KR101526565B1 - Flame-retarding composition using waste powder of artificial marble and coal ash, and method of preparing the same - Google Patents

Abstract

The present invention relates to a flame retardant composition comprising artificial marble waste powder and cola ash and a method for producing the same. More particularly, the present invention relates to a process for producing a polyester resin composition which comprises, by weight per 100 phr of a polymer resin, from 0 to 120 phr of colloidal, 0 to 120 phr of artificial marble waste powder, 0 to 20 phr of ethylene vinylene acetate, 0 to 7 phr of ammonium polyphosphate, And a method for producing a flame-retardant polymer compound using the same. According to the present invention, waste artificial marble waste powder and coal ash are used for flame retardation of polymer compounds, thereby reducing waste treatment costs and environmentally friendly effects. Also, it is possible to manufacture non-toxic flame retardant products There is an effect. In the meantime, the present invention relates to a method for improving the compatibility between a polymer resin and a cola ash as a flame retardant substitute material and an artificial marble waste powder in the production of a flame-retardant macromolecule compound, And a technique of enhancing the adhesive force with the polymer resin by solution / melt coating with a compatibilizing agent.

Softening, artificial marble, coal ash,

Description

TECHNICAL FIELD The present invention relates to an artificial marble waste powder and a cola ash, and a flame-retarding composition using waste powder of artificial marble and coal ash,

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

A flame retardant is a substance that is physically and chemically modified to improve the burning property of a polymer material, thereby adding a compound having a high flame retarding effect such as halogen, phosphorus, nitrogen, and metal hydroxide to a polymer material It is a substance that prevents the expansion of combustion. These flame retardants should be good in mixing with raw materials and additives, have no influence on the mechanical properties of the final product, and have less fuming and toxic gases during combustion.

(2) chemically bonding the flame retardant component to the plastic structure (reactive flame retardant); and (3) adding the flame retardant to the polymer (Addition type flame retardant), and fourth, other flame retardant coating or painting, or improvement of heat resistance by changing product design, and general flame retardant is mainly added by adding flame retardant.

In recent years, the development of new flame retardants has been focused on environmental considerations, that is, on environmental friendliness, which is causing rapid change of flame retardant. Even though only a few years ago, new flame retardants and flame retardants have been studied with economic efficiency. However, since excellent properties excluding environmental compatibility cause deterioration of useful value, flame retardants and flame retardants Has been developed. Currently, the social demand for flame retardants can be summarized as safety, waste disposal and recycling, and it is possible to respond positively to environmental standards and regulations, It seems likely.

Therefore, it is necessary to pay attention to current environmental regulations and flame retardancy standards and regulations in Europe. In particular, the European RoHS regulation, which came into effect in 2006, has been applied to all electric and electronic products, including the international regulations limiting the use of flame retardants such as brominated flame retardants (PBBs and PBDEs) As a result of environmental regulations, all companies involved in the production of electrical and electronic products in Korea have developed analytical technologies to prepare for this, and are developing flame retarding technologies that exclude the use of halogen-based flame retardants.

The demand for flame retardant materials in various fields such as automobiles, construction materials, shipbuilding, etc. starting from electric and electronic devices, and the requirements for the flame retardant materials have been diversified, the development direction of the flame retardant materials is as follows.

First, the development of environmentally friendly non-halogen low-smoke materials. Since flame retardant materials are required to suppress the deterioration of physical properties and workability, and since it is claimed that toxic gases are emitted when PVC is burned, development of flame retardant materials based on polyolefins as base materials has been under way to replace PVC .

Second, the development of flame retardant materials with excellent heat resistance. In recent years, there has been a demand for a higher level of heat resistance compared with a tendency of high performance and miniaturization of products, and it is urgent to develop a flame retardant material having excellent thermal stability. Particularly, there is a high demand in the field of electric / electronic equipment parts.

Third, the development of multi-functional flame retardant materials. Development of materials having not only flame retardancy but also characteristics such as damping resistance, electrical characteristics, optical functionality, and antibacterial properties is required.

