KR100496175B1 - A composition and manufacturing method of flame retarding rubber/plastics foams with low toxic gas liberation and low smoke density under fire atmosphere - Google Patents

Abstract

The present invention relates to a flame retardant rubber / plastic foam composition which minimizes toxic gas and smoke density, and a method of manufacturing the same, and more particularly, to a rubber resin, a polyolefin resin, and, in some cases, a (waste) tire rubber powder ( GTR), cumarone resin blended with inorganic metal hydroxide, organophosphorus compound, zinc-borate, loess, charcoal, etc. as flame retardant, and other additives (foaming agent, crosslinking agent and preparation), etc. Excellent environmental friendliness, stability, flame retardancy and mechanical properties, it can be used in a wide range of applications such as building materials, automobile parts, railway parts, sporting goods and other industrial products by extrusion, compression or injection molding. Flame retardant with minimized toxic gas and smoke density with new composition that can be used very usefully by securing stability and flame retardancy Rubber / plastic foam relates to a composition and a method of manufacturing the same. Therefore, the present invention is completely excluded from the halogen compound that emits harmful gases in the event of fire and is designed to relatively increase the char (char) formation.

Description

A composition and manufacturing method of flame retarding rubber / plastics foams with low toxic gas liberation and low smoke density under fire atmosphere

The present invention relates to a flame retardant rubber / plastic foam composition which minimizes toxic gas and smoke density, and a method of manufacturing the same, and more particularly, to a rubber resin, a polyolefin resin, and, in some cases, a (waste) tire rubber powder ( GTR), cumarone resin blended with inorganic metal hydroxide, organophosphorus compound, zinc-borate, loess, charcoal, etc. as flame retardant, and other additives (foaming agent, crosslinking agent and preparation), etc. Excellent environmental friendliness, stability, flame retardancy and mechanical properties, it can be used in a wide range of applications such as building materials, automobile parts, railway parts, sporting goods and other industrial products by extrusion, compression or injection molding. Flame retardant with minimized toxic gas and smoke density with new composition that can be used very usefully by securing stability and flame retardancy Rubber / plastic foam relates to a composition and a method of manufacturing the same.

Existing foams are molding compositions widely used in construction, construction, automobiles, railways, sporting goods and other fields, and are considered to be flame retardant and harmful to humans in the event of fire due to various regulations around the world and domestic countries based on environment and stability. However, minimization of toxic gas and smoke density is required. However, in case of conventional products, the degree of flame retardancy is low, and the use of halogen-based flame retardants releases toxic gases such as hydrogen chloride (HCl), which is applicable to human health. The scope is shrinking.

Known flame retardant polyolefin foams, in the case of flame retardant foams of VO grade according to ASTM-D-2863 or class "O" according to BS 476, the composition of which only blends nitrile rubber (NBR) and polyvinyl chloride (PVC) A case has been disclosed in which a resin is added with a flame retardant and other additives, and a material which is not a foam but whose smoke density is reduced for thermal insulation and wire coating is used in polyvinyl chloride (PVC) and chlorinated polyvinyl chloride (molybdemum oxide). , alumina trihydrate, isodecyl dipheyl phosphate and other additives have been disclosed. (US Pat. No. 5,518,033, Ronald S. Lenox, Lancaster, Pa .; Kim S. Boyd, Quincy, Mass .; William S. Vought, Jr., Landisville, Pa, Feb. 16, 1993), (US Patent No. 4670494, Gary Chemical Corp., Leominster, Mass, Jun. 2, 1987), (US Patent No. 4245055, Wayne E) Smith, Washington Boro, Pa, Jan. 13, 1981). 607, David M. Florence, Lancaster, Pa, Nov. 23, 1976).

Although such a flame retardant composition is slightly different depending on its specification, one of the compositions is representatively exemplified by 15 to 85 parts by weight of polyvinyl chloride or 1 to 200 parts by weight, plasticizer based on 100 parts by weight of nitrile rubber. 10 to 100 parts by weight, flame retardant 100 parts by weight (5 to 75 parts by weight of iron oxide) / 10 to 85 parts by weight of lubricant, 0.1 to 10 parts by weight of stabilizer, 10 to 20 parts by weight of blowing agent, 2.5 parts by weight of sulfur, zinc oxide (ZnO 5 parts by weight, 2.1 parts by weight of stearic acid, 0.8 parts by weight of benzothial disulfides (MBTS), and 0.4 parts by weight of tetramethylthinram monosulfide (Monex).

