KR100415682B1 - A composition for flame retarding polyolefin foams with ground tire rubber and its manufacturing method - Google Patents

Abstract

The present invention relates to a flame-retardant polyolefin foam composition using a tire powder and a method for manufacturing the same, and more specifically, to a polyolefin-based, rubber-based resin, and a tire rubber powder (hereinafter referred to as GTR), and a flame retardant ( Inorganic type), foaming agent, crosslinking agent and other additives, which can be recycled GTR efficiently, and in some cases more environmentally friendly flame retardant by eliminating the use of halogen compounds that have been used for the provision and enhancement of flame retardancy It can manufacture products with excellent mechanical properties and when applied to a wide range of fields such as building materials, automobile parts, sporting goods and other industrial products by extrusion, compression or injection molding, Flame retardant polyols of improved composition which can be very usefully used It relates to a pin foam composition and method for making him.

Description

A composition for flame retarding polyolefin foams with ground tire rubber and its manufacturing method}

The present invention relates to a flame-retardant polyolefin foam composition using a tire rubber powder and a method for manufacturing the same, and more particularly to blending polyolefin-based, rubber-based resins and ground rubber (GTR), and flame retardant (Machine-free), foaming agent, crosslinking agent, and other additives, a composition that can be recycled GTR efficiently, and in some cases more environmentally friendly by eliminating the use of halogen compounds that have been used for the provision and enhancement of flame retardancy Products with excellent flame retardancy and mechanical properties can be manufactured. When applied to a wide range of fields such as building materials, automobile parts, sporting goods, and other industrial products by extrusion, compression, or injection molding, environmental friendliness, stability, and flame retardancy are secured. Flame retardant poly of improved composition which can be used very usefully Olefin foam compositions and methods of making the same.

Existing polyolefin foam is a molding composition that is widely used in construction, construction, automobiles, sporting goods, and other fields. Flame retardancy is required due to various regulations in the world and domestically based on environment and safety. In this case, by using halogen-based compounds (resin and flame retardant) to impart flame retardancy and increase in toxicity due to the release of toxic and corrosive gases such as hydrogen halide, the scope of application is being reduced due to the low flame retardancy.

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) It has been suggested that the resin is prepared by adding a flame retardant and other additives (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. 4245055, Wayne E. Smith, Washington Boro, Pa, Jan. 13, 1981), (US Patent No. 3993607, 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).

However, such a conventional polyolefin foam composition has a certain degree of flame retardancy, but other physical properties are relatively poor, and there is a need to improve the product to a better physical property. In particular, as described above, a halogen-based flame retardant is used. There was much room for improvement due to the harmfulness of humans and the environmental friendliness of halogen compounds.

Accordingly, in the present invention, in order to improve the disadvantages of the conventional flame retardant polyolefin foam composition, nitrile rubber is used as it is in the conventional resin composition, but unlike the conventional ethylene-propylene copolymer (EPDM) and tire rubber powder (GTR) , Ground tire rubber) and polyethylene (PE), and in some cases, some halogen-containing compositions may use conventional nitrile rubber and polyvinyl chloride as they are, but unlike conventional blends combining GTR and chlorinated polyethylene (CPE) The new composition of the flame retardant and other additives is excellent in flame retardancy and mechanical properties compared to the conventional composition, and is environmentally friendly. It is an object to provide a polyolefin foam composition.

1 is an electron microscope (SEM) photograph confirming the cell structure (A), the additive dispersion degree (B) and the surface state (C) with respect to the foam composition (sample 1) according to Example 1 of the present invention.

2 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) with respect to the foam composition (sample 2) according to Example 1 of the present invention.

3 is an electron microscope (SEM) photograph confirming the cell structure (A), the additive dispersion degree (B), and the surface state (C) of the foam composition (sample 6) according to Example 2 of the present invention.

4 is an electron microscope (SEM) photograph confirming the cell structure (A), the additive dispersion degree (B), and the surface state (C) of the foam composition (sample 15) according to Example 2 of the present invention.

5 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) with respect to the conventional foam,

6 is an electron microscope (SEM) photograph confirming the cell structure (A) and the additive dispersion degree (B) with respect to the foam composition (sample 18) according to Example 3 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 28) according to Example 3 of the present invention.

The present invention is directed to a flame retardant polyolefin foam composition comprising nitrile rubber essentially as a resin component and comprising at least one additive of a flame retardant, crosslinker, plasticizer, foaming agent, filler, moisture absorbent, anti-aging agent, lubricant, stabilizer as conventional additives. In addition, components such as nitrile rubber, polyvinyl chloride, and chlorinated polyethylene, which have been used as tire resin powders (GTR) as essential resin components, and natural rubber, styrene-butadiene rubber, ethylene-propylene copolymers, polyethylene, etc. It is possible to manufacture a product of excellent physical properties without using a halogen compound, in particular without using a halogen compound, characterized by a flame-retardant polyolefin foam composition composed by adding a predetermined flame retardant and conventional additives.

The present invention is described in detail as follows.

In the flame retardant polyolefin foam composition containing nitrile rubber as a resin component and at least one additive of a flame retardant, a crosslinking agent, a plasticizer, a foaming agent, a filler, a moisture absorbent, an anti-aging agent, a lubricant, and a stabilizer as a conventional additive, The component is composed of 50 to 100 parts by weight of nitrile rubber, 10 to 30 parts by weight of polyvinyl chloride or chlorinated polyethylene, 1 to 100 parts by weight of ethylene-propylene copolymer, and 1 to 50 parts by weight of GTR. (OH) ₃ 10 to 300 parts by weight, Mg (OH) ₂ 1 to 300 parts by weight, Sb ₂ O ₃ 1 to 50 parts by weight, ocher 1 to 20 parts by weight, phosphorus flame retardant (H-205 or H-201) 1 It is composed of ~ 50 parts by weight, but 100 to 350 parts by weight of the flame retardant with respect to 100 parts by weight of the resin component, characterized in that it contains a conventional additive.

The present invention also relates to a flame retardant polyolefin foam composition containing nitrile rubber as a resin component and comprising a flame retardant, a crosslinking agent, a plasticizer, a foaming agent, a filler, a moisture absorbent, an anti-aging agent, a lubricant, and a stabilizer as a conventional additive, wherein the resin component is nitrile. 50-100 parts by weight of any one or more of rubber, natural rubber, styrene rubber and ethylene-propylene copolymer, 1 to 80 parts by weight of polyethylene and 1 to 50 parts by weight of GTR, wherein the flame retardant added is Al (OH ₃ ) 10 to 300 parts by weight, Mg (OH) ₂ 1 to 300 parts by weight, 1 to 50 parts by weight of Sb ₂ O _3, 1 to 20 parts by weight of ocher, and 1 to 20 parts by weight of phosphorus flame retardant (H-205 or H-201), respectively. It is composed of 50 parts by weight, but 100 to 350 parts by weight of the flame retardant with respect to 100 parts by weight of the resin component, characterized in that it contains a conventional additive.

