KR101465225B1 - Anti-biotic Plastic Resin Composition Having High Hardness with Low Lightweight and Method of Producing the Same - Google Patents
Anti-biotic Plastic Resin Composition Having High Hardness with Low Lightweight and Method of Producing the Same Download PDFInfo
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- KR101465225B1 KR101465225B1 KR1020140083865A KR20140083865A KR101465225B1 KR 101465225 B1 KR101465225 B1 KR 101465225B1 KR 1020140083865 A KR1020140083865 A KR 1020140083865A KR 20140083865 A KR20140083865 A KR 20140083865A KR 101465225 B1 KR101465225 B1 KR 101465225B1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
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Abstract
Description
TECHNICAL FIELD The present invention relates to an antimicrobial synthetic resin tube composition having high rigidity, and more particularly, to a polyvinyl chloride synthetic resin tube composition having polyvinyl chloride as a main component and high rigidity, light weight and antibacterial properties, will be.
In general, the vinyl chloride resin composition has excellent mechanical strength, low friction resistance, chemical resistance, electrical insulation, light weight, easy construction and low cost, and is widely used in various fields such as pipes, building materials, .
Most of the vinyl chloride resin composition used as the pipe material is produced by extruding pellets of a polyvinyl chloride (PVC) resin into an extruder and extruding into a pipe shape. PVC resin pipes have excellent mechanical strength, are relatively easy to process and easy to install, and are widely used as fluid transfer pipes by extrusion molding.
However, the PVC resin tube has a disadvantage in that the strength is lowered at high temperature and low temperature, and aging occurs rapidly when exposed to direct sunlight for a long period of time. Thus, its use is limited to high temperature piping such as heating. There arises a problem that the coloring is deteriorated due to the temperature change of the film, or the physical properties are deteriorated and warped or deformed.
In addition, the PVC resin pipe is mainly used as a fluid transfer pipe. When used as a water pipe for transferring water such as a water pipe, there is a possibility that microorganisms in the water will grow in a static water pipe.
In order to solve these problems, the resin composition is mixed with an additive for strengthening the strength to improve the strength. However, when the strength is supplemented, the impact resistance is lowered. When the impact resistance is strengthened, the strength is weakened. It is difficult to improve the physical properties.
A conventional prior art is Korean Patent No. 10-917765 entitled "Polyvinyl Chloride Resin Composition for Fluid Pipe ". However, this method adds bamboo charcoal powder, nano-scale scorching and general wonder to improve the impact resistance. As the addition of additives increases, the interface between the additive surface and the polyvinyl chloride resin increases Therefore, the impact strength of the final synthetic resin may be weakened in proportion to the amount of the additive.
As a conventional prior art, Korean Patent Registration No. 10-1038648 entitled " A method of manufacturing a resin tube with improved heat resistance and a resin tube manufactured by the method ". However, this method is disadvantageous in that chlorinated polyvinyl chloride must be added in order to improve the heat resistance, and the heat stabilizer must be simultaneously supplied in consideration of decomposition by heat during the molding process.
As a conventional prior art, Korean Patent No. 10-1212456 entitled "Synthetic Resin Tubes with Improved Impact Resistance" However, in this method, 1 to 50 parts by weight of an acryl-vinyl chloride graft copolymer is added to 100 parts by weight of polyvinyl chloride to improve impact resistance, and 5 to 15 parts by weight of an impact modifier is added.
In this case, in order to improve the impact resistance, at least 6% to 65% of the polyvinyl chloride component, which is the basic raw material of the synthetic resin pipe, is supplied. However, the physical properties of the synthetic resin pipe It is difficult to distinguish whether or not it exists.
The present invention provides a polyvinyl chloride synthetic resin tube composition having polyvinyl chloride as a main component, high rigidity and light weight and antibacterial property, and a method for producing the same. .
In order to attain the above object, the present invention provides a thermoplastic resin composition comprising 3 to 6 parts by weight of an ethylene-modified copolymer, 2 to 4 parts by weight of an impact modifier, 3 to 8 parts by weight of glass-fired ceramic powder, 5 to 10 parts by weight of fine powder of mineral, 1 to 3 parts by weight of processing aid and 1 to 5 parts by weight of other filler.
