KR101465450B1 - Rubber foam adiabatic material and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a rubber foam insulation material and a preparation method thereof. The rubber foam insulation material according to an embodiment of the present invention is manufactured by extruding and foaming a second master batch. The second master batch is prepared by adding sulfur, vulcanization booster, flavoring materials, and old plasticizer satisfying the formula 1 represented as []. The first master batch includes the acrylonitrile-butadiene-rubber (NBR); hydro magnesite, 2 to 5-dimethyl-2 to 5-di (tetra-hydroxy-butylperoxy) hexane, resorcinol-phenolic polymer binder, lubricant, kaolin, charcoal, inorganic filler, antioxidant, and a foaming agent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an environmentally friendly antimicrobial rubber foam insulation having improved heat resistance and flame retardancy by using steel slag without rubber odor,

The present invention relates to a rubber foam insulation which satisfies the formaldehyde emission standards of recently reinforced multi-use facilities while maintaining excellent heat insulation and moisture permeability of rubber foam insulation, and also eliminates odor specific to rubber, reduces manufacturing cost and has a flame retardancy and heat resistance of 35% Improved rubber foam insulation and a method of manufacturing the same.

Rubber foam insulation is an insulation material with independent bubble structure which is made by foaming synthetic rubber and has excellent heat insulating property and moisture resistance. Due to these advantages, rubber foam insulation has been used in various fields such as hot and cold water piping, air conditioning, industrial plants, ships, etc. and has been used as standard insulation in Europe for a long time.

In recent years, the use of rubber foam insulation, which is environmentally friendly and excellent in flame retardancy and heat insulation property, is increasing rapidly due to the weak flame retardancy and insulation of polyethylene insulation, harmfulness and hygroscopicity of glass fiber insulation.

However, there is a small amount of odor of synthetic rubber and foam gas, which are the main materials of rubber foam insulation, inside the insulation cell. Rubber foam insulation has a characteristic odor due to the smell of synthetic rubber and foaming agent gas, and it can cause occupant headache due to odor when rubber foam insulation is used in a closed room for a long time. Rubber foam insulation is mainly used for facilities and it is not applied to a space where people live directly, but there is no problem due to bad odor. Recently, the demand for expansion in the interior of a building is rapidly increasing due to excellent heat insulation and flame retardancy of rubber foam insulation. In addition, the recent "multi-use facilities such as indoor air quality laws enforced rule" amendment (20/03/2014) strengthened the emission standards for formaldehyde emitted from building materials in the current 0.12mg / m ² h to 0.05mg / m ² h And the standard will be strengthened to 0.02 mg / m ² h or less from 2017. Therefore, in order to expand the rubber foam insulation to the interior of the building, it is required to keep the advantages of the conventional rubber foam insulation while satisfying the formaldehyde standards, and to have the anti-bacterial rubber foam insulation excellent in flame retardancy without the rubber odor and odor .

Therefore, there is a need for a technique for removing the odor of formaldehyde and the peculiar smell of synthetic rubber, and simultaneously removing the odor inside the cell by the blowing agent gas. Although there are many chemicals and fragrances for deodorizing rubber products, most of the fragrance evaporates in the pre-foaming process, which is a pre-stage before foaming when applied to rubber foam insulation, so that the odor inside the insulation cell can not be effectively removed.

In addition, due to the rapid development of the domestic steel industry, steel byproducts are continuously increasing, but due to an increase in the amount of steel byproducts, efficient treatment methods and application fields are not properly developed. Therefore, the steel industry is having difficulty in processing the slag and securing the aging site .

Therefore, it is required to study the technology to prevent the environmental pollution and to reduce the cost through recycling of resources by using steel slag as a flame retardant and heat resisting agent for rubber foam insulation and rubber recycled powder. When steel slag is used as a raw material for rubber foam insulation, it has poor compatibility with existing rubber foam insulation materials, and it has to be solved because of low density of insulation material due to high density of blast furnace slag, deterioration of performance and physical properties.

Disclosed is a rubber foam insulation which reduces formaldehyde emission while effectively retaining excellent heat insulation and moisture resistance, which is an advantage of existing rubber foam insulation, effectively removes rubber odor and improves flame retardancy and heat resistance by using steel slag .

Further, it is an object of the present invention to provide a rubber foam insulation having reduced formaldehyde emission using kaolin and charcoal, and improved antibacterial and odor removal function.

It is also an object of the present invention to provide a rubber foam insulation having improved price competitiveness by using rubber recycled powder.

In order to accomplish the above object, the present invention provides a method for producing a rubber composition comprising acrylonitrile-butadiene rubber (NBR), blast furnace slag, hydro-magneite, 2,5-dimethyl-2,5-di (tetra-butylperoxy) Vulcanization accelerator, fragrance, and a cold-resistant plasticizer satisfying the following formula 1 are added to a first master batch composition containing a binder, a lubricant, a kaolin, a charcoal, an inorganic filler, an antioxidant and a foaming agent, And then extruded and foamed.

[Formula 1]

E _t ? V _t

(Where E _t is the foaming temperature of the blowing agent and V _t is the volatilization temperature of the cold resistance plasticizer).

