, aromatic polyester amide fibers, glass fibers, carbon fibers and paper.
  • the prepreg may further include 0.0001 to 300 parts by weight of at least one filler of the organic filler and the inorganic filler based on 100 parts by weight of the total content of the composition for preparing the thermosetting resin and the cured product thereof.
  • the coefficient of thermal expansion in one direction of the prepreg, measured after the cured product contained in the prepreg is completely cured, may be 20 ppm / K or less.
  • the dielectric constant of the prepreg measured after fully curing the cured product included in the prepreg, may be 4.0 or less, and the dielectric loss may be 0.01 or less.
  • the glass transition temperature of the cured product may be 170 ⁇ 270 °C.
  • a metal foil laminate comprising at least one metal thin film disposed on at least one surface of the prepreg.
  • the printed wiring board obtained by etching the metal thin film of the said metal foil laminated board is provided.
  • thermosetting resin film formed by printing a metal circuit pattern on at least one surface of the thermosetting resin film.
  • an aromatic polyester amide copolymer having excellent flame retardancy having at least one of an amine end group and a hydroxy end group, an epoxy resin, and optionally bismaleimide can be dissolved in a non-halogen solvent.
  • a composition for producing a thermosetting resin may be provided.
  • thermosetting resin film and prepreg having excellent flame retardancy, low thermal expansion rate, low dielectric constant and low dielectric loss and low hygroscopicity may be provided.
  • the cured product has a high glass transition temperature.
  • a metal foil laminate and a printed wiring board employing the prepreg may be provided.
  • thermosetting resin a thermosetting resin
  • cured product thereof a prepreg including the cured product according to an embodiment of the present invention
  • composition for preparing a thermosetting resin according to an embodiment of the present invention includes 100 parts by weight of an aromatic polyester amide copolymer having at least one of amine end groups and hydroxy end groups and 10 to 300 parts by weight of an epoxy resin.
  • the cured product (that is, the crosslinked resin) of the composition for preparing a thermosetting resin has low thermal expansion characteristics and low dielectric properties, and also has a high degree of crosslinking. High hygroscopicity results in low hygroscopicity.
  • the content of the repeating unit (A) is within the above range, the mechanical strength of the aromatic polyester amide copolymer is high and the thermal property is excellent, and the total content of the repeating unit (B) and the repeating unit (B ') is within the above range.
  • the aromatic polyester amide copolymer has a high solubility in solvents and a melting temperature of the appropriate level, if the content of the repeating unit (C) is within the above range, the aromatic polyester amide copolymer is high in the solvent It has a solubility and a melting temperature of an appropriate level, and if the content of the repeating unit (D) is within the above range, the aromatic polyester amide copolymer has a high solubility in solvents, low thermal expansion properties and low dielectric properties.
  • the repeating unit (C) derived from the aromatic diol may further include a repeating unit (HQ) derived from at least one compound of 4,4′-biphenol and hydroquinone.
  • HQ repeating unit
  • the number of moles (n (DOPO-HQ)) of the repeating unit (DOPO-HQ) and the number of moles (n (HQ)) of the repeating unit (HQ) included in the wholly aromatic polyester amide copolymer are as follows. Can be satisfied:
  • the number of moles (n (DOPO-HQ)) of the repeating unit (DOPO-HQ) and the number of moles (n (HQ)) of the repeating unit (HQ) satisfy the above conditions, so that the wholly aromatic polyester amide copolymer is excellent. It has flame retardancy and excellent solubility in solvents.
  • the repeating unit (A) is para hydroxy benzoic acid, meta hydroxy benzoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid and 2 -Is derived from at least one compound selected from the group consisting of hydroxy-1-naphthoic acid
  • the repeating unit (B) is 3-aminophenol, 4-aminophenol, 5-amino-1-naphthol, 8- It is derived from at least one compound selected from the group consisting of amino-2-naphthol and 3-amino-2-naphthol
  • the repeating unit (B ′) is 1,4-phenylene diamine, 1,3-phenylene Is derived from at least one compound selected from the group consisting of diamine, 1,5-diaminonaphthalene, 2,3-diaminonaphthalene and 1,8-diaminonaphthalene
  • repeating unit (B), repeating unit (B '), repeating unit (C) and repeating unit (D) may satisfy the following conditions:
  • n (B), n (B '), n (C) and n (D) are the repeating units (B), repeating units (B') and repeating units (B) contained in the aromatic polyester amide copolymer, respectively. C) and the number of moles of the repeating unit (D).