The present invention also relates to a process for producing a waste glass product by pulverizing a waste glass product by collecting, cleaning and crushing waste glass bottles and the like and uniformly mixing 95 wt% to 97 wt% of the waste glass product with 3 wt% to 5 wt% The waste glass raw material is put into a high temperature firing furnace and subjected to a high temperature heat treatment at a high temperature of 750 ° C. to 1100 ° C. for 30 minutes to 1 hour to obtain a glass ceramic reaction product, A first step of preparing a powdered glass fired ceramic powder by cooling and pulverizing the powdered glass fired ceramic powder;
10 to 20% by weight of at least two ores selected from the group consisting of feldspar, zeolite, mica stone, talc and pyrophyllite are weighed and finely pulverized to about 100 to 200 mesh and mixed with each other Next, the mixed raw materials are firstly low-temperature-firstly cooled at a low-temperature sintering furnace at 200 to 300 ° C for about 1 to 2 hours, and then the primary-cooled products are heated again at a calcination temperature of 500 to 900 ° C for 2 to 3 hours The second cooled product is further subjected to secondary heating and then thirdly heated for 2 to 4 hours while supplying nitrogen gas at a high temperature baking furnace at a temperature of 800 to 1300 DEG C, and gradually cooled to obtain tertiary titanium ceramic powder A second step of:
3 to 6 parts by weight of an ethylene-modified copolymer, 2 to 4 parts by weight of an impact modifier, 3 to 8 parts by weight of the glass-fired ceramic powder, 5 to 10 parts by weight of the titanium-ceramic powder, 1 to 3 parts by weight of the preparation, and 1 to 5 parts by weight of other fillers into a reaction vessel to prepare a highly rigid polyvinyl chloride synthetic resin composition; The present invention provides a method for producing an antimicrobial polyvinyl chloride synthetic resin tube composition.
The composition for polyvinyl chloride synthetic resin tube according to the present invention is characterized in that its performance is not inferior to that of a conventional synthetic resin tube for impact resistance while adding a small amount of an impact resistant material.
In addition, the composition for polyvinyl chloride synthetic resin tube according to the present invention is advantageous in that it is lighter in weight than the conventional composition for functional synthetic resin tube even when an inorganic additive is added thereto. This lightweight is expected to be of great help in creating new uses for building materials or for plumbing and waterworks.
In addition, since the composition for polyvinyl chloride synthetic resin tube according to the present invention has antimicrobial activity by the fine powder of titanium titanium mineral, it can be said that it is useful for sanitary piping because it can prevent the propagation of microorganisms in stagnant water during flow.
The composition for polyvinyl chloride synthetic resin tube according to the present invention comprises 3 to 6 parts by weight of an ethylene-modified copolymer, 2 to 4 parts by weight of an impact modifier, 3 to 8 parts by weight of glass-fired ceramic powder, 5 to 10 parts by weight of titanium ceramic powder, 1 to 3 parts by weight of processing aid and 1 to 5 parts by weight of other filler.
The polyvinyl chloride synthetic resin composition according to the present invention is composed mainly of polyvinyl chloride, which is easy to color, relatively hard, has excellent moldability and is widely used.
The polyvinyl chloride may be prepared by a suspension polymerization method or an emulsion polymerization method according to a production process, and is distributed in the form of a resin granular powder of a solution polymer, and can be produced using the same. The degree of polymerization of the polyvinyl chloride is preferably in the range of 500 to 2,500. The production method of the polyvinyl chloride is conventional, and there is no particular limitation thereon.
The polyvinyl chloride synthetic resin composition according to the present invention contains 3 to 6 parts by weight of an ethylene-modified copolymer with respect to 100 parts by weight of the polyvinyl chloride.
The ethylene-modified copolymer is obtained by copolymerizing a first segment constituent component composed of an ethylene homopolymer, an ethylene /? - olefin copolymer or an ethylene / polar group-containing vinyl copolymer, and a second segment constituent composed of an unsaturated carboxylic acid or an aromatic vinyl compound And the first segment constituent component and the second segment constituent constitute an ester bond or an ether bond. The first segment component may have an average molecular weight (Mw) of about 5,000 to about 500,000, preferably about 10,000 to about 50,000, and a melt flow rate (MFR) of about 30% It is preferably 0.05 to 100 g / 10 min, and the second segment component preferably has an average molecular weight (Mw) of about 500 to 500,000.
More preferably, the ethylene-modified copolymer is an ethylene-vinyl copolymer having an ethylene content of 1 to 99 mol% and a vinyl group-containing vinyl copolymer content of 1 to 55 mol%, and the second segment The constituent components are (meth) acrylic acid ester copolymers, and they preferably have an ether bond with each other.
When the ethylene-modified copolymer is used in an amount of 3 parts by weight or less based on 100 parts by weight of the polyvinyl chloride, it is difficult to exhibit the impact resistance of the final synthetic resin. On the other hand, when the ethylene-modified copolymer is used in an amount of 6 parts by weight or more, Which is undesirable.
The polyvinyl chloride synthetic resin composition according to the present invention comprises 2 to 4 parts by weight of an impact modifier based on 100 parts by weight of the polyvinyl chloride.
The impact modifier is used to further reinforce impact resistance on the synthetic resin composition. The impact modifier may be a component commonly used in the art. The impact modifier is more efficient when used in combination with the ethylene modified copolymer, as compared to when used alone. As the impact modifier, for example, an MBS impact modifier is preferable. Since the MBS impact modifier is commonly used in the technical field, a detailed description thereof will be omitted. When the impact modifier is used in an amount of 2 parts by weight or less, it is difficult to expect an impact resistance strengthening effect. On the other hand, when the impact modifier is used in an amount of 4 parts by weight or more, the impact resistance increase rate is not increased.
The polyvinyl chloride synthetic resin composition according to the present invention comprises 3 to 8 parts by weight of glass-fired ceramic powder per 100 parts by weight of the polyvinyl chloride.