Such a foam composition according to the present invention contains 1 to 70 parts by weight of a plasticizer, 1 to 20 parts by weight of a stabilizer, 10 to 40 parts by weight of a foaming agent, etc., as a conventional additive in a mixture of the above-described selectively composed resin, GTR and flame retardant. 1 to 5 parts by weight of the crosslinking agent and 0.1 to 5 parts by weight of the crosslinking accelerator, respectively, and second mixture at 60 to 70 ° C to extrude, compress or inject to prepare the composition. .

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 50 to 100 parts by weight of nitrile rubber, 10 to 30 parts by weight of polyvinyl chloride or chlorinated polyethylene, 1 to 100 parts by weight of ethylene-propylene copolymer, It is composed of 1 to 50 parts by weight of GTR, and the flame retardant added thereto is 10 to 300 parts by weight of Al (OH) ₃ , _{1 to} 300 parts by weight of Mg (OH) _2, 1 to 50 parts by weight of Sb ₂ O ₃ , and yellow clay 1 It is composed of 1 to 50 parts by weight of -20 parts by weight and 1 to 50 parts by weight of phosphorus-based flame retardant (H-205 or H-201), respectively, and 100 to 350 parts by weight of a flame retardant based on 100 parts by weight of the resin component. ˜70 parts by weight, stabilizer 1-20 parts by weight, crosslinking agent 0.1-5 parts by weight, 2-melcap benzothiazole (M), di-benzothiadyl disulfide (DM) and Zn-dimethyl-di Chioka Abamate (PZ) is 0.1 to 5 parts by weight, 10 to 40 parts by weight of foaming agent, 0.1 to 10 parts by weight of foaming aid, heat transfer head 0.1 to 10 parts by weight, 1 to 20 parts by weight of an external mold release agent, 1 to 20 parts by weight of an internal mold release agent, 0.1 to 10 parts by weight of a moisture absorbent, 0.1 to 10 parts by weight of an antioxidant, and 1 to 20 parts by weight of a filler. have.

In addition, as a specific example of a foam-friendly composition of the composition without using a chlorinated compound in a similar composition, the resin component is selected from at least one of nitrile rubber, natural rubber, styrene rubber and ethylene-propylene copolymer It consists of 50-100 weight part, 1-80 weight part of polyethylene, and 1-50 weight part of GTR, and the other flame retardant and a normal additive can be comprised with the same structure as the said composition.

According to the present invention, in order to prepare the foam composition as described above, after adding a flame retardant component composition to the resin composition, the plasticizer 1 to 70 parts by weight, stabilizer 1 to 20 parts by weight, foaming agent 10 to 40 weight Part was added, followed by primary mixing at 110 to 120 ° C., where 2-melcap-benzothiazole (M) and di-benzothiadyl disulfide (DM) were used as 0.1 to 5 parts by weight of the crosslinking agent and the crosslinking accelerator. and 0.1 to 5 parts by weight was added to each of the Zn-, dimethyl di Bang car Ava formate (PZ) and the secondary mixing at 60~70 ℃ can be produced by extrusion, compression or injection. In addition, in order to improve physical properties, for example, 1 to 20 parts by weight of a coumarone resin may be further used as an adhesion improving agent.

In the present invention, the resin composition is selected from nitrile rubber, natural rubber, styrene rubber, ethylene-propylene copolymer, polyvinyl chloride, chlorinated polyethylene, and polyethylene, and has never been used before. It is composed of using as an essential component, in particular, GTR is preferably used in consideration of recycling in the present invention is made of powder by crushing the car tires, such as ordinary cars, trucks, buses, chemical stability is high and atmospheric Its low content of contaminants allows it to be used as a good filler in polyolefin blend materials.

According to the present invention, since GTR has a crosslinked structure and is high in carbon black content and strong, it can be well harmonized with the plastic used therewith, and also has high UV resistance and high chemical stability, and thus contains activated carbon in itself. Since it is suitable for this particle-reinforced composite material, it shows 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 the particle size greatly affects the mechanical properties of the composite, and as the size increases, problems in interfacial adhesion occur. Tensile properties will be degraded. 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 using ocher as flame retardant component in addition to the above GTR, the ocher used in the present invention is preferably kaolin mineral (kaolin; Al ₂ O ₃ · 2SiO ₂ · nH ₂ O) And montmorillonite (Al ₂ O ₃ · ₄ SiO ₂ · 6 H ₂ O), pyrophyllite (Al ₂ O ₃ · 4 SiO ₂ · H ₂ O), illite (KAl ₂ (OH) ₂ (AlSi) ₃ (O, OH) ₁₀ ]) and talc (3MgO. 4SiO ₂ .H ₂ O). Depending on the type of loess, they can intercalate organic materials and have an extremely high specific surface area of about 800 m ² / g, which acts as an absorbent and can serve as an efficient filler due to their high surface adsorption. do.

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.

Analysis item PC ^a PC + LT ^b TB ^c Rubber powder Rubber powder Rubber powder Type of rubber polymer Compounding ratio ^d (%) NR 20 40 70 SBR 80 45 20 BR - 15 10

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.

division car truck Tread SBR-BR NR ^a -BR or SBR-BR belt NR NR Caucas NR-SBR-BR NR-BR Side wall (black) NR-SBR or NR-BR NR-BR Side wall (bag) NR-SBR-EPDM-IIR ^b - Lina NR-SBR or NR-SBR-IIR NR-IIR

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

As described above, in the present invention, mechanical properties and chemistry are achieved by blending GTR at a predetermined ratio with a resin selected from nitrile rubber, natural rubber, styrene rubber, ethylene-propylene copolymer, polyvinyl chloride, chlorinated polyethylene, and polyethylene in a specific composition. In addition to enhancing physical properties such as stability, tires, which have been mostly discarded or inefficiently used and partly recycled, can be recycled very effectively, usefully and fundamentally to maximize economics, and in some cases, to produce eco-friendly products. It is of great significance to be used as a core essential ingredient.

In particular, the present invention maximized flame retardancy by using only inorganic flame retardants (Al (OH) _3, etc.) in consideration of the environment and safety, as well as using two components as well as three or more of the six components as the resin component. In addition, it is possible to contribute to the maximization of physical properties, diversification of the field of application, environmentally friendly product production, etc. while appropriately utilizing the GTR through a predetermined formulation.

In general, halogenated compounds have a flame retardant effect by fundamentally stabilizing radicals generated in a gas phase, and the mechanism is inferred by the following chemical reaction.

