WO2016052990A1 - Flame-retardant epoxy resin, method for preparing same, and flame-retardant epoxy resin composition containing same - Google Patents
Flame-retardant epoxy resin, method for preparing same, and flame-retardant epoxy resin composition containing same Download PDFInfo
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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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- 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
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- 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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Abstract
The present invention relates to a flame-retardant epoxy resin, a method for preparing the same, and a flame-retardant epoxy resin composition containing the same and, more specifically, to a flame-retardant epoxy resin, which satisfies physical properties while improving flame retardancy by increasing the phosphorus content, to a method for preparing the same, and to a flame-retardant epoxy resin composition containing the same.
Description
본 발명은 난연성 에폭시 수지, 이의 제조방법 및 이를 포함하는 난연성 에폭시 수지 조성물에 관한 것이다.The present invention relates to a flame retardant epoxy resin, a method for preparing the same, and a flame retardant epoxy resin composition including the same.
종래 가연성 고분자 재료에 대한 난연제로서, 난연 효과 및 경제적 관점에서 우수한 할로겐계 난연제가 많이 사용되어 왔다. 그중에서도 난연성이 뛰어난 브롬계 화합물이 대부분의 범용 수지에 이용되고 있으며, 난연성 확보가 어려운 수지에서는 난연성 향상을 위해 브롬계 난연제와 함께 난연증진제 또는 보조제로서 삼산화안티몬등의 안티몬계 난연제를 사용하고 있다. 그러나, 브롬계 난연제는 화재시 HBr 등의 유독가스를 발생시켜 질식사를 유발할 뿐만 아니라 소각시 강력한 발암물질인 다이옥신(dioxine)을 생성시킬 우려가 있다. 더욱이 브롬계 난연제와 함께 사용하는 안티몬계 난연제 또한 자체적으로 발암성을 나타내기 때문에 유럽을 선두로 하여 그 사용이 점차 규제되고 있다. As flame retardants for conventional flammable polymer materials, halogen-based flame retardants excellent in flame retardant effects and economics have been used. Among them, 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. However, 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. Moreover, since antimony flame retardants used in combination with bromine flame retardants also show their own carcinogenicity, their use is gradually being regulated in Europe.
이에 따라, 최근에는 비할로겐계 난연성 화합물에 대한 연구가 활발히 진행되고 있으며, 다양한 친환경성 난연제 화합물들이 개발되고 있다. 이러한 비할로겐 난연성 화합물로는 인계, 질소화합물계, 실리콘계, 붕소계 난연제, 또는 금속산화물이나 금속 수산화물 등이 있다. 이 중 할로겐계 난연제를 대체할 수 있는 난연성 화합물로 가장 적극적으로 고려되고 있는 것이 인계 화합물이나, 질소계 화합물이다. Accordingly, in recent years, research on non-halogen flame retardant compounds has been actively conducted, and various eco-friendly flame retardant compounds have been developed. Such 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.
특히, 인계 화합물인 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(이하, DOPO라 약칭한다.)가 많이 사용되고 있다. 상기 DOPO는 첨가형으로도 사용 가능하지만 에폭시 수지와 반응하여 인계 변성 에폭시 수지를 생성할 수 있고 이를 에폭시 수지 조성 중 주제로 사용하면 난연 특성을 부여할 수 있다. In particular, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter, simply abbreviated as DOPO), which is a phosphorus compound, is widely used. 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.
상기 DOPO가 많이 사용되는 이유는 인 함량이 14.5%로 상당히 높고 한쪽 방향이 열려있는 구조이므로 쉽게 난연 특성을 나타내기 때문이다. 또한 에폭사이드기와 반응성이 좋아 인계 변성 에폭시 수지 제조가 용이하다는 장점이 있다. The reason why the DOPO is used a lot is because the phosphorus content is very high as 14.5% and one side is open so that the flame retardant properties are easily shown. In addition, there is an advantage that it is easy to manufacture a phosphorus-based modified epoxy resin having good reactivity with epoxide groups.
그러나 기존의 DOPO를 이용한 인계 변성 에폭시 수지는 난연성은 확보되지만, 인 함량을 높이기엔 그 한계가 있고, 인(P) 함량이 높아 질수록 물성이 저하되는 문제가 있다. 따라서 인 함량을 높혀 난연성이 확보되면서 반응에 직접 참여하여 물성 또한 향상시킬 수 있는 에폭시 수지에 대한 개발이 시급한 상황이다. However, 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.
본 발명은 인 함량을 증가시켜 난연성을 향상시키면서도 내열성, 흡습율, 접착성을 만족하는 난연성 에폭시 수지 및 이의 제조방법과 이를 포함하는 난연성 에폭시 수지 조성물을 제공하고자 한다.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.
이에 본 발명은 바람직한 제1 구현예로서, 하기 화학식 1로 표시되는 화합물을 포함하는 난연성 에폭시 수지를 제공한다. Accordingly, the present invention provides a flame retardant epoxy resin comprising a compound represented by the following formula (1) as a first preferred embodiment.
<화학식 1><Formula 1>
(상기 식에서, X1은 하기 화학식 2 내지 11로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1 내지 10이고, m은 0 내지 10이고, n은 1 내지 10의 정수이다.)Wherein 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, and n is 1 to 10 Is an integer.)
<화학식 2><Formula 2>
<화학식 3><Formula 3>
<화학식 4><Formula 4>
<화학식 5><Formula 5>
<화학식 6><Formula 6>
<화학식 7><Formula 7>
<화학식 8><Formula 8>
<화학식 9><Formula 9>
<화학식 10><Formula 10>
<화학식 11><Formula 11>
<화학식 12><Formula 12>
상기 화학식 1로 표시되는 화합물은 인 함량이 6 내지 8질량%인 것을 특징으로 한다. Compound represented by the formula (1) is characterized in that the phosphorus content of 6 to 8% by mass.
상기 화학식 1로 표시되는 화합물은 유리전이온도가 150 내지 190℃인 것을 특징으로 한다. Compound represented by the formula (1) is characterized in that the glass transition temperature is 150 to 190 ℃.
상기 화학식 1로 표시되는 화합물은 중량평균분자량이 500 내지 1500g/mol인 것을 특징으로 한다.Compound represented by the formula (1) is characterized in that the weight average molecular weight of 500 to 1500g / mol.
상기 화학식 1로 표시되는 화합물은 에폭시 당량이 350 내지 500g/eq인 것을 특징으로 한다.The compound represented by Formula 1 is characterized in that the epoxy equivalent of 350 to 500g / eq.
본 발명은 바람직한 제2 구현예로서, 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 반응시켜 중간체 화합물을 제조하는 단계(S1); 및 상기 제조된 중간체 화합물에 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물을 첨가하여 반응시키는 단계(S2)를 포함하는 난연성 에폭시 수지의 제조방법을 제공한다.According to a second preferred embodiment of the present invention, 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.
상기 S1 단계에서 상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물은 클로로히드린계 화합물 대비 1/6 내지 1/2의 몰비로 첨가하여 반응시키는 것을 특징으로 한다. In the step S1, 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.
상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 반응시킨 후, 염층을 제거하고 100 내지 200℃의 온도에서 미반응물인 클로로히드린계 화합물 및 수분을 제거하는 탈기공정을 100 내지 760torr의 감압상태에서 실시하는 것을 특징으로 한다.After reacting the hydroquinone compound containing the phosphorus (P) atom with 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.
상기 탈기 공정 전에, 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 50 내지 80℃의 온도로 유지하면서 2 내지 24시간 동안 1차 숙성을 시킨 후, 100 내지 760torr의 감압상태에서 50 내지 100℃의 온도로 유지하면서 10분 내지 4시간 동안 2차 숙성을 실시하는 것을 특징으로 한다.Before the degassing process, 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 ℃ in a reduced pressure of 760torr.
상기 탈기공정 후, 염기성 촉매를 이용하여 염소이온을 제거하고 산으로 중화시키는 단계를 실시하는 것을 특징으로 하는 한다.After the degassing process, using a basic catalyst Removing chlorine ions and neutralizing with an acid.
상기 S1 단계에서 상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물은 디페닐포스피닐하이드로-퀴논(Diphenylphosphinyl hydro-quinone)이다. The hydroquinone compound including the phosphorus (P) atom in the step S1 is diphenylphosphinyl hydro-quinone.
상기 S1 단계에서 상기 클로로히드린계 화합물은 에피클로로하이드린, 에피요오드히드린, 에피브로모히드린, 메틸에틸브로모히드린 및 메틸에틸요오드히드린 중에서 선택되는 것을 특징으로 한다.In the step S1, the chlorohydrin-based compound is characterized in that it is selected from epichlorohydrin, epiiodhydrin, epibromohydrin, methylethyl bromohydrin and methylethyl iodine hydrin.
상기 S2단계에서 상기 중간체 화합 100 중량부를 기준으로 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물을 0.1 내지 100의 중량비로 첨가하여 반응시키는 것을 특징으로 한다.In the 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.
상기 S2 단계에서 페닐계 화합물인 촉매를 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물 100중량부에 대하여 0.01 내지 5중량부의 함량으로 첨가시키는 것을 특징으로 한다.In the step S2, 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.
상기 S2 단계에서 상기 인계 화합물은 10-(2',5'-Dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO-HQ) 및 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphsophorin-6-yl)-1,4-naphthalenediol (DOPO-NQ) 중에서 선택되는 것을 특징으로 한다.In the step S2, 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).