Fourthly, the development of a flame retardant material having few problems in molding processability and molding process. It is required to develop a material which has little problems such as corrosion, abrasion and adhesion in facilities requiring fluidity in processing steps such as extrusion molding and injection molding.

Fifth, development of flame retardant materials with excellent recycling. As interest and concern about industrial wastes increase, it is difficult to dispose of materials that do not burn well, which is a problem to be solved in the future.

Sixth, development of high flame retardant materials. Research on the flame retardant structure of the polymer itself and the application of the flame retardant material of the Nano Composite have been carried out by the development of the high-kinetics material which can access to the inorganic material, and the more effective char production ability It is also observed that a study on effective flame retardants will be made.

On the other hand, due to environmental pollution and fire accidents coming from technological development, various regulations based on environment and stability have been introduced and revised in advanced countries and other countries around the world. Polymer burnout technology is required to be environmentally friendly and flame retardant. Therefore, it is required to satisfy the applicable standards (ASTM, ISO, UL, KS, etc.) in case of export or domestic demand. In recent years, there is a continuing increase in the need for flame retardation considering safety in the event of a fire, and as environmental problems have arisen, there has been a demand for development of flame retardant technology considering not only simple flame retarding effect but also environmental and human stability.

The present invention was made to satisfy the necessity of development of the above-mentioned flame retardant technology, and an object of the present invention is to provide an flame retardant composition comprising coal ash or artificial marble waste powder.

Another object of the present invention is to provide a flame retardant composition which is obtained by modifying the surface of a coal ash or artificial marble waste powder by using a strong alkaline solution, solution coating or melt coating with a compatibilizer solution and then mixing with a polymer resin and a flame retardant aid And a method for producing the same.

It is another object of the present invention to reduce the environmental pollution by recycling waste coal ash or artificial marble waste powder and to suppress the generation of toxic gas in the case of fire by using the flame retardant polymer resin produced by the manufacturing method of the present invention To provide a flame retardant building material.

In order to accomplish the above-mentioned object, the present invention provides a method of manufacturing a honeycomb structure comprising at least one of coal ash and artificial marble powder; And a polymer resin.

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

The 'artificial marble' used in the present invention contains crosslinked acrylic and about 60 to 65% of aluminum hydroxide (ATH, alumina trihydroxide). According to the method of producing artificial marble Can be manufactured. As a representative example of the production method of such artificial marble, there is a slight difference according to the specifications. As a representative example of DuPont artificial marble manufacturing method, ATH is added in an amount of about 65%, and a vinyl or acrylic For example, a method of dissolving 20% of the resin in MMA (methyl methacrylate), using a peroxide azo compound or the like as a crosslinking agent, and using a phosphoric acid ester (mono- di-) as a coupling agent.

Aluminum hydroxide (ATH), which is the main component of artificial marble, generates a water vapor (H ₂ O) by pyrolysis during combustion and lowers the concentration of the combustion gas and lowers the temperature around the combustion point to suppress combustion. Mechanism is deduced by the chemical reaction as in the following [Reaction 1].

[Reaction Scheme 1]

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

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

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

On the other hand, the powder of the artificial marble can be used as it is without processing in the case of disposal and crushing of artificial marble. In the present invention, the particles having a particle size of about 5 to 10 mu m are used, but when the particles are made into powder, a certain effect can be sufficiently achieved even if the particle size is somewhat large. In the present invention, waste powder of artificial marble is used for the purpose of reducing the environment-friendly effect and waste disposal cost, but it is obvious that the same effect can be obtained in the flame retardancy even when using artificial marble powder, The term 'artificial marble waste powder' and 'artificial marble powder' are used in combination.

In the present invention, 'Coal ash' refers to SiO ₂ (55 to 65%), Al ₂ O ₃ (27 to 33%), Fe ₂ O ₃ And dispersing the artificial marble powder in a matrix by reducing mixing torque during polymer blending with porous spherical particles having a particle size of about 3 to 20 μm. .