  • the aromatic polyester amide copolymer has a plurality of amine end groups and / or hydroxides. It includes a hydroxy end group, and subsequently cures with an epoxy resin and / or a bismaleimide resin to form a thermosetting resin having a high crosslinking density.
  • Such aromatic polyester amide copolymers include (1) aromatic hydroxy carboxylic acids or derivatives for ester formation thereof; (2) at least one member selected from the group consisting of an aromatic amine having a phenolic hydroxy group or a derivative for forming an amide, and an aromatic diamine or a derivative for forming an amide; (3) aromatic diols or derivatives for ester formation thereof; And (4) polymerizing an aromatic dicarboxylic acid or a derivative for forming an ester thereof.
  • the derivative for forming an ester of the aromatic hydroxy carboxylic acid or aromatic dicarboxylic acid may be a highly reactive derivative such as an acid chloride or an acid anhydride, or may form an ester bond with alcohols or ethylene glycol.
  • 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 derivative for forming an ester of the aromatic diol may be one whose hydroxy group forms an ester bond with carboxylic acids.
  • the aromatic polyester amide copolymer prepared as described above may be a thermotropic liquid crystalline polyester amide copolymer which may be dissolved in a solvent, for example, to form a melt exhibiting optical anisotropy at 400 ° C. or lower. have.
  • the aromatic polyester amide copolymer may have a melting temperature of 250 to 400 ° C. and a number average molecular weight of 1,000 to 20,000.
  • the aromatic polyester amide copolymer as described above can be prepared by the following method. That is, the aromatic polyester amide copolymer is an aromatic hydroxy carboxylic acid corresponding to the repeating unit (A), an aromatic amine corresponding to the repeating unit (B) and / or the repeating unit (B '), and / or Or an aromatic diamine and the hydroxyl group or amine group of the aromatic diol corresponding to the repeating unit (C) by acylating with an acid anhydride to obtain an acyl compound, followed by melt polymerization by transesterifying the acyl compound and aromatic dicarboxylic acid thus obtained. It can be produced by the method.
  • an aromatic polyester amide copolymer having an amine end group and / or hydroxy end group but not a carboxy end group and having a predetermined degree of polymerization can be prepared.
  • the amount of the acid anhydride is increased, the number of amine end groups and / or hydroxy end groups in the resulting aromatic polyester amide copolymer is decreased, the number of carboxy end groups and the degree of polymerization are increased, and the acid anhydride Reducing the amount of amine increases the number of amine end groups and / or hydroxy end groups, and the number of carboxy end groups and the degree of polymerization decrease.
  • the amount of the acid anhydride added may be 0.9 to 1.2 times the equivalent, for example, 0.95 to 1.05 times the equivalent of the total equivalent of the hydroxy group and the amine group.
  • the amount of the acid anhydride added is within the above range, the resulting aromatic polyester amide copolymer has an amine end group and / or hydroxy end group but no carboxy end group, and coloring of the resulting aromatic polyester amide copolymer As a result, the resulting aromatic polyester amide copolymer does not cause sublimation of the raw material monomer and the like, and the amount of phenol gas generated is also reduced.
  • the acylation reaction may be performed for 30 minutes to 8 hours at 130 to 170 ° C, for example, for 2 to 4 hours at 140 to 160 ° C.
  • Acid anhydrides used in the acylation reaction include acetic anhydride, propionic anhydride, isobutyric anhydride, gluconic anhydride, pivalic anhydride, butyric anhydride, and the like. Moreover, 2 or more types of these can be mixed and used.
  • the transesterification and amide exchange reaction may be carried out at a temperature increase rate of 0.1 to 2 °C / min at 130 ⁇ 400 °C, for example, at a temperature increase rate of 0.3 ⁇ 1 °C / min at 140 ⁇ 350 °C.
  • the acylation reaction, transesterification reaction and amide exchange reaction can proceed in the presence of a catalyst.
  • the catalyst is conventionally known as a catalyst for producing a polyester resin, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, N, N-dimethylaminopyridine, N-methyl Imidazole and the like.
  • the catalyst is usually added simultaneously with the monomer when the monomer is added, and the acylation reaction and the transesterification reaction take place in the presence of the catalyst.
