KR20130002621A - Photo sensitive -biodegradable combined plastic and its composition and its processing film and its manufacturing method - Google Patents

Abstract

PURPOSE: A photo-sensitive-biodegradable composite resin is provided to reduce molecular weight by collision of a polymer backbone through sunlight and to have excellent biodegradability. CONSTITUTION: A photo-sensitive-biodegradable composite resin is manufactured by: a step of a manufacturing a metal stearate by filtering, washing and drying a precipitate which is obtained by dropping and reacting a stearic acid and a metal sulfate hydrate into a potassium hydrate solution; a step of melt-mixing the metal stearate and a decomposition-controlling compound into a polymer resin to form a photo-sensitive-biodegradable composite resin composition; and a step of manufacturing a photo-sensitive-biodegradable pellet by melting and extrusion molding the composition. [Reference numerals] (AA) Metal stearate manufacturing step; (BB) Photo-sensitive-biodegradable composite resin composition forming step; (CC) Pelletizing step

Description

Photosensitive -biodegradable combined plastic and its composition and its processing film and its Manufacturing Method}

FIELD OF THE INVENTION The present invention relates to light decay-biodegradable composites, films and compositions thereof for industrial or agricultural use.

Recently, the importance of protecting the global environment has been widely recognized, and it acts as a cause of serious environmental pollution such as incineration of various plastic products, leakage of environmental hormones caused by landfill, and air pollution caused by incomplete combustion of toxic dioxin-detecting waste. have.

While polymer materials such as plastics have contributed greatly to modern people's abundant daily life and industrial development at low prices, in order to solve the problems of plastic waste generated in large quantities, the processability, durability, and mechanical properties of plastics are further maintained. There is an urgent need for the development of plastics with added degradability, and recently, the development of eco-friendly plastics that can be decomposed within a short period of time has been actively made in the case of short-lived plastic products such as disposable food containers, garbage bags and packaging materials. Its use is expanding.

  Natural biodegradable resins developed as substitutes for conventional petroleum resources include chitin, chitosan, alginic acid, collagen, bacterial cellulose, polyamino acid, and the like. Hydroxybutyrate valerate, polycaprolactone, polybutylene succinate, polyhydroxybutyrate, polyhydroxyalkanoate, etc., but it is more mechanical than general general-purpose resins such as polyethylene, polypropylene, polystyrene, polyester, and nylon. Due to poor properties, heat resistance, and processability, and high raw material prices, economical efficiency is lowered, and solidification time is long after product production.

Accordingly, various efforts have been made to improve the properties, formability, and processability of existing biodegradable materials by combining two or more conventionally developed biodegradable resins or developing new biodegradable materials by monomer copolymerization. .

In order to solve such a conventional problem, various studies have been made with a mixture of general-purpose resins such as polyethylene to expensive aliphatic polyester resins such as polymatic acid and polycaprolactone, which are deformed even in hot hot water. There was a drawback of easily tearing in the direction of the grain pattern when forming products due to low compatibility between the two.

Accordingly, Korean Patent Application No. 10-2002-0058408 is a method of adding starch and a fibrous material, and in the case of Korean Patent Application No. 10-2005-0032965, the physical properties of aliphatic polyester are partially improved by adding modified corn starch. However, there is a disadvantage in that the manufacturing process is complicated and the productivity is low, and as it is known in the domestic patent application No. 10-2007-0089849 still has a disadvantage that is expensive, the industrial availability is low.

Although biodegradable plastics are being applied to agricultural mulching films, etc., films such as agricultural houses and coating materials must satisfy mechanical properties, transparency, weather resistance, and flexibility, and general general purpose for improving flexibility and impact resistance. Although there are biodegradable agricultural film production methods in which aliphatic polyester is blended with resin in a specific ratio, all of them are low in transparency, and durability deterioration occurs due to climate change, making them difficult to use as agricultural houses or coating materials.

Domestic Patent Application No. 10-2002-0058408, Domestic Patent Application No. 10-2005-0032965, Domestic Patent Application No. 10-2007-0089849.

In order to solve the above problems, the present invention solves the problems of poor industrial applicability due to low moldability, heat resistance, mechanical properties and productivity of the existing biodegradable resin composition as well as low price competitiveness, and decomposability during disposal or dumping. The purpose is to produce and disperse this excellent yet inexpensive photo decay-biodegradable composite resin and film.

Therefore, the photodegradation-biodegradable resins and films according to the present invention have a carbonyl or (-CO-) carboxyl (-COO-) group introduced by the chemical reaction during the disposal or landfill of the product after the collapse of the plastic polymer backbone It should be characterized by a decrease in molecular weight, which leads to the progress of biodegradation by microorganisms.