In addition, the present inventors have applied for an improved composition of a flame retardant polyolefin foam composition and a method for producing the same, by blending polyolefin and rubber-based resins and adding inorganic and chlorine-based flame retardants and other additives to improve the problems of conventional flame retardant compositions. Korean Patent Application No. 1999-0047008] And based on rubber-based resin (NBR) alone, flame retardant (inorganic metal hydroxide, organophosphorus compound, etc.) and other additives are added to minimize the toxic gas and smoke density of the improved composition A flame retardant foam composition and a method of manufacturing the same have been applied for. [Korean Patent Application No. 10-2002-0016508]

Although the conventional flame retardant polyolefin foam composition has a certain degree of flame retardancy, other physical properties are not good, and in particular, it is difficult to consider it as an environmentally friendly material because a large amount of toxic gas and smoke density are released during a fire, and there is much room for improvement. . In the case of the composition of the flame retardant polyolefin foam and the method for producing the same filed by the present inventors (Korean Patent Application No. 1999-0047008), the flame retardancy is improved and the toxic gas and the smoke density have been reduced. In addition, in the case of a flame-retardant foam composition which minimizes toxic gas and smoke density based on rubber resin (NBR) only and its manufacturing method [Korean Patent Application No. 10-2002-0016508] Has been significantly reduced.

Therefore, in the present invention, in order to greatly improve the disadvantages in the conventional flame retardant polyolefin foam composition and the composition filed by the present inventors, in particular, in order to minimize the toxic gas and smoke density in consideration of human harmfulness in the event of a fire, and the present inventors In order to minimize the toxic gas in the filed composition and maximize the smoke density reduction, it is possible to completely remove the halogen compound and to use nitrile rubber and ethylene propylene copolymer, polyethylene, waste polyethylene, ethylene vinyl copolymer, waste ethylene vinyl In particular, environmentally friendly and stable materials are used in comparison with conventional compositions by using a combination of polymers, blending (waste) tire rubber powder (GTR) and cumarone resins, and newly forming a series of compositions such as the composition of flame retardants and other additives. Flame retardant rubber / plastic foot with excellent flame retardancy and mechanical properties To provide a body composition it is an object.

The present invention comprises nitrile rubber, ethylene propylene copolymer, polyethylene, waste polyethylene, ethylene vinyl copolymer, waste ethylene vinyl copolymer, waste tire rubber (GTR), and guarone resin as additives, and as a additive, a flame retardant and a foaming agent. In the flame retardant rubber / plastic foam composition containing a crosslinking agent, etc., the resin component is 5 to 100 parts by weight of nitrile rubber, 5 to 100 parts by weight of ethylene propylene copolymer, 5 to 100 parts by weight of polyethylene, 5 to 100 parts by weight of pepolyethylene. , 5 to 100 parts by weight of ethylene vinyl copolymer, 5 to 100 parts by weight of waste ethylene vinyl copolymer, or 1 to 40 parts by weight of waste tire rubber powder (GTR), and 1 to 10 parts by weight of guarone. OH) ₃ 30 to 300 parts by weight Mg (OH) ₂ 20 to 250 parts by weight, Sb ₂ O ₃ 1 to 30 parts by weight, Sb ₂ O ₅ 1 to 20 parts by weight, diphenylcresylphosphate [Diphenylchresylphosphate; DPK] 5 to 100 parts by weight, zinc borate 1 to 50 parts by weight, red 1 to 30 parts by weight, ocher 1 to 30 parts by weight, charcoal to 1 to 20 parts by weight, 3- (hydroxyphenylphosphinyl) propanoic acid [3- (Hydroxyphenylphosphinyl) propanoic acid; H-205] or 9,10-dihydro-9-oxa-10- [2,3-di- (hydroxyethoxy) carbonylpropyl] -10-phosphaphenanthrene-10-oxide [9,10 -Dihydro-9-oxa-10- [2,3-di- (hydroxyethoxy) carbonyl propyl] -10-phosphaphenanthrene-10-oxide; H-201] 1 to 50 parts by weight, zinc sulfate (1-20 parts by weight), expandable graphite (expandable graphite) 1-30 parts by weight, ammonium polyphosphate (ammonium polyphosphate) 1-30 parts by weight, A flame retardant is contained in an amount of 1.9 to 3.6 parts by weight based on 1 part by weight of the resin component, and it is characterized by containing a conventional additive.

Such a foam composition according to the present invention, when NBR and EPDM (NBR / EPDM / PE / EVA / GTR / Cuumarone) is used as the base resin, 1 to 20 parts by weight of a stabilizer as an additive to a mixed composition of a resin and a flame retardant and a foaming agent 10 A composition containing ˜40 parts by weight is mixed at 110 to 130 ° C., and 0.1 to 5 parts by weight of a vulcanizing agent and 0.1 to 5.5 parts by weight of a vulcanization accelerator are added thereto, followed by extrusion, compression or injection. (virgin, waste) and EVA (virgin, waste) (PE / W-PE / EVA / W-EVA / EPDM), which also contains 10 to 40 parts by weight of blowing agent as an additive in the mixed composition of resin and flame retardant. The composition can be prepared by mixing at 110 to 138 ° C, adding 1 to 20 parts by weight of a crosslinking agent and then extruding, compressing or injecting it.

