WO2016033074A1 - Époxy à base de naphtalène pour compositions ignifugeantes et exemptes de composés halogénés - Google Patents

Époxy à base de naphtalène pour compositions ignifugeantes et exemptes de composés halogénés Download PDF

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Publication number
WO2016033074A1
WO2016033074A1 PCT/US2015/046741 US2015046741W WO2016033074A1 WO 2016033074 A1 WO2016033074 A1 WO 2016033074A1 US 2015046741 W US2015046741 W US 2015046741W WO 2016033074 A1 WO2016033074 A1 WO 2016033074A1
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weight percent
curable composition
naphthol
range
epoxy
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PCT/US2015/046741
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English (en)
Inventor
Xiaomei Song
Hongyu Chen
Michael J. Mullins
Fujun LU
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Blue Cube Ip Llc
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Publication of WO2016033074A1 publication Critical patent/WO2016033074A1/fr

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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds

Definitions

  • the present invention is related to epoxy resin compositions. More particularly, the present invention is related to halogen-free or substantially halogen-free formulations.
  • Epoxy resins are widely used in coatings, adhesives, printed circuit boards, semiconductor encapsulants, adhesives and aerospace composites thanks to the excellent mechanical strength; chemical, moisture, and corrosion resistance; good thermal, adhesive, and electrical properties.
  • Copper plated-through holes (PTH) and copper plate vias will suffer cracks within the copper due to the substantially higher expansion of the PWB.
  • a composition having a lower CTE in x- and y- axis towards silicon and in z-axis towards copper resulting in lower stress between the PWB and its components is desirable.
  • the instant invention is a curable composition
  • a curable composition comprising, consisting of, or consisting essentially of: a) an epoxy component comprising a dinaphthalene epoxy having the structure
  • each Ri group is independently a C1-C20 hydrocarbon; a is an integer in the range of from 0 to 6; m is an integer in the range of from 0 to 5; b) a hardener component comprising i) a naphthol novolac which is a reaction product of I) from 1 to 99 weight percent 1-naphthol and II) from 1 to 99 weight percent 2-naphthol; ii) a phosphorus-containing composition which is the reaction product of an etherified resole with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO); and iii) optionally a phenolic resin selected from the group consisting of a molecule having at least one substituted or unsubstituted naphthalene ring, a high functionality phenolic resin, and combinations thereof.
  • DETAILED DESCRIPTION DETAILED DESCRIPTION
  • the instant invention is a curable composition.
  • the instant invention is a curable composition comprising, consisting of, or consisting essentially of a) an epoxy component comprising a dinaphthalene epoxy having the structure
  • each Ri group is independently a C1-C20 hydrocarbon; a is an integer in the range of from 0 to 6; m is an integer in the range of 0 to 5; b) a hardener component comprising i) a naphthol novolac which is a reaction product of I) from 1 to 99 weight percent 1-naphthol and II) from 1 to 99 weight percent 2-naphthol; ii) a phosphorus-containing composition which is the reaction product of an etherified resole with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO); and iii) optionally a phenolic resin selected from the group consisting of a molecule having at least one substituted or unsubstituted naphthalene ring, a high functionality phenolic resin, and combinations thereof.
  • a hardener component comprising i) a naphthol novolac which is a reaction product of I) from 1
  • the curable composition can further include optionally a filler.
  • the curable composition can further include optionally a catalyst and/or a solvent.
  • the curable composition comprises an epoxy component and a hardener component, as described in further details herein below.
  • the curable composition may further include one or more fillers selected from the group consisting of natural silica, fused silica, alumina, hydrated alumina, talc, alumina trihydrate, magnesium hydroxide and combinations thereof.
  • the curable composition may comprise 10 to 80 percent by weight of one or more fillers. All individual values and subranges from 10 to 80 weight percent are included herein and disclosed herein, for example, the weight percent of filler can be from a lower limit of 10, 12, 15, 20, or 25 weight percent to an upper limit of 62, 65, 70, 75, or 80 weight percent.
