KR101451846B1 - Mixture composition for functional packaging or containers, food packaging, food container and its manufacturing method - Google Patents
Mixture composition for functional packaging or containers, food packaging, food container and its manufacturing method Download PDFInfo
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Abstract
Description
More particularly, the present invention relates to a composition for hygienic packaging or containers, food packaging material, food packaging material, food packaging material, food packaging material, , A container for food, and a manufacturing method thereof.
Rhus verniciflua or Rhus vernicifera ) is a deciduous tree belonging to Anacardiaceae . It is originated from the Central Asian Highlands and the Himalayas. It is widely distributed in the subtropics and temperate regions around the world. It is widely distributed in Korea, China and Japan. It is used as a natural paint in crafts and household goods in East Asia.
Raw lacquer or rhubarb extract collected from lacquer trees promotes blood circulation in one room and is known to be effective against various diseases such as insecticide and fungicide such as insecticide, abdominal pain, tuberculosis, constipation, constipation, diabetes and schizophrenia. Lacquer, and lacquer are used in medicinal dishes such as duck. In recent years, scientific research on the efficacy of traditional lacquer has been carried out.
Urushi is made up of urushiol, water, gum, lacase and nitrogenous substance. Urushiol is the main component of 70% of the rusk liquor, which is a 3-substituted (8'Z, 11'E, 13'Z-pentadecatrienyl) catechol (3- (8'Z, 11'E, 13'Z, 'Z-pentadecatrienyl) catechol). Up to now, thirteen components of 3-substituted alkylcatechols having 0, 1, 2 or 3 double bonds in the C15 side chain have been identified (Yumin Du and Ryuichi Oshima, J. of Chromatography, 284, 463-473 (1984) , And urushiol is a mixture of these monomers and polymers which are naturally polymerized monomers by the racecases. Yamauchi, Y., R. Oshima and J. Kumanotani, J. of Chromatography, 243, 71-83 (1981), J. of Chromatography, 84 (1982), and Y. Du, R. Oshima and H. Iwatsuki, J. of Chromatography, 295, 179-186 (1984)).
Urushiol, which is a major constituent of lacquer, has been reported to cause allergic reaction in the early stage. Since then, its strong antioxidant ability, antibacterial power, waterproofing, chemical resistance, insecticide and preservative effect have been proved and chemically proved durability traditionally possessed by lacquer I got it. In addition, urushiol did not have a significant effect on normal cells, and killed cancer cells selectively, thus showing possibility as an anticancer drug. Based on these basic effects, effective and various extraction methods and practical applications of urushiol have been studied.
However, unlike the synthetic resin paint, the conventional lacquer has a drawback that the workability is high and the price is high because of its characteristic of being dried under a special environmental condition with high humidity (relative humidity 70%, 20-25 ° C). In addition, lacquer has a disadvantage in that it is difficult to use it for living products and industrial residues due to additives and water which are naturally contained, and can not solve side effects that cause allergic phenomenon when the skin is contacted.
It is an object of the present invention to provide a polypropylene resin composition which is capable of preventing allergic reaction and alleviating process conditions by mixing high-purity polyurusiol powder having heat resistance with polypropylene, enhancing dispersion efficiency by mixing at a higher temperature, And to provide a functional composition for packaging or containers for food, a packaging material for food, and a food container.
Still another object of the present invention is to provide a method for producing the above-mentioned mixed composition for functional packaging or container.
To achieve the above object, a mixed composition for a functional packaging or a container prepared by mixing polypropylene with polyurusiol powder may be provided.
In order to achieve the above object, the polypropylene may be provided with a mixed composition for a functional packaging or a container, which comprises 3 to 30 parts by weight of the polyurusiol powder in 100 parts by weight of the polypropylene.
For the above purpose, the polyurusiol powder may have a particle size of 5-30 mu m.
To achieve the above object, a packaging material for food or a food container made using the mixed composition for functional packaging or container may be provided.
In order to accomplish the above object, the present invention provides a method for producing a polyurusiol, comprising the steps of: mixing raw lacquer with a hydrophilic organic solvent; centrifuging the separated raw lacquer and separating the mixture with a filter cloth to extract urushiol; reacting the urushiol, the hydrophilic monomer, Preparing a polyurusiol powder by spraying the aqueous polyurusol solution under a hot air condition; and mixing the polyurusol powder with the polyurusol powder to prepare a mixed composition. A method of making a composition may be provided.
In order to achieve the above-mentioned another object, the polyurusiol powder may have a particle size of 5-30 mu m.
In order to achieve the above-mentioned object, 3-30 parts by weight of the polyurusiol powder is mixed with 100 parts by weight of the polypropylene at a temperature of 50-90 ° C and a pressure of 0.1-0.5 atm, and the mixture is extruded at an extrusion temperature of 150-250 ° C and an extrusion speed of 200-400rpm And then extruding the mixture into a container for a functional packaging or a container.
The mixed composition for functional packaging or container prepared by mixing polypropylene with polyurusiol powder has allergenicity and heat resistance. Also, it can be used for various purposes by having antimicrobial, antiseptic and insecticidal properties.