Referring to the present invention in more detail as follows.

Specific examples of the component composition of the composition of the present invention, the resin component is nitrile rubber, ethylene propylene copolymer, polyethylene, waste polyethylene, ethylene vinyl copolymer, waste ethylene vinyl copolymer and in some cases (waste) In a flame retardant rubber / plastic foam composition containing tire rubber powder (GTR) and cumarone resin and containing as a additive a flame retardant, a foaming agent, a crosslinking agent, etc., the resin component is 5 to 100 parts by weight of nitrile rubber and 5 to 100 ethylene propylene copolymer. 5 parts by weight of polyethylene, 5 to 100 parts by weight of polyethylene, 5 to 100 parts by weight of pepolyethylene, 5 to 100 parts by weight of ethylene vinyl copolymer, 5 to 100 parts by weight of waste ethylene vinyl copolymer or (waste) tire rubber powder (GTR) 1 to 40 parts by weight, obtain a mixed composition, and 1 to 10 weight parts maroon, as the flame retardant Al (OH) Mg (OH) 2 20 ~250 parts by weight of _330-300 parts by weight of Sb ₂ O ₃ 1~30 parts by weight, Sb ₂ O ₅ 1-20 parts by weight, deep Ylcresylphosphate [Diphenylchresylphosphate; DPK] 5 to 100 parts by weight, zinc borate 1 to 50 parts by weight, red 1 to 30 parts by weight, ocher 1 to 30 parts by weight, charcoal to 1 to 20 parts by weight, 3- (hydroxyphenylphosphinyl) propanoic acid [3- (Hydroxyphenylphosphinyl) propanoic acid; H-205] or 9,10-dihydro-9-oxa-10- [2,3-di- (hydroxyethoxy) carbonylpropyl] -10-phosphaphenanthrene-10-oxide [9,10 -Dihydro-9-oxa-10- [2,3-di- (hydroxyethoxy) carbonyl propyl] -10-phosphaphenanthrene-10-oxide; H-201] 1 to 50 parts by weight, zinc sulfate (1-20 parts by weight), expandable graphite (expandable graphite) 1-30 parts by weight, ammonium polyphosphate (ammonium polyphosphate) 1-30 parts by weight, A flame retardant is contained in an amount of 1.9 to 3.6 parts by weight based on 1 part by weight of the resin component. Here, as the additive, 1 to 20 parts by weight of a stabilizer, 1 to 20 parts by weight of a crosslinking agent and 2-melcap benzotia as a crosslinking accelerator. 0.1 to 5.5 parts by weight of sol (M), dibenzothiadyl disulfide (DM) and Zn-dimethyl dithiocarbamate (PZ), 10 to 40 parts by weight of blowing agent, and 0.1 to 5 parts by weight of foaming aid At least one of 0.1 to 10 parts by weight of the heat transfer accelerator, 0.1 to 10 parts by weight of the external release agent, 0.1 to 10 parts by weight of the internal mold release agent, 0.1 to 10 parts by weight of the anti-aging agent, 0.1 to 10 parts by weight of the moisture absorbent, and 1 to 20 parts by weight of the filler. The above can be produced by further including. In particular, in the present invention, in consideration of recycling According to the preliminary experiments, W-PE as a waste resource preferably used has a molecular weight of about 5,000 to 15,000, which is lower than that of the original pure PE, and W-EVA also has a value of 1/2 to 2/3 of the pure EVA molecular weight. It is just too low. Therefore, such W-PE, W-EVA can be made much easier crosslinking than a pure raw material and makes the foaming process easier. In addition, GTR as waste resources is made by pulverizing automobile (waste) tires of ordinary cars, trucks, buses, etc., and has a high chemical stability and low air pollutant content. It can be used as a good filler.

(Rubber) tire rubber powder (GTR) has a crosslinked structure, and has a high carbon black content and toughness, so it can be well matched with the plastic used with it. Activated carbon and the like are suitable for the particle-reinforced composite material, and thus have a very useful effect. Furthermore, in the combustion state, char is easily formed, thereby forming a heat insulation layer on the surface and blocking the combustion propagation into the inside. In addition, since the GTR is added in a powder form, it is easy to disperse in the matrix resin, and according to the size of the particles, it greatly affects the mechanical properties of the composite. The characteristics will fall. Therefore, in consideration of the above, the GTR used in the present invention is preferably used having a particle size of 0.5mm or less, but the present invention does not place any particular limitation on its size.

On the other hand, the present invention is characterized by the use of ocher as a flame retardant component in addition to the above GTR, the ocher used in the present invention is preferably kaolin (Al2O3 · 2SiO2 · nH2O) and montmorillonite (monmorillonite; Al2O3) 4SiO2, 6H2O), pyrophyllite (Al2O3, 4SiO2, H2O), illite (KAl2 (OH) 2 [AlSi3 (O, OH) 10]) and talc (3MgO4SiO2H2O) Refers to one or more mixtures selected from. Depending on the type of loess, they can intercalate organic materials and have an extremely high specific surface area of more than about 800 m2 / g, which acts as an absorbent and can serve as an efficient filler due to their high surface adsorption. .