  • curable composition may comprise 15 to 75 percent by weight of one or more fillers; or in the alternative, curable composition may comprise 20 to 70 percent by weight of one or more fillers.
  • Such fillers include, but are not limited to natural silica, fused silica, alumina, hydrated alumina, talc, alumina trihydrate, magnesium hydroxide and combinations thereof.
  • the curable composition may further include one or more catalysts.
  • the curable composition may comprise 0.01 to 10 percent by weight of one or more catalysts. All individual values and subranges from 0.01 to 10 weight percent are included herein and disclosed herein, for example, the weight percent of catalyst can be from a lower limit of 0.01, 0.03, 0.05, 0.07, or 1 weight percent to an upper limit of 2, 6, or 10 weight percent.
  • the curable composition may comprise 0.05 to 10 percent by weight of one or more catalysts; or in the alternative, the curable composition may comprise 0.05 to 2 percent by weight of one or more catalysts.
  • Such catalysts include, but are not limited to, 2-methyl imidazole (2MI), 2-phenyl imidazole (2PI), 2-ethyl-4-methyl imidazole (2E4MI), l-benzyl-2-phenylimidazole (1B2PZ), boric acid, triphenylphosphine (TPP),
  • TPP-k tetraphenylphosphonium-tetraphenylborate
  • the curable composition may further include one or more tougheners.
  • the curable composition may comprise 0.01 to 70 percent by weight of one or more tougheners. All individual values and subranges from 0.01 to 70 weight percent are included herein and disclosed herein, for example, the weight percent of toughener can be from a lower limit of 0.01, 0.05, 1, 1.5, or 2 weight percent to an upper limit of 15, 30, 50, 60, or 70 weight percent.
  • the curable composition may comprise 1 to 50 percent by weight of one or more tougheners; or in the alternative, the curable composition may comprise 2 to 30 percent by weight of one or more tougheners.
  • Such tougheners include, but are not limited to core shell rubbers.
  • a core shell rubber is a polymer comprising a rubber particle core formed by a polymer comprising an elastomeric or rubbery polymer as a main ingredient and a shell layer formed by a polymer graft polymerized on the core. The shell layer partially or entirely covers the surface of the rubber particle core by graft polymerizing a monomer to the core.
  • the rubber particle core is constituted from acrylic or methacrylic acid ester monomers or diene (conjugated diene) monomers or vinyl monomers or siloxane type monomers and combinations thereof.
  • the toughening agent may be selected from commercially available products; for example, Paraloid EXL 2650A, EXL 2655, EXL2691 A, each available from The Dow Chemical Company, or Kane Ace® MX series from Kaneka Corporation, such as MX 120, MX 125, MX 130, MX 136, MX 551, or METABLEN SX-006 available from Mitsubishi Rayon.
  • the curable composition may further include one or more solvents. Solvents can be used to solubilize the epoxy and hardener component or to adjust the viscosity of the final varnish.
  • the curable composition may comprise 0.01 to 50 percent by weight of one or more solvents. All individual values and subranges from 0.01 to 50 weight percent are included herein and disclosed herein, for example, the weight percent of catalyst can be from a lower limit of 0.01, 0.03, 0.05, 0.07, or 1 weight percent to an upper limit of 2, 6, 10, 15, 30, or 50 weight percent.
  • the curable composition may comprise 1 to 50 percent by weight of one or more solvents; or in the alternative, the curable composition may comprise 2 to 30 percent by weight of one or more solvents.
  • Such solvents include, but are not limited to methanol, acetone, n-butanol, methyl ethyl ketone (MEK), benzene, toluene, xylene, cyclohexanone, dimethylformamide (DMF), ethyl alcohol (EtOH), propylene glycol methyl ether (PM), propylene glycol methyl ether acetate (DOWANOLTM PMA) and mixtures thereof.