The glass-fired ceramic powder is obtained by collecting waste glass bottles, washing, crushing and pulverizing them, mixing them together with a binder, firing at a high temperature to obtain a glass ceramic material, cooling it to room temperature and pulverizing . The glass-fired ceramic powder is cooled after being fired at a high temperature, and has many fine bubbles formed on the surface thereof. As shown in enlarged view, when the fine bubbles are open, an open cell structure and fine bubbles are closed And a closed cell structure.
The glass fired ceramic powder has numerous micropores formed on the surface and inside thereof. The pores on the surface thereof have a size generally within about 1 mm, and the specific gravity thereof is about 0.4 to 0.5. Therefore, It will easily float in the water. Therefore, when the glass fired ceramic powder is used as a filler for a synthetic resin, it is possible to achieve weight reduction of products which can not be provided by other strength reinforcements while improving the strength of the product.
When the glass fired ceramic powder is added in an amount of less than 3 parts by weight based on 100 parts by weight of the polyvinyl chloride, the strength reinforcing effect is weak. When the glass fired ceramic powder is added in an amount of more than 8 parts by weight, The proportion of the inorganic additive is increased along with the content of the inorganic additive, which tends to weaken the strength reinforcing effect as a whole, which is not preferable.
In fact, since the glass fired ceramic powder has numerous microbubble-like open cells on the surface thereof, the synthetic resin composition enters the open cell, so that even when the glass fired ceramic powder is charged in an amount of 8 parts by weight or more The glass fired ceramic powder and the synthetic resin composition are firmly combined with each other, so that the effect of strengthening the strength is increased, and the glass fired ceramic powder is not weakened by itself. However, if the glass fired ceramic powder is added in an amount of 8 parts by weight or more, the proportion of the total inorganic additive increases and the proportion of the polyvinyl chloride component becomes relatively low when other inorganic additives are added. The strength reinforcement effect is weakened.
The polyvinyl chloride synthetic resin composition according to the present invention contains 5 to 10 parts by weight of a fine powder of a titanium titanium mineral with respect to 100 parts by weight of the polyvinyl chloride.
The fine powder of the titanium-containing minerals is produced by pulverizing the pulverized mixed minerals at a low temperature and a high temperature by mixing the feldspar with the minerals consisting of zeolite and mica stone and using the magnetite containing titanium as the main raw material, Or more of the ceramic powder is a ceramic powder having antimicrobial properties.
The fine powders of the titanium-containing minerals are dark gray to black when viewed from the outward appearance, and they are the same even in the state of finely pulverized. Although the ceramic powder is considered to have electromagnetic shielding properties, it is independent of the electromagnetic shielding property in the nature of the present invention, and therefore, only the antibacterial property of the ceramic powder is used.
The microfine powder of titanium-containing minerals has a weak antimicrobial effect when it is added in an amount of less than 5 parts by weight based on 100 parts by weight of the polyvinyl chloride, and when it is added in an amount of 10 parts by weight or more, But the ratio of the inorganic additives together with the content of other fillers becomes excessive, which tends to weaken the strength reinforcing effect as a whole, which is not preferable.
The polyvinyl chloride synthetic resin composition according to the present invention contains 1 to 3 parts by weight of the processing aid per 100 parts by weight of the polyvinyl chloride.
The processing aid is used for the improvement of processability, prevention of melt fracture, reduction of flow mark, improvement of gloss and the like without affecting the overall physical properties of the synthetic resin by injecting a relatively small amount . As the processing aid, materials conventionally used in this technical field can be used. As the processing aid, an acrylic, styrene or organic aryl ester compound processing aid is preferable, and more specifically, a processing aid having a molecular weight of 500,000 to 3,000,000 which is a main component of polymethyl methacrylate (PMMA) is more preferable.
When the processing aid is used in an amount of 1 part by weight or less based on 100 parts by weight of polyvinyl chloride, a flow mark or the like appears during processing at a low temperature, resulting in poor processability. Therefore, when the amount is more than 3 parts by weight, It is not desirable because it causes cost increase.
The polyvinyl chloride synthetic resin composition according to the present invention contains 1 to 5 parts by weight of other filler based on 100 parts by weight of the polyvinyl chloride.
The above-mentioned other fillers refer to an extender added for cost reduction, a lubricant to be added to improve workability, and a pigment to impart color to synthetic resin. The other fillers may be used in a conventional manner.
Depending on the intended use of the final product, the amount of the other filler to be added and the amount of the other filler are determined. The extender, the lubricant, the pigment, and the like may be put in, respectively, or put in together.
Examples of the filler include inorganic fillers such as calcium carbonate, talc, mica, and silica. The inorganic filler is most preferably calcium carbonate. The above-mentioned calcium carbonate is low in unit cost, improves the formability, reduces the abrasion of the mixing and processing apparatus, is harmless to the human body, and is easy to use because of a wide range of particle size adjustment. In particular, it is known that calcium carbonate having a particle size of less than 0.1 탆 functions to disperse impact applied to the outside of a resin tube produced due to its small particle diameter to strengthen impact resistance.
