KR100913771B1 - A rubber composition of environmental-friendly using heat-expandable microcapsules and rubber molding using the same - Google Patents

Abstract

An environment-friendly rubber composition is provided to effectively control radiant quantities of compounds which are irritant and harmful to the human body and are radiated from various rubber additives. An environment-friendly rubber composition is obtained by mixing porous adsorbent 3~50 parts by weight and thermal expandable microcapsule 1~20 parts by weight to a rubber composition, based on a base rubber 100 parts by weight. The rubber composition consists of a rubber base 100 parts by weight, reinforcing filler 10~300 parts by weight, tackifier 1~50 parts by weight, sulfur or insoluble sulfur 0.1~10 parts by weight, vulcanization accelerator 0.01~10 parts by weight and vulcanization accelerating aid 0.01~8 parts by weight.

Description

A rubber composition of environmental-friendly using heat-expandable microcapsules and Rubber molding using the same}

The present invention relates to an environmentally friendly rubber composition to which the thermally expandable microcapsules are applied, and a rubber molded product using the same, and more specifically, by mixing the thermally expandable microcapsules together with an adsorbent to a rubber substrate when the rubber composition is formulated, The thermally expandable microcapsules provide a void inside the rubber by using the principle of expansion and contraction by heat, so that the adsorbent expresses sufficient adsorption function, thereby effectively controlling the radiation dose of irritating and harmful compounds. It relates to an environmentally friendly rubber composition and a rubber molding using the same.

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 from living spaces to daily necessities to 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 general, rubber materials used for building flooring, window gaskets, and automobile interior materials are mixed with various additives, and materials capable of realizing desired physical properties through crosslinking reactions by molding process under high temperature and high pressure, and most offensive odors such as carbon disulfide and amines. Contains substances 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.

On the other hand, when looking at the patents related to the adsorbent to remove the odor in general, the manufacturing method of a deodorizing filter for a refrigerator using a metal salt oxidant of the Republic of Korea Patent No. 98-013721 as an adsorbent and copper, manganese, of the Republic of Korea Patent No. 10-2244775 Deodorizer filter for refrigerator using catalyst such as gold and activated carbon as adsorbent and deodorizer for refrigerator using honeycomb activated carbon containing manganese dioxide, copper oxide and artificial enzyme catalyst of Korea Patent No. 10-523019 at a certain ratio as adsorbent Patents related to the deodorant for removing the odor generated in the refrigerator, such as a filter, and a manufacturing method are known, but in the case of the above patents, the odor generated in the inside of the refrigerator space is adsorbed by using an adsorbent in the space. Relates to a technique for removing it.

In addition, the patents related to the adsorbents for removing toxic substances and odors generated from its own components by mixing the adsorbents with the polymer composition raw materials are described. The odor remover using aluminum phosphate and activated bentonite of Korea Patent No. 10-0413243 And adsorbents that remove odors, such as layered silicates and nano-structured odor removers using organic cations and metal cations, are disclosed in Korean Patent No. 10-0424788, but most rubber materials are formed under high temperature and high pressure. Since the manufactured rubber bulk has a fairly dense internal structure because it is manufactured through the process, the adsorbent is a porous material, and thus the adsorption function cannot be sufficiently expressed when dispersed in the dense rubber internal structure. Indicates.

Accordingly, the present inventors use a thermally expandable microcapsules to effectively adsorb the radiation amount of irritating and harmful compounds emitted from various rubber additive compounds added to the rubber composition by the adsorbent to the rubber composition. The present invention was completed by providing.

In order to solve such a problem, the present inventors improved the adsorption efficiency by using powdered rubber as in Korean Patent Registration No. 10-0806735, but there was a problem that the mechanical properties of the rubber molding were lowered.

Accordingly, the present invention has been made to solve the above problems, by mixing the adsorbent and thermally expandable microcapsules in the rubber substrate when the rubber composition is formulated to prepare a rubber composition, while the thermally expandable microcapsules expand and contract by heat The purpose of the present invention is to provide an environmentally friendly rubber composition, which can effectively control the radiation amount of irritating and harmful compounds emitted in the rubber composition as a void is provided in the rubber so that the adsorbent exhibits sufficient adsorption function. have.

In addition, the present invention is irritating and harmful to the compound emitted from the compound of the various rubber additives added to the rubber composition when the molded product prepared using the environmentally friendly rubber composition, especially in a closed place, such as inside the building or car interior 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.