  • MEK methyl ethyl ketone
  • DMF dimethylformamide
  • EtOH ethyl alcohol
  • PM propylene glycol methyl ether
  • DOWANOLTM PMA propylene glycol methyl ether acetate
  • the curable composition comprises a) an epoxy component; b) a hardener component comprising i) a naphthol novolac which is a reaction product of I) from 1 to 99 weight percent 1- naphthol and II) from 1 to 99 weight percent 2-naphthol; and ii) an oligomeric compound comprising a phosphorus composition which is the reaction product of an etherified resole with DOPO; and iii) optionally a phenolic resin selected from the group consisting of a molecule having at least one substituted or unsubstituted naphthalene ring, a high functionality phenolic resin, and combinations thereof.
  • the epoxy component is a dinaphthalene epoxy.
  • An example of the epoxy component is depicted in Formula 1.
  • each Ri group is independently a hydrocarbon with 1 to 20 carbon atoms per molecule. All individual values and subranges from 1 to 20 are included herein and disclosed herein, for example Rl can be a hydrocarbon with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms per molecule, a is an integer between 0 and 6. All individual values and subranges from 0 to 6 are included herein and disclosed herein, for example a can be 0, 1, 2, 3, 4, 5, or 6. m is an integer in the range of 0 to 5. All individual values and subranges from 0 to 5 are included herein and disclosed herein, for example m can be 0, 1, 2, 3, 4, or 5.
  • the dinaphthalene epoxy is made by contacting a dihydroxydinaphthyl with an epihalohydrin.
  • the dihydroxydinaphthyl can be trans-isomers or cis-isomers or a mixture of cis and trans isomers.
  • the epihalohydrin is epichlorohydrin (EPI).
  • EPI epichlorohydrin
  • the curable composition may comprise 1 to 99 percent by weight of the epoxy component. All individual values and subranges from 1 to 99 weight percent are included herein and disclosed herein, for example, the weight percent of epoxy resin can be from a lower limit of 12, 17, 20, 30, or 35 weight percent to an upper limit of 55, 70, 86, 90, or 98 weight percent.
  • curable composition may comprise 20 to 98 percent by weight of one or more epoxy resins or in the alternative, curable composition may comprise 30 to 90 percent by weight of one or more epoxy resins.
  • the curable composition may comprise 1 to 99 percent by weight of one or more naphthol novolac resins.
  • Such naphthol novolac resins ensure that the epoxy resin composition in the cured state has a low coefficient of linear expansion and a high Tg in a temperature range from room temperature to equal to or above Tg. All individual values and subranges from 1 to 99 weight percent are included herein and disclosed herein, for example, the weight percent of naphthol novolac resin can be from a lower limit of 1, 1.2, 1.5, 12, or 20 weight percent to an upper limit of 45, 50, 54, 60, or 70 weight percent.
  • the naphthol novolac resin is formed by a naphthol component contacted with aldehyde.
  • An example of the reaction scheme is depicted in Formula 3, below.
  • the naphthol novolac is a reaction product of I) from 1 to 99 weight percent 1-naphthol and II) from 1 to 99 weight percent 2-naphthol. All individual values and subranges from 1 to 99 weight percent are included herein and disclosed herein, for example, the weight percent of 1-naphthol can be from a lower limit of 1, 10, 14, 25, 33, 50, 66, 71, or 80 weight percent to an upper limit of 25, 33, 55, 66, 75, 82, or 95 weight percent. Likewise, the weight percent of 2-naphthol can be from a lower limit of 1, 10, 14, 33, 50, 66, 71, or 80 weight percent to an upper limit of 25, 33, 55, 66, 82, or 95 weight percent.
  • paraformaldehyde can be used as the aldehyde.
  • aldehydes that can be used include, but are not limited to formaldehyde, aliphatic aldehydes, and aromatic aldehydes.
  • the naphthol component can be added to a solvent before contact with the aldehyde.
  • Any suitable solvent can be used such as, for example, toluene and xylene.
  • phenolic resins can be added to the curable composition.
  • the phenolic resin can be selected from the group consisting of a molecule having at least one substituted or unsubstituted naphthalene ring, a high functionality phenolic resin, and combinations thereof.
