KR102434208B1 - Method for manufacturing highly flame resistant and eco-friendly rubber-based nanocomposite foam using waste rubber foam powder - Google Patents

Abstract

The present invention relates to a method for manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using waste rubber foam powder, and more particularly, to a waste rubber powder comprising rubber, a flame retardant mixture including waste rubber foam powder, and a processing aid. Flame-retardant masterbatch manufacturing step of manufacturing high-flammability eco-friendly rubber-based nanocomposite masterbatch, rubber resin, high-flammability eco-friendly rubber-based nanocomposite masterbatch using waste rubber powder manufactured through the above flame-retardant masterbatch manufacturing step, masterbatch for foaming and crosslinking A raw material mixing step of mixing the master batch for a raw material, an extrusion step of extruding the mixture prepared through the raw material mixing step, a foaming step of foaming the extruded product manufactured through the extrusion step. and a cutting step of cutting the foamed product through the foaming step.
The foam produced through the above process does not contain a halogen-based flame retardant component and is eco-friendly by recycling waste rubber foam powder, is light in weight and exhibits excellent sound absorption performance, and has excellent flame retardancy, heat insulation, heat resistance and mechanical properties.

Description

Manufacturing method of high-flammability and eco-friendly rubber-based nanocomposite foam using waste rubber foam powder

The present invention relates to a method for manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using waste rubber foam powder, and more particularly, it does not contain a halogen-based flame retardant component and is eco-friendly by recycling waste rubber foam powder, light in weight It relates to a method for manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using a waste rubber foam powder that not only exhibits excellent sound-absorbing performance, but also has excellent flame retardancy, heat insulation, heat resistance and mechanical properties.

Foams are used as internal insulators, cushioning materials, vibration-proofing materials, sound insulation materials, heat insulating materials for electronic devices and the like, food packaging materials, clothing materials, building materials, and interior and exterior parts of automobiles and home appliances.

Such foams are required to have properties such as flexibility, cushioning properties, and heat insulating properties from the viewpoint of ensuring sealing properties and the like when assembled as parts, and polyolefin resin foams such as polyethylene and polypropylene are known as foam materials.

For foams made of the above components, the expansion ratio is increased or the material itself is softened by blending a rubber component with a polyolefin-based resin. Even when trying to obtain a low, high foaming ratio, the cell walls are destroyed during foaming, causing gas leakage or unity of the cells, so that it is difficult to obtain a foam exhibiting soft physical properties due to a high foaming ratio.

As a conventionally known flame-retardant polyolefin foam, Korean Patent Application Laid-Open No. 10-1997-0042714 discloses ASTM D 2863 prepared by adding a flame retardant and other additives to a resin obtained by mixing only low-density polyethylene (LDPE) and ethylene vinyl copolymer (EVA) alone or in a blend. A flame retardant foam having a limiting oxygen index (LOI) of 26 has been disclosed. In addition, Japanese Patent Application Laid-Open No. 2000-106041 has presented a flame-retardant foamed rubber composition for covering electric wires and cables, but the foams and flame-retardant foamed rubber compositions listed above have a very low foaming rate while ensuring flame retardancy. .

In addition to polyolefin-based resin foams, rubber foams made of rubber components are also used, and the rubber foams are used in a wide range of fields such as various building materials, automobile parts, ship parts, railway parts, sporting goods, and toy articles depending on the cell structure and flame retardancy. It is used as an insulator, sound absorbing and insulating material, structural material, toy material, and auxiliary material, and its usage is showing a rapid increase.

These rubber foams are mainly made of nitrile butadiene rubber (NBR), ethylene polypropylene diene rubber (EPDM), etc. In order to induce a foam with high flame retardancy and foaming rate by using it, the mixing process of raw materials is complicated, and the manufacturing process is complicated because the content of the foaming agent has to be adjusted during the foaming process.

In addition, conventionally, there is a problem in that the air or soil is polluted by simply incinerating the foamed rubber waste or treating it through a process such as landfill.

Accordingly, the present inventors use waste rubber foam powder that does not contain halogen-based flame retardant components, is eco-friendly by using waste rubber foam powder, is light in weight and exhibits excellent sound absorption performance, and has excellent flame retardancy, heat insulation, heat resistance and mechanical properties. The present invention was completed by developing a method for manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam.