The present invention for solving the above problems in a rubber composition consisting of a rubber base material and a conventional rubber additives,

The rubber composition is a thermally expandable microcapsules are mixed with a porous adsorbent,

And the thermally expandable microcapsules as an environmentally friendly rubber composition characterized in that the pores are formed in the rubber composition while expanding and contracting by heat to improve the adsorption performance of the porous adsorbent through the pores,

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) one or more of the selected and used,

The porous adsorbent is selected from one or more of activated carbon, zeolite, perlite and nanostructured porous silicate, bentonite, and added 3 to 50 parts by weight based on 100 parts by weight of the rubber substrate,

The thermally expandable microcapsules have a thermal expansion initiation temperature of 140-150 ° C., a maximum thermal expansion temperature of 160-170 ° C., ultra-fine thermal expansion microcapsules having an average particle of 5-50 μm, and a membrane thickness of 2-15 μm. The environmentally-friendly rubber composition which contains the hydrocarbon which is not harmful to a human body and which can expand and contract by heat is used 0.1-20 weight part with respect to 100 weight part of rubber base materials.

As described above, the environmentally-friendly rubber composition of the present invention mixes thermally expandable microcapsules in addition to the usual rubber additives and porous adsorbents to the rubber substrate, thereby allowing the thermally expandable microcapsules to expand and contract by heat, thereby forming voids in the rubber composition. Forming and thereby improving the adsorption performance of the porous adsorbent has the advantage of removing the harmful components generated in the rubber.

The rubber composition prepared as described above may be manufactured in various forms such as plate and hose through various forms of molding including calendering, and is applicable to various fields. When used in a place, excellent environmentally friendly effects can be expected.

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,

In a rubber composition composed of a rubber substrate and a conventional rubber additive,

The rubber composition is a thermally expandable microcapsules are mixed with a porous adsorbent,

In addition, the thermally expandable microcapsules relate to an environmentally friendly rubber composition, wherein the pores are formed in the rubber composition while expanding and contracting by heat, thereby improving the adsorption performance of the porous adsorbent through the pores.

A feature of the present invention is that the thermally expandable microcapsules added to the rubber composition form minute pores in the molded rubber molding as they expand and contract by heat, thereby irritating and harmful to the human body, which are emitted from the compounds of various rubber additives added to the rubber composition. Since the radiation rate of the compound can be controlled effectively, when used in a closed place such as inside a building or inside a car, the adsorbent contained in the rubber molding can effectively absorb various harmful components emitted from the rubber molding, thereby reducing the emission of harmful gas. It has 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.

First, the porous sorbents and thermally expandable microcapsules which are the main constituents of the present invention will be described in detail as follows.

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, preferably 100 parts by weight of a rubber substrate. 3 to 50 parts by weight can be used. At this time, if the amount of the porous adsorbent is less than 3 parts by weight, it is difficult to expect effective adsorption performance. If the amount of the porous adsorbent is more than 50 parts by weight, it is difficult to mix the adsorbent, brittle the moldings, and the cost of the compound increases. 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.

In addition, the thermally expandable microcapsules, which are the characteristic constituents of the present invention, are ultra-fine thermally expandable microcapsules having an average particle of 5 to 50 µm, and have a thickness of 2 to 15 µm and contain a hydrocarbon which is not harmful to the human body as an expanding agent inside the capsule. It has the feature of being able to expand and contract by heat. When the thermally expandable microcapsule membrane is less than 2 μm, when the heat is applied to the microcapsule, the membrane is thin and the membrane may be damaged. When the thickness exceeds 15 μm, the membrane is thick and the microcapsule is properly expanded. There is a fear not.

As a swelling agent sealed in the microcapsules in the present invention, a hydrocarbon which is not harmful to the human body is a gas which is gasified below the softening point of the capsule membrane polymer. It is preferable to use one or more of a mixture of low boiling point liquids, such as normal pentane, normal hexane, isohexane, heptane, octane, nonane, decane and petroleum ether.

In addition, the thermally expandable microcapsules preferably have a thermal expansion starting temperature of 140 to 150 ° C and a maximum thermal expansion temperature of 160 to 170 ° C in consideration of the fact that the molding temperature range of the rubber composition is 160 to 165 ° C. If the thermal expansion start temperature is equal to or higher than the molding temperature of the rubber composition, since the thermally expandable microcapsules start expansion after the rubber composition is crosslinked, expansion of the thermally expandable microcapsules is suppressed by the already crosslinked rubber composition, or When the foaming is started after crosslinking, the rubber composition may be deteriorated or cracked. When the maximum thermal expansion temperature is less than or equal to the molding temperature of the rubber composition, the rubber composition starts to shrink during the crosslinking process. Expansion does not occur.

