KR101224420B1 - Manufacturing method of flexible poly lactic acid composition - Google Patents
Manufacturing method of flexible poly lactic acid composition Download PDFInfo
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- KR101224420B1 KR101224420B1 KR1020100135432A KR20100135432A KR101224420B1 KR 101224420 B1 KR101224420 B1 KR 101224420B1 KR 1020100135432 A KR1020100135432 A KR 1020100135432A KR 20100135432 A KR20100135432 A KR 20100135432A KR 101224420 B1 KR101224420 B1 KR 101224420B1
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Abstract
The present invention provides a softened polylactic acid composition, characterized in that the polylactic acid is softened to facilitate processing even at low temperature by lowering the melting point by using an acrylic powder and a plasticizer masterbatch prepared by mixing an acrylic powder and a plasticizer. The present invention relates to a manufacturing method thereof, which prevents the occurrence of migration problems and deterioration of mechanical strength caused by using a conventional plasticizer directly mixed with a polylactic acid resin, and improves workability, thereby improving polylactic acid as a biodegradable material. The advantage is that the material can be usefully used for various industrial materials such as industrial, shoe parts, and packaging containers.
Description
The present invention relates to a method for producing a softened polylactic acid composition, and more specifically, to a polylactic acid using an acrylic powder and a plasticizer masterbatch prepared by mixing an acrylic powder and a plasticizer to lower the melting point to process at low temperatures. The present invention relates to a method for producing a softened polylactic acid composition, by minimizing the problem of lowering the mechanical strength and the migration problem of using a conventional plasticizer directly mixed with the polylactic acid resin. .
In general, biodegradable plastics change their chemical structure over time under specific environmental conditions such as light, heat, and moisture, and lose the properties of existing materials. It refers to a plastic that can be measured and encompasses biodegradation, biodegradation, photolysis and complex decomposition plastics.
Since most of the commonly used packaging, living and agricultural plastics are not decomposed in the natural environment, how to handle a large amount of plastic waste that is thrown away after use has become a big social problem. Others are left unattended and are recognized as the main contributors to the environment.
On the other hand, the definition of degradable plastics is not precisely defined, but in the United States, according to the American American Society for Testing And Materials (ASTM), the chemical structure changes considerably over a certain period of time under certain environmental conditions. Plastics that can be measured are defined as degradable plastics.
The BEDPS (Bio / Environmentally Degradable Plastic Society) is a photo-degradable plastic, oxidatively-degradable plastic, hydrolytically-degradable plastic, and bio-degradable plastic. There are four categories.
On the other hand, bioplastic materials include biomass-based plastics and biodegradable plastics produced through chemical or biological processes using renewable materials such as plant-derived resources, that is, biomass as raw materials. This includes.
The recent global trend of bioplastics is a market that is forming around polylactic acid. The polylactic acid has excellent heat resistance, transparency, rigidity, and the like in a renewable bioplastic, and is easy to process. In addition, price competitiveness is also cheaper than that of naphtha, a raw material for plastics.
The polylactic acid is an eco-friendly biodegradable resin made mainly from raw materials extracted from corn, and is a next generation advanced material that is highly evaluated in terms of processability, practicality, stability, economical efficiency, and eco-friendliness as a packaging material in the world.
Therefore, the situation is expected to be used as an eco-friendly packaging material that can reduce the expenditure on waste charges of the Ministry of Environment. As such, polylactic acid is widely used as a packaging material, and is gradually being used as a petrochemical-based plastic substitute, adding its function.
In addition, the effect of the effect or image in the area that directly affects the human body such as food due to the eco-friendliness of the material itself is emerging. In addition, it has already been approved by the US FDA, GPAS, and government agencies such as Canada and Japan as ingredients that are harmless to humans when in contact with food.
However, polylactic acid, which is known as a material that is harmless to humans or has excellent biodegradability, is still in a situation of being limited in application because of its poor performance in various applications requiring durability.
In other words, due to the seriousness of the environmental pollution caused by household and industrial plastic waste, the necessity of technology development for biodegradable products has emerged, but until now, most of biodegradable plastic materials have not been commercialized due to their poor biodegradability and durability. Some applied products are also at a level that is not as good as biodegradable products.
In addition, due to the high melting point and high hardness characteristics of polylactic acid, there is a limit to the development of polylactic acid material that can replace biodegradable soft materials. In the case of soft materials, plasticized polylactic acid is used by overseas company Holstar (US), but this product is expensive and it is difficult to be used for industrial purposes.