The lubricant is used for the purpose of lowering the flow viscosity of the resin dissolved in the molding process and preventing frictional heat generation. Examples of the lubricant include butyl stearate, lauryl alcohol, stearyl stearate, epoxidized soybean oil, glycerin monostearate, stearic acid, and bis-amide. When the lubricant is added below the lubricant, the lubrication action is not properly performed. On the other hand, when the lubricant is added beyond the reference lubricant, the improvement of the lubrication performance is limited and the surface processability is lowered later.
The pigment may be used when it is desired to impart color to a synthetic resin product. The pigment may also be carried out in a conventional manner.
The present invention also provides a method for producing the polyvinyl chloride resin tube composition.
The method for producing the polyvinyl chloride resin tube composition according to the present invention comprises a first step of preparing a glass-fired ceramic powder which is primarily capable of imparting high rigidity to a synthetic resin composition, Wow; A mixture of minerals such as feldspar as a main component and a titanium oxide powder as a main component, and gradually increasing the temperature from a low temperature to a high temperature to be subjected to a firing process three times or more to impart antimicrobial properties to the ceramic powder components of the mineral phase, Step 2; A third step of preparing a polyvinyl chloride resin composition having light weight, impact resistance and antimicrobial properties on the polyvinyl chloride synthetic resin using the glass fired ceramic powder obtained in the first step and the antibacterial mineral ceramic powder obtained in the second step; Lt; / RTI >
The method for producing the polyvinyl chloride resin tube composition according to the present invention comprises the steps of collecting, washing and crushing waste glass bottles and the like to pulverize the waste glass product, and mixing 95 wt% to 97 wt% of the waste glass product with the binder 3 The waste glass raw material is put into a high temperature firing furnace and subjected to a high temperature heat treatment at a high temperature of 750 to 1100 DEG C for 30 minutes to 1 hour to obtain a glass ceramic reaction product A first step of preparing a powdered glass-fired ceramic powder by cooling the glass-ceramic reaction product to a room temperature and then pulverizing the powder; .
The method for producing the polyvinyl chloride synthetic resin pipe composition according to the present invention comprises the steps of mixing 80 to 90 wt% of titanium magnetite and 10 to 20 wt% of two or more minerals selected from the group consisting of feldspar, zeolite, mica stone, talc, The mixture is firstly cooled at a low temperature baking furnace at a temperature of 200 to 300 DEG C for about 1 to 2 hours and then subjected to primary cooling so that the primary The cooled product is further heated again in a firing furnace at 500 to 900 占 폚 for 2 to 3 hours and then cooled secondarily. The second cooled product is heated again at a high temperature firing furnace at 800 to 1300 占 폚, A third step of heating for 4 hours and then a third cooling step to prepare a titanium titanium powder; .
The method for producing the polyvinyl chloride resin tube composition according to the present invention is characterized in that after the first step and the first step, 3 to 6 parts by weight of an ethylene-modified copolymer, 2 to 4 parts by weight of reinforcing agent, 3 to 8 parts by weight of glass-fired ceramic powder, 5 to 10 parts by weight of titanium-titanium ceramic powder, 1 to 3 parts by weight of processing aid and 1 to 5 parts by weight of other filler, A third step of producing a stiff antimicrobial polyvinyl chloride synthetic resin composition; .
In the present invention, the first step and the second step are the technical features of the present invention, and the third step is performed on the premise that the first step and the second step are performed. The third step may be performed by applying a method known in the art.
Hereinafter, preferred embodiments of the first step and the second step of the present invention will be described in more detail and in detail. Meanwhile, preferred embodiments of the third step of the present invention will be described with reference to the following Examples and Comparative Examples.
The preferred embodiment of the first step of the present invention can be performed as follows.
1-1). Powdering step of waste glassware:
It is preferred that the present invention is used for industrial purposes, or for collecting glass products that have been disposed of in daily life, and then simply washed and crushed. Shredded waste glass products are shredded to a size of about 3 centimeters or less, or in powder form. When the waste glass product is crushed and used, a high-quality final product can be obtained by mixing with the following inorganic binder and firing at a high temperature.
The present invention is preferably used to collect and use the collected waste glass products, but does not exclude conventional glass products. Please note that the collection and use of waste glassware is not recommended for glassware because it is recommended for environmental protection and recycling of resources.
1-2). Mixing step of waste glass raw material:
The present invention includes a step of mixing waste glass raw material prepared by uniformly mixing 95 wt% to 97 wt% of the waste glass product collected in the collection step of the waste glass product with 3 wt% to 5 wt% of the binder.
The waste glass product uses finely divided glass or powdered glass as the main raw material. When the amount of the waste glass product is less than 95% by weight, the following binder component becomes excessive, so that excessive bubbles are formed when the waste glass product is softened in a high-temperature firing process to weaken the strength of the final product, When the content of the product is 97% by weight or more, the action by the binder component is weak and the glassy component is partially present in the final product, which is not preferable.
