TWI402307B - Corrosion resistance and transparency of epoxy resin composition and its preparation method - Google Patents

Description

Epoxy resin composition with flame resistance and transparency and preparation method thereof

The invention relates to an epoxy resin composition, in particular to an epoxy resin composition having flame resistance and transparency and a preparation method thereof.

Because the general polymer material is easy to burn and the burning speed is quite fast, when the fire occurs, the burning of the polymer material is often an important factor that the fire cannot be controlled. Therefore, foreign countries have formulated the material's flame resistance regulations for the polymer material. Although there is no mandatory regulation in China, the function of flame retardant and self-extinguishing is one of the key developments of polymer synthetic materials based on the protection of life and property safety, especially in the aviation, electromechanical, electronics and coating industries. The polymer materials used should have a certain degree of flame resistance.

Among them, epoxy resin is widely used in coatings because of its low shrinkage, excellent mechanical properties, excellent chemical resistance, corrosion resistance, thermal stability and good electrical insulation. Electrical insulation materials, printed circuit laminates, electronic packaging and other applications. The existing methods for improving the flame resistance of epoxy resins mainly include adding various flame retardants to the epoxy resin, and the flame retardant may include a bromine-based flame retardant, a phosphorus-based flame retardant, and an inorganic (phosphorus/phosphorus) system. Compounds, etc. However, the addition of a bromine-based flame retardant reduces the crack resistance of the epoxy resin, and the processability of the epoxy resin is poor, and the bromine-based flame retardant may generate toxic fumes when burned, so some countries such as the European Union have The use of halogen flame retardants is restricted by laws and regulations; the addition of phosphorus-based flame retardants increases the brittleness of epoxy resins, resulting in processing difficulties, and the amount of additives is higher than that of brominated flame retardants, due to the need for the above two flame retardants. Adding to a certain amount has sufficient flame retardant effect, and thus tends to cause a decrease in transparency of the epoxy resin. Inorganic (yttrium/phosphorus) compounds are added to the epoxy resin in the order of millimeter, micron or submicron particle size, and the opaque phenomenon of the epoxy resin is also caused by the larger particles.

In view of the existing method of adding a flame retardant to improve the flame resistance of the epoxy resin, the transparency of the epoxy resin is often lowered, and an object of the present invention is to provide an epoxy resin composition having flame resistance and transparency, which can make the ring Oxygen resin retains the flame retardancy while maintaining the transparency of the epoxy resin.

In order to achieve the above object, the flame resistant and transparent epoxy resin composition of the present invention comprises: a hardenable epoxy resin; and a flame resistant inorganic oxide particle uniformly dispersed in the epoxy resin and The particle size is not more than 300 nanometers (nm), and the flame resistant inorganic oxide particles are hydrolyzed and condensed by a metal alkoxide precursor of the flame resistant inorganic oxide by a sol-gel technique. (In-situ) growth preparation of flame resistant inorganic oxide particles in an epoxy resin; and a hardener reactive with an epoxy resin.

Preferably, the flame resistant inorganic oxide is selected from at least one of the group consisting of cerium oxide, cerium oxide, phosphorus oxide and magnesium oxide.

Preferably, the particle size of the flame resistant inorganic oxide particles is not more than 200 nm.

Preferably, the weight ratio of the metal of the flame resistant inorganic oxide to the hardened epoxy resin coating film or block is from 0.2 to 12% by weight.