In addition,

a) a binder which is an acrylonitrile-butadiene rubber (NBR), blast furnace slag, hydro-magneite, 2,5-dimethyl-2,5-di (tetra-butylperoxy) hexane, a resorcinol- Mixing a first master batch composition comprising kaolin, charcoal, an inorganic filler, an antioxidant and a foaming agent, followed by aging;

b) adding a sulfur, a vulcanization accelerator, a perfume, and a cold-resistant plasticizer satisfying the following formula 1 to the first masterbatch composition to prepare a second masterbatch and then aging;

[Formula 1]

E _t ? V _t

(Where E _t is the foaming temperature of the blowing agent and V _t is the volatilization temperature of the cold resistance plasticizer).

c) feeding the aged second master batch into an extruder;

d) foaming the extruded extrudate in the range of E _t of the formula 1;

The present invention relates to a method for producing a rubber foam insulation.

The inventors of the present invention have conducted studies to remove the odor of the rubber foam insulation, and found that by adding foaming agents with a low-temperature plasticizer in the range satisfying the above-mentioned formula 1 together with the fragrance and more preferably by mixing the fragrance with the cold- The fragrance can be confined in the rubber foam insulator cell by matching the time when the composition is foamed by the foaming agent with the time when the fragrance and the mixture of the low temperature plasticizer are evaporated by adding the foaming agent so that odor due to the foaming agent gas can be removed , It is possible to achieve the smell effect of the perfume, thereby completing the present invention.

In addition, as a result of studies to further improve flame retardancy and heat resistance by adding blast furnace slag generated by steel slag, it was found that hydro-magnesite, 2,5-dimethyl- (Tetra-butylperoxy) hexane and a binder to improve the miscibility and to provide a rubber foam insulation which is more excellent in flame retardancy and heat resistance, thereby completing the present invention.

The rubber foam insulation according to the present invention has not only excellent heat insulation, flame retardancy, moisture permeability but also rubber odor, so that it can be used as an indoor and outdoor interior material.

In addition, by recycling resources including steel slag, it is not only environmentally friendly, but also has an effect of further improving flame retardancy and heat resistance. Further, it contains kaolin and charcoal, thereby reducing the formaldehyde emission and the antibacterial and odor removal effect.

In addition, price competitiveness including rubber recycled powder is more excellent.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to certain embodiments. However, the present invention is not limited to the following embodiments.

One aspect of the present invention relates to a process for the preparation of a composition comprising an acrylonitrile-butadiene rubber (NBR), blast furnace slag, hydro-magneite, 2,5-dimethyl-2,5-di (tetra-butylperoxy) A sulfur-containing accelerator, a perfume, and a cold-resistant plasticizer satisfying the following formula (1) are added to a first master batch composition containing a binder, lubricant, kaolin, charcoal, inorganic filler, antioxidant and foaming agent, Extruded and foamed rubber foam insulation.

[Formula 1]

E _t ? V _t

(Where E _t is the foaming temperature of the blowing agent and V _t is the volatilization temperature of the cold resistance plasticizer).

In still another embodiment of the present invention, the first master batch composition may further comprise rubber recycled powder selected from rubber waste thermal insulation waste powder, waste tire powder and mixed powder thereof, and powdered polyurethane.

Hereinafter, each configuration of the present invention will be described in more detail.

In one embodiment of the present invention, the acrylonitrile-butadiene rubber (NBR) has a nitrile content of 30 to 40% by weight, a viscosity (Mooney viscosity, ML 1 + 4, 100 ° C.) of 50 to 60, Is preferably 400000 to 500000 g / mole. Specifically, for example, there are a series of 35LM, 35M, 25M, etc. of KKPC, but the present invention is not limited thereto. When the nitrile content is higher than the above-mentioned range, the thermal resistance of the heat insulating material is drastically lowered at a low temperature, so that the restoring force and elasticity of the heat insulating material in winter can be weakened. In addition, when the viscosity is higher than the above range, the curing time of the heat insulating material is shortened, so that the occurrence of defects is high and the hardness of the heat insulating material is increased to cause difficulty in the construction of the heat insulating material. When the viscosity is lower than the above value, The cell of the heat insulator becomes larger and the restoring force may be lowered.

In one embodiment of the present invention, the blast furnace slag is used to further improve the flame retardancy and heat resistance of the rubber foam insulation, and the one produced from the steel slag can be used. Steel slag is divided into blast furnace slag and steel slag. Steel slag is a material generated during iron smelting process. It is inadequate as raw material of rubber foam insulation because free-CaO component remains and expands by reacting with water . The blast furnace slag has almost no free-CaO and is composed of components of lime (CaO), silica (SiO ₂ ) and alumina (Al ₂ O ₃ ), which is suitable for improving the flame retardancy and heat resistance of rubber foam insulation. However, when the blast furnace slag is used alone as a flame retardant for rubber foam insulation, it does not satisfy the performance of oxygen index of 35% or more and the density of the blast furnace slag is high, so that the foaming rate of the heat insulating material is decreased and the thermal insulation property and physical properties are deteriorated. In addition, the silica and inorganic components contained in the blast furnace slag are not compatible with the synthetic rubber, so that it is difficult to disperse in the mixing process, the vulcanization rate is slow, and free-CaO may be partially present. It can be a cause.