On the other hand, the product or molded article of the resin composition should not change or deteriorate in physical properties during distribution and use.

In addition, the master batch should be able to be easily produced by simply mixing and processing with other raw materials before final final product production without compounding with conventional general purpose polymer resin.

Dissolve 0.9-1.5 parts by weight of potassium hydroxide (KOH) in 100 parts by weight of ion-exchanged water, add 4.0-6.0 parts by weight of stearic acid, stir at 200 RPM until complete dissolution, and then 2.7-3.0 parts by weight of ferric Metal stearate, which is filtered, washed and dried, is reacted by dropwise addition of metal sulphate hydrate such as ferric sulphate hydrate or calcium sulphate hydrate. metal stearate) manufacturing step;

0.1-10 parts by weight of the metal stearate prepared in the metal stearate forming step and iron 2,4-pentanedione (iron 2) in 100 parts by weight of a polymer resin such as polyolefin, polyvinyl chloride, polyester, polystyrene, acryl or nylon , 4-pentanedione, titanyl 2,4-pentanedione, zirconyl 2,4-pentanedione, magnesium 2,4-pentanedione, magnesium 2,4-pentanedione , 4-pentanedione, copper 2,4-pentanedione, calcium 2,4-pentanedione or aluminum 2,4-pentanedione or aluminum 2,4-pentanedione 0.1-20 parts by weight of metal pentanedione, such as -pentanedione, 0.1-1.0 parts by weight of UV absorber, UV stabilizer, poly (1,2-dihydro-2,2,4-trimethylquinoline, a thermal antioxidant ) [poly (1,2-dihydro-2,2,4-trimethyl quinoline)], 2,6-di-tert-butyl-4-methylphenol (2,6-di-tert-butyl-4-methyl phenol ), Tetrakis [methylene (3,5-di-tert-butyl-4-hi Drooxy-hydrocinnamate) methane [tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane] or tris (2,4-di-tert-butyl-phenyl) phosphite [ tris (2,4-di-tert-butyl-phenyl) phosphite] 0.1-5 parts by weight, pigment 0.001-4.0 parts by weight, nickel diethylglyoxime 0.01-0.5 part, phenolphthalein 0.01-5 Parts by weight and 0.1-10 parts by weight of decomposition control compounds such as latic acid, maleic anhydride, citric acid and the like in a conventional Henschel mixer, super mixer or dispensing kneader Melt mixing to form a photo-decomposition-biodegradable composite resin composition;

 Pelletizing the composition obtained in the step of forming the light decay-biodegradable composite resin into a light decay-biodegradable composite pellet having a size of 2-3mm through melt extrusion molding process using a single or twin screw extruder And a step of obtaining the light decay-biodegradable composite resin, and putting the light decay-biodegradable composite pellet obtained in the pelletizing step into a hopper and forming a film in a uniaxial or biaxial extrusion sheet machine to which a die for sheet forming is attached. The molding step yields a light decay-biodegradable composite film.

As described above, the light dissociation-biodegradable composite resin composition and the film using the same according to the present invention are disposed upon disposal due to a combination of molecular weight reduction and biodegradation of microorganisms due to the collapse of the polymer main chain after carbonyl or carboxyl groups are introduced by sunlight. Or, it has the advantage of being inexpensive and inexpensive when dumping.

In addition, compared to the existing biodegradable resin composition has excellent advantages in moldability, heat resistance, mechanical properties as well as productivity and low-cost raw materials can be mass-produced at a low price.

1 is an exemplary view illustrating a step of manufacturing a composite resin of the present invention.
Figure 2 is an illustration of the film production step of the present invention.

To exemplify a specific method for the practice of the present invention, 0.9-1.5 parts by weight of potassium hydroxide is dissolved in 100 parts by weight of ion-exchanged water, and stirred at 200 RPM until it is dissolved completely by adding dropwise 4.0-6.0 parts by weight of stearic acid, and then 2.7-3.0. A step of preparing a metal stearate by filtering, washing and drying the precipitate produced by the reaction while dropwise adding the weight part of the metal sulfate hydrate;

 0.1-10 parts by weight of metal stearate and 0.1-20 parts by weight of metal pentanedion, 0.1-1.0 parts by weight of UV stabilizer, 0.1-5 parts by weight of antioxidant, pigment 0.001 to 4.0 parts by weight, 0.01-4 parts by weight of nickel dimethylglyoxime, 0.01-5 parts by weight of phenolphthalein, and 0.1-10 parts by weight of decomposition control compound by melt mixing in a conventional Henschel mixer, super mixer or dispersion kneader to decompose and biodegrade A melt mixing step of making the composite resin composition;

 A pelletization step of making the plastic composition obtained in the melt mixing step into a photo-decomposition-biodegradable composite resin polymer pellet having a size of about 2-3 mm through a melt extrusion molding process using a single screw or twin screw extruder; Obtaining the pellets, the light decay-biodegradable composite resin obtained by the pelletizing step into the hopper and the film forming step of forming a film in a uniaxial or biaxial extrusion sheet machine attached to the sheet forming die attached to the light decay-biodegradable composite resin Get a film.