Another object of the present invention is to provide a method for producing the above-mentioned flame retardant and transparent epoxy resin composition, which comprises the steps of providing one or more epoxy resin solutions: each epoxy resin solution can be hardened. The epoxy resin is uniformly dissolved in the solvent; the flame resistant inorganic oxide particles are prepared by the hydrolysis condensation reaction: one or more metal alkoxy precursors are uniformly dissolved in the solvent to form one or more metal alkoxide precursor solutions, and then Adding water to each metal alkoxide precursor solution and stirring uniformly, and adjusting the pH of each metal alkoxide precursor solution to 2~4 or 8-10, so that the metal alkoxy precursor is subjected to hydrolysis condensation reaction and Producing flame resistant inorganic oxide particles; preferably, the hydrolysis condensation time is 10 to 90 minutes; preferably, the weight ratio of water to metal alkoxy precursor is between 0.005:1 and 3:1; In the metal alkoxide precursor solution, the ratio of the solvent to the metal alkoxide precursor is from 0.1:1 to 20:1; the metal alkoxide precursor is selected from at least one of the group consisting of: alkane oxygen Compound, phosphorus alkoxide, decane oxide and magnesium alkoxide; providing a hardener; mixing solution and hardener: mixing each epoxy resin solution, each precursor solution and hardener and stirring uniformly to form a mixed solution The mixed solution may be directly formed into a coating film; or the mixed solution may be removed from the solvent to form a bulk material.

Specific achievable effects of the present invention include: 1. The invention adopts a sol-gel technique to hydrolyze and condense a metal alkoxy precursor, and in-situ growth to prepare flame-resistant inorganic oxide particles in an epoxy resin, due to a sol-gel method. The infiltration method is a molecular level, so the flame-resistant inorganic oxide particles are uniformly dispersed in the epoxy resin, and nano-grade flame-resistant inorganic oxide particles having a uniform particle size can be obtained, so that it is not necessary to add a large amount of flame-resistant inorganic oxide particles. The epoxy resin composition can be made to have a flame resistance effect.

2. The flame-resistant inorganic oxide particles prepared in the epoxy resin of the invention are nanometer-sized particle size, so when the light enters the epoxy resin, the phenomenon of refraction and diffraction is not easily generated, and the appearance of the epoxy resin is still clarified. It is transparent, that is, the composition of the present invention has both flame resistance and transparency.

A preferred embodiment of the composition of the present invention comprises a hardenable epoxy resin, a hardener reactive with an epoxy resin and a flame resistant inorganic oxide particle, wherein the epoxy resin is not subjected to a bridging reaction. A hardenable epoxy resin material selected from the group consisting of at least one of the following materials: (1) an epoxy resin of a diepoxy group, such as diglycidyl ortho- ( Phthalate), diglycidyl ether of bisphenol A (Bis-A), diglycidyl ether of bisphenol F (Bis-F), cyclized aliphatic epoxy resin (eg 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate); (2) epoxy resin of tricyclooxy group, such as triglycidyl-p-aminophenol; (3) epoxy resin of polyepoxy group, such as tetraglycidyl A group of tetraglycidylmethylene-dianiline, glycidyl ether of novolac, epoxy cresol novolac, and derivatives thereof. The appearance can be a liquid epoxy resin, a high viscosity epoxy resin, and a solid epoxy resin. These epoxy resins include alkyl-containing epoxy resins, aromatic ring-based epoxy resins, polyaromatic ring-based epoxy resins, aromatic rings and alkyl-bonded epoxy resins, and phosphorus atom-containing epoxy resins. An epoxy resin containing a sulfur atom group and a derivative thereof.

Preferably, the epoxy resin is a liquid epoxy resin of a diepoxy group, such as diglycidyl ortho-phthalate, diglycidyl ether of bisphenol A (dilycidyl ether of bisphenol A, Bis-A), diglycidyl ether of bisphenol F (Bis-F), cyclized aliphatic epoxy resin (such as 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane-carboxylate).

The flame-resistant inorganic oxide particles are uniformly dispersed in an epoxy resin and have a particle diameter of not more than 300 nanometers (nm), and the flame-resistant inorganic oxide particles are a metal alkoxy precursor by a sol-gel technique. Hydrolysis condensation, in-situ growth, preparation of flame resistant inorganic oxide particles in an epoxy resin; in the preferred embodiment, the flame resistant inorganic oxide is selected from at least one of the group consisting of the following materials; : cerium oxide, cerium oxide, phosphorus oxide and magnesium oxide; preferably, the flame resistant inorganic oxide has a particle size of not more than 200 nm; preferably, the metal of the flame resistant inorganic oxide, such as cerium oxide The weight ratio of cerium to magnesium oxide of magnesium oxide or the like to the hardened epoxy resin composition is from 0.2% by weight to 12% by weight.