In addition, when the maximum thermal expansion temperature of the thermally expandable microcapsules is 180 ° C. or more, the rubber composition for shrinking has a high temperature necessary for a post-processing process, and thus a thermal aging phenomenon of the rubber composition appears.

The temperature at which the thermally expandable microcapsules initiate thermal expansion (thermal expansion start temperature) means a temperature at which the thermally expandable microcapsules initiate thermal expansion, and the maximum thermal expansion temperature of the thermally expandable microcapsules is substantially thermally expandable microcapsules. Heating the capsule does not expand much more, but rather means the temperature at which shrinkage begins. Table 1 below shows the thermal expansion start temperature and the maximum thermal expansion temperature of the thermally expandable microcapsules. In the present invention, the thermally expandable microcapsules used in the rubber composition have a thermal expansion initiation temperature of 140 to 150 ° C and a maximum thermal expansion temperature of 160 to 170 ° C in consideration of the molding temperature range of the rubber composition. It is preferable that it is 80SD (Japan Matsumoto Yushi-Seiyaku company).

division Thermal expansion start temperature (℃) Thermal expansion maximum temperature (℃) F-85D 145-150 160-170 F-80SD 140-150 160-170 F-55D 130-135 135-145 F-100D 135-140 170-180

In the rubber composition of the present invention, the amount of the thermally expandable microcapsules may be 0.05 to 50 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the rubber substrate. At this time, when the amount of the thermal expansion microcapsules is less than 0.1 parts by weight, it is difficult to expect effective expansion performance. When the amount of the thermal expansion microcapsules exceeds 20 parts by weight, it is not preferable because a problem of severe size change and a sharp drop in physical properties occurs.

In addition, conventional rubber additives used in the present invention include reinforcing fillers, tackifiers, antioxidants, ozonation inhibitors, and various pigments in consideration of color, and such additives are not features of the present invention.

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, the reinforcing effect may not be exhibited. If the amount of the reinforcing filler is less than 300 parts by weight, the mixing of the filler is difficult and the hardness is rapidly increased, which is not preferable.

The tackifier is 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 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 vulcanization accelerator.

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

If the amount of the vulcanization accelerator is less than 0.01 part by weight, it is difficult to expect an effective promoting effect. If the amount of the vulcanization accelerator is more than 10 parts by weight, it is not preferable because the pre-vulcanization appears, the hardness of the molded article rises sharply, and the bulging appears after the production of the product.

  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.

In addition, a vulcanization accelerator may be used to activate the vulcanization accelerator, 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 base, and when the amount is less than 0.01 part by weight, the activation effect of the vulcanization accelerator is expected. If it exceeds 8 parts by weight, the preliminary vulcanization appears due to excessive accelerated activation 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 substrate, and if it is less than 0.05 parts by weight, the crosslinking is insufficient.

Examples of the crosslinking agent usable in the present invention include cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxylaurylate, t-butylperoxyacetate, 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) hexane, di-t-butylperoxide, 2,5-dimethyl -2,5- (t-butylperoxy) -3-hexyne, n-butyl-4,4-bis (t-part Peroxy) hexane, di-t-butylperoxide, 2,5-dimethyl-2,5- (t-butylperoxy) -3-hexyne, n-butyl-4,4-bis (t-butylperoxy ) A valency, a, a'-bis (t-butylperoxy) diisopropyl benzene, etc. can be used, selecting one or more.

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 product 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, polyethyleneglycol 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 form a microcavity in the rubber molding while the thermally expandable microcapsules added in the rubber composition are expanded and shrunk by heat, especially when used in a closed place such as inside a building or a car. Adsorption agent can effectively control the radiation amount of irritating and harmful compound emitted from various rubber additive compounds so that it can show 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, and oprol, and then the porous adsorbent in an open roll. , Compound containing thermally expandable microcapsules and crosslinking agent is prepared in a sheet form. The sheet-like kneaded material is calendered to a thickness of 1 to 5 mm depending on the application to form a rotacure, thereby producing an environmentally friendly rubber molded product 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 1)