Herein, the polymer resin used in the melt-mixing step of making the light decay-biodegradable composite resin film may be any resin capable of melt extrusion such as polyolefin, polyvinyl chloride, polyester, polystyrene, polyacrylic or nylon, and the present invention. Is not limited thereto.

The metal pentanedione is used 0.1-20 parts by weight as a photocatalytic accelerator of the polymer, such metal pentanethione is iron 2,4-pentanedione, titanyl 2,4-pentanedione, zirconyl 2,4-pentanedione , Magnesium 2,4-pentanedione, copper 2,4-pentanedione, vanadil 2,4-pentanedione, calcium 2,4-pentanedione or aluminum 2,4-pentanedione can be used.

Where the metal pentanedione is less than 0.1 parts by weight of the light-collecting property, when more than 20 parts by weight of the final product properties are inferior.

The metal stearate is used to adjust the lubricity and light disintegration, 0.1-10 parts by weight, preferably iron stearate or calcium stearate, magnesium stearate, zinc stearate can also be used.

If it is less than 0.1 part by weight, the lubricity is inferior, and when more than 10 parts by weight is added, it is rapidly accelerated to photodegradability.

The thermal antioxidants include poly (1,2-dihydro-2,2,4-trimethylquinoline), 2,6-di-tert-butyl-4-methylphenol, tetrakis [methylene (3,5-di 0.1-5 parts by weight of -tert-butyl-4-hydrooxy-hydrocinamate) methane or tris (2,4-di-tert-butyl-phenyl) phosphite.

Here, if the polyphosphite is less than 0.1 parts by weight, the polymer resin is oxidized during processing, and when 5 parts by weight or more is added, photodegradation is rapidly promoted.

Titanium oxide, iron oxide, calcium carbonate, chromium oxide, ocher, umber, carbon black and the like are used, and 0.001 to 4 parts by weight are used to impart the color of the photodegradable-biodegradable composition.

Table 1 summarizes the pigments and colors.

 <Table 1> Pigments by Color

The decomposition control compound is used in 0.1-10 parts by weight to promote biodegradation when the product is embedded, latic acid (salticlic acid), salicylic acid (salicylic acid), maleic anhydride (maleic anhydride), sheet rikaek sheet (citric acid) of low-cost acid, or is composed of epoxidized vegetable oils, such as blood-life (P-Life)'s SMC2360, SMC2522 or Symphony Invar theory Advanced Performance (Symphony Environmental Ltd) 's d ₂ w additive is also used It is possible.

Here, the degradation control compound is less than 0.1 parts by weight of biodegradability, and when added 10 parts by weight or more promote microbial growth even at room temperature.

The UV stabilizer is 0.1-1.0 parts by weight to suppress the progress of the oxidation reaction during the product life and salicylic acid (salicylic acid), benzophenone (benzophenone) or benzotriazol derivatives (benzotriazol) derivatives can be used Do. If less than 0.1 parts by weight of light decay occurs rapidly, if more than 1.0 parts by weight of the photodegradation reaction does not proceed.

Table 2 shows the wavelengths of light that cause photochemical reactions of polymers and Table 3 shows examples of typical UV absorbers.

<Table 2> Wavelength of light causing photochemical reaction of polymer

Table 3 Examples of Typical UV Stabilizers

Looking at the photo-degradation-biodegradable resin composition and a method for producing a film using the same according to the present invention in more detail, and describes the examples according to the following.

 Hereinafter, the present invention will be described in more detail with reference to examples.

However, the scope of the present invention is not limited only to the illustrated embodiment.

The components described in Table 4 were mixed at the respective mixing ratios using a mixer to produce a photodegradable biodegradable resin composition and a film.

Table 4 Examples of Composition and Preparation of Photodegradable-Biodegradable Resins

1.0 parts by weight of potassium hydroxide was dissolved in 100 parts by weight of ion-exchanged water, and 4.7 parts by weight of stearic acid was added dropwise, stirred at 200 RPM until complete dissolution, and then 2.7 parts by weight of ferric sulfate hydrate was added dropwise to filter and wash the resulting precipitate. After drying, iron stearate is prepared.