In order to solve the problem of polylactic acid, there is a method of softening by lowering the glass transition temperature by adding a plasticizer. As a related prior art, Korean Patent Publication No. 10-0989116 discloses a polycarbonate resin in a polylactic acid. And a composition including a compatibilizer. In the case of the patent, a compounding agent is added to the polylactic acid to increase the heat resistance of the material and provide a composition having improved impact strength, but there is a problem in that it is difficult to be used as a soft material due to high molding temperature.
In addition, Korean Laid-Open Patent Publication No. 10-2010-0098367 discloses a resin composition obtained by blending a peroxide, a plasticizer, a fiber reinforcing material, a polyhydric carbodiimide compound, and the like directly with a polylactic acid resin, and a molded article formed by molding the same. In the case of the patent to increase the crystallization degree of the polylactic acid by applying an additive to increase the strength of the composition and the molded article, there is a problem that is not suitable for use as a soft material.
In addition, Korean Laid-Open Patent Publication No. 10-2010-0108683 discloses a polylactic acid-containing biodegradable comprising a mixture of maleic anhydride and glycidyl methacrylate or a mixture of maleic anhydride and octenylsuccinic anhydride as a compatibilizer. It is an object of the present invention to provide a biodegradable sheet which is prepared by mixing a plasticizer directly into a resin composition, and the molding is limited to a sheet, and thus there is a problem that it is difficult to apply to various parts materials using polylactic acid of a soft material. .
On the other hand, in addition to the patents proposed above, as a prior art to add a plasticizer directly to the polylactic acid resin composition, Korean Patent Publication Nos. 10-2010-0068423, 10-2009-0118938, 10-2010-0098529 , Korean Patent Publication No. 10-0544852 has been proposed, but in the case of the prior art as described above, the glass transition temperature is low enough to be used as a soft material by using a plasticizer directly mixed with the polylactic acid resin composition Not only were there problems that could not be solved, especially the migration.
In addition, as another prior art in which a plasticizer is added to polylactic acid, Korean Patent Publication No. 10-0722529 has been proposed.
In the case of the prior art, it may be misunderstood as if it is manufactured in the form of a film to implement a soft property, the prior art is to apply a 'liquid polylactic acid' to a film having a soft property, 'polylactic acid resin' There is a problem that can not be applied to soften itself.
The present invention is to solve the above-described problems, so that the polylactic acid having a high melting point, high hardness properties to have a low melting point, low hardness properties to soften the polylactic acid as well as to facilitate processing at low temperatures The object of the present invention is to provide a method for producing a softened polylactic acid composition which can be used as a material for industrial, shoe parts, packaging containers, and the like.
In addition, the present invention by softening the polylactic acid using an acrylic powder plasticizer master batch prepared by mixing the acrylic powder and a plasticizer in advance, the plasticizer is a polylactic acid by the commercialization action of the polylactic acid and acrylic resin It is an object of the present invention to provide a method for producing a softened polylactic acid composition, which is easily compatible with the present invention, thereby minimizing the problem of migration and the decrease of mechanical strength by using a conventional plasticizer.
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The present invention is a method for producing a softened polylactic acid composition, S1) 50 to 300 parts by weight of a plasticizer is mixed with respect to 100 parts by weight of acrylic powder and stirred in a stirrer for 5 to 10 minutes and then 10 to 10 in 50 ~ 70 ℃ oven After 30 minutes of aging, the acrylic powder and plasticizer masterbatch was prepared, and the acrylic powder and plasticizer masterbatch prepared above was added 10 to 100 parts by weight to the kneader with respect to 100 parts by weight of polylactic acid. A method for producing a softened polylactic acid composition prepared by mixing for 20 minutes is used as a means for solving the problem.
On the other hand, it is preferable that the said acrylic powder plasticizer masterbatch is made by mixing 50-300 weight part of plasticizers with respect to 100 weight part of acrylic powders.
In addition, the plasticizer is a hydroxycarboxylic acid ester-based plasticizer, tributyl o-acetylcitrate, triethyl o-acetylcitrate, tributyl citrate It is preferable to use alone or in combination of two or more of the natural oil plasticizer oxidized castor oil, palm oil, olive oil (Oxidized natural oil).