The hardener is mixed with the epoxy resin to cause a bridging reaction of the epoxy resin to cause hardening; it may be selected from at least one of the following groups: (1) diamines or polyamines. Classes such as ethylenediamine, m-diminated benzene, polyethylenimide (PEI); (2) glycols or polyols such as ethylene glycol, trimellitic acid ethanol, polysulfide An alcohol or the like; (3) a polybasic acid or an acid anhydride such as methyltetrahydrofurfuric anhydride, and a group of the foregoing derivatives.

Preferably, the hardener is a liquid amine hardener such as Polyethylenimide (PEI).

A preferred embodiment of the method for forming a composition of the present invention comprises the steps of providing one or more epoxy resin solutions: each epoxy resin solution is formed by uniformly dissolving a hardenable epoxy resin in a solvent, wherein the epoxy resin is formed. It is a hardenable epoxy resin which is not bridged, and is selected from at least one of the following materials: (1) a epoxy group of a diepoxide group, such as diglycidyl ortho-benzene. Dilycyldyl ortho-phthalate, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F; (2) epoxy resin of tricyclooxy group, Such as triglycidyl-p-aminophenol; (3) polyepoxy group epoxy resin, such as tetraglycidylmethylene-dianiline, glycolic glycoether (glycidyl ether of novolac), epoxy cresol novolac (epoxy cresol novolac), a group of derivatives thereof. The appearance can be a liquid epoxy resin, a high viscosity epoxy resin, and a solid epoxy resin. These epoxy resins include alkyl-containing epoxy resins, aromatic ring-based epoxy resins, polyaromatic ring-based epoxy resins, aromatic rings and alkyl-bonded epoxy resins, and phosphorus atom-containing epoxy resins. An epoxy resin containing a sulfur atom group, and a derivative thereof. The solvent of the epoxy resin solution may be acetone (acetone), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), acetyl acetone, AcAc. ), dimethyl sulfoxide (DMSO), dimethyl furan (DMF), tetrahydrofuran (THF), N-methylformamide (NMF) or acetic acid (acetic) Acid) and so on. Preferably, the solvent of the epoxy resin solution is acetone (acetone), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK); and flammability condensation reaction is used to prepare flame resistance. Inorganic oxide particles: one or more metal alkoxy precursors are uniformly dissolved in a solvent to form one or more metal alkoxide precursor solutions, and then water is added to each metal alkoxy precursor solution and stirred uniformly, and Adjusting the pH of each metal alkoxide precursor solution to 2~4 or 8~10, so that the metal alkoxy precursor is subjected to hydrolysis condensation reaction and producing flame resistant inorganic oxide particles; wherein the metal alkoxy precursor is optional At least one of the group consisting of: a decane oxide, a phosphorus alkoxide, a decane oxide, and a magnesium alkoxide, wherein the decane oxide may be ruthenium (III) oxide (Antimony ( III) ethoxide, Sb(OEt) ₃ ), antimony (III) acetate, Sb(OAc) ₃ , and the phosphoal alkoxide may be Triethyl phosphate (TEP). The decane oxide system may be methyl trimethyl decane (M Ethyltrimethoxysilane (MTMOS), Methyltriethoxysilane (MTEOS), tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), 3-glycidylpropane trimethyl decane (3-Glycidoxypropyl) Trimethoxysilane, GPOS), the magnesium alkoxide system may be Magnesium ethoxide (Mg(OEt) ₂ ); the solvent of each metal alkoxy precursor solution may be water, acetone, methyl Isobutyl ketone (MIBK), methyl ethyl ketone (MEK), acetyl acetone (AcAc), dimethyl sulfoxide (DMSO), dimethyl Dimethyl furan (DMF), tetrahydrofuran (THF), N-methylformamide (NMF) or acetic acid. Preferably, the solvent of the metal alkoxide precursor solution is water and acetone, tetrahydrofuran (THF), acetyl acetone (AcAc); preferably, water and metal alkane The weight ratio of the oxygen precursor is between 0.005:1 and 3:1, and the weight ratio of the solvent to the metal alkoxide precursor is 0.1:1 to 20:1 in each metal alkoxide precursor solution; The alkoxy precursor solution solution is adjusted by adding hydrochloric acid or triethylamine (Et ₃ N); preferably, the hydrolysis condensation time is 10 to 90 minutes; providing a hardener; mixing the solution and hardening Agent: mixing each epoxy resin solution, each precursor solution and hardener and stirring uniformly to form a mixed solution, which can be directly formed into a coating film; or the mixed solution is removed from the solvent to form a block The solvent is removed by heating the mixed solution to 50-80 ° C and vacuuming for 0.5-6 hours to remove the solvent, and the mixed solution can be further evacuated for 1 to 40 minutes to remove bubbles, and the mixed solution is heated to 80. ~120 ° C for 1 to 6 hours for hardening reaction; The preferred embodiment is a sol-gel technique for hydrolytic condensation of a metal alkoxy precursor, in-situ growth to prepare flame-resistant inorganic oxide particles in an epoxy resin, due to sol-gel The method of infiltration of the method is a molecular level, which is not a general physical infiltration, so that phase separation is less likely to occur, and nano-scale flame-resistant inorganic oxide particles having a uniform particle size can be obtained. Since the flame resistant inorganic oxide particles are uniformly dispersed in the epoxy resin, the flame resistant inorganic oxide particles do not require a large amount of addition to make the epoxy resin have a flame resistance effect. In addition, since the flame resistant inorganic oxide particles are of a nanometer size, when the light enters the epoxy resin, the phenomenon of refraction and diffraction is less likely to occur, so that the appearance of the epoxy resin is clear and transparent, that is, the epoxy The resin composition has both flame resistance and transparency.