상기 S2 단계에서 상기 비스페놀계 화합물은 비스페놀 A, 비스페놀 F, 비스페놀 Z, 비스페놀-TMC, 비스페놀 AP, 비스페놀 BP, 비스페놀 B, 비스페놀 C 및 비스페놀 E중에서 선택되는 것을 특징으로 한다.In the step S2, 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.
상기 S2 단계에서 페닐계 화합물인 촉매는 에티트리페닐포스포늄아이오다이드(Ethytriphenylphosphonium Iodide;ETPPI), 2-메틸이미다졸(2-Methylimidazole)(2MI), 2-에틸-4-메틸 이미다졸(2-ethyl-4-methyl imidazole)(2E4MZ) 및 2-페닐이미다졸(2-phenylimidazole, 2PI) 중에서 선택되는 것을 특징으로 한다.In the step S2, 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).
본 발명은 바람직한 제3 구현예로서, 하기 화학식 1로 표시되는 화합물, 경화제 및 경화촉진제를 포함하는 난연성 에폭시 수지 조성물을 제공한다. As a third preferred embodiment, the present invention provides a flame retardant epoxy resin composition comprising a compound represented by the following Chemical Formula 1, a curing agent, and a curing accelerator.
<화학식 1><Formula 1>
(상기 식에서, X1은 하기 화학식 2 내지 11로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1 내지 10이고, m은 0 내지 10이고, n은 1 내지 10의 정수이다.)Wherein 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, and n is 1 to 10 Is an integer.)
<화학식 2><Formula 2>
<화학식 3><Formula 3>
<화학식 4><Formula 4>
<화학식 5><Formula 5>
<화학식 6><Formula 6>
<화학식 7><Formula 7>
<화학식 8><Formula 8>
<화학식 9><Formula 9>
<화학식 10><Formula 10>
<화학식 11><Formula 11>
<화학식 12><Formula 12>
상기 화학식 1로 표시되는 화합물 100중량부에 대하여 경화제 0.1 내지 50중량부 및 경화촉진제 0.0001 내지 0.05중량부를 포함한다. It contains 0.1 to 50 parts by weight of the curing agent and 0.0001 to 0.05 parts by weight of the curing accelerator based on 100 parts by weight of the compound represented by Formula 1.
상기 화학식 1로 표시되는 화합물은 상술한 제조방법에 따라 제조된 것을 특징으로 한다.Compound represented by the formula (1) is characterized in that it was prepared according to the above-described manufacturing method.
본 발명에 따르면, 인 함량을 증가시켜 난연성을 향상시키면서도 내열성, 흡습율, 접찹성을 만족하는 난연성 에폭시 수지 및 이의 제조방법과 이를 포함하는 난연성 에폭시 수지 조성물을 제공할 수 있다.According to the present invention, it is possible to provide 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.
도 1은 본 발명의 실시예 1에 따른 화학식 1로 표시되는 화합물의 IR 측정 그래프이다.1 is an IR measurement graph of a compound represented by Formula 1 according to Example 1 of the present invention.
도 2는 본 발명의 실시예 2에 따른 화학식 1로 표시되는 화합물의 IR 측정 그래프이다.2 is an IR measurement graph of the compound represented by Formula 1 according to Example 2 of the present invention.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 하기 화학식 1로 표시되는 화합물을 포함하는 난연성 에폭시 수지에 관한 것이다.The present invention relates to a flame retardant epoxy resin comprising a compound represented by the following formula (1).
<화학식 1><Formula 1>
(상기 식에서, X1은 하기 화학식 2 내지 11로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1 내지 10이고, m은 0 내지 10이고, n은 1 내지 10의 정수이다.)Wherein 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, and n is 1 to 10 Is an integer.)
<화학식 2><Formula 2>
<화학식 3><Formula 3>
<화학식 4><Formula 4>
<화학식 5><Formula 5>
<화학식 6><Formula 6>
<화학식 7><Formula 7>
<화학식 8><Formula 8>
<화학식 9><Formula 9>
<화학식 10><Formula 10>
<화학식 11><Formula 11>
<화학식 12><Formula 12>
상기 화학식 1에서 l과 m과 n이 각각 10을 초과하는 경우 중량평균분자량이 너무 커져서 점도가 높아지고 작업성이 저하되는 문제가 있고, 상기 l과 n이 각각 1 미만인 중량평균분자량이 너무 작아지고, 용제와의 상용성도 떨어져 작업성이 저하되는 문제가 있다.
When l, m and n in Formula 1 each exceeds 10, the weight average molecular weight is too large, there is a problem that the viscosity is high and workability is lowered, the weight average molecular weight of l and n are less than 1, respectively, is too small, There is also a problem in that the workability is lowered because of compatibility with the solvent.
또한 상기 화학식 1에서 X1이 상기 화학식 2 내지 11인 경우 벤젠링이 많아져서 내열성이 향상되는 효과가 있다. In addition, in the general formula (1), when X 1 is the general formulas (2) to (11), the benzene ring is increased, thereby improving heat resistance.
또한 상기 화학식 1에서 X2가 상기 화학식 12인 경우 -OH 기가 많아짐에 따라 접착력이 향상되는 효과가 있다. 상기 화학식 1로 표시되는 화합물은 인 함량이 6 내지 8질량%까지 많이 포함할 수 있다. 따라서, 난연성 수지 조성물의 나머지 조성의 자유도를 높일 수 있다. 즉, 통상적으로 난연성 에폭시 수지 화합물을 포함하는 조성물을 제조하는 경우, 상기 조성물 내에서는 난연성 에폭시 수지 화합물 성분 이외에 조성물의 여러 특성을 나타낼 수 있는 다른 성분들도 포함하여야 하는데, 난연성 에폭시 수지 화합물 자체 내에 인 함량을 소량 가지고 있으면, 조성물 내에 인 함량을 높이기 위하여 난연성 에폭시 수지 화합물 성분의 함량을 높여야 하고, 이에 따라 다른 성분들의 함량 비율이 줄어들어 결국 조성물이 가지고자 하는 특성이 발현될 수 없게 된다. In addition, in the general formula (1), when X 2 is the general formula (12), 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. In other words, when preparing a composition including a flame retardant epoxy resin compound, 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.
본 발명에 따른 상기 화학식 1로 표시되는 화합물은 6 내지 8질량%의 고 함량으로 인을 포함하기 때문에 난연성 에폭시 수지 화합물을 포함하는 조성물을 제조하는 경우, 난연성 에폭시 수지 화합물인 화학식 1로 표시되는 화합물을 소량 첨가할 수 있어, 조성물 내에 여러 특성을 나타낼 수 있는 다른 성분들을 다량 포함할 수 있어, 목적하는 바대로 조성물의 특성을 발현시킬 수 있는 장점을 가진다. Since 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.
상기 화학식 1로 표시되는 화합물은 150 내지 190℃의 유리전이온도를 가진다. 상기 유리전이온도가 상기 범위 내에 있는 경우 우수한 내열성을 가진다.The compound represented by Formula 1 has a glass transition temperature of 150 to 190 ℃. When the glass transition temperature is in the above range has excellent heat resistance.
상기 화학식 1로 표시되는 화합물은 500 내지 1500g/mol인 중량평균분자량을 가진다. 상기 중량평균분자량이 상기 범위 내에 있는 경우 용제와의 상용성이 좋아 점도가 낮아 응용하기 좋은 장점을 가진다.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.
상기 화학식 1로 표시되는 화합물은 350 내지 500g/eq인 에폭시 당량을 가진다. 상기 에폭시 당량이 상기 범위 내에 있는 경우 고 인함량이면서 경화제와 반응 할 수 있다는 장점을 가진다.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.
상기 화학식 1로 표시되는 화합물은 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 반응시켜 중간체 화합물을 제조하는 단계(S1); 및 상기 제조된 중간체 화합물에 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물을 첨가하여 반응시키는 단계(S2)를 포함하여 제조될 수 있다. 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.
먼저, 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 반응시켜 중간체 화합물을 제조한다(S1).First, an intermediate compound is prepared by reacting a hydroquinone compound including a phosphorus (P) atom with a chlorohydrin compound (S1).
상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물은 클로로히드린계 화합물 대비 1/6 내지 1/2의 몰비로 첨가하여 반응시킨다. 상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 상기 몰비 범위로 반응시키는 경우 반응이 균일하게 가는 장점을 가진다. 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. When the hydroquinone compound containing the phosphorus (P) atom and the chlorohydrin compound are reacted in the molar ratio range, the reaction is uniformly thin.
상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 반응시키는 과정에서 반응 촉매로서, 수산화나트륨, 수산화칼륨 등을 첨가할 수 있고, 바람직하게는 30~60% 농도의 수산화나트륨을 사용하는 것이 제조된 수지와 부산물 생성의 최소화 및 반응속도에 있어서 적합하다. 그 함량은 상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물 100중량부에 대하여 10~100중량부로 사용하는 것이 바람직하다. 상기 반응 촉매의 함량이 10중량부 미만으로 첨가될 경우 에폭시 환이 충분히 형성되지 않아 전술된 에폭시 당량을 만족 못하고, 100중량부를 초과할 경우 과반응으로 겔화가 발생되는 문제가 있다.
