KR20090092882A - Flame-retarding composition using waste powder of artificial marble and coal ash, and method of preparing the same - Google Patents

Abstract

A flame-retarding composition is provided to reduce processing costs of waste and to be environment-friendly by recycling artificial marble waste powder and coal ash, and to prepare non-toxic flame retardant product which is suitable for international environment standard. A flame-retarding composition comprises coal ash 0~120 phr, artificial marble waste powder 0~120 phr, ethylene vinylene aceta 0~20 phr, ammonium polyphosphate 0~7 phr and magnesium hydroxide 30~200 phr based on the polymer resin 100.0 phr. A method for manufacturing the flame-retarding composition comprises the steps of: (a) solution coating coal ash, artificial marble powder or combination thereof with a compatibilizer solution, drying and filtering the product; and (b) mixing the dried coal ash or artificial marble powder with a flame-retardant aid, compatibilizer and polymer resin.

Description

Flame-retarding composition using waste powder of artificial marble and coal ash, and method of preparing the same}

The present invention relates to a flame retardant composition using artificial marble waste powder and call ash and a method for producing the same. More specifically, the present invention relates to a flame retardant composition capable of recycling artificial marble waste powder and call ash, and a method of manufacturing the same.

A flame retardant is a material that is added to prevent burning by physicochemically improving the combustible property of a polymer material, that is, adding a compound having a high flame retardant effect such as halogen, phosphorus, nitrogen, and a metal hydroxide compound to the polymer material to slow ignition and It is a substance that prevents the expansion of combustion. These flame retardants should be well mixed with raw materials and additives, not affect the mechanical properties of the final product, and produce less fumes and toxic gases during combustion.

The flame retardant method of the polymer includes, firstly, the manufacture of heat-resistant polymers by modifying the molecular structure (CPE, PVC, etc.), second, chemically bonding the flame retardant components in the plastic structure (reactive flame retardant), and third, physically incorporating the flame retardant into the polymer. (Additional flame retardant), and fourth, and other flame retardant coating or painting, or to improve the heat resistance through a change in the design of the product, and the general flame retardant is mainly by the addition of flame retardant.

Recently, the development of new flame retardants has been made in the direction of environmental considerations, namely, environmental friendliness, which is causing a sharp change in flame retardants. In the past few years, research has focused on new methods of flame retardant and production of flame retardants that have added economic feasibility, but now, excellent physical properties, which are excluded from environmental friendliness, have caused useful value to be deteriorated. Development is taking place. The current social demand for flame retardants can be summarized as recycling, along with safety and disposal, and the scope of inquiring companies to take responsibility for social issues in the final disposal of products can be actively responded to environmental standards and regulations. It seems to be.

Therefore, it is necessary to pay attention to the current environmental regulations, flame retardant standards and regulations in Europe, and in particular, the European RoHS regulations, which entered into force in 2006, are international regulations that restrict the use of brominated flame retardants (PBBs, PBDEs), which are halogen flame retardants, in all electrical and electronic products. All companies involved in the production of electrical and electronic products in Korea have developed analytical technology to prepare for this, and are developing flame retardant technology that eliminates the use of halogen-based flame retardants.

The demand for flame retardant materials is increasing in various fields such as automobiles, building materials, ships, etc., starting with electric and electronic devices, and the requirements of the flame retardant materials are diversified.

First, the development of environmentally friendly non-halogen low smoke materials. Flame retardant materials are required to reduce the physical properties and processability and the development of flame retardant materials based on polyolefins to replace PVC has been actively conducted since the claim that toxic gas is emitted during the combustion of PVC. .

Second, the development of flame retardant materials with excellent heat resistance. Compared with the recent trend toward higher performance and miniaturization of products, the demand for heat resistance level is increasing, and it is urgent to develop a flame retardant material having excellent thermal stability. In particular, there is a high demand in the field of electric and electronic components.

