WO2016052990A1 - Résine époxy retardatrice de flammes, procédé pour sa préparation, et composition de résine époxy retardatrice de flammes la contenant - Google Patents

Résine époxy retardatrice de flammes, procédé pour sa préparation, et composition de résine époxy retardatrice de flammes la contenant Download PDF

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WO2016052990A1
WO2016052990A1 PCT/KR2015/010305 KR2015010305W WO2016052990A1 WO 2016052990 A1 WO2016052990 A1 WO 2016052990A1 KR 2015010305 W KR2015010305 W KR 2015010305W WO 2016052990 A1 WO2016052990 A1 WO 2016052990A1
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compound
formula
epoxy resin
retardant epoxy
flame
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PCT/KR2015/010305
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English (en)
Korean (ko)
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강성규
황광춘
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코오롱인더스트리 주식회사
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Priority to US15/514,676 priority Critical patent/US20170218273A1/en
Priority to CN201580061434.5A priority patent/CN107001581A/zh
Priority claimed from KR1020150138234A external-priority patent/KR101827475B1/ko
Publication of WO2016052990A1 publication Critical patent/WO2016052990A1/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
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • 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

  • halogen-based flame retardants excellent in flame retardant effects and economics have been used.
  • bromine-based compounds having excellent flame retardancy are used in most general-purpose resins, and in resins having difficulty in securing flame retardancy, antimony-based flame retardants such as antimony trioxide and the like are used as a flame retardant or adjuvant with bromine-based flame retardants to improve flame retardancy.
  • antimony-based flame retardants such as antimony trioxide and the like are used as a flame retardant or adjuvant with bromine-based flame retardants to improve flame retardancy.
  • bromine-based flame retardants not only cause suffocation by generating toxic gases such as HBr during fire, but may also generate dioxins, which are powerful carcinogens when incinerated.
  • antimony flame retardants used in combination with bromine flame retardants also show their own carcinogenicity, their use is gradually being regulated in Europe.
  • non-halogen flame retardant compounds include phosphorus-based, nitrogen-based compounds, silicon-based, boron-based flame retardants, or metal oxides or metal hydroxides. Of these, phosphorus compounds and nitrogen compounds are most actively considered as flame retardant compounds that can replace halogen flame retardants.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • the DOPO can also be used as an additive, but may react with an epoxy resin to produce a phosphorus-based modified epoxy resin, and when used as a main ingredient in an epoxy resin composition, flame retardant properties may be imparted.
  • the phosphorus-based modified epoxy resin using the existing DOPO is flame retardant is secure, but there is a limit to increase the phosphorus content, there is a problem that the physical properties are lowered as the phosphorus (P) content is higher. Therefore, it is urgent to develop an epoxy resin that can improve the physical properties by directly participating in the reaction while increasing the phosphorus content to ensure flame retardancy.
  • the present invention is to provide a flame-retardant epoxy resin and a method of manufacturing the same and a flame-retardant epoxy resin composition comprising the same while increasing the phosphorus content to improve the flame resistance, while satisfying the heat resistance, moisture absorption rate, adhesion.
  • the present invention provides a flame retardant epoxy resin comprising a compound represented by the following formula (1) as a first preferred embodiment.
  • X 1 is a compound represented by the following Chemical Formulas 2 to 11
  • X 2 is a compound represented by the following Chemical Formula 12
  • l is 1 to 10
  • m is 0 to 10
  • n is 1 to 10 Is an integer.
  • Compound represented by the formula (1) is characterized in that the phosphorus content of 6 to 8% by mass.
  • Compound represented by the formula (1) is characterized in that the glass transition temperature is 150 to 190 °C.
  • Compound represented by the formula (1) is characterized in that the weight average molecular weight of 500 to 1500g / mol.
  • the compound represented by Formula 1 is characterized in that the epoxy equivalent of 350 to 500g / eq.