The following examples are intended to illustrate the invention in detail. These examples are not intended to limit the scope of the invention in any way, but are intended to indicate how to practice the combinations of materials of the invention.

Example 1 Production of an epoxy resin containing inorganic cerium oxide (Sb _x O _y ) particles

Mix acetylacetone (AcAc) with ruthenium(III) oxide (Antimony(III) ethoxide, Sb(OEt) ₃ ) and stir at room temperature for 12 hours, then add a little water. Hydrolysis condensation reaction (weight ratio AcAc:Sb(OEt) ₃ :H ₂ O=5:1:0.03) can be generated by different hydrolysis condensation time (three samples are respectively 40 minutes, 60 minutes, 90 minutes) Different quantities and sizes of inorganic cerium oxide (Sb _x O _y ) particles. The above ruthenium-containing solution was added to an epoxy resin (Bis-A) solution (weight ratio Bis-A: AcAc = 2.5:1), stirred at room temperature for 30 minutes, and vacuumed at 85 ° C for 4 hours to remove the solvent. . After cooling to room temperature, add 20 phr of hardener (PEI) (for Bis-A of 100 phr (partial)), stir for 10 minutes, then pour into the mold and evacuate for 10 minutes to remove the bubbles, followed by three samples. The epoxy resin composite material (EPA-Sb(OEt) ₃ ) containing flame resistant inorganic cerium oxide particles can be obtained by performing a hardening reaction at 80 ° C, 110 ° C, and 120 ° C for 1 hour, 1 hour, and 2 hours, respectively. The material contains 6 wt% of the flame resistant component 锑.