The polyurusiol powder has a particle size of 5-30 mu m, thereby increasing the antibacterial, antiseptic and insect repellent effect and inhibiting the allergic action.
Food packaging materials and food containers manufactured using a mixed composition for functional packaging or containers can contribute to food hygiene by having heat resistance, antimicrobial property, anticorrosive property, and repellency.
By mixing the raw lacquer with a hydrophilic organic solvent and subjecting to a centrifugal separation and a filtration process, the yield of urushiol can be increased. The urushiol may be reacted with a hydrophilic monomer, an oxidizing agent and a neutralizing agent, and water may be added to prepare an aqueous polyurusiol solution to inhibit the allergic action. The polyurusiol aqueous solution is injected under hot air condition to prepare polyurusiol powder and use thereof to facilitate the future process. Polypropylene and the polyurusiol powder are mixed and extruded to prepare a mixed composition, whereby a mixed composition for packaging or containers having heat resistance, antimicrobial property, antiseptic property, and repellency is produced.
To 100 parts by weight of the above polypropylene, 3 to 30 parts by weight of the polyurusiol powder was mixed with the mixture at a temperature of 50 to 90 DEG C and a pressure of 0.1 to 0.5 atm, extruded at an extrusion temperature of 150 to 250 DEG C and an extrusion speed of 200 to 400 rpm, Or containers. ≪ / RTI >
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart illustrating a method for manufacturing a mixed composition for functional packaging or containers, a method for manufacturing a food packaging material, and a method for manufacturing a food container.
Figure 2 is a photograph of a food container made using a mixed composition for a functional packaging or container.
3 is a photograph of a food packaging material prepared using a mixed composition for functional packaging or containers.
4A and 4B are test reports for food containers prepared using a mixed composition for functional packaging or containers.
5 is an inspection report for a food container manufactured using a mixed composition for functional packaging or container.
Hereinafter, the present invention will be described in detail. However, the detailed description of known functions and configurations that may unnecessarily obscure the subject matter of the present invention will be omitted.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. It is to be understood that in the present application, the term " comprising "or the like is intended to designate the presence of stated features, integers, steps, operations, elements, components or combinations thereof, , Components, parts, or combinations thereof without departing from the spirit and scope of the invention. The scope of the present invention is not limited by the following examples.
Polypropylene is not limited to a specific molecular weight but includes both isotactic, syndiotactic, and atactic. Only low cost atactic polypropylene is preferred.
The polyurusol powder includes a polymer powder polymerized with urushiol extracted from raw lacquer. However, according to one embodiment of the present invention, the polyurusiol powder prepared through the process described below is preferable.
Mix the raw lacquer with the organic solvent and allow to stand for 24 hours or longer to precipitate the nitrogen compound and rubber material, and then centrifuge only the supernatant liquid to extract urushiol solution. The precipitated nitrogen compounds and rubbery materials are dehydrated by using a filter cloth to further extract urushiol solution. When the urushiol solution is centrifuged, the urushiol contained in the raw lacquer can be extracted by 95% or more, and the yield is greatly improved.
A hydrophilic monomer and an oxidizing agent are added to the obtained urushiol and subjected to a polymerization reaction to prepare a first polymer. At this time, urushiol is polymerized with the hydrophilic monomer by the oxidizing agent to produce the first polymer.
URUSHIOL extracts pure urushiol except for water, rubber quality and laccase enzyme by using ethanol from raw lacquer derived from lacquer tree, and uses purified raw material having 98% or more purity by centrifugation and vacuum distillation. When the purity of urushiol is low, the degree of polymerization during polymerization tends to lower, causing allergies still to occur or the particle size to be large, resulting in a problem of stability.
Further, according to one embodiment of the present invention, a hydrophilic monomer is required for producing polyurusiol. The hydrophilic monomer may have a functional group containing a polymerizable unsaturated bond in the bond. The hydrophilic monomer may have an anionic hydrophilic functional group containing an unsaturated bond, which makes the polymerization reaction easier. The number of carbon atoms is preferably from 2 to 8. Examples of anionic hydrophilic functional groups include -SO 3 M, -COOM, -PO 3 M 2 (wherein M is a hydrogen atom, an alkaline earth metal atom or an ammonium salt), and PO 3 AH Wherein A is an alkaline earth metal atom or ammonium salt. Examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, aconitic acid, maleic acid or an anhydride thereof, monomethyl maleate, monomethyl fumarate, monomethyl itaconate, vinylsulfonic acid and vinyl phosphate .
The hydrophilic monomer is preferably used in an amount of 1 to 99 parts by weight based on 100 parts by weight of urushiol. When the hydrophilic monomer is used in an amount of less than 1 part by weight, the content of the hydrophilic group is low and the phase transition to o / w (oil-in-water) phase does not sufficiently take place in water dispersion, that is, w / ) Emulsion may be somewhat difficult, and when the use amount of the hydrophilic monomer exceeds 100 parts by weight, it may become difficult to control the reaction by the viscosity increase.
