KR100806735B1 - A composition of environmental-friendly rubber and its shaped article - Google Patents

Abstract

An eco-friendly rubber composition is provided to inhibit emission of harmful and irritative compounds from a rubber composition by virtue of an adsorption function provided by a porous adsorbing agent. An eco-friendly rubber composition containing base rubber and conventional additives for rubber comprises a porous adsorbing agent and powder rubber so that the powder rubber forms voids inside the rubber composition, thereby improving the adsorption property of the porous adsorbing agent through the voids. The porous adsorbing agent is at least one selected from active carbon, zeolite, pearlite, nano-structured porous silicate and bentonite and is added in an amount of 1-100 parts by weight based on 100 parts by weight of the base rubber. The powder rubber is obtained by finely dividing waste rubber, includes at least one powder rubber having a particle size of 100 micrometers-4 mm, and is added in an amount of 3-80 parts by weight based on 100 parts by weight of the base rubber.

Description

A composition of environmental-friendly rubber and its shaped article

The present invention relates to an environmentally friendly rubber composition and a rubber molded product using the same, and more particularly, a rubber powder is added together with an adsorbent to a rubber substrate when the rubber composition is blended, thereby adsorbing a sufficient adsorbent by imparting voids to the rubber powder. It relates to an environmentally friendly rubber composition and a rubber molded product using the same, characterized in that it can effectively control the radiation amount of a compound that is irritating and harmful to the human body as the function is expressed.

In order to improve human health and quality of life worldwide, we have strictly regulated the risks of chemical products containing harmful substances.In particular, in the 2000s, when the millennium began, environmental pollution and quality of life As the global concern of improvement has surfaced, consumers are demanding environment-friendly products that are more comfortable and harmless to the human body for the living environment and major daily necessities. In particular, polymer materials, which are used in a variety of areas ranging from modern living spaces to daily necessities and the automobile industry, generate many substances that are harmful to the human body and cause psychological discomfort. As a result, the EU has been strengthening environmental regulations related to chemicals from next year, such as the recent introduction of the REACH System. In Korea, the “Indoor Air Quality Control Act” was enacted in May 2004 to regulate the emission of harmful or odorous substances generated indoors such as multi-use facilities (public housing, libraries, terminals, etc.). Manufacturers are also trying to tighten regulations on the release of hazardous and odorous substances for polymers and rubber materials.

In particular, rubber materials used for building flooring materials, window gaskets, and automobile interior materials are mixed with various additives, and materials capable of realizing desired physical properties through crosslinking reaction by molding process under high temperature and high pressure, and mostly odorous substances such as carbon disulfide and amines. And volatile organic compounds (VOCs). Therefore, in order to give environmentally friendly characteristics to these rubber materials, there is an urgent need for technology for effective removal of harmful substances such as odorous substances and volatile organic compounds.

As a result of these efforts, various studies on adsorbents capable of removing harmful substances have been conducted, and various types of functional adsorbents have been reported from known adsorbents such as zeolite, activated carbon, and perlite, as well as chemically modified porous nano adsorbents. It is becoming.

Meanwhile, Korean Patent Application Publication No. 98-013721 relates to a method of manufacturing a deodorizing filter for a refrigerator using a metal salt oxidant as an adsorbent, and 99-016787 is a copper, The present invention relates to a deodorizing filter for refrigerators using a catalyst such as manganese, gold, and activated carbon as an adsorbent. No. 99-0071045 uses a honeycomb activated carbon having a certain ratio of manganese dioxide, copper oxide, and an artificial enzyme catalyst as an adsorbent. It relates to a deodorizing filter for a refrigerator. In addition, Korean Patent No. 10-0413234 is an odor remover using aluminum phosphate and activated bentonite, No. 10-0424788 relates to a nano structure odor remover using a layered silicate, organic cations, metal cations, -2007-0005402 relates to a volatile organic compound or an aqueous oil-based adsorbent in air using a porous organic / inorganic hybrid silica gel as an active ingredient.

Since most rubber materials are manufactured through the molding process under high temperature and high pressure as mentioned above, the manufactured rubber bulk has a fairly dense internal structure, but since the adsorbent is a porous material, the dense rubber internal structure In the state dispersed in, the adsorption function cannot be sufficiently expressed.