  • a step of preparing an intermediate compound by reacting a hydroquinone compound containing a phosphorus (P) atom with a chlorohydrin compound may include (S1); And it provides a method for producing a flame-retardant epoxy resin comprising the step (S2) by adding a compound selected from a phosphorus compound or a bisphenol compound or a mixture of two or more selected from them to the intermediate compound prepared above.
  • the hydroquinone compound including the phosphorus (P) atom may be added and reacted at a molar ratio of 1/6 to 1/2 to the chlorohydrin compound.
  • the salt layer is removed and the unreacted chlorohydrin compound and water are removed at a temperature of 100 to 200 ° C. Degassing process under reduced pressure of 100 to 760torr It is characterized by performing.
  • the hydroquinone compound containing a phosphorus (P) atom and the chlorohydrin compound are subjected to primary aging for 2 to 24 hours while maintaining the temperature at 50 to 80 ° C., and then 100 to It is characterized in that the secondary aging for 10 minutes to 4 hours while maintaining a temperature of 50 to 100 °C in a reduced pressure of 760torr.
  • the hydroquinone compound including the phosphorus (P) atom in the step S1 is diphenylphosphinyl hydro-quinone.
  • the chlorohydrin-based compound is characterized in that it is selected from epichlorohydrin, epiiodhydrin, epibromohydrin, methylethyl bromohydrin and methylethyl iodine hydrin.
  • step S2 based on 100 parts by weight of the intermediate compound, a compound selected from a phosphorus compound or a bisphenol compound, or a mixture of two or more selected from them is added and reacted by adding a weight ratio of 0.1 to 100.
  • the catalyst which is a phenyl compound is added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of a compound selected from phosphorus compounds or bisphenol compounds or a mixture of two or more selected from them.
  • the phosphorus compound is 10- (2 ', 5'-Dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) and 2- (6-oxido- 6H-dibenz (c, e) (1,2) oxaphsophorin-6-yl) -1,4-naphthalenediol (DOPO-NQ).
  • the bisphenol-based compound is selected from bisphenol A, bisphenol F, bisphenol Z, bisphenol-TMC, bisphenol AP, bisphenol BP, bisphenol B, bisphenol C and bisphenol E.
  • the catalyst which is a phenyl-based compound is Ethytriphenylphosphonium Iodide (ETPPI), 2-Methylimidazole (2MI), 2-ethyl-4-methyl imidazole ( 2-ethyl-4-methyl imidazole) (2E4MZ) and 2-phenylimidazole (2-PI).
  • EPPI Ethytriphenylphosphonium Iodide
  • MI 2-Methylimidazole
  • 2-ethyl-4-methyl imidazole 2-ethyl-4-methyl imidazole
  • 2-phenylimidazole 2-PI
  • the present invention provides a flame retardant epoxy resin composition
  • a flame retardant epoxy resin composition comprising a compound represented by the following Chemical Formula 1, a curing agent, and a curing accelerator.
  • X 1 is a compound represented by the following Chemical Formulas 2 to 11
  • X 2 is a compound represented by the following Chemical Formula 12
  • l is 1 to 10
  • m is 0 to 10
  • n is 1 to 10 Is an integer.
  • Compound represented by the formula (1) is characterized in that it was prepared according to the above-described manufacturing method.
  • a flame-retardant epoxy resin and a method for preparing the same and a flame-retardant epoxy resin composition comprising the same while increasing the phosphorus content to improve flame retardancy while satisfying heat resistance, moisture absorption rate, and tackiness.
  • Example 1 is an IR measurement graph of a compound represented by Formula 1 according to Example 1 of the present invention.
  • X 1 is a compound represented by the following Chemical Formulas 2 to 11
  • X 2 is a compound represented by the following Chemical Formula 12
  • l is 1 to 10
  • m is 0 to 10
  • n is 1 to 10 Is an integer.
  • the adhesion increases as the -OH group increases.