As a reaction catalyst in the process of reacting the hydroquinone compound containing the phosphorus (P) atom with the chlorohydrin compound, sodium hydroxide, potassium hydroxide and the like may be added, preferably 30 to 60%. The use of 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. When the content of the reaction catalyst is added less than 10 parts by weight, the epoxy ring is not sufficiently formed to satisfy the above-described epoxy equivalent, and if it exceeds 100 parts by weight, there is a problem that gelation occurs due to overreaction.
이 때, 상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물은 50 내지 80℃의 온도로 가열하여 반응시키는데, 상기 반응공정 후, 50 내지 80℃의 온도로 유지하면서 2 내지 24시간 동안 1차 숙성을 시킨 후, 100 내지 760torr의 감압상태에서 50 내지 100℃의 온도로 유지하면서 10분 내지 4시간 동안 2차 숙성을 실시할 수 있다. At this time, the hydroquinone compound containing the phosphorus (P) atom and the chlorohydrin compound are heated and reacted at a temperature of 50 to 80 ℃, after the reaction step, at a temperature of 50 to 80 ℃ After primary aging for 2 to 24 hours while maintaining, the secondary aging may be carried out for 10 minutes to 4 hours while maintaining the temperature of 50 to 100 ℃ at a reduced pressure of 100 to 760 torr.
본 발명에 따른 난연성 에폭시 수지 화합물은 상기 숙성 공정을 1차 및 2차로 실시하여 균일한 구조를 얻을 수 있는 효과를 얻을 수 있다. 또한, 상기 1차 및 2차 숙성공정을 상기 온도 및 시간의 범위 내로 실시하는 경우 균일한 구조를 얻을 수 있는 효과가 있다.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. In addition, when 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.
이 때, 상기 1차 및 2차 숙성공정 시 용매로서 이소프로필알코올, 메틸에틸케톤, 메틸이소부틸케논, 톨루엔, 크실렌 등을 사용할 수 있으며, 그 함량은 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물 100중량부에 대하여 20~80중량부로 사용하는 것이 바람직하다. At this time, 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.
이어서, 상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 반응시킨 후, 염층을 제거하고 100 내지 200℃의 온도에서 미반응물인 클로로히드린계 화합물 및 수분을 제거하는 탈기공정을 100 내지 760torr의 감압상태에서 실시하는 것이 바람직하다.Subsequently, after reacting the hydroquinone compound containing the phosphorus (P) atom with the chlorohydrin compound, 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.
상기 탈기공정 후, 염기성 촉매를 이용하여 염소이온을 제거하고 산으로 중화시키는 단계를 실시한다. 이를 구체적으로 설명하면, 상기 탈기공정 후, 120 내지 180℃의 온도에서 용매를 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물 100중량부에 대하여 10~80중량부의 함량으로 첨가한 후, 염기성 촉매를 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물 100중량부에 대하여 10~100중량부로 첨가하여 용해시킨 후, 염소이온을 제거하고 산으로 중화시키는 것이다. 이때에 용매로서는 이소프로필알코올, 메틸에틸케톤, 메틸이소부틸케논, 톨루엔, 크실렌 등을 사용할 수 있고, 산으로는 인산, 황산, 염산, 카르복실산 등 그 종류에 제한은 없다.After the degassing process, the step of removing the chlorine ions using a basic catalyst and neutralizing with acid. Specifically, after the degassing process, the solvent 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. At this time, as a solvent, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl kenone, toluene, xylene, etc. can be used, and as an acid, there is no restriction | limiting in the kind, such as phosphoric acid, sulfuric acid, hydrochloric acid, carboxylic acid.
상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물은 디페닐포스피닐하이드로-퀴논(Diphenylphosphinyl hydro-quinone)인 것을 특징으로 한다. The hydroquinone compound including the phosphorus (P) atom is characterized in that diphenylphosphinyl hydro-quinone (Diphenylphosphinyl hydro-quinone).
상기 클로로히드린계 화합물은 에피클로로하이드린, 에피요도으히드린, 에피브모로히드린, 메틸에틸브로모히드린 및 메틸에틸요오드히드린 중에서 선택되는 것을 특징으로 한다.The chlorohydrin-based compound is characterized in that it is selected from epichlorohydrin, epiyodohydrin, epibromohydrin, methyl ethyl bromohydrin and methyl ethyl iodine hydrin.
본 발명에 따른 난연성 에폭시 수지는 상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물을 도입하여 물성을 유지시키면서도 고 인 함량을 가지는 에폭시 수지를 제조할 수 있다. 이를 구체적으로 설명하면, 기존 DOPO와 에폭시 수지를 반응시켜 제조된 인계 에폭시 수지는 이론 인 함유량을 7.8질량%까지 올릴 수 있다. 하지만 그 만큼 물성이 저하되는 문제가 있다. 이에 본 발명은 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물을 사용하여 에폭시 수지를 제조하여 이러한 문제점을 해결하였다. 상술한 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물, 예를 들어 디페닐포스피닐하이드로-퀴논(Diphenylphosphinyl hydro-quinone)는 인 함유량이 9.99질량%로써 인 함유량이 14.5질량%인 DOPO보다 인 함유량이 낮지만, -OH기가 두 개를 함유하고 있어, 기존 DOPO와 에폭시 수지를 반응시켜 인계 에폭시 수지를 제조하는 과정과는 달리 본 발명에서는 상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물의 -OH에 클로로히드린계 화합물을 반응시켜 인 함량을 높이면서도 물성을 만족시키는 신규 고 인함량 에폭시 수지를 제조할 수 있다.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. Specifically, 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. However, there is a problem that physical properties are reduced by that much. Accordingly, 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.
상술한 바와 같이 S1 단계에서 제조된 중간체 화합물에 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물을 첨가하여 반응시켜 상기 화학식 1로 표시되는 화합물을 제조한다(S2). As described above, 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).
상기 중간체 화합물 및 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물은 중간체 화합물 100중량부에 대하여 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물을 0.1 내지 100중량부의 함량으로 첨가한다. 상기 중간체 화합물 및 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물의 함량이 상기 범위 내에 있는 경우 반응 점도가 적절하여 공정이 수월한 장점을 가진다.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. When the content of the compound selected from the intermediate compound, the phosphorus compound or the bisphenol compound, or a mixture of two or more selected from these compounds is within the above range, the reaction viscosity is appropriate and the process is easy.
상기 S2 단계는 100 내지 160℃의 온도에서 1 내지 8시간 동안 실시하는 것이 공정이 안정적인 측면에서 바람직하다. The step S2 is preferably carried out for 1 to 8 hours at a temperature of 100 to 160 ℃ in terms of stable process.
이 때, 상기 반응 시 용매로서 메톡시프로판올-2올, 2-메톡시에탄올, 아세톤, 디옥산 등을 사용할 수 있으며, 그 함량은 중간체 화합물 100중량부에 대하여 10 내지 50중량부로 사용하는 것이 바람직하다. At this time, 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.
상기 인계 화합물은 10-(2',5'-Dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO-HQ) 및 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphsophorin-6-yl)-1,4-naphthalenediol (DOPO-NQ) 중에서 선택되는 것이다. 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).
상기 비스페놀계 화합물은 비스페놀 A, 비스페놀 F, 비스페놀 Z, 비스페놀-TMC, 비스페놀 AP, 비스페놀 BP, 비스페놀 B, 비스페놀 C 및 비스페놀 E 중에서 선택되는 것이다. 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.
상기 S2 단계에서 페닐계 화합물인 촉매를 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물 100중량부에 대하여 0.01 내지 5중량부의 함량으로 첨가시키는 것이 반응 속도를 높이는 측면에서 바람직하다.In the step S2, it is preferable to add 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.
상기 페닐계 화합물은 에티트리페닐포스포늄아이오다이드(Ethytriphenylphosphonium Iodide;ETPPI), 2-메틸이미다졸(2-Methylimidazole)(2MI), 2-에틸-4-메틸 이미다졸(2-ethyl-4-methyl imidazole)(2E4MZ) 및 2-페닐이미다졸(2-phenylimidazole, 2PI) 중에서 선택되는 것이다.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).
또한, 본 발명에 따른 난연성 에폭시 수지 조성물은 상기 제조방법으로 제조된 상기 화학식 1로 표시되는 화합물, 경화제 및 경화촉진제를 포함하는 것이다. 상기 난연성 에폭시 수지 조성물은 상기 화학식 1로 표시되는 화합물 100중량부에 대하여 경화제 0.1 내지 50중량부 및 경화촉진제 0.0001 내지 0.05중량부를 포함한다.In addition, 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.
상기 경화제가 상기 범위 내로 포함되는 경우 적절한 경화속도를 가지는 장점을 가진다. When the curing agent is included in the above range has the advantage of having an appropriate curing rate.
상기 경화제는 본 발명이 속하는 분야에서 통상적으로 사용되는 것을 사용할 수 있으며, 예를 들어, 디시안디아마이드(Dicyandiamide), 페놀노볼락(Phenolnovolac), 4-아미노페닐 설폰(4-aminophenyl sulfone) 등을 들 수 있다. 상기 경화촉진제가 상기 범위보다 낮을 경우 경화 반응이 잘 일어나지 않을 수 있고, 상기 범위보다 높을 경우 과반응이 일어날 수 있다.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. When 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.