Third is the development of flame retardant materials with multifunction. In addition to flame retardancy, there is a demand for development of materials having properties such as vibration damping, electrical properties, optical functionality, and antibacterial properties.

Fourth, the development of flame retardant materials with less molding processability and molding problems. It is required to develop a material with less problems such as corrosion, abrasion, and adhesion to facilities requiring fluidity in processing processes such as extrusion molding and injection molding.

Fifth, the development of flame retardant materials with excellent recycling. Increasing interest and concern for industrial waste has made it difficult to dispose of poorly burned materials, which is a challenge to be solved in the future.

Sixth, development of highly flame retardant materials. Research on flame retardant structure of polymer itself and application of flame retardant material of Nano Composite by developing high flame retardant material that can access inorganic material, and more effective char production capacity It is also expected to study the effective flame retardant.

On the other hand, due to environmental pollution and fire accidents resulting from technological development, various countries based on environment and stability have been revised and revised in accordance with advanced countries and other countries. Environmentally friendly and flame retardant properties are required in the polymer flame retardant technology, and therefore, in case of export or domestic demand, the relevant standards (ASTM, ISO, UL, KS, etc.) must be satisfied. In recent years, the necessity of flame retardant in consideration of safety in the event of a fire is continuously increasing, and as the environmental problem is raised, the necessity of developing a flame retardant technique considering the safety of the environment and the human body as well as a simple flame retardant effect is required.

The present invention was devised to meet the necessity of developing the above-described flame retardant technology, and an object of the present invention is to provide a flame retardant composition comprising coal ash or artificial marble waste powder.

Another object of the present invention is to modify the surface of the coal ash or artificial marble waste powder using a strong alkaline solution, a flame retardant composition which is mixed with a polymer resin and a flame retardant adjuvant after solution coating or melt coating with a compatibilizer solution To provide a method of manufacturing.

Another object of the present invention is to reduce the environmental pollution by recycling the waste ash of call ash or artificial marble that is disposed of, and to suppress the generation of toxic gas in the fire by using the flame-retardant polymer resin prepared by the manufacturing method of the present invention. To provide flame retardant building materials.

The present invention to achieve the above object is at least one of the coal ash (coal ash) and artificial marble powder; And it provides a flame retardant composition comprising a polymer resin.

First, the call ash and artificial marble powder which are the main components of the flame retardant composition of the present invention will be described.

'Artificial marble' used in the present invention contains cross-linked acrylic and about 60 to 65% of aluminum hydroxide (ATH, alumina trihydroxide), by a conventional method of manufacturing artificial marble (Artificial marble) It can be manufactured. Although the manufacturing method of such artificial marble is slightly different according to its specification, one example of the manufacturing method is representative of Du Pont's manufacturing method of artificial marble, in which 65% of ATH is added and vinyl or acrylic type is used. A manufacturing method using 20% of a resin dissolved in MMA (methyl methacrylate), using a peroxide azo compound, etc. as a crosslinking agent, and using phosphate esters (mono-, di-) as a coupling agent.

Aluminum hydroxide (ATH), the main component of artificial marble, produces water vapor (H ₂ O) by pyrolysis during combustion to lower the concentration of the combustion gas and to suppress combustion by lowering the temperature around the combustion point. Is inferred from the following chemical reaction.

Scheme 1

2 Al ( OH ) ₃ → Al ₂ O ₃  + 3 H ₂ O   -298 KJ Of mol

In addition, the small amount of phosphorus contained in the artificial marble powder increases the effect of the flame retardant together with aluminum hydroxide.

Therefore, the artificial marble powder containing aluminum hydroxide and phosphorus in the present invention serves as a flame retardant of the polymer compound.