  • Compound represented by the formula (1) may contain a large amount of phosphorus content up to 6 to 8% by mass. Therefore, the freedom degree of the remaining composition of the flame retardant resin composition can be increased.
  • the composition should also include other components that can exhibit various properties of the composition in addition to the flame retardant epoxy resin compound component. If the content is small, the content of the flame retardant epoxy resin compound component must be increased in order to increase the phosphorus content in the composition, and thus the content ratio of other components is reduced, so that the properties desired by the composition cannot be expressed.
  • the compound represented by Chemical Formula 1 according to the present invention contains phosphorus in a high content of 6 to 8% by mass, when preparing a composition comprising a flame retardant epoxy resin compound, the compound represented by Chemical Formula 1, which is a flame retardant epoxy resin compound It can be added in small amounts, it may include a large amount of other components that can exhibit various properties in the composition, has the advantage of expressing the properties of the composition as desired.
  • the compound represented by Formula 1 has a glass transition temperature of 150 to 190 °C. When the glass transition temperature is in the above range has excellent heat resistance.
  • the compound represented by Chemical Formula 1 has a weight average molecular weight of 500 to 1500 g / mol. When the weight average molecular weight is within the above range, the compatibility with the solvent has a good viscosity has a good advantage to apply.
  • the compound represented by Chemical Formula 1 has an epoxy equivalent weight of 350 to 500 g / eq. If the epoxy equivalent is in the above range has the advantage that it can react with the curing agent while having a high phosphorus content.
  • Compound represented by Formula 1 is prepared by reacting a hydroquinone compound containing a phosphorus (P) atom with a chlorohydrin compound to prepare an intermediate compound (S1); And a step (S2) of adding a compound selected from phosphorus compounds or bisphenol compounds or a mixture of two or more selected from them to the intermediate compound prepared above.
  • an intermediate compound is prepared by reacting a hydroquinone compound including a phosphorus (P) atom with a chlorohydrin compound (S1).
  • the hydroquinone compound including the phosphorus (P) atom is added in a molar ratio of 1/6 to 1/2 to the chlorohydrin compound to react.
  • the hydroquinone compound containing the phosphorus (P) atom and the chlorohydrin compound are reacted in the molar ratio range, the reaction is uniformly thin.
  • sodium hydroxide, potassium hydroxide and the like may be added, preferably 30 to 60%.
  • concentrations of sodium hydroxide is suitable for the minimization of reactions and the production of by-products and resins produced.
  • the content is preferably used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the hydroquinone compound including the phosphorus (P) atom.
  • the hydroquinone compound containing the phosphorus (P) atom and the chlorohydrin compound are heated and reacted at a temperature of 50 to 80 °C, after the reaction step, at a temperature of 50 to 80 °C
  • the secondary aging may be carried out for 10 minutes to 4 hours while maintaining the temperature of 50 to 100 °C at a reduced pressure of 100 to 760 torr.
  • the flame-retardant epoxy resin compound according to the present invention can obtain the effect of obtaining a uniform structure by performing the aging process first and second.
  • the primary and secondary aging process is carried out within the range of the temperature and time, there is an effect that a uniform structure can be obtained.
  • isopropyl alcohol, methyl ethyl ketone, methyl isobutyl kenone, toluene, xylene, etc. may be used as a solvent in the first and second aging processes, the content of which is a hydroquinone containing a phosphorus (P) atom ( It is preferable to use 20-80 weight part with respect to 100 weight part of hydroquinone type compounds.
  • the salt layer is removed and the unreacted chlorohydrin compound and water at a temperature of 100 to 200 ° C. It is preferable to perform a degassing process to remove the gas at a reduced pressure of 100 to 760 torr.
  • the step of removing the chlorine ions using a basic catalyst and neutralizing with acid is added at a temperature of 120 to 180 ° C. in an amount of 10 to 80 parts by weight based on 100 parts by weight of a hydroquinone compound containing a phosphorus (P) atom.