Another commercially available Sb, Sb ₂ O ₃ and Sb ₂ O ₅ powders were mixed with epoxy resin (Bis-A) by mechanical stirring, and then added with a hardener (PEI) of 20 phr (with Bis-A of 100 phr ( Partially) After stirring for 10 minutes, it was poured into a mold and evacuated for 20 minutes to drive out the bubbles, followed by hardening reactions at 80 ° C, 110 ° C and 120 ° C for 1 hour, 1 hour and 2 hours, respectively. At this time, each material contains 6 wt% of the flame resistant component 锑, and then a sample of the composite material obtained by mechanical infiltration (EPA-Sb, EPA-Sb ₂ O ₃ , EPA-Sb ₂ O ₅ ) and the sample obtained by the above method and The pure epoxy cured product (EPA) containing no metal oxides tested its flame resistance and light penetration. The test results are shown in Table 1 below.

From the above test results, samples prepared by infiltration of solid metal oxides or metal powders (Sb, Sb ₂ O ₃ and Sb ₂ O ₅ powders) (EPA-Sb, EPA-Sb ₂ O ₃ , EPA-Sb) ₂ O ₅ ) all have an opaque appearance, while the samples prepared by the method of the first embodiment are transparent in appearance, and the penetration is comparable to that of the pure EPA material, and the minimum oxygen index (Limited oxygen index, The LOI) is also higher than the pure EPA material, indicating that it has high flame resistance, and since the material having an LOI value of more than 28 is a flame resistant material, the sample of the present embodiment has remarkable flame resistance.

Example 2: Preparation of epoxy resin containing inorganic phosphorus oxide (P _x O _y ) particles

Mix acetone (Acetone) with Triethyl phosphate (TEP) (weight ratio Acetone: TEP = 40:100), and then add a quantitative amount of ultrapure water (molar ratio is water: TEP = 2.5:1) And adjust the pH of the solution to 2 with hydrochloric acid, stir different hydrolysis condensation time at room temperature (three samples are 40 minutes, 60 minutes, 90 minutes respectively) to carry out hydrolysis condensation reaction, which can produce different amounts and sizes of inorganic Phosphorus oxide (P _x O _y ) particles. The above phosphorus-containing solution was added to an epoxy resin (Bis-A) solution (weight ratio Bis-A: Acetone = 2.5:1), and stirred at room temperature for 30 minutes to continue the hydrolysis condensation reaction. Vacuum was then applied at 85 ° C for 4 hours to remove the solvent. After cooling to room temperature, adding 20 phr of hardener (PEI) (for Bis-A of 100 phr (partial)), stirring for 10 minutes, pouring into the mold and then vacuuming for 20 minutes to remove the bubbles, then the three samples were respectively The epoxy resin composite material (EPA-6P) containing flame-resistant inorganic phosphorus oxide particles can be obtained by performing a hardening reaction at 80 ° C, 110 ° C and 120 ° C for 1 hour, 1 hour and 2 hours, in which the material contains 6 wt. % of the flame resistant component of phosphorus. The samples obtained by the above method and the pure EPA were then tested for their flame resistance and light penetration. The test results are shown in Table 2 below.

From the above test results, the samples prepared by the method of the second embodiment are transparent in appearance, and the penetration degree is also comparable to that of the pure EPA material, and the LOI value thereof is higher than that of the pure EPA material, and is greater than 28, showing It has significant flame resistance.

Example 3: Preparation of epoxy resin containing inorganic cerium oxide (Si _x O _y ) particles