In addition, the addition of cola ash to a resin having a low melt viscosity such as PP (polypropylene) not only improves the flame retardancy but also increases the melt viscosity during processing. Porous cola ash containing 55 to 65% of SiO ₂ also improves the compatibility, processability and flame retardancy of the polymer blend. In the present invention, by adding coal ash, the amount of poly methyl methacrylate (PMMA) in the artificial marble powder is lowered and the amount of flame retardant such as ATH, coal ash relative to the resin is increased It is expected to contribute to the improvement of flame retardancy. In addition, SiO ₂ and Al ₂ O _{3, which} are the main components of coal ash, form a silicate hydrate, alumina hydrate, in the form of a crystalline or gel by hydration reaction. These hydrates can be used as a flame retardant to pyrolyze when burning to form a char to prevent diffusion of the flame.

It is preferable that the cola ash used in the present invention is treated with a strong alkali solution to increase its surface area. Such a chemical surface modification technique was first introduced in the present invention, and roughened the surface of the cola ash to increase the adhesion surface with the polymer resin and the compatibilizer. As the strong alkaline solution, NaOH or KOH solution is preferably used, and the concentration of the strong alkaline solution is preferably 0.01 N to 5.0 N.

In one experimental example of the present invention, it was confirmed that as a result of treatment with a strong alkaline solution in the case of coal ash, the surface area was increased (see FIG. 2).

In addition, it is preferable that the cola ash or the artificial marble powder is solution-coated or melt-coated with the compatibilizing agent solution to improve the adhesion to the polymer resin. The solution coating or the melt coating will be described in the following production process.

The flame retardant composition according to the present invention comprises 0 to 120 phr of colloidal ash, 0 to 120 phr of artificial marble powder, 0 to 20 phr of compatibilizer and 30 to 200 phr of flame retardant aid per 100 phr of polymer resin. Preferably, the composition contains more than 0 to 100 phr of cola ash, more than 0 to 120 phr of artificial marble powder, more than 0 to 20 phr of compatibilizer and 30 to 200 phr of flame retardant auxiliary agent per 100 phr of polymer resin, 0 to 100 phr of colloid, 0 to 120 phr of artificial marble powder, 0 to 20 phr of ethylene vinylene acetate, 0 to 7 phr of ammonium polyphosphate and 30 to 200 phr of magnesium hydroxide per 100 phr of the polymer resin of the present invention , Most preferably those shown in Tables 1 to 3.

If the addition amount of the artificial marble powder is more than 120 phr and the amount of the colloidal ash is more than 120 phr, processing becomes difficult, the physical properties of the flame-retardant blend are lowered, and the cost increases.

In the present invention, the polymer resin may be selected from the group consisting of low density polyethylene (abbreviated as LDPE), virgin polypropylene (R301) (abbreviated as V-PP), and acrylonitrile butadiene styrene copolymer. Abbreviated as " ABS "). Other low flammability materials such as high density polyethylene (abbreviated as HDPE) can be used.

In the present invention, the compatibilizer enhances the adhesion between the artificial marble powder and the colloidal ash and the polymer resin. Ethylene-vinyl acetate copolymer (abbreviated as EVA), polyethylene-grafted maleic anhydride (abbreviated as PE-g-MA) and polypropylene-grafted maleic anhydride maleic anhydride (PP-g-MA)).

In the present invention, the flame-retardant auxiliary is selected from the group consisting of ammonium polyphosphate (abbreviated as APP), magnesium hydroxide (abbreviated as MH), magnesium silicate, zinc borate, zinc sulfate, antimony oxide (Sb ₂ O ₃ ) diphosphorus pentoxide, antimony (Sb ₂ O _5), melamine pyrophosphate, tris (chloroisopropyl) phosphate, tris (2-chloroethyl) phosphate, diphenyl cresyl phosphate, of, Decabromodiphenyl ether, yellow earth, expanded graphite, nano Clay, and the like. It is more preferable to use at least one of ammonium polyphosphate and magnesium hydroxide.

The compositions of the present invention have the composition ratios as described above, and thus have the results satisfying the flame retardant grade 3 (LOI 23, UL-V1,2 grade) as disclosed in Tables 1 to 3.