On the other hand, the powder of artificial marble can be used as it is without processing what is generated during the disposal and grinding of artificial marble. In the present invention, the particle size is about 5 ~ 10㎛ used, but if the particle size is somewhat large, even if the effect of a certain degree can be sufficiently achieved in the present invention does not limit the size of the particles. In addition, although the waste powder of artificial marble was used in the present invention for the environmentally friendly effect and the reduction of the waste disposal cost, it will be apparent that the same effect can be obtained in flame retardancy even when using ordinary marble. The term 'artificial marble waste powder' and 'artificial marble powder' are used interchangeably.

'Coal ash' in the present invention is SiO ₂ (55 ~ 65%), Al ₂ O ₃ (27-33%), Fe ₂ O ₃ It is composed of porous spherical particles (Glass Sphere) having a particle size of 3 ~ 20 ㎛, which reduces the mixing torque when processing the polymer blend, and dispersion of artificial marble powder in the matrix. To promote this.

In addition, when the call ash is added to a resin having a low melt viscosity such as polypropylene (PP), not only the flame retardancy may be enhanced, but also the melt viscosity may be increased during processing. Porous call ash containing 55 to 65% of SiO ₂ also plays a role in enhancing the compatibility, processability and flame retardancy of the polymer blend. In the present invention, by adding coal ash, the relative amount of polymethyl methacrylate (PMMA) in artificial marble powder is lowered, and the amount of flame retardant such as ATH and coal ash is increased compared to resin. It is expected to contribute to the improvement of flame retardancy. In addition, SiO ₂ and Al ₂ O ₃ , which are main components of the coal ash, form silicate hydrates and alumina hydrates having a crystalline or gel form by hydration reaction. When applied as a flame retardant, these hydrates can pyrolyze during combustion to form char, preventing flame spreading.

The call ash used in the present invention is preferably treated with a strong alkali solution to increase the surface area. This chemical surface modification technique was first introduced in the present invention to roughen the surface of the call ash to increase the adhesive surface with the polymer resin and the compatibilizer. As the strong alkali solution, NaOH or KOH solution is preferably used, and the concentration of the strong alkali solution is preferably set to 0.01 N to 5.0 N.

In one experimental example of the present invention, as a result of treating the strong alkali solution in the call ash, it was confirmed that the surface area is increased (see Fig. 2).

In addition, the call ash or artificial marble powder is preferably used in the solution coating or melt-coated with a compatibilizer solution in order to enhance the adhesion with the polymer resin. The solution coating or the melt coating will be described in the following manufacturing method.

The flame retardant composition according to the present invention comprises 100 to phr of the polymer resin, call ash 0 to 120 phr, artificial marble powder 0 to 120 phr, compatibilizer 0 to 20 phr and flame retardant adjuvant 30 to 200 phr. Preferably, 100 phr of the polymer resin, more than 0 to 100 phr of call ash, artificial marble powder of more than 0 to 120 phr, 0 to 20 phr compatibilizer and 30 to 200 phr flame retardant aid, more preferably, For 100 phr of the polymer resin of the present invention, it comprises call ash 0-100 phr, artificial marble powder 0-120 phr, ethylene vinylene acetate 0-20 phr, ammonium polyphosphate 0-7 phr and magnesium hydroxide 30-200 phr And most preferably have the composition ratios disclosed in Tables 1-3.

If the amount of artificial marble powder is added in an amount of 120 phr or more and the amount of call ash is added in an amount of 120 phr or more, processing becomes difficult, physical properties of the flame retardant blend are lowered, and cost increases.

In the present invention, the polymer resin is low density polyethylene (abbreviated as LDPE), virgin polypropylene (virgin polypropylene (R301); abbreviated as V-PP) and acrylonitrile butadiene styrene copolymer (acrylonitrile butadiene styrene copolymer; It is preferable to use any one or more selected from the group consisting of (abbreviated as ABS). In addition, low flame retardant materials such as high density polyethylene (abbreviated as HDPE) may be used.