  • the polycondensation by the transesterification reaction and the amide exchange reaction may be carried out by melt polymerization, and the resulting aromatic polyester amide copolymer is subsequently crosslinked with the epoxy resin (ie, cured) to have a high degree of polymerization and excellent mechanical strength. Solid phase polymerization is unnecessary because it forms a cargo.
  • 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.
  • An aromatic polyester amide copolymer according to an embodiment of the present invention having the above configuration has an amine end group and / or a hydroxy end group, but does not have a carboxy end group, which will be described later. And can cause a high degree of crosslinking reaction.
  • the aromatic polyester amide copolymer may have a thermal expansion rate of 3 ppm / K or less.
  • the epoxy resin may include at least one selected from the group consisting of bifunctional and trifunctional or higher polyfunctional epoxy resins.
  • the bifunctional epoxy resin is, for example, a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bixenol type epoxy resin, or It may be a biphenol type epoxy resin.
  • the said trifunctional or more than polyfunctional epoxy resin is a novolak-type epoxy resin, a phenol novolak-type epoxy resin, a bixylenol-type epoxy resin, a cresol novolak-type epoxy resin, N-glycidyl-type epoxy resin, Novolak-type epoxy resin of bisphenol A, biphenol novolak-type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino-group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, tetrakisphenol It may be an ethane type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl ethane resin, silicone modified epoxy resin or ⁇ -caprolactone modified epoxy resin.
  • a composition for preparing a thermosetting resin according to an embodiment of the present invention may be prepared by mixing the aromatic polyester amide copolymer, the epoxy resin, and optionally bismaleimide with a known curing agent and / or a known curing catalyst at a predetermined ratio. Can be.
  • thermosetting resin film can be manufactured from the said composition for thermosetting resin manufacture using a general solvent casting method.
  • thermosetting resin such a composition for preparing a thermosetting resin may be dissolved in a solvent. Therefore, the prepreg can be manufactured by impregnating or apply
  • thermosetting mainly semi-hardening
  • the cured product has the physical properties of the aromatic polyester amide copolymer as it is, has a low thermal expansion coefficient, a low dielectric constant and a low dielectric loss.
  • the term 'semi-curing' means that when the curing reaction of the composition for preparing a resin proceeds to some extent and heat is applied, the resultant resin is not melted by heat but becomes soft, and when the resin is in contact with a specific solvent, It does not dissolve in solvent but means swelling state.
  • the resin obtained by semi-curing a composition is generally called B-stage resin.
  • "Full hardening” means a state in which the curing reaction of the composition proceeds completely, and the resulting resin does not become soft by heat or swell by a solvent.
  • the resin obtained by completely hardening a composition is generally called C-stage resin.
  • composition for preparing a thermosetting resin may be used for various applications other than prepreg.
  • the prepreg is, for example, a composition solution (also referred to as varnish) in which the composition for preparing the thermosetting resin is dissolved in a solvent, based on organic or inorganic fabrics, and / or organic or inorganic nonwoven fabrics (non- fabrics) or by applying the composition solution to the woven and / or nonwoven substrates and then drying and semi-curing them.
  • a composition solution also referred to as varnish
  • the molding method that can be used at this time is a solution impregnation method or varnish impregnation method.
  • the solvent for dissolving the composition for preparing the thermosetting resin may be used in an amount of 100 to 100,000 parts by weight based on 100 parts by weight of the composition for preparing the thermosetting resin, and the composition for preparing the thermosetting resin is sufficiently dissolved when the content ratio of the solvent is within the above range. At the same time, productivity is good.
  • a non-halogen solvent may be used as the solvent for dissolving the composition for preparing the thermosetting resin.
  • the present invention is not limited thereto, and as the solvent, 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 composition for producing a thermosetting resin is well dissolved in a non-halogen solvent and does not have to use a solvent containing a halogen element.
  • the composition contains a halogen element. It is possible to prevent the phenomenon that the metal thin film is corroded by the halogen element, which is a problem that occurs when using a solvent.
  • woven and / or nonwoven fabrics comprising aromatic polyester fibers, aromatic polyester amide fibers, glass fibers, carbon fibers and paper or mixtures of two or more thereof may be used.
  • the time for impregnating the composition solution to the substrate may be, for example, 0.001 minutes to 1 hour.
  • the impregnation time is within the above range, the composition solution is uniformly impregnated and the productivity is high.
