阅读说明：本技术 利用麦闪石颗粒的放射远红外线及阴离子的硅橡胶组合物及其制备方法 (Silicone rubber composition emitting far infrared rays and anions using mackerel particles and method for preparing the same ) 是由 郭成根 郭多恩 于 2020-04-21 设计创作，主要内容包括：本发明涉及利用麦闪石颗粒的放射远红外线及阴离子的硅橡胶组合物及其制备方法。本发明的利用麦闪石颗粒的放射远红外线及阴离子的硅橡胶组合物的制备方法包括：浆料制备步骤,以规定比例混合麦闪石粉碎物与水来获得浆料；第一次混合步骤,向上述浆料添加抗菌物质和发泡剂来获得颗粒混合物；颗粒形成步骤,使用造粒机颗粒通过喷雾干燥工艺将上述颗粒混合物加工为具有0.1mm～1.5mm范围的平均粒径的麦闪石颗粒；以及第二次混合步骤,准备硅组合物粉末后,与麦闪石颗粒混合来制备硅橡胶组合物。通过本发明,在硅橡胶组合物的制备过程中添加麦闪石颗粒不但可以实现无臭的功能,还可以提高抗菌性。(The present invention relates to a silicone rubber composition emitting far infrared rays and anions using a glimmer particle and a preparation method thereof. The preparation method of the silicone rubber composition using the glimmer particles to radiate far infrared rays and anions comprises the following steps: a slurry preparation step of mixing the crushed matter of the amphibole and water at a prescribed ratio to obtain a slurry; a first mixing step of adding an antibacterial substance and a foaming agent to the slurry to obtain a particle mixture; a granule forming step of processing the above granule mixture into a mackerel granule having an average particle diameter ranging from 0.1mm to 1.5mm by a spray drying process using a granulator granule; and a second mixing step of preparing the silicon composition powder and mixing with the Maillard stone particles to prepare the silicone rubber composition. According to the invention, the addition of the medical stone particles in the preparation process of the silicone rubber composition can realize the odorless function and improve the antibacterial property.)

1. A method for preparing a silicone rubber composition emitting far infrared rays and anions by using glimmer particles, comprising:

a slurry preparation step of sintering the crushed material of the medical stone to obtain a sintered body, and mixing the sintered body with water at a weight ratio of 2: 1 to obtain slurry;

a first mixing step of adding an antibacterial substance and a foaming agent to the slurry to obtain a particle mixture;

a granule forming step of processing the above granule mixture into a mackerel granule having an average particle diameter ranging from 0.1mm to 1.5mm by a spray drying process using a granulator granule; and

and a second mixing step of preparing a silicon composition containing a methyl ethyl ketone soluble substance, an alkenyl cyanide compound and a styrene resin and walnut endocarp powder, and mixing the prepared 8 weight percent of mallite particles, 91 weight percent of the silicon composition and 1 weight percent of walnut endocarp powder to prepare the silicon rubber composition.

2. The method of preparing a far infrared ray and anion emitting silicone rubber composition using mackerel particles according to claim 1, wherein the antibacterial material is composed of 0.3 to 1.5 parts by weight of titanium dioxide, 0.001 to 0.01 parts by weight of nano silver, and 0.1 to 0.5 parts by weight of zirconium oxide, based on 100 parts by weight of the slurry.

3. The method of preparing a silicone rubber composition emitting far infrared rays and anions using mackerel particles according to claim 2, wherein the foaming agent is formed by mixing calcium carbonate and sodium carbonate at a weight ratio of 1: 1, and 0.15 to 1.5 parts by weight based on 100 parts by weight of the slurry is added.

4. A silicone rubber composition emitting far infrared rays and anions using a glimmer particle, characterized by being prepared by the preparation method of any one of claims 1 to 3.

Technical Field

The invention relates to a silicon rubber composition and a preparation method thereof, in particular to a far infrared ray and anion radiating silicon rubber composition which utilizes glimmer particles to enable the glimmer particles to have the functions of radiating far infrared rays and anions and a preparation method thereof.

Background

Silicon is Silicon whose element symbol is Si, and is a metallic substance (for example, a Silicon wafer for a semiconductor) in dark gray, and Silicone (Silicone) is a Polymer (Polymer) in which Silicon (organic Silicon) containing an organic group and oxygen are chemically bonded to each other, and is a unique chemical material having both organic and inorganic properties, and is a highly functional material (Polymer in which Silicon to which an organic group is bonded by a siloxane bond (Si-O-Si)) which is essential in most modern industrial fields, and is applied in various forms. This is a polymer formed by bonding silicon (Si) having an organic group and oxygen to each other by a chemical bond, and is a polymer formed by bonding silicon having an organic group bonded thereto by a siloxane bond (Si-O-Si), and is synthesized artificially.