The compatibilizer in the present invention serves to enhance the adhesion of artificial marble powder and call ash with the polymer resin. Ethylene-Vinyl acetate copolymer (abbreviated EVA), polyethylene-grafted maleic anhydride (abbreviated PE-g-MA) and polypropylene-grafted maleic anhydride (polypropylene-grafted It is preferable to use at least one selected from the group consisting of maleic anhydride (abbreviated as PP-g-MA).

In the present invention, the flame retardant auxiliary agent is ammonium polyphosphate (abbreviated as APP), magnesium hydroxide (abbreviated as MH), magnesium silicate, zinc boronic acid, zinc sulfate, antimony oxide (Sb ₂ O ₃ ), Diantimony pentoxide (Sb ₂ O ₅ ), melamine pyrophosphate, tris (chloroisopropyl) phosphate, tris (2-chloroethyl) phosphate, diphenylcresylphosphate, red, decabromodiphenyl ether, ocher, expanded graphite, nano It is preferable to use at least one selected from the group consisting of clay, and more preferably, at least one of ammonium polyphosphate and magnesium hydroxide can be used.

Since the composition of the present invention has the composition ratio described above, the flame retardant grade 3 (LOI 23, UL-V1,2 grade) as described in Tables 1 to 3 showed a result.

On the other hand, the present invention comprises the steps of (a) a solution coating with a compatibilizer solution (alone) or a combination of the call ash or artificial marble powder by filtration and drying; And

(b) it provides a method for producing a flame retardant polymer compound comprising the step of mixing the dried call ash or artificial marble powder and a polymer resin, a flame retardant aid and a compatibilizer.

More specifically, the solution coating (solution coating) is added to 0 to 20 parts by weight of 1-5% compatibilizer solution, 20 to 50 parts by weight of call ash or artificial marble waste powder alone or in combination and at 250 to 300 rpm at room temperature Stir for 30 to 60 minutes, then filter / dry.

Next, the dried call ash and / or artificial marble waste powder is mixed with the polymer resin, the flame retardant aid, and the compatibilizer at the aforementioned composition ratio.

In addition, the present invention comprises the steps of (a) melt coating (melt coating) with a compatibilizer by using a single or a combination of call ash or artificial marble powder; And

(b) adding a polymer resin and a flame retardant adjuvant to provide a method for producing a flame retardant polymer compound comprising the step of mixing.

More specifically, the melt coating is 120 to 20 parts by weight of a 1-5% compatibilizer solution, 0 to 120 parts by weight of call ash or 0 to 120 parts by weight of artificial marble powder alone or in combination and 120 ~ Stirring for 10 to 20 minutes at 30 ~ 50rpm at 175 ℃, at this time, the coating conditions may vary depending on the type of polymer resin. For example, it is most preferable to perform at 50 rpm at 165 ° C for LDPE, 185 ° C for 50 PP, 50 rpm for 160 ° C, 50 rpm for ABS.

Next, the melt-coated call ash and / or artificial marble powder is mixed with the polymer resin and the flame retardant aid at the aforementioned composition ratio.

In the process of the present invention, too, it is preferable to use a call ash which has been modified with a strong alkali solution to modify the surface area.

 In the present invention, by modifying the surface by solution coating or melt coating the artificial marble powder and / or call ash with a compatibilizer as described above to improve the compatibility and dispersibility of the artificial marble powder and call ash, in one embodiment of the invention Introducing such a solution coating and melt coating method to prepare a flame-retardant polymer resin, which was examined by a scanning electron microscope, it can be seen that each particle is well dispersed, and the adhesion to the polymer resin is enhanced (Fig. 6 and See FIG. 8).

Furthermore, the present invention provides materials such as flame retardant electronics, electricity, automobiles, ships, buildings, and the like, which are manufactured using a flame retardant polymer resin prepared according to a method of preparing a flame retardant composition using call ash and / or artificial marble powder.

That is, the flame-retardant resin prepared according to the manufacturing method can be produced in the form of various molded articles by extrusion molding, compression molding or injection molding. For example, it can be used in a tube gun or molded into a mold to make materials for flame retardant electronics, electricity, automobiles, ships, and construction.