Therefore, it is preferable to use the blast furnace slag after aging the blast furnace slag at room temperature for 12 to 24 hours, and more preferably, the blast furnace slag is cooled by utilizing the air-cooled conveyor and aged for 1 to 3 hours.

The blast furnace slag is preferably used in an amount of 30 to 50 parts by weight based on 100 parts by weight of the synthetic rubber, but is not limited thereto. When used in an amount of more than 50 parts by weight, the specific gravity of the heat insulating material is increased due to the high density of the blast furnace slag, which leads to a reduction in the expansion ratio and a decrease in the physical properties .

In order to solve the problems in using the blast furnace slag as described above and to secure flame retardancy with an oxygen index of 35% or more, it is preferable to use the hydro-magnesite together with the blast furnace slag. The hydro- Is preferably used. Within the above range, flame retardancy of the target oxygen index of 35% or more can be ensured, and the miscibility between the blast furnace slag and the rubber can be further improved.

In addition, 2,5-dimethyl-2,5-di (tetra-butylperoxy) hexane (2,5-dimethyl-2,5- di (t-butylperoxy) hexane, more preferably a liquid phase, having a peroxide content of 92% or more and an active oxygen content of 10% or more is preferably used. Examples of such materials include Trigonox 101 of Akzo Nobel, PEROXAN HX from Pergan, and the like. The content thereof is preferably 1 to 15 parts by weight based on 100 parts by weight of the synthetic rubber, because the effect of improving the miscibility is excellent.

Further, miscibility can be further improved by using a binder together with 2,5-dimethyl-2,5-di (tetra-butylperoxy) hexane. The binder is a resorcinol donor compound which improves the bonding force between the rubber and the blast furnace slag. Specifically, for example, a resorcinol-phenol polymer can be used, and a resorcinol acetaldehyde condensate Is preferably used. Commercialized examples include, but are not limited to, R-6 from UNIROYAL CHEMICAL. It is preferable to use 1 to 10 parts by weight with respect to 100 parts by weight of the synthetic rubber. In order to further improve the flame retardancy and heat resistance by improving the desired bonding force and miscibility without adversely affecting the heat insulating property and physical properties of the heat insulating material Suffice.

The lubricant facilitates compounding of various raw materials and is used for the decompression effect of the chamber. The lubricant is selected from the group consisting of white oil, calcium stearate, zinc stearate, magnesium stearate, aluminum stearate, glycerin stearate, butyl stearate, Paraffin, and liquid paraffin can be used. The content thereof is preferably 20 to 30 parts by weight based on 100 parts by weight of the synthetic rubber. When the amount is less than 20 parts by weight, the effect is insignificant. When the amount is used in excess of 30 parts by weight, it causes low viscosity of the compounding raw material, which may cause degradation of the restoring force of the heat insulating material.

The kaolin and charcoal can be used to add odor removal and antimicrobial properties of synthetic rubbers. Charcoal is composed mainly of carbon and minerals, and it is easy to mix with synthetic rubber, and it plays a role of absorbing positron which is the cause of odor and prevents microbial habitat. Kaolin is composed of Al ₂ O ₃ and SiO ₂ as porcelain raw materials produced by the collapse of feldspar rocks, and can play a role as a filler in insulation and remove rubber odor. The content of the kaolin is preferably 10 to 30 parts by weight based on 100 parts by weight of the synthetic rubber, and the char is preferably used in an amount of 10 to 30 parts by weight based on 100 parts by weight of the synthetic rubber. The kaolin and charcoal are preferably prepared by adding powders and the average particle diameter is preferably 10-100 탆, which is easily dispersed, but is not limited thereto.

The inorganic filler is used for cost reduction, and any one or a mixture of two or more selected from talc, carbon black, and zinc oxide may be used. The filler is preferably used in an amount of 20 to 60 parts by weight based on 100 parts by weight of the synthetic rubber. If it is used in an amount of less than 20 parts by weight, the effect is insignificant. If it is used in an amount exceeding 60 parts by weight, the elastic properties of the elastomer may be lost, and the foaming ratio may decrease.

The antioxidant is used for further improving the heat resistance and improving the durability, and may be any one or a mixture of two or more selected from stearic acid, butylated hydroxy toluene (BHT), and the like. The content thereof is preferably 20 to 30 parts by weight based on 100 parts by weight of the synthetic rubber. When it is used in an amount less than 20 parts by weight, the effect is insignificant, and when it is used in an amount exceeding 30 parts by weight, dispersibility may be lowered.

The blowing agent may be selected from the group consisting of azodicarbonamide (ADCA), azodiisobutyronitrile (ABBN), dinitrosopentamethyltetramine (DNPT), para toluenesulfonyl hydrazide (TSH) and oxybisbenzenesulfonyl And hydrazide (OBSH) may be used. The content thereof is preferably 40 to 60 parts by weight based on 100 parts by weight of the synthetic rubber. If it is less than 40 parts by weight, the foam may be foamed to have a high density to deteriorate the heat insulating performance. If the amount is more than 60 parts by weight, the amount of gas generated increases and the number of cells per unit area of the heat insulating material The heat insulating property may be lowered.