On the other hand, the composition of the GTR used in the present invention can be used that generally shows a chemical composition as shown in Table 1.

In Table 1, a denotes a passenger car tire, b denotes a light truck tire, c denotes a truck and a bus tire, d denotes a value obtained by gas chromatographic analysis, e denotes a value obtained by sodium sulfite method, and f denotes a nitrate analysis method. The figures are shown.

In general, tires are mainly composed of natural rubber (NB), styrene-butadiene rubber (SBR) and butadiene rubber (BR). The composition is determined as shown in Table 2.

In Table 2, a includes polyisoprene rubber (IR), and b includes butyl halide (IIR) isobutylene-isoprene rubber (IIR).

In the present invention, the case of using one component among the eight components as the resin component, as well as the case of using two or more components and all eight components.

In the present invention, in consideration of the environment and safety, that is, in the event of a fire in consideration of the harmful effects of the human body caused by the release of toxic gases such as hydrogen chloride (HCl) without using a halogen-based flame retardant, inorganic flame retardant (Al (OH) 3, etc.) and phosphorus The flame retardant was maximized by using a flame retardant. In general, halogenated compounds have a flame retardant effect by fundamentally stabilizing radicals generated in the gas phase, and the mechanism is inferred by a chemical reaction as in Scheme 1 below.

HO · + HX ---> HOH + X

X · + RH ---> HX + R · Regeneration (Stop chain reaction)

XO · + · OH ---> HX + O2 (flame retardant effect by reducing the concentration of active O · and · OH and stopping the chain reaction)

X + O + M ---> XO + M

X2 + O · ---> XO · + X · (Effect of blocking O2 by generating incombustible gas during decomposition)

O + OX ---> O2 + X

In the chemical formula 1, activating radicals such as OH radicals generate heat through a chemical reaction, and the latent heat generated acts as an energy source required for combustion of surrounding flammable materials.

On the other hand, the flame retardant gives the flame retardant effect by reducing the concentration of the active radicals O · and · OH and stopping the chain reaction as in the above mechanism, the cleavage of CX bond during combustion has the effect of reducing the heat of combustion of the combustible material by the endothermic reaction. . It also has the effect of blocking oxygen by generating incombustible gases during decomposition. Therefore, the actual flame retardant effect is given by HX and reacts and is converted into X radical of low energy source. In addition, the halogen-containing flame retardant exhibits a flame retardant effect even in the solid phase. HX acts as an oxidation catalyst of the combustible material, and the oxidized material is ring-structured, resulting in a carbon compound char. The carbon compound thus produced serves to help prevent the combustible material from below the combustion zone by blocking oxygen and latent heat.

In the present invention, as mentioned above, the inorganic flame retardant is completely used in view of human hazards in view of human hazards, and inorganic and phosphorus-based flame retardants. For example, aluminum hydroxide, antimony oxide, magnesium hydroxide, and boron-containing compounds may be used. As the phosphorus-based flame retardant, DPK (trade name), red, ammonium polyphosphate, H-205 (trade name), H-201 (trade name) and the like can be used. Unlike organic flame retardants, inorganic flame retardants are not volatilized by heat and decompose to release nonflammable gases such as H2O, CO2, SO2, HCl and are mostly endothermic. In the gas phase, the flammable gas is diluted and the plastic surface is coated to prevent the access of oxygen. At the same time, there is an effect of reducing the generation of plastic cooling and pyrolysis through endothermic reactions on the solid phase surface. For example, aluminum hydroxide and magnesium hydroxide produce water after decomposition as shown in Scheme 2, where a large amount of endotherm is accompanied to impart flame retardancy.

2Al (OH) 3 + Heating ------> Al2O3 + 3H2O -298KJ / mol

Mg (OH) 2 + Heating ------> MgO + H2O -328KJ / mol

In addition, antimony trioxide and antimony pentoxide may be used as antimony oxide, and it is used as an adjuvant that exhibits a flame retardant synergistic effect of a halogen-containing flame retardant without being used as such. The mechanism is inferred as follows. That is, SbCl 3 produced in each step reaction of Scheme 3 has an effect of lowering the temperature of the plastic through endothermic reaction, and acts as a radical interceptor like HCl and HBr. Some have suggested that both SbCl3 and SbOCl have a flame retardant synergistic effect by lowering the rate of halogen release in the combustion zone to increase the time to act as a radical interceptor.

In addition, the generated heavy gas surrounds the surface of the solid phase, thereby blocking oxygen access and thus exhibiting a flame retardant effect. This reaction mechanism can be summarized as in Scheme 3 below.