  • Phenolic resins that can be used include, but are not limited to novolac type phenolic resins (e.g., phenol novolac resins, cresol novolac resins), triphenolalkane type phenolic resins (e.g., triphenolmethane phenolic resins, triphenolpropane phenolic resins), phenol aralkyl type phenolic resins, biphenyl aralkyl type phenolic resins, biphenyl type phenolic resins.
  • the phenolic resin is a naphthalene type phenolic resin. These phenolic resins may be employed alone or in combination of two or more.
  • the curable composition may comprise 1 to 70 percent by weight of one or more optional phenolic resins. All individual values and subranges from 1 to 99 weight percent are included herein and disclosed herein, for example, the weight percent of phenolic resin can be from a lower limit of 1, 1.2, 1.5, 12, or 20 weight percent to an upper limit of 45, 50, 54, 60, or 70 weight percent.
  • the curable composition may comprise 1 to 80 percent by weight of one or more oligomeric compounds comprising a phosphorus composition which is the reaction product of an etherified resole with DOPO. All individual values and subranges from 1 to 80 weight percent are included herein and disclosed herein, for example, the weight percent of DOPO compound can be from a lower limit of 1.5, 2, 3, 5, or 10 weight percent to an upper limit of 20, 40, 55, 60, or 70 weight percent.
  • curable composition may comprise 2 to 60 percent by weight of one or more DOPO compound or in the alternative, curable composition may comprise 5 to 40 percent by weight of one or more DOPO compound.
  • the DOPO-containing compound is an oligomeric composition comprising a phosphorus-containing compound which is the reaction product of an etherified resole with DOPO. This reaction product is depicted in Formula 4, below.
  • the composition can be produced by any suitable process known to those skilled in the art.
  • the components are prepared by any suitable method.
  • dihydroxydinapthyl is contacted with an epihalohydrin in a reaction zone under reaction conditions to form a dinaphthalene epoxy; and 1-naphthol and 2-naphthol are contacted in a reaction zone under reaction conditions to form a naphthol novolac composition.
  • solutions of the epoxy component, naphthol novolac, and phosphorus-containing composition are mixed together. Any other desired component, such as the optional components described above, are then added to the mixture.
  • Embodiments of the present disclosure provide prepregs that include a reinforcement component and the curable composition, as discussed herein.
  • the prepreg can be obtained by a process that includes impregnating a matrix component into the reinforcement component.
  • the matrix component surrounds and/or supports the reinforcement component.
  • the disclosed curable compositions can be used for the matrix component.
  • the matrix component and the reinforcement component of the prepreg provide a synergism. This synergism provides that the prepregs and/or products obtained by curing the prepregs have mechanical and/or physical properties that are unattainable with only the individual components.
  • the prepregs can be used to make electrical laminates for printed circuit boards.
  • the reinforcement component can be a fiber.
  • fibers include, but are not limited to, glass, aramid, carbon, polyester, polyethylene, quartz, metal, ceramic, biomass, and combinations thereof.
  • the fibers can be coated.
  • An example of a fiber coating includes, but is not limited to, boron.
  • glass fibers include, but are not limited to, A-glass fibers, E-glass fibers, C-glass fibers, R-glass fibers, S-glass fibers, T-glass fibers, and combinations thereof.
  • Aramids are organic polymers, examples of which include, but are not limited to, Kevlar®, Twaron®, and combinations thereof.
  • carbon fibers include, but are not limited to, those fibers formed from polyacrylonitrile, pitch, rayon, cellulose, and combinations thereof.
  • metal fibers include, but are not limited to, stainless steel, chromium, nickel, platinum, titanium, copper, aluminum, beryllium, tungsten, and combinations thereof.
  • Ceramic fibers include, but are not limited to, those fibers formed from aluminum oxide, silicon dioxide, zirconium dioxide, silicon nitride, silicon carbide, boron carbide, boron nitride, silicon boride, and combinations thereof.
  • biomass fibers include, but are not limited to, those fibers formed from wood, non- wood, and combinations thereof.
  • the reinforcement component can be a fabric.
  • the fabric can be formed from the fiber, as discussed herein. Examples of fabrics include, but are not limited to, stitched fabrics, woven fabrics, and combinations thereof.