At this time, the natural oil (Oxidized natural oil) plasticizer, the reaction temperature is adjusted to 70 ~ 140 ℃ while stirring and injecting 100g of castor oil and radical initiator 1.5-14% by weight into a reactor equipped with a reflux cooler, aeration pump It is preferable to prepare by supplying oxygen into the reaction composition using the stirring reaction at a rate of 50 ~ 250rpm for 6 to 10 hours, purifying the low boiling point compound contained in the reactant through reduced pressure distillation.
In addition, it is preferable to use the said acrylic powder whose molecular weight is 50-1 million, and particle | grains are 20-40 microns.
According to the present invention, by using an acrylic powder and a plasticizer masterbatch prepared by mixing an acrylic powder and a plasticizer, the polylactic acid is softened to lower the melting point and to be easily processed even at low temperatures. Migration problems and mechanical strength deterioration problems caused by direct mixing are not generated, and the processability is easy, and thus it is expected to be widely applied to various industries such as industrial, shoe parts, and packaging containers.
1 is a block diagram showing a method of manufacturing a softened polylactic acid composition according to an embodiment of the present invention.
Figure 2 is a photograph showing the specimens of Examples 1 to 5 to which the acrylic powder plasticizer masterbatch according to the present invention is added and Comparative Examples 1 to 3 not added.
Figure 3 is a differential scanning calorimetry graph shown to compare the glass transition temperature of the amorphous polylactic acid and crystalline polylactic acid used in the present invention
4 is a differential scanning calorimeter graph of decreasing glass transition temperature due to an increase in the content of acrylic powder and plasticizer masterbatch in polylactic acid;
Figure 5 is a comparison of the conventional polylactic acid and polylactic acid in accordance with the present invention
The present invention for achieving the above effect relates to a method for producing a softened polylactic acid composition, only the parts necessary for understanding the technical configuration of the present invention will be described, the description of other parts scatter the gist of the present invention. Note that it will be omitted so as not to fall short.
Hereinafter, the softened polylactic acid composition and the preparation method thereof according to the present invention will be described in detail.
The present invention is characterized in that the softened polylactic acid composition of 10 to 100 parts by weight of the acrylic powder plasticizer masterbatch based on 100 parts by weight of polylactic acid.
As the polylactic acid used in the present invention, a melt flow index of crystalline polylactic acid and amorphous polylactic acid was used in the range of 1 to 300 g / 10 min.
When the melt flow index is less than 1g / 10min, the soft-nitrification characteristics by plasticization of the polylactic acid using the modified plasticizer or the conventional plasticizer in the present invention is inferior, and when it exceeds 300g / 10min, the modified plasticizer and polylactic There is a problem that the commercialization characteristics of the seed is poor.
The acrylic powder and plasticizer masterbatch used in this invention is a mixture of a plasticizer and an acrylic powder, and is plasticized using 10-100 weight part with respect to 100 weight part of polylactic acid. Therefore, when processing a molded product by mixing a plasticizer directly to polylactic acid by a conventional method, the glass transition temperature is not sufficiently lowered to be used as a soft material, and in particular, does not solve the migration. On the other hand, the present invention is to soften the polylactic acid using an acrylic powder and a plasticizer masterbatch prepared in advance by mixing the acrylic powder and the plasticizer in advance, the plasticizer is pleated by the commercialization action of the polylactic acid and acrylic resin By being easily compatible with the lactic acid, it is possible to prevent the occurrence of the problems described above.
When the amount of the acrylic powder / plasticizer masterbatch is less than 10 parts by weight, there is a problem in that the soft-nitriding effect of the polylactic acid is inferior. When it exceeds 100 parts by weight, migration occurs and a sharp decrease in mechanical strength occurs. There is a problem that occurs.
On the other hand, the acrylic powder plasticizer masterbatch is prepared by mixing 50 to 300 parts by weight of a plasticizer with respect to 100 parts by weight of acrylic powder.
When the amount of the plasticizer is less than 50 parts by weight, there is a problem that the plasticization effect of the polylactic acid is inferior, and when it exceeds 300 parts by weight, there is a problem that the migration prevention effect of the plasticizer is decreased when the polylactic acid is softened.
At this time, the plasticizer is a hydroxycarboxylic acid ester-based plasticizer, tributyl acetyl citrate, triethyl acetyl citrate, tributyl citrate Alternatively, one or two or more kinds of plasticizers prepared by oxidizing fats and oils such as castor oil, palm oil and olive oil can be selected and used in combination.