The method for producing a flame retardant composition of the present invention adds flame retardance to a polymer resin while maintaining the intrinsic properties of raw materials.

That is, the flame retardant polymer resin can be prepared by solution coating or melt coating the call ash and / or artificial marble powder with a compatibilizer solution, and then adding a polymer resin and a flame retardant aid, and various flame retardant electrons using the flame retardant polymer resin, Electricity and building materials can be manufactured.

The flame retardant composition comprising artificial marble waste powder and call ash according to the present invention and a method for preparing a flame retardant polymer compound using the same are used as a substitute for expensive inorganic flame retardant and artificial ash waste powder and coal ash (coal ash) It is used for flame retardant, so it is environmentally friendly by reducing waste disposal cost and reusing.

Furthermore, the flame retardant composition comprising the artificial marble waste powder and the call ash of the present invention has the advantage that it can be used in the manufacture of non-toxic flame retardant products suitable for international environmental regulations restricting the use of brominated flame retardants which are halogen flame retardants.

In addition, the present invention provides a chemical surface modification technology and a compatibilizer using a strong alkaline aqueous solution to enhance the compatibility of the polymer resin and the flame retardant substitutes ash ash and artificial marble waste powder in the manufacture of flame retardant polymer compounds ( solution / melt coating with a compatibilizer) to provide a technique for enhancing adhesion with a polymer resin.

1 is a flowchart illustrating a process of treating 0.1N NaOH to increase the surface area of the call ash.

FIG. 2A is a scanning electron micrograph of a call ash before treatment with 0.1N NaOH aqueous solution, and (B) is a scanning electron microscope photograph after treatment with 0.1N NaOH aqueous solution.

3 is a flow chart illustrating a process of solution coating a compatibilizer to call ash and artificial marble waste powder in order to enhance adhesion with the polymer resin.

Figure 4 (A) is a scanning electron micrograph of a call ash coated with a 1% EVA solution, (B) is a scanning electron microscope picture of a call ash and artificial marble waste powder coated with a 1% EVA solution.

5 is a flowchart illustrating a process of preparing a flame retardant polymer compound by mixing a solution-coated call ash and artificial marble waste powder with a polymer resin and a flame retardant.

FIG. 6A is a scanning electron micrograph of a melt blend of CA / LDPE / AM / EVA / MH / APP (= 50/100/50/20/30/7, unit; phr), and (B) is CA Scanning electron micrograph of melted blend / PP / AM / EVA / MH / APP (= 50/100/50/20/30/7, unit; phr).

FIG. 7 is a flowchart illustrating a process of manufacturing a flame retardant polymer compound by melt-coating call ash and artificial marble waste powder and mixing them with a polymer resin and a flame retardant.

8A is a scanning electron micrograph of a melt blend of CA / LDPE / AM / Pe-g-MA / MH / APP (= 50/100/50/20/30/7, unit; phr) (B) ) Is a scanning electron micrograph of a melt blend of CA / PP / AM / Pe-g-MA / MH / APP (= 50/100/50/20/30/7, units; phr).

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms or words used in the specification and claims should not be construed as having a conventional or dictionary meaning, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.

Therefore, the configuration shown in the drawings and the embodiments described herein are only one of the most preferred embodiments of the present invention and do not represent all of the technical spirit of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

Example  One : In the ash ash Strong alkali  Solution treatment

As shown in FIG. 1, 1 kg of call ash was added to 3 L of 0.1N NaOH solution, followed by stirring for 1 hour, which was filtered, washed with distilled water, and dried for about 24 hours. The surface area of the dried call ash was observed by scanning electron microscopy (SEM). On the other hand, the call ash was used to supply from Kum-Ryun Co., Ltd.

As a result, as shown in Figure 2, it was found that the surface of the call ash (B) after the treatment was rough compared to the call ash (A) before treatment with 0.1N NaOH aqueous solution to increase the surface area.