  • the temperature for impregnating the composition solution to the substrate may be 20 ⁇ 190 °C.
  • the amount of the thermosetting resin composition is impregnated per unit area of the substrate may be in the range of 0.1 ⁇ 1,000g / m 2 . If the amount of impregnation of the composition for thermosetting resin production is within the above range, productivity is high and processing is easy. Therefore, the prepreg after semi-curing may include a composition for preparing a thermosetting resin of about 0.1 to 1,000 g / m 2 and a cured product thereof based on the unit area of the substrate.
  • the composition solution may include an inorganic filler such as silica, aluminum hydroxide or calcium carbonate in order to adjust the dielectric constant and thermal expansion coefficient; And / or organic fillers such as cured epoxy or crosslinked acrylics may be added.
  • an inorganic filler of high dielectric constant may be added.
  • a titanate such as barium titanate or strontium titanate, or a part of titanium or barium of barium titanate may be replaced with another metal.
  • the content of the inorganic filler and / or the organic filler in the composition solution may be 0.0001 to 300 parts by weight based on 100 parts by weight of the composition for preparing the thermosetting resin.
  • the prepreg after semi-curing may include 0.0001 to 300 parts by weight of the inorganic filler and / or the organic filler based on 100 parts by weight of the total content of the composition for preparing the thermosetting resin and its cured product.
  • Prepreg according to an embodiment of the present invention is excellent in flame retardancy, the cured product of the composition for producing a thermosetting resin having a low thermal expansion coefficient, low hygroscopicity and low dielectric properties, and an organic or inorganic woven fabric and / or organic or inorganic excellent in mechanical strength Since it contains a nonwoven fabric, it is excellent in dimensional stability, less heat deformation and hard, which is advantageous for via hole drilling and lamination.
  • the method of impregnating the composition solution to the substrate or removing the solvent after applying the composition solution to the substrate is not particularly limited, but may be achieved by solvent evaporation. can do.
  • evaporation methods such as heating, reduced pressure or ventilation are possible.
  • the prepreg impregnated with the composition solution may be dried at 20 ⁇ 190 °C for 1 minute to 2 hours to remove the solvent.
  • the dried prepreg may be heat treated at 120 to 320 ° C. for 1 to 8 hours to semi-cure the composition for preparing a thermosetting resin contained in the prepreg.
  • Prepreg according to an embodiment of the present invention obtained as described above may have a thickness of about 5 ⁇ 200 ⁇ m, for example, about 30 ⁇ 150 ⁇ m.
  • the thermal expansion rate in one direction of the prepreg may be 20 ppm / K or less.
  • the coefficient of thermal expansion of the prepreg is within the above range, no peeling phenomenon occurs in the metal foil laminated plate employing the prepreg.
  • the dielectric constant of the prepreg may be 4.0 or less, and the dielectric loss may be 0.01 or less.
  • 'dielectric loss' refers to an energy loss lost by heat in the dielectric when an alternating electric field is applied to the dielectric.
  • the glass transition temperature of the cured product may be 170 ⁇ 270 °C. If the glass transition temperature of the cured product is within the above range, warpage does not occur while having high heat resistance.
  • Flame retardancy, thermal expansion and dielectric properties of the prepreg described above, and the glass transition temperature of the cured product can usually be measured by the following method. That is, after laminating metal thin films on both sides of the prepreg (that is, the semi-cured composition for preparing a thermosetting resin impregnated into the base material), heating and pressurizing to prepare a metal foil laminate, then a metal thin film from the metal foil laminate After removing all, the prepreg portion may be analyzed to measure flame retardancy, thermal expansion and dielectric properties, and glass transition temperature of the cured product included in the prepreg. Upon heating and pressing, the semi-cured resin is completely cured.
  • a prepreg laminated body can be manufactured by laminating a predetermined number of said prepregs, and heating and pressurizing it. Upon heating and pressurization, the semi-cured resin is fully cured and mostly converted to the crosslinked resin.
  • a metal foil laminate may be manufactured by disposing a metal thin film such as copper foil, silver foil or aluminum foil on one or both surfaces of the prepreg or prepreg laminate, and heating and pressing. Upon heating and pressurization, the semi-cured resin, if present, is completely cured and converted into a crosslinked resin mostly.