Mix acetone (Acetone) with 3-Glycidoxypropyl trimethoxysilane (GPOS) (weight ratio Acetone: GPOS = 40:100), and add a quantification of ultrapure water (mole ratio water: GPOS=2:1), and adjust the pH of the solution to 2 with hydrochloric acid, and stir the different hydrolysis condensation time (three samples are 40 minutes, 60 minutes, 90 minutes respectively) at room temperature to carry out hydrolysis condensation reaction, which can be generated. Different quantities and sizes of inorganic cerium oxide (Si _x O _y ) particles. The above ruthenium-containing solution was added to an epoxy resin (Bis-A) solution (weight ratio Bis-A: Acetone = 2.5:1) and stirred at room temperature for 30 minutes to continue the hydrolysis condensation reaction. Vacuum was then applied at 85 ° C for 4 hours to remove the solvent. After cooling to room temperature, adding 20 phr of hardener (PEI) (for Bis-A of 100 phr (partial)), stirring for 10 minutes, pouring into the mold and then vacuuming for 20 minutes to remove the bubbles, then the three samples were respectively The epoxy resin composite material (Bis-A-6Si) containing flame-resistant inorganic cerium oxide particles can be obtained by performing a hardening reaction at 80 ° C, 110 ° C and 120 ° C for 1 hour, 1 hour and 2 hours. Contains 6wt% bismuth. The samples obtained by the above method and the pure Bis-A were tested for their flame resistance and light transmittance. The test results are shown in Table 3 below.

From the above test results, the samples prepared by the method of the third embodiment are all transparent, and the penetration is also comparable to that of the pure EPA material, and the LOI value is higher than that of the pure EPA material, and is greater than 28, showing It has significant flame resistance.

Example 4: Preparation of an epoxy resin containing both inorganic cerium oxide (Sb _x O _y ) particles and inorganic phosphorus oxide (P _x O _y ) particles

Ethyl ruthenium (III) (Antimony (III) acetate, Sb (OAc) ₃ ) was heated to 60 ° C with glacial acetic acid (weight ratio Sb (OAc) ₃ : glacial acetic acid = 1:5) to dissolve, and then added B The acetonylacetone (AcAc) and water (weight ratio AcAc:Sb(OAc) ₃ :H ₂ O=5:1:0.01) were stirred for 90 minutes. On the other hand, Triethyl phosphate (TEP) and water (molar ratio H ₂ O: TEP = 2:1) were mixed in AcAc (weight ratio AcAc: TEP = 40:100), and then The pH of the solution was adjusted with hydrochloric acid so that the pH was 2 and uniformly stirred for 90 min. After the hydrolysis condensation time was 90 minutes, the two solutions were mixed with each other in the desired ratio and stirred at room temperature for 30 min. Subsequently, the mixture was added to an epoxy resin (Bis-A) (weight ratio Bis-A: AcAc = 2.5:1), and the solvent was removed by vacuuming at 85 ° C for 4 hr, and the hardener was added while cooling to room temperature. (PEI) 20 phr (for Bis-A as 100 phr (partial)) After stirring for 10 minutes, it was poured into a mold, and vacuum was removed for 20 minutes immediately, and the bubbles contained in the substrate were removed at 80 ° C, respectively. A hardening reaction at 110 ° C and 120 ° C for 1 hour, 1 hour and 2 hours provides a ring containing both flame resistant inorganic cerium oxide (Sb _x O _y ) particles and flame resistant inorganic phosphorus oxide (P _x O _y ) particles. Oxygen resin composite (E-3Sb(OAc) ₃ -3P, E-5Sb(OAc) ₃ -1P). The sample obtained by the above method and the sample containing only one kind of flame resistant inorganic particles were tested for flame resistance and light transmittance with pure EPA. The test results are shown in Table 4 below.

Table 4, flame resistance and penetration of each sample

From the above test results, the samples prepared by the method of the fourth embodiment are all transparent, and the penetration is also comparable to that of the pure EPA material, and the LOI value is higher than that of the pure EPA material, and is greater than 28, showing At the same time, inorganic cerium oxide (Sb _x O _y ) particles and inorganic phosphorus oxide (P _x O _y ) particles have significant flame resistance.

