WO2016029450A1 - Formulations de résine époxy exemptes d'halogène - Google Patents

Formulations de résine époxy exemptes d'halogène Download PDF

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Publication number
WO2016029450A1
WO2016029450A1 PCT/CN2014/085576 CN2014085576W WO2016029450A1 WO 2016029450 A1 WO2016029450 A1 WO 2016029450A1 CN 2014085576 W CN2014085576 W CN 2014085576W WO 2016029450 A1 WO2016029450 A1 WO 2016029450A1
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WO
WIPO (PCT)
Prior art keywords
curable composition
weight percent
accordance
naphthol
epoxy
Prior art date
Application number
PCT/CN2014/085576
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English (en)
Inventor
Jingjing YAN
Guihong LIAO
Hongyu Chen
Mark B. Wilson
Xiangyang Tai
Xiaorong He
Lu Zhu
Yanli FENG
Original Assignee
Blue Cube Ip Llc
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Application filed by Blue Cube Ip Llc filed Critical Blue Cube Ip Llc
Priority to PCT/CN2014/085576 priority Critical patent/WO2016029450A1/fr
Priority to PCT/US2015/046849 priority patent/WO2016033136A1/fr
Priority to TW104128360A priority patent/TW201615740A/zh
Publication of WO2016029450A1 publication Critical patent/WO2016029450A1/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
    • C08G59/40—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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • 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