In the reaction for preparing the first polymer, a redox active catalyst may be further added to promote the oxidation reaction. If the redox active catalyst is used, the polymerization of urushiol may occur more easily. According to one embodiment of the present invention, at least one compound selected from a metal salt, a metal complex, a hydrophilic amine and a mixture thereof can be used as the redox active catalyst that can be used. The metal salt may be a metal salt such as sodium or calcium having a monovalent or higher valence, and a metal complex such as nickel, cobalt, manganese, iron or copper having a monovalent or higher valence may be used, and a hydrophilic amine is preferably a tertiary amine.
At this time, the amount of the oxidative active catalyst to be used is preferably 0.01 to 1 part by weight based on 100 parts by weight of urushiol, because the reaction can be controlled to induce a uniform reaction. In the case of exceeding the above-mentioned range, for example, even if 1 part by weight or more of the reaction is used, the reaction is accelerated, and the reaction can be difficult to be controlled by a uniform reaction.
The first polymer thus prepared is neutralized by adding a neutralizing agent, for example, an inorganic base, an organic base, or a mixture thereof to prepare a hydrophilic salt. As the neutralizing agent for neutralizing the first polymer, examples of the organic base include tertiary amines such as triethylamine, triethanolamine, dimethylethanolamine and the like. Examples of inorganic bases include sodium hydroxide and sodium carbonate.
When water (pure water) is slowly added to the first polymer subjected to the neutralization reaction as described above and agitated, the phase transition to o / w (oil-water) phase is carried out on w / o (water in oil) An o / w (water-in-oil) emulsion having silver nanoparticles is prepared. When the oxidizing agent is further mixed therewith, further polymerization of urushiol occurs in the emulsion of the nanoparticles, so that a second polymer can be prepared.
On the other hand, according to one embodiment of the present invention, in the reaction for producing the first polymer or the second polymer, peroxide may be used as the above-mentioned oxidizing agent. For example, they may be selected from the group consisting of ketone peroxide, hydroperoxide, diacyl peroxide, peroxyketal, peroxy ester, peroxydicarbonate, and mixtures thereof. More preferably, hydroperoxide can be used as the above-mentioned oxidizing agent. Examples thereof include t-butyl hydroperoxide, t-ethyl hydroperoxide and hydrogen peroxide.
According to one embodiment of the present invention, the amount of the oxidizing agent is preferably 0.1 to 30 parts by weight based on 100 parts by weight of urushiol in the production of the first polymer, and 50 to 500 parts by weight based on 100 parts by weight of urushiol in the production of the second polymer. When the amount of the oxidizing agent used is more than 30 parts by weight, viscosity control may be difficult. When the amount of the oxidizing agent is less than 0.1 parts by weight, polymerization may be difficult. If the amount of the oxidizing agent used is less than 50 parts by weight, the degree of polymerization may be lowered, resulting in allergy. If the amount of the oxidizing agent is more than 500 parts by weight, unreacted oxidizing agent may remain.
According to one embodiment of the present invention, the temperature for the polymerization reaction for preparing the first polymer is preferably 0 ° C to 80 ° C, and the temperature for the polymerization reaction for preparing the second polymer is preferably 50 ° C to 100 ° C. If the temperature is lowered below the lower limit of the above-mentioned reaction temperature, the reaction may be slowed down and the reaction accuracy may be decreased. If the temperature is higher than the upper limit value, the reaction temperature may become difficult to control.
As described above, a hydrophilic salt is prepared by adding a neutralizing agent to a first polymer produced by polymerizing urushiol and a hydrophilic monomer, and a hydrophilic salt is prepared. When water (pure water) is added to the hydrophilic salt and water is dispersed, w / o (Heavy water) to o / w (oil-in-water) and stable nanoparticle polyurusiol emulsion is produced. When an additional oxidizing agent is added so that the urushiol reactant that has not yet reacted in the step of preparing the first polymer can be polymerized, a secondary polymerization reaction takes place in the particle, so that the polymerized polyurusol nanoparticle, that is, the second polymer can be prepared have. As a result, a polyurusiol aqueous solution is produced.
According to an embodiment of the present invention, the polyurusol aqueous solution prepared by the above-mentioned process may be dried with a spray dryer to produce the lacquer powder. A vacuum closed space portion capable of maintaining a temperature of 200 ° C is provided on the inside of the vacuum closed space portion, and a storage tank capable of holding a predetermined amount of aqueous polyurusol solution is formed on the upper side of the vacuum open space portion, And a hot air supply device capable of supplying hot air with an amount of heat of about 40 to 60 kcal / hr and an air volume of about 15 to 20
As described above, it is preferable that the polyurusiol powder prepared through the above-described process is mixed with polypropylene to prepare a mixed composition for functional packaging or container.