Silicone rubbers are classified into high temperature curing (HTV) which requires a large amount of heat to cure and normal temperature curing (RTV) which cures naturally at normal temperature, depending on the curing temperature, but with the recent commercialization of liquid silicone rubbers using addition reaction, silicone cannot be classified solely on the curing temperature of the past. Accordingly, silicones can be classified into high consistency silicone rubber (HCR), Liquid Silicone Rubber (LSR), and normal temperature curing silicone according to the degree of polymerization or viscosity of the polymer.

Silicone rubber is formed from molecules of a network structure, usually from every few hundred R₂The Si-O is formed in a loose structure containing only one bonding site (crosslinking site).

In such a structure, molecular chains cannot move relative to each other and do not have fluidity, but rather, the rubber exhibits properties due to the expansion and contraction caused by a large degree of freedom of the molecules, and as the crosslinking of the rubber progresses, the degree of freedom of the molecules decreases, the expansion and contraction properties decrease, and the rubber becomes hard.

One of the characteristics of the silicone rubber is that the silicone rubber maintains excellent physical characteristics in a wide temperature range of-100 ℃ to 350 ℃ due to its acid resistance/heat resistance, has a saturation point of-60 ℃ to 70 ℃ (the saturation point of ordinary rubber: -20 ℃ to-40 ℃), and also maintains elasticity at low temperature when ordinary rubber is broken. The temperature range of the use is usually 150 to 250 ℃ and may be up to 350 ℃ in the case of intermittent short-term use.

The second characteristic is non-toxic and is an inert substance harmless to the human body, and thus can be used in various aspects, and can be widely used in food equipment, cosmetic industry, food containers and medical supplies.

The third property is chemical resistance, which is affected by strong acid or strong base, but has excellent chemical resistance to inorganic chemicals such as general acid, alkali, and salt, or polar organic compounds such as alcohols and animal and vegetable oils.

The fourth property is oil resistance, which is outstanding at high temperatures at which ordinary organic rubbers other than fluororubbers cannot be used.

And, the fifth characteristic is flame retardancy, and the silicone rubber has a molecular structure containing less hydrocarbon than the general organic rubber, so it is not easily burnt, and it does not contain halogen and does not generate toxic gas when burnt.

Conventional silicone rubbers are cured by a hydrosilylation reaction to form rubber-like liquid silicone rubber compositions having insulating properties or electrical conductivity, and are widely used in the fields of electricity, electromagnetism, construction, machinery, and the like. The insulating liquid silicone rubber matrix as the insulating silicone rubber composition matrix is prepared from an alkenyl group-containing organopolysiloxane, a reinforcing silicone filler, and, if necessary, an insulating inorganic filler.

The conductive liquid silicone rubber matrix as the conductive silicone rubber composition matrix is prepared from an organopolysiloxane containing alkenyl groups, a reinforcing silica gel filler, and if necessary, an insulating inorganic filler. In most cases, these raw materials are put into a stirrer such as a double arm kneader (dough mixer), a Henschel mixer or a planetary stirrer and stirred uniformly, and prepared in batches, and Japanese patent publication No. 1992-280082 discloses a continuous preparation method in which an alkenyl group-containing organopolysiloxane and a filler are continuously put into a twin-shaft compressor, heated and mixed, and discharged.

In Japanese laid-open patent publication No. 1998-152563, a method of preparing a liquid silicone rubber substrate by mixing and dispersing a fine conductive filler such as carbon black to an alkenyl group-containing organopolysiloxane by means of a stirring device having a rotating disk rotating at a high speed is disclosed.

However, these liquid silicone rubber substrates become high in temperature due to heating or frictional heat during production, and are cured by adding a crosslinking agent and a curing catalyst after cooling to room temperature, and cannot be cured immediately after production.

Japanese patent publication No. 1995-122000 discloses a method of preparing a silicone elastomer sponge by compounding and curing a silicone rubber substrate with a foaming agent formed of an aqueous emulsion composed of a curing agent, organopolysiloxane, an emulsifier, water and a thickener, and curing the silicone rubber substrate after cooling to room temperature by compounding a crosslinking agent and a curing catalyst, and the silicone rubber substrate cannot be cured immediately after the preparation.

Japanese laid-open patent publication No. 1984-12832 discloses a method for obtaining silicone rubber sponges from aqueous emulsions, which describes a preparation method in which a condensation polymerization curing type silicone emulsion composed of a hydroxyl-terminated diorganopolysiloxane and an organotin catalyst and colloidal silica is frozen, then thawed, and then water is removed, in which case organic amines, thickeners, and fillers other than colloidal silica may be mixed in the emulsion. However, the freezing, thawing and water removal of the silica gel emulsion requires enormous energy and time and is therefore very inefficient.