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.
  • Epoxy resins are inherently flammable, thus many phosphorous based flame retardants (such as phosphate, phosphazene, DOPO (9, 10-Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide), etc. ) have been employed to obtain flame retardancy due to fire safety and environmental concerns.
  • the phosphorous based flame retardants may cause moisture uptake issues and sometimes result in cured resins with lower glass transition temperatures (T g ). Therefore, a non-halogen flame retardant (FR) epoxy composition, which offers not only good flame retardant performance but also higher T g and moisture resistant properties, would be desirable.
  • FR non-halogen flame retardant
  • the instant invention is a curable composition
  • a curable composition comprising, consisting of, or consisting essentially of a) an epoxy resin; and b) a hardener component comprising i) an oligomeric compound comprising a phosphorus composition which is the reaction product of an etherified resole with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and ii) naphthol novolac.
  • the instant invention is a curable composition.
  • the instant invention is a curable composition comprising, consisting of, or consisting essentially of a) an epoxy resin; and b) a hardener component comprising i) an oligomeric compound comprising a phosphorus composition which is the reaction product of an etherified resole with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and ii) naphthol novolac.
  • the curable composition can further include optionally a filler selected from the group consisting of natural silica, fused silica, alumina, hydrated alumina, and combinations thereof.
  • the curable composition can further include optionally a catalyst.
  • the curable composition comprises an epoxy resin and a hardener, as described in further details herein below.
  • the curable composition may further include one or more fillers.
  • 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, and combinations thereof.
  • the curable composition may further include one or more catalysts.
  • the curable composition may comprise 0.01 to 20 percent by weight of one or more catalysts. All individual values and subranges from 0.01 to 20 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, 8, 10, 15, or 20 weight percent.
  • curable composition may comprise 0.05 to 10 percent by weight of one or more catalysts; or in the alternative, 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), 1-benzyl-2-phenylimidazole (1B2PZ), boric acid, triphenylphosphine (TPP), tetraphenylphosphonium-tetraphenylborate (TPP-k) and combinations thereof.
  • 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.
  • curable composition may comprise 1 to 50 percent by weight of one or more tougheners; or in the alternative, 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 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 comprises a) an epoxy resin; and b) a hardener component comprising i) an oligomeric compound comprising a phosphorus composition which is the reaction product of an etherified resole with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and ii) naphthol novolac.
  • the curable composition may comprise 1 to 90 percent by weight of one or more epoxy resins. 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 epoxy resin is a multifunctional epoxy which has more than two epoxy functionalities.
  • Such epoxy resins include, but are not limited to epoxy resins obtained by glycidifying the condensation product of a phenol or a naphthol with an aldehyde, such as naphthol novolac epoxies, epoxy resins obtained by glycidifying the co-condensation product of naphthol, phenol, and formaldehyde, bisphenol-A novolac epoxies, bisphenol-F novolac epoxies and combinations thereof.
  • the present invention curable composition includes at least one epoxy resin.
  • the epoxy resin may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted.
  • the epoxy resin may also be monomeric or polymeric.
  • the epoxy resins used in embodiments disclosed herein for component (a) of the present invention, may vary and include conventional and commercially available epoxy resins, which may be used alone or in combinations of two or more. In choosing epoxy resins for compositions disclosed herein, consideration should not only be given to properties of the final product, but also to viscosity and other properties that may influence the processing of the resin composition.
  • epoxy compounds include, but are not limited to epoxies based on reaction products of polyfunctional alcohols, phenols, cycloaliphatic carboxylic acids, aromatic amines, or aminophenols with epichlorohydrin.
  • a few non-limiting embodiments include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcinol diglycidyl ether, and triglycidyl ethers of para-aminophenols.
  • Other suitable epoxy resins known to the skilled worker include reaction products of epichlorohydrin with o-cresol and, respectively, phenol novolacs.
  • Further epoxy resins include epoxides of divinylbenzene or divinylnaphthalene. It is also possible to use a mixture of two or more epoxy resins.
  • the epoxy resins useful in the present invention may be selected from commercially available products; for example, D. E. 331, D. E. R. 332, D. E. R. 383, D. E. R. 334, D. E. N. 431, D. E. N. 438, D. E. R. 736, or D. E. R. 732 epoxy resins available from The Dow Chemical Company or Syna 21 cycloaliphatic epoxy resin from Synasia.
  • the curable composition may comprise 1 to 99 percent by weight of one or more naphthol novolacs. 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 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.
  • curable composition may comprise 1 to 60 percent by weight of one or more naphthol novolacs or in the alternative, curable composition may comprise 1 to 50 percent by weight of one or more naphthol novolacs.
  • Such naphthol novolacs include but are not limited to the condensate of substituted and/or unsubstituted naphthols with monoaldehyde, such as the condensate of 1-naphthol ( ⁇ -naphthol) with formaldehyde, the condensate of 1-naphthol with acetaldehyde, the condensate of 1-naphthol with butyraldehyde, the condensate of 2-naphthol ( ⁇ -naphthol) with formaldehyde, the condensate of 2-naphthol with acetaldehyde, the condensate of 2-naphthol with butyraldehyde, the condensate of 1-naphthol and phenol with formaldehyde, the condensate of 1-naphthol and phenol with acetaldehyde, the condensate of 1-naph
  • 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 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (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 curable composition has a total weight percent of atomic phosphorus in the range of from 0.01 weight percent to 20 weight percent. All individual values and subranges from 0.01 to 20 weight percent are included herein and disclosed herein, for example, the weight percent of atomic phosphorus can be from a lower limit of 0.01, 0.5, 1.25, 2.65 and 3.0 to an upper limit of 2.65, 7, 11, 16, and 20.
  • the DOPO-containing compound is an oligomeric composition comprising a phosphorus-containing compound which is the reaction product of an etherified resole with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ('H-DOP').
  • 'DOP-BN This reaction product, referred to hereinafter as 'DOP-BN, 'is depicted in Formula I, below.
  • the curable composition can contain a solvent.
  • Solvents can be used to solubilize the epoxy and hardener component or to adjust the viscosity of the final varnish.
  • solvents include, but are not limited to methanol, acetone, n-butanol, methyl ethyl ketone (MEK), cyclohexanone, benzene, toluene, xylene, dimethylformamide (DMF), ethyl alcohol (EtOH), propylene glycol methyl ether (PM) , propylene glycol methyl ether acetate (DOWANOL TM PMA) and mixtures thereof.
  • solvents include, but are not limited to methanol, acetone, n-butanol, methyl ethyl ketone (MEK), cyclohexanone, benzene, toluene, xylene, dimethylformamide (DMF), ethyl alcohol (EtOH), propylene
  • composition can be produced by any suitable process known to those skilled in the art.
  • solutions of the epoxy component, phosphorus-containing compound, and polymeric anhydride 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 includes 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, 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°C; for example 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.
  • the electrical laminates have a copper peel strength in the range of from 4 lb/in to 12 lb/in. In various embodiments, the electrical laminates have a Tg of greater than or equal to 160°C. In various embodiments, the electrical laminates have a UL-94 classification of V-0.
  • the raw materials used are shown below.
  • KEB-3165 an epoxy bisphenol-A novolac, from Kolon
  • Styrene maleic anhydride copolymer EF-60 from Cray Valley
  • the reaction mixture was allowed to cool to 50°C and a solid was precipitated from the solution.
  • the upper toluene solution was poured out and 200 mL ethyl acetate was added and stirred for additional 10 minutes.
  • the ethyl acetate solution was washed with water three times and the organic phase was collected and dried over anhydrous sodium sulfate for 2 hours.
  • the solid was filtrated and most of the solvent was removed under vacuum.
  • the residual was dissolved in 20 mL acetone and poured into a plastic container. The acetone was removed by standing overnight in the fume hood and was dried under vacuum at 80°C overnight to yield the naphthol novolac.
  • Epoxy XZ92748 (phenol novolac epoxy: 85% in Propylene Glycol Monomethyl Ether/Methanol), from The Dow Chemical Company;
  • Epoxy DER TM ('DER') 383 (100% Diglycidyl ether of bisphenol A epoxy), from The Dow Chemical Company;
  • 2-methylimidazole curing catalyst (10% in Propylene Glycol Monomethyl Ether), from Sinapharm Chemical and Reagent Company;
  • Laminates were prepared by the procedure shown in Table 1, below. The testing results were shown in Table 2.
  • T d values of all the inventive examples tested by TGA are all higher than 350°C, which meet the requirements of epoxy laminate application.
  • the upper toluene solution was poured out and 200 mL ethyl acetate was added and stirred for additional 10 minutes.
  • the ethyl acetate solution was washed with water once and then with saturated brine twice.
  • the organic phase was collected and dried over anhydrous sodium sulfate for 2 hours. Then the salt was filtrated and most of the solvent was removed under vacuum. Finally, the product was dried in vacuum oven at 100°C overnight. The yield was 80%.
  • the naphthol monomer content in the final product is 0.4%.
  • Epoxy eCHTP four functionality epoxy, 74.2% in methyl ethyl ketone, from The Dow Chemical Company;
  • Epoxy eDCPD-TP four functionality epoxy
  • Epoxy XZ 97109 (75% in methyl ethyl ketone), from The Dow Chemical Company;
  • Epoxy Tactix 742 (three functionality epoxy, 75% in methyl ethyl ketone), from Huntsman;
  • 2-phenylimidazole curing catalyst (10% in methyl ethyl ketone), from Sinopharm Chemical and Reagent Company;
  • 2-methylimidazole curing catalyst (10% in Propylene Glycol Monomethyl Ether) , from Sinopharm Chemical and Reagent Company;
  • Silica Silbond 600EST (amorphous silica filler with amino-silane treatment), from Sibelco Minerals Co., Ltd.
  • Inventive Example 5 has a T g improvement as high as 30°C by replacing the phenol novolac hardener with the inventive naphthol novolac hardener. The same improvement was also found when comparing Inventive Example 7 and Comparative Example E.
  • a laminate based on an inventive composition (Inventive Example 6) and a control BT laminate sample (Comparative Example E) were prepared.
  • the detailed varnish formulation is listed in Table 5.
  • the polymer ingredients were mixed to form a uniform 60% solution in MEK, and then defoamer BYK A530 and wetting agent BYK W996 were added.
  • the above mixture was shaken in a shaker for 1 hour, and then Silbond 600 EST was added along with MEK.
  • the varnish was shaken until the filler was dispersed well.
  • the varnish was then painted on the glass sheets (Hexcel 7628) and partially cured at 171°C in a ventilated oven for a given time to make prepregs.
  • the glass transition temperature (T g ) of the laminate was also measured by dynamic mechanic thermal analysis (DMTA).
  • DMTA dynamic mechanic thermal analysis
  • Example 6 has a substantially higher glass transition temperature and lower Z-axis coefficient of thermal expansion compared with the control BT resin, while retaining almost all the other properties such as heat resistance (copper delamination time), dielectrical properties (such as D k and D f ), as well as good FR performance.
  • Table 7 shows the test results for laminates based on different formulations comprising eCHTP, NPN and DOP-BN (Inventive Examples 7-10).
  • the T g is above 210°C after 3 hours of curing at 220°C and can be further improved to above 225°C after post cure of the laminate at 250°C for another 2 hours.
  • the phosphorus content can be decreased to as low as 1.15% (based on the total solid part) to pass the UL94 V-0 testing.
  • the inventive composition was also tested in a treater run (Inventive example 11).
  • the formulation is as shown in Table 8, and the properties of laminates prepared by treater run are shown in Table 9.
  • the results indicate the laminates prepared with the inventive composition has high T g and T d , low CTE, low moisture uptake and excellent resistance to solder drip.