상기 경화촉진제는 본 발명이 속하는 분야에서 통상적으로 사용되는 것을 사용할 수 있으며, 예를 들어, 에티트리페닐포스포늄아이오다이드(Ethytriphenylphosphonium Iodide)(ETPPI), 2-메틸이미다졸(2-Methylimidazole)(2MI), 2-에틸-4-메틸 이미다졸(2-ethyl-4-methyl imidazole)(2E4MZ), ETPPI 등을 들 수 있다.
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.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 있어 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.
실시예 1Example 1
10리터들이 다목 플라스크에 Diphenylphosphinyl hydro-quinone(DPPQ) (1500g, 1 mol)와 에피클로로하이드린 (4470g, 5 mol)을 이소프로필알코올 (1970g)에 넣고 잘 혼합한 후 60±5℃까지 교반을 시키면서 가열을 하였다. 60±5℃로 유지하면서 50% 수산화 나트륨 수용액 81g을 일괄주입 한 후 60±5℃로 유지하면서 4시간 숙성시켰다. 숙성이 끝난 후 250±10torr 감압상태에서 온도를 60±5℃로 유지하면서 50% 수산화 나트륨 수용액 810g을 2시간에 걸쳐 투입 한 후, 30분간 숙성시켰다. 이어 물 714g을 넣고 분액 깔때기를 사용하여 하단의 염층을 제거하고, 150℃까지 온도를 높여 과량의 에피클로로하이드린 및 수분을 제거하였다. 탈기가 완료된 화합물을 70±10℃까지 온도를 낮춘 후 Methyl Isobutyl Ketone (이하 MIBK) 4990g을 투입하였다. 이어서, 20% 수산화 나트륨 수용액을 2~3회 사용하여 상기 MIBK에 용해된 수지의 유기층 내에 남아있는 염소이온을 제거하고 인산으로 중화 후, 여과하고 MIBK 탈기를 통하여 에폭시 산물인 짙은 색의 중간체 화합물인 약1840g을 얻었다. 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 ℃. 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. Then, 714 g of water was added thereto, and the salt layer at the bottom was removed using a separatory funnel, and the temperature was raised to 150 ° C. to remove excess epichlorohydrin and water. After degassing, the temperature was lowered to 70 ± 10 ° C., and 4990 g of Methyl Isobutyl Ketone (hereinafter referred to as MIBK) was added thereto. Then, using a 20% aqueous sodium hydroxide solution two or three times to remove the chlorine ions remaining in the organic layer of the resin dissolved in the MIBK, neutralized with phosphoric acid, and then filtered and through the MIBK degassing a dark intermediate compound of the epoxy product About 1840 g were obtained.
이어서, 2리터들이 다목 플라스크에 상기 제조된 중간체 화합물200g 과 10-(2',5'-Dihydroxyphenyl)-9,10-dihydro-9oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) 29.2g을 넣고 110±10℃까지 교반시키면서 가열하였다. 110±10℃ 에서 메탄올에 10% 용해된 Ethytriphenylphosphonium Iodide (이하ETPPI) 용액을 0.15g 투입 후 157±2℃까지 가열하였다. 157±2℃까지 도달하였을 때의 반응시간을 초기시간으로 기준을 잡고, 매시간 샘플링을 하여 목표당량이 출현 할 때까지 157±2℃에서 반응시켰다. 목표당량이 출현 후 온도를 120±10℃까지 낮춘 후 Propylene glycol monomethyl ether(이하,PGME)을 주입하여 최종 물질인 하기 화학식 1로 표시되는 화합물 약 470g을 얻었다. 상기 화학식 1로 표시되는 화합물의 인 함량은 7.7질량%이고, 유리전이온도가 165.1℃이고, 중량평균분자량은 1013g/mol이고, 에폭시 당량은 343.1g/eq이였다. Subsequently, 200 g of the prepared intermediate compound and 29.2 g of 10- (2 ', 5'-Dihydroxyphenyl) -9,10-dihydro-9oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) were prepared in a 2-liter multi-neck flask. It was heated while stirring to 110 ± 10 ℃. 0.15 g of a solution of Ethytriphenylphosphonium Iodide (ETPPI) dissolved in methanol at 110 ± 10 ° C. in 10% was heated to 157 ± 2 ° C. 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. After 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, and epoxy equivalent was 343.1 g / eq.
<화학식 1><Formula 1>
(상기 식에서, X1은 화학식 2이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1~2이고, m은 1~2이고, n은 1~2인 정수이다.)(Wherein, 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).
<화학식 2><Formula 2>
<화학식 12><Formula 12>
실시예 2 Example 2
2리터들이 다목 플라스크에 상기 실시예 1에서 제조된 방법과 동일한 방법으로 제조된 중간체 화합물 200g 과 Bisphenol-A (BPA) 22.7g을 넣고 110±10℃까지 교반시키면서 가열하였다. 110±10℃ 에서 메탄올에 10% 용해된 ETPPI 용액을 0.15g 투입 후 157±2℃까지 가열하였다. 157±2℃까지 도달하였을 때의 반응시간을 초기시간으로 기준을 잡고, 매시간 샘플링을 하여 에폭시 당량이 340g/eq이 출현 할 때까지 157±2℃에서 반응시켰다. 상기 에폭시 당량인 340g/eq이 출현한 후 온도를 120±10℃까지 낮춘 후 PGME을 주입하여 최종 물질인 하기 화학식 1로 표시되는 화합물 약 470g을 얻었다. 하기 화학식 1로 표시되는 화합물의 인 함량은 6.7질량%이고, 유리전이온도가 170.1℃이고, 중량평균분자량은 893 g/mo이고, 에폭시 당량은 370.5g/eq이였다. In a 2-liter multi-necked flask, 200 g of intermediate compound and 22.7 g of Bisphenol-A (BPA) prepared in the same manner as in Example 1 were added and heated with stirring to 110 ± 10 ° C. 0.15 g of ETPPI solution dissolved in methanol at 110 ± 10 ° C. was heated to 157 ± 2 ° C. after the addition of 0.15 g. The reaction time when the temperature reached 157 ± 2 ° C. was set as an initial time, and sampled every hour to react at 157 ± 2 ° C. until an epoxy equivalent of 340 g / eq appeared. After the appearance of the epoxy equivalent of 340g / eq after the temperature was lowered to 120 ± 10 ℃ and PGME was injected to obtain about 470g of the compound represented by the following formula (1) as a final material. The phosphorus content of the compound represented by the following Formula 1 was 6.7 mass%, the glass transition temperature was 170.1 ° C., the weight average molecular weight was 893 g / mo, and the epoxy equivalent was 370.5 g / eq.
<화학식 1><Formula 1>
(상기 식에서, X1은 하기 화학식 3으로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1~2이고, m은 1~2이고, n은 1~2인 정수이다.)(Wherein, 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. .)
<화학식 3><Formula 3>
<화학식 12><Formula 12>
실시예 3 Example 3
2리터들이 다목 플라스크에 상기 실시예 1에서 제조된 방법과 동일한 방법으로 제조된 중간체 화합물 200g 과 Bisphenol F 10g을 넣고 110±10℃까지 교반을 시키면서 가열을 하였다. 110±10℃ 에서 메탄올에 10% 용해된 ETPPI 용액을 0.15g 투입 후 157±2℃까지 가열을 하였다. 157±2℃까지 도달하였을 때의 반응시간을 초기시간으로 기준을 잡고, 매시간 샘플링을 하여 에폭시 당량이 320g/eq에 도달할 때까지 157±2℃에서 반응을 시켰다. 상기 에폭시 당량이 320g/eq에 도달한 온도를 120±10℃까지 낮추고 PGME을 주입하여 최종 물질인 하기 화학식 1로 표시되는 화합물 약 205g을 얻었다. 하기 화학식 1로 표시되는 화합물의 인 함량은 7.0질량%이고, 유리전이온도가 168.7℃이고, 중량평균분자량은 843g/mol이고, 에폭시 당량은 322.1g/eq이였다. In a 2-liter multi-necked flask, 200 g of Bisphenol F and 10 g of Intermediate Compound, prepared in the same manner as in Example 1, were heated while stirring to 110 ± 10 ° C. 0.15 g of an ETPPI solution dissolved in 10% in methanol at 110 ± 10 ° C. was heated to 157 ± 2 ° C. The reaction time when the temperature reached 157 ± 2 ° C. was set as the initial time, and sampled every hour to react at 157 ± 2 ° C. until the epoxy equivalent reached 320 g / eq. The epoxy equivalent was reached to 320 g / eq was lowered to 120 ± 10 ℃ 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 ℃, the weight average molecular weight was 843 g / mol, epoxy equivalent was 322.1 g / eq.
<화학식 1> <Formula 1>
(상기 식에서, X1은 하기 화학식 4로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1~2이고, m은 1~2이고, n은 1~2인 정수이다.)Wherein 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, and n is an integer of 1 to 2 .)