  • the basic catalyst is added in an amount of 10 to 100 parts by weight based on 100 parts by weight of a hydroquinone compound containing a phosphorus (P) atom to dissolve, followed by removal of chlorine ions and neutralization with an acid.
  • isopropyl alcohol methyl ethyl ketone, methyl isobutyl kenone, toluene, xylene, etc.
  • an acid there is no restriction
  • the hydroquinone compound including the phosphorus (P) atom is characterized in that diphenylphosphinyl hydro-quinone (Diphenylphosphinyl hydro-quinone).
  • the chlorohydrin-based compound is characterized in that it is selected from epichlorohydrin, epiyodohydrin, epibromohydrin, methyl ethyl bromohydrin and methyl ethyl iodine hydrin.
  • the flame-retardant epoxy resin according to the present invention can be prepared by introducing a hydroquinone-based compound containing the phosphorus (P) atoms while maintaining the physical properties while having an epoxy resin having a high phosphorus content.
  • the phosphorus-based epoxy resin prepared by reacting the existing DOPO and epoxy resin can raise the theoretical phosphorus content to 7.8% by mass.
  • the present invention solved this problem by preparing an epoxy resin using a hydroquinone-based compound containing a phosphorus (P) atom.
  • Hydroquinone-based compounds containing phosphorus (P) atoms for example, diphenylphosphinyl hydro-quinone, have a phosphorus content of 9.99% by mass and a phosphorus content of 14.5% by mass. Although the phosphorus content is lower, two -OH groups are contained, and unlike the process of preparing a phosphorus epoxy resin by reacting an existing DOPO and an epoxy resin, in the present invention, a hydroquinone containing the phosphorus (P) atom ( By reacting the chlorohydrin-based compound with -OH of the hydroquinone-based compound, it is possible to prepare a novel high phosphorus content epoxy resin that satisfies the physical properties while increasing the phosphorus content.
  • P phosphorus
  • a compound represented by Chemical Formula 1 is prepared by adding a compound selected from phosphorus compounds or bisphenol compounds or a mixture of two or more selected from them to the intermediate compound prepared in step S1 (S2).
  • the intermediate compound, a compound selected from phosphorus compounds or bisphenol compounds, or a mixture of two or more selected from these compounds may be selected from 0.1 to 2 parts by weight of a compound selected from phosphorus compounds or bisphenol compounds or a mixture of two or more thereof selected from 100 parts by weight of the intermediate compound. To 100 parts by weight is added.
  • the reaction viscosity is appropriate and the process is easy.
  • the step S2 is preferably carried out for 1 to 8 hours at a temperature of 100 to 160 °C in terms of stable process.
  • methoxypropanol-2ol, 2-methoxyethanol, acetone, dioxane, etc. may be used as a solvent during the reaction, and the content thereof is preferably used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the intermediate compound. Do.
  • the phosphorus compound is 10- (2 ', 5'-Dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) and 2- (6-oxido-6H-dibenz ( c, e) (1,2) oxaphsophorin-6-yl) -1,4-naphthalenediol (DOPO-NQ).
  • the bisphenol-based compound is selected from bisphenol A, bisphenol F, bisphenol Z, bisphenol-TMC, bisphenol AP, bisphenol BP, bisphenol B, bisphenol C and bisphenol E.
  • a catalyst which is a phenyl compound in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of a compound selected from phosphorus compounds or bisphenol compounds or a mixture of two or more selected from them. Do.
  • the phenyl-based compound is Ethytriphenylphosphonium Iodide (ETPPI), 2-Methylimidazole (2MI), 2-ethyl-4-methyl imidazole (2-ethyl-4 -methyl imidazole) (2E4MZ) and 2-phenylimidazole (2PI).
  • EPPI Ethytriphenylphosphonium Iodide
  • MI 2-Methylimidazole
  • E4MZ 2-ethyl-4-methyl imidazole
  • 2-phenylimidazole (2PI) 2-phenylimidazole
  • the flame-retardant epoxy resin composition according to the present invention is to include a compound represented by the formula (1), a curing agent and a curing accelerator prepared by the production method.