The binder component chemically reacts the waste glass component under a high temperature reaction temperature condition to modify the molecular structure as a glass to form fine bubbles in the softening process of the waste glass product, It is the reaction binder component that keeps shape. Further, the binder component transforms the molecular structure of the waste glass product as a glass into a glass ceramic ceramic.
As the binder component, titanium dioxide (TiO 2 ) is most preferable, and a platinum catalyst (Pt 3 Fe) can be used. When the amount of the binder component is less than 3% by weight, the components of the waste glass product are numerous, so that the glass component can not be partially disintegrated in the final product and the glass component is partially retained. If it is contained in an amount of more than 10% by weight, excessive bubbles are formed in the process of softening the waste glass, resulting in poor performance of the final product, and it is also undesirable because it involves high cost.
In the present invention, it is preferable that the waste glass product and the binder component are uniformly kneaded and then molded at a high pressure of about 150 MPa to 200 MPa in a certain mold frame. Even if the high-pressure forming operation is not performed, it is possible to carry out the ceramicizing reaction operation of the waste glass product in the high-temperature firing process, but it is necessary for the final product to be appropriately used to be.
1-3). Ceramicization of Waste Glass Material Step:
The present invention includes a glass ceramic conversion step of a waste glass raw material in which the waste glass raw material is charged into a high-temperature firing furnace and subjected to a high-temperature heat treatment at a high temperature of 750 ° C. to 1100 ° C. for 30 minutes to 1 hour to obtain a glass ceramic reaction product.
In the present invention, the waste glass raw material is charged into a high-temperature firing furnace to induce a high-temperature reaction with the binder. As a high-temperature reaction method, a high-temperature heat treatment is performed at a high temperature of 750 ° C to 1100 ° C for 30 minutes to 1 hour in a high temperature baking furnace.
When the waste glass raw material and the binder component are reacted at a high temperature, the glassy structure of the waste glass is deformed and transformed into a ceramic material while forming disordered and non-uniform amorphous structure. At this time, predetermined bubbles are generated in a state in which the glass material is softened at a high temperature, and a large number of minute bubbles are formed in the glass ceramic material by the bubbles.
In the present invention, the waste glass raw material and the binder component are fired at a high temperature of 750 ° C to 1100 ° C. When firing at 750 ° C or lower, it is difficult to modify the glassy structure of the waste glass, (CaO-Al 2 O 3 -TiO 2 -SiO 2 ) structure, although it is possible to complete the work in a relatively short period of time. The baking time at the high temperature can be selected from about 30 minutes to about 1 hour. Generally, a long time is required at low temperature baking, while a short time baking at high temperature baking is preferable.
1-4). Finishing steps:
The present invention includes a finishing step of cooling the glass ceramic reaction product to room temperature and grinding to obtain a glass fired ceramic powder.
When the high temperature reaction is terminated in the high-temperature firing furnace, the present invention is cooled and obtained as a glass ceramic composition at room temperature. The cooling method can be performed in a conventional manner. The cooling system can be forced or cooled to a natural state. The cooled glass ceramic composition is ground and pulverized by a ball mill or the like.
The glass-fired ceramic powder of the first step is obtained through the above-described steps.
The preferred embodiment of the second step of the present invention can be performed as follows.
2-1). Preparation process after mixed grinding of titaniferous magnetite water and auxiliary minerals:
In the present invention, a mineral containing 15 to 25% by weight of titanium (TiO 2 ) in the magnetite extracted in a natural state is referred to as a titanium-titanium mineral, and the titanium-titanium mineral is used. The titanium-containing minerals are weighed by 80 to 90% by weight with respect to the total mineral mixture and used as the main raw material. For the titanium-containing minerals used as the main raw materials, weigh stone and mica stone including feldspar as an auxiliary raw material and use them. The above-mentioned minerals including feldspar, mica stone, talc, and pyrophyllite are weighed by 10 to 20% by weight with respect to the total mineral mixture. The feldspar includes potassium feldspar, sodium feldspar, or calcium feldspar, and commonly referred to as quartzite, talc, or mixtures thereof. The feldspar is a kind of silicate and is used to further reinforce the silicic acid component among the components of the above-mentioned titaniferous magnetite.
It is preferable that the various ores are crushed after they are collected. Optical rotation and grinding can proceed in a conventional manner. For example, the gemstones may be pulverized with a blaker, the broken ore may be pulverized into a jaw crusher, the pulverized into a cone crusher, and finally pulverized into fine particles of 100 to 200 mesh by a ball mill.
Once the various ores are pulverized, the powdered fine-particle ores of each ore are weighed and mixed together. Uniformly mixed particulate ores are reacted by different elements during the calcination at high temperature.
2-2). Sequential multiple calcination of mixed minerals:
In the present invention, the above-mentioned fine-grain ore mixture is used as a feedstock and is firstly subjected to low-temperature heating at a low temperature baking furnace at 200 to 300 ° C for about 2 to 3 hours. Normally, it is preferable to maintain a long time at a low temperature and maintain a short time at a high temperature. The reason for going through the low-temperature firing step is that all the feedstocks are mineral minerals and they are gradually heated at low temperatures rather than directly heating them to high temperatures, so that the heating effect can be seen uniformly throughout the whole, To prevent the internal mineral structure from being destroyed. After the first heating, cooling is carried out while the supply heat is shut off.