HOH + X

HX + R · regeneration reaction (stop of chain reaction)

HX + O ₂ (Retardant effect by reducing the concentration of active O and OH and stopping the chain reaction)

XO + M

X ₂ XO · + X · (decomposition upon the effect of blocking the generation of non-combustible gas, O ₂₎

O ₂ + 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 a 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 the CX bond during combustion is an endothermic reaction to reduce the heat of combustion of the combustible material have. 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. HX acts as an oxidation catalyst of the combustible material, and the oxidized material is ring-structured, resulting in char, a carbon compound. 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 a flame retardant, in view of human harmfulness, an inorganic type is used without the halogen system, and aluminum hydroxide, antimony oxide, magnesium hydroxide and a boron-containing compound may be used, and 3- (Hydroxyphenylphosphinyl) propanoic acid (trade name) H-205), 9,10-Dihydro-9-oxa-10- [2,3-di- (hydroxyethoxy) carbonylpropyl] -10phosphaphenanthrene-10-oxide (trade name H-201) and the like can be used. Unlike organic flame retardants, inorganic flame retardants are not volatilized by heat and decompose to release incombustible gases such as H ₂ O, CO ₂ , SO ₂ , HCl, and most of them are 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 water through the endothermic reaction on the solid phase surface. For example, aluminum hydroxide and magnesium hydroxide produce water after decomposition as follows, whereby a large amount of endotherm is accompanied to impart flame retardancy.

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

Mg (OH) ₂ MgO + H ₂ O -328KJ / mol

Antimony oxide has antimony trioxide and antimony pentoxide, and 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 below has an effect of lowering the temperature of the plastic through the endothermic reaction, and acts as a radical interceptor like HCl and HBr. Some have suggested that both SbCl ₃ and SbOCl have a flame retardant synergistic effect by lowering the rate of halogen release in the combustion zone, increasing 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.

Sb ₂ O ₃ 2SbOCl + H ₂ O

Sb ₄ O ₅ Cl + SbCl ₃ ↑

4Sb ₄ O ₅ Cl ₂ 5Sb ₃ O ₄ Cl + SbCl ₃ ↑

3Sb ₃ O ₄ 4Sb ₂ O ₃ + SbCl ₃ ↑

Sb ₂ O ₃ Sb ₂ O ₃ (I)

In the present invention, as the resin, nitrile rubber, natural rubber, styrene rubber, and ethylene-propylene copolymer are used. Preferably, in the case of nitrile rubber, acrylonitrile-butadiene having an acrylonitrile (AN) content of 28 to 35%. In the case of rubber and styrene rubber, in the case of styrene-butadiene rubber and ethylene-propylene copolymer, it is preferable to use 1.5% to 9wt% of Ethylidene-Norbornene (ENB) as the basic resin.

In the present invention, some halogen-containing compositions include polyvinyl chloride (PVC) and chlorinated polyethylene (CPE), which are basic flame retardant resins, and preferably, CPE having a chlorine content of 36 to 42% is blended. It is useful to provide basic flame retardancy of mixed resin itself and to improve compatibility with other olefin resins.

In the present invention, it is preferable to use a particle size of 0.5 mm or less when the GTR is mixed and used to improve properties and recycle the resin.

In the present invention, in order to prepare an environment-friendly composition in consideration of the effect on the environmental surface and processability as a flame retardant, to exclude the use of a halogen-based flame retardant, Al (OH) ₃ , Mg ( OH) ₂ , Sb ₂ O ₃ , zinc bromide, loess, phosphorus-based flame retardant, etc. are preferred to have an effect of improving flame retardancy while considering environmental aspects. The present invention also includes using all five components or selecting one or more of them as a flame retardant.

In addition, it is preferable to use azodicarbonamides (7000MC, 5000F, 3000F, ADCA), which are azo compounds, as the blowing agent, and to adjust the foamability and temperature which will affect processability and productivity, A foaming aid (trade name Cellex-A) and ZnO can be preferably used as the heat transfer accelerator.

Sulfur is used as the crosslinking agent used in the present invention, and 2-mercapt benzothia is relatively scorched with thiazoles in consideration of vulcanization promoting effect, scorch resistance, aging resistance, activating temperature, dispersibility, and contamination. Sol (M), di-benzothiadyl disulfide (DM) with relatively low scorch, dithioates, and scorch and vulcanized Zn-dimethyl dithiocarbamate (PZ) at an appropriate ratio as described above. It is preferable. In addition, tetraphenyl chiramide disulfide (TMT), tetraethyl duram disulfide (TET), tetramethyl turram monosulfide (TS), and guanidine can also use diphenyl guanidine (DPG) as tulam. In addition, as a stabilizer, a Ba-Zn-based stabilizer is used in consideration of the foaming rate and the effect of obtaining a uniform cell according to the use of a large amount of filler. For example, trade names BZ-806F and BZ-119 are preferably used. Can be used.

As the plasticizer, it is preferable to use diethylhexyl phthalate (DOP) and paraffin oil (P3 to P6) in consideration of compatibility with the resin, processability, and foamability. It is preferable to use a kind of silitin and CaO, and an anti-aging agent can preferably use 2,2,4-trimethyl-1,2-dihydroquinone (Kumanox RD) in consideration of the effect on vulcanization. The internal release agent is polyethylene wax (LC-102N) as a rubber processing enhancer, stearic acid as an external release agent in consideration of extrudability, and the filler is color imparting and anti-oxidation, reinforcing effect and cost reduction. It is preferable to use carbon black (N550FEF) in consideration of the above.

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 limit It is not intended that in the examples, the percentage (%) indicating the content of the composition means weight percent unless otherwise indicated, and the absence of units means parts by weight.

The abbreviation of the components used in the examples is NBR is acrylonitrile-butadiene rubber, NR is natural rubber, SBR is styrene-butadiene rubber, EPDM is ethylene-propylene copolymer, PVC is polyvinyl chloride, PE is polyethylene, CPE is Chlorinated polyethylene and GTR shall mean tire rubber powder and DOP shall mean diethylhexyl phthalate.

Example 1

In the composition of the flame-retardant polyolefin foam filed by the present inventors and a method of manufacturing the same (Korean Patent Application No. 99-47008), the thermal and dynamic behaviors of NBR / PVC and PE blends according to the composition ratio, temperature, and time were observed, According to the morphology of NBR / PVC blends, PVC particles decrease with time, and after 30 minutes, they are dispersed in a particle size of about 0.1 to 0.2 µm. It can be seen that the dispersed phase of, NBR / PE blends showed that no significant phase separation after 10 minutes, NBR / PVC = 1/1, 0.8, 0.6 Wt In the case of%, the compatibility of CPE content is clearly shown. The composition of NBR, EPDM / PVC, CPE, PE / GTR blend is shown based on the characteristics of homogeneous phase within the range of 10 ~ 30 Wt% of CPE. Thermal and kinetic behaviors over time, temperature, and time were observed and correlated with foaming (foaming rate, cell structure, surface state, etc.) and flame retardancy (LOI; limiting oxygen index). In particular, halogen-based compounds are excluded in consideration of environmental friendliness, and resins are composed of only NBR and GTR, and in order to control their composition ratio and other additives, and to control GTR particle size and drying, and to prevent bubbles from being formed after foaming. The use of an absorbent [silica (silitin)] and also in consideration of dehydration, deodorization, flame retardant is also used ocher, and adjusted and carried out the composition ratio of resin and additives (particularly flame retardant and absorbent).