  • the flame retardant epoxy resin composition includes 0.1 to 50 parts by weight of a curing agent and 0.0001 to 0.05 parts by weight of a curing accelerator based on 100 parts by weight of the compound represented by Chemical Formula 1.
  • the curing agent may be used that is commonly used in the field of the present invention, for example, dicyandiamide, phenol novolak (Phenolnovolac), 4-aminophenyl sulfone (4-aminophenyl sulfone) and the like Can be.
  • dicyandiamide phenol novolak (Phenolnovolac)
  • 4-aminophenyl sulfone 4-aminophenyl sulfone (4-aminophenyl sulfone) and the like
  • the curing accelerator is lower than the above range, the curing reaction may not occur well, and when the curing accelerator is higher than the above range, overreaction may occur.
  • the curing accelerator may be used as is commonly used in the field of the present invention, for example, Ethytriphenylphosphonium Iodide (ETPPI), 2-methylimidazole (2-Methylimidazole) (2MI), 2-ethyl-4-methyl imidazole (2E4MZ), ETPPI, etc. are mentioned.
  • Ethytriphenylphosphonium Iodide Ethytriphenylphosphonium Iodide
  • MI 2-methylimidazole
  • E4MZ 2-ethyl-4-methyl imidazole
  • ETPPI ETPPI
  • Diphenylphosphinyl hydro-quinone (DPPQ) (1500g, 1mol) and epichlorohydrin (4470g, 5mol) were added to isopropyl alcohol (1970g) in a 10-liter multi-necked flask, followed by stirring to 60 ⁇ 5 °C. Heating was carried out. After injecting 81 g of 50% aqueous sodium hydroxide solution in batches while maintaining the temperature at 60 ⁇ 5 ° C, the mixture was aged for 4 hours while maintaining the temperature at 60 ⁇ 5 ° C. After aging, 810 g of 50% aqueous sodium hydroxide solution was added over 2 hours while maintaining the temperature at 60 ⁇ 5 ° C under reduced pressure of 250 ⁇ 10torr, and then aged for 30 minutes.
  • DPPQ Diphenylphosphinyl hydro-quinone
  • MIBK Methyl Isobutyl Ketone
  • the reaction time when the temperature reached 157 ⁇ 2 ° C was set as the initial time, sampled every hour, and reacted at 157 ⁇ 2 ° C until the target equivalent appeared.
  • the target equivalent temperature was lowered to 120 ⁇ 10 ° C.
  • Propylene glycol monomethyl ether (hereinafter, PGME) was injected to obtain about 470 g of a compound represented by Chemical Formula 1 as a final substance.
  • Phosphorus content of the compound represented by Formula 1 was 7.7% by mass
  • glass transition temperature was 165.1 ° C
  • weight average molecular weight was 1013 g / mol
  • epoxy equivalent was 343.1 g / eq.
  • X 1 is a formula (2)
  • X 2 is a compound represented by the following formula (12)
  • l is 1 to 2
  • m is 1 to 2
  • n is an integer of 1 to 2).
  • X 1 is a compound represented by the formula (3)
  • X 2 is a compound represented by the formula (12)
  • l is 1 to 2
  • m is 1 to 2
  • n is an integer of 1 to 2.
  • the epoxy equivalent was reached to 320 g / eq was lowered to 120 ⁇ 10 °C and PGME was injected to obtain about 205 g of a compound represented by the following formula (1) as a final material.
  • Phosphorus content of the compound represented by the following formula (1) was 7.0 mass%
  • the glass transition temperature was 168.7 °C
  • the weight average molecular weight was 843 g / mol
  • epoxy equivalent was 322.1 g / eq.