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

Abstract

L'invention concerne une composition durcissable comprenant : a) une résine époxy; et b) un composant durcisseur comportant i) un composé oligomère comportant une composition phosphore qui est le produit de réaction d'un résol éthérifié mis en contact avec un 9, 10-dihydro-9-oxa -10-phosphaphénanthrène -10-oxyde, et ii) un novolaque naphtol. La composition durcissable peut être utilisée dans la préparation de stratifiés électrotechniques et de cartes de circuits imprimés.
PCT/CN2014/085576 2014-08-29 2014-08-29 Formulations de résine époxy exemptes d'halogène WO2016029450A1 (fr)

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PCT/CN2014/085576 WO2016029450A1 (fr) 2014-08-29 2014-08-29 Formulations de résine époxy exemptes d'halogène
PCT/US2015/046849 WO2016033136A1 (fr) 2014-08-29 2015-08-26 Constituant phénolique à haute performance
TW104128360A TW201615740A (zh) 2014-08-29 2015-08-28 高性能酚類成分

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009045817A1 (fr) * 2007-09-28 2009-04-09 Dow Global Technologies Inc. Formulations de résine époxy
WO2011094004A2 (fr) * 2010-01-29 2011-08-04 Dow Global Technologies Llc Compositions comprenant des composés contenant du phosphore
WO2013095908A2 (fr) * 2011-12-20 2013-06-27 Dow Global Technologies Llc Composites de résine époxy

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