<화학식 4><Formula 4>
<화학식 12><Formula 12>
실시예 4Example 4
2리터들이 다목 플라스크에 상기 실시예 1에서 제조된 방법과 동일한 방법으로 제조된 중간체 화합물 200g 과 Bisphenol Z 40g을 넣고 110±10℃까지 교반을 시키면서 가열을 하였다. 110±10℃ 에서 메탄올에 10% 용해된 ETPPI 용액을 0.15g 투입 후 157±2℃까지 가열을 하였다. 157±2℃까지 도달하였을 때의 반응시간을 초기시간으로 기준을 잡고, 매시간 샘플링을 하여 에폭시 당량이 340g/eq에 도달 할 때까지 157±2℃에서 반응을 시켰다. 상기 에폭시 당량이 340g/eq에 출현한 후, 온도를 120±10℃까지 낮추고 PGME을 주입하여 최종 물질인 하기 화학식 1로 표시되는 화합물 약 240g을 얻었다. 하기 화학식 1로 표시되는 화합물의 인 함량은 6.6질량%이고, 유리전이온도가 169.1℃이고, 중량평균분자량은 943 g/mol이고, 에폭시 당량은 345.5g/eq이였다. In a 2-liter multi-necked flask, 200 g of Intermediate Compound and 40 g of Bisphenol Z, prepared in the same manner as in Example 1, were heated while stirring to 110 ± 10 ° C. 0.15 g of an ETPPI solution dissolved in 10% in methanol at 110 ± 10 ° C. was heated to 157 ± 2 ° C. The reaction time when the temperature reached 157 ± 2 ° C. was set as the initial time, and sampled every hour to react at 157 ± 2 ° C. until the epoxy equivalent reached 340 g / eq. After the epoxy equivalent appeared at 340 g / eq, the temperature was lowered to 120 ± 10 ℃ 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.
<화학식 1> <Formula 1>
(상기 식에서, X1은 하기 화학식 5로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1~2이고, m은 1~2이고, n은 1~2인 정수이다.)(Wherein, 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. .)
<화학식 5><Formula 5>
<화학식 12><Formula 12>
실시예 5Example 5
2리터들이 다목 플라스크에 상기 실시예 1에서 제조된 방법과 동일한 방법으로 제조된 중간체 화합물 200g 과 Bisphenol TMC 5g을 넣고 110±10℃까지 교반을 시키면서 가열을 하였다. 110±10℃ 에서 메탄올에 10% 용해된 ETPPI 용액을 0.15g 투입 후 157±2℃까지 가열을 하였다. 157±2℃까지 도달하였을 때의 반응시간을 초기시간으로 기준을 잡고, 매시간 샘플링을 하여 에폭시 당량이 380g/eq에 도달할 때까지 157±2℃에서 반응을 시켰다. 상기 에폭시 당량이 380g/eq에 도달한 후 온도를 120±10℃까지 낮추고 PGME을 주입하여 최종 물질인 하기 화학식 1로 표시되는 화합물 약 205g을 얻었다. 하기 화학식 1로 표시되는 화합물의 인 함량은 6.5질량%이고, 유리전이온도가 163.5℃이고, 중량평균분자량은 987 g/mol이고, 에폭시 당량은 390.1g/eq이였다. In a 2-liter multi-necked flask, 200 g of intermediate compound and 5 g of Bisphenol TMC prepared in the same manner as in Example 1 were added, followed by heating to 110 ± 10 ° C. with stirring. 0.15 g of an ETPPI solution dissolved in 10% in methanol at 110 ± 10 ° C. was heated to 157 ± 2 ° C. The reaction time when the temperature reached 157 ± 2 ° C. was set as the initial time, and sampled every hour to react at 157 ± 2 ° C. until the epoxy equivalent reached 380 g / eq. After the epoxy equivalent reached 380 g / eq, the temperature was lowered to 120 ± 10 ° C. and PGME was injected to obtain about 205 g of a compound represented by the following Chemical Formula 1 as a final substance. Phosphorus content of the compound represented by Formula 1 was 6.5% by mass, glass transition temperature was 163.5 ° C, weight average molecular weight was 987 g / mol, and epoxy equivalent was 390.1 g / eq.
<화학식 1> <Formula 1>
(상기 식에서, X1은 하기 화학식 6으로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1~2이고, m은 1~2이고, n은 1~2인 정수이다.)Wherein 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, and n is an integer of 1 to 2 .)
<화학식 6><Formula 6>
<화학식 12><Formula 12>
실시예 6Example 6
2리터들이 다목 플라스크에 상기 실시예 1에서 제조된 방법과 동일한 방법으로 제조된 중간체 화합물 200g 과 Bisphenol AP 50g을 넣고 110±10℃까지 교반을 시키면서 가열을 하였다. 110±10℃ 에서 메탄올에 10% 용해된 ETPPI 용액을 0.15g 투입 후 157±2℃까지 가열을 하였다. 157±2℃까지 도달하였을 때의 반응시간을 초기시간으로 기준을 잡고, 매시간 샘플링을 하여 목표 에폭시 당량이 390g/eq에 도달 할 때까지 157±2℃에서 반응을 시켰다. 상기 목표 에폭시 당량이 390g/eq에 도달한 후 온도를 120±10℃까지 낮추고 PGME 을 주입하여 최종 물질인 하기 화학식 1로 표시되는 화합물 약 250g을 얻었다.하기 화학식 1로 표시되는 화합물의 인 함량은 6.5질량%이고, 유리전이온도가 175.4℃이고, 중량평균분자량은 1027 g/mol이고, 에폭시 당량은 400g/eq이였다. In a 2-liter multi-necked flask, 200 g of intermediate compound prepared in the same manner as in Example 1 and 50 g of Bisphenol AP were added, followed by heating with stirring to 110 ± 10 ° C. 0.15 g of an ETPPI solution dissolved in 10% in methanol at 110 ± 10 ° C. was heated to 157 ± 2 ° C. The reaction time when the temperature reached 157 ± 2 ° C. was set as an initial time, and sampled every hour to react at 157 ± 2 ° C. until the target epoxy equivalent reached 390 g / eq. After the target epoxy equivalent reached 390 g / eq, the temperature was lowered to 120 ± 10 ° C. and PGME was injected to obtain about 250 g of a compound represented by the following Chemical Formula 1 as a final substance. It was 6.5 mass%, the glass transition temperature was 175.4 degreeC, the weight average molecular weight was 1027 g / mol, and the epoxy equivalent was 400 g / eq.
<화학식 1> <Formula 1>
(상기 식에서, X1은 하기 화학식 7로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1~2이고, m은 1~2이고, n은 1~2인 정수이다.)(Wherein 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, and n is an integer of 1 to 2 .)
<화학식 7><Formula 7>
<화학식 12><Formula 12>
실시예 7Example 7
2리터들이 다목 플라스크에 상기 실시예 1에서 제조된 방법과 동일한 방법으로 제조된 중간체 화합물 200g 과 Bisphenol BP 50g을 넣고 110±10℃까지 교반을 시키면서 가열을 하였다. 110±10℃ 에서 메탄올에 10% 용해된 ETPPI 용액을 0.15g 투입 후 157±2℃까지 가열을 하였다. 157±2℃까지 도달하였을 때의 반응시간을 초기시간으로 기준을 잡고, 매시간 샘플링을 하여 목표 에폭시 당량이 410g/eq에 출현 할 때까지 157±2℃에서 반응을 시켰다. 상기 목표 에폭시 당량이 출현한 후 온도를 120±10℃까지 낮추고 PGME을 주입하여 최종 물질인 하기 화학식 1로 표시되는 화합물 약 250g을 얻었다. 하기 화학식 1로 표시되는 화합물의 인 함량은 6.4질량%이고, 유리전이온도가 177.1℃이고, 중량평균분자량은 1127 g/mol이고, 에폭시 당량은 420g/eq이였다. In a 2-liter multi-necked flask, 200 g of intermediate compound and 50 g of Bisphenol BP prepared in the same manner as in Example 1 were added, followed by heating with stirring to 110 ± 10 ° C. 0.15 g of an ETPPI solution dissolved in 10% in methanol at 110 ± 10 ° C. was heated to 157 ± 2 ° C. The reaction time when the temperature reached 157 ± 2 ° C. was set as an initial time, and sampled every hour to react at 157 ± 2 ° C. until the target epoxy equivalent appeared at 410 g / eq. After the target epoxy equivalent appeared, 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 6.4 mass%, glass transition temperature was 177.1 ° C., weight average molecular weight was 1127 g / mol, and epoxy equivalent was 420 g / eq.
<화학식 1> <Formula 1>
(상기 식에서, X1은 하기 화학식 8로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1~2이고, m은 1~2이고, n은 1~2인 정수이다.)(Wherein, 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. .)
<화학식 8><Formula 8>
<화학식 12><Formula 12>
실시예 8Example 8
2리터들이 다목 플라스크에 상기 실시예 1에서 제조된 방법과 동일한 방법으로 제조된 중간체 화합물 200g 과 Bisphenol B 50g을 넣고 110±10℃까지 교반을 시키면서 가열을 하였다. 110±10℃ 에서 메탄올에 10% 용해된 ETPPI 용액을 0.15g 투입 후 157±2℃까지 가열을 하였다. 157±2℃까지 도달하였을 때의 반응시간을 초기시간으로 기준을 잡고, 매시간 샘플링을 하여 목표 에폭시 당량이 380g/eq로 출현 할 때까지 157±2℃에서 반응을 시켰다. 상기 목표 에폭시 당량이 출현한 후 온도를 120±10℃까지 낮추고 PGME을 주입하여 최종 물질인 하기 화학식 1로 표시되는 화합물 약 250g을 얻었다. 하기 화학식 1로 표시되는 화합물의 인 함량은 6.7질량%이고, 유리전이온도가 168.3℃이고, 중량평균분자량은 827 g/mol이고, 에폭시 당량은 388g/eq이였다. In a 2-liter multi-necked flask, 200 g of Intermediate Compound and 50 g of Bisphenol B prepared in the same manner as in Example 1 were added, followed by heating to 110 ± 10 ° C. with stirring. 0.15 g of an ETPPI solution dissolved in 10% in methanol at 110 ± 10 ° C. was heated to 157 ± 2 ° C. The reaction time when the temperature reached 157 ± 2 ° C. was set as the initial time, and sampled every hour to react at 157 ± 2 ° C. until the target epoxy equivalent appeared at 380 g / eq. After the target epoxy equivalent appeared, 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.