  • the thickness of the prepreg or the prepreg laminate and the metal thin film may be 0.1 to 300 ⁇ m, respectively. If the thickness of the prepreg or the prepreg laminate is within the above range, cracks are less likely to occur during the processing of the winding method, and are advantageous for multilayer lamination of a limited thickness. If the thickness of the said metal thin film is within the said range, it is suitable for light and small size reduction, and pattern formation is easy.
  • the heating and pressurization conditions applied during the production of the metal foil laminate may be, for example, 150 to 250 ° C. and 10 to 30 MPa, but the properties of the prepreg, the reactivity of the composition for preparing the thermosetting resin, the ability of the press, and the metal foil laminate for the purpose. It may be appropriately determined in consideration of the thickness and the like, and is not particularly limited.
  • the metal foil laminate according to an embodiment of the present invention may further include an adhesive layer interposed therebetween in order to increase the bonding strength between the prepreg laminate and the metal thin film.
  • an adhesive layer interposed therebetween in order to increase the bonding strength between the prepreg laminate and the metal thin film.
  • a thermoplastic resin or a thermosetting resin may be used in the preparation of the adhesive layer.
  • the thickness of the adhesive layer may be 0.1 ⁇ 100 ⁇ m. When the thickness of the adhesive layer is within the above range, the thickness is moderate and the adhesive strength is high.
  • a printed wiring board can be manufactured by etching the metal thin film of the said metal foil laminated board, and forming a circuit. Moreover, a printed wiring board can also be manufactured by printing a metal circuit pattern on at least one surface of the said thermosetting resin film. Moreover, a through hole etc. can also be formed in the said printed wiring board as needed.
  • a predetermined number of sheets of the prepreg are disposed between constituent materials, such as an inner substrate or a metal thin film, in accordance with a desired thickness of an insulating layer, and heated and pressed. It can be produced by molding. Heating and pressurization conditions at this time may be the same as the conditions at the time of manufacturing the metal foil laminate.
  • a prepreg laminate, a metal foil laminate, a printed wiring board, or the like used as an electrical insulation material may be used, and two or more kinds thereof may be used in combination.
  • HNA 6-hydroxy-2-naphthoic acid
  • HBA para hydroxy benzoic acid
  • AP 4-aminophenol
  • a reactor equipped with a stirring device, a torque meter, a nitrogen gas introduction tube, a thermometer and a reflux condenser Compound represented by Formula 1 (DOPO-HQ), resorcinol (RCN), hydroquinone (HQ), isophthalic acid (IPA) and acetic anhydride (Ac 2 O) was added in the ratios listed in Table 1.
  • DOPO-HQ resorcinol
  • HQ hydroquinone
  • IPA isophthalic acid
  • Ac 2 O acetic anhydride
  • Step 2 preparing a composition solution for preparing a thermosetting resin
  • the aromatic polyester amide copolymer powder prepared in step 1 and an epoxy resin were added to dimethylacetamide (DMAc) in the ratios listed in Table 2 below, and a curing agent (Samjeon Chemical, DICY). 3 g and 4 mg of a curing catalyst (Shikoku Co., 2E4MZ) were further added, followed by stirring at 25 ° C. for 4 hours to obtain a composition solution for producing a thermosetting resin.
  • composition solution prepared in step 2 was impregnated with a glass cloth (IPC 1078) at room temperature, and passed through a double roller to remove excess composition solution and to have a constant thickness. Thereafter, the contents were placed in a high temperature hot air dryer to remove the solvent at 180 ° C. to obtain a prepreg.
  • a glass cloth IPC 1078
  • the laminate After placing one sheet of electrolytic copper foil having a thickness of 18 ⁇ m on each side of the prepreg prepared in step 3, the laminate was heated and pressurized under a condition of 200 ° C. and 30 MPa using a hot plate press for 3 hours. Prepared.
  • the prepreg portion was analyzed to determine the crosslinking degree and glass transition temperature of the resin (ie, cured resin) contained therein, And flame retardancy, thermal expansion coefficient and dielectric properties of the prepreg were measured and shown in Table 3 below.
  • the degree of crosslinking was measured by analyzing the exothermic peak obtained by increasing the temperature at 20 ° C./min from room temperature to 300 ° C. using a differential scanning thermal analyzer (DSC) (TA Instrument, DSC 2910). Measurement was carried out using a scanning thermal analyzer (DSC) (TA Instrument, DSC 2910) under conditions of raising the temperature from room temperature to 300 ° C. at 20 ° C./min, and flame retardancy was measured using UL94 (Underwriters Laboratories, USA). Was measured at a temperature range of 50 ⁇ 200 °C using TMA (TMA Q400), dielectric constant and dielectric loss was measured at room temperature using an impedance analyzer (Agilent, E4991A).