  • X 1 is a compound represented by the following formula (4)
  • X 2 is a compound represented by the following formula (12)
  • l is 1 to 2
  • m is 1 to 2
  • n is an integer of 1 to 2 .
  • the temperature was lowered to 120 ⁇ 10 °C and PGME was injected to obtain about 240 g of a compound represented by the following formula (1) as a final material.
  • the phosphorus content of the compound represented by the following Formula 1 was 6.6 mass%, the glass transition temperature was 169.1 ° C., the weight average molecular weight was 943 g / mol, and the epoxy equivalent was 345.5 g / eq.
  • X 1 is a compound represented by the formula (5)
  • X 2 is a compound represented by the formula (12)
  • l is 1 to 2
  • m is 1 to 2
  • n is an integer of 1 to 2.
  • X 1 is a compound represented by the following formula (6)
  • X 2 is a compound represented by the following formula (12)
  • l is 1 to 2
  • m is 1 to 2
  • n is an integer of 1 to 2 .
  • X 1 is a compound represented by the following formula (7)
  • X 2 is a compound represented by the following formula (12)
  • l is 1 to 2
  • m is 1 to 2
  • n is an integer of 1 to 2 .
  • X 1 is a compound represented by the formula (8)
  • X 2 is a compound represented by the formula (12)
  • l is 1 to 2
  • m is 1 to 2
  • n is an integer of 1 to 2.
  • the temperature was lowered to 120 ⁇ 10 ° C., and PGME was injected to obtain about 250 g of a compound represented by Chemical Formula 1 as a final substance.
  • the phosphorus content of the compound represented by Formula 1 was 6.7 mass%, the glass transition temperature was 168.3 ° C., the weight average molecular weight was 827 g / mol, and the epoxy equivalent was 388 g / eq.
  • X 1 is a compound represented by the following formula (9)
  • X 2 is a compound represented by the following formula (12)
  • l is 1 to 2
  • m is 1 to 2
  • n is an integer of 1 to 2 .
  • the temperature was lowered to 120 ⁇ 10 ° C., and PGME was injected to obtain about 250 g of a compound represented by Chemical Formula 1 as a final substance.
  • the phosphorus content represented by the following Chemical Formula 1 was 6.6 mass%, the glass transition temperature was 167.4 ° C., the weight average molecular weight was 727 g / mol, and the epoxy equivalent was 373 g / eq.
  • X 1 is a compound represented by the formula (10)
  • X 2 is a compound represented by the formula (12)
  • l is 1 to 2
  • m is 1 to 2
  • n is an integer of 1 to 2.
  • X 1 is a compound represented by the following formula (11)
  • X 2 is a compound represented by the following formula (12)
  • l is 1 to 2
  • m is 1 to 2
  • n is an integer of 1 to 2 .
  • FIG. 1 is an IR measurement graph of a compound represented by Formula 1 according to Example 1 of the present invention
  • FIG. 2 is an IR measurement graph of a compound represented by Formula 1 according to Example 2 of the present invention.
  • the IR measurement graphs of the compounds represented by Formula 1 prepared according to Examples 3 to 10 also showed similar trends with those of FIGS. 1 and 2, and thus, illustrations thereof may be omitted.
  • KEG-HQ5538 (Kolon Industries Co., Ltd., EEW: 310.0 g / eq, phosphorus content: 3.0 mass%) which is a phosphorus modified flame-retardant phenol novolak epoxy resin was used. Foot formula is represented by the following formula (14).
  • the flame-retardant epoxy resin compounds according to Examples 1 to 10 and Comparative Examples 1 to 2 were prepared by mixing the flame-retardant epoxy resin composition (varnish) in a composition as described in Table 1 below by adjusting the phosphorus content to 2.5 mass%.
  • DICY Dicyandiamide
  • KEP-113P8 Kolon Industries Co., Ltd., EEW: 180 g / eq
  • the amount of DICY was calculated by mixing the equivalent amount of KEP-113P85 and epoxy resin and then added in a molar ratio corresponding thereto.