At this time, the oxidation process of the fat and oil is a reaction caused by the absorption of oxygen in the air, the autoxidation process characterized by the chain reaction of active radicals and the heating that occurs when heated at a high temperature (80 ~ 200 ℃) It is caused by a thermal oxidation process. The various active radicals generated above combine with each other to form a polymer that crosslinks oxygen to form a new oxidized natural oil. In the present invention, the oxidation of castor oil, palm oil, olive oil, etc., produced through a heat oxidation process Oxidized natural oil can be used as a plasticizer.
On the other hand, in the present invention, the method for producing an oxidized natural oil plasticizer (Oxidized natural oil) plasticizer 100g of castor oil and 1.5 to 14% by weight of the radical initiator in a reactor equipped with a reflux cooler and the reaction temperature to 70 ~ 140 ℃ while stirring Adjust. In addition, by continuously supplying oxygen into the reaction composition by using an aeration pump and stirred at a speed of 50 ~ 250rpm for 6 to 10 hours, to prepare a plasticizer by purifying the low-boiling compounds contained in the reaction through reduced pressure distillation. .
As the type of radical initiator used in the present invention, various radical initiators of the peroxide type can be used, and specifically, hydrogen peroxide, benzoyl peroxide, methyl ethyl ketone peroxide ) Can be used.
On the other hand, the amount of the radical initiator is effective when added 1.5 to 14% by weight, preferably 5.0 to 8.0% by weight. In addition, if the reaction temperature is less than 70 ℃ takes a lot of time to oxidize, if the productivity is lowered and exceeds 140 ℃, there is a possibility of discoloration is adjusted. In addition, if the reaction time is less than 6 hours, the degree of oxidation is low, if more than 10 hours, there is a problem that all oxidized. In addition, if the stirring speed is less than 50rpm it takes a long time to oxidize and exceeds 250rpm, because the reactivity is lowered, stirring at a speed of 50 ~ 250rpm, preferably 100rpm.
In addition, it is preferable to use the acrylic powder having a molecular weight of 50 to 1 million and particles of 20 to 40 microns. If the molecular weight is less than 500,000 acrylic powder is less effective in controlling the occurrence of migration, when using more than one million acrylic powder there is a problem that the plasticization effect of the polylactic acid according to the rise of the viscosity of the plasticizer is inferior.
In addition, when the particle size is less than 20 microns, there is a problem that the effect of controlling the migration of the plasticizer is inferior to the commercialization action of the acrylic compound and polylactic acid, and when the particle size exceeds 40 microns, the powder of the acrylic powder There is a problem in that the acidity falls and the mechanical strength falls.
Hereinafter, a method for preparing a softened polylactic acid composition according to the present invention will be described in detail.
The present invention, as shown in Figure 1, in the method for producing a softened polylactic acid composition, by producing an acrylic powder plasticizer masterbatch (S1), and mixed with the polylactic acid (S2), Specifically,
S1) Mixing 50 to 300 parts by weight of plasticizer with respect to 100 parts by weight of acrylic powder and stirred for 5 to 10 minutes in a stirrer and then aged for 10 to 30 minutes in 50-70 ℃ oven to prepare an acrylic powder and plasticizer masterbatch,
S2) 10 to 100 parts by weight of the acrylic powder / plasticizer masterbatch prepared above is added to 100 parts by weight of polylactic acid and mixed at 120 to 170 ° C. for 5 to 20 minutes.
The present invention having the technical configuration as described above by using the acrylic powder and plasticizer master batch prepared by mixing the acrylic powder and the plasticizer polylactic acid by lowering the melting point to soften to facilitate processing at low temperatures, the conventional problems As it is solved, the processability is expected to be widely applied in the industry.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to the following Examples.
1. Preparation of Softened Polylactic Acid
Example 1
In order to prepare an acrylic powder and plasticizer master batch, the composition of the acrylic powder and the plasticizer was mixed in a ratio of 100: 100, and then mixed in a stirrer for 5 minutes, and aged in an oven at 50 to 70 ° C. for 20 minutes to prepare an acrylic powder and plasticizer master batch. . The prepared plasticizer was mixed for 10 minutes in a mixer set to 100 ~ 120 ℃ 60 parts by weight based on 100 parts by weight of polylactic Axis. In order to measure the mechanical properties, hardness, and specific gravity of the mixed composition, the sheet was molded for 5 to 7 minutes using a flat sheet mold at 160 ° C., followed by sheeting for 10 to 15 minutes in a cold press. In the method, the composition mixed in the mixer was pelletized through an extruder, and injection molded at a temperature of 120-130-140-150 ° C. and a temperature of 5-20 ° C. of an injection mold to mold a specimen. The molded specimens were evaluated for their properties by the method specified in the test examples.