5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 160 parts by weight of crayfish, silica 35 to 130 parts by weight of a substrate composed of 90 parts by weight of ethylene-propene-diene rubber 1 and 40 parts by weight of ethylene-propene-diene rubber 2 Parts by weight, 60 parts by weight of calcium carbonate, 5 parts by weight of tackifier, 4 parts by weight of activator, 3 parts by weight of dispersant, 3 parts by weight of antifoaming agent and 1.5 parts by weight of coupling agent in a closed mixer at 100-120 ° C. for about 15 minutes. After kneading, in an open roll having a surface temperature of 70 to 80 ° C., 3 parts by weight of an adsorbent, 0.1 parts by weight of thermal expansion microcapsules 1, 0.5 parts by weight of sulfur, and 4.4 parts by weight of an accelerator are added to 130 parts by weight of the substrate, and then sufficiently kneaded. 6 mm kneaded sheet is prepared and aged at room temperature (23 ° C.) for at least 24 hours. The kneaded sheet thus prepared was calendered to 3 mm and then rotacure molded at 160 ° C. for a suitable time to prepare a rubber molded specimen having a thickness of 3 mm. The rubber specimen was cooled at room temperature and then reheated at 180 ° C. for 5 minutes to thermally expand microcapsules. Again to form voids in the rubber.

(Example 2)

5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 160 parts by weight of crayfish, silica 35 to 130 parts by weight of a substrate composed of 90 parts by weight of ethylene-propene-diene rubber 1 and 40 parts by weight of ethylene-propene-diene rubber 2 Parts by weight, 60 parts by weight of calcium carbonate, 5 parts by weight of tackifier, 4 parts by weight of activator, 3 parts by weight of dispersant, 3 parts by weight of antifoaming agent and 1.5 parts by weight of coupling agent in a closed mixer at 100-120 ° C. for about 15 minutes. After kneading, in an open roll having a surface temperature of 70 ° C. to 80 ° C., 30 parts by weight of an adsorbent, 20 parts by weight of thermal expansion microcapsules 2, 0.5 parts by weight of sulfur and 4.4 parts by weight of an accelerator are added to the 130 parts by weight of the substrate, and then sufficiently kneaded. 6 mm kneaded sheet is prepared and aged at room temperature (23 ° C.) for at least 24 hours. The kneaded sheet thus prepared was calendered to 3 mm, and then rotacure-molded at 160 ° C. for a suitable time to prepare a rubber molded specimen having a thickness of 3 mm. The rubber specimen was cooled at room temperature and then reheated at 180 ° C. for 5 minutes to provide thermally expandable microscopy. The capsule is retracted to form voids in the rubber.

(Comparative Examples 1-4)

According to the composition of Table 2, rubber molded specimens were prepared in the same manner as in Example, and then voids were formed in the rubber using thermally expandable microcapsules according to the method of the above Example.

                                                        (Unit: parts by weight) division Example Comparative example One 2 One 2 3 4 Ethylene-propylene-diene rubber1 ¹⁾ 90 90 90 90 90 90 Ethylene-propylene-diene rubber2 ²⁾ 40 40 40 40 40 40 Zinc oxide ³⁾ 5 5 5 5 5 5  Stearic acid 2 2 2 2 2 2 Cray ⁴⁾ 160 160 160 160 160 160 Silica ⁵⁾ 35 35 35 35 35 35 Calcium carbonate ⁶⁾ 60 60 60 60 60 60 Tackifier ⁷⁾ 5 5 5 5 5 5 Activator ⁸⁾ 4 4 4 4 4 4 Dispersant ⁹⁾ 3 3 3 3 3 3 Antifoam ¹⁰⁾ 3 3 3 3 3 3 Coupling Agent ¹¹⁾ 1.5 1.5 1.5 1.5 1.5 1.5 Sorbent ¹²⁾ 3 50 - 10 10 10 Thermally Expandable Microcapsules1 ¹³⁾ 0.1 - - - - - Thermally Expandable Microcapsules2 ¹⁴⁾ - 20 - - - - Thermally Expandable Microcapsules3 ¹⁵⁾ - - - - 7 - Thermally Expandable Microcapsules4 ¹⁶⁾ - - - - - 7  sulfur 0.5 0.5 0.5 0.5 0.5 0.5 Promoter 1 ¹⁷⁾ One One One One One One Accelerator2 ¹⁸⁾ 0.7 0.7 0.7 0.7 0.7 0.7 Accelerator 3 ¹⁹⁾ 1.5 1.5 1.5 1.5 1.5 1.5 Accelerators 4 ²⁰⁾ 0.7 0.7 0.7 0.7 0.7 0.7 Accelerators 5 ²¹⁾ 0.5 0.5 0.5 0.5 0.5 0.5 1) Kumho Petrochemical KEP 960F 11) Degussa, SI-69 2) Kumho Petrochemical KEP 510 12) Taesung Environmental Research Institute, M-52 3) Rubber for rubber industry 13 No. 13) SDI, F-85D (Japan) Matsumoto Yushi-Seiyaku) 4) Vanderbilt, Dixie Clay 14) SDI, F-80SD (Matsumoto Yushi-Seiyaku, Japan) 5) Rhodia, Zeosil155 15) SDI, F-55D (Matsumoto Yushi-Seiyaku, Japan) 6 Eugene, Light CaCO ₃ 16) SDI, F-100D (Matsumoto Yushi-Seiyaku, Japan) 7) Kolon Oil, C / R-90 17) Kangshin Industries, DTDM 8) Green Soft Chem, PEG4000 18) Yangmyung Trade, EZ 9) Structol, WB-215 19) Yangmyung Trade, BZ 10) Hwasung Chemical, KML Yangmyung Trade, TT 21) Yangmyung Trade, TS