According to one embodiment of the present invention, the mixing process of the polypropylene and the polyurusiol powder is performed by connecting a vacuum pump to a closed container and heating under reduced pressure. When heated under reduced pressure, the surface of the polypropylene is melted and the polyurusol powder is attached to the surface of the polypropylene. When the polyurusiol is attached to the polypropylene surface, the polyurusiol powder is not scattered and maintained at a constant level in a subsequent step. In addition, when heated under reduced pressure, the polypropylene and volatile substances such as moisture remaining in the polyurusol are evaporated, thereby suppressing the generation of bubbles and the like in the subsequent process, and consequently, a mixed composition for packaging or containers with high purity can be produced . In this case, the pressure is preferably reduced to 0.1 to 0.5 atm. If the pressure is reduced to more than 0.5 atmospheres, it is difficult to evaporate volatile substances such as water because the decompression pressure is too low. If the pressure is reduced to less than 0.1 atm, it is disadvantageous in terms of time and cost. It is also preferable that the internal temperature is 50 占 폚 to 90 占 폚. If the temperature is less than 50 ° C, surface melting of the polypropylene is difficult, and if it exceeds 90 ° C, the time and cost are disadvantageous. The mixing time is preferably 2 to 4 hours. If the time is less than 2 hours, a part of the polyurusiol powder may not adhere to the surface of the resin, so that the polyurusiol powder may be scattered in a subsequent step and a certain amount may not be maintained. In this case, it is preferable that 100 parts by weight of polypropylene contains 3-30 parts by weight of polyurusol. When polyurusiol is less than 3 parts by weight, it is difficult to exert effects such as antimicrobial effect, antifogging property and insolubility. When polyurusuric acid exceeds 30 parts by weight, excessive polyurusol adheres to the surface of polypropylene, And the merchantability may be deteriorated. In this case, 100 parts by weight of the polypropylene and 3-30 parts by weight of the polyurusol may further include 1-8 parts by weight of silica. By including the silica, the heat resistance can be improved during the mixing process and the extrusion process, and the process can be performed at a higher temperature.
According to one embodiment of the present invention, the polypropylene in which the polyurusol powder and the polypropylene are mixed and the polyurusol is adhered to the surface may be manufactured by extruding into a mixed composition for functional packaging or containers. Also, the polypropylene and the silica mixture in which the polyurusiol powder, the polypropylene and the silica are mixed, and the polyurusol is attached to the surface may be extruded to be made into a functional packaging or container composition. In this case, the extrusion temperature is preferably 150 ° C. to 200 ° C., and the extrusion speed is preferably 200 rpm to 400 rpm. It may be crushed and packed with a cutter while being extruded. The extruder used in this case is preferably a twin extruder. The twin extruder is advantageous in that the polyurusol and the polypropylene are well mixed and dispersed by rotating the two screws and extruding them.
According to one embodiment of the present invention, the mixed composition for functional packaging or container may be manufactured into a food packaging material or a food container through injection molding or vacuum molding. In addition, the functional composition for packaging or container can be made into a sheet through extrusion or injection process, and then can be manufactured into a food packaging material or a food container through injection molding, vacuum molding or the like. In some cases, polypropylene may be further mixed with the functional composition for packaging or packaging, and the composition may be manufactured into a food packaging material or a food container by injection molding or vacuum molding. In addition, the polypropylene may be mixed with the functional composition for packaging or container, and the composition may be made into a sheet through extrusion or injection process and then molded into a food packaging or food container by injection molding or vacuum molding.
According to one embodiment of the present invention, a sheet having two layers can be manufactured by extruding a material different from the mixed composition for functional packaging or containers. In this case, one layer is made of a mixed composition for the functional packaging or container. It is preferable that the separate material has a transparent property. A food packaging material or a food container can be manufactured using the sheet having the two layers. In this case, it is preferable that the food packaging material or the food container is a single layer made of a mixed composition for the functional packaging or the container, the surface contacting with the food.
FIG. 1 is a flowchart showing a method for manufacturing a mixed composition for functional packaging or containers, a method for manufacturing a food packaging material, and a method for manufacturing a food container according to an embodiment of the present invention. Referring to FIG. 1, a method for manufacturing a functional packaging or container mixed composition according to an embodiment of the present invention may include
Step 1: The 'urushiol extraction step' in which the raw lacquer and the hydrophilic organic solvent are mixed and centrifuged and separated by the filter cloth may include the following steps.
Step 1: Mixing 50 kg of raw lacquer with 30-100 L of organic solvent, stirring, and allowing to stand for 24 to 96 hours;
Step 2: a first centrifugation step of centrifuging the supernatant at a rate of 0.5-2 L / min at 5000-15,000 rpm with a centrifuge to extract urushiol solution first;
Third step: a secondary centrifugation process in which 25-50 L of a hydrophilic organic solvent is mixed with a sediment, agitated well, allowed to stand for 24 hours to 96 hours or less, and centrifuged to extract urushiol solution secondarily;
Step 4: Third centrifugation process in which 25-50 L of a hydrophilic organic solvent is mixed with the sediment, agitated well, allowed to stand for 24 hours to 96 hours or less, and then centrifuged to extract urushiol solution in a tertiary manner; And
Fifth process: After filtration of the sediment into the filter cloth, it is dehydrated by a dehydrator, and the filtration centrifuge
Step 2: The 'polyurusol aqueous solution preparation step' in which urushiol, a hydrophilic monomer, an oxidizing agent and a neutralizing agent are reacted and water is added may include the following steps.