Example  2 : Call ash  And artificial marble In waste powder  Compatibilizer coating treatment (solution coating) and preparation of polymer flame retardant resin using the same

<2-1> Call ash  And artificial marble In waste powder  Compatibilizer Coating Treatment

As shown in FIG. 3, 10 g of EVA was dissolved in 1 L of chloroform, and then 500 g of chemically treated call ash (CA) of Example 1 was added to the 1% compatibilizer solution, or 300 g of call ash and artificial marble waste. 200 g of the powder was mixed and added, stirred for at least 10 minutes, and then filtered and dried. The surface area of the coated call ash or call ash and artificial marble waste powder was observed by scanning electron microscopy. The artificial marble waste powder was purchased from LG Chem.

As a result, as shown in Fig. 4, the EVA is well coated both when the call ash is used alone (Fig. 4A) and when the call ash and artificial marble waste powder is mixed (Fig. 4B). Could confirm.

<2-2> Preparation of Polymer Flame Retardant Resin

A polymer flame retardant was prepared using the coated call ash and artificial marble waste powder prepared in Example <2-1>. First, as shown in FIG. 5, polymer resins (LDPE, PP, ABS), compatibilizers (EVA), flame retardant aids (APP, Mg (OH) ₂ ) are added to solution coated CA and MA, and then at 165 ° C. A polymer flame retardant was prepared by mixing at 50 rpm for about 20 minutes and observed with a scanning electron microscope.

As a result, CA / LDPE / AM / EVA / MH / APP (= 50/100/50/20/30/7, unit; phr) melt blend (LD of FIG. 6) when LDPE was used as a polymer resin, and CA / PP / AM / EVA / MH / APP (= 50/100/50/20/30/7, unit; phr) in the case of using PP as the polymer resin in the melt blend (B of FIG. 6) It was observed that the adhesive strength of the resin was excellent.

Example  3: Call ash  And artificial marble Waste powder  Preparation of polymer flame retardant resin using (melt coating)

As shown in FIG. 7, primary ash kneading, ie, melting, chemically treated call ash, artificial marble waste powder (AM) and compatibilizer (PE-g-MA) at 50 rpm at a temperature of 120 to 175 ° C. for 10 to 20 minutes. After coating (melt coating) was mixed with LDPE (165 ℃, 50rpm), PP (185 ℃, 50rpm), ABS (160 ℃, 50rpm) resin, respectively, and observed with a scanning electron microscope.

Observation results show that the melt blend (CA in Figure 8A) and CA / PP / AM are CA / LDPE / AM / PE-g-MA / MH / APP (= 50/100/50/20/30/7, units; phr). / PE-g-MA / MH / APP (= 50/100/50/20/30/7, unit; phr) melt blend (B of Fig. 8) are all well dispersed in the inorganic flame retardant, excellent adhesion Could know.

Example  4: Measurement of flame retardancy of the polymer flame retardant of the present invention

According to the method of Example 2 to the composition of the following Table 1 to Table 3, chemically treated call ash and a compatibilizer (EVA) solution coated artificial marble waste powder by mixing with a flame retardant (APP, MH) flame retardant polymer resin ( Blend), and the LOI (Limit Oxygen Index) was measured by ASTM 2863 method to measure its flame retardancy, and UL94 rating was measured by measuring after flame time of flame after ignition with UL94.

As a result of the measurement, the flame retardant formulation containing the call ash and artificial marble waste powder of the present invention has an average LOI of 23 in terms of flame retardancy, and a relatively high flame retardance can be obtained with UL-94 V-1, 2 grade, and thus a preferable composition And it was able to identify that it is a manufacturing method.