The composition ratios of the resin components were composed as shown in Table 3, respectively, and the blend was prepared at Rheomixer (HAAKE) without adding crosslinking and crosslinking accelerators at a temperature of 110 to 130 ° C, RPM50 for 20 to 40 minutes, and then crosslinking and crosslinking. With the addition of the accelerator, the temperature is 60-70 ° C., RPM 50, time 5-10 minutes, and the extrusion is carried out within a temperature range of 70-80 ° C., Rs 5, time 1-3 minutes in a minimax molder (Csi-183MMV). Hot-press (Carver) was carried out at a temperature of 160 ~ 250 ℃. In addition, the foaming test investigated the surface condition, foaming rate, cell structure, etc. after foaming, and the flame retardancy test was a LOI (Atlas) test, and the specimen size was 6.5 +/- 0.5mm wide and 2.0 thick according to ASTM-D-2863. Limiting Oxygen Index (LOI) was measured by arbitrarily adjusting the injection amount of oxygen and nitrogen at +/- 0.25mm and length of 7.0 ~ 150mm, and morphology investigation was performed by electron microscope SEM (JEOL JSM-840A). The fracture surface of the specimen was observed.

As a result, when NBR / PVC / GTR = 70/20/10 wt% as in sample 1, foaming occurred at a temperature range of 160 to 190 ° C, and the time required was about 5 minutes, the surface was smooth, and the cell structure It was confirmed that is uniform as a closed cell and has a foaming ratio of about 150% (about 2.5 times) in the radial direction.

In addition, the LOI test showed that the marginal oxygen index was 26.9, which is practically high.

In case of sample 2 composed of NBR / GTR considering environmental friendliness, we wanted to see the effect of the change of the absorbent and flame retardant content on the foamability and flame retardancy. When the other flame retardant content is the same, the content of loess is 10phr, and When the content is 5 phr, foaming occurs at a temperature range of 150 to 160 ° C., and the time required is about 15 minutes, the cell structure is uniform, smoothness without bubbles on the surface, and the foaming rate is about 200 in the radial direction. It was confirmed that three times the foaming occurred in%. In addition, deodorization, dehumidification, and decrease in smoke density were observed according to the use of ocher, and when the GTR particle size was 0.3mm, it was confirmed that the cell structure was uniform compared to 0.5mm. In addition, the LOI test showed that the marginal oxygen index was 26.5, which was also quite high in practical terms. The cell structure (A), additive dispersion degree (B), and surface state (C) as a result of the composition and electron microscopic confirmation of the above contents are shown in Table 3 and FIG. 1 (Sample 1) and FIG. 2 (Sample 2). Represented in each. In the following Table 3, the numerical value means 'parts by weight' as the amount of the corresponding ingredient.

Sample Number Composition One 2 Suzy NBR 70 80 PVC 20 CPE 20 GTR 10 20 Flame retardant Al (OH) ₃ 20 50 Mg (OH) ₂ 60 40 Sb ₂ O ₃ 10 20 Chlorinated Paraffin 10 ocher 20 External release agent Stearic acid 2.5 2.5 Absorbent sillitin 5 Internal release agent PE wax 4 4 PVC stabilizer Ba-Zn system 15 Plasticizer DOP 30 35 Anti-aging 2,2,4-trimethyl dihydroquinoline 2.5 2.5 Filler Carbon black 5 3 Crosslinking agent sulfur 3 2 Crosslinking accelerator M One One DM One One PZ One One blowing agent Azodicarbonamide (Cellcom-AC system) 18 18 Foaming aid Urea system (Celex-A) 1.5 Heat transfer accelerator ZnO 4

Example 2

As a result of Example 1, the composition and processing conditions for obtaining a foam having a foaming ratio of about 2.5 times or more in the radial direction and a uniform cell structure and a smooth surface could be identified. Considering the prevention of bubble generation on the surface and controlling the content of the flame retardant, hygroscopic, plasticizer and other additives compared to the resin. In addition, in the case of the composition consisting of only EPDM / GTR, and also focused on the foamability (foaming rate, surface, cell structure, elastic modulus) and flame retardancy to control the additives relative to the resin, in particular the content of the crosslinking agent and crosslinking accelerator. Composition ratios related to these are shown in Table 4 below, and blend, extrusion, crosslinking and foaming, and foaming, flame retardancy, and morphology investigation were performed in the same manner as in Sample 1.

As a result, in the case of the foam composed of NBR / GTR, foaming occurs at a temperature range of 156 to 170 ° C, and the time required is about 6 to 12 minutes, the surface is smooth, and the cell structure is a closed cell. It was confirmed that it was uniform and had a foaming rate of about 150 to 200% (about 2.5 to 3 times) in the radial direction.

In addition, the LOI test result shows that the critical oxygen index is 26.1 ~ 28.9, which is quite high in practical terms. In particular, in some samples, the marginal oxygen index was 28.3 to 28.9, which showed very high flame retardancy of 28 or more.

On the other hand, in the case of the foam composed of EPDM / GTR, foaming occurs at a temperature range of 160 to 210 ° C, and the time required is about 7 to 16 minutes, the surface is smooth, and the cell structure is a closed cell. It was confirmed that it was uniform, had a foaming ratio of about 150 to 200% (about 2.5 to 3 times) in the radial direction, and had an elastic modulus equivalent to that of the NBR-based foam. In addition, the LOI test result showed that the limit oxygen index was about 28.

As a result, a foam composed of NBR and EPDM / GTR was found to have a foaming ratio of 2.5 to 3 times, a smooth surface, a uniform cell structure, and formulation and processing conditions for obtaining a foam having excellent elastic modulus.

Therefore, it was confirmed experimentally that the mixing ratio condition corresponding to the above-described constitution of the present invention is preferable in the mixing under the defined mixing and processing conditions.

And, in the processing conditions for processing into foam using such a composition, the blend was brought to Rheomixer (HAAKE) at a temperature of 110 to 130 ° C., RPM50 for 20 to 40 minutes without addition of a crosslinking accelerator, and then crosslinking and crosslinking. A predetermined amount of accelerator is added and the temperature is 60-70 ° C, RPM 50, time 5-10 minutes, and the extrusion is carried out within a temperature range of 70-80 ° C, Rs 5, time 1-3 minutes in a minimax molder (Csi-183MMV), When foaming was performed at a temperature of 160 to 250 ° C. in a hot press (Carver), foams having excellent foamability and flame retardancy were obtained as described above.