Accordingly, the present invention has been made in order to solve the above problems, by incorporating the adsorbent and the rubber powder in the rubber substrate when the rubber composition is formulated, the rubber powder gives a void in the rubber, so that the adsorbent exhibits sufficient adsorption function It is an object of the present invention to provide an environment-friendly rubber composition, characterized in that it can effectively control the radiation amount of irritating and harmful compounds emitted in the composition.

In addition, the present invention is to produce a molding using the environmentally friendly rubber composition, especially when used in an enclosed place, such as inside the building or inside the car, irritating and harmful to the compound emitted from the compound of various rubber additives added to the rubber composition Another object of the present invention is to provide a molded product manufactured using an environmentally friendly rubber composition, which can effectively control the radiation amount of the product to exhibit an excellent environmentally friendly effect.

Referring to the preferred technical configuration of the present invention for solving the above problems in detail as follows. In the following description, only parts necessary for understanding the manufacturing method of the present invention will be described, and it should be noted that the description of other parts will be omitted within the scope of not disturbing the gist of the present invention.

The present invention relates to an environmentally friendly rubber composition, and more particularly, in a rubber composition composed of a rubber substrate and a conventional rubber additive,

The rubber composition relates to an environmentally friendly rubber composition comprising mixing powdered rubber with a porous adsorbent to form pores in the rubber composition, thereby improving the adsorption performance of the porous adsorbent through the pores.

A feature of the present invention is that the fine pores formed in the rubber moldings formed by the rubber powder added to the rubber composition can effectively control the radiation dose of irritating and harmful substances emitted from the compounds of various rubber additives added in the rubber composition. When used in an enclosed place such as inside a building or inside an automobile, the adsorbent contained in the rubber molding effectively adsorbs various harmful components emitted from the rubber molding, thereby reducing the emission of harmful gases, thus showing an environmentally friendly effect.

Rubber base material used in the present invention is a natural rubber (NR), butadiene rubber (BR), general purpose rubber such as styrene-butadiene rubber (SBR) or isoprene rubber (IR), nitrile rubber (NBR), ethylene-propylene rubber (EPM Or EPDM) chloroprene rubber (CR), butyl rubber (IIR), chlorosulfonated polyethylene (CSM), acrylic rubber, urethane rubber, hydrogenated styrene-butadiene rubber (HSBR), hydrogenated nitrile rubber (HNBR) Select to use.

Such conventional rubber additives include reinforcing fillers, tackifiers, extended oil antioxidants, ozonation agents, and various pigments in consideration of color.

The reinforcing filler includes mineral fillers such as carbon black, silica, calcium carbonate and talc, and it is preferable to use 10 to 300 parts by weight based on 100 parts by weight of the rubber substrate. If the amount of the reinforcing filler is less than 10 parts by weight, there is a fear that the reinforcing effect does not appear. If the amount of the reinforcing filler is more than 300 parts by weight, the mixing of the filler is difficult and the hardness rises rapidly.

The tackifier may be selected from one or more of rosin derivatives, terpene resins, petroleum resins, coumarone resins, styrene resins, and phenol resins, and the amount of the tackifier is 1 to 50 parts by weight based on 100 parts by weight of the rubber substrate. It is preferable that it is a weight part. If the amount of the tackifier is less than 1 part by weight, the tackifying performance may not appear, and when the amount of the tackifier is more than 50 parts by weight, the physical properties may be drastically deteriorated and problems may occur in the processing equipment.

In addition, the extended oil used in the present invention may be selected from one or more selected from hydrocarbon-based processing oils such as naphthenic, aromatic and paraffin-based oils, and natural oils such as rapeseed oil and castor oil, and the amount thereof is 100 parts by weight of the rubber base. 1 to 50 parts by weight can be used. If it is less than 1 part by weight, it is difficult to expect an improvement in workability and an increase effect, and if it exceeds 50 parts by weight, it is not preferable because a problem in which physical properties are sharply lowered occurs.