Korean Patent Registration No. 10-0415680 (January 6, 2004) Korean Patent Publication No. 10-2015-0093146 (2015.08.17) Korean Patent Registration No. 10-0916534 (2009.09.02)

An object of the present invention is to produce a waste rubber foam powder that does not contain halogen-based flame retardant components, is environmentally friendly by recycling waste rubber foam powder, is light in weight and exhibits excellent sound absorption performance, and has excellent flame retardancy, heat insulation, heat resistance and mechanical properties. To provide a method for manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using the.

An object of the present invention is a flame retardant masterbatch manufacturing step for manufacturing a high flame retardant eco-friendly rubber-based nanocomposite masterbatch using waste rubber foam powder consisting of rubber, a flame retardant mixture and a processing aid, a rubber resin, manufactured through the flame retardant masterbatch manufacturing step A raw material mixing step of mixing a high-flammability eco-friendly rubber-based nanocomposite masterbatch, a foaming masterbatch and a crosslinking masterbatch, an extruding step of extruding the mixture prepared through the raw material mixing step, and foaming the extruded product through the extrusion step It is achieved by providing a method for manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using a waste rubber foam powder, characterized in that it comprises a foaming step, and a cutting step of cutting the foamed product through the foaming step.

According to a preferred feature of the present invention, the high-flammability eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder is made of 100 parts by weight of rubber, 100 to 150 parts by weight of a flame retardant mixture, and 0.1 to 10 parts by weight of a processing aid.

According to a more preferred feature of the present invention, the rubber is made of at least one selected from the group consisting of nitrile butadiene rubber and ethylene propylene diene monomer.

According to a more preferred feature of the present invention, the flame retardant mixture is composed of 10 to 30% by weight of the polymer nanoclay composite, 10 to 50% by weight of the waste rubber foam powder, and 30 to 80% by weight of the eco-friendly flame retardant.

According to an even more preferred feature of the present invention, the polymer nanoclay composite is composed of 100 parts by weight of the rubber resin, 1 to 15 parts by weight of the nanoclay, and 1 to 15 parts by weight of the compatibilizer.

According to an even more preferred feature of the present invention, the eco-friendly flame retardant is 100 parts by weight of inorganic metal hydroxide, 30 to 40 parts by weight of expanded graphite, 60 to 70 parts by weight of a phosphorus-based flame retardant, and 70 to 90 parts by weight of zinc borate.

According to an even more preferred feature of the present invention, the inorganic metal hydroxide is made of at least one selected from the group consisting of aluminum hydroxide and magnesium hydroxide.

According to an even more preferred feature of the present invention, the raw material mixing step includes 100 parts by weight of a rubber resin, 100 to 200 parts by weight of a high-flammability eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder prepared through the flame-retardant masterbatch manufacturing step. , it shall be made by mixing 100 to 200 parts by weight of the master batch for foaming and 10 to 20 parts by weight of the master batch for crosslinking.

According to an even more preferred feature of the present invention, the master batch for foaming consists of 100 parts by weight of rubber and 25 to 100 parts by weight of a foaming agent, and the foaming agent is made of azodicarbonamide.

According to an even more preferred feature of the present invention, the crosslinking masterbatch consists of 100 parts by weight of rubber and 5 to 100 parts by weight of a crosslinking agent mixture, and the crosslinking agent mixture is a sulfur compound, 2-mercaptbenzothiazole (M), di It shall consist of benzothiadyl disulfide (DM) and Zn-dimethyldithiocarbamate (PZ).

According to an even more preferred feature of the present invention, the raw material mixing step is to be performed at a temperature of 100 to 130 ℃ for 5 to 60 minutes.

According to an even more preferred feature of the present invention, the foaming step is to be made at a temperature of 100 to 180 ℃ for 5 to 60 minutes.

The method for manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder according to the present invention does not contain a halogen-based flame retardant component, is eco-friendly by recycling waste rubber foam powder, is light in weight, and exhibits excellent sound absorption performance In addition, it exhibits an excellent effect of providing a foam having excellent flame retardancy, heat insulation, heat resistance and mechanical properties.

1 is a flowchart showing a method of manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using a waste rubber foam powder according to the present invention.