The results are shown in Table 4 and the accompanying drawings, Fig. 3 (Sample 6) and Fig. 4 (Sample 15), respectively, in the same manner as described above. The degree of dispersion of the additives is shown in the accompanying drawings of FIG. 5, which shows better characteristics than those of FIG. 5.

Sample Number Composition 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Suzy NBR 80 80 80 80 80 80 80 80 80 80 EPDM 90 80 80 80 80 GTR 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Flame retardant Al (OH) ₃ 70 50 60 70 70 70 70 70 70 70 50 50 40 60 70 Mg (OH) ₂ 40 40 50 40 40 40 40 40 40 35 70 70 50 90 80 Sb ₂ O ₃ 10 10 10 30 10 30 10 20 10 10 10 10 10 10 20 ocher 10 10 10 10 10 10 10 10 10 10 15 10 20 10 10 External release agent Stearic acid 2.5 2.5 2.5 2.5 2.5 3 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Absorbent silitin 10 5 10 10 10 10 10 10 10 10 2 One One 10 10 Internal release agent PE wax 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Plasticizer DOP 40 40 35 35 40 35 35 40 35 30 40 40 40 30 30 Anti-aging 2,2,4-trimethyl dihydroquinoline 2.5 2.5 2.5 2.5 3 3 4 5 6 5 2.5 2.5 2.5 5 5 Filler Carbon black 3 3 3 3 3 3 3 3 3 3 2 2 3 3 3 Crosslinking agent sulfur 1.5 2 2 2 2 2 2 2 2 2 1.25 1.25 2 2 2 Crosslinking accelerator M One One One One One One One One One One One One One One One DM One One One One One One One One One One One One One One One PZ One One One One One One One One One One One One One One One blowing agent Azodicarbonamide (Cellcom-AC system) 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 Foaming aid Urea system (Celex-A) 1.5 Heat transfer accelerator ZnO 4 4 4 5 5 6 6 7 6 4 4 6 6

Sample number Foot Po Composition water LOI (Limit Oxygen Index) Foaming method Firing degree Effervescent Composition ratio (wt%) 160 → 250 ℃ Foaming temperature / time required (℃ / min) Foaming rate (%) surface Cell structure R / F-R Resin (N / E / G) Flame Retardant (Al / Mg / Sb / Ocher) P / B-A (DOP / AC system) 3 190/8 ′ 200 Good Uniformity 1 / 1.3 0.8 / 0 / 0.2 70/40/10/10 40/18 28.1 4 156-170/10 ' 150-200 〃 〃 1 / 1.1 〃 50/40/10/10 〃 26.2 5 〃 〃 〃 〃 1 / 1.3 〃 60/50/10/10 35/18 27.5 6 〃 〃 Good (△) 〃 1 / 1.5 〃 70/40/30/10 〃 28.6 7 166-172/6 ' 200 Good 〃 1 / 1.3 〃 70/40/10/10 40/18 28.2 8 〃 〃 Good (△) 〃 1 / 1.5 〃 70/40/30/10 35/18 28.6 9 163-170/8 '50 " 150-200 Good 〃 1 / 1.3 〃 70/40/10/10 〃 28.6 10 〃 〃 〃 〃 1 / 1.4 〃 70/40/20/10 40/18 28.9 11 165-167 / 11'20 " 150 〃 〃 1 / 1.3 〃 70/40/10/10 35/18 28.3 12 170/8 ′ 150-200 〃 〃 1 / 1.25 〃 70/35/10/10 30/18 28.6 13 180 to 210 / 8'40 ″ 150 Good (△) 〃 1 / 1.45 0 / 0.82 / 0.18 50/70/10/15 40/18 27.3 14 210 / 7′25 ″ 〃 Good 〃 1 / 1.4 0 / 0.8 / 0.2 50/70/10/10 〃 27 15 180 ~ 210 / 16′32 ″ 200 〃 〃 1 / 1.2 〃 40/50/10/20 〃 26.1 16 160 to 185 / 15′30 ″ 〃 〃 〃 1 / 1.7 〃 60/90/10/10 30/18 28.3 17 160 to 185 / 12'45 ″ 150-200 〃 〃 1 / 1.8 〃 70/80/20/10 〃 28.7

In Table 5, R / FR is the weight ratio of resin / flame retardant, resin (N / E / G) is NBR / EPDM / GTR composition ratio, flame retardant (Al / Mg / Sb / ocher) is Al (OH) ₃ , Mg (OH) ₂ , Sb ₂ O ₃ , use parts by weight of ocher, and P / BA (DOP / 5000F) are expressed in parts by weight of the plasticizer / foaming agent.

As can be seen from the progress of Table 5, in the case of the foam composition according to the present invention, the foaming degree (foaming rate) was at least 150% or more, and the foaming rate was about 200%. In addition, the limiting oxygen index (LOI) was also found to be about 28 or more when the flame retardants were used normally (samples 4, 13, 14, and 15 used relatively few flame retardants), and non-halogen flame retardants were used. At the same time, it showed very excellent properties in flame retardancy.

Example 3

The experiment was carried out in the same manner as in Example 2, but using an adhesive improver as an additive, and the results were as shown in Table 7 below with the composition shown in Table 6 below.

According to this result, in the case of the foam composed of NR, SBR / GTR and NR / SBR / GTR, foaming occurs at a temperature range of 150 to 170 ° C, and the time required is about 20 minutes, the surface is smooth, and the cell structure is It was confirmed that it was uniform as a closed cell and had a foaming rate of about 150 to 200% (about 2.5 to 3 times) in the radial direction. As a result of LOI test, the marginal oxygen index was 28.1 to 31.1, and it was confirmed that the flame retardancy was higher than 28.

In the following Table 6 and Table 7 was written in the manner described above.