Example 2
In order to prepare an acrylic powder and plasticizer master batch, the composition of the acrylic powder and the plasticizer was mixed in a ratio of 100: 150, and then mixed in a stirrer for 5 minutes and aged in an oven at 65 ° C. for 20 minutes to prepare an acrylic powder and plasticizer master batch. The prepared acrylic powder plasticizer masterbatch was mixed at 50 parts by weight in a mixer set at 110 ° C. for 10 minutes with respect to 100 parts by weight of polylactic Axis. In order to measure the mechanical properties, hardness and specific gravity of the mixed composition, the sheet was molded for 6 minutes using a flat sheet mold at 160 ° C., followed by molding for 15 minutes in a cold press. The mixture was pelletized through an extruder and injection molded at an injection part temperature of 120-130-140-150 ° C. and a temperature of 20 ° C. of an injection mold to form a specimen. The molded specimens were evaluated for their properties by the method specified in the test examples below.
Example 3
To prepare the acrylic powder and plasticizer masterbatch, the composition of the acrylic powder and the plasticizer was mixed in a ratio of 100: 200, and then mixed in a stirrer for 5 minutes, and aged in a 50-70 ° C. oven for 20 minutes to prepare an acrylic powder / plasticizer masterbatch. . The prepared acrylic powder plasticizer masterbatch was mixed for 10 minutes in a mixer set at 110 ° C for 45 parts by weight with respect to 100 parts by weight of polylactic Axis. In order to measure the mechanical properties, hardness and specific gravity of the mixed composition, the sheet was molded for 6 minutes using a flat sheet mold at 160 ° C., followed by molding for 15 minutes in a cold press. The mixture was pelletized through an extruder and injection molded at an injection part temperature of 120-130-140-150 ° C. and a temperature of 20 ° C. of an injection mold to form a specimen. The molded specimens were evaluated for their properties by the method specified in the test examples below.
Example 4
To prepare the acrylic powder and plasticizer masterbatch, the composition of the acrylic powder and the plasticizer was mixed in a ratio of 100: 250 and mixed for 5 minutes in a stirrer, and then aged in a 50-70 ° C. oven for 20 minutes to prepare an acrylic powder and plasticizer masterbatch. . The prepared acrylic powder and plasticizer masterbatch was mixed for 10 minutes in a mixer set to 110 parts by weight with respect to 100 parts by weight of polylactic Axis. In order to measure the mechanical properties, hardness and specific gravity of the mixed composition, the sheet was molded for 6 minutes using a flat sheet mold at 160 ° C., followed by molding for 15 minutes in a cold press. The mixture was pelletized through an extruder and injection molded at an injection part temperature of 120-130-140-150 ° C. and a temperature of 20 ° C. of an injection mold to form a specimen. The molded specimens were evaluated for their properties by the method specified in the test examples below.
Example 5
To prepare the acrylic powder and plasticizer masterbatch, the composition of the acrylic powder and the plasticizer was mixed in a ratio of 100: 300 and mixed for 5 minutes in a stirrer, and then aged in a 50-70 ° C. oven for 20 minutes to prepare an acrylic powder and plasticizer masterbatch. . The prepared acrylic powder plasticizer masterbatch was mixed for 10 minutes in a mixer set at 110 ° C. with respect to 100 parts by weight of polylactic Axis. In order to measure the mechanical properties, hardness and specific gravity of the mixed composition, the sheet was molded for 6 minutes using a flat sheet mold at 160 ° C., followed by molding for 15 minutes in a cold press. The mixture was pelletized through an extruder and injection molded at an injection part temperature of 120-130-140-150 ° C. and a temperature of 20 ° C. of an injection mold to form a specimen. The molded specimens were evaluated for their properties by the method specified in the test examples below.
Comparative Example 1
100 parts by weight of polylactic acid was melted in a mixer set at 110 ° C, and 20 parts by weight of a plasticizer was added and mixed. In order to measure the mechanical properties, hardness and specific gravity of the mixed composition, the sheet was molded for 6 minutes using a flat sheet mold at 160 ° C., followed by molding for 15 minutes in a cold press. The mixture was pelletized through an extruder and injection molded at an injection part temperature of 120-130-140-150 ° C. and a temperature of 20 ° C. of an injection mold to form a specimen. The molded specimens were evaluated for their properties by the method specified in the test examples.