In the present invention, the porous adsorbent is selected from one or more of known activated carbon, zeolite, perlite and nanostructured porous silicate, bentonite, and the amount thereof is used in an amount of 1 to 100 parts by weight, based on 100 parts by weight of the rubber substrate, Preferably 3 to 50 parts by weight can be used. At this time, if the amount of the porous adsorbent is less than 1 part by weight, it is difficult to expect effective adsorption performance. If the amount of the porous adsorbent is more than 100 parts by weight, it is difficult to mix the adsorbent, brittle the moldings, and the unit cost increases, which is undesirable. The porous adsorbent includes a product that is partially modified with an adsorbent surface in order to maximize adsorption performance and improve selectivity for harmful substances.

Powder rubber, which is a characteristic constituent of the present invention, is a rubber waste made of small particles as a recycling method of rubber waste, and has a particle size of 100 microns (μm) to 4 millimeters (mm). Alternatively, more than 3 to 80 parts by weight, preferably 5 to 40 parts by weight can be used with respect to 100 parts by weight of the rubber substrate. At this time, if the amount of powder rubber used is less than 3 parts by weight, it is difficult to expect the formation of internal voids, and if it exceeds 80 parts by weight, it is not preferable because the physical properties rapidly decrease. In addition, powder rubber having an average particle size of less than 100 microns is difficult to manufacture, and if it exceeds 4 mm, it is not preferable because the physical properties of the rubber are sharply lowered.

In general, rubber compositions composed of such substrates can be crosslinked for physical properties, performance and durability, and these properties are directly related to the number and form of crosslinks formed during the crosslinking reaction.

As the crosslinking form that can be used in the present invention, one of a sulfur crosslinking mechanism and an organic peroxide crosslinking mechanism can be selected and used.

In the sulfur crosslinking mechanism, it is preferable to add sulfur or insoluble sulfur to 0.1 to 10 parts by weight with respect to 100 parts by weight of the rubber substrate, and 0.01 to 10 parts by weight with respect to 100 parts by weight of the rubber substrate.

When the amount of sulfur or insoluble sulfur is less than 1 part by weight, it is difficult to manufacture a molded product because effective crosslinking is difficult, and when it exceeds 10 parts by weight, premature vulcanization appears and the hardness of the molded product rapidly rises and blooms after the production of the product. Is not preferred because

When the amount of the vulcanization accelerator is less than 0.01 part by weight, it is difficult to expect an effective promoting effect. When the amount of the vulcanization accelerator is more than 10 parts by weight, it is not preferable because early vulcanization appears, the hardness of the molded article rises sharply, and after the manufacture of the product, the blooming occurs.

The vulcanization accelerator used may be selected from one or more of aldehydes, ammonia, aldehydes, amines, guanidines, thioureas, thiazoles, sulfenamides, thiurams and dithiocarbamate salts. Can be.

Also to activate the vulcanization accelerator A vulcanization accelerator may be used, and the amount of the vulcanization accelerator may be used in an amount of 0.01 to 8 parts by weight based on 100 parts by weight of the rubber substrate, and when the amount is less than 0.01 parts by weight, it is difficult to expect the activating effect of the vulcanization accelerator, and exceeds 8 parts by weight. In this case, excessive vulcanization activates premature vulcanization and the hardness of the molded article rises rapidly. The vulcanization accelerator aid usable in the present invention is preferably selected from among metal oxides such as zinc oxide and fatty acids such as stearic acid.

In the organic peroxide crosslinking mechanism, the organic peroxide may be used in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the rubber base material, and if it is less than 0.05 parts by weight, the crosslinking is insufficient.

Examples of the crosslinking agent that can be used in the present invention include cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy laurate, t-butylperoxy acetate, and di-t-butyl as organic peroxides. Diperoxyphthalate, t-dibutyl peroxymaleic acid, t-butyl cumyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, dibenzoyl peroxide, dicumyl peroxide, 1,3-bis (t- Butylperoxyisopropyl) benzene, methylethylkeponperoxide, di- (2,4-dichlorobenzoyl) peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5- (t-benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5 -Dimethyl-2,5- (t-butylperoxy) -3-hexyne, n-butyl-4,4-bis (t-butylperoxy) valerate, a, a'-bis (t-butylperoxy ) From diisopropylbenzene or the like or It can be used to select at least.