Hereinafter, a preferred embodiment of the present invention and the physical properties of each component will be described in detail, which is intended to describe in detail enough that a person of ordinary skill in the art to which the present invention pertains can easily carry out the invention, This does not mean that the technical spirit and scope of the present invention is limited.

The method for producing a high-flammability and eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder according to the present invention is a flame-retardant method for manufacturing a high-flammability eco-friendly rubber-based nanocomposite masterbatch using a waste rubber foam powder consisting of rubber, a flame retardant mixture and a processing aid Mixing the masterbatch manufacturing step (S101), the rubber resin, the high flame retardant eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder produced through the flame retardant masterbatch manufacturing step (S101), the foaming masterbatch and the crosslinking masterbatch a raw material mixing step (S103), an extrusion step (S105) of extruding the mixture prepared through the raw material mixing step (S103), a foaming step of foaming the extrudate prepared through the extrusion step (S105) (S107) and , consists of a cutting step (S109) of cutting the foamed product through the foaming step (S107).

The flame-retardant masterbatch manufacturing step (S101) is a step of preparing a non-flammable eco-friendly rubber-based nanocomposite masterbatch using waste rubber foam powder consisting of rubber, a flame retardant mixture, and a processing aid, 100 parts by weight of rubber, 100 to 150 parts by weight of a flame retardant mixture It is made by mixing 0.1 to 15 parts by weight of parts and processing aids.

The rubber serves to ensure that the high-flammability eco-friendly rubber-based nanocomposite masterbatch exhibits even dispersion performance when mixed with the rubber component. It is preferably made of one or more selected from the group consisting of nitrile butadiene rubber and ethylene propylene diene monomer.

The flame retardant mixture contains 100 to 150 parts by weight, and preferably consists of 10 to 30% by weight of the polymer nanoclay composite, 10 to 50% by weight of the waste rubber foam powder, and 30 to 80% by weight of an eco-friendly flame retardant.

The polymer nanoclay composite is contained in an amount of 10 to 30% by weight in the flame retardant mixture, and 100 parts by weight of a rubber resin, 1 to 15 parts by weight of nanoclay, and 1 to 15 parts by weight of a compatibilizer. It gives heat resistance and flame retardancy to the masterbatch, and plays a role in giving eco-friendly properties by recycling waste rubber foam powder without using halogen-based components.

The rubber resin is at least one selected from the group consisting of nitrile butadiene rubber and ethylene propylene diene monomer, preferably nitrile butadiene rubber having an acrylonitrile content of 28 to 34%, and an ethylene propylene diene monomer having an ENB content of 4.5 to 8.0% It is preferable that it consists of one or more selected from the group consisting of.

The nanoclay contains 1 to 15 parts by weight, and serves to improve the heat resistance and flame retardancy of the polymer nanoclay composite. It is not particularly limited as long as it is commonly used and any kind can be used. Specifically, montmorillonite, hecto Light, bentonite, vermiculite, and volconite can be used. The montmorillonite is a modified form with an organic compound, and specifically, Cloisite 10A, Cloisite 15A, Cloisite 20A, Cloisite 25A, Cloisite 30B, Cloisite 93A, etc. manufactured by Southern Clay Products may be used.

In addition, when the nanoclay is contained, the decomposition temperature of the polymer nanoclay composite is increased by 50% or more (increased by 50 to 150°C), so that the heat resistance of the masterbatch according to the present invention is improved, and the composite structure {Intercalation (insertion type) structure and exfoliation (Releasable) structure coexists}, so flame retardancy is improved by maximizing char formation and flame propagation blocking power is improved.

The polymer nanoclay composite has a form in which a polymer is inserted between nanoclay layers (insertion type, intercalation) and a form in which the nanoclay layered structure is peeled off and exists in the polymer (exfoliation type), unlike the structure in a conventional mixture or compound. Because it is manufactured, it is possible to provide a masterbatch with improved flame retardancy and shielding properties.

At this time, if the content of the nanoclay is less than 1 part by weight, the effect of improving mechanical properties such as compressive strength of the masterbatch according to the present invention is insignificant, and when the content of the nanoclay exceeds 15 parts by weight, the waste rubber foam powder As the dispersion effect on the nanoclay decreases, agglomeration between the nanoclay components may occur, thereby reducing the physical properties of the polymer nanoclay composite.