Japanese laid-open patent publication No. 2000-169590 discloses a method for preparing an elastomer by mixing an adhesion promoter, a silicone resin, and an aqueous dispersion of carbon black in an aqueous emulsion of a hydrosilylation reaction-curable silicone composition to prepare an aqueous emulsion/dispersion, applying the aqueous emulsion/dispersion to a fabric, and curing the applied aqueous emulsion/dispersion, but has a problem that it is difficult to prepare an aqueous dispersion of carbon black.

Japanese laid-open patent publication No. 2002-114860 discloses a method of preparing a silicone rubber sponge by heating and curing a silicone rubber matrix composed of a base-containing polyorganosiloxane and a reinforcing silicon filler, a polyorganohydrogensiloxane, and a platinum catalyst or an organic peroxide, and a foaming agent composed of a water-absorbent polymer gelled by absorbing water or water and an emulsifier, but since the gelled water-absorbent polymer is very viscous, a great load is imposed on a stirrer when it is mixed with other components under stirring.

Examples of the synthetic silica include styrene-butadiene silica gel (SBR: a copolymer of styrene and butadiene), acrylonitrile-butadiene silica gel (NBR: a copolymer of acrylonitrile and butadiene), butyl silica gel (a copolymer of isobutylene and 2 to 3% of isoprene or other unsaturated hydrocarbon), chloroprene silica gel (a polymer of chloroprene), polysulfide silica gel (synthesized from ethylene dihalide and basic polysulfide), and also cubic silica gel, fluorosilicone gel, and the like are used.

In the process of producing a polymer by the above polymerization reaction, a polymer having predictable and preferable performance characteristics can be produced by adjusting parameters such as the molecular weight of the post-treated polymer and the uniformity of the polymer.

Moreover, silica gel has a disadvantage of emitting a peculiar malodor of silica gel. Further, as a method for preparing butyl silica gel as described above, korean patent application No. 1997-36022 describes synthesis of acrylonitrile and 1, 3-butadiene as monomers by copolymerization in an aqueous emulsion, and describes an improved method for recovering a polymer from an aqueous emulsion after polymerizing the monomers, and the specific method is as follows: preparing a stabilized butyronitrile silica gel emulsion by adding an antioxidant to the emulsion containing butyronitrile silica gel, preparing a solidified butyronitrile silica gel slurry consisting of a liquid and butyronitrile silica gel fragments by adding hydrochloric acid to the stabilized butyronitrile silica gel emulsion, separating the butyronitrile silica gel fragments from the liquid of the solidified butyronitrile silica gel slurry, preparing the butyronitrile silica gel slurry by mixing the butyronitrile silica gel fragments with washing water, and separating the butyronitrile silica gel fragments from the washing water of the butyronitrile silica gel slurry by adjusting the pH of the butyronitrile silica gel slurry to a range of 5 to 8, thereby preparing the butyronitrile silica gel recovered from the emulsion.

Among them, nitrile (nitrile), also called cyano compound, is an organic compound having a molecular structure in which a cyano group (-C ═ N) is bonded to a carbon atom, and nitrile (nitrile) is a neutral substance in which a nitrogen atom is substituted for an oxygen atom in carboxylic acid. Acrylonitrile can be obtained by the reaction of hydrogen cyanide with acetylene or ethylene oxide or by the ammoxidation of ammonia with propylene over a catalyst.

Residual acid remaining in the polymer after coagulation can increase the corrosiveness of the polymer, causing serious problems, and the presence of acid in the polymer can adversely affect the vulcanization rate, with acidic polymers having a low pH being slower than neutral or basic polymers.

Such a decrease in the vulcanization rate is not preferable, and causes an increase in the time required for curing the silica gel in various bottleneck zones in industrial production, and also has a drawback that uncertainty occurs at least in part due to a possibility of variation in the amount of acid added to the solidified emulsion, thereby causing the emission of a silica gel-specific malodor.

And, in the general silica gel production industry, calcium carbonate (CaCO) is mainly used₃) Glass fiber, mica (mica), etc. are used as the filler (filler). However, these fillers often undergo thermal deformation, and have a disadvantage that durability, corrosion resistance, abrasion resistance, deodorizing effect, and the like are deteriorated, and therefore, they can only function as a simple extender.