In addition, in the present invention, in order to shorten the molding time during peroxide crosslinking and to obtain an appropriate crosslinking structure, the crosslinking aid may be used in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the rubber substrate. If the amount of the crosslinking aid is less than 0.05 part by weight, it is difficult to obtain an appropriate crosslinking structure because the crosslinking promoting effect is insufficient, and when it exceeds 2 parts by weight, it is not preferable because early crosslinking occurs or the molded article is easily broken.

The crosslinking aids are, for example, p-quinonedioxime, p, p-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine and trimethylolpropane-N, Peroxy crosslinking aids such as N'-m-phenylenedimaleimide; Divinylbenzene, triarylcyanurate (TAC) and triarylisocyanurate (TAIC); One or more polyfunctional vinyl monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and vinyl stearate can be selected and used. .

Using the environmentally friendly rubber composition composed of the above composition components it can be produced an environmentally friendly rubber molding using a calender, injection molding machine and compression molding machine which is a conventional molding method of rubber products.

Environmentally-friendly rubber moldings according to the present invention, particularly when used in a closed place, such as in the interior of a building or automobile, are formed from the rubber powder added in the rubber composition to form a microcavity in the rubber molding is emitted from the compound of various rubber additives The adsorbent can effectively control the radiation dose of irritating and harmful to the human body so that it can show an excellent environmentally friendly effect.

Hereinafter, the manufacturing process of the environmentally friendly rubber molding according to the present invention will be described.

First, in addition to the usual rubber additives and porous adsorbents on a substrate selected from one or more rubber elastomers, powdered rubber is mixed with a conventional rubber mixer device such as a half-barrier mixer, kneader, open roll, and the like. The compound composition which mix | blended the powder rubber | gum and a crosslinking agent is manufactured in the sheet form. According to the application, the sheet-like kneaded material is calendered to a thickness of 1 to 5 mm and molded into a rotacure to produce an environmentally friendly rubber molded article of a desired form.

Hereinafter, the present invention will be described in more detail based on the examples prepared in the configuration of Table 1, but the present invention is not limited to the examples.

1, Preparation of Rubber Molded Specimen

Example  One

5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 150 parts by weight of cray, 20 parts by weight of silica, 20 parts by weight of calcium carbonate, based on 100 parts by weight of the substrate consisting of 90% by weight of ethylene-propylene-diene rubber and 10% by weight of styrene / butadiene rubber 40 parts by weight, 5 parts by weight of tackifier, 3 parts by weight of activator, 2 parts by weight of dispersant, 3 parts by weight of extension oil and 1.5 parts by weight of coupling agent were kneaded in a closed mixer at 100 to 120 ° C. for about 15 minutes. In an open roll having a temperature of 70 to 80 ° C., 25 parts by weight of zeolite, 15 parts by weight of 2 mm powder rubber, 2 parts by weight of sulfur, and 3.7 parts by weight of accelerator are added to the 100 parts by weight of the substrate, followed by sufficient kneading, followed by 2 to 6 mm. After preparing a kneaded sheet of the sheet (aging) at room temperature (23 ℃) and aged over 24 hours. The kneaded sheet thus prepared was calendered to 3 mm, and then rotacure-molded at 165 ° C. for an appropriate time to prepare an environmentally friendly rubber molded specimen having a thickness of 3 mm.

Example  2

5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 150 parts by weight of cray, 20 parts by weight of silica, 20 parts by weight of calcium carbonate, based on 100 parts by weight of the substrate consisting of 90% by weight of ethylene-propylene-diene rubber and 10% by weight of styrene / butadiene rubber 40 parts by weight, 5 parts by weight of tackifier, 3 parts by weight of activator, 2 parts by weight of dispersant, 3 parts by weight of extension oil and 1.5 parts by weight of coupling agent were kneaded in a closed mixer at 100 to 120 ° C. for about 15 minutes. In an open roll having a temperature of 70 to 80 ° C., 25 parts by weight of NSB, 15 parts by weight of 2 mm powder rubber, 2 parts by weight of sulfur, and 3.7 parts by weight of accelerator were added to the 100 parts by weight of the substrate, followed by sufficient kneading. In the same manner as in the environmentally friendly rubber molded specimens were prepared.