1 to 15 parts by weight of the compatibilizer is mixed, and it is composed of polyethylene graft maleic anhydride, and since it allows the waste rubber foam powder and the nanoclay to be mixed evenly, providing a polymer nanoclay composite exhibiting homogeneous physical properties play a role

When the content of the compatibilizer is less than 1 part by weight, the above effect is insignificant, and when the content of the compatibilizer exceeds 15 parts by weight, the effect is not significantly improved and an excessively large amount is contained. may decrease the physical properties of

In the polymer nanoclay composite, rubber resin, nanoclay, and a compatibilizer are added to a mixer, and a high speed of 200 RPM or more, preferably a high speed of 200 to 500 RPM, a high temperature of 180 ° C. or more, preferably a high temperature of 180 to 220 ° C. , can be prepared by mixing in a short time of 5 min or less, preferably in a short time of 3 to 5 min.

The waste rubber foam powder is contained in an amount of 10 to 50% by weight, and serves to not only mix with the rubber component, but also to provide a masterbatch exhibiting an eco-friendly effect because the waste rubber foam to be disposed of is recycled.

The waste rubber foam powder varies depending on the rubber component to which the masterbatch according to the present invention is applied, but natural rubber (NR), strenbutadiene rubber (SBR), butadiene rubber (BR), nitrile butadiene rubber (NBR) and ethylene It is manufactured by pulverizing rubber foam waste for building insulation and automobile interiors, which has one selected from the group consisting of propylene rubber (EPDM) as a main component. It is preferably made of waste rubber foam powder.

The waste rubber foam powder has a particle size of 1 to 10 μm, and it is preferable to use liquid nitrogen, a crushing method using a milling machine, or a pulverizer. As such, the waste rubber foam powder produced through liquid nitrogen, a milling machine (especially a high-speed milling machine), or a pulverizer minimizes physical damage and carbonization of the raw material, so that the physical properties of the foam are maintained, and it is easy to manufacture in various particle sizes. shows an effect. In addition, the waste rubber foam powder produced through the above process has a cross-linked structure of about 20%, so it can play a role of heat resistance and flame retardancy, and has high strength due to its high content of carbon black, and has high chemical stability due to its high UV resistance. indicates characteristics.

When the particle size of the waste rubber foam powder is less than 1 μm, it scatters easily and contaminates the workplace, and due to agglomeration, it is not uniformly mixed with the components constituting the high-flammability eco-friendly rubber-based nanocomposite masterbatch, as well as rubber manufactured The flame retardancy and strength of the foam are lowered, and the economic feasibility of the recycling process is reduced, and when the particle size of the waste rubber foam powder exceeds 10 μm, the mixability with the components constituting the high-flammability eco-friendly rubber-based nanocomposite masterbatch Not only this lowers, but also the tensile properties and quality of the rubber foam produced.

The eco-friendly flame retardant is contained in an amount of 30 to 80% by weight, and serves to provide flame retardant performance to the flame retardant mixture to provide a high flame retardant masterbatch, 100 parts by weight of inorganic metal hydroxide, 30 to 40 parts by weight of expanded graphite It is preferably composed of 60 to 70 parts by weight of the phosphorus-based flame retardant and 70 to 90 parts by weight of zinc borate.

The inorganic metal hydroxide is a component that is the main material of an eco-friendly flame retardant, and exhibits eco-friendliness and excellent flame retardancy, thereby providing flame retardancy to the masterbatch according to the present invention. Preferably, it is made of at least one selected from the group consisting of aluminum hydroxide and magnesium hydroxide do.

The expanded graphite contains 30 to 40 parts by weight, and serves to impart heat insulation to the masterbatch. After the graphite is purified with water and treated with sulfuric acid for primary expansion, it is purified with purified water and heated to secondary It expands, and through sulfuric acid and heat treatment, the first graphite is manufactured through a process of expanding tens to hundreds of times.

Looking at the general manufacturing method of expanded graphite produced through the above process, graphite is mined from natural mines, then crushed and water graded to make graphite, and the graphite is first expanded using a strong acid such as sulfuric acid. After sintering at high temperature and alkali state, it goes through a washing process to make graphite with a purity of 99.5%, and the cleaned graphite is prepared by expanding the graphite through preheating.