On the other hand, Japanese laid-open patent publication No. Hei 6-200081 discloses a silica gel mixture, wherein the use of hydrous magnesium silicate clay minerals to reduce the generation of offensive odor due to thermal decomposition or gasification during vulcanization is described, but 5 to 75 parts by weight of the above clay minerals can be used per 100 parts by weight of the silica gel composition, and in practical examples, the amount of the clay minerals used is 20 parts by weight at the lowest and 70 parts by weight at the highest, thereby producing silica gels with low offensive odor, but the use of the silica gel composition is limited due to changes in the physical properties of the silica gel caused by the excessively high content of the clay minerals compared to the practical silica gel composition.

On the other hand, the applicant of the present invention filed for and granted "a method for preparing an odorless rubber composition using a Maillard stone powder and an odorless rubber composition obtained by the method" (Korean granted patent publication No. 10-0668105, patent document 1).

Patent document 1 describes the following method: after the tricrystal powder is fired, the tricrystal powder in the form of nano fine particles is obtained by a supercritical fluid rapid expansion method, and then the obtained mixture is added to a general rubber raw material to prepare an odorless rubber composition.

Patent document 1 discloses that the addition of nanoparticies of maiden stone improves the odorless function.

However, the research on improving the antibacterial property by using the malpighiate as the raw material is still very little.

However, the applicant of the present invention disclosed an attempt to improve the antibacterial property of plastic products by adding the maifanite particles in the preparation of plastic master batches in another patent application, "method for preparing an antibacterial plastic master batch of maifanite particles" (korean laid-open patent publication No. 10-1975955, patent document 2), but this is only relevant to plastic products and is not relevant to silicone rubber products.

Documents of the prior art

Patent document 1: KR 10-0668105(2007 year, 01, 05 and month)

Patent document 2: KR 10-1975955(2019, 04 and 30 months)

Disclosure of Invention

Technical problem

The present invention provides a silicone rubber composition emitting far infrared rays and anions using amphibole particles and a method for preparing the same, which solves the above problems, and aims to achieve an odorless function and to improve antibacterial properties by adding amphibole particles during the preparation of the silicone rubber composition.

Means for solving the problems

In order to solve the above problems, the method for preparing a silicone rubber composition emitting far infrared rays and anions using mackerel particles of the present invention comprises: a slurry preparation step of mixing the crushed matter of the amphibole and water at a prescribed ratio to obtain a slurry; a first mixing step of adding an antibacterial substance and a foaming agent to the slurry to obtain a particle mixture; a granule forming step of processing the above granule mixture into a mackerel granule having an average particle diameter ranging from 0.1mm to 1.5mm by a spray drying process using a granulator granule; and a second mixing step of preparing the silicon composition powder and mixing with the Maillard stone particles to prepare the silicone rubber composition.

In the above-described structure, the present invention is characterized in that the antibiotic substance is composed of 0.3 to 1.5 parts by weight of titanium dioxide, 0.001 to 0.01 parts by weight of nano silver, and 0.1 to 0.5 parts by weight of zirconium oxide, based on 100 parts by weight of the slurry.

The foaming agent is prepared by mixing calcium carbonate and sodium carbonate at a weight ratio of 1: 1, and is added in an amount of 0.15 to 1.5 parts by weight based on 100 parts by weight of the slurry.

In the second mixing step, 0.1 to 10 wt% of the silicon composition is mixed with the balance.

The silicone rubber composition of the invention is characterized by being prepared by the above-described preparation method.

ADVANTAGEOUS EFFECTS OF INVENTION

In the invention, the addition of the medical stone particles in the preparation process of the silicone rubber composition can not only realize the odorless function, but also improve the antibacterial property.

Drawings

Fig. 1 is a graph showing the emissivity of a amphibole.

Fig. 2 is a graph showing the spectral radiance of the amphibole.

Fig. 3 is a photomicrograph showing the particles of the amphibole in the present invention.

Fig. 4 to 12 are photographs showing reports of experimental example 3.

Fig. 5 to 17 are photographs showing reports of experimental example 4. .

Figure 18 is a photograph showing a silicone rubber plaque (also known as a "mackerel monster") prepared by the composition of the present invention.

Detailed Description

Hereinafter, the silicone rubber composition emitting far infrared rays and anions using the mackerel particles of the present invention and the method for preparing the same will be described in detail.

1. Slurry preparation step

The crushed matter of the masonite and water were mixed in a prescribed ratio to obtain a slurry.

The crushed material of the maifanite may be used by directly crushing the raw ore, but is preferably used by crushing after sintering.

The composition of such a maitreite is shown in table 1 below.

TABLE 1

Component and content of Maitreya stone

The mackerel, which is a rock belonging to quartz porphyry in igneous rock, has characteristics of easy weathering and friability as a whole, and in particular, white feldspar is often kaolinized, and biotite is also almost oxidized and dispersed in the form of iron oxide.