A first step of reacting urushiol, a hydrophilic monomer and an oxidizing agent to prepare a first polymer;
Step 2: a step of neutralizing the first polymer with a neutralizing agent to prepare a hydrophilic salt;
Third step: a process for preparing an emulsion having nanoparticles by adding water to the hydrophilic salt;
Step 4: Process of preparing a second polymer by mixing an oxidizing agent with the emulsion
Step 3: The 'polyurusol powder preparation step' in which the polyurusol aqueous liquid is injected under a hot air condition may include the following process.
The first step is a step of injecting the aqueous polyurusol solution into a closed space at 150 ° C to 200 ° C under a pressure of 15-25 kg / hr using a mist nozzle; And
Step 2: Process of applying hot wind at an air volume of 5-20 m < 3 > / min and a heat quantity of 40-60 kcal / hr to the aqueous polyurusol solution
Step 4: 'Mixed composition manufacturing step of mixing and extruding polypropylene and polyurusiol powder' may include the following process.
100 parts by weight of the polypropylene and 3 to 30 parts by weight of the polyurusiol powder are heated to 50 to 90 캜 under a condition of 0.1 to 0.5 atm and mixed for 2 hours to 4 hours; And
Step 2: The result of the mixing process is extruded at an extrusion temperature of 150 ° C to 200 ° C and an extrusion rate of 200rpm to 400rpm and mixed
Step 5-1: The 'food packaging material manufacturing step' using the above mixed composition may include the following process.
Process 1: A process for producing a functional packaging or container sheet having two layers by making a transparent new material into a thick main layer and extruding the mixed composition into a thin auxiliary layer
Step 2: A process for producing a food packaging material by vacuum molding using a functional packaging sheet or container sheet having the two layers
Step 5-2: The 'food container manufacturing step' using the above mixed composition may include the following process.
Step 1: A process of preparing a food container by further mixing and injecting polypropylene into the mixed composition
Hereinafter, a method for producing a mixed composition for a functional packaging or container will be described in more detail.
According to an embodiment of the present invention, the hydrophilic organic solvent may be ethanol in the solvent mixing step, preferably 50 L of ethanol is mixed, agitated, and allowed to stand for 48 hours. In the first centrifugation process, the supernatant is centrifuged at 15,000 rpm at a rate of 1 l / min using a centrifuge to extract 33 l of urushiol solution. In the second centrifugation step, 25 L of ethanol is mixed with the sediment, stirred well, allowed to stand for 24 hours, and centrifuged to extract 24 L of urushiol solution. In the third centrifugation process, 25 l of ethanol is added to the sediment again, and the mixture is stirred well and allowed to stand for 24 hours and centrifuged to extract 25 l of urushiol solution. In the filtration centrifuge process, the precipitate is desorbed again in the filter cloth and dehydrated by a dehydrator, so that 24 liters of urushiol solution can be extracted. As a result, 106 l of urushiol solution which can be extracted can be vacuum-dried at 60 ° C to produce 21.8 kg of 98% pure urushiol.
Preferably, the hydrophilic monomer may have an anionic hydrophilic functional group containing a polymerizable unsaturated bond in the bond. Specifically, -SO 3 M, -COOM, -PO 3 M 2 , M is a hydrogen atom, an alkaline earth metal atom or an ammonium salt) and PO 3 AH (wherein A is an alkaline earth metal atom or ammonium salt). For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, aconitic acid, maleic acid or an anhydride thereof, monomethyl maleate, monomethyl fumarate, monomethyl itaconate, vinylsulfonic acid, . The hydrophilic monomer is preferably used in an amount of 1 to 99 parts by weight based on 100 parts by weight of urushiol. When the hydrophilic monomer is used in an amount of less than 1 part by weight, the content of the hydrophilic group is low and the phase transition to o / w (oil-in-water) phase does not sufficiently take place in water dispersion, that is, w / ) Emulsion may be somewhat difficult, and when the use amount of the hydrophilic monomer exceeds 100 parts by weight, it may become difficult to control the reaction by the viscosity increase. In the process of preparing the first polymer, a redox active catalyst may be further added to promote the oxidation reaction. If the redox active catalyst is used, the polymerization of urushiol may occur more easily. As the oxidation-reduction active catalyst that can be used, at least one compound selected from a metal salt, a metal complex, a hydrophilic amine and a mixture thereof can be used. The metal salt may be a metal salt such as sodium or calcium having a monovalent or higher valence, and a metal complex such as nickel, cobalt, manganese, iron or copper having a monovalent or higher valence may be used, and a hydrophilic amine is preferably a tertiary amine. At this time, the amount of the oxidative active catalyst to be used is preferably 0.01 to 1 part by weight based on 100 parts by weight of urushiol, because the reaction can be controlled to induce a uniform reaction. In the case of exceeding the above-mentioned range, for example, even if 1 part by weight or more of the reaction is used, the reaction is accelerated, and the reaction can be difficult to be controlled by a uniform reaction.