Sample Number Composition 20 21 22 23 24 25 26 27 28 Suzy NBR NR 80 80 80 60 60 60 SBR 80 80 80 20 20 20 EPDM GTR 20 20 20 20 20 20 20 20 20 Flame retardant Al (OH) ₃ 90 80 70 90 90 70 90 90 60 Mg (OH) ₂ 60 65 40 60 55 45 60 55 50 Sb ₂ O ₃ 10 10 10 10 10 10 10 10 10 ocher 5 10 10 5 10 5 5 10 5 External release agent Stearic acid 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Absorbent silitin 5 5 5 5 5 5 5 5 5 Adhesive Enhancer Coumarone resin 3 3 3 One One 3 2 5 3 Internal release agent PE wax 4 4 4 4 4 4 4 4 4 Plasticizer DOP 10 10 5 5 5 Anti-aging 2,2,4-trimethyl dihydroquinoline 5 5 5 5 5 5 5 5 5 Filler Carbon black 3 3 3 3 3 3 3 3 3 Crosslinking agent sulfur 3 2.5 2.5 3 2.5 2.5 3 2.5 2.5 Crosslinking accelerator M DM 2 2 2 2 2 2 2 2 2 PZ blowing agent Azodicarbonamide (Cellcom-AC system) 18 18 18 18 18 18 18 18 18 Foaming aid Urea system (Celex-A) 1.5 2 2 1.5 2 2 1.5 2 2 Heat transfer accelerator ZnO

Sample number Foot Po Composition water LOI (Limit Oxygen Index) Foaming method Firing degree Effervescent Composition ratio (wt%) 160 → 250 ℃ Foaming temperature / time required (℃ / min) Foaming rate (%) surface Cell structure R / F-R Resin (N / NR / S / E / G) Flame Retardant (Al / Mg / Sb / Ocher) P / B-A (DOP / AC system) 20 150 to 160/20 ′ 150-200 〃 〃 1 / 1.65 0 / 0.8 / 0/0 / 0.2 90/60/10/5 0/18 28.7 21 160-170 / 20 ' 〃 〃 〃 1 / 1.65 〃 80/65/10/10 〃 28.6 22 〃 200 〃 〃 1 / 1.7 〃 90/60/10/10 〃 29.3 23 150 to 160/20 ′ 150-200 〃 〃 1 / 1.65 0/0 / 0.8 / 0 / 0.2 90/60/10/5 10/18 28.7 24 〃 〃 〃 〃 1 / 1.65 〃 90/55/10/10 〃 28.6 25 〃 〃 〃 〃 1 / 1.6 85/60/10/5 5/18 28.1 26 165-167 / 11'20 " 200 〃 〃 1 / 1.65 0 / 0.6 / 0.2 / 0 / 0.2 90/60/10/5 〃 28.3 27 〃 150-200 〃 〃 1 / 1.65 〃 90/55/10/10 〃 28.6 28 150 to 165/20 ′ 〃 〃 〃 1 / 1.7 〃 90/65/10/5 〃 31.1

Example 4

As a result of Example 2, as a foam composed of NBR and EPDM / GTR, the foaming ratio was about 2.5 to 3 times, and the blending and processing conditions for obtaining the foam having a smooth surface, uniform cell structure, and excellent elastic modulus were identified.

Therefore, based on the flame retardancy focusing on the control of the additives relative to the resin, in particular, the content of the flame retardant, plasticizer, crosslinking agent and crosslinking accelerator was adjusted to prepare a foam composition. Composition ratios related to this are shown in Tables 8 and 9, and blend, extrusion, crosslinking, foaming, foaming, morphology, and flame retardancy were carried out in the same manner as in Example 2.

As a result, samples 1 to 26 were all foamed at about 160 to 190 DEG C when the resin composition ratio was NBR / GTR = 80 to 90/10 to 20 Wt%, and the time required was about 15 to 25 minutes. And it was found that the surface was smooth, had a closed cell, the cell structure was uniform, and had a foaming rate of about 2-3 times in the radial direction. As a result of the LOI test, the non-combustible foam having excellent flame retardancy was obtained with the limit oxygen index of 36 to 45, compared to 34.5 of the imported commercial product (Armstrong). In addition, for samples 27 and 28, when the resin composition ratio was EPDM / GTR = 80/20 Wt%, the foaming took place at about 170 to 180 ° C for all samples, and the time required was about 30 minutes, and the surface was smooth. It has been found that the cell has a closed cell, the cell structure is uniform, and a foaming rate of about 2 times in the radial direction. As a result of LOI test, the limit oxygen index of all samples was 43, resulting in a nonflammable foam having excellent flame retardancy compared to 34.5 of an imported commercial product (manufactured by Armstrong). As a result, the compounding and processing conditions for obtaining a foam having a foaming ratio of about 2 to 3 times, a smooth surface, a uniform cell structure, and excellent flame retardancy could be identified.

And comparing the flame retardancy and the foaming rate change between the representative samples according to the composition ratio of the resin and each additive is as follows.

Samples 4 and 6 are intended to see the change in flame retardancy and foaming rate according to the change in the content of other additives when the content of the flame retardant is the same as that of resin. 38.5, and in case of Sample 6, the foaming rate was about 2.5 times in the radial direction and the limiting oxygen index was found to be 37. This may be due to the relatively higher content of plasticizer in Sample 6 than in Sample 4. Samples 13 and 16 are intended to see the change in flame retardancy and foaming rate according to the type of flame retardant when the content of other additives is the same as that of the resin. The exponent was 42, and in the case of sample 16, the foaming rate was about 2.5 times in the radial direction and the limiting oxygen index was confirmed to be 44. This may be due to the composition ratio of the flame retardant to the resin and their particle size. In addition, samples 16 and 18 were intended to see the change in the flame retardancy and the foaming rate according to the change of the resin composition ratio when the content of other additives to the resin is the same. The sample 18 was 43, which was higher than that of the sample 16, 42. This may be due to the increase in the GTR content of the sample 18. Therefore, it is considered a representative example to prove the flame retardant effect of GTR.

This suggests that the proper selection and appropriate amounts, and the appropriate processing techniques, considering the interaction with resins and other additives, are important factors in determining the foamability (foam rate, cell structure and size, etc.).

Therefore, the composition ratio of the resin is NBR / PVC / CPE / EPDM / GTR = 50 to 100/10 to 30/10 to 30/0 to 100/1 to 50 wt% in the formulation under the defined formulation and processing conditions. The composition ratio is Al (OH) ₃ / Mg (OH) ₂ / Sb ₂ O ₃ / ocher / H-205 / H-201 = 10 to 300/0 to 300/0 to 50/0 to 20/0 to 50/0 50 to 50 wt%, resin / flame retardant composition ratio of 100/100 to 300 wt%, plasticizer / foaming agent (DOP, DPK / Cellcom-AC type) in the range of 0 to 70/10 to 40 Wt% and processing conditions The blend was prepared at rheomixer (HAAKE) without adding crosslinking and crosslinking promoter at a temperature of 110 to 120 ° C, RPM50 for 20 to 40min, then adding crosslinking and crosslinking promoter to a temperature of 60 to 70 ° C, for 50 rpm 5 to 10 min, and extrusion was carried out in a minimax molder (Csi-183MMV) at a temperature of 70 to 80 ° C., Rs 5 within a time of 1 to 3 min, and foaming was performed at an oven (HB-503M) to a temperature of 120 to 220 ° C. As described above, a foam having excellent foamability and flame retardancy was obtained.

The results are shown in the following Table 10 and in FIG. 6 (Sample 18) and 7 (Sample 28).