  • 2-Methylimidazole (hereinafter referred to as 2MI) was used as a curing accelerator, and the amount thereof was the total epoxy charged amount (KEP-113P85 + epoxy resin (Compounds represented by Formula 1 prepared in Examples 1 to 10 or Comparative Examples 1 to 2, respectively). 500 ppm was injected relative to the compound represented by Chemical Formulas 13 and 14)).
  • Example 1 Varnish Compounding Ratio (g) KEP-113P85 DICY 2MI Compounds represented by Formula 1 prepared in Examples 1 to 10 or compounds represented by Formulas 13 and 14 prepared in Comparative Examples 1 to 2, respectively.
  • Example 1 512 32.9 0.33 225
  • Example 2 411 27.4 0.28 225
  • Example 3 441 29.7 0.30 225
  • Example 4 400 27.3 0.28 225
  • Example 5 392 26.1 0.29 225
  • Example 6 392 26.0 0.28 225
  • Example 7 382 25.3 0.28 225
  • Example 9 402 26.7 0.28 225
  • Example 10 422 28.0 0.28 225 Comparative Example 1 32 9.26 0.12 225 Comparative Example 2 31 8.45 0.12 225
  • the compounds represented by Formula 1 prepared in Examples 1 to 10 each had a high phosphorus content, and thus, the content of the curing agent and the curing accelerator could be increased during varnish preparation, and according to the present invention.
  • the prepared flame-retardant epoxy resin it can be seen that it can include a large amount of other components that can exhibit a variety of properties in the composition, it can have the advantage of expressing the properties of the composition as desired there was.
  • the varnish prepared according to Table 1 was impregnated into glass fibers, and then dried at 155 ° C. for 3 minutes to make a prepreg.
  • Four prepregs thus prepared were laminated and copper foil was laminated on the upper and lower surfaces of the prepregs.
  • To prepare a copper-clad laminate. Pressure condition: Temperature 190 °C, Pressure 25 kgf / cm2, Process time 2 hours
  • Phosphorus content measurement was calculated by the theoretical value through the monomer of each structure.
  • the glass transition temperature of the obtained copper-clad laminate was measured with a quaternary scanning calorimeter (DSC, manufactured by TA Instrument, Q2000). (Measurement part: center part, 20mg, measuring condition: nitrogen atmosphere, temperature rising up to 250 ° C at a heating rate of 20 ° C / min.)
  • Weight average molecular weight measuring method The weight average molecular weight (Mw) was calculated
  • the polymer to be measured was dissolved in tetrahydrofuran to a concentration of 40000 ppm, and 100 ⁇ l was injected into GPC.
  • the mobile phase of GPC used tetrahydrofuran and was introduced at a flow rate of 1.0 ml / min, and the analysis was performed at 35 ° C.
  • the column connected four Waters HR-05, 1, 2, 4E in series. The detector was measured at 35 ° C. using RI and PAD Detector.
  • the drying center after drying for 24 hours in 50 minutes of 5 degreeC was measured, and the weight after storing for 72 hours in the process tank adjusted to 85 degreeC / 85% RH was then measured.
  • Example 1 165.1 V-0 1.48 1.08 0.57
  • Example 2 170.1 V-0 1.52 1.05 0.56
  • Example 3 168.7 V-0 1.45 1.02 0.58
  • Example 4 169.1 V-0 1.43 1.01 0.57
  • Example 5 163.5 V-0 1.42 1.04 0.60
  • Example 6 175.4 V-0 1.45 1.06 0.59
  • Example 7 177.1 V-0 1.43 1.02 0.53
  • Example 8 168.3 V-0 1.42 1.04 0.59
  • Example 9 167.4 V-0 1.42 1.05 0.59
  • Example 10 166.1 V-0 1.43 1.04 0.57 Comparative Example 1 141.2 V-0 1.38 0.99 0.68 Comparative Example 2 149.2 V-0 1.41 1.01 0.65
  • Examples 1 to 11 have a high phosphorus content and can exhibit flame retardant properties in a small amount, and participate in a curing reaction, so that the bezeling and -OH groups in the resin have high heat resistance and contact force. It was found to be effective. However, it can be seen that Comparative Examples 1 and 2 have a problem of deterioration in physical properties since a large amount of P-modified epoxy resin is contained as compared with Examples.