The foaming agent is preferably an azo type foaming agent having a decomposition temperature of 90 to 110 ° C, a gas generating temperature of 170 to 180 ° C and a foaming temperature of 140 to 180 ° C. In this case, It is preferable to use a material having a temperature equal to or higher than the foaming temperature.

As a result of research conducted by the inventors of the present invention, it has been found that odor can be removed by preventing the volatilization of fragrance at the foaming temperature of the rubber foaming heat insulator by adding the mixture of the cold resisting plasticizer and the perfume, It was confirmed that this effect can be achieved by using a cold-resistant plasticizer satisfying

[Formula 1]

E _t ? V _t

(Where E _t is the foaming temperature of the blowing agent and V _t is the volatilization temperature of the cold resistance plasticizer).

In an embodiment of the present invention, the fragrance is preferably a liquid fragrance because it is easy to formulate, and it is preferable to use the same or higher than the foaming temperature of the foaming agent. The mixing ratio of the low temperature plasticizer with the low temperature plasticizer is not limited, but it is confirmed that the aimed smell removal and smell effect can be exhibited by mixing the fragrance: cold resisting plasticizer at a ratio of 80 to 90:20 to 10 by weight and adding it as a mixture.

The mixture of the perfume and the cold-resistant plasticizer is not limited, but it is preferable to use 10 to 30 parts by weight with respect to 100 parts by weight of the synthetic rubber. In the above range, it is sufficient to achieve the aimed odor removal and smell- Do.

In one embodiment of the present invention, the sulfur acts as a vulcanizing agent to maintain the rubber in a specific shape. Further, the strength and the elasticity of the cell suitable for the heat insulator are determined, and the content thereof is preferably 1 to 5 parts by weight based on 100 parts by weight of the synthetic rubber.

In one embodiment of the present invention, the vulcanization accelerator serves as a crosslinking control agent for crosslinking and is useful for forming a skin of a foam. Examples of the vulcanization accelerator include 2-mercapto benzothiazole, tetramethylthiuram disulfide tetramethyl thiuram disulide, dipenta methylene thiuram tertiary sulfite, and mixtures thereof. The content thereof is preferably 1 to 5 parts by weight based on 100 parts by weight of the synthetic rubber.

In one embodiment of the present invention, the first masterbatch composition may further comprise a rubber recycling powder and a powdery polyurethane, if necessary, selected from rubber foam insulation waste powder, waste tire powder and mixed powder thereof.

The rubber recycled powder is used for improving the environmental pollution caused by the recycling of resources and for reducing the cost. It is preferable that the waste powder of the rubber foam insulation is stored in a place where ultraviolet rays are not exposed. Rubber foam insulation Waste is exposed to ultraviolet rays for a long period of time, resulting in surface hardening and can not be used as a raw material for recycling. Recyclable rubber foam insulation is a mixture of acrylonitrile butadiene rubber (NBR), ethylene-propylene-diene terpolymer (EPDM), isoprene rubber (IR), emulsion polymerized styrene-butadiene rubber (SBR) Mixed can be used.

In order to use the rubber foam insulation and the waste tire powder as recycled raw materials for rubber foam insulation, a desulfurized powder having an average particle size of 50 to 400 mu m is required for easy dispersion. Therefore, rubber foam insulation and waste tires are pulverized to a size of 0.5 to 1 mm or less through a pulverizer, and heated using a microwave to produce a desulfurized rubber recycled powder having a particle size of 50 to 400 μm which is easily dispersed. The rubber recycled powder processed in the above-described manner serves as a filler and a reinforcing agent for rubber foam insulation, thereby reducing the cost. However, when the rubber recycled powder is used, the foaming rate and the restoring force of the heat insulating material are lowered. Therefore, the content of the rubber recycled powder is preferably 30 to 50 parts by weight based on 100 parts by weight of the synthetic rubber. The use of less than 30 parts by weight results in a small cost-saving effect, and when used in excess of 50 parts by weight, the synthetic rubber is not completely bonded and precipitates on the surface of the heat insulating material. By using millable urethane (Millable Urethane) in the above content range, it is possible to reduce the cost without lowering the physical properties of the heat insulating material.

More specifically, in the desulfurization process, the temperature of the desulfurization chamber is suitably in the range of 180 to 200 ° C. If the temperature is higher than the proper temperature, carbonization occurs and it can not be used as a raw material for regeneration. In the desulfurization process, hot air or the like may be used, but it is more preferable to irradiate the microwave, and the microwave penetrates evenly into the powder, so that the molecular structure of the rubber can be pulverized in a short time. It is preferable that the microwave is heated at an intensity of 40 to 60 kW for 30 to 60 minutes. As described above, when a desulfurization process is performed using a microwave, a recycled desulfurized powder having an average particle size of 50 to 400 μm is processed. If such a method for processing a recycled raw material is omitted, there is a problem that the added recycled filler is deposited on the surface, which causes deterioration in the performance of the heat insulating material.