  • DSC differential scanning thermal analyzer
  • the copper foil laminates prepared in Examples 1 to 3 have excellent flame retardancy, low thermal expansion coefficient, low dielectric constant and low dielectric loss except for copper foil (ie, prepreg portion) and are included in the prepreg.
  • the resin has a high glass transition temperature.
  • the copper foil laminate prepared in Comparative Example 1 has a high glass transition temperature, low thermal expansion coefficient and low dielectric constant of the resin, but has a disadvantage of low flame retardancy and high dielectric loss.
  • the copper foil laminate prepared in Comparative Example 2 has a low dielectric constant, but has a low glass transition temperature, high thermal expansion coefficient, high dielectric loss, and low flame retardancy of the resin.
  • the copper foil laminate prepared in Comparative Example 3 has a high glass transition temperature, low thermal expansion coefficient, low dielectric constant and low dielectric loss of the resin, but has a disadvantage of low flame retardancy.
  • Comparative Examples 5-6 the amount of epoxy resins or the amount of aromatic polyester amide copolymers were large, and the copper clad laminated board could not be manufactured. In particular, in Comparative Example 6, the amount of the epoxy resin was excessively large so that the progress to the B-Stage was impossible.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une composition servant à préparer une résine thermodurcissable et un article durci préparé à partir de cette résine, un préimprégné contenant l'article durci et une plaque stratifiée en feuilles de métal et une carte de câblage imprimé utilisant le préimprégné. La composition de l'invention contient un copolymère de polyester aromatique-amide présentant d'excellentes propriétés d'ininflammabilité, le copolymère contenant un groupe terminal aminé et/ou un groupe terminal hydroxylé, une résine époxy et éventuellement un bismaléimide.
PCT/KR2012/006180 2011-08-04 2012-08-03 Composition servant à préparer une résine thermodurcissable et article durci préparé à partir de cette résine, préimprégné contenant un article durci et plaque stratifiée en feuilles de métal et carte de câblage imprimé utilisant un préimprégné Ceased WO2013019085A2 (fr)

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JP2014523850A JP6111247B2 (ja) 2011-08-04 2012-08-03 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
CN201280038714.0A CN103732687B (zh) 2011-08-04 2012-08-03 制备热固树脂的组合物和其固化制品、包含固化制品的预浸材料以及使用预浸材料的覆金属箔层压板和印刷电路板

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KR10-2011-0077845 2011-08-04
KR20110077845 2011-08-04
KR1020120084187A KR101767691B1 (ko) 2011-08-04 2012-07-31 열경화성 수지 제조용 조성물 및 그의 경화물, 상기 경화물을 포함하는 프리프레그, 및 상기 프리프레그를 채용한 금속박 적층판과 프린트 배선판
KR10-2012-0084187 2012-07-31

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109593200A (zh) * 2018-11-28 2019-04-09 苏州生益科技有限公司 一种阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板

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JP2003206392A (ja) * 2002-01-16 2003-07-22 Hitachi Chem Co Ltd 難燃性樹脂組成物及びこの組成物を用いるプリプレグ、積層板、プリント配線板
KR101054272B1 (ko) * 2008-12-31 2011-08-08 삼성정밀화학 주식회사 다가지형 폴리에스테르 아미드 공중합체, 상기 다가지형 폴리에스테르 아미드 공중합체를 채용한 프리프레그와 프리프레그 적층체, 및 상기 프리프레그 또는 프리프레그 적층체를 채용한 금속박 적층판과 프린트 배선판
KR101111644B1 (ko) * 2009-06-17 2012-02-14 삼성정밀화학 주식회사 방향족 폴리에스테르 아미드 공중합체, 상기 방향족 폴리에스테르 아미드 공중합체를 채용한 프리프레그와 프리프레그 적층체, 및 상기 프리프레그 또는 프리프레그 적층체를 채용한 금속박 적층판과 프린트 배선판

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109593200A (zh) * 2018-11-28 2019-04-09 苏州生益科技有限公司 一种阻燃型树脂预聚物及使用其制备的树脂组合物、半固化片和层压板

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