NO CA (phr) LDPE (phr) AM (phr) EVA (phr) APP (phr) MH (phr) LOI UL94 One 70 100 - - - 30 20.0 V-2 2 100 100 - - - 30 20.5 V-2 3 120 100 - - - 30 20.4 V-2 4 80 100 20 - - 30 22.4 v-2 5 50 100 50 - - 30 22.4 V-2 6 20 100 80 - - 30 22.8 V-2 7 - 100 70 - - 30 21.4 v-2 8 - 100 90 - - 30 21.7 V-2 9 - 100 120 - - 30 21.2 V-2 10 80 100 20 20 - 30 22.3 v-2 11 50 100 50 20 - 30 22.6 V-2 12 20 100 80 20 - 30 22.8 V-2 13 70 100 - - 5 30 21.0 v-2 14 100 100 - - 6 30 22.3 V-1 15 120 100 - - 7 30 23.5 V-1 16 50 100 50 - 7 30 23.5 v-1 17 - 100 70 - 5 30 20.3 V-2 18 - 100 90 - 6 30 22.1 V-2 19 - 100 120 - 7 30 23.6 v-1 20 50 100 50 20 7 30 23.5 v-1

CA: coal ash, LDPE: low density polyethylene, AM: artificial marble powder (LG), EVA: ethlene vinylene acetate (VA22%), APP: Ammonium polyphosphate, MH: magnesium hydroxide (Mg (OH) ₂ ) LOI: Limit of Oxygen index.

NO CA (phr) V-PP (phr) AM (phr) EVA (phr) APP (phr) MH (phr) LOI UL94 21 70 100 - - - 30 21.0 V-2 22 100 100 - - - 30 21.5 V-2 23 120 100 - - - 30 22.0 V-2 24 80 100 20 - - 30 23.0 v-1 25 50 100 50 - - 30 22.5 V-1 26 20 100 80 - - 30 23.0 V-1 27 - 100 70 - - 30 22.0 v-2 28 - 100 90 - - 30 21.5 V-2 29 - 100 120 - - 30 22.8 V-1 30 80 100 20 20 - 30 24.0 v-1 31 50 100 50 20 - 30 24.5 V-1 32 20 100 80 20 - 30 25.0 V-1 33 70 100 - - 5 30 21.5 v-1 34 100 100 - - 6 30 22.5 V-1 35 120 100 - - 7 30 24.5 V-1 36 50 100 50 - 7 30 24.0 v-1 37 - 100 70 - 5 30 21.5 V-2 38 - 100 90 - 6 30 22.5 V-1 39 - 100 120 - 7 30 24.0 v-1 40 50 100 50 20 7 30 24.5 v-1

CA: coal ash, V-PP: virgin polypropylene (R301), AM: artificial marble powder (LG), EVA: ethlene vinylene acetate (VA22%) )), APP: ammonium polyphosphate, MH: magnesium hydroxide (Mg (OH) ₂ ) LOI: Limit of Oxygen index.

NO CA (phr) ABS (phr) AM (phr) EVA (phr) APP (phr) MH (phr) LOI UL94 41 70 100 - - - 30 20.5 V-2 42 100 100 - - - 30 22.0 V-2 43 120 100 - - - 30 23.5 V-1 44 80 100 20 - - 30 25.0 v-1 45 50 100 50 - - 30 25.0 V-1 46 20 100 80 - - 30 25.0 V-1 47 - 100 70 - - 30 22.0 v-2 48 - 100 90 - - 30 25.0 V-1 49 - 100 120 - - 30 23.0 V-1 50 80 100 20 20 - 30 24.0 v-1 51 50 100 50 20 - 30 24.0 V-1 52 20 100 80 20 - 30 23.0 V-1 53 70 100 - - 5 30 24.0 v-1 54 100 100 - - 6.5 30 24.5 V-1 55 120 100 - - 7.5 30 26.5 V-1 56 50 100 50 - 7 30 25.0 v-1 57 - 100 70 - 5 30 25.0 V-1 58 - 100 90 - 6 30 25.5 V-1 59 - 100 120 - 7 30 26.5 v-1 60 50 100 50 20 7 30 27.0 v-1

CA: coal ash, ABS: acrylonitrile butadiene styrene copolymer, AM: artificial marble powder (LG), EVA: ethlene vinylene acetate (VA22) %)), APP: ammonium polyphosphate, MH: magnesium hydroxide (Mg (OH) ₂ ) LOI: Limit of Oxygen index.