It is also possible to mix the rubber foam insulation with waste powder and waste tire powder. In case of mixing, the rubber foam insulation material waste powder: waste tire powder is mixed at a ratio of 1 ~ 99: 99 ~ 1 weight, Can be used. More preferably 60 to 70:40 to 30 weight ratio. If the weight ratio of the waste tire powder is higher than that of the rubber foam insulation material waste powder, the density of the heat insulating material may be increased and the foaming ratio may be lowered.

In one embodiment of the present invention, the powdery polyurethane is a powdery polyurethane elastomer, which is used for preventing the deterioration of the mechanical properties of the foam when the rubber recycled powder is added and further improving the mechanical properties. MILLATHANE 500, MILLATHANE 76, MILLATHANE 66, MILLATHANE E34, MILLATHANE 97, MILLATHANE 26, and the like may be used. The content thereof may be 5 to 15 parts by weight based on 100 parts by weight of the synthetic rubber, and is sufficient to improve the intended mechanical properties within the above range.

If necessary, a flame retardant may be further added. The flame retardant is used for further improving the flame retardancy. Any one selected from aluminum hydroxide, magnesium hydroxide, or a mixture thereof may be used. The content thereof is preferably 50 to 90 parts by weight based on 100 parts by weight of the synthetic rubber. When the amount is less than 50 parts by weight, the effect is insignificant and the desired oxygen index of 35% can not be satisfied. When the amount exceeds 90 parts by weight, the cost of the product increases, .

In addition, the present invention can further include pigments of various colors as required, and such pigments can be used without limitation as long as they are conventionally used in this field within a range that does not affect the physical properties of the heat insulating material.

The method for producing the rubber foam insulator of the present invention comprises a primary raw material compounding and aging process, a secondary raw material compounding process, an aging process, an extrusion process, and a foaming process.

More specifically, a method for manufacturing the rubber foam insulator of the present invention will be described.

a) a binder which is an acrylonitrile-butadiene rubber (NBR), blast furnace slag, hydro-magneite, 2,5-dimethyl-2,5-di (tetra-butylperoxy) hexane, a resorcinol- Mixing a first master batch composition comprising kaolin, charcoal, an inorganic filler, an antioxidant and a foaming agent, followed by aging;

b) adding a sulfur, a vulcanization accelerator, a perfume, and a cold-resistant plasticizer satisfying the following formula 1 to the first masterbatch composition to prepare a second masterbatch and then aging;

[Formula 1]

E _t ? V _t

(Where E _t is the foaming temperature of the blowing agent and V _t is the volatilization temperature of the cold resistance plasticizer).

c) feeding the aged second master batch into an extruder;

d) foaming the extruded extrudate in the range of E _t of the formula 1;

.

In the present invention, the step a) is a step for improving the miscibility by mixing the raw materials uniformly. Preferably, the mixing is performed using a bubbly mixer or a kneader during mixing of raw materials. Mixing for 15 minutes is preferred. The miscibility in the temperature and time ranges is improved, and if it exceeds the above range, the viscosity of the composition is rapidly lowered, which may cause deterioration of the physical properties of the heat insulating material.

In order to solve this problem, it is preferable to carry out aging for 24 hours or more, more preferably 48 hours, until the secondary raw material blending process in order to solve the problem, Do. The aging is preferably carried out at a temperature of 24 ° C and a humidity of 60% for 2 to 10 hours at room temperature and humidity, but can be carried out at room temperature for 24 to 72 hours.

Next, in the step b), a mixture of sulfur, a vulcanization accelerator and a fragrance and a cold-resistant plasticizer satisfying the formula 1 is added to the aged first master batch composition to prepare a secondary master batch and then aged.

When only the liquid perfume is used alone, most of the perfume is evaporated by heat in the pre-foaming stage before the insulation material is foamed, so that odor can not be removed inside the cell. In the present invention, however, , It is possible to make the foaming time of the foaming agent coincide with the evaporation point of the perfume, and the fragrance evaporating inside the cell can be confined, so that the odor can be removed and the long-term perfume can be maintained.

The mixing of the secondary master batch (FMB) is preferably carried out using a kneader and an open mill, and the screw temperature is preferably mixed at 90 to 110 ° C for 2 to 3 minutes. If the screw temperature is higher than 110 ° C, vulcanization can be caused by the added vulcanization accelerator and defective products may be generated. If the screw temperature is lower than 90 ° C, the dispersion between the raw materials may not be smooth and the physical properties of the final product may be deteriorated. According to the present invention, the secondary master batch (FMB) can be stored easily during aging and easily injected into an extruder.

The aging is preferably carried out at a temperature of 24 ° C and a humidity of 60% for 2 to 10 hours at room temperature and humidity, but can be carried out at room temperature for 24 to 72 hours.

Next, the step (c) is a step of putting into the extruder, and it can be extruded in a desired size and shape. The extruder preferably has a head temperature of 40 to 80 ° C. If the temperature is lower than 40 ° C., the extrusion is not smooth. If the extrusion temperature is higher than 80 ° C., the temperature of the extruded composition is increased to decrease the viscosity, Can not do it.

