JP2020521834A - Manufacturing method and application of enhanced toughening and transparent masterbatch - Google Patents

Abstract

The present invention belongs to the field of biodegradable polymer materials, and particularly relates to an enhanced toughening and transparent masterbatch (Masterbatches capable of enhancing strength, toughness and transparency). This masterbatch is manufactured by using polyadipate/terephthalate and an enhanced toughening/transparent agent (an enhancer that increases toughness and transparency) as main raw materials. It can be processed not only into film but also into multi-film. It can facilitate the processing of ultra-thin, fully biodegradable film products, maintain the mechanical and optical performance and stability of use, and can significantly reduce the cost of film production. Its production process is simple and easy to grasp. The finished masterbatch has stable properties, is completely decomposed, and has good dispersibility. If a small amount of the masterbatch of the present invention and a decomposed resin (PBAT+PLA, etc.) are added and used, an ultrathin completely biodegradable film product having a size of 6 μm or less can be prepared. In addition, it has good openability in the process of production, strengthens the stability of processing, and has excellent mechanical properties. It can be widely used for film packaging, shopping bags, agricultural mulch film, garbage bags and separate landfills, composting processing, etc.

Description

TECHNICAL FIELD The present invention belongs to the field of materials, and more particularly to a completely biodegradable plastic masterbatch, and more particularly to an enhanced toughening and transparent masterbatch, a method for producing the same and an application thereof.

Plastic films and mulch films play a major role in daily life, industrial and agricultural production. However, most of the plastic films and mulch films currently used are polyolefin films that are difficult to decompose in a short time, or incompletely decomposed films to which starch and a photodegradation accelerator are added. The use of these film materials causes plastic pollution problems and poses a hidden danger to the sustainable development of mankind. The fully biodegradable film is produced by blow molding, casting or calendering process of completely biodegradable plastic, and can be completely decomposed by microorganisms. The end product of biodegradation is carbon dioxide and water. Since it can be completely decomposed by nature, it is an important means for solving white pollution by substituting polyolefin products.

Currently, the completely biodegradable film is mainly composed of polylactic acid, polycaprolactone, aliphatic polyester, aliphatic polycarbonate, polyhydroxyester, starch, etc. However, due to the above-mentioned characteristics and defects of the polymer itself, a single polymer film is used. It is difficult to use as a material. Current research has mainly improved the overall performance of the film by blend modification, copolymerization modification, plasticization modification and composite modification. Chinese patent document CN103589124B discloses a fully biodegradable PLA/PBAT composite film and a manufacturing method thereof, and Chinese patent document CN1047444898A discloses a fully biodegradable film and a manufacturing method thereof, of which the corresponding film is It is composed of polylactic acid (PLA), polypropylene carbonate (PPC), polyadipate/butylene terephthalate (PBAT) and a heat stabilizer, but the above-mentioned film product thickness is 6 μm to 50 μm, which is generally thick and therefore costly. However, if the thickness is too large, the light transmissivity deteriorates, and if it is too small, the strength becomes weak, so that it cannot be commercialized in a short period of time and the optimum functional balance cannot be reached. Unlike polyolefin films, which are difficult to decompose, a fully biodegradable film is preferable as the film product is thinner, in the range where processing is convenient and performance is excellent. However, through the tests, ultra-thin films of less than 6 μm have problems that it is difficult to open bubbles in the film blow molding process, tensile strength and tear strength are significantly reduced, and haze is large. When used as a film in the field, solar radiation causes crosslinking of resin molecular chains, a decrease in toughness of the film, an increase in brittleness, and premature tearing of the film. Therefore, it is a problem to be solved to overcome the drawbacks in processing and performance of existing ultra-thin fully biodegradable film products and to provide a dedicated enhanced toughening and transparency masterbatch.

The present invention provides an enhanced toughening and translucent masterbatch and its manufacturing method and application to many problems existing in the prior art. This masterbatch is manufactured using polyadipate/terephthalate as the main raw material, and it can be processed not only into film but also into multi-film. The smoothness and mechanics of processing ultra-thin fully biodegradable film products The cost of the film can be significantly reduced while maintaining the optical properties and stability. The production process of this masterbatch is simple and easy to grasp, and the obtained masterbatch has stable properties, is completely decomposed and has good dispersibility. By adding a small amount of the masterbatch of the present invention and mixing it with a decomposition resin (PBAT+PLA, etc.), an ultrathin completely biodegradable film product having a size of 6 μm or less can be produced. With its easy opening of air bubbles, improved processing stability, and excellent mechanical function, it can be widely used for film packaging, shopping bags, agricultural mulch film, waste landfill, composting, etc.

The concrete technical solution means of the present invention is as follows.
An enhanced toughening and transparency masterbatch containing 65 to 88 parts by weight of a polyadipate/terephthalate and 10 to 20 parts by weight of an enhanced toughening and transparency agent as main components, calculated in parts by weight.

Among them, the polyadipate/terephthalate is a carrier resin, the melt flow rate is 2 to 5 g/10 min, and the acid value is less than 15. The polyadipate/terephthalate used in the present invention is very important for the production and use performance of the masterbatch for ultrathin fully biodegradable film, not only melting all materials, but also capable of withstanding high temperature and volatilizing. And without causing decomposition, when producing an ultrathin fully biodegradable film using the masterbatch provided by the present invention in a later step, has a better compatibility with other fully biodegradable films, And since it is necessary not to cause the film to decompose, the inventor selects the resin from many resins as the masterbatch carrier resin and limits the specific dose as described above. The dose range provides the optimum balance of each function of the masterbatch.