<화학식 1> <Formula 1>
(상기 식에서, X1은 하기 화학식 9로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1~2이고, m은 1~2이고, n은 1~2인 정수이다.)Wherein 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, and n is an integer of 1 to 2 .)
<화학식 9><Formula 9>
<화학식 12><Formula 12>
실시예 9Example 9
2리터들이 다목 플라스크에 상기 실시예 1에서 제조된 방법과 동일한 방법으로 제조된 중간체 화합물 200g 과 Bisphenol C 50g을 넣고 110±10℃까지 교반을 시키면서 가열을 하였다. 110±10℃ 에서 메탄올에 10% 용해된 ETPPI 용액을 0.15g 투입 후 157±2℃까지 가열을 하였다. 157±2℃까지 도달하였을 때의 반응시간을 초기시간으로 기준을 잡고, 매시간 샘플링을 하여 목표 에폭시 당량이 370g/eq으로 출현 할 때까지 157±2℃에서 반응을 시켰다. 상기 목표 에폭시 당량이 출현한 후 온도를 120±10℃까지 낮추고 PGME을 주입하여 최종 물질인 하기 화학식 1로 표시되는 화합물 약 250g을 얻었다. 하기 화학식 1로 표시되는 인 함량은 6.6질량%이고, 유리전이온도가 167.4℃이고, 중량평균분자량은 727 g/mol이고, 에폭시 당량은 373g/eq이였다. In a 2-liter multi-necked flask, 200 g of intermediate compound and 50 g of Bisphenol C prepared in the same manner as in Example 1 were added, followed by heating with stirring to 110 ± 10 ° C. 0.15 g of an ETPPI solution dissolved in 10% in methanol at 110 ± 10 ° C. was heated to 157 ± 2 ° C. The reaction time when the temperature reached 157 ± 2 ° C. was set as the initial time, and sampled every hour to react at 157 ± 2 ° C. until the target epoxy equivalent appeared at 370 g / eq. After the target epoxy equivalent appeared, 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.
<화학식 1> <Formula 1>
(상기 식에서, X1은 하기 화학식 10으로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1~2이고, m은 1~2이고, n은 1~2인 정수이다.)(Wherein, 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. .)
<화학식 10><Formula 10>
<화학식 12><Formula 12>
실시예 10Example 10
2리터들이 다목 플라스크에 상기 실시예 1에서 제조된 방법과 동일한 방법으로 제조된 중간체 화합물 200g 과 Bisphenol E 50g을 넣고 110±10℃까지 교반을 시키면서 가열을 하였다. 110±10℃ 에서 메탄올에 10% 용해된 ETPPI 용액을 0.15g 투입 후 157±2℃까지 가열을 하였다. 157±2℃까지 도달하였을 때의 반응시간을 초기시간으로 기준을 잡고, 매시간 샘플링을 하여 목표 에폭시 당량이 360g/eq로 출현 할 때까지 157±2℃에서 반응을 시켰다. 상기 목표 에폭시 당량이 출현한 후 온도를 120±10℃까지 낮추고 PGME을 주입하여 최종 물질인 하기 화학식 1로 표시되는 화합물 약 250g을 얻었다. 하기 화학식 1로 표시되는 화합물의 인 함량은 6.8질량%이고, 유리전이온도가 166.1℃이고, 중량평균분자량은 627 g/mol이고, 에폭시 당량은 364g/eq이였다. In a 2-liter multi-necked flask, 200 g of intermediate compound and 50 g of Bisphenol E prepared in the same manner as in Example 1 were added, followed by heating with stirring to 110 ± 10 ° C. 0.15 g of an ETPPI solution dissolved in 10% in methanol at 110 ± 10 ° C. was heated to 157 ± 2 ° C. The reaction time when the temperature reached 157 ± 2 ° C. was set as the initial time, and sampled every hour to react at 157 ± 2 ° C. until the target epoxy equivalent appeared at 360 g / eq. After the target epoxy equivalent appeared, 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. Phosphorus content of the compound represented by the following formula (1) was 6.8 mass%, the glass transition temperature was 166.1 ℃, the weight average molecular weight was 627 g / mol, epoxy equivalent was 364 g / eq.
<화학식 1><Formula 1>
(상기 식에서, X1은 하기 화학식 11로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1~2이고, m은 1~2이고, n은 1~2인 정수이다.)Wherein 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, and n is an integer of 1 to 2 .)
<화학식 11><Formula 11>
<화학식 12><Formula 12>
도 1은 본 발명의 실시예 1에 따른 화학식 1로 표시되는 화합물의 IR 측정 그래프이고, 도 2는 본 발명의 실시예 2에 따른 화학식 1로 표시되는 화합물의 IR 측정 그래프이다. 상기 실시예 3 내지 10에 따라 제조된 화학식 1로 표시되는 화합물의 IR 측정 그래프도 도 1 및 2와 유사한 경향을 보였으며, 따라서 이에 대한 도시는 생략해도 무방하다. FIG. 1 is an IR measurement graph of a compound represented by Formula 1 according to Example 1 of the present invention, and 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.
비교예 1Comparative Example 1
인 변성 난연 페놀 노볼락 에폭시 수지인 KEG-H5138 (코오롱인더스트리 주식회사, EEW : 297.0 g/eq, 인함량 : 2.9질량%)를 사용하였다. 구조식은 하기 화학식 13과 같다KEG-H5138 (Kolon Industries Co., Ltd., EEW: 297.0 g / eq, phosphorus content: 2.9 mass%) which is a phosphorus modified flame-retardant phenol novolak epoxy resin was used. Structural formula is the same as
<화학식 13><Formula 13>
비교예 2Comparative Example 2
인 변성 난연 페놀 노볼락 에폭시 수지인 KEG-HQ5538(코오롱인더스트리 주식회사, EEW : 310.0 g/eq, 인함량 : 3.0질량%)를 사용하였다. 구족식은 하기 화학식 14와 같다.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).
<화학식 14><Formula 14>
<난연성 에폭시 수지 조성물><Flame Retardant Epoxy Resin Composition>
실시예 1 내지 10 및 비교예 1 내지 2에 따른 난연성 에폭시 수지 화합물을 조성물 내에 인 함량을 2.5질량%에 맞추어 난연성 에폭시 수지 조성물(바니쉬)를 하기 표 1에 기재된 바와 같은 함량으로 혼합하여 제조하였다. 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%.
상기 바니쉬를 제조하는 구체적인 내용은 아래와 같다.Specific details of manufacturing the varnish are as follows.
경화제는 범용적으로 많이 쓰이는 Dicyandiamide (이하 DICY)를 사용하였으며, 바니쉬 인함량을 맞추기 위하여 페놀 변성 노볼락 수지인 KEP-113P8(코오롱인더스트리 주식회사, EEW : 180 g/eq) 를 사용하였다. DICY 의 양은 KEP-113P85과 에폭시 수지의 혼합 당량을 구한 후 그에 맞는 몰비로 투입하였다. 경화촉진제로서 2-Methylimidazole (이하 2MI)를 사용하였으며, 그 양은, 전체 에폭시 투입 양(KEP-113P85 + 에폭시 수지(실시예 1 내지 10에서 각각 제조된 화학식 1로 표시되는 화합물 또는 비교예 1 내지 2에서 각각 제조된 화학식 13 및 14로 표시되는 화합물)) 대비 500ppm을 주입하였다. Dicyandiamide (hereinafter referred to as DICY), which is widely used as a curing agent, was used, and KEP-113P8 (Kolon Industries Co., Ltd., EEW: 180 g / eq), a phenol-modified novolak resin, was used to match varnish phosphorus content. 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)).
표 1
Table 1
바니쉬 배합비(g) | KEP-113P85 | DICY | 2MI | 실시예 1 내지 10에서 각각 제조된 화학식 1로 표시되는 화합물 또는 비교예 1 내지 2에서 각각 제조된 화학식 13 및 14로 표시되는 화합물 |
실시예 1 | 512 | 32.9 | 0.33 | 225 |
실시예 2 | 411 | 27.4 | 0.28 | 225 |
실시예 3 | 441 | 29.7 | 0.30 | 225 |
실시예 4 | 400 | 27.3 | 0.28 | 225 |
실시예 5 | 392 | 26.1 | 0.29 | 225 |
실시예 6 | 392 | 26.0 | 0.28 | 225 |
실시예 7 | 382 | 25.3 | 0.28 | 225 |
실시예 8 | 412 | 26.9 | 0.28 | 225 |
실시예 9 | 402 | 26.7 | 0.28 | 225 |
실시예 10 | 422 | 28.0 | 0.28 | 225 |
비교예 1 | 32 | 9.26 | 0.12 | 225 |
비교예 2 | 31 | 8.45 | 0.12 | 225 |
Varnish Compounding Ratio (g) | KEP-113P85 | DICY | 2MI | Compounds represented by |
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 8 | 412 | 26.9 | 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 |
상기 표 1에서 보는 바와 같이, 실시예 1 내지 10에서 각각 제조된 화학식 1로 표시되는 화합물은 인 함량이 높아, 바니쉬 제조시, 경화제 및 경화촉진제의 함량을 높일 수 있었고, 이로부터 본 발명에 따라 제조된 난연성 에폭시 수지를 사용하여 조성물을 제조하는 경우 조성물 내에 여러 특성을 나타낼 수 있는 다른 성분들을 다량 포함할 수 있어, 목적하는 바대로 조성물의 특성을 발현시킬 수 있는 장점을 가질 수 있음을 알 수 있었다. As shown in Table 1, 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. When preparing a composition using 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.