Next, the step d) is a step of foaming the extrudate, and the foaming step comprises a vulcanizing step, a pre-foaming step, a foaming step and a foaming-aging step. It is preferable that the heating temperature gradually increases from the vulcanizing step to the foaming aging step and that the foaming aging step is heated to a temperature lower than the foaming step. In the pre-foaming step, a raw material which has not been vulcanized in the vulcanization step is further vulcanized, and a part of the vulcanized raw material starts to be foamed. The extrudate is foamed in the foaming step, and the unfoamed part is foamed in the foaming and aging step. Since it is important that the high heat-resistant insulating material is used at a high temperature, it is important that the surface layer is firmly formed. Therefore, it is preferable to form a solid surface layer by lengthening the vulcanization and pre-foaming step time before the foaming in the foaming step.

More specifically, the foaming step is a vulcanization step of heating to 50 to 80 캜; A pre-foaming step of heating to 110 to 130 캜; A foaming step of heating to 140 to 180 캜; And a foaming aging step of lowering the temperature to 130 to 150 ° C. The temperature of the foaming step may be controlled depending on the type of foaming agent.

The cell generation time of the heat insulator by the foaming agent and the evaporation of the fragrance may occur at the same time in the foaming step so that the fragrance which evaporates in the heat insulating material cell can be confined and the odor inside the cell can be removed.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

The performance of the following products was measured by the following method.

1) Flammability (oxygen index (%)): KS M ISO 4589-2

2) Heat resistance (Dimensional stability 70 ℃ 48 hours (%)): KS M 6962

3) Heat insulation (thermal conductivity (W / mK)): KS M 6962

4) Odor

The test pieces were placed in a 4 L container at a temperature of 60 ± 2 ° C for 2 hours, and the panel was subjected to sensory evaluation and the average value was calculated.

The grades were as follows.

1 = No smell

2 = I do not know what the smell is, but I feel the smell

3 = The smell is weakly detected and the smell is known

4 = Easy to detect strong smell

5 = Very strong odor

6 = intense odor that makes you feel difficulty breathing

None: When the average value is 1 to 3 in sensory evaluation

Yes: average value in sensory evaluation is 4 to 6

5) Antimicrobial activity: ASTM G 21

Four types of fungal strains were used.

Aspergillus niger ATCC 9642

Penicillium pinophilum ATCC 11797

Chaetomium golobosum ATCC 9645

Aureobasidium pullulans ATCC 15233

Antibacterial: No growth of mycelium during antifungal test

US Antibacterial: Mycelium develops during antifungal test

6) Formaldehyde (mg / m ² h): indoor air quality process test standard (Ministry of Environment Notice No. 2010-24)

7) Mechanical properties (compressive strain (%)): KS M ISO 1856

[Example 1]

1) Production of first master batch

50 parts by weight of carbon black (N-774, manufactured by DYOKU CHEMICAL CHEMICAL INDUSTRIES, LTD.) As an inorganic filler, 100 parts by weight of chloroparaffin (CP-1) as a lubricant was added to 100 parts by weight of acrylonitrile-butadiene rubber (NBR) 25 parts by weight of stearic acid (stearic acid, St / acid), 75 parts by weight of hydro-magneite (LIKYA MINELCO, UC1251), 40 parts by weight of blast furnace slag (phosphoric acid, slag powder) 10 parts by weight of dimethyl-2,5-di (tetrabutylperoxy) hexane (AkzoNobel, Trigonox 101), 5 parts by weight of a binder (UNIROYAL CHEMICAL, R-6), a foaming agent (Azodicarbonamide, ), 25 parts by weight of kaolin powder (average particle diameter 10 占 퐉) and 25 parts by weight of charcoal powder (average particle diameter 10 占 퐉) were put into a chestnut mixer and mixed at a chamber temperature of 140 占 폚 for 10 minutes.

The mixed raw materials were aged at room temperature for 24 hours to solve fatigue.

2) Preparation of the second master batch

0.25 part by weight of sulfur (MICROFINE), 0.25 part by weight of dipentamethylenethiuramtetrasulfite (Link Well, DPTT) as a vulcanization accelerator, and 0.25 part by weight of liquid perfume (# , A volatilization temperature of 140 占 폚) and a cold-resistant plasticizer (Mediaplast NB-4 from KETTLITZ Co.) at a weight ratio of 90:10 were added to the kneader and mixed at 50 占 폚 for 3 minutes.

In order to lower the fatigue of the blended raw materials, it was aged in a constant temperature and humidity facility (24 ° C, 60% humidity) for 3 hours.

3) Extrusion

The secondary master batch was placed in an extruder (Cylinder: 150 Press Gage: 500 bar, 150 kW), melted and kneaded at a head temperature of 50 캜 for 10 minutes, and extruded in a sheet and tube form under a pressure of 130 bar.

4) Foam

More specifically, the vulcanization step is carried out at 70 DEG C for 25 seconds, the preliminary foaming step is carried out at 120 DEG C for 20 seconds, the foaming step is carried out at 180 DEG C ° C for 15 seconds and the foaming and aging step at 140 ° C for 10 seconds to obtain rubber foam insulation.