  • the fabric can be unidirectional, multiaxial, and combinations thereof.
  • the reinforcement component can be a combination of the fiber and the fabric.
  • the prepreg is obtainable by impregnating the matrix component into the reinforcement component. Impregnating the matrix component into the reinforcement component may be accomplished by a variety of processes.
  • the prepreg can be formed by contacting the reinforcement component and the matrix component via rolling, dipping, spraying, or other such procedures.
  • the solvent can be removed via volatilization. While and/or after the solvent is volatilized the prepreg matrix component can be cured, e.g. partially cured. This volatilization of the solvent and/or the partial curing can be referred to as B-staging.
  • the B-staged product can be referred to as the prepreg.
  • B-staging can occur via an exposure to a temperature of 60 °C to 250
  • B-staging can occur via an exposure to a temperature from 65 °C to 240 °C , or 70 °C to 230 °C.
  • B-staging can occur for a period of time of 1 minute (min) to 60 min; for example B-staging can occur for a period of time from, 2 min to 50 min, or 5 min to 40 min.
  • the B-staging can occur at another temperature and/or another period of time.
  • One or more of the prepregs may be cured (e.g. more fully cured) to obtain a cured product.
  • the prepregs can be layered and/or formed into a shape before being cured further.
  • layers of the prepreg can be alternated with layers of a conductive material.
  • An example of the conductive material includes, but is not limited to, copper foil.
  • the prepreg layers can then be exposed to conditions so that the matrix component becomes more fully cured.
  • One example of a process for obtaining the more fully cured product is pressing.
  • One or more prepregs may be placed into a press where it subjected to a curing force for a predetermined curing time interval to obtain the more fully cured product.
  • the press has a curing temperature in the curing temperature ranges stated above.
  • the press has a curing temperature that is ramped from a lower curing temperature to a higher curing temperature over a ramp time interval.
  • the one or more prepregs can be subjected to a curing force via the press.
  • the curing force may have a value that is 10 kilopascals (kPa) to 350 kPa; for example the curing force may have a value that is 20 kPa to 300 kPa, or 30 kPa to 275 kPa.
  • the predetermined curing time interval may have a value that is 5 s to 500 s; for example the predetermined curing time interval may have a value that is 25 s to 540 s, or 45 s to 520 s.
  • the process may be repeated to further cure the prepreg and obtain the cured product.
  • the prepregs can be used to make composites, electrical laminates, and coatings.
  • Printed circuit boards prepared from the electrical laminates can be used for a variety of applications. In an embodiment, the printed circuit boards are used in smartphones and tablets. In various embodiments
  • the electrical laminates have a copper peel strength in the range of from 4 lb/in to 12 lb/in.
  • Epoxy EN-1 (dinaphthalene epoxy, 60% in methyl ethyl ketone), from the above process
  • 2-methylimidazole (2-MI) curing catalyst (10% in Propylene Glycol Monomethyl Ether), from Sinopharm Chemical and Reagent Company
  • the type of phenol novolac hardener influenced Tg performance. Comparing Inventive Examples 5-6 and Inventive Examples 7-11 shows that using high functional hardeners result in higher Tg while maintaining comparative CTE performance.
  • the reactivity of the different varnish formulations was determined in terms of time required for the material to gel.
  • the gel point is the point at which the resin turns from a viscous liquid to an elastomer.
  • the gel time was measured and recorded using approximately 0.7 ml of liquid dispensed on a hot plate maintained at 171°C, stroking the liquid back and forth after 60s on the hot-plate until it gels.
  • the hand lay-up technique was developed to make prepreg on a small scale quickly and easily.
  • a single sheet of glass fabric approximately twelve inches square was stapled to a wood frame.
  • the frame with e-glass fabric was placed on a flat surface that was covered with a disposable plastic sheet.
  • About 25-35 g varnish was poured onto the e-glass fabrics and then evenly spreaded with a paint brush two inches in width.
  • the frame with wetted glass fabrics was subsequently suspended in an air circulating oven at a temperature of 171 °C to remove solvent. After one minute, the frame was removed and allowed to cool to room temperature.