<동박적층판 제조>Manufacture of Copper Clad Laminate
상기 표 1에 따라 제조된 바니쉬를 유리섬유에 함침한 다음, 155℃에서 3분간 건조하여 프리프레그를 만들고, 이렇게 제조된 프리프레그 4장을 적층하고 적층된 프리프레그 상하면에 동박을 적층한 후에 프레스하여 동박적층판을 제조하였다. (프레스 조건 : 온도 190℃, 압력 25 kgf/cm2, 공정시간 2시간)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. (Press condition: Temperature 190 ℃, Pressure 25 kgf / cm2, Process time 2 hours)
본 발명에서는 이하의 분석방법을 사용하였다.In the present invention, the following analysis method was used.
1) 인 함량 측정방법1) How to measure phosphorus content
인 함량 측정은 각 구조의 단량체를 통하여 이론치로 계산하였다.Phosphorus content measurement was calculated by the theoretical value through the monomer of each structure.
2) 유리전이온도 측정방법 2) Glass transition temperature measurement method
수득된 동박적층판의 유리전이온도를 사차주사열량계(DSC, TA Instrument社제, Q2000)로 측정하였다. (측정부위 : 중앙부, 20mg, 측정조건 : 질소 분위기, 20℃/min.의 승온속도로 250℃까지 승온)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.)
3) 중량평균분자량 측정방법겔 투과 크로마토그래피(GPC, Waters: Waters707)에 의해 중량평균분자량(Mw)을 구하였다. 측정하는 중합체는 40000ppm의 농도가 되도록 테트라히드로푸란에 용해시켜 GPC에 100㎕를 주입하였다. GPC의 이동상은 테트라히드로푸란을 사용하고, 1.0ml/분의 유속으로 유입하였으며, 분석은 35℃ 에서 수행하였다. 컬럼은 Waters HR-05, 1, 2, 4E 4개를 직렬로 연결하였다. 검출기로는 RI and PAD Detector를 이용하여 35℃에서 측정하였다.3) Weight average molecular weight measuring method The weight average molecular weight (Mw) was calculated | required by the gel permeation chromatography (GPC, Waters: Waters707). The polymer to be measured was dissolved in tetrahydrofuran to a concentration of 40000 ppm, and 100 µl 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.
4) 에폭시 당량 측정방법4) Epoxy equivalent measuring method
시료 적당량을 공전삼각 Flask에 채취하고 2-Methoxyethanol 10ml로 가하여 완전히 용해한다. 용해 후 0.2N HCl Dioxane 25ml를 정확히 가한다. 뚜껑을 닫고 Flask 경계에 Dioxane 한 두방울 떨어뜨려 잘 닫은 후 30분간 실온에서 반응 시킨다. 반응 후 약 10ml 2-Methoxyethanol 로 Flask 및 마개를 씻어 Flask에 포함시킨다. Cresol Red 지시약을 3방울 가하고 0.1N NaOH Methanol 용액으로 적정한다. 동시에 Blank Test를 실시한다. 에폭시 당량은 다음과 같은 식1로 계산하였다. W는 시료의 무게, Bs는 Blank의 적정 부피, A는 시료의 적정 부피, F는 Factor 값이다.Take an appropriate amount of sample into the revolving triangle flask and add 10 ml of 2-Methoxyethanol to dissolve completely. After dissolution, accurately add 25 ml of 0.2N HCl Dioxane. Close the lid, add a drop of Dioxane to the Flask boundary, close well, and allow to react at room temperature for 30 minutes. After the reaction, the flask and the stopper are washed with about 10 ml 2-Methoxyethanol and included in the flask. Three drops of Cresol Red indicator are added and titrated with 0.1N NaOH Methanol solution. At the same time, perform Blank Test. Epoxy equivalent was calculated by the following equation. W is the weight of sample, Bs is the proper volume of blank, A is the proper volume of sample, and F is the value of Factor.
[식1][Equation 1]
에폭시 당량 : 10000 × W / ((B-A) × F)Epoxy Equivalent: 10000 × W / ((B-A) × F)
5) 박리 강도(Peel-strength) 및 겹간 접착력(Inter-ply Adhension) 측정방법5) Peel-strength and Inter-ply Adhension
Asida의 Asida-DZC-5를 사용하여 측정하였다.Measurement was made using Asida-DZC-5 from Asida.
6)흡습율 측정방법6) How to measure moisture absorption
50mm × 50mm로 컷트한 시험편을 사용하여, 50℃의 오분 중에서 24시간 건조한 후의 건조중랴을 측정하고, 계속해서 85℃/85%RH로 조정한 처리조 내에 72시간 보관후 후의 중량을 측정하였다.Using the test piece cut into 50 mm x 50 mm, 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.
7) 난연성 측정방법7) Flame retardancy measurement method
UL-94 방법에 의해 측정하였다.It measured by the UL-94 method.
표 2
TABLE 2
Tg | 난연성(UL-94) | 박리 강도(N/㎜) | 겹간 접착력(N/㎜) | 흡습률(wt%) | |
실시예 1 | 165.1 | V-0 | 1.48 | 1.08 | 0.57 |
실시예 2 | 170.1 | V-0 | 1.52 | 1.05 | 0.56 |
실시예 3 | 168.7 | V-0 | 1.45 | 1.02 | 0.58 |
실시예 4 | 169.1 | V-0 | 1.43 | 1.01 | 0.57 |
실시예 5 | 163.5 | V-0 | 1.42 | 1.04 | 0.60 |
실시예 6 | 175.4 | V-0 | 1.45 | 1.06 | 0.59 |
실시예 7 | 177.1 | V-0 | 1.43 | 1.02 | 0.53 |
실시예 8 | 168.3 | V-0 | 1.42 | 1.04 | 0.59 |
실시예 9 | 167.4 | V-0 | 1.42 | 1.05 | 0.59 |
실시예 10 | 166.1 | V-0 | 1.43 | 1.04 | 0.57 |
비교예 1 | 141.2 | V-0 | 1.38 | 0.99 | 0.68 |
비교예 2 | 149.2 | V-0 | 1.41 | 1.01 | 0.65 |
Tg | Flame Retardant (UL-94) | Peel Strength (N / mm) | Double adhesive force (N / mm) | Hygroscopicity (wt%) | |
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 |
상기 표 2에서 보는 바와 같이, 실시예 1 내지 11은 인 함량이 높아 적은 양으로 난연특성을 발휘 할 수 있고, 경화반응에 참여하여, 수지내 벤젤링과 -OH기가 많기 때문에 내열성 및 접차력의 효과가 있음을 알 수 있었다. 그러나 비교예 1 및 2는 실시예에 비해 많은 양의 P 변성 에폭시 수지가 들어가기 때문에 물성이 저하하는 문제가 있음을 알 수 있다.As shown in Table 2, 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.
본 발명은 난연성 에폭시 수지, 이의 제조방법 및 이를 포함하는 난연성 에폭시 수지 조성물에 이용될 수 있다. 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.
Claims (20)
- 하기 화학식 1로 표시되는 화합물을 포함하는 난연성 에폭시 수지.Flame retardant epoxy resin containing a compound represented by the formula (1).<화학식 1><Formula 1>(상기 식에서, X1은 하기 화학식 2 내지 11로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1 내지 10이고, m은 0 내지 10이고, n은 1 내지 10의 정수이다.)Wherein 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, and n is 1 to 10 Is an integer.)<화학식 2><Formula 2><화학식 3><Formula 3><화학식 4><Formula 4><화학식 5><Formula 5><화학식 6><Formula 6><화학식 7><Formula 7><화학식 8><Formula 8><화학식 9><Formula 9><화학식 10><Formula 10><화학식 11><Formula 11><화학식 12><Formula 12>
- 제1항에 있어서, 상기 화학식 1로 표시되는 화합물은 인 함량이 6 내지 8질량%인 것을 특징으로 하는 난연성 에폭시 수지 화합물.The flame retardant epoxy resin compound according to claim 1, wherein the compound represented by Chemical Formula 1 has a phosphorus content of 6 to 8% by mass.
- 제1항에 있어서, 상기 화학식 1로 표시되는 화합물은 유리전이온도가 150 내지 190℃인 것을 특징으로 하는 난연성 에폭시 수지 화합물.The flame retardant epoxy resin compound according to claim 1, wherein the compound represented by Chemical Formula 1 has a glass transition temperature of 150 to 190 ° C.