Claims (16)

At least one of coal ash and artificial marble powder; And a polymer resin. The flame retardant composition according to claim 1, wherein the call ash is treated with a strong alkali solution of 0.01N to 5N. The flame retardant composition of claim 1, wherein the call ash or artificial marble powder is solution coated or melt coated with a compatibilizer solution. The flame retardant composition according to claim 1, wherein the flame retardant composition comprises about 100 phr of polymer resin, 0 to 120 phr of call ash, 0 to 120 phr of artificial marble powder, 0 to 20 phr of compatibilizer and 30 to 200 phr of flame retardant aid. A flame retardant composition characterized by the above. The flame retardant composition according to claim 1, wherein the flame retardant composition is based on 100 phr of the polymer resin, call ash 0 to 120 phr, artificial marble powder 0 to 120 phr, ethylene vinylene acetate 0 to 20 phr, ammonium polyphosphate 0 to 7 phr and Flame retardant composition, characterized in that it comprises 30 ~ 200 phr magnesium hydroxide. The method of claim 1, wherein the polymer resin is any one or more selected from the group consisting of low density polyethylene, virgin polypropylene, and acrylonitrile butadiene styrene copolymer. Flame retardant composition. The method of claim 3 or 4, wherein the compatibilizer is an ethylene vinyl acetate copolymer, polyethylene-grafted maleic anhydride and polypropylene-grafted maleic anhydride. maleic anhydride) flame retardant composition, characterized in that any one or more selected from the group consisting of. The flame retardant composition according to claim 4, wherein the flame retardant adjuvant is at least one of ammonium polyphosphate and magnesium hydroxide. (a) solution coating with a compatibilizer solution by using call ash or artificial marble powder alone or in combination, followed by filtration and drying; And (b) mixing the dried call ash or artificial marble powder with a flame retardant adjuvant, a compatibilizer, and a polymer resin. 10. The method of claim 9, wherein the solution coating is characterized in that stirring by adding alone or in combination of 0 to 20 parts by weight of 1-5% compatibilizer solution, and 20 to 50 parts by weight of call ash or artificial marble waste powder. Method for preparing a flame retardant composition. (a) melt coating the call ash or artificial marble powder alone or in combination with a compatibilizer solution; And (b) adding a polymer resin and a flame retardant adjuvant, followed by blending. 12. The method of claim 11, wherein the melt coating is added to 0 to 20 parts by weight of 1 to 5% compatibilizer solution, 0 to 120 parts by weight of call ash or 0 to 120 parts by weight of artificial marble powder alone or in combination, 120 ~ Method for producing a flame retardant composition characterized in that the stirring for 10 to 20 minutes at 175 ℃. 12. The method of claim 9 or 11, further comprising the step of treating the call ash with a strong alkali solution. According to claim 9 or 11, wherein the polymer resin is any one selected from the group consisting of low density polyethylene (virgin polypropylene) and acryronitrile butadiene styrene copolymer (acrylonitrile butadiene styrene copolymer) Method for producing a flame retardant composition, characterized in that above. The method according to claim 9 or 11, wherein the compatibilizer is an ethylene vinyl acetate copolymer, polyethylene-grafted maleic anhydride and polypropylene-grafted maleic anhydride. maleic anhydride) method for producing a flame retardant composition, characterized in that any one or more selected from the group consisting of. The method for producing a flame retardant composition according to claim 9 or 11, wherein the flame retardant auxiliary agent is any one or more of ammonium polyphosphate and magnesium hydroxide.