It features high content of amphibole, containing a lot of magnesium oxide (MgO), existence of alpha ray and positive influence on living things.

The wavelength generated in the above-mentioned mackerel is in the range of 8 μm to 14 μm, and is the far infrared ray in the most favorable wavelength range for living things. The far infrared rays in the above wavelength range activate biological cells to promote metabolism of animals.

In view of the fact that far infrared radiation generated when the amphibole is micronized (1 to 6 μm) is higher than that generated in the rock state, the present invention is characterized in that the amphibole is powdered, particularly powdered after firing (powdering), and is prepared into a pellet to be used as a carrier for containing a molten plastic material therein. In the case of the above-described formation, the plastic raw material and the inorganic component of the maiden form a strong bond inside, and a decrease in physical properties such as strength of the plastic injection product can be suppressed, and a decrease in quality of appearance can be prevented.

Further, the action of the amphibole exhibits functions such as adsorption based on porosity, precipitation of inorganic substances and the like, adjustment of water quality, and increase of dissolved oxygen amount in water.

In particular, the maltite reacts with oxygen to have very high oxidation states of 02 and OH (hydroxyl), and has very high oxidation and reduction properties. This allows the bacteria to penetrate the cell membrane and denature the cell membrane protein to destroy the cell membrane, thereby having a bactericidal effect.

This means that the amount of the antimicrobial substance used alone can be minimized.

Fig. 1 shows the amount of far infrared radiation from the mackerel, and fig. 2 shows the spectral radiance. The radiation dose of FIG. 1 is in W/m, based on detection at a temperature of 180 ℃²μ m, a high far infrared radiation amount similar to that of a black body can be confirmed. FIG. 2 is a graph for evaluation of far infrared ray application in KoreaResults of institute testing.

The present step is specifically explained as follows.

First, raw ore such as maltite crushed to 20mm or less, kaolin, zeolite, bentonite, and micaceite is charged into a furnace, and the temperature and pressure are adjusted to 1150 ℃.

The first ignition was carried out by adjusting the pressure of furnace LPG (hereinafter referred to as gas) to 0.1kg/hr and allowing the temperature to reach 300 ℃ in 1 hour. After 1 hour, the gas pressure was adjusted to 0.125kg/hr and the temperature was brought to 500 ℃ in 1 hour.

If the temperature reached 500 ℃, the gas pressure was adjusted to 0.15kg/hr and the temperature was allowed to reach 700 ℃ in 1 hour. When the temperature in the furnace reached 700 ℃, the gas pressure was adjusted to 0.2kg/hr to make the temperature 850 ℃. When the temperature reached 850 ℃, the gas pressure was kept constant at 0.2kg/hr for 1 hour to completely combust the organic substances contained in the raw materials.

When the combustion of the organic matter was completed, the gas pressure was adjusted to 0.25kg/hr and the temperature was raised to 950 ℃ in 1 hour. After reaching 950 ℃, the gas pressure was again increased to 0.3kg/hr to raise the temperature to 1040 ℃ in 1 hour.

After 1 hour, when the temperature reached 1040 ℃, the furnace interior was in an incomplete combustion state, the pressure in the furnace was increased to make the temperature in the furnace uniform to stabilize the sintering state of the entire raw material, and then the temperature reached 1150 ℃ within 5 hours while maintaining the furnace pressure.

After the temperature reached 1150 ℃, the amount of exhaust gas was reduced to increase the furnace pressure in a state of a fixed gas pressure and the temperature of 1150 ℃ was maintained for 1 hour to recrystallize and bond the chemical components of the glimmerite, that is, to bond the glimmerite by covalent bonding, and after the sintering, the temperature was gradually decreased and burned in a state of turning off the fire in the furnace and turning off the exhaust port, and then the temperature was reached 1000 ℃ in 2 hours. After 30 hours to about 300 c, the tube was completely open and the temperature was allowed to cool at 100 c per hour.

Then, the prepared sintered body was first pulverized into particles of 10mm or less using a crusher, and then pulverized again into particles of 5mm or less. Then, the sintered particles pulverized to 5mm or less were mixed with water at a ratio of about 2: 1, and then put into a wet powder crushed machine to be finely pulverized into a slurry having an average particle size of 20 μm or less.

2. First mixing step

The foaming agent is added to increase the porosity of the pellets, and after the antibacterial substance for imparting the antibacterial function is added, the pellet mixture is obtained by stirring.

A mixture of calcium carbonate and sodium carbonate in a weight ratio of 1: 1 was used as a foaming agent, and 0.15 to 1.5 parts by weight based on 100 parts by weight of the slurry was added.