0.5 part by weight of metal stearate, 0.5 part by weight of metal 2,4-pentanedione, 0.1 part by weight of UV stabilizer, poly (1,2-) in 100 parts by weight of polymer resin mixed with 30 parts by weight of low density polyethylene and 70 parts by weight of linear low density polyethylene 0.6 parts by weight of dihydro-2,2,4-trimethylquinoline), 0.1 parts by weight of pigment, 0.2 parts by weight of nickel dimethylglyoxime as additive, 0.1 parts by weight of phenolphthalein, and 1 part by weight of decomposition control compound were sequentially added to the dispersion kneader. After mixing 20 to 30 hours at 3,000 rpm, 140 ℃ to make a composition of the form of a lump dough, it is made into pellets having a size of 2-3mm through melt extrusion molding process using a single screw and twin screw extruder, for 380mm sheet molding In twin-screw extruder sheet with die (80Φ, L / D 36, hanger type die), cylinder 1 is 160 ℃, cylinder 2 is 170 ℃, cylinder 3 is 180 ℃, die is 175 ℃ at 70 ℃. 0.2 mm at a speed of kg / hr Kkeui the film was formed.

Specimens were prepared using the film thus prepared, and biodegradability, water resistance, oil resistance, and tensile properties were evaluated, and the results are shown in <Table 5>.

The performance of the specimens prepared according to the Examples is evaluated according to the following various functional test methods.

(1) biodegradable;

The biodegradable composition was made into sheet specimens having a width of 10 cm and a length of 10 cm and buried in the soil of the farming area. After 6 months, the shape was completely decayed, and after 6 months, the shape was partially decayed.

(2) melt flow index;

 It was measured by ASTM D-1238 method. (Measurement condition: 190 ℃, 2.16㎏, Measuring equipment: MI measuring instrument of Haake company)

(3) water resistance, oil resistance;

Test vessels of 10 cm wide, 10 cm long and 1 cm high were prepared, poured with water and cooking oil, and left for 24 hours at 50 ° C. in a hot air oven. Then, the traces and surfaces of the eluate were observed. If there was no change of state, it was classified as excellent, and if there was a change of trace or surface state of eluate, it was classified as bad.

(4) degree of photooxidation;

The intensity of the C = O (1710cm ^-1 ) group, which is formed in units of 25 hours, by irradiating the specimen with UV lamps, was measured by FT-IR, and the time taken until the ratio of the CH (729cm ^-1 ) group to 0.5 was determined. .

(5) Tensile test: Tensile strength and tensile elongation were measured using a universal test machine.

<Table 5> Measurement result of each experiment according to the experiment example

As shown in Table 5, the light decay-biodegradable resin composition and the film using the same according to the embodiment of the present invention can be confirmed that excellent in the degree of photooxidation, water resistance, oil resistance and tensile properties, and biodegradability.

Here, the thermoplastic polymer resin and other components required in Table 4 may be mixed in an appropriate ratio according to the use to prepare a compound, and then a desired product may be prepared.

In addition, when preparing a conventional thermoplastic polymer resin and photodegradation-biodegradable resin required according to the application as in the embodiment of <Table 6> it can be molded into a product to be mixed by instant mixing.

Finished products that can be produced can be produced in a variety of known forms such as films, sheets, vacuum molded articles, injection molded articles, and the like.

Such a masterbatch or compound for decomposition additives is suitably prepared to the extent that it can be mixed and used in a ratio of about 1-20 parts by weight relative to the total weight of the conventional polymer resin, but the present invention is not limited thereto.

TABLE 6 Examples of Composition and Preparation of Photodegradation-Biodegradable Masterbatches

1 and 2 illustrate exemplary steps of the light dissociation-biodegradable composite resin composition of the present invention and a film using the same.

By using the light disintegration-biodegradable composite resin composition of the present invention, the existing production facility can be used as it is, and cost reduction can be achieved by using no expensive aliphatic polyester biodegradable resin, and easily disposed of in a natural state after disposal. Not only does it decompose to increase soil organic matter and pollute the environment, but also it can be easily mixed with various polymers to produce products without deterioration of physical properties, so it will be of great industrial use value.