  • the prepreg was crushed to obtain powder for further testing.
  • Thermogravity analysis (TGA) of the cured resins was performed with Instrument TGA Q5000 V3.10 Build 258.
  • the test temperature ranges from room temperature to 600°C; the heating rate is 20°C/min, nitrogen flow protection.
  • the decomposition temperature (Td) was determined through selecting the corresponding temperature at 5% of weight loss (residual weight 95%) of materials.
  • Glass transition temperature (Tg) of the cured resins was determined by both DSC and DMTA.
  • the DSC testing condition is as follows:
  • DMTA Tg of the cured resins was determined with RSA III dynamic mechanical thermal analyzer (DMTA). Samples were heated from -50 to 250°C at 3°C/min heating rate. Test frequency was 6.28 rad/s. The Tg of the cured epoxy resin was obtained from the tangent delta peak.
  • Samples for CTE test were prepared and tested according to IPC-TM-650 2.4.41 by following steps: 1: Ramp 10.00°C/min to Tg;
  • the prepreg sheets were molded into a laminate and cured at 220°C for 3 hrs by a regular hot press machine.
  • the final laminate was cut into the standard samples for UL-94 FR testing.
  • UL94 vertical flame testing was conducted in a CZF-2 vertical/horizontal burning tester made by Nanjing Jiangning Analytical Equipment Company.
  • the chamber size was 720 mm x 370 mm x 500 mm, with natural gas as the burner gas resource.
  • the chamber was opened during the whole testing process, with air flow around the testing device prohibited.
  • Each specimen was ignited twice, with after flame time (AFT) tl and t2 recorded.
  • AFT tl and t2 were obtained as follows: The test flame was applied to the specimen for 10 seconds and then removed.
  • the length of time (tl) was the duration between the flame removal and the time at which the flame on the specimen extinguished. Once the flame had extinguished, the test flame was applied for another 10 seconds and then removed. The duration of the burning of the specimen (t2) was again recorded.
  • Water uptake was performed by exposing 4 or 5 coupons in steam (121°C, 2atm) for 1 hour in an autoclave. The coupon was removed and quickly baked, then weighed to determine the water uptake.
  • Copper peel strength was tested by an IMASS SP-2000 Slip/Peel Tester according to the method described in IPC TM-650 2.4.8.1.
  • the 35 ⁇ standard copper foils were used for preparing laminates.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une composition durcissable comprenant, constituée de, ou constituée essentiellement de a) un constituant époxy comprenant un dinaphtalène époxy ayant la structure dans laquelle chaque groupe R1 représente indépendamment un hydrocarbure en C1-C20 ; a représente un nombre entier situé dans la plage allant de 0 à 6 ; m représente un nombre entier situé dans la plage allant de 0 à 5 ; et b) un constituant durcisseur comprenant i) une naphtol novolaque qui est un produit de la réaction de I) de 1 à 99 pour cent en poids de 1-naphtol et de II) de 1 à 99 pour cent en poids de 2-naphtol ; ii) une composition contenant du phosphore qui est le produit de la réaction d'un résol éthérifié avec un 9,10-dihydro-9-oxa-10-phosphaphénanthrène-10-oxyde ; et iii) éventuellement une résine phénolique choisie dans le groupe constitué par une molécule comprenant au moins un cycle naphtalène substitué ou non substitué, une résine phénolique hautement fonctionnalisée, et des combinaisons de celles-ci. La composition durcissable peut être utilisée pour préparer des préimprégnés et des stratifiés électriques.
PCT/US2015/046741 2014-08-29 2015-08-25 Époxy à base de naphtalène pour compositions ignifugeantes et exemptes de composés halogénés WO2016033074A1 (fr)

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KR101377356B1 (ko) * 2012-12-26 2014-03-25 주식회사 두산 접착성이 우수한 에폭시 수지 조성물 및 이를 이용한 수지 복합 동박
US20140178656A1 (en) * 2012-12-20 2014-06-26 Elite Electronic Material (Zhongshan) Co.,Ltd Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same

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