Preferably, silver nanoparticles, titanium dioxide and zirconium oxide (ZrO) are used₂) As an antibacterial substance.

The foaming agent generates carbon dioxide by thermal decomposition during firing, and after the carbon dioxide generated inside the particles forms pores inside the particles, the gas is released between the particles to increase the porosity, and the silicon composition is impregnated into the interior, thereby improving the physical properties of the silicone rubber product during molding.

Preferably, 0.401 to 2.1 parts by weight of the antibacterial material is added based on 100 parts by weight of the slurry.

More specifically, it is preferable to use 0.3 to 1.5 parts by weight of titanium dioxide, 0.001 to 0.1 parts by weight of nano silver, and 0.1 to 0.5 parts by weight of zirconium oxide (ZrO) together₂)。

3. Particle formation step

The above pellet mixture was formed into pellets having an average particle diameter within a range of 0.1 to 100 μm by using a pelletizer to obtain Maillard pellets.

Preferably, the granulator employs a spray drying process.

More specifically, the granule forming step comprises igniting a burner with hot air of a granulator to raise the temperature to 1000 deg.C, starting a blower to move heat into a cyclone furnace after the temperature reaches 1000 deg.C, and introducing a nozzle at 40kgf/cm into the lower end of the cyclone furnace when the internal temperature reaches 300 deg.C²The pump pressure of (2) sprays the finely divided particulate mixture to an upper point of gravimetric inflow.

In this case, the liquid to be irradiated falls down by forming a vortex by hot air flowing from the upper side surface of the cyclone furnace, and thus, the liquid is formed into a pellet form, and moisture contained in the raw material is evaporated by internal heat kept at 300 ℃, thereby obtaining particles of maltite having a particle size of 80 to 900 μm and forming pores.

In this process, if the moisture content of the slurry is increased, the moisture contained in the granular particles is rapidly vaporized in the interior, and the pressure of the formed bubbles is increased by the expansion of the temperature, and when the pressure becomes higher than a certain level, the bubbles break through the spherical surface and form a pellet-like granular form as shown in fig. 3. The water vapor-releasing pellet-shaped particles have pores formed at positions where water molecules have been present, and have a pellet shape of 10 to 500 μm formed at positions where bubbles are broken inside, thereby reducing the specific gravity of the particles and the carrier of the silicon composition, and thus having excellent binding force.

4. A second mixing step

The silicone rubber composition is prepared by mixing the prepared Maillard particles with the prepared silicon composition.

More preferably, 0.5 to 15 weight percent of the Maillard particles are mixed with the balance of the silicon composition.

In this case, the Maillard particles may be pulverized again so that the average particle size is about 0.1 μm to 50 μm and then mixed with the silicon composition.

Example 1

After putting the raw ore crushed to below 20mm into a furnace, adjusting LPG gas pressure in the furnace to enable the temperature in the furnace to reach 1150 ℃, keeping the temperature at 1150 ℃ for 1 hour to enable chemical components of the glimmerite to be combined in a crystallization mode, namely, covalent bond combination, after sintering, enabling the temperature to reach 1000 ℃ after burning slowly by reducing the temperature under the state that fire in the furnace is turned off and an exhaust port is closed. After 30 hours to about 300 ℃, the material is completely opened, and the temperature is 100 ℃ per hour

Next, the prepared sintered body was first pulverized into particles of 10mm or less using a crusher, and then pulverized again into particles of 5mm or less. Then, the sintered particles pulverized to 5mm or less were mixed with water at a ratio of about 2: 1, and put into a wet powder crushed machine to prepare a slurry finely pulverized to an average particle size of 20 μm or less.

Then, a foaming agent in which calcium carbonate and sodium carbonate were mixed in a weight ratio of 1: 1 was prepared, and 0.3 parts by weight of the foaming agent was added based on 100 parts by weight of the slurry.

Further, 0.8 parts by weight of titanium dioxide, 0.005 parts by weight of nano silver, and 0.3 parts by weight of zirconium oxide as an antibacterial material were added to 100 parts by weight of the slurry and stirred to prepare a particle mixture.

Then, after the pelletizer is prepared, the burner is ignited by hot air of the pelletizer to raise the temperature so that the temperature in the furnace reaches 1000 ℃, after the temperature reaches 1000 ℃, the blower is started to move the heat into the cyclone furnace, when the internal temperature reaches 300 ℃, a nozzle is put into the lower end part of the cyclone furnace at 40kgf/cm²The finely pulverized granular mixture is sprayed to the upper point of the inflow by the pump pressure of (1), and the radiated liquid is made to fall down by forming a vortex by hot air flowing from the upper side of the cyclone furnace, thereby forming a pellet form as shown in fig. 3, and the moisture contained in the raw material is evaporated by the internal heat kept at 300 ℃, thereby preparing the mallite granules having a particle size of 80 to 900 μm, which form pores.