The present invention also relates to a method for producing a marble, which comprises (a) solution-coating a solution of colloidal ash or artificial marble, either alone or in combination, with a compatibilizer solution, followed by filtration and drying; And

(b) mixing the dried coal ash or artificial marble powder with a polymer resin, a flame-retardant aid, and a compatibilizer to prepare a flame-retardant macromolecule compound.

More specifically, the solution coating is carried out by adding from 0 to 20 parts by weight of 1 to 5% compatibilizing agent solution, from 20 to 50 parts by weight of coal ash or artificial marble waste powder, alone or in combination, at a temperature of 250 to 300 rpm Stir for 30 to 60 minutes and then filter / dry.

Next, the dried coal ash and / or artificial marble waste powder is mixed with the polymer resin, the flame-retarding auxiliary agent and the compatibilizing agent in the composition ratio mentioned above.

The present invention also relates to a method for producing a granulated product, comprising the steps of: (a) melt-coating a colloidal or artificial marble powder alone or in combination with a compatibilizer; And

(b) adding a polymer resin and a flame retardant adjuvant and then mixing the flame retardant.

More specifically, the melt coating is prepared by adding from 0 to 20 parts by weight of a 1 to 5% compatibilizing agent solution, 0 to 120 parts by weight of coal ash or 0 to 120 parts by weight of artificial marble powder alone or in combination, And the mixture is stirred at 175 DEG C at 30 to 50 rpm for 10 to 20 minutes. At this time, coating conditions may be different depending on the kind of the polymer resin. For example, LDPE is most preferably performed at 50 rpm at 165 DEG C, 185 DEG C at 50 DEG C for PP, and 160 DEG C at 50 rpm for ABS.

Next, the melt-coated cola ash and / or artificial marble powder is mixed with the polymer resin and the flame-retardant auxiliary agent in the composition ratio mentioned above.

In the method of the present invention, it is also preferable to use a solution in which the surface area is modified by treatment with a strong alkali solution.

 In the present invention, as described above, the surface is modified by solution coating or melt coating with artificial marble powder and / or cola ash as a compatibilizer to increase the compatibility and dispersibility of artificial marble powder and cola ash. In one embodiment of the invention The flame-retardant polymer resin was prepared by introducing the solution coating and the melt coating method, and it was confirmed by scanning electron microscope that the particles were well dispersed and the adhesion with the polymer resin was improved (FIGS. 6 and 7) 8).

Further, the present invention provides materials such as flame retardant electronic, electric, automobile, ship, and construction manufactured by using the flame-retardant polymer resin produced according to the method of producing the flame retardant composition using call ash and / or artificial marble powder.

That is, the flame-retardant resin produced according to the above-described production method can be extruded, compression molded or injection molded into various molded products. For example, it can be put into a tube gun or molded into a mold of a certain mold to make materials such as flammable electronic, electric, automobile, ship, and construction.

The method for producing the flame retardant composition of the present invention adds flame retardancy to the polymer resin while maintaining the inherent characteristics of the raw material.

That is, it is possible to prepare a flame-retardant polymer resin by solution-coating or melt-coating a call ash and / or an artificial marble powder with a compatibilizing agent solution, and then adding a polymer resin and a flame retardant aid to the flame-retardant polymer resin. Electrical and building materials.

The flame retardant composition including the artificial marble waste powder and the cola ash and the method for producing the flame retardant polymer compound using the artificial marble waste powder and the coal ash according to the present invention can be used as a substitute for the expensive inorganic flame retardant, It can be used for softening, reducing waste disposal costs and reusing environmentally friendly effects.

Further, the flame retardant composition including the artificial marble waste powder and the cola ash of the present invention has an advantage that it can be used in the production of a non-toxic flame retardant product suitable for international environmental regulations, which restricts the use of brominated flame retardant, which is a halogen flame retardant.

The present invention also relates to a method for improving the compatibility between a polymer resin and a fire-resistant substitute substance, cola ash and artificial marble waste powder, in the production of a flame-retardant macromolecule compound, a chemical surface modification technique using a strong alkaline aqueous solution and a compatibilizer compatibilizer) to improve the adhesive strength with the polymer resin.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.