Expanded graphite is a flame retardant that forms a solid layer, and the expanded carbon layer acts as an insulating layer to prevent heat transfer. In the direction perpendicular to each other, it exhibits excellent thermal insulation properties. In addition, expanded graphite has advantages such as non-toxic, light, does not contain halogen components, insoluble in water, and does not generate toxic gas.

If the content of the expanded graphite is less than 30 parts by weight, the effect of flame retardancy and thermal insulation properties is insignificant, and when the content of the expanded graphite exceeds 40 parts by weight, the mechanical properties of the foam to which the masterbatch prepared according to the present invention is applied may be reduced. have.

The phosphorus-based flame retardant contains 60 to 70 parts by weight, and is made of at least one selected from the group consisting of phosphoric acid esters, oligomers of phosphoric acid esters, inorganic phosphorus compounds, ammonium polyphosphate, melamine polyammonium polyphosphate, and ammonium phosphate. It serves to impart flame retardancy to the masterbatch.

If the content of the phosphorus-based flame retardant is less than 60 parts by weight, the flame retardant effect is insignificant, and if the content of the phosphorus-based flame retardant exceeds 70 parts by weight, the processability and impact resistance of the waste rubber foam powder may be deteriorated.

The zinc borate contains 70 to 90 parts by weight, and serves to improve the binding force of the components constituting the waste rubber foam powder and the flame retardant mixture. When the content of the zinc borate exceeds 90 parts by weight, the viscosity of the masterbatch prepared through the present invention is excessively increased, which is not preferable.

The processing aid contains 0.1 to 15 parts by weight, and includes any one or more of the group consisting of a terephthalate-based plasticizer, polyethylene wax, and stearic acid. Specifically, the terephthalate-based plasticizer alone or polyethylene wax and stearic acid is 1:1 Preferably, it is mixed in a weight ratio or a terephthalate-based plasticizer, polyethylene wax, and stearic acid are mixed in a weight ratio of 8: 1: 1 or 6: 2: 2 or 5: 2.5: 2.5 by weight, the rubber and the flame retardant In addition to ensuring that the mixture is evenly mixed, when the masterbatch prepared through the present invention is mixed with the rubber component, it serves to improve the processability of rubber to be molded into various shapes.

When the content of the processing aid is less than 0.1 parts by weight, the above effect is insignificant, and when the content of the processing aid exceeds 15 parts by weight, the effect is not significantly improved and the molded article to which the masterbatch manufactured through the present invention is applied. may reduce the mechanical properties of

In the raw material mixing step (S103), a rubber resin, a high-flammability eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder produced through the flame-retardant masterbatch manufacturing step (S101), a foaming masterbatch and a crosslinking masterbatch are mixed. 100 to 200 parts by weight of a rubber resin, 100 to 200 parts by weight of a non-flammable eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder prepared through the flame retardant masterbatch manufacturing step (S101), 100 to 200 parts by weight of the foaming masterbatch It is made by mixing 10 to 20 parts by weight of the masterbatch for crosslinking and 10 parts by weight.

At this time, the master batch for foaming consists of 100 parts by weight of a rubber resin and 25 to 100 parts by weight of a foaming agent, and the foaming agent is preferably made of azodicarbonamide. By allowing the mixture prepared through (S103) to be foamed in the foaming step (S105), it serves to provide a foam that is light in weight and exhibits excellent sound absorption and thermal insulation properties.

If the content of the master batch for foaming is less than 100 parts by weight, the above effect is insignificant. may be lowered.

In addition, the crosslinking masterbatch consists of 100 parts by weight of a rubber resin and 5 to 100 parts by weight of a crosslinking agent mixture, and the crosslinking agent mixture is a sulfur compound, 2-mercaptbenzothiazole (M), dibenzothiadyl disulfide (DM) and Zn-dimethyldithiocaabamate (PZ). The crosslinking masterbatch made of the above components is a mixture prepared through the raw material mixing step (S103) is foamed in the foaming step (S107). In the process, it induces a crosslinking reaction and serves to provide a foam with excellent mechanical properties.

If the content of the masterbatch for crosslinking is less than 10 parts by weight, the crosslinking reaction proceeds slowly, and the above effect is insignificant because the crosslinking rate is low. When the content of the masterbatch for crosslinking exceeds 20 parts by weight, the crosslinking rate increases excessively. Processability of the foam may be reduced.