After completing the first firing step, the fired product is heated again at a firing temperature of about 500 to 900 DEG C for about 2 hours to about 4 hours, and then a second firing step for cooling them again is performed. It is preferable that the secondary baking furnace maintains a heating temperature higher than that of the primary baking furnace, which is preferably at least 500 캜. However, if the secondary heating furnace exceeds about 900 占 폚, the performance of the product may be deteriorated. In addition, it is preferable to maintain at least about 2 hours in the firing furnace, and if the firing is performed for 4 hours or more, there is no significant difference in the performance of the final product. Therefore, firing is preferably performed for about 4 hours or less. Thereafter, the fired product is naturally cooled.
After the second sintering step, the third sintering step is further performed at a high-temperature sintering furnace at about 800 ° C to about 1300 ° C. It is important to heat the third firing step to a temperature higher than the second firing temperature, and it is also important to supply a gas containing a nitrogen component in this process. The third firing time should be from about 2 hours to 4 hours, and then slowly cooled again.
2-3). Obtaining the fired product and pulverizing step:
As described above, the titanium ceramic powder is obtained through the steps of repeatedly firing at a gradually increasing temperature, as described above. The above-mentioned titanium-titanium ceramic powder is pulverized again to prepare it as a particulate form.
The titanium carbide ceramic powder according to the present invention has a dark gray to black appearance in appearance, and is also the same even in a finely pulverized state. The above titanium carbide ceramic powder has excellent antimicrobial properties and also has excellent electromagnetic wave absorption ability.
In the present invention, the titanium carbamate powder of the second step is obtained through the above steps.
The present invention provides a method for producing a high strength antimicrobial polyvinyl chloride synthetic resin composition using the glass-ceramics ceramic powder obtained in the first step and the titanium carbamate ceramic powder obtained in the second step; ≪ / RTI >
The third step is explained in more detail by Example 3 below.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the manufacturing process. It should be noted, however, that the specific numerical values shown in the embodiments are only for explaining the technical idea of the present invention in more detail, and that the technical idea of the present invention is not limited thereto and that various modifications are possible.
≪ Example 1: Preparation of glass fired ceramic powder >
The waste glass was collected, washed, finely crushed, and then 500 g of titanium dioxide was weighed and weighed uniformly to 10 kg of waste glass. Mixed waste glass and titanium dioxide were put into a high-temperature firing furnace at 850 DEG C, and the temperature was maintained at 950 DEG C while heating for 40 minutes to gradually increase the temperature.
After completing the firing operation, the heating was stopped and the cooling was gradually carried out. After cooling to room temperature, the fired glass ceramic material was found to have fine bubbles formed on its surface. When the surface of the glass ceramic material was observed at a magnification of about 150 times, a fine open cell structure and a closed cell structure were confirmed.
≪ Example 2: Production of titanium titanium ceramic powder >
Weigh 85 kg magnetite, 9 kg of feldspar, and 6 kg of ore containing masonite and mica, respectively, and clean them with water, then crush them with Bleuka, Joe Crusher and Concrete, Mesh. When the temperature of the calcination furnace reached about 250 ° C., the mixture was maintained at that temperature for about 3 hours and slowly cooled again slowly. After cooling naturally, it was lightly crushed again, and then it was slowly heated in a second firing furnace. The firing furnace temperature was maintained at about 800 ° C for about 3 hours. The intermediate product which was cooled again was placed in a third firing furnace, and ammonia gas was injected into the third firing furnace from about 1000 ° C., and the temperature was gradually lowered to about 1250 ° C. and maintained for about 3 hours Respectively. Again naturally cooled, and finely pulverized by a ball mill.
The above-mentioned titanium-titanium ceramic powder was dark gray to black when viewed from its appearance, and was also the same even in a finely pulverized state.
≪ Example 3: Production of polyvinyl chloride synthetic resin >
After filling the jacket-equipped reaction tank with pure water, 100 kg of a polyvinyl chloride resin, 5 kg of an ethylene-vinyl- (meth) acrylate copolymer, 4 kg of an MBS impact modifier, 7 g of a glass fired ceramic powder 7 kg, 8 kg of the titanium carbide ceramic powder according to Example 2, 2 kg of processing aid, 1 kg of epoxidized soybean oil as a lubricant, and 3 kg of calcium carbonate as other fillers were weighed and added, and polyoxyethylene nonylphenyl ether ammonium Sulfate was added in an appropriate amount.
The interior of the reaction vessel was reduced in pressure to remove oxygen, filled with nitrogen, sufficiently emulsified in a nitrogen atmosphere with stirring, and the polymerization reaction vessel was heated to 75 캜 and allowed to react.
When the pressure in the reaction tank reached 4.5 g / cm < 2 >, the reactor was cooled, unreacted material was removed, and then dehydrated and dried to prepare a vinyl chloride resin.