Therefore, the configurations shown in the drawings and the embodiments described herein are merely the most preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

Example  One : In coal ash River alkaline  Solution treatment

As shown in FIG. 1, 3 L of 0.1 N NaOH solution was added to 1 kg of cola ash, stirred for 1 hour, filtered, washed with distilled water and dried for about 24 hours. The surface area of the dried cola ash was observed with a scanning electron microscope (SEM). On the other hand, the above-mentioned cola ash was supplied from Gold Rinse Co., Ltd. and used.

As a result of observation, as shown in Fig. 2, it was found that the surface of the cola ash (B) after the treatment was roughened and the surface area was increased as compared with the cola ash (A) before treatment with the aqueous 0.1N NaOH solution.

Example  2 : Call ash  And artificial marble In the pulp powder  Compatibilizer coating (solution coating) and production of polymer flame retardant resin using it

<2-1> Call ash  And artificial marble In the pulp 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 the chemically treated cola ash (CA) of Example 1 was added to the 1% compatibilizing agent solution, or 300 g of cola ash And 200 g of powder were mixed and added, stirred for 10 minutes or longer, and then filtered and dried. The surface area of the coated cola ash or cola ash and artificial marble waste powder was observed with a scanning electron microscope. The artificial marble waste powder was purchased from LG Chemical and used.

As a result of the observation, as shown in Fig. 4, EVA was well coated in the case of using the coal ash alone (Fig. 4A) and the case of using the coal ash and artificial marble waste powder mixed (Fig. 4B) .

<2-2> Production of Polymer Flame Retardant Resin

Polymer flame retardants were prepared using the coated cola ash and artificial marble waste powder prepared in Example <2-1>. First, as shown in FIG. 5, a polymer resin (LDPE, PP, ABS), a compatibilizer (EVA), a flame retardant aid (APP, Mg (OH) ₂ ) The mixture was stirred at 50 rpm for about 20 minutes to prepare a polymer flame retarding agent, which was observed with a scanning electron microscope.

As a result of observation, a melt blend (A in FIG. 6) of CA / LDPE / AM / EVA / MH / APP (= 50/100/50/20/30/7, In the melt blend (FIG. 6B) of PP / AM / EVA / MH / APP (= 50/100/50/20/30 / 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 (melt coating)

7, the chemically treated coal ash, artificial marble waste powder (AM) and compatibilizer (PE-g-MA) were first kneaded at a temperature of 120 to 175 ° C at 50 rpm for 10 to 20 minutes, (165 ℃, 50 rpm), PP (185 ℃, 50 rpm) and ABS (160 ℃, 50 rpm) resin, respectively, and observed with a scanning electron microscope.

Observations, CA / LDPE / AM / PE -g-MA / MH / APP (= 50/100/50/20/30/7, the unit; phr) (A in Fig. 8) the melt blend and CA / PP / AM (B) of the molten blend (FIG. 8B) was well dispersed, and the adhesion was excellent, it was found that the inorganic flame retardant was well dispersed in the melt blend (PE / g-MA / MH / APP = 50/100/50/20/30/7, Could know.

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

According to the method of Example 2, artificial marble waste powder coated with chemically treated cola ash and compatibilizer (EVA) solution was mixed with a flame retarding auxiliary agent (APP, MH) in the composition of the following Tables 1 to 3 to obtain a flame retardant polymer resin The limit of oxygen index (LOI) was measured by ASTM 2863 method and the after flame time of flame after UL94 was measured to measure UL94 grade.

As a result of the measurement, the flame retardant formulation containing the coal ash and artificial marble waste powder of the present invention had an average LOI 23 in the flame retardancy and UL-94 V-1 and 2 grades, And 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: ethylene vinyl acetate (VA22% 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: ethvlene 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: ethylenevinylene acetate (VA22) %)), APP: ammonium polyphosphate, MH: magnesium hydroxide (Mg (OH) ₂ ) LOI: Limit of Oxygen index.

FIG. 1 is a flow chart showing the process of treating 0.1 N NaOH to increase the surface area of the call ash.