Claims (3)

Dissolve 0.9-1.5 parts by weight of potassium hydroxide (KOH) in 100 parts by weight of ion-exchanged water, add 4.0-6.0 parts by weight of stearic acid, and stir at 200 RPM until complete dissolution, then 2.7-3.0 parts by weight of ferric sulfate hydrate or calcium sulfate. A metal stearate manufacturing step of filtering, washing, and drying the precipitate generated by reacting dropwise addition of a metal sulfate hydrate such as hydrate;
A metal stearate and a metal pentanedion prepared in the step of forming the metal stearate in a polymer resin such as polyolefin, polyvinyl chloride, polyester, polystyrene, polyacrylic or nylon, and an ultraviolet stabilizer. The decomposition control compound consisting of polymethane or phosphite, a thermal antioxidant, a pigment, nickel dimethylglyoxime, phenolphthalein, and a low-cost acid or epoxidized vegetable oil is melted in a conventional Henschel mixer, super mixer or dispersion kneader. Mixing the light decay-biodegradable resin composition to form;
A pelletization step of making the composition obtained in the light decay-biodegradable composite resin composition forming step into a light decay-biodegradable composite resin pellet having a size of about 2 to 3 mm through a melt extrusion molding process using a single or twin screw extruder;
Stearate and a metal pentanedione, an ultraviolet stabilizer to a polymer resin. A photodegradation-biodegradation composite characterized by melting and mixing a thermal antioxidant polymethane or phosphite, a pigment, nickel dimethylglyoxime, phenolphthalein, and a decomposition control compound composed of a low-cost acid or epoxidized vegetable oil. Suzy . Dissolve 0.9-1.5 parts of potassium hydroxide (KOH) in 100 parts of ion-exchanged water, add 4.0-6.0 parts of stearic acid dropwise, stir at 200 RPM until completely dissolved, and then 2.7-3.0 parts of ferric sulfate hydrate or calcium sulfate. A metal stearate manufacturing step of filtering, washing, and drying the precipitate generated by reacting dropwise addition of a metal sulfate hydrate such as hydrate;
A metal stearate and a metal pentanedion prepared in the step of forming the metal stearate in a polymer resin such as polyolefin, polyvinyl chloride, polyester, polystyrene, polyacrylic or nylon, and an ultraviolet stabilizer. The decomposition control compound consisting of polymethane or phosphite, a thermal antioxidant, pigment, nickel dimethylglyoxime, phenolphthalein, low-cost acid or epoxidized vegetable oil, is melted in a conventional Henschel mixer, super mixer or dispersing kneader. Mixing the light decay-biodegradable resin composition to form;
A pelletization step of making the composition obtained in the light decay-biodegradable composite resin forming step into a light decay-biodegradable composite resin pellet having a size of about 2 to 3 mm through a melt extrusion molding process using a single screw or twin screw extruder;
A film forming step of placing the film in the uniaxial or biaxial extrusion sheet machine in which the light disintegrating-biodegradable composite resin pellet obtained in the pelletizing step is placed in a hopper and a die for sheet forming is attached;
Decomposition control compound composed of stearate and metal pentanedione, UV stabilizer and polymethane or phosphite as UV stabilizer, pigment, nickel dimethylglyoxime, phenolphthalein and low cost acid or epoxidized vegetable oil Characterized in that it is made by melt mixing Light decay-biodegradable composite film. The method according to claim 1 or 2,
0.1-10 parts by weight of the metal stearate prepared in the step of forming metal stearate and 100 parts by weight of a polymer resin such as polyolefin, polyvinyl chloride, polyester, polystyrene, polyacrylic or nylon in the composition forming step and iron 2,4- Pentanedione, titanyl 2,4-pentanedione, zirconyl 2,4-pentanedione, magnesium 2,4-pentanedione, copper 2,4-pentanedione, calcium 2,4-pentanedione or aluminum 2,4- 0.1-20 parts by weight of a metal pentanedion such as pentanedion, 0.1-1.0 part by weight of UV stabilizer, poly (1,2-dihydro-2,2,4-trimethylquinoline), 2,6-di- which is a thermal antioxidant Tert-butyl-4-methylphenol, tetrakis [methylene (3,5-di-tert-butyl-4-hydrooxy-hydrocinnamate) methane or tris (2,4-di-tert-butyl-phenyl) force 0.1-5 parts by weight of the pigment, 0.001-4.0 parts by weight of the pigment, 0.01-0.5 parts by weight of nickel dimethylglyoxime, 0.01-5 parts by weight of phenolphthalein and a lactose acid, Photo-degradation-biodegradation composite, characterized in that the composition is melt-mixed 0.1-10 parts by weight of a decomposition control compound composed of low-cost acid, such as salicylic acid, maleic hydride, citric liquid sheet and epoxidized vegetable oil Resin composition.

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