<Example 4>
In all of the other conditions except that the amount of the ethylene-vinyl- (meth) acrylate copolymer and 7 kg of the glass-fired ceramic powder were changed to 100 kg of the polyvinyl chloride resin in Example 3 .
≪ Example 5 >
In the same manner as in Example 3, except that 4 kg of the glass-fired ceramic powder and 7 kg of the titanium ceramic powder were changed to 100 kg of the polyvinyl chloride resin, all other conditions were the same.
≪ Example 6 >
Except that 6 kg of the glass fired ceramic powder and 9 kg of the titanium titanium ceramic powder were changed to 100 kg of the polyvinyl chloride resin in Example 3 and the other conditions were changed to 1.5 kg of the lubricant and 2.5 kg of the calcium carbonate, .
≪ Comparative Example 1 &
In Example 1, the glass fired ceramic powder and the titanium titanium ceramic powder were not used for 100 kg of the polyvinyl chloride resin, and all other conditions were the same.
≪ Comparative Example 2 &
In Comparative Example 1, 1 kg of the glass fired ceramic powder was used for 100 kg of the polyvinyl chloride resin, and 1.5 kg of the titanium titanium ceramic powder was used, and all other conditions were the same.
≪ Evaluation of Impact Strength and Tensile Strength >
Using the synthetic resins obtained in Examples 3 to 6 and Comparative Example 1 and Comparative Example 2, a synthetic resin tube was manufactured in a usual manner. Tests were conducted according to JIS K 7777 and JIS K 7113 (measuring temperature 23 ° C) to determine the impact strength and tensile strength of the manufactured synthetic resin pipes.
The samples of the synthetic resins prepared according to the examples and comparative examples were prepared and the impact strength and the tensile strength of the samples were measured. The results are shown in Table 1 below.
(kg · cm / cm 2)
(kg / cm2)
As can be seen in Table 1, the polyvinyl chloride synthetic resin composition according to the present invention showed much improved impact strength and tensile strength compared with the synthetic resins of Comparative Examples 1 and 2, .
By using the ethylene-modified copolymer and the glass fired ceramic powder, a lightweight synthetic resin tube can be manufactured while improving the impact strength and tensile strength of the polyvinyl chloride synthetic resin.
≪ Evaluation of antimicrobial activity &
The antibacterial properties of the polyvinyl chloride synthetic resin compositions according to Examples 3 to 6 and Comparative Examples 1 and 2 were examined.
The antibacterial properties were determined by the Shake Flask method used in the technical field. The shake flask method is a method of putting a test piece as a sample of an antibacterial product in a culture solution in which a specific bacterium has been cultured and keeping the culture medium and the test piece shaking the bacterium for a predetermined time and then measuring the number of viable bacteria. When comparing viable counts later, it is possible to examine the antibacterial activity of the test piece.
Escherichia coli was selected as a specific bacterium. The initial number of bacteria in the culture was 1.8 x 10 5, and the number of viable Escherichia coli was measured after 24 hours at 10 ° C. The results are shown in Table 2 below.
[cfu / ml]
[cfu / ml]
[%]
※ Decrease rate (%) = (initial number of E. coli - number of bacteria in the last) / (initial number of bacteria) X 100
As can be seen from Table 2, the polyvinyl chloride synthetic resin composition according to the present invention has a survival rate of 99% or more after E. coli has been cultured for 24 hours. However, in the case of the synthetic resin according to Comparative Example 1 and Comparative Example 2, But rather the number of E. coli is increased.
The polyvinyl chloride synthetic resin tube composition having antimicrobial properties while having high rigidity and light weight according to the present invention and its preparation method have been specifically described. However, the present invention is not limited thereto, The scope of which is to be determined and limited by the scope of the appended claims.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope of the present invention.
Claims (5)
3 to 6 parts by weight of an ethylene-modified copolymer, 2 to 4 parts by weight of an impact modifier, 3 to 8 parts by weight of a glass-fired ceramic powder, 5 to 10 parts by weight of a titanium-titanium ceramic powder, And 3 to 5 parts by weight of other filler. The composition for an antimicrobial polyvinyl chloride synthetic resin tube having high rigidity and light weight.
The glass fired ceramic powder
Collecting, washing and crushing waste glass bottles and the like to pulverize the waste glass product;
95 wt% to 97 wt% of the waste glass product and 3 wt% to 5 wt% of the binder are uniformly mixed to produce a waste glass raw material;
The waste glass raw material is placed in a high-temperature firing furnace and subjected to a high-temperature heat treatment at a high temperature of 750 ° C to 1100 ° C for 30 minutes to 1 hour to obtain a glass-ceramic reaction product;
And then the glass ceramic reaction product is cooled to room temperature and pulverized to obtain a powdered product. The composition for an antimicrobial polyvinyl chloride synthetic resin tube having high rigidity and light weight.