Sb2O3 + 2HCl (~ 250 ℃) ----------> 2SbOCl + H2O

5SbOCl (Maintain 245 ~ 280 ℃) ----------> Sb4O5Cl2 + SbCl3 ↑

4Sb4O5Cl2 (Maintain 410 ~ 475 ℃) ----------> 5Sb3O4Cl + SbCl3 ↑

3Sb3O4Cl (Maintain 475 ~ 565 ℃) ----------> 4Sb2O3 + SbCl3 ↑

Sb2O3 (S) (Maintain at 685 ℃) ----------> Sb2O3 (I)

At this time, pyrophosphoric acid and metaphosphoric acid on the surface play a role of enhancing char formation through dehydration effect, and metaphosphate easily reacts. And because of the generated char, it is difficult for heat to penetrate inside the material, and thus a self insulating layer is generated. In addition, the water generated by the dehydration reaction has the effect of diluting the concentration of the flammable gas to enhance the flame retardant effect, and the amount of soot generated is significantly reduced by converting the generated carbonizable intermediate into char.

In addition, in the present invention, in order to prepare an environmentally friendly composition having a stable stability in consideration of the effects on stability and environmental aspects and processability, especially considering the human hazards, to completely exclude the use of halogen-based flame retardant, preferably Are inorganic flame retardants Al (OH) 3, Mg (OH) 2, zinc borate, Sb2O3, Sb2O5, phosphorus flame retardants H-205 (trade name), H-201 (trade name), DPK (trade name), Red, ammonium polyphosphate and ocher, charcoal, zinc sulfate and expandable graphite are used to ensure stability and environmental friendliness by minimizing toxic gas and smoke density considering human toxicity. It is desirable to have an effect. The present invention includes all of the above 14 components as flame retardants, or one or more components selected from them.

As the blowing agent, azodicarbonamides (7000MC, 5000F, 3000F, ADCA, AC-1000) or N, N'-dinitrosopentamethylenetetramine (N, N'-Dinitrosopentamethylenetetramine; DPT) which are azo compounds Sodium bicarbonate (trade name kycerol-91) is preferably used as the inorganic chemical foaming agent, and urea-based foaming aid (trade name Cellex-A) is used as a foaming aid to control the foamability and temperature which will affect the processability and productivity. ), ZnO can be preferably used as the heat transfer accelerator.

Examples of the crosslinking agent used in the present invention include bis (tert-butylperoxy isopropylbenzene; perkadox) or dicumyl peroxide (DCP) as the peroxide crosslinking agent, sulfur as the vulcanizing agent, and vulcanization accelerator effect, scorch resistance, and furnace resistance. 2-mercapt benzothiazole (M) which is relatively scorch fast as thiazoles in consideration of chemical conversion, activation temperature, dispersibility, contaminant, etc., dibenzothiadyl disulfide (DM) which is relatively scorch slow, and dithio acid It is preferable to use scorch and vulcanized Zn-dimethyl dithiocarbamate (PZ) as a salt in an appropriate ratio as described above, and as a stabilizer, the foaming rate and uniform cell ( Ba-Zn-based stabilizers may be used in consideration of the effect on obtaining the cells, and for example, the trade names BZ-806F and BZ-119 may be preferably used. 2,2,4-trimethyl-1,2-dihydroquinone (Kumanox RD), N- (1,3-Dimethylbutyl)-N'phenyl-ρphenylene diamine (Kumanox 13), N'-isopropyl- N-phenyl-ρ-Phenylene diamine (Kumanox 3C) and Styrenated phenol (Kumanox SP, SP-N) may be preferably used, and as a hygroscopic agent, silitine of silica is considered in consideration of preventing foaming on the foam surface. And CaO is preferably used. The internal mold release agent is polyethylene wax (LC-102N) as a rubber processing enhancer, stearic acid is used as an external mold release agent in consideration of extrudability, and the filler is colored and photooxidized. It is preferable to use carbon black (N550FEF) in consideration of prevention, reinforcing effect and cost reduction.

Method for producing a composition according to the present invention as described above will be described as an example of the present invention through each of the following examples, this embodiment of the present invention is to illustrate the case that is manufactured according to the intended use of the present invention is limited It is not intended that, in the examples, the percentage (%) indicating the content of the composition means% by weight unless otherwise indicated.

The abbreviations of the components used in the examples are NBR is nitrile rubber, EPDM is ethylene propylene copolymer, PE is polyethylene, W-PE is waste polyethylene, EVA is enylene vinyl copolymer, W-EVA is waste ethylene vinyl copolymer, GTR shall mean a (waste) tire rubber powder.

Example 1.