Example 5: Preparation of an epoxy resin containing both inorganic cerium oxide (Sb _x O _y ) particles and inorganic cerium oxide (Si _x O _y ) particles

Ethyl ruthenium (III) (Antimony (III) acetate, Sb (OAc) ₃ ) was heated to 60 ° C with glacial acetic acid (weight ratio Sb (OAc) ₃ : glacial acetic acid = 1:5) to dissolve, and then added B The acetonylacetone (AcAc) and water (weight ratio AcAc:Sb(OAc) ₃ :H ₂ O=5:1:0.01) were stirred for 90 minutes. On the other hand, 3-Glycidoxypropyl trimethoxysilane (GPOS) and water (molar ratio H ₂ O: GPOS = 2:1) were mixed in AcAc (weight ratio AcAc: GPOS = 40:100), adjust the pH of the solution with hydrochloric acid to make the pH 2 and stir evenly for 90 min. After the hydrolysis condensation time was 90 minutes, the two solutions were mixed with each other in the desired ratio and stirred at room temperature for 30 min. The mixture was then added to the resin (weight ratio Bis-A: AcAc = 2.5:1), the solvent was removed by vacuuming at 85 ° C for 4 hr, and 20 phr of hardener (PEI) was added to cool to room temperature. Bis-A is 100 phr (partially). After stirring for 10 minutes, it is poured into the mold, and the air bubbles contained in the substrate are removed by vacuuming for 20 minutes, respectively, at 80 ° C, 110 ° C and 120 ° C. 1 hour, 1 hour and 2 hours hardening reaction, epoxy resin composite material containing flame resistant inorganic cerium oxide (Sb _x O _y ) particles and flame resistant inorganic cerium oxide (Si _x O _y ) particles (E- 3Sb(OAc) ₃ -3Si, E-5Sb(OAc) ₃ -1Si). Then, the samples obtained by the above method and the pure EPA were tested for their flame resistance and light transmittance, and the test results are shown in Table 5 below.

From the above test results, the samples prepared by the method of the fifth embodiment are all transparent, the penetration is comparable to that of the pure EPA material, and the LOI value is higher than that of the pure EPA material, and is greater than 28, showing At the same time, inorganic cerium oxide (Sb _x O _y ) particles and inorganic cerium oxide (Si _x O _y ) particles have significant flame resistance. Although the flame resistance of the epoxy resin composite containing inorganic cerium oxide (Si _x O _y ) particles alone does not increase much, even in the case of coexistence with inorganic cerium oxide (Sb _x O _y ) particles, even the same metal content When it is (6 wt% in this example), it shows excellent flame resistance, indicating that inorganic cerium oxide (Sb _x O _y ) particles and inorganic cerium oxide (Si _x O _y ) particles have synergistic effect. .

Claims (17)