Comparative Example 2
100 parts by weight of polylactic acid was softened in a mixer set at 110 ° C, and then 30 parts by weight of a plasticizer was added and mixed. In order to measure the mechanical properties, hardness and specific gravity of the mixed composition, sheeting was performed for 5-7 minutes using a flat sheet mold at 160 ° C., followed by molding for 15 minutes in a cold press. Pelletized the composition mixed in the mixer through an extruder and injection molding at a temperature of 120-130-140-150 ℃ of the injection part, 20 ℃ of the injection mold to mold the specimen. The molded specimens were evaluated for their properties by the method specified in the test examples.
Comparative Example 3
100 parts by weight of polylactic acid was softened in a mixer set at 110 ° C, and then 30 parts by weight of a plasticizer and 10 parts by weight of acrylic powder were added and mixed. In order to measure the mechanical properties, hardness and specific gravity of the mixed composition, the sheet was molded for 6 minutes using a flat sheet mold at 160 ° C., followed by molding for 15 minutes in a cold press. The mixture was pelletized through an extruder and injection molded at an injection part temperature of 120-130-140-150 ° C. and a temperature of 20 ° C. of an injection mold to form a specimen. The molded specimens were evaluated for their properties by the method specified in the test examples.
The composition table of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in the following [Table 1].
2) Mixing acrylpowder, dabi (Korea) and plasticizer citrocizer-A, Aekyung Petrochemical Co., Ltd. (Korea)
3) Acrylic Powder: Plasticizer = 100: 100
4) Acrylic Powder: Plasticizer = 100: 150
5) Acrylic Powder: Plasticizer = 100: 200
6) Acrylic Powder: Plasticizer = 100: 250
7) Acrylic Powder: Plasticizer = 100: 300
2. Test method
The sheets and molded specimens of the softened polylactic acid prepared by Examples 1 to 5 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in the following [Table 2].
1) Specipic gravity
Specific gravity was measured by measuring the polylactic acid sheet and injection molded specimens five times using an automatic specific gravity measuring device, and the average value was taken.
2) Hardness
Hardness was measured in accordance with ASTM D-2240 by using an Escker D type hardness meter on the surface using a polylactic acid sheet and an injection molded specimen.
3) Tensile strength and elongation
After making the specimen of polylactic acid to 3mm, a test specimen was made with a die A cutter, or a tensile strength specimen was prepared by injection molding and measured according to ASTM D-412. At this time, five test pieces were used for the same test, and the tensile speed was 200 mm / min.
4) Migration
The plasticized specimens are cut to shape to a certain size, sealed and left for a certain period of time. It was observed for two weeks after the test piece was fabricated and the migration was confirmed by checking the plasticizer on the sealed packaging container surface.
5) Tg (glass transition temperature)
The plasticized polylactic acid specimen was measured by using a differential scanning calorimeter.
As shown in [Table 2], the softened polylactic acid of Examples 1 to 5 according to the present invention had excellent tensile strength as compared with Comparative Examples 2 and 3, and shortened the processing time to be efficient and migrated. It was confirmed that this did not appear.
In addition, the processing time was decreased as the composition ratio of the acrylic powder in the modified plasticizer composition increased, and tensile strength and hardness also increased.
In addition, when compared with Comparative Example 2 to which 30 parts by weight of plasticizer was added, the tensile strength was higher and the glass transition temperature was found to be lower.
Comparative Example 3 was mixed using 30 parts by weight of plasticizer and 10 parts by weight of acrylic powder with respect to 100 parts by weight of polylactic acid. The composition ratio of the base material, the plasticizer and the acrylic powder was the same as in Example 5, but in the case of Example 5 Is a plasticized polylactic acid by applying an acrylic powder and a plasticizer masterbatch prepared by mixing an acrylic powder and a plasticizer. Compared with Comparative Example 3 having the same composition ratio, no migration occurred and the tensile strength was also high. And it was found.
That is, when the acrylic powder and the plasticizer masterbatch prepared by mixing the acrylic powder and the plasticizer by applying the production method of the present invention and simply mixing the plasticizer and the acrylic powder in a mixer to plasticize the polylactic acid are the result of migration It was confirmed that a difference in mechanical strength occurs.