Sample Number Composition One 2 3 4 5 6 7 8 9 10 11 12 13 14 Suzy NBR 80 80 80 80 80 80 85 90 90 85 80 80 90 80 GTR 20 20 20 20 20 20 15 10 10 15 20 20 10 20 Flame retardant Al (OH) ₃ 100 100 100 100 100 100 100 110 90 100 100 100 110 260 Mg (OH) ₂ 35 60 40 80 100 80 80 10 120 120 150 100 150 Sb ₂ O ₃ 10 10 10 10 10 10 10 10 10 10 10 10 10 10 ocher 5 5 5 5 5 5 5 H-205 20 40 50 30 25 30 30 20 20 H-201 20 External release agent Stearic acid 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 4 2.5 4 4 Absorbent silitin 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Adhesive Enhancer coumarone resin Internal release agent PE wax 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Plasticizer DOP 25 25 25 25 35 35 30 30 30 30 30 30 30 30 Anti-aging 2,2,4-trimethyl dihydroquinoline 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Filler Carbon black 3 3 3 3 3 3 3 3 3 3 5 3 5 5 Crosslinking agent sulfur 2 2 2 2 1.5 1.5 2 1.5 2 2 1.5 1.5 1.5 1.5 Crosslinking accelerator M One One One One 2 2 1.5 2 1.5 1.5 1.5 1.5 1.5 1.5 DM One One One One 2 2 1.5 2 1.5 1.5 2 2 2 2 PZ One One One One 2 2 One 2 One One 2 2 2 2 blowing agent Azodicarbonamide (Cellcom-AC system) 12 12 12 12 18 18 18 18 18 18 18 18 18 18 Foaming aid Urea system (Celex-A) 3 3 3 4 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2 Heat transfer accelerator ZnO

Sample Number Composition 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Suzy NBR 90 90 80 80 80 80 80 80 80 80 80 80 EPDM 80 80 GTR 10 10 20 20 20 20 20 20 20 20 20 20 20 20 Flame retardant Al (OH) ₃ 80 260 100 260 170 280 275 275 275 275 275 275 255 255 Mg (OH) ₂ 185 175 110 Sb ₂ O ₃ 10 10 10 10 10 10 10 10 10 10 10 10 10 10 ocher 5 5 H-205 15 15 H-201 External release agent Stearic acid 2.5 2.5 3 2.5 3 2.5 5 5 5 5 5 5 5 5 Absorbent silitin 5 5 5 5 5 5 4 4 4 4 4 4 4 4 Adhesive Enhancer coumarone resin 5 Internal release agent PE wax 4 4 4 4 4 4 5 5 8 10 12 20 5 5 Plasticizer DOP 30 30 30 30 30 30 30 30 30 30 30 30 35 35 Anti-aging 2,2,4-trimethyl dihydroquinoline 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Filler Carbon black 3 3 3 3 3 3 5 5 5 5 5 5 5 5 Crosslinking agent sulfur 1.5 2 2 1.5 2 2 2 1.8 1.5 1.5 1.5 1.5 1.5 1.5 Crosslinking accelerator M 2 1.5 One 2 1.5 1.5 1.5 1.8 2 2 2 2 2.5 2.5 DM 2 1.5 1.5 2 2 2 2 2 2 2 2 2 2.5 2.5 PZ 2 One 1.5 2 2 2 2 2 2 2 2 2 2 2 blowing agent Azodicarbonamide (Cellcom-AC system) 18 18 18 18 18 18 18 18 18 18 18 18 18 18 Foaming aid Urea system (Celex-A) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Heat transfer accelerator ZnO One

Sample number Foot Po Composition water LOI (Limit Oxygen Index) Foaming method Firing degree Effervescent Composition ratio (wt%) 120 → 220 ℃ Foaming temperature / time required (℃ / min) Foaming rate (%) surface Cell structure R / F-R Resin (N / E / G) Flame Retardant (Al / Mg / Sb / Ocher / H-205 / H-201) P / B-A (DOP / AC system) One 170 ~ 190/20 ′ 200 Good Uniformity 1 / 1.7 80/0/20 100/35/10/5/20/0 25/12 35 2 165-195/25 ' 〃 〃 〃 1 / 2.15 〃 100/60/10/5/40/0 〃 36.6 3 〃 〃 〃 〃 1 / 2.05 〃 100/40/10/5/50/0 〃 37.4 4 〃 〃 〃 〃 1 / 2.25 〃 100/80/10/5/30/0 〃 38.5 5 165-185/15 ' 250 〃 〃 1 / 2.35 〃 100/100/10/0/25/0 35/18 38.1 6 〃 〃 〃 〃 1 / 2.25 〃 100/80/10/5/30/0 〃 37 7 〃 200 〃 〃 〃 85/0/15 〃 30/18 36.6 8 〃 〃 〃 〃 〃 90/0/10 110/100/10/5/0/0 〃 36.6 9 〃 〃 〃 〃 1 / 2.4 〃 90/120/10/0/20/0 〃 38 10 〃 〃 〃 〃 1 / 2.5 85/0/15 100/120/10/0/20/0 〃 40 11 165-185/20 ' 300 〃 〃 1 / 2.6 80/0/20 100/150/10/0/0/0 〃 41 12 185/15 ′ 250 〃 〃 1 / 2.3 〃 100/100/10/0/0/20 〃 42 13 160-190 / 10 ' 200 〃 〃 1 / 2.7 90/0/10 110/150/10/0/0/0 〃 〃 14 185/15 ′ 250 〃 〃 〃 80/0/20 260/0/10/0/0/0 〃 42.5 15 165-185/20 ' 230 〃 〃 1 / 2.75 90/0/10 80/185/10/0/0/0 〃 42 16 〃 250 〃 〃 1 / 2.7 〃 260/0/10/0/0/0 〃 44 17 180/20 ′ 220 〃 〃 1 / 2.85 80/0/20 100/175/10/0/0/0 〃 42 18 175 ~ 180/20 ′ 250 〃 〃 1 / 2.7 〃 260/0/10/0/0/0 〃 〃 19 180/20 ′ 200 〃 〃 1 / 2.9 〃 170/110/10/0/0/0 〃 45 20 〃 〃 〃 〃 〃 〃 280/0/10/0/0/0 〃 〃 21 170 ~ 175/20 ′ 230 〃 〃 1 / 2.85 〃 275/0/10/0/0/0 〃 44 22 〃 〃 〃 〃 〃 〃 〃 〃 〃 23 〃 〃 〃 〃 〃 〃 〃 〃 〃 24 〃 〃 〃 〃 〃 〃 〃 〃 〃 25 〃 〃 〃 〃 〃 〃 〃 〃 〃 26 〃 〃 〃 〃 〃 〃 〃 〃 〃 27 170 ~ 180/30 ′ 220 〃 〃 〃 0/80/20 255/0/10/5/15/0 35/18 43 〃 230 〃 〃 〃 〃 〃 〃 〃

In the abbreviations shown in the above table, R / FR means resin / flame retardant, resin (N / E / G) means NBR / EPDM / GTR, and flame retardant (Al / Mg / Sb / ocher / H-205 / H). -201) means Al (OH) ₃ / Mg (OH) ₂ / Sb ₂ O ₃ / ocher / H-205 / H-201, and P / BA (DOP / 5000F) means a plasticizer / foaming agent.