In preparing the hydrophilic salt, a neutralizing agent such as an inorganic base, an organic base, or a mixture thereof may be added to the first polymer and neutralized to prepare a hydrophilic salt. In the neutralizing agent for neutralizing the first polymer, examples of the organic base include tertiary amines such as triethylamine, triethanolamine, dimethylethanolamine and the like. Examples of inorganic bases include sodium hydroxide and sodium carbonate.
When the water (pure water) is slowly added to the first polymer neutralized in the process of preparing the emulsion having the nanoparticles, the water (pure water) Phase transition process wherein the hydrophilic salt can be converted to an o / w (oil-in-water) emulsion with nanoparticles.
During the preparation of the second polymer, an oxidant is further added to the nanoparticle emulsion to further polymerize urushiol in the nanoparticle emulsion, thereby preparing a second polymer.
In the process of preparing the first polymer and the process of producing the second polymer, peroxide may be used as the oxidizing agent. For example, it may be selected from the group consisting of ketone peroxide, hydroperoxide, diacyl peroxide, peroxyketal, peroxy ester, peroxydicarbonate, and mixtures thereof. More preferably, hydroperoxide can be used as the above-mentioned oxidizing agent. Examples thereof include t-butyl hydroperoxide, t-ethyl hydroperoxide, hydrogen peroxide and the like. The amount of the oxidizing agent is preferably from 0.1 to 30 parts by weight based on 100 parts by weight of urushiol in the production of the first polymer, and from 50 to 500 parts by weight based on 100 parts by weight of urushiol in the production of the second polymer. When the amount of the oxidizing agent used is more than 30 parts by weight, viscosity control may be difficult. When the amount of the oxidizing agent is less than 0.1 parts by weight, polymerization may be difficult. If the amount of the oxidizing agent used is less than 50 parts by weight, the degree of polymerization may be lowered, resulting in allergy. If the amount of the oxidizing agent is more than 500 parts by weight, unreacted oxidizing agent may remain. The temperature of the step of preparing the first polymer is preferably 0 ° C to 80 ° C, and the temperature of the step of preparing the second polymer is preferably 50 ° C to 100 ° C. If the temperature is lowered below the lower limit of the above-mentioned reaction temperature, the reaction may be slowed down and the reaction accuracy may be decreased. If the temperature is higher than the upper limit value, the reaction temperature may become difficult to control. As described above, the hydrophilic salt is prepared by adding the neutralizing agent to the first polymer produced by polymerization of the urushiol and the hydrophilic monomer, and neutralizing the hydrophilic salt. When water (pure water) is added to the hydrophilic salt and dispersed in water, w / o (w / w) to o / w (oil-in-water) form and a stable nanoparticle polyurusiol emulsion is produced. When an additional oxidizing agent is added so that urushiol reactant that has not yet reacted can be polymerized in the course of preparing the first polymer, a secondary polymerization reaction occurs in the particle to produce polymerized polyuricol nanoparticles and the second polymer . As a result, a polyurusiol aqueous solution is produced.
The step of preparing the polyurusiol powder preferably refers to a process condition in which a polyurusol powder having a particle size of 1 to 30 탆 is produced. This is because, when a powder having a small particle size is used, it is well dispersed and adheres well to the surface of the polypropylene resin, so that it can be dispersed well when mixed with polypropylene in the future, maximizing the effects such as antimicrobial activity, dustproofness and longevity.
The process of heating and mixing the polypropylene and the polyurusiol powder under a reduced pressure condition is performed by connecting a vacuum pump to a sealed container and heating under reduced pressure. When heated under reduced pressure, the surface of the polypropylene is melted and the polyurusol powder is attached to the surface of the polypropylene. When the polyurusiol is attached to the polypropylene surface, the polyurusiol powder is not scattered and maintained at a constant level in a subsequent step. In addition, when heated under reduced pressure, the polypropylene and volatile substances such as moisture remaining in the polyurusol are evaporated, thereby suppressing the generation of bubbles and the like in the subsequent process, and consequently, a mixed composition for packaging or containers with high purity can be produced . In this case, the pressure is preferably reduced to 0.1 to 0.5 atm. If the pressure is reduced to more than 0.5 atmospheres, it is difficult to evaporate volatile substances such as water because the decompression pressure is too low. If the pressure is reduced to less than 0.1 atm, it is disadvantageous in terms of time and cost. It is also preferable that the internal temperature is 50 占 폚 to 90 占 폚. If the temperature is less than 50 ° C, surface melting of the polypropylene is difficult, and if it exceeds 90 ° C, the time and cost are disadvantageous. The mixing time is preferably 2 to 4 hours. If the time is less than 2 hours, a part of the polyurusiol powder may not adhere to the surface of the resin, so that the polyurusiol powder may be scattered in a subsequent step and a certain amount may not be maintained. In this case, it is preferable that 100 parts by weight of polypropylene contains 3-30 parts by weight of polyurusol, and further, 1-8 parts by weight of silica may be included. When polyurusiol is less than 3 parts by weight, it is difficult to exert effects such as antimicrobial effect, antifogging property and insolubility. When polyurusuric acid exceeds 30 parts by weight, excessive polyurusol adheres to the surface of polypropylene, And the merchantability may be deteriorated. By adding 1-8 parts by weight of silica, heat resistance can be increased.