In the composition of the flame-retardant polyolefin foam filed by the present inventors and a method for manufacturing the same (Korean Patent Application No. 99-47008), the thermal and dynamic behaviors of NBR / PE blends according to the composition ratio, temperature, and time were observed, and the morphology at the phase interface was observed. As a result of this study, it was found that no significant phase separation occurred after 10 minutes, and based on this, the thermal and dynamic behaviors of the resin / additive blend, temperature and time were observed, and flame retardancy, toxic gas emission and smoke were observed. Examination was made with regard to density and foamability (foaming rate, cell structure, surface state, etc.). In particular, the resin is composed of NBR, EPDM, PE, W-PE, EVA, and W-EVA in consideration of stability and environmental friendliness (i.e. minimizing toxic gas and smoke density) and flame retardancy, and in some cases, GTR and cumarone resins. The resin composition ratio, the resin / flame retardant composition ratio, the type and content of the flame retardant, and the type and content of other additives were adjusted.

The composition ratio of the resin component was composed as following Tables 3 and 4, respectively, and when NBR and EPDM were used as the basic resin, the blend was used at Rheomixer (HAAKE) without adding crosslinking and crosslinking accelerators. 20-40 minutes, crosslinking and crosslinking accelerator were added, temperature 60-70 ° C., RPM 50, time 5-10 minutes, and extrusion was carried out at a Minimax molder (Bau 915L) at temperature 70-80 ° C., Rs 5 Within 1 to 3 minutes, foaming was carried out in an oven (Carver) at a temperature of 120 to 200 ° C. And when PE (virgin, waste) and EVA (virgin, waste) were used as the base resin, the blend was used at Rheomixer (HAAKE) at 110 ~ 138 ℃, RPM50, 20 ~ 25 minutes, and extrusion was carried out using Minimax Molder (Bau). The foaming was carried out in an oven (HB-503M) at a temperature of 120 to 210 ° C., at a temperature of 110 to 138 ° C., Rs 5, and within 1 to 3 minutes at .915 L). In addition, the foaming investigation was carried out to investigate the surface condition, foaming rate, cell structure after foaming, flame retardancy and toxic gas emission irradiation was used LOI tester (Atlas) and Cone calorimeter (FTT), LOI test ASTM-D-2863 Based on the specimen size of 6.5 +/- 0.5mm, 2.0 +/- 0.25mm and 7.0 ~ 150mm in length, the limiting Oxygen Index (LOI) was measured while arbitrarily adjusting the injection amount of oxygen and nitrogen. In addition, Cone calorimeter test was conducted in accordance with ASTM E 1354-94. The specimen size was 100mm in width, 100mm in length and 9mm in thickness, and the heat flux was 50 ㎾ / m2. HRR (heat release rate), COY (CO yield), CO2Y ( CO2 yield). In addition, the light density was measured using the Atlas smoke density control system, and the morphology survey observed the fracture surface of the specimen using the SEM (JEOL JSM-840A, Hitachi S 4700). It was.

As a result, the resin composition ratio is NBR / EPDM / PE / W-PE / EVA / W-EVA / Cumarone = 0 to 100/0 to 100/0 to 20/0 to 20/0 to 20/0 to 20/0 to 20 wt In case that NBR and EPDM are used as the basic resin, samples 1 to 17 have proper foaming in the temperature range of 120 to 165 ℃, and the time required is 30 minutes, the surface is smooth, and the cell structure Was uniform as a closed cell, and the foaming rate was 200-250%. As a result of LOI test, the marginal oxygen index was found to be 28 ~ 31.5, which is higher than that of conventional commercial foams, and the smoke density, ie, light transmittance, was measured and the smoke density (1-optical transmittance) was 0.065 ~ 0.174. It was found to be significantly lower than 0.267 of the foam. Cone-calorimeter measurement results show that the average HRR is 52 ~ 84㎾ / m2, which is significantly lower than 112㎾ / m2 of the commercialized foam, and the average CO yield is 0.034 ~ 0.068kg / kg, which is less than 0.091kg / kg of the commercialized foam. It was found to be significantly lower. Therefore, it was confirmed that the flame retardancy is much higher than the existing commercialized foam, and the human harmfulness is significantly reduced.

In the case where the resin composition ratio was made of NBR / EPDM / GTR = 0 to 90/0 to 80/10 to 20 wt%, that is, when GTR was used, samples 18 to 31 had a proper foaming at a temperature range of 120 to 170 ° C. At this time, the time required was 30 minutes, the surface was smooth, the cell structure was uniform as a semi-closed cell, and the foaming rate was confirmed to have 200 to 300%. As a result of the LOI test, the marginal oxygen index was found to be significantly higher than the commercialized foams of 37.0 to 39.4, and the smoke density, ie, light transmittance, was found to be significantly lower than the commercialized foams of 0.013 to 0.052. The cone-calorimeter measurement result shows that the average HRR is 42 ~ 61㎾ / m2 and the average CO yield is 0.025 ~ 0.058kg / kg. Therefore, it was also confirmed that the flame retardancy is significantly higher than that of the conventional commercialized foam, and the human harmfulness is significantly reduced.