Comparative example  1 to 4

According to the composition of Table 1, a rubber molded specimen was prepared in the same manner as in Example.

                                         [Unit: parts by weight] division Example Comparative example One 2 One 2 3 4 Ethylene-propylene-diene rubber ^{1 )} 90 90 90 90 90 90 Styrene-butadiene rubber ^{2 )} 10 10 10 10 10 10 Zinc Oxide ^{3 )} 5 5 5 5 5 5  Stearic acid 2 2 2 2 2 2 Cray ^{4 )} 150 150 150 150 150 150 Silica ^{5 )} 20 20 20 20 20 20 Calcium Carbonate ^{6 )} 40 40 40 40 40 40 Tackifier ^{7 )} 5 5 5 5 5 5 Activator ^{8 )} 3 3 3 3 3 3 Dispersants ^{9 )} 2 2 2 2 2 2 Extension oil ^{10 )} 3 3 3 3 3 3 Coupling Agents ^{11 )} 1.5 1.5 1.5 1.5 1.5 1.5 Adsorbents1 ^{12 )} 25 - - 25 - - Adsorbents2 ^{13 )} - 25 - - 25 25 Powdered rubber1 ^{14 )} 15 15 - - - - Powdered rubber2 ^{15 )} - - - - - 15  sulfur 2.0 2.0 2.0 2.0 2.0 2.0 Accelerator ¹¹⁶⁾ 1.5 1.5 1.5 1.5 1.5 1.5 Accelerators 2 ^{17 )} 1.0 1.0 1.0 1.0 1.0 1.0 Accelerators 3 ^{18 )} 1.0 1.0 1.0 1.0 1.0 1.0 Accelerators4 ^{19 )} 0.2 0.2 0.2 0.2 0.2 0.2 1) Kumho Petrochemical KEP 960F 2) Kumho Petrochemical, SBR1502 3) Gilcheon Rubber No. 1 4) Vanderbilt, Dixie Clay 5) Rhodia, Zeosil155 6) SamKwang, Light CaCO ₃ 7) Kolon Oil, C- 90 8) Southeast Synthesis, PEG4000 9) Structol. WB-120 10) Michang Petrochemical. Paraffin oil 11) Degussa, SI-69 12) Cosmo Materials Co., Ltd., Zeolite 4A type 13) Ecopro, NSB 14) Buoyancy recycling, 2mm particle size 15) Buoyancy recycling, 5mm particle size 16) Dongyang Steel Chemical, Oricel -CZ 17) Dongyang Steel Chemical, Oricel-TT 18) Dongyang Steel Chemical, Oricel-DM 19) Yongjin Petrochemical, TRA-75

The rubber molded specimens prepared in 3 mm sheets according to Examples 1 to 2 and Comparative Examples 1 to 4 were tested for properties in the following manner, and the results are shown in [Table 2].

Physical properties unit Example Comparative example One 2 One 2 3 4 importance - 1.46 1.47 1.54 1.55 1.56 1.49 Hardness A type 80 81 77 80 81 81 The tensile strength kg / cm ² 71 69 90 78 74 39 Hazardous Gas Removal Rate % 58 69 - 24 29 50

2. Test method

1) Specific gravity

In accordance with KS M6519, the measurement was performed 5 times using a model DMA-3, an automatic specific gravity measurement apparatus of Ueshima Corporation, and the average value was taken.

2) hardness

It was measured using a Shore A hardness tester according to KS M6518.

3) tensile strength

In accordance with KS M6518 it was measured using a Zwick universal testing machine.

4) Removal rate of harmful gas

5 grams of the sample was accurately collected into a 20 ml vial, and sealed, and left in a chamber of a head-space sampler set at 100 ° C. for 30 minutes, and 300 μl of gas was collected and injected into GC-MS. . The column temperature of the GC-MS used at this time was raised from 40 ℃ (holding for 5 minutes) to 280 ℃ (holding for 10 minutes) at a rate of 10 ℃ per minute. By comparing the area of the peak detected in the same range, the type and amount of harmful gas released were measured, and the average value was taken after measuring three times by the above method. At this time, the harmful gases to be considered include carbon disulfide (CS ₂ ), styrene monomer (styrene monomer), ethylene norbornene (5-Ethylene-2-norbonene) and toluene.