Therefore, the present invention solved the migration problem by using a conventional plasticizer, as shown in Figure 2, as shown in Table 2, to minimize the problem of lowering the mechanical strength.
In addition, the conventional polylactic acid has a high glass transition temperature, as shown in Figure 3, as shown in Figure 5 (a), not easily softened without softening, such as industrial, shoe parts, packaging containers, etc. Not available as a material.
However, the softened polylactic acid according to the present invention, as shown in Figure 4, the glass transition temperature is lowered, as shown in Figure 5 (b), can be softened and bent, industrial, shoe parts It can be easily used as a material such as packaging containers.
As described above, the method for producing a softened polylactic acid composition according to the present invention has been described through the above-described preferred embodiments, and the superiority thereof has been confirmed, but those skilled in the art will appreciate the present invention described in the following claims. It will be understood that various modifications and changes can be made in the present invention without departing from the spirit and scope of the invention.
S1: Manufacture of acrylic powder and plasticizer masterbatch
S2: Mixed in polylactic acid, acrylic powder and plasticizer masterbatch
Claims (6)
A) 50 to 300 parts by weight of an oxygenated natural oil plasticizer is mixed with 100 parts by weight of acrylic powder, stirred in a stirrer for 5 to 10 minutes, and aged in an oven for 50 to 70 ° C. for 10 to 30 minutes. To make a masterbatch,
B) 10 to 100 parts by weight of the acrylic powder and plasticizer masterbatch prepared in A) was added to 100 parts by weight of the polylactic acid in the kneader and mixed for 5 to 20 minutes at 120 to 170 ° C.
The acrylic powder, the molecular weight is 50 to 1 million, particles are used 20 to 40 microns,
The plasticized natural oil (Oxidized natural oil) plasticizer, injecting 100 g of castor oil and 1.5 to 14% by weight of a radical initiator into a reactor equipped with a reflux condenser and adjusting the reaction temperature to 70 ~ 140 ℃ while stirring, using an aeration pump Supplying oxygen to the reaction composition and stirring at a rate of 50 to 250 rpm for 6 to 10 hours, and a softened poly-characterized product, which is prepared by purifying the low boiling point compound included in the reactant through vacuum distillation. Method for producing a lactic acid composition.
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| CN108047667B (en) * | 2017-12-06 | 2019-11-12 | 海南大学 | A kind of polylactic acid/castor oil blend and preparation method thereof |
| US11053361B2 (en) * | 2019-03-15 | 2021-07-06 | Chroma Color Corporation | Colorant and additive concentrate carrier system with efficacy over a wide range of polymeric processing temperatures |
| KR102478218B1 (en) * | 2022-05-06 | 2022-12-20 | 주식회사 모빅신소재기술 | Manufacturing method of composite by mixing cnf and biodegradable polymer to enhance the mechanical properties of biodegradable plastics |
| CN115850933A (en) * | 2022-12-31 | 2023-03-28 | 浙江工业大学 | Method for reducing migration and volatilization of vegetable oil plasticizer in polymer matrix |
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| JP2002210886A (en) | 2001-01-19 | 2002-07-31 | Toray Ind Inc | Softened biodegradable resin stretched film |
| JP2007262339A (en) * | 2006-03-30 | 2007-10-11 | Unitika Ltd | Polylactic acid-based polyester resin composition, method for producing the same and molding using the same |
| KR20080043041A (en) * | 2006-11-13 | 2008-05-16 | 제일모직주식회사 | Polylactic acid resin composition with good elongation and impact strength |
| KR20110106655A (en) * | 2010-03-23 | 2011-09-29 | (주)엘지하우시스 | Polylactic acid resin compositions for finish materials |
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2010
- 2010-12-27 KR KR1020100135432A patent/KR101224420B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002210886A (en) | 2001-01-19 | 2002-07-31 | Toray Ind Inc | Softened biodegradable resin stretched film |
| JP2007262339A (en) * | 2006-03-30 | 2007-10-11 | Unitika Ltd | Polylactic acid-based polyester resin composition, method for producing the same and molding using the same |
| KR20080043041A (en) * | 2006-11-13 | 2008-05-16 | 제일모직주식회사 | Polylactic acid resin composition with good elongation and impact strength |
| KR20110106655A (en) * | 2010-03-23 | 2011-09-29 | (주)엘지하우시스 | Polylactic acid resin compositions for finish materials |
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