  • the present invention can be used in a flame retardant epoxy resin, a method for preparing the same, and a flame retardant epoxy resin composition including the same.

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  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une résine époxy retardatrice de flammes, un procédé de préparation de celle-ci, et une composition de résine époxy retardatrice de flammes la contenant et, plus spécifiquement, une résine époxy retardatrice de flammes qui satisfait à certaines propriétés physiques tout en améliorant les capacités de retard des flammes par augmentation de la teneur en phosphore, un procédé de préparation de celle-ci, et une composition de résine époxy retardatrice de flammes la contenant.
PCT/KR2015/010305 2014-09-30 2015-09-30 Résine époxy retardatrice de flammes, procédé pour sa préparation, et composition de résine époxy retardatrice de flammes la contenant WO2016052990A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US15/514,676 US20170218273A1 (en) 2014-09-30 2015-09-30 Flame-retardant epoxy resin, method for preparing same, and flame-retardant epoxy resin composition containing same
CN201580061434.5A CN107001581A (zh) 2014-09-30 2015-09-30 阻燃性环氧树脂、该阻燃性环氧树脂的制备方法，以及包含该阻燃性环氧树脂的阻燃性环氧树脂组合物

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2014-0131352 2014-09-30
KR20140131352 2014-09-30
KR10-2015-0136859 2015-09-25
KR20150136859 2015-09-25
KR10-2015-0138234 2015-09-30
KR1020150138234A KR101827475B1 (ko) 2014-09-30 2015-09-30 난연성 에폭시 수지, 이의 제조방법 및 이를 포함하는 난연성 에폭시 수지 조성물

Publications (1)

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WO2016052990A1 true WO2016052990A1 (fr) 2016-04-07

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19980018709A (ko) * 1996-08-22 1998-06-05 가나이 쓰토무 수지봉지형 반도체장치 및 그 제조방법
US7064157B2 (en) * 2000-07-19 2006-06-20 Chang Chun Plastics Co., Ltd. Flame retardant resin and flame retardant composition containing the same
WO2009064707A1 (fr) * 2007-11-15 2009-05-22 Dow Global Technologies Inc. Procédé de préparation de résines époxy modernes
US20110224345A1 (en) * 2010-03-15 2011-09-15 Ming Jen Tzou Novel low dielectric resin varnish composition for laminates and the preparation thereof
JP5464304B1 (ja) * 2012-03-27 2014-04-09 Ｄｉｃ株式会社 エポキシ樹脂、エポキシ樹脂の製造方法、エポキシ樹脂組成物、その硬化物、及び放熱樹脂材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19980018709A (ko) * 1996-08-22 1998-06-05 가나이 쓰토무 수지봉지형 반도체장치 및 그 제조방법
US7064157B2 (en) * 2000-07-19 2006-06-20 Chang Chun Plastics Co., Ltd. Flame retardant resin and flame retardant composition containing the same
WO2009064707A1 (fr) * 2007-11-15 2009-05-22 Dow Global Technologies Inc. Procédé de préparation de résines époxy modernes
US20110224345A1 (en) * 2010-03-15 2011-09-15 Ming Jen Tzou Novel low dielectric resin varnish composition for laminates and the preparation thereof
JP5464304B1 (ja) * 2012-03-27 2014-04-09 Ｄｉｃ株式会社 エポキシ樹脂、エポキシ樹脂の製造方法、エポキシ樹脂組成物、その硬化物、及び放熱樹脂材料

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