The process of extruding and mixing the result of the mixing process is performed by mixing the polyurusiol powder and the polypropylene and extruding the polypropylene having the polyurusol attached to its surface. Alternatively, the process of extruding and mixing the result of the mixing process is performed by extruding the polypropylene and the silica mixture in which the polyurusol, the polypropylene, and the silica are mixed and the polyurusol is adhered to the surface. After such an extrusion process, it is manufactured as a mixed composition for functional packaging or containers. In this case, the extrusion temperature is preferably 150 ° C. to 200 ° C., and the extrusion speed is preferably 200 rpm to 400 rpm. It can be crushed and packed with a cutter while being extruded. The extruder used in this case is preferably a twin extruder. The twin extruder is advantageous in that the polyurusol and the polypropylene are well mixed and dispersed by rotating the two screws and extruding them.
According to one embodiment of the present invention, the result of the method for producing a mixed composition for a functional packaging or a container can be manufactured into a food packaging material or a food container through injection molding or vacuum molding. In addition, the result of the method for manufacturing a functional packaging or container mixed composition may be made into a sheet through an extrusion or an injection process, and then be formed into a food packaging material or a food container through injection molding or vacuum molding. In some cases, polypropylene may be further mixed with the result of the above-mentioned method for producing a mixed composition for functional packaging or container, and the packaging material for food or the container for food may be manufactured through injection molding or vacuum molding. In addition, the polypropylene may be mixed with the result of the above-mentioned method for producing a functional packing or a mixed composition for a container and made into a sheet through an extrusion or an injection process, followed by injection molding or vacuum molding to form a food packaging material or a food container .
According to one embodiment of the present invention, a sheet having two layers can be produced by extruding a material different from the product of the method for producing a mixed composition for a functional packing or a container. In this case, one layer is the result of the method of manufacturing the mixed composition for functional packaging or container. It is preferable that the separate material has a transparent property. A food packaging material or a food container can be manufactured using the sheet having the two layers. In this case, it is preferable that the food packaging material or the food container is a single layer made of the result of the method for producing a mixed composition for a functional packaging or a container.
According to one embodiment of the present invention, a food container or food packaging material manufacturing method using a functional packaging or container composition may include the following steps.
1. Step 1: 50 kg of raw lacquer containing 45% of urushiol and 50 l of a hydrophilic organic solvent were mixed and agitated for 48 hours.
2. Step 2: The supernatant was centrifuged at 15,000 rpm at a rate of 1 l / min using a centrifuge to extract 33 l of urushiol solution.
3. Third step: 25 L of ethanol was mixed with the precipitate, stirred well, left to stand for 24 hours, and centrifuged to extract 24 L of urushiol solution.
4. Step 4: Again, the precipitate was mixed with 25 liters of ethanol, stirred well, allowed to stand for 24 hours, and then centrifuged to extract 25 liters of urushiol solution.
5. Step 5: The precipitate was dipped in a filter cloth and dehydrated with a dehydrator to extract 24 l of urushiol solution. A total of 106 l of the extracted urushiol solution was vacuum dried at 60 ° C to produce 21.8 kg of 98% urushiol.
6. Step 6: In a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 5 kg of purified urushiol and 900 g of marein phosphate were mixed and 15 g of cobalt octoate (10% solution) was added. 15 g of hydrogen peroxide (30% solution) was then added dropwise over 30 minutes at 40 DEG C, the temperature was raised to 80 DEG C and maintained for 1 hour and then cooled to room temperature to prepare a first polymer. Then, 25 g of triethylamine was added dropwise over 15 minutes to neutralize, and then 4.5 kg of pure water was added dropwise thereto over 1 hour while stirring, and water was added thereto to prepare an emulsion of the hydrophilic salt. The emulsion was heated to 50 占 폚 and 4.5 kg of hydrogen peroxide was added dropwise over 3 hours, and the mixture was allowed to stand at 80 占 폚 for 2 hours and then cooled to room temperature to prepare 14.5 kg of a second polymer. This procedure was repeated 10 times to produce a total of 145 kg.
7. Seventh process: The aqueous polyurusol solution was injected at a pneumatic pressure of 20 kg / hr, and hot air was supplied at a rate of 55 kcal / hr and a flow rate of 20
8. Step 8: 8 kg of the polyurusiol powder of the bag filter, 40 kg of polypropylene and 2 kg of silica were charged into a vacuum conical mixer, the vacuum pump was operated to reduce the pressure to 0.3 atm, The temperature was maintained at 70 캜 and mixed for 4 hours to obtain 49.2 kg of a polyurusiol powder, polypropylene and silica mixture. The mixture was poured into a twin extruder and extruded to produce 44 kg of a mixed composition for functional packaging or container mixed with 20 parts by weight of polyurusiol and 2 parts by weight of silica in 100 parts by weight of polypropylene. The polypropylene used had a MI (Melting Index) of 16.