The far infrared ray emissivity of the prepared glimmer particles was 0.901 when measured at a detection temperature of 40 ℃, and the measurement result of anion released from the detection object as the ion number was 1.815ion/cc when measured by a charged ion detection device at an indoor temperature of 20 ℃, a relative humidity of 30%, and an anion number in the atmosphere of 54/cc.

Example 2 preparation of Silicone rubber composition 1

A silicone rubber composition was prepared by mixing and stirring 4.0 weight percent of the embodied 1 glimmer particles with 96 weight percent of the silicon composition.

The silicon composition was used by mixing 23.0 wt% of polyphenylene ether, 33.0 wt% of a thermoplastic resin obtained by polymerizing an aromatic alkenyl compound, an alkenyl cyanide compound and an alkenyl monomer mixture polymerizable with the monomers thereof, 21.0 wt% of a styrene resin, 12.0 wt% of a methyl ethyl ketone-soluble substance (total free polymer) and 11.0 wt% of a total alkenyl cyanide compound.

In this case, the methyl ethyl ketone soluble substance contains: 13 weight percent of a polymer comprising 6 weight percent of an alkenyl cyanide compound (hereinafter 'AC'); 30 weight percent of a polymer comprising 15 weight percent AC; 21 weight percent of a polymer comprising 30 weight percent AC; and 36 weight percent of a polymer comprising 50 weight percent AC.

EXAMPLE 3 preparation of Silicone rubber composition 2

A composition was prepared by mixing 8 weight percent of the glimmer particles with 92 weight percent of the silicon composition in the same manner as in example 2.

Experimental example 1 testing the deodorizing Effect

The deodorizing effects of the examples and comparative examples were tested by using a simple silicon composition as a rubber composition for comparative example 1.

The odor levels of the silicone rubber compositions of example 2, example 3 and comparative example 1 were measured every 3 hours from the production thereof, and the results are shown in table 2 below.

In this case, the detection of the odor intensity described above is performed by a method of sensory testing in the following manner.

Healthy students were selected to detect the odor intensity of the malodor by using the sense of smell in a state where the silicone rubber composition of the comparative example of the above example was immediately taken out. During detection, a place which is completely free of wind and does not transmit malodor from the surroundings is selected as a test place, and a judge person of the malodor test selects 10 healthy students with normal smell who first come to the place generating the malodor. The intensity of the malodor in the selected place as perceived by the judge was recorded together with the personal information. The sensory malodor evaluation method showed the malodor degree shown in table 2 below.

Table 2 malodor degree sensory test differentiation

In the above evaluation method, the evaluation is performed by the malodor degree which is evaluated by most of the evaluators in the malodor degrees sensed by each evaluators, and when the evaluation number is the same, the evaluation is performed by selecting a mode in which the malodor degree is high, preferably 2 degrees or less, and preferably 3 degrees or more. Further, as test conditions, immediately after the silicone rubber compositions of the above examples and comparative examples were prepared, they were put into a sealed bag (50 cm in length, width and height, respectively), and then taken out every 3 hours to be tested by an organoleptic method. In order to minimize the opening of the door, the opening is performed in a sealed state.

TABLE 3

Sensory test results for malodor

As shown in the above table, in the case of the silicone rubber composition of the present invention, the deodorizing effect at the initial stage of production was excellent, and the odor of the silica gel was further eliminated with the lapse of time, whereas the comparative example had almost no deodorizing effect of the silica gel odor, and thus it was confirmed that the inclusion and stirring of the mitsunobrite particles of the present invention at the time of preparation of the silicone composition could considerably eliminate the odor of the silica gel.

Experimental example 2 confirmation of protein deformation of milk powder

The silicone rubber composition of example 2 was manufactured as a mackerel monster (silicone rubber) by a feeding bottle container manufacturing company (fig. 18) and sandwiched between feeding bottle type containers, and experiments for confirming the degree of protein deformation of milk powder were conducted by the institute of food science at the university of korean celebration, and the experimental reports are shown in fig. 4 to 11.

In the report of fig. 4 to 11, "new Wellion bottle" means a bottle using the rubber composition of example 2 as a raw material, "ordinary bottle" and a bottle commercially available from "Wellion bottle" using a master batch of a mixed polyphenylene sulfone resin (PPSU) substance and mackerel particles.