An epoxy resin composition having flame resistance and transparency, comprising: a hardenable epoxy resin; and a flame resistant inorganic oxide particle uniformly dispersed in the epoxy resin and granules The diameter is not more than 300 nanometers (nm), and the flame resistant inorganic oxide particles are hydrolyzed and condensed by a sol-gel technique to a metal alkoxide precursor of the flame resistant inorganic oxide. In-situ) growing the flame resistant inorganic oxide particles in an epoxy resin; and a hardener reactive with the epoxy resin, wherein the flame resistant inorganic oxide comprises at least one selected from the group consisting of the following materials Materials: cerium oxide, phosphorus oxide and magnesium oxide, and the weight ratio of the metal of the flame resistant inorganic oxide to the epoxy resin composition is from 0.2 to 12% by weight. The flame retardant and transparent epoxy resin composition according to claim 1, wherein the flame resistant inorganic oxide further comprises a cerium oxide. An epoxy resin composition having flame resistance and transparency as described in claim 1 wherein the flame resistant inorganic oxide particles have a particle diameter of not more than 200 nm. An epoxy resin composition having flame resistance and transparency as described in claim 1, wherein the epoxy resin is selected from at least one selected from the group consisting of a ring of a diepoxide group. Oxygen resin, three An epoxy resin of an epoxy group and an epoxy resin of a polyepoxy group. An epoxy resin composition having flame resistance and transparency as described in claim 1 wherein the hardener is a liquid amine hardener. A method for preparing an epoxy resin composition having flame resistance and transparency, comprising the steps of: providing one or more epoxy resin solutions: each epoxy resin solution is such that the hardenable epoxy resin is uniformly dissolved in a solvent. Forming; using a hydrolysis condensation reaction to prepare a flame resistant inorganic oxide particle having a particle diameter of not more than 300 nm: uniformly dissolving more than one metal alkoxy precursor in a solvent to form one or more metal alkoxide precursor solutions, and then Water is added to each metal alkoxide precursor solution and stirred uniformly, and the pH of each metal alkoxide precursor solution is adjusted to 2 to 4 or 8 to 10 to cause hydrolysis and condensation reaction of the metal alkoxide precursor and generate Flame resistant inorganic oxide particles, wherein the metal alkoxy precursor comprises at least one material selected from the group consisting of decane oxides, phosphorus alkoxides, and magnesium alkoxides; providing a hardener; Mixing solution and hardener: mixing each epoxy resin solution, each precursor solution and hardener and stirring uniformly to form a mixed solution, wherein the flame resistant inorganic oxide The proportion of metal in the epoxy resin composition in a weight ratio from 0.2 ~ 12wt%. The method for producing an epoxy resin composition having flame resistance and transparency as described in claim 6 wherein the metal alkoxy precursor further comprises a decane oxide. The method for preparing an epoxy resin composition having flame resistance and transparency as described in claim 6 wherein the decane oxide is erbium ethoxide (III) (Antimony (III) ethoxide, Sb (OEt) ₃ ) or antimony (III) acetate, Sb(OAc) ₃ ; the phosphoal alkoxide is Triethyl phosphate (TEP); the magnesium alkoxide is ethoxylated Magnesium ethoxide (Mg(OEt) ₂ ). The method for preparing an epoxy resin composition having flame resistance and transparency as described in claim 7 wherein the decane oxide is Methyltrimethoxysilane (MTMOS) or methyltriethyl. Methyltriethoxysilane (MTEOS), tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) or 3-Glycidoxypropyl trimethoxysilane (GPOS). The method for preparing an epoxy resin composition having flame resistance and transparency as described in claim 6 wherein the solvent of each metal alkoxide precursor solution is water, acetone, methyl isobutyl ketone ( Methyl isobutyl ketone, MIBK), methyl ethyl ketone (MEK), acetyl acetone (AcAc), dimethyl sulfoxide (DMSO), dimethyl furan , DMF), tetrahydrofuran (THF), N-methylformamide (NMF) or acetic acid. The method for preparing an epoxy resin composition having flame resistance and transparency as described in claim 6 wherein when the flammable condensation reaction is used to prepare the flame resistant inorganic oxide particles, the weight ratio of the water to the metal alkoxy precursor is Between 0.005:1~3:1. The method for preparing an epoxy resin composition having flame resistance and transparency as described in claim 6 wherein, when the flammable condensation reaction is used to prepare the flame resistant inorganic oxide particles, the solvent and the metal alkoxide precursor solution are used. The weight ratio of the metal alkoxide precursor is from 0.1:1 to 20:1. The method for producing an epoxy resin composition having flame resistance and transparency as described in claim 6, wherein in the step of preparing the flame resistant inorganic oxide particles, the hydrolysis condensation time is 10 to 90 minutes. The method for producing an epoxy resin composition having flame resistance and transparency as described in claim 6 wherein the mixed solution is heated to 50 to 85 ° C and evacuated for 0.5 to 6 hours to remove the solvent. The method for producing an epoxy resin composition having flame resistance and transparency as described in claim 6 wherein the mixed solution is evacuated for 1 to 40 minutes to remove air bubbles. The method for preparing an epoxy resin composition having flame resistance and transparency as described in claim 14 or 15, wherein the mixed solution is heated to 80 to 120 ° C for 1 to 6 hours for hardening reaction. The method for preparing an epoxy resin composition having flame resistance and transparency as described in claim 6 wherein the solvent of the metal alkoxide precursor solution is water and acetone, tetrahydrofuran or acetonitrile.