When the resin composition ratio is made of PE / W-PE / EVA / W-EVA / EPDM = 0 to 100/0 to 100/0 to 100/0 to 100/0 to 10 wt%, that is, PE (virgin, waste) and EVA (virgin, waste) (samples 32-38), the proper foaming occurs at a temperature range of 120-190 ° C, and the time required is 30 minutes, the surface is smooth, and the cell structure is closed. As a result, it was confirmed that the foaming ratio had 325 to 415%. As a result of the LOI test, the marginal oxygen index was found to be 28.1 to 29.1, which is higher than that of the commercialized foam, and the smoke density, that is, the light transmittance, was measured to be 0.004 to 0.030, which was significantly higher than the commercialized foam. And cone-calorimeter measurement results showed that the average HRR is 64 ~ 91㎾ / m2, the average CO yield is 0.004 ~ 0.030kg / kg is significantly lower than the commercialized foam. Therefore, it was also confirmed that the flame retardancy is significantly higher than that of the conventional commercialized foam, and the human harmfulness is significantly reduced.

As a result, the foaming rate is 200 to 415%, the surface is smooth, the cell structure is uniform to clsed-cell and semi-closed cell, and the human harmfulness is greatly reduced (the smoke density, that is, the light transmittance is high, and the complete elimination of halogen compounds) No emission of toxic gases such as hydrogen chloride (HCl), significantly reduced emissions of carbon monoxide and carbon dioxide), and a limiting oxygen index (LOI) of 28.0 to 39.4 with excellent foaming rate and flame retardancy, and toxic gas and smoke density. Minimized foams have been developed, and processing methods and conditions have also been identified.

Therefore, when NBR and EPDM were used as the basic resins in the identified mixing and processing conditions, the blend was prepared at a temperature of 110 to 130 ° C., RPM50 and a time of 20 to 40 minutes without adding a crosslinking and crosslinking accelerator in Rheer (HAAKE). , Crosslinking and crosslinking accelerators were added and the temperature was 60-70 ° C., RPM 50, time 5-10 minutes, and extrusion was carried out within a temperature range of 70-80 ° C., Rs 5, time 1-3 minutes in a Minimax molder (Bau 915L). , Foaming was carried out in an oven (Carver) at a temperature of 120 ~ 200 ℃. And when PE (virgin, waste) and EVA (virgin, waste) were used as the base resin, the blend was used at Rheomixer (HAAKE) at 110 ~ 138 ℃, RPM50, 20 ~ 25 minutes, and extrusion was carried out using Minimax Molder (Bau). Within a temperature range of 110 to 138 ° C, Rs 5, and 1 to 3 minutes at .915 L), foaming is minimized to toxic gases and smoke densities when foamed at an oven temperature of 120 to 210 ° C in an oven (HB-503M). And foams excellent in flame retardancy.

In addition, the observation results for the above results are shown in Tables 5 and 6 and accompanying drawings, Fig. 1 (Sample 3), Fig. 2 (Sample 10), Fig. 3 (Sample 12), Fig. 4 (Sample 18), and Fig. 5 (Sample). 34), FIG. 6 (Sample 35) and FIG. 7 (Sample 36), the cell structure of the conventionally known flame retardant polyolefin foam and the degree of dispersion of additives are shown in FIG. 8 (Company A). And cone-calorimeter measurement results are shown in Figures 9-15.

As described above, the present invention is based on nitrile rubber (NBR), ethylene propylene copolymer (EPDM), polyethylene (PE), waste polyethylene (W-PE), ethylene vinyl copolymer (EVA), The waste ethylene vinyl copolymer (W-EVA) and optionally (waste) tire rubber powder (GTR) and cumarone resin are blended, and the flame retardant is completely eliminated in consideration of the harmful effects of human body in case of fire. It is a composition made of inorganic metal hydroxide, organophosphorus compound, zinc-borate, ocher, charcoal, etc., and mixed with other additives (foaming agent, crosslinking agent and preparation) in an appropriate amount. It has excellent flame retardancy and mechanical properties, especially toxic gas and smoke As it minimizes the density, it has excellent environmental friendliness and stability. Extrusion, compression, or injection molding make it suitable for a wide range of construction materials, automobile parts, railway parts, sporting goods, and other industrial products. Which can be very useful to apply to that effect.

1 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) of the foam composition (sample 3) prepared in Example 1 of the present invention.

Figure 2 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) for the foam composition (sample 10) prepared in Example 1 of the present invention,

3 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) of the foam composition (sample 12) prepared in Example 1 of the present invention.

4 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) of the foam composition (sample 18) prepared in Example 1 of the present invention.

5 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) of the foam composition (sample 34) prepared in Example 1 of the present invention.

6 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) of the foam composition (sample 35) prepared in Example 1 of the present invention.

7 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) of the foam composition (sample 36) prepared in Example 1 of the present invention.