The extruding step (S105) is a step of extruding the mixture prepared through the raw material mixing step (S103), and the mixture prepared through the raw material mixing step (S103) is put into the extruder and a temperature of 35 to 80° C., preferably Preferably, it is a step of preparing an extrudate at a temperature of 35 to 50 °C.

The foaming step (S107) is a step of putting the extrudate prepared through the extrusion step (S105) into a foaming furnace and foaming, at a temperature of 100 to 180° C., preferably at a temperature of 100 to 170° C. for 10 to 30 minutes. During the firing process is made.

At this time, the foaming step (S107) may be made using a mold such as a press in addition to the foaming furnace, and in the foaming step (S107), not only the foaming process but also the crosslinking of the foamed product due to the masterbatch for crosslinking proceeds at the same time.

The cutting step (S107) is a step of cutting the foamed product through the foaming step (S105). After cooling the foamed product in various shapes and thicknesses through the foaming step (S105) to room temperature, it is suitable for use. It consists of a process of cutting to various sizes to fit.

At this time, the process of cutting the foam is not particularly limited, and it proceeds as a cutting process of a conventional foam, and is performed using a conventional cutting device.

Hereinafter, a method for producing a high-flammability and eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder according to the present invention and the physical properties of the foam produced by the method will be described by way of examples.

<Preparation Example 1> Preparation of polymer nanoclay composite

100 parts by weight of rubber, 7 parts by weight of nanoclay (Cloisite 10A) and 7 parts by weight of compatibilizer (polyethylene graft maleic anhydride) were put into a mixer, and high speed (>200 RPM), high temperature (>180 ℃), short time (<5 min.) to prepare a polymer nanocomposite.

<Preparation Example 2> Preparation of high-flammability eco-friendly rubber-based nanocomposite masterbatch using waste rubber foam powder

20% by weight of the polymer nanoclay composite prepared in Preparation Example 1, 30% by weight of waste rubber foam powder (nitrile-butadiene rubber), and an eco-friendly flame retardant {inorganic metal hydroxide (magnesium hydroxide) 100 parts by weight, expanded graphite 35 parts by weight, phosphorus-based 65 parts by weight of a flame retardant (ammonium polyphosphate) and 80 parts by weight of zinc borate} 125 parts by weight of a flame retardant mixture in which 60% by weight is mixed, and 10 parts by weight of a processing aid (a 1:1 mixture of polyethylene wax and stearic acid) are added to the mixer, After mixing at 120±5° C., extruded in a single screw extruder to form a sheet or pellet, and cooled to prepare a high-flammability eco-friendly rubber-based nanocomposite masterbatch using waste rubber foam powder.

<Preparation Example 3> Preparation of high-flammability eco-friendly rubber-based nanocomposite masterbatch using waste rubber foam powder

Proceeds in the same manner as in Preparation Example 2, but 100 parts by weight of the flame retardant mixture prepared in Preparation Example 1 and 5 parts by weight of a processing aid were mixed to prepare a high-flammability eco-friendly rubber-based nanocomposite masterbatch using waste rubber foam powder.

<Preparation Example 4> Preparation of high-flammability eco-friendly rubber-based nanocomposite masterbatch using waste rubber foam powder

Proceeds in the same manner as in Preparation Example 2, but 150 parts by weight of the flame retardant mixture prepared in Preparation Example 1 and 15 parts by weight of a processing aid were mixed to prepare a high-flammability eco-friendly rubber-based nanocomposite masterbatch.

<Preparation Example 5> Preparation of masterbatch for foaming

100 parts by weight of a rubber resin (nitrile butadiene rubber) (Preparation Example 5-1) or a rubber resin (ethylene propylene diene monomer) (Preparation Example 5-2) and 60 parts by weight of a foaming agent (azodicarbonamide) at 110 to 120° C. Thus, a master batch for foaming was prepared.

<Preparation Example 6> Preparation of masterbatch for crosslinking

100 parts by weight of a rubber resin (nitrile butadiene rubber) (Preparation Example 6-1) or a rubber resin (ethylene propylene diene monomer) (Preparation Example 6-2), a crosslinking agent mixture (sulfur, [2-mercaptbenzothiazole (M)) , dibenzothiadyl disulfide (DM), Zn-dimethyldithiocabamate (PZ)] 40 parts by weight were mixed at 70 to 75° C. to prepare a crosslinking masterbatch.