The harmful gas removal rate (%) was calculated by the following equation based on Comparative Example 1, which did not contain both the adsorbent and the powdered rubber.

Hazardous Gas Removal Rate (%) = (A _ref -A _N ) / A _ref * 100

Where A _ref is the sum of the area of each noxious gas measured by GC-MS for Comparative Example 1, and A _N is the sum of the area of each noxious gas measured by GC-MS for Example (or Comparative Example) N, respectively. do.

As shown in [Table 2], the removal rate of harmful gases in Comparative Examples 2 and 3 was 24 and 29%, respectively, whereas Examples 1 and 2 and Comparative Example 4 were 58, 61 and 50%, respectively. It can be seen that the effective adsorption performance. In addition, Comparative Examples 2 and 3, which did not apply powder rubber, showed relatively high specific gravity, whereas Examples 1 and 2 and Comparative Example 4, which used powder rubber, showed relatively low specific gravity. You can see that the effect can be obtained. This reduction in specific gravity means indirectly that the porosity inside the rubber molding increases with the use of powder rubber, and thus the adsorption performance of the adsorbent is improved through the removal rate of harmful gases.

In addition, looking at the tensile strength results shown in [Table 2], Comparative Example 4 applying the powder rubber of 5mm particle size compared to Examples 1 to 2 applying the powder rubber of 2mm particle size, the value of the tensile strength sharply decreased It can be seen that it is not suitable for application to a rubber product.

Therefore, Examples 1 and 2 can be more effectively applied to the environmentally-friendly rubber composition than Comparative Examples 1 to 4 because the generated harmful gas can be more effectively removed through the added adsorbent.

In the above embodiment, the rubber product is mainly produced by calendering a plate having a predetermined thickness and then rotacure, but the present invention may be manufactured in various forms according to the type of the molding machine.

As described above, the environmentally friendly rubber composition of the present invention has been proved to have excellent physical properties through the above embodiments, but the present invention is not necessarily limited only by the above configuration, and does not depart from the technical spirit of the present invention. Various substitutions, modifications and variations are possible within the scope.

As described above, the environmentally-friendly rubber composition of the present invention mixes the rubber base with a rubber additive in addition to the conventional rubber additives and the porous adsorbent, thereby forming the pores in the rubber composition, thereby improving the adsorption performance of the porous adsorbent. By improving, there is an advantage that can remove the harmful components generated in the rubber.

The rubber composition prepared as described above is manufactured in various forms of moldings such as plate, hose, etc. through various forms of molding, including calender molding, and is applicable to various fields, particularly in closed places such as inside buildings or automobiles. It can be expected to have an excellent environmentally friendly effect.

Claims (5)

In a rubber composition composed of a rubber substrate and a conventional rubber additive, The rubber composition is to mix the powder rubber with the porous adsorbent to form a pore inside the rubber composition of the powder rubber to improve the adsorption performance of the porous adsorbent through the pore, The porous adsorbent is selected from one or more of activated carbon, zeolite, perlite and nanostructured porous silicate, bentonite, and added 1 to 100 parts by weight based on 100 parts by weight of the rubber substrate, The powdered rubber may be made of small particles of rubber waste as a method of recycling rubber waste, and may be selected from one or more powdered rubbers having a particle size of 100 microns (μm) to 4 millimeters (mm). 3 to 80 parts by weight of the environmentally friendly rubber composition, characterized in that added. The method of claim 1, The rubber base may be a general-purpose rubber such as natural rubber (NR), butadiene rubber (BR), styrene-butadiene rubber (SBR) or isoprene rubber (IR), nitrile rubber (NBR), ethylene-propylene rubber (EPM or EPDM) environmentally friendly rubber composition, characterized in that the use of one or more. An environmentally friendly rubber molded article manufactured by using a environmentally friendly rubber composition according to claim 1 or 2 using a calender, an injection molding machine, and a compression molding machine, which are conventional molding methods for rubber products. delete delete