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

FIG. 3 is a flowchart showing a process of solution-coating a co-solvent and a synthetic marble waste powder with a compatibilizer to improve adhesion to a polymer resin.

4 (A) is a scanning electron microscope (SEM) image of a coal ash coated with a 1% EVA solution, and (B) is a scanning electron microscope photograph of a coal ash and artificial marble waste powder coated with a 1% EVA solution.

5 is a flow chart showing a process for producing a flame-retardant polymer compound by mixing solution-coated cola ash and artificial marble waste powder with a polymer resin and a flame retardant.

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

7 is a flowchart showing a process for producing a flame-retardant macromolecule compound by melt-coating cola-ash and artificial marble waste powder and mixing it with a polymer resin and a flame retardant agent.

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, ) 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).

Claims (16)

At least one of coal ash and artificial marble powder solution coated or melt coated with a compatibilizing agent solution; 1. A flame retardant composition comprising a polymer resin and a flame retardant aid, Wherein the call ash is treated with a strong alkaline solution of 0.01N to 5N. delete delete The composition according to claim 1, wherein the flame retardant composition comprises: from more than 0 to 120 phr of colloidal, 100 to 120 phr of artificial marble powder, 0 to 20 phr of compatibilizer, and 30 to 200 phr of flame- &Lt; / RTI &gt; The composition according to claim 1, wherein the flame retardant composition comprises: from more than 0 to 120 phr of a coalescence, from more than 0 to 120 phr of artificial marble powder, from 0 to 20 phr of ethylene vinylene acetate, from 0 to 7 of ammonium polyphosphate phr and magnesium hydroxide in an amount of 30 to 200 phr. [5] The method of claim 1, wherein the polymer resin is at least one selected from the group consisting of low density polyethylene, virgin polypropylene, and acrylonitrile butadiene styrene copolymer. Lt; / RTI &gt; The method of claim 1, wherein the compatibilizing agent is selected from the group consisting of ethylene-vinyl acetate copolymer, polyethylene-grafted maleic anhydride, and polypropylene-grafted maleic anhydride. Wherein the composition is at least one selected from the group consisting of: The flame retardant auxiliary composition according to claim 1, wherein the flame retardant aid is at least one of ammonium polyphosphate and magnesium hydroxide. (a) solution coating with a solution of colloidal ash or synthetic marble powder, either alone or in combination, with a compatibilizer solution, followed by filtration and drying; And (b) mixing the dried coal ash or artificial marble powder with a flame retardant aid, a compatibilizing agent, and a polymer resin. The method according to claim 9, wherein the solution coating is carried out by adding from 0 to 20 parts by weight of a 1 to 5% compatibilizing agent solution and from 20 to 50 parts by weight of coal ash or artificial marble waste powder alone or in combination A method for producing a flame retardant composition. (a) melt-coating colloidal ash or artificial marble powder, alone or in combination, into a compatibilizing agent solution; And (b) adding a polymer resin and a flame retardant aid, and then blending the blend. 12. The method of claim 11, wherein the molten coating comprises 0 to 20 parts by weight of a 1 to 5% compatibilizing agent solution, 0 to 120 parts by weight of coal ash or 0 to 120 parts by weight of artificial marble powder alone or in combination, And the mixture is stirred at 120 to 175 ° C for 10 to 20 minutes. 12. The method of claim 9 or 11, further comprising treating the coal ash with a strong alkaline solution. 12. The method of claim 9 or 11, wherein the polymer resin is selected from the group consisting of low density polyethylene, virgin polypropylene, and acrylonitrile butadiene styrene copolymer By weight based on the total weight of the composition. 11. The method of claim 9 or 11, wherein the compatibilizer is selected from the group consisting of ethylene-vinyl acetate copolymer, polyethylene-grafted maleic anhydride, and polypropylene grafted maleic anhydride. -grafted maleic anhydride). &lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt; The method for producing an flame retardant composition according to claim 9 or 11, wherein the flame retardant aid is at least one of ammonium polyphosphate and magnesium hydroxide.

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