5) Cooling

The rubber foam insulation foamed through Hot Air Tunnel was cooled by air cooling for 5 minutes in order to stabilize the cell by cooling the high temperature gas inside the cell.

The performance of the manufactured rubber foam insulation was measured and shown in the following table.

[Example 2]

In Example 1, except for adding 40 parts by weight of rubber foamed thermal insulation waste powder as a rubber recycled powder and 10 parts by weight of powdered polyurethane (TSE yarn, millathane 5004) in the production of the first master batch, The rubber foam insulation was prepared.

At this time, the waste powder of the rubber foam insulation was pulverized into 0.5 mm of rubber foam insulation, and then irradiated with microwaves at an intensity of 50 kW for 50 minutes.

The performance of the manufactured rubber foam insulation was measured and shown in the following table.

[Example 3]

In Example 1, rubber foam insulation was prepared in the same manner as in Example 1, except that the contents of blast furnace slag and hydro-magnesite were different in the production of the first master batch.

The performance of the manufactured rubber foam insulation was measured and shown in the following table.

[Example 4]

In Example 1, rubber foam insulation was prepared in the same manner as in Example 1, except that the content of the mixture of the perfume and the cold-resistant plasticizer was different in the production of the first master batch.

The rubber recycled powder was prepared by mixing powder of rubber foam insulation and powder of waste tire. The powder of rubber foam insulation with a size of 400 mu m and the waste tire powder of 400 mu m were mixed at a weight ratio of 60:40, And 50 kW for 50 minutes, respectively.

The performance of the manufactured rubber foam insulation was measured and shown in the following table.

[Comparative Example 1]

In Example 1, except that blast furnace slag, 2,5-dimethyl-2,5-di (tetra-butylperoxy) hexane, binder, kaolin powder and charcoal powder were not used in the production of the first master batch Was prepared in the same manner as in Example 1.

The performance of the manufactured rubber foam insulation was measured and shown in the following table.

[Comparative Example 2]

In Example 1, rubber foam insulation was prepared in the same manner as in Example 1, except that a mixture of kaolin powder, charcoal powder, liquid fragrance and a cold-resistant plasticizer was not used at the time of producing the second master batch.

The performance of the manufactured rubber foam insulation was measured and shown in the following table.

[Comparative Example 3]

In Example 1, the same procedure as in Example 1 was carried out except that hydro-magneite, 2,5-dimethyl-2,5-di (tetra-butylperoxy) Rubber foam insulation was prepared.

The performance of the manufactured rubber foam insulation was measured and shown in the following table.

[Comparative Example 4]

In the same manner as in Example 1 except that 2,5-dimethyl-2,5-di (tetra-butylperoxy) hexane and a binder were not used in the preparation of the first master batch in Example 1, Foam insulation was prepared.

The performance of the manufactured rubber foam insulation was measured and shown in the following table.

[Comparative Example 5]

In Example 2, a rubber foam insulator was produced in the same manner as in Example 1, except that powdered polyurethane was not used in the first master batch production.

The performance of the manufactured rubber foam insulation was measured and shown in the following table.

[Comparative Example 6]

In the same manner as in Example 1, except that only the liquid level flavoring agent (FP-2190, # p-2190, volatilization temperature 140 ° C) was used in the preparation of the second master batch in Example 1, Rubber foam insulation.

The performance of the manufactured rubber foam insulation was measured and shown in the following table.

(Unit: parts by weight) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 My
One
Master batch Synthetic rubber 100 100 100 100 100 100 100 100 100 100 Filler 50 50 50 50 50 50 50 50 50 50 slush 25 25 25 25 25 25 25 25 25 25 Antioxidant 25 25 25 25 25 25 25 25 25 25 Hydro Magnesite 75 75 80 75 75 75 - 75 75 75 Blast furnace slag 40 40 50 40 - 40 40 40 40 40 2,5-dimethyl-2,5-di (tetra-butylperoxy) hexane 10 10 10 10 - 10 - - 10 10 Binder 5 5 5 5 - 5 - - 5 5 blowing agent 50 50 50 50 50 50 50 50 50 50 Powder type polyurethane - 10 - 10 - - - - - - Rubber recycled powder - 40 - 40 - - - - 40 - china clay 25 25 25 25 - - 25 25 25 25 charcoal 25 25 25 25 - - 25 25 25 25 My
2
Master batch sulfur 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Vulcanization accelerator 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Mixture of fragrance and cold tolerant plasticizer 15 15 15 30 15 - 15 15 15 - Liquid fragrance - - - - - - - - - 15

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Thermal conductivity (W / mk) 0.035 0.035 0.035 0.035 0.035 0.035 inferior goods
(Bubble generation) inferior goods
(Bubble generation) 0.035 0.035 stink none none none none none has exist none has exist Antimicrobial activity Antibacterial Antibacterial Antibacterial Antibacterial Antimicrobial Antimicrobial Antibacterial Antibacterial Formaldehyde (mg / m ² h) 0.02 or less 0.02 or less 0.02 or less 0.02 or less 0.05 or less 0.05 or less 0.02 or less 0.02 or less Oxygen Index (%) 35 35 36 35 30 35 35 35 Dimensional stability (%) -2 -2 -1.8 -2 -5 -2 -2 -2 Compressive strain (%) 11 11 11 11 11 11 16 11

As shown in Table 2, it was found that the embodiments of the present invention have reduced formaldehyde emission, are odorless, have antibacterial properties, have excellent heat resistance, flame retardancy and mechanical properties.