9. Ninth process: 6 kg of the mixed composition for functional packaging or container and 50 kg of polypropylene new material were mixed and the container was injected under the conditions shown in Table 2 (see FIG. 2). (See FIGS. 4A, 4B, and 5). The results of the dissolution tests are shown in FIG.
According to one embodiment of the present invention, a food container or food packaging material manufacturing method using a functional packaging or container composition may include the following steps.
In the method for manufacturing a hermetically sealed container for food using the functional packaging or container composition, the seventh process is the same as the first process, and the eighth process, the ninth process, and the tenth process described below may be further included.
8. Step 8: 2 kg of the polyurusiol powder of the bag filter and 40 kg of polypropylene were mixed and extruded in a twin extruder, and 36 kg of the above mixed composition for functional packaging or containers, which was prepared by mixing 100 parts by weight of polypropylene and 5 parts by weight of polyurusol, . The MI (Melt Index) of the polypropylene used was 2.
9. Ninth Process: For a functional packaging with two layers while a transparent new material is made into a main layer of 0.65 mm thickness and the functional composition for packaging or the container containing the polyurusol is extruded into a 20 탆 thick auxiliary layer or A sheet for containers can be produced. The manufactured functional packaging or container sheet has a thickness of 0.67 mm and a width of 900 mm, and only one side thereof is composed of a mixed composition for functional packaging or container containing polyurusiol. The extrusion conditions of functional wrapping or container sheets containing polyurusiol are as follows.
10. Tenth Step: A food container or food packaging material containing polyurusol can be produced by vacuum-molding a sheet for functional packaging or containers containing polyurusol in a vacuum molding machine (see FIG. 3). It is preferable that the food container or packaging material containing polyurusol is composed of a mixed composition for functional packaging or containers containing polyurusol on the side in contact with the food.
Claims (8)
100 parts by weight of the polypropylene contains 5-30 parts by weight of the polyurusiol powder,
Wherein the polyurusiol powder has a particle size of 5-30 mu m.
Reacting the urushiol, the hydrophilic monomer, the oxidizing agent and the neutralizing agent, and adding water to make a polyurusiol aqueous solution;
Spraying the aqueous polyurusol solution under a hot air condition to prepare a polyurusiol powder having a particle size of 5-30 탆; And
Mixing 5 to 30 parts by weight of polyurusiol powder having a particle size of 5-30 占 퐉 in 100 parts by weight of polypropylene and extruding the mixture to prepare a mixed composition.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893574A (en) * | 2015-05-23 | 2015-09-09 | 张家界娄江生态农业开发有限公司 | High-temperature-resistant raw lacquer coating and preparation method thereof |
| KR102265343B1 (en) * | 2021-05-27 | 2021-06-14 | 손동희 | Basalt fiber sheet for repairing and reinforcing concrete structure and repairing and reinforcing method for concrete structure using same |
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| KR20000024493A (en) * | 2000-02-16 | 2000-05-06 | 김차봉 | Functional synthetic-resin mixed Lacquer constituent and manufacture method thereof |
| KR100662862B1 (en) | 2005-07-12 | 2006-12-28 | 한국내쇼날주식회사 | Production method of molding mixture of synthetic resin comprising an urushi lacquer and molding mixture of synthetic resin produced by thereof |
| KR20130081886A (en) * | 2012-01-10 | 2013-07-18 | 박근식 | Manufacturing method and high polymer composite using lacquer sap |
| KR20140008576A (en) * | 2012-07-06 | 2014-01-22 | 연세대학교 원주산학협력단 | Nonallergenic polyurushiol powder and method for manufacturing thereof |
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| KR20000024493A (en) * | 2000-02-16 | 2000-05-06 | 김차봉 | Functional synthetic-resin mixed Lacquer constituent and manufacture method thereof |
| KR100662862B1 (en) | 2005-07-12 | 2006-12-28 | 한국내쇼날주식회사 | Production method of molding mixture of synthetic resin comprising an urushi lacquer and molding mixture of synthetic resin produced by thereof |
| KR20130081886A (en) * | 2012-01-10 | 2013-07-18 | 박근식 | Manufacturing method and high polymer composite using lacquer sap |
| KR20140008576A (en) * | 2012-07-06 | 2014-01-22 | 연세대학교 원주산학협력단 | Nonallergenic polyurushiol powder and method for manufacturing thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104893574A (en) * | 2015-05-23 | 2015-09-09 | 张家界娄江生态农业开发有限公司 | High-temperature-resistant raw lacquer coating and preparation method thereof |
| KR102265343B1 (en) * | 2021-05-27 | 2021-06-14 | 손동희 | Basalt fiber sheet for repairing and reinforcing concrete structure and repairing and reinforcing method for concrete structure using same |
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