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 the following [Table 3].

Physical properties unit Example Comparative example One 2 One 2 3 4 importance - 1.54 1.52 1.60 1.61 1.59 1.53 Hardness A type 83 83 85 86 84 84 The tensile strength kg / cm ² 52 51 58 57 53 54 Hazardous Gas Removal Rate % 64 72 - 33 36 38

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 and injected into a 20 ml vial, which was 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, harmful gases under consideration include carbon disulfide (CS ₂ ), 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 3, the removal rate of harmful gases in Comparative Examples 2, 3, and 4 was 33%, 36%, and 38%, respectively, while Examples 1 and 2 were 64 and 72%, respectively. It can be seen that the effective adsorption performance. Also, Examples 1 and 2 and Comparative Example 4 in which the maximum thermal expansion temperature was higher than the molding temperature showed relatively low specific gravity, while Comparative Example 3 in which thermal expansion microcapsules having a maximum thermal expansion temperature was lower than the molding temperature had a specific gravity compared to Comparative Example 2. It can be seen indirectly that the thermally expandable microcapsules do not expand inside the rubber composition.

In addition, when looking at the harmful gas removal rate results shown in [Table 3], Comparative Example 4 applying the thermal expansion microcapsules having a high maximum thermal expansion temperature, the specific gravity was reduced, but showed a relatively low harmful gas removal rate compared to Examples 1 and 2 The thermally expandable microcapsules were expanded in the rubber, but the shrinkage was not sufficient due to the high maximum thermal expansion temperature, so that the voids were formed in the rubber to improve the adsorption performance of the porous adsorbent. Higher temperatures are required for shrinkage, which is not suitable for rubber products at temperatures higher than 180 ° C because of the thermal aging of rubber and the uneconomical aspects of production.

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.

Claims (8)

One or more of general purpose rubber such as natural rubber (NR), butadiene rubber (BR), styrene-butadiene rubber (SBR), isoprene rubber (IR), nitrile rubber (NBR), ethylene-propylene rubber (EPM or EPDM) 10 to 300 parts by weight of reinforcing filler, 1 to 50 parts by weight of tackifier, 0.1 to 10 parts by weight of sulfur or insoluble sulfur, 0.01 to 10 parts by weight of vulcanization accelerator, based on 100 parts by weight of the rubber base and the rubber base to be selected and used. In the rubber composition consisting of 0.01 to 8 parts by weight of a vulcanization accelerator, To the rubber composition, 3 to 50 parts by weight of one or more selected porous adsorbents from activated carbon, zeolite, perlite and nanostructured porous silicate and bentonite, and 1 to 20 parts by weight of thermally expandable microcapsules are mixed with 100 parts by weight of the rubber base. , The thermally expandable microcapsules are ultrafine thermally expandable microcapsules having an average particle of 5 to 50 µm and a film thickness of 2 to 15 µm. The expansion agent inside the capsule has a thermal expansion initiation temperature of 140 to 150 ° C. and a maximum thermal expansion temperature of 160 to 170. As F-85D, F-80SD expanding agent (Matsumoto Yushi-Seiyaku, Japan) which is ℃, The expanding agent is one or more of low boiling liquids such as propane, propylene, butene, normal butane, isobutane, isopentane, neopentane, normalpentane, normal hexane, isohexane, heptane, octane, nonane, decane and petroleum ether. Select to mix, And the thermally expandable microcapsules form voids in the rubber composition while expanding and contracting with heat, thereby improving the adsorption performance of the porous adsorbent through the voids. delete delete delete delete delete delete An environmentally-friendly rubber molding, which is manufactured using a calender, an injection molding machine, and a compression molding machine, which are conventional molding methods of rubber products, using the environmentally-friendly rubber composition according to claim 1.