In particular, the addition of kaolin and charcoal added the antimicrobial effect to the insulation, so that it can be used indoors in the building because there is no occurrence of mold and development, and the odor inside the insulation cell is removed by using a mixture of spices and cold resistant plastic. In addition, it was found that the use of rubber recycled powder and millable polyurethane can reduce cost without deteriorating physical properties and performance.

Claims (13)

Butadiene rubber (NBR), blast furnace slag, hydro-magneite, 2,5-dimethyl-2,5-di (tetra-butylperoxy) hexane, resorcinol-phenol polymer binders, lubricants, kaolin, A first masterbatch composition comprising charcoal, an inorganic filler, an antioxidant and a foaming agent is prepared by adding sulfur, a vulcanization accelerator, a fragrance and a cold-resistant plasticizer satisfying the following formula 1 to a secondary master batch, Rubber foam insulation.
[Formula 1]
E _t ? V _t
(Where E _t is the foaming temperature of the blowing agent and V _t is the volatilization temperature of the cold resistance plasticizer). The method according to claim 1,
Wherein the first master batch composition further comprises a rubber recycled powder selected from rubber waste thermal insulation waste powder, waste tire powder and mixed powder thereof, and powdered polyurethane. The method according to claim 1,
The vulcanization accelerator may be one or two selected from 2-mercapto benzothiazole, tetramethyl thiuram disulide, dipenta methylene thiuram tertiary sulfide, Rubber foam insulation. The method according to claim 1,
In the above formula (1), the foaming temperature of the blowing agent is preferably in the range of 140 to 180 DEG C such as azodicarbonamide (ADCA), azodiisobutyronitrile (ABBN), dinitrosopentamethyltetramine (DNPT) (TSH), and oxybisbenzenesulfonylhydrazide (OBSH). ≪ / RTI > delete The method according to claim 1,
30 to 50 parts by weight of blast furnace slag, 70 to 80 parts by weight of hydro-magnesite, 2,5-dimethyl-2,5-di (tetra-butylperoxy) 1 to 15 parts by weight of hexane, 1 to 10 parts by weight of a binder which is a resorcinol-phenol polymer, 20 to 30 parts by weight of a lubricant, 10 to 30 parts by weight of kaolin, 10 to 30 parts by weight of charcoal, 20 to 60 parts by weight of an inorganic filler, 20 to 30 parts by weight of an antioxidant and 40 to 60 parts by weight of a foaming agent are aged and then mixed with 1 to 5 parts by weight of sulfur, 1 to 5 parts by weight of a vulcanization accelerator, And 10 to 30 parts by weight of a mixture of a plasticizer and a plasticizer. The method according to claim 1,
Wherein the fragrance and the cold-resistant plasticizer are added as a mixture of fragrance: cold-resistant plasticizer in an amount of 80 to 90:20 to 10 by weight. 3. The method of claim 2,
Wherein the rubber recycled powder further comprises 30 to 50 parts by weight and the powdered polyurethane further comprises 5 to 15 parts by weight. a) a binder which is an acrylonitrile-butadiene rubber (NBR), blast furnace slag, hydro-magneite, 2,5-dimethyl-2,5-di (tetra-butylperoxy) hexane, a resorcinol- Mixing a first master batch composition comprising kaolin, charcoal, an inorganic filler, an antioxidant and a foaming agent, followed by aging;
b) adding a sulfur, a vulcanization accelerator, a perfume, and a cold-resistant plasticizer satisfying the following formula 1 to the first masterbatch composition to prepare a second masterbatch and then aging;
[Formula 1]
E _t ? V _t
(Where E _t is the foaming temperature of the blowing agent and V _t is the volatilization temperature of the cold resistance plasticizer).
c) feeding the aged second master batch into an extruder;
d) extruding the extrudate at a temperature of from 50 to 180 占 폚 Firing in a range;
Wherein the rubber foaming heat insulating material is a thermoplastic resin. 10. The method of claim 9,
Wherein the mixing in the step a) is performed using a Bubert mixer, and the temperature of the Bubert screw is from 130 to 150 ° C. 10. The method of claim 9,
Wherein the aging in steps (a) and (b) is carried out at a temperature of 24 ° C and a relative humidity of 60% or at room temperature for 24 to 72 hours. 10. The method of claim 9,
And the outlet temperature of the extruder is maintained at 30 ° C to 70 ° C in the step c). 10. The method of claim 9,
In the step d)
A vulcanization step of heating to 50 to 80 캜;
A pre-foaming step of heating to 110 to 130 캜;
A foaming step of heating to 140 to 180 캜; And
A foaming aging step of lowering the temperature to 130 to 150 캜;
Wherein the rubber foaming heat insulating material is a thermoplastic resin.