As shown in fig. 4 to 11, in the milk bottle prepared using the silicone rubber composition of the present invention as a raw material, the most protein hydrolysate was produced, and it is known that the difference in protein hydrolysis with the lapse of storage time shows a greater difference between the ordinary milk bottle and the milk bottle of the example as the time is longer.

Experimental example 3 antibacterial Properties in Water

The silicone rubber composition of example 2 was used as a raw material, and the manufacturer was requested to cut the mackerel monster (silicone rubber) (fig. 18) prepared as a film into the size of the inner liner of the water bottle cap and insert the water bottle cap into the inner liner, and then requested to perform the test on the antibacterial property in water by the institute of food science at the university of korean celebration, and the experimental report is shown in fig. 12 and 17.

As shown in fig. 12 to 17, the bottle cap liner using the silicone rubber composition of example 2 showed higher antibacterial properties than the control group using the conventional bottle cap liner.

Example 4 preparation of Silicone rubber composition 3

In the same manner as in example 2, after mixing 8 weight percent of the maltite particles with 91 weight percent of the silicon composition, 1 weight percent of the walnut endocarp powder was mixed to prepare a composition.

Walnut endocarp refers to the very hard powder of the outermost layer of the endocarp.

Experimental example 4 mechanical Property testing

The following measurements of mechanical properties were carried out on test pieces prepared using the rubber compositions of examples 2 to 4, and the results are shown in table 4.

First, test pieces were prepared and tested for hardness according to ASTM D2240.

Specifically, the above hardness represents the hardness of silicone rubber, and in general, the hardness of thermosetting silicone rubber is 15 degrees to 20 degrees at the lowest and 90 degrees at the highest. The detector uses a SHORE A TYPE hardness tester, the thickness of the test piece is 6mm, or 3 test pieces with the thickness of 2mm are stacked for detection, the detection needs to be carried out more than 1/2 inches (inch) from the edge position, the value is read within 1 second when the needle contacts the test piece, and the average value is taken for more than 5 times of repeated detection to represent the hardness value.

Plasticity is used to show softness or diffusibility of rubber, and when the plasticity is low (too soft) during operation in a Two-roll mill, it is difficult to extract a sheet, and when the sheet is injected into an injection molding machine, the sheet should be continuously injected in the form of a ribbon (ribbon), but too soft may easily break and affect the operation of the injection molding machine. The measuring apparatus used a Plastometer, plasticized (softened) for 5 minutes by using a Williams Plasticity (Williams Plasticity) method of JISK6249, passed through a defoaming step for 2 minutes, cooled for 5 minutes by taking a mass of 2 times the specific gravity, and then displayed the degree of diffusion in 5 minutes under a load of 5kg as a numerical value.

The tear strength is a numerical value obtained by quantifying the force which can be received when the rubber is torn due to a fine scratch or a heavy weight in a use environment, and the force received per unit length is detected. The test pieces of silicone rubber prepared in accordance with the specifications of ASTM D624-DIEC (DUMBBLE TYPE) were tested in a Universal Testing Machine (Universal Testing Machine) by pulling them at a speed of 500mm/min, and the average value of the test pieces was expressed as 4 pieces.

The tensile strength is a force numerically expressing the maximum stress per unit area of the silicone rubber test piece, and the degree of tensile strength is expressed in units of MPa and pounds (pound). Testing apparatus a silicone rubber test piece prepared in accordance with the specification of ASTM D624D 412 (dumble TYPE) was tested in a testing apparatus by pulling at a speed of 500mm/min using a universal testing machine, and expressed as an average of 4 test pieces.

In Table 4 below, the units of hardness are Shore A, the units of tear strength are N/mm, the units of tensile strength are MPa, and the units of plasticity are none.

TABLE 4

Distinguishing	Hardness of	Plasticity	Tensile strength	Tear strength
					Comparative example	62	220	8.5	19.0
Example 2	59	219	8.3	18.8
					Example 3	58	221	8.1	18.4
Example 4	63	220	8.7	19.2

As is clear from the results shown in table 4, the test pieces prepared using the silicone rubber composition of the present invention have less difference in physical properties than the test pieces prepared using only the silicone rubber composition. In this case, it was confirmed that the addition of a trace amount of walnut endocarp powder as in example 4 gave superior physical properties to the test piece prepared solely from the silicone rubber composition.

Industrial applicability of the invention

The silicone rubber composition of the invention can be applied to the manufacture of various known silicone rubber products such as feeding bottles, water cups, chopping boards, medical containers, food supports, medical instrument pads, bed sheets, shoe pads, wrapping paper, table pads, seat cushions, storage containers, storage bottle caps, agricultural plates, car mats and the like.