Figure 8 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) for the conventional foam.

Figure 9 shows the heat release rate of the cone-calorimeter measurement results for the foam composition prepared in Example 1 of the present invention,

10 shows the CO yield which is a cone-calorimeter measurement result for the foam composition prepared in Example 1 of the present invention.

Figure 11 shows the CO production rate of the cone-calorimeter measurement results for the foam composition prepared in Example 1 of the present invention,

12 shows the CO 2 yield as a result of cone-calorimeter measurement for the foam composition prepared in Example 1 of the present invention.

Figure 13 shows the CO 2 production rate which is the result of cone-calorimeter measurement for the foam composition prepared in Example 1 of the present invention,

14 shows smoke density (1-optical transmittance), which is a cone-calorimeter measurement result for the foam composition prepared in Example 1 of the present invention.

Figure 15 shows the effective heat of combustion which is a cone-calorimeter measurement results for the foam composition prepared in Example 1 of the present invention.

Claims (6)

Resin components include nitrile rubber, ethylene propylene copolymer, polyethylene, waste polyethylene, ethylene vinyl copolymer, waste ethylene vinyl copolymer, waste tire rubber (GTR), and guaron resin, and as additives, flame retardant, foaming agent, crosslinking agent, etc. A flame retardant rubber / plastic foam composition comprising The resin component is 5 to 100 parts by weight of nitrile rubber, 5 to 100 parts by weight of ethylene propylene copolymer, 5 to 100 parts by weight of polyethylene, 5 to 100 parts by weight of pepolyethylene, 5 to 100 parts by weight of ethylene vinyl copolymer, waste ethylene vinyl air 5 to 100 parts by weight or 1 to 40 parts by weight of waste tire rubber powder (GTR) and 1 to 10 parts by weight of guarone are mixed, and as a flame retardant, Al (OH) ₃ 30 to 300 parts by weight Mg (OH) ₂ 20 250 parts by weight, Sb ₂ O ₃ 1-30 parts, Sb ₂ O ₅ 1-20 parts by weight, diphenylcresylphosphate [Diphenylchresylphosphate; DPK] 5 to 100 parts by weight, zinc borate 1 to 50 parts by weight, red 1 to 30 parts by weight, ocher 1 to 30 parts by weight, charcoal to 1 to 20 parts by weight, 3- (hydroxyphenylphosphinyl) propanoic acid [3- (Hydroxyphenylphosphinyl) propanoic acid; H-205] or 9,10-dihydro-9-oxa-10- [2,3-di- (hydroxyethoxy) carbonylpropyl] -10-phosphaphenanthrene-10-oxide [9,10 -Dihydro-9-oxa-10- [2,3-di- (hydroxyethoxy) carbonyl propyl] -10-phosphaphenanthrene-10-oxide; H-201] 1 to 50 parts by weight of zinc sulfate, 1 to 20 parts by weight of zinc sulfate, 1 to 30 parts by weight of expandable graphite, and 1 to 30 parts by weight of ammonium polyphosphate. Flame retardant rubber / plastic foam composition minimized. The method of claim 1, As the additive, 1 to 20 parts by weight of a crosslinking agent, 2-melcap benzothiazole (M), dibenzothiadyl disulfide (DM), and Zn-dimethyl dithiocarbamate (PZ) 0.1 to 5.5 parts by weight, 10 to 40 parts by weight of foaming agent, 0.1 to 5 parts by weight of foaming aid, 1 to 20 parts by weight of stabilizer, 0.1 to 10 parts by weight of heat transfer accelerator, 0.1 to 10 parts by weight of external mold release agent, 0.1 to 10 parts of internal mold release agent Flame retardant rubber / plastic minimized toxic gas and smoke density, characterized in that at least any one or more of parts by weight, 0.1 to 10 parts by weight of antioxidant, 0.1 to 10 parts by weight of moisture absorbent, 1 to 20 parts by weight of filler Foam composition. The method of claim 1 or 2, wherein the waste polyethylene resin has a melting point of 100 ~ 130 ℃, the waste ethylene vinyl copolymer has a vinyl acetate content of 10 to 50% to minimize the toxic gas and smoke density Flame Retardant Rubber / Plastic Foam Compositions. The flame retardant rubber / plastic foam composition according to claim 1 or 2, wherein the nitrile rubber has an acrylonitrile content of 28 to 34% by weight. The flame retardant rubber / plastic foam composition of claim 1 or 2, wherein the ethylene-propylene copolymer has an ENB content of 4.5 to 8% by weight. The composition according to claim 1 or 2, wherein NBR and EPDM are used as the base resin in the composition at 110 to 130 ° C, and PE (virgin, waste) and EVA (virgin, waste) when the base resin is used. Mixing, Extrusion, and Compression at 138 ° C Or a flame retardant rubber / plastic foam composition which minimizes the toxic gas and the smoke density, which is produced by injection.