As described above, in the present invention, when constructing a flame retardant polyolefin foam composition using tire powder, unlike the prior art, the tire rubber powder (GTR) is blended to a predetermined composition of polyolefin-based and rubber-based resins, but is composed of specific component blending conditions. By pursuing recycling that creates efficient and high value-added GTR, in some cases, the resin composition is effectively constructed and halogen-free compounds are not used. Because of its excellent flame retardancy, mechanical properties and environmentally friendly properties, it can be applied to a wide range of applications such as building materials, automobile parts, sporting goods and other industrial products by extrusion, compression or injection molding. Also, by adding a phosphorus flame retardant The flame retardant effect and flame retardancy can be improved, and by adjusting the mixing ratio of the flame retardant and the additive to the resin, there is an advantage that a non-flammable foam having excellent flame retardancy having a limiting oxygen index (LOI) of 36 to 45 can be obtained.

Claims (11)

The resin component is composed of 50 to 100 parts by weight of nitrile rubber, 10 to 30 parts by weight of polyvinyl chloride or chlorinated polyethylene, ethylene-propylene copolymer, and 1 to 50 parts by weight of GTR (tire powder). In the flame retardant polyolefin foam composition comprising any one or more additives of a plasticizer, a foaming agent, a filler, a moisture absorbent, an anti-aging agent, a lubricant, a stabilizer, In the resin component, the ethylene-propylene copolymer is mixed in an amount of 1 to 100 parts by weight, and the flame retardant is 10 to 300 parts by weight of Al (OH) ₃ , _{1 to} 300 parts by weight of Mg (OH) ₂ and Sb ₂ O ₃ 1 to 50 parts by weight, 1 to 20 parts by weight of ocher, 1 to 50 parts by weight of phosphorus flame retardant (H-205 or H-201), and 100 to 350 parts by weight of flame retardant based on 100 parts by weight of the resin component. Flame retardant polyolefin foam composition using a tire powder, characterized in that the additive contains. 2. The conventional additive according to claim 1, which is 1 to 70 parts by weight of a plasticizer, 1 to 20 parts by weight of a stabilizer, 1 to 5 parts by weight of a crosslinking agent, 2-melcap benzothiazole (M), dibenzothiazine as a crosslinking accelerator. 1 to 5 parts by weight of dill disulfide (DM) and Zn-dimethyl dithiocaramate (PZ), 10 to 40 parts by weight of blowing agent, 0.1 to 10 parts by weight of foaming aid, 0.1 to 10 parts by weight of heat transfer accelerator, Flame retardant polyolefin foam using tire powder, comprising 1 to 20 parts by weight of external mold release agent, 1 to 20 parts by weight of internal mold release agent, 0.1 to 10 parts by weight of moisture absorbent, 0.1 to 10 parts by weight of antioxidant, and 1 to 20 parts by weight of filler. Composition. The flame retardant polyolefin foam composition using tire powder according to claim 1 or 2, wherein the nitrile rubber is acrylonitrile-butadiene rubber having an acrylonitrile content of 28 to 34%. The flame retardant polyolefin foam composition according to claim 1 or 2, wherein the ethylene-propylene copolymer has an Ethylidene-Norbornene (ENB) content of 1.5 to 9 wt%. The flame retardant polyolefin foam composition according to claim 1 or 2, wherein the chlorinated polyethylene has a chlorine content of 36 to 42%. The resin component is composed of 50 to 100 parts by weight of a component selected from at least one of nitrile rubber, natural rubber, styrene rubber and ethylene-propylene copolymer, polyethylene and 1 to 50 parts by weight of GTR. A flame retardant polyolefin foam composition comprising a plasticizer, a foaming agent, a filler, a moisture absorbent, an anti-aging agent, a lubricant, and a stabilizer, In the resin component, the polyethylene is mixed in an amount of 1 to 100 parts by weight, the flame retardant is 10 to 300 parts by weight of Al (OH) ₃ , _{1 to} 300 parts by weight of Mg (OH) _2, 1 to 50 parts by weight of Sb ₂ O ₃ , It is composed of 1 to 20 parts by weight of ocher, 1 to 50 parts by weight of phosphorus-based flame retardant (H-205 or H-201), and 100 to 350 parts by weight of flame retardant with respect to 100 parts by weight of the resin component, and contains ordinary additives. A flame-retardant polyolefin foam composition using tire powder, characterized by the above-mentioned. The conventional additive according to claim 6, wherein 1 to 70 parts by weight of a plasticizer, 1 to 20 parts by weight of a stabilizer, 0.1 to 5 parts by weight of a crosslinking agent, 2-melcap benzothiazole (M) as a crosslinking accelerator, and dibenzothia 0.1 to 5 parts by weight of dill disulfide (DM) and Zn-dimethyl dithiocaramate (PZ), 10 to 40 parts by weight of blowing agent, 0.1 to 10 parts by weight of foaming aid, 0.1 to 10 parts by weight of heat transfer accelerator, Flame retardant polyolefin foam using tire powder, comprising 1 to 20 parts by weight of external mold release agent, 1 to 20 parts by weight of internal mold release agent, 0.1 to 10 parts by weight of moisture absorbent, 0.1 to 10 parts by weight of antioxidant, and 1 to 20 parts by weight of filler. Composition. The flame retardant polyolefin foam according to claim 6 or 7, wherein the nitrile rubber is an acrylonitrile-butadiene rubber having an acrylonitrile content of 28 to 34%, and the styrene rubber is a styrene-butadiene rubber. Composition. The flame retardant polyolefin foam composition according to claim 6 or 7, wherein the ethylene-propylene copolymer has an Ethylidene-Norbornene (ENB) content of 1.5 to 9 wt%. The flame-retardant polyolefin foam composition using tire powder according to claim 7, wherein the additive further contains 1 to 20 parts by weight of an adhesive enhancer. To the resin component and flame retardant mixture according to claim 1 or 6, 1 to 70 parts by weight of a plasticizer, 1 to 20 parts by weight of a stabilizer and 10 to 40 parts by weight of a blowing agent are added, and then at 110 to 120 ° C. Primary mixing was carried out, and as a crosslinking agent, 0.1-5 weight part and 2-melcap benzothiazole (M), di benzothiadyl disulfide (DM), and Zn-dimethyl dithiocarbamate ( A method of producing a flame retardant polyolefin foam composition using a tire powder, wherein 0.1 to 5 parts by weight of PZ) is added and secondly mixed at 60 to 70 ° C. for extrusion, compression or injection.