<Example 1>

150 parts by weight of a high-flammability eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder prepared in Preparation Example 2 in 100 parts by weight of a rubber resin (nitrile butadiene rubber) and a foaming master prepared in Preparation Example 5-1 150 parts by weight of the batch and 15 parts by weight of the masterbatch for crosslinking prepared in Preparation Example 6-1 were put into an extruder and extruded at a temperature of 40° C., and then the extruded product was put into a foaming furnace to a temperature of 100 to 170° C. After cross-linking and foam molding for 20 minutes, cooling and cutting were performed to prepare a high-flammability and eco-friendly rubber-based nanocomposite foam using waste rubber foam powder.

<Example 2>

Proceed in the same manner as in Example 1, but using the high-flammability eco-friendly rubber-based nano-composite masterbatch using the waste rubber foam powder prepared in Preparation Example 3, high-flammability and eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder was prepared.

<Example 3>

Proceed in the same manner as in Example 1, but using the high-flammability eco-friendly rubber-based nano-composite masterbatch using the waste rubber foam powder prepared in Preparation Example 4, high-flammability and eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder was prepared.

<Example 4>

150 parts by weight of a non-flammable eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder prepared in Preparation Example 2 in 100 parts by weight of a rubber resin (ethylene propylene diene monomer) and for foaming prepared in Preparation Example 5-2 150 parts by weight of the masterbatch and 15 parts by weight of the masterbatch for crosslinking prepared through 6-2 in the above preparation were put into an extruder and extruded at a temperature of 40° C. After crosslinking and foam molding at a temperature for 20 minutes, cooling and cutting were performed to prepare a high-flammability and eco-friendly rubber-based nanocomposite foam using waste rubber foam powder.

<Example 5>

Proceeds in the same manner as in Example 4, but using the high-flammability eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder prepared in Preparation Example 3, high-flammability and eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder was prepared.

<Example 6>

Proceeded in the same manner as in Example 4, but using the high-flammability eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder prepared in Preparation Example 4, high-flammability and eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder was prepared.

Harm of high-flammability eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder prepared in Preparation Examples 2 to 4 and the high-flammability eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder prepared in Preparation Examples 1 to 6 The content of the components was measured and shown in Table 1 below.

{However, the method of checking the content of 6 major hazardous substances using IEC 62321 was used for the presence or absence of harmful ingredients.}

division Cadmium (Cd) Mercury (Hg) Lead (Pb) Hexavalent chromium (Cr ⁶⁺ ) Polybrominated biphenyls (PBBs) Polyvinyl bromide (PBDEs) Preparation 2 non-detection non-detection non-detection non-detection non-detection non-detection Preparation 3 non-detection non-detection non-detection non-detection non-detection non-detection Preparation 4 non-detection non-detection non-detection non-detection non-detection non-detection Example 1 non-detection non-detection non-detection non-detection non-detection non-detection Example 2 non-detection non-detection non-detection non-detection non-detection non-detection Example 3 non-detection non-detection non-detection non-detection non-detection non-detection Example 4 non-detection non-detection non-detection non-detection non-detection non-detection Example 5 non-detection non-detection non-detection non-detection non-detection non-detection Example 6 non-detection non-detection non-detection non-detection non-detection non-detection

As shown in Table 1, it can be seen that the high-flammability eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder prepared in Preparation Examples 2 to 4 of the present invention does not contain harmful components and is therefore eco-friendly.

The flame retardancy and drying loss of the high-flammability eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder prepared in Preparation Examples 2 to 4 were measured and shown in Table 2 below.

{However, the measurement method of KSM ISO 4589-2 was used for flame retardancy, and the measurement method of KSM 0009:2010 was used for loss on drying.}

division Flame retardant (LOI, %) Loss on drying (%) Preparation 2 ≤ 47 0.02 Preparation 3 ≤ 46 0.01 Preparation 4 ≤ 48 0.02

In addition, the flame retardancy, heat insulation and impact resistance of the high-flammability and eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder prepared in Examples 1 to 6 were measured and shown in Table 3 below.