- 제1항에 있어서, 상기 화학식 1로 표시되는 화합물은 중량평균분자량이 500 내지 1500g/mol인 것을 특징으로 하는 난연성 에폭시 수지 화합물.The flame-retardant epoxy resin compound according to claim 1, wherein the compound represented by Chemical Formula 1 has a weight average molecular weight of 500 to 1500 g / mol.
- 제1항에 있어서, 상기 화학식 1로 표시되는 화합물은 에폭시 당량이 350 내지 500g/eq인 것을 특징으로 하는 난연성 에폭시 수지 화합물.The flame retardant epoxy resin compound according to claim 1, wherein the compound represented by Chemical Formula 1 has an epoxy equivalent weight of 350 to 500 g / eq.
- 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 반응시켜 중간체 화합물을 제조하는 단계(S1); 및 Preparing an intermediate compound by reacting a hydroquinone compound containing a phosphorus (P) atom with a chlorohydrin compound (S1); And상기 제조된 중간체 화합물에 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 및 페닐계 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물을 첨가하여 반응시키는 단계(S2)를 포함하는 난연성 에폭시 수지의 제조방법.Method for producing a flame-retardant epoxy resin comprising the step (S2) of the intermediate compound prepared by adding a compound selected from a phosphorus compound or a bisphenol compound and a phenyl compound or a mixture of two or more selected from them.
- 제6항에 있어서, 상기 S1 단계에서 상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물은 클로로히드린계 화합물 대비 1/6 내지 1/2의 몰비로 첨가하여 반응시키는 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The method of claim 6, wherein the hydroquinone compound containing the phosphorus (P) atom in the step S1 is characterized in that the reaction by adding in a molar ratio of 1/6 to 1/2 to the chlorohydrin-based compound A method for producing a flame retardant epoxy resin compound.
- 제6항에 있어서, 상기 S1 단계에서 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 반응시킨 후, 염층을 제거하고 100 내지 200℃의 온도에서 미반응물인 클로로히드린계 화합물 및 수분을 제거하는 탈기공정을 100 내지 760torr의 감압상태에서 실시하는 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The method of claim 6, wherein after reacting a hydroquinone compound containing a phosphorus (P) atom and a chlorohydrin compound in the step S1, the salt layer is removed and the unreacted material at a temperature of 100 to 200 ℃ A method for producing a flame retardant epoxy resin compound, characterized in that the degassing step of removing the chlorohydrin compound and water is carried out at a reduced pressure of 100 to 760 torr.
- 제8항에 있어서, 상기 탈기 공정 전에, 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물과 클로로히드린계 화합물을 50 내지 80℃의 온도로 유지하면서 2 내지 24시간 동안 1차 숙성을 시킨 후, 100 내지 760torr의 감압상태에서 50 내지 100℃의 온도로 유지하면서 10분 내지 4시간 동안 2차 숙성을 실시하는 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The method of claim 8, wherein before the degassing process, the hydroquinone compound and the chlorohydrin compound containing a phosphorus (P) atom is first aged for 2 to 24 hours while maintaining at a temperature of 50 to 80 ℃ After the step, while maintaining a temperature of 50 to 100 ℃ in a reduced pressure of 100 to 760 torr, secondary aging for 10 minutes to 4 hours, the method for producing a flame-retardant epoxy resin compound.
- 제8항에 있어서, 상기 탈기공정 후, 염소이온을 제거하고 산으로 중화시키는 단계를 실시하는 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The method for preparing a flame retardant epoxy resin compound according to claim 8, wherein after the degassing step, a step of removing chlorine ions and neutralizing with an acid is performed.
- 제6항에 있어서, 상기 S1 단계에서 상기 인(P) 원자를 포함하는 하이드로퀴논(hydroquinone)계 화합물은 디페닐포스피닐하이드로-퀴논(Diphenylphosphinyl hydro-quinone)인 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The flame retardant epoxy resin compound of claim 6, wherein the hydroquinone compound including the phosphorus (P) atom in step S1 is diphenylphosphinyl hydro-quinone. Manufacturing method.
- 제6항에 있어서, 상기 S1 단계에서 상기 클로로히드린계 화합물은 에피클로로하이드린, 에피요오드히드린, 에피브로모히드린, 메틸에틸브로모히드린 및 메틸에틸요오드히드린 중에서 선택되는 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The method of claim 6, wherein the chlorohydrin compound in the step S1 is characterized in that it is selected from epichlorohydrin, epiiod hydrin, epibromohydrin, methyl ethyl bromohydrin and methyl ethyl iodine hydrin Method for producing a flame retardant epoxy resin compound.
- 제6항에 있어서, 상기 S2 단계에서 상기 중간체 화합물 100중량부에 대하여 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물을 0.1 내지 100중량부로 첨가하여 반응시키는 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The method according to claim 6, wherein in step S2, 0.1 to 100 parts by weight of a compound selected from phosphorus compounds or bisphenol compounds or a mixture of two or more selected from these compounds is added to 100 parts by weight of the intermediate compound to react. Method for producing a flame retardant epoxy resin compound.
- 제6항에 있어서, 상기 S2 단계에서 페닐계 화합물인 촉매를 인계 화합물 또는 비스페놀계 화합물 중에서 선택된 일종의 화합물 또는 이들 중에서 선택된 2종 이상의 혼합물 100중량부에 대하여 0.01 내지 5중량부의 함량으로 첨가시키는 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The method according to claim 6, wherein in step S2, a 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 manufacturing method of the flame-retardant epoxy resin compound made into.
- 제6항에 있어서, 상기 S2 단계에서 상기 인계 화합물은 10-(2',5'-Dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;DOPO-HQ) 및 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphsophorin-6-yl)-1,4-naphthalenediol (DOPO-NQ) 중에서 선택되는 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The method of claim 6, wherein in the step S2, 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) A method for producing a flame-retardant epoxy resin compound, characterized in that selected from .
- 제6항에 있어서, 상기 S2 단계에서 상기 비스페놀계 화합물은 비스페놀 A, 비스페놀 F, 비스페놀 Z, 비스페놀-TMC, 비스페놀 AP, 비스페놀 BP, 비스페놀 B, 비스페놀 C 및 비스페놀 E 중에서 선택되는 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The flame retardant according to claim 6, wherein the bisphenol compound is selected from bisphenol A, bisphenol F, bisphenol Z, bisphenol-TMC, bisphenol AP, bisphenol BP, bisphenol B, bisphenol C and bisphenol E in the step S2. Method for producing an epoxy resin compound.
- 제6항에 있어서, 상기 S2 단계에서 상기 페닐계 화합물은 에티트리페닐포스포늄아이오다이드(Ethytriphenylphosphonium Iodide, ETPPI), 2-메틸이미다졸(2-Methylimidazole)(2MI), 2-에틸-4-메틸 이미다졸(2-ethyl-4-methyl imidazole)(2E4MZ) 및 2-페닐이미다졸(2-phenylimidazole, 2PI) 중에서 선택되는 것을 특징으로 하는 난연성 에폭시 수지 화합물의 제조방법.The method of claim 6, wherein the phenyl compound in the step S2 is Ethytriphenylphosphonium Iodide (Ethytriphenylphosphonium Iodide, ETPPI), 2-methylimidazole (2MI), 2-ethyl-4 A method for producing a flame retardant epoxy resin compound, characterized in that it is selected from 2-methyl-4-methyl imidazole (2E4MZ) and 2-phenylimidazole (2PI).
- 하기 화학식 1로 표시되는 화합물, 경화제 및 경화촉진제를 포함하는 난연성 에폭시 수지 조성물. Flame retardant epoxy resin composition comprising a compound represented by the formula (1), a curing agent and a curing accelerator.<화학식 1><Formula 1>(상기 식에서, X1은 하기 화학식 2 내지 11로 표시되는 화합물이고, X2는 하기 화학식 12로 표시되는 화합물이고, l은 1 내지 10이고, m은 0 내지 10이고, n은 1 내지 10의 정수이다.)Wherein 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, and n is 1 to 10 Is an integer.)<화학식 2><Formula 2><화학식 3><Formula 3><화학식 4><Formula 4><화학식 5><Formula 5><화학식 6><Formula 6><화학식 7><Formula 7><화학식 8><Formula 8><화학식 9><Formula 9><화학식 10><Formula 10><화학식 11><Formula 11><화학식 12><Formula 12>
- 제18항에 있어서, 상기 화학식 1로 표시되는 화합물 100중량부에 대하여 경화제 0.1 내지 50중량부 및 경화촉진제 0.0001 내지 0.05중량부를 포함하는 난연성 에폭시 수지 조성물. The flame-retardant epoxy resin composition according to claim 18, comprising 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 Formula 1.
- 제18항에 있어서, 상기 화학식 1로 표시되는 화합물은 제6항 내지 제17항 중 어느 한 항에 따라 제조된 것을 특징으로 하는 난연성 에폭시 수지 조성물. The flame-retardant epoxy resin composition of claim 18, wherein the compound represented by Chemical Formula 1 is prepared according to any one of claims 6 to 17.
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US7064157B2 (en) * | 2000-07-19 | 2006-06-20 | Chang Chun Plastics Co., Ltd. | Flame retardant resin and flame retardant composition containing the same |
WO2009064707A1 (en) * | 2007-11-15 | 2009-05-22 | Dow Global Technologies Inc. | Process for preparing advanced epoxi resins |
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