The titanium-titanium ceramic powder
10 to 20% by weight of at least two or more minerals selected from the group consisting of feldspar, zeolite, mica stone, talc and pyrophyllite are weighed and finely pulverized to about 100 to 200 mesh and mixed with each other next;
The mixed raw materials are firstly low-temperature-heated for 1 to 2 hours in a low-temperature sintering furnace at 200 to 300 占 폚 and firstly cooled;
The primary cooled product is further heated for 2 to 3 hours in a calcination furnace at 500 to 900 占 폚 and secondarily cooled;
Wherein the second cooled product is further subjected to a third heating step for 2 to 4 hours while supplying nitrogen gas at a high temperature baking furnace at a temperature of 800 to 1300 占 폚 and then slowly cooled and pulverized to obtain a pulverized product. A composition for an antimicrobial polyvinyl chloride synthetic resin tube having high rigidity and light weight.
Collecting, cleaning and crushing the waste glass product to make a waste glass powder product, mixing the waste glass powder product 95wt% to 97wt% and the binder 3wt% to 5wt% uniformly to make a waste glass raw material, The waste glass raw material is put into a high-temperature firing furnace and subjected to a high-temperature heat treatment at a high temperature of 750 ° C. to 1100 ° C. for 30 minutes to 1 hour to obtain a glass ceramic reaction product. Thereafter, the glass ceramic reaction product is cooled to room temperature, A first step of preparing a glass fired ceramic powder;
10 to 20% by weight of at least two minerals selected from the group consisting of feldspar, zeolite, mica stone, talc, and pyrophyllite are weighed, finely pulverized to 100 to 200 mesh, mixed with each other An antimicrobial titanium ceramic powder which imparts antimicrobiality to the ceramic powder component of the mineral phase by firing the mineral mixture at a temperature of 200 ° C to 1300 ° C while gradually raising and firing the mixture at least three times, A second step of preparation;
3 to 6 parts by weight of the ethylene-modified copolymer, 2 to 4 parts by weight of the impact modifier, 3 to 8 parts by weight of the glass-fired ceramic powder in the first step, and 3 to 8 parts by weight of the antibacterial titanium- 5 to 10 parts by weight of a ceramic powder, 1 to 3 parts by weight of a processing aid and 1 to 5 parts by weight of other fillers into a reaction tank to prepare a polyvinyl chloride synthetic resin composition; To
Wherein the composition has a high rigidity and light weight.
The second step
The mineral mixture is subjected to a first low-temperature heating for 1 to 2 hours in a low-temperature sintering furnace at 200 to 300 ° C, followed by primary cooling, and the primary-cooled product is further subjected to secondary heating And the secondary cooled product is further heated for 3 to 4 hours while nitrogen gas is supplied from a high-temperature sintering furnace at 800 to 1300 DEG C, and gradually cooled and pulverized to obtain an antibacterial titanium ceramic powder Wherein the polyvinyl chloride resin composition has a high rigidity and light weight.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286518A (en) * | 2017-07-31 | 2017-10-24 | 东莞市安拓普塑胶聚合物科技有限公司 | A kind of low-smoke and flame retardant can ceramic PVC material and its preparation method and application |
| KR102468145B1 (en) | 2022-02-23 | 2022-11-28 | 김주환 | Antibacterial synthetic resin composition and synthetic resin pipe manufactured the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101033830B1 (en) * | 2010-12-15 | 2011-05-13 | 주식회사 뉴보텍 | Method for manufacturing resin pipe improved weather proof property |
| KR101034495B1 (en) * | 2010-10-11 | 2011-05-17 | 신우산업주식회사 | Antibacterial synthetic resin compositions and synthetic resins pipe made of the same |
| KR101191784B1 (en) * | 2012-04-16 | 2012-10-16 | 주식회사 삼진프라코 | A multiple-walled tube |
| KR101239843B1 (en) * | 2012-07-04 | 2013-03-18 | 주식회사 뉴보텍 | Synthetic resin composition having improved impact resistance and synthetic resin pipe using the composition |
-
2014
- 2014-07-04 KR KR1020140083865A patent/KR101465225B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101034495B1 (en) * | 2010-10-11 | 2011-05-17 | 신우산업주식회사 | Antibacterial synthetic resin compositions and synthetic resins pipe made of the same |
| KR101033830B1 (en) * | 2010-12-15 | 2011-05-13 | 주식회사 뉴보텍 | Method for manufacturing resin pipe improved weather proof property |
| KR101191784B1 (en) * | 2012-04-16 | 2012-10-16 | 주식회사 삼진프라코 | A multiple-walled tube |
| KR101239843B1 (en) * | 2012-07-04 | 2013-03-18 | 주식회사 뉴보텍 | Synthetic resin composition having improved impact resistance and synthetic resin pipe using the composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286518A (en) * | 2017-07-31 | 2017-10-24 | 东莞市安拓普塑胶聚合物科技有限公司 | A kind of low-smoke and flame retardant can ceramic PVC material and its preparation method and application |
| KR102468145B1 (en) | 2022-02-23 | 2022-11-28 | 김주환 | Antibacterial synthetic resin composition and synthetic resin pipe manufactured the same |
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