{However, the measurement method of KSM ISO 4589-2 was used for flame retardancy, the measurement method of KSL 9016 was used for thermal insulation, and the impact resistance of the foam prepared in Examples 1 to 6 was 150 mm horizontal × 150 mm vertical × 0.9 mm thick. It was cut into a specimen and the measurement method of JIS P8134 (1976) was used.}

division Flame retardant (LOI, %) Insulation (W/m.K) Impact resistance (kgf cm) Example 1 ≤ 40 ≤ 0.035 138 Example 2 ≤ 38 ≤ 0.034 146 Example 3 ≤ 37 ≤ 0.037 136 Example 4 ≤ 39 ≤ 0.033 152 Example 5 ≤ 36 ≤ 0.032 163 Example 6 ≤ 34 ≤ 0.033 152

As shown in Table 3, it can be seen that the high-flammability and eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder prepared in Examples 1 to 6 of the present invention has excellent flame retardancy, heat insulation and impact resistance.

Therefore, the method of manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using the waste rubber foam powder according to the present invention is environmentally friendly by recycling waste rubber foam powder without containing a halogen-based flame retardant component, light weight and excellent sound absorption performance It also provides a foam excellent in flame retardancy, heat insulation, heat resistance and mechanical properties.

S101; Flame retardant masterbatch manufacturing stage
S103; Raw material mixing step
S105 ; Extrusion step
S107; foaming step
S109; cutting step

Claims (10)

100 parts by weight of rubber; 100 to 150 parts by weight of a flame retardant mixture consisting of 10 to 30% by weight of a polymer nanoclay composite, 10 to 50% by weight of waste rubber foam powder, and 30 to 80% by weight of an eco-friendly flame retardant; and 0.1 to 10 parts by weight of a processing aid; a flame retardant masterbatch manufacturing step of preparing a high-flammability eco-friendly rubber-based nanocomposite masterbatch using waste rubber foam powder consisting of;
A raw material mixing step of mixing a rubber resin, a high-flammability eco-friendly rubber-based nano-composite masterbatch manufactured through the flame-retardant masterbatch manufacturing step, a foaming masterbatch and a crosslinking masterbatch;
an extrusion step of extruding the mixture prepared through the raw material mixing step;
a foaming step of foaming the extrudate prepared through the extrusion step; and
A cutting step of cutting the foamed product through the foaming step;
The waste rubber foam powder has a particle size of 1 to 10 μm, characterized in that it is prepared by liquid nitrogen, a milling machine, or crushing,
The polymer nanoclay composite is prepared by adding 100 parts by weight of a rubber resin, 1 to 15 parts by weight of nanoclay, and 1 to 15 parts by weight of a compatibilizer to a mixer, and mixing at 200 to 500 RPM at a temperature of 180 to 220° C. for 3 to 5 min. It is characterized by
The eco-friendly flame retardant comprises 100 parts by weight of inorganic metal hydroxide, 30 to 40 parts by weight of expanded graphite, 60 to 70 parts by weight of phosphorus-based flame retardant, and 70 to 90 parts by weight of zinc borate. A method for producing a rubber-based nanocomposite foam.
delete The method according to claim 1,
The rubber is a method of manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using a waste rubber foam powder, characterized in that it consists of at least one selected from the group consisting of nitrile butadiene rubber and ethylene propylene diene monomer.
delete delete delete The method according to claim 1,
The inorganic metal hydroxide is a method of manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using a waste rubber foam powder, characterized in that it consists of at least one selected from the group consisting of aluminum hydroxide and magnesium hydroxide.
The method according to claim 1,
The raw material mixing step includes 100 parts by weight of a rubber resin, 100 to 200 parts by weight of a non-flammable eco-friendly rubber-based nanocomposite masterbatch using the waste rubber foam powder produced through the flame retardant masterbatch manufacturing step, 100 to 200 parts by weight of a foaming masterbatch and 10 to 20 parts by weight of the masterbatch for crosslinking.
The method according to claim 1,
The master batch for foaming is a method of manufacturing a high-flammability and eco-friendly rubber-based nanocomposite foam using waste rubber foam powder, characterized in that it consists of 100 parts by weight of rubber and 25 to 100 parts by weight of a foaming agent.
The method according to claim 1,
The foaming step is a method for producing a high-flammability and eco-friendly rubber-based nanocomposite foam using a waste rubber foam powder, characterized in that made at a temperature of 100 to 180 ℃ for 5 to 60 minutes.

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