The enhanced toughening agent is one or more of an inorganic enhanced toughening agent and an organic enhanced toughening agent, and the inorganic enhanced toughening agent is selected from hydrophobic nanosilica. The hydrophobic nanosilica has a particle size of 5 to 25 nm, and the organic enhanced toughening and transparent agent is one of Akerma AX to 8900, ADX to 1200s resin compatibilizer or Hangzhou Aike CE to AZ01 compatibilizer. Or, there are multiple types.

The reason why the strengthening/toughening/permeabilizing agent does not exceed 20 parts by weight is to reduce the loss of powder in the process of mixing the resin and the raw materials, to ensure the uniformity of distribution and the convenience of granulation. This is because the compatibility of a plurality of kinds of resins in the film processing is increased and the mechanical performance of the film is not deteriorated by the excessive addition of the plurality of kinds of fillers.

When the above-mentioned reinforced toughening agent and transparency agent are selected, the compatibility with the carrier resin is good, so that a high-concentration masterbatch can be obtained, and it acts as a nucleating agent and a compatibilizing agent in the later processing step of the film. In addition to being advantageous in the stability of processing of the ultrathin film, it is possible to enhance the mechanical properties of the ultrathin completely biodegradable film.

Further, other additive components may be added to the above-mentioned combination group depending on the use.

More specifically, the inventor has also provided enhanced toughening and transparency masterbatch for ultrathin fully biodegradable films. When calculated in parts by weight, as the main component,
Includes 65 to 88 parts by weight of polyadipate/terephthalate, 10 to 20 parts by weight of reinforcing and toughening agent, 0.5 to 30 parts by weight of lubricant, and 1 to 5 parts by weight of dispersant.

Among them, the lubricant is one or two of polymer PMMA microspheres and silica microspheres. The particle size of the polymer PMMA microspheres is 0.5 to 5 μm, and the particle size of the silica microspheres is 1 to 5 μm, both of which can be directly purchased on the market.

In the present invention, the lubricant acts to lubricate the openings of the film, is advantageous for opening the film when processing an ultrathin fully biodegradable film, and the particle size of the microspheres is less than 5 μm. Therefore, the mechanical properties and translucency of the ultrathin fully biodegradable film produced later can be guaranteed.

The dispersant according to the present invention is one or two selected from the epoxidized soybean oil and the organic silicone diffusion oil. By selectively using the dispersant, the dispersant can be better blended with the toughening and transparency enhancing agent, which is advantageous for dispersion of the toughening and transparency enhancing agent in the carrier resin. Further, in the technique of the present invention, it is possible to disperse by a known physical dispersion method instead of the addition of the dispersant and the organic solvent, but the effect is lower than when the dispersant is added. The method of addition is preferred.

All additives according to the present invention are environmentally friendly reagents and materials and are completely decomposed in nature.

The method for producing an enhanced toughening and transparent masterbatch for the ultrathin completely biodegradable film,
A step (1) of obtaining a mixture by melting a predetermined amount of an enhanced toughening agent and a dispersant in carbon tetrachloride for dispersion, stirring the mixture uniformly, and distilling carbon tetrachloride;
A step (2) in which the mixture obtained from the step (1), the polyadipate/terephthalate, and the lubricant are sequentially put in a high-speed mixer in parts by weight and kneaded for 10 to 30 minutes;
For the ultrathin completely biodegradable film, the homogeneously mixed mixture obtained from step (2) is put into a twin-screw extruder, extruded under the condition of 135 to 160° C., air cooled and granulated. A step (3) of obtaining an enhanced toughening and transparent masterbatch.

In the above-mentioned production method, the inventor first dissolves and disperses the enhanced toughening agent in carbon tetrachloride as a solvent, and then coats the dispersant on the surface of the enhanced toughening agent using a volatile solvent, The dispersing effect of the strengthening toughening agent is better than that of known mixing methods.

In addition, the manufacturing method without adding a dispersant and an organic solvent is
A step (1) of sequentially adding a predetermined amount of a strengthening/toughening agent, a polyadipate/terephthalate, and a lubricant in a high-speed mixer in parts by weight and kneading for 10 to 30 minutes;
The uniformly mixed mixture obtained from the step (1) is put in a twin-screw extruder, extruded under the condition of 135 to 160° C., air-cooled and granulated, and for ultrathin completely biodegradable film A step (2) of obtaining an enhanced toughening and transparent masterbatch.

After obtaining the enhanced toughening/transparency masterbatch for the ultrathin fully biodegradable film, the inventor further provides a specific application of the masterbatch, which is an ultrathin ultratransparent fully biodegradable film. Used for blow molded film grade materials. This film blow molding film grade material, when calculated in parts by weight, as the main component,
Includes 80 to 90 parts by weight of polyadipate/terephthalate, 0.5 to 20 parts by weight of polylactic acid, and 1 to 5 parts by weight of enhanced toughening and transparent masterbatch for ultrathin completely biodegradable film.

Among them, polyadipate/terephthalate and polylactic acid are used as carrier resins, the melt flow rate is 2 to 5 g/10 min, the acid value is less than 15, which is the same as the standard of polyadipate/terephthalate in the masterbatch material. And the melt flow rate of the polylactic acid is 2 to 5 g/10 min.

The manufacturing method of the corresponding blow molded film grade material is
A process of adding polyadipate/terephthalate, polylactic acid, and an ultra-thin ultra-transparent type fully enhanced biodegradable film toughening and increasing transparency masterbatch into a high-speed mixer and stirring at a speed stirring speed of 700 to 1000 r/min for 5 to 8 minutes. (1),
The step (2) of putting the uniformly mixed mixture in a twin-screw extruder, extruding the mixture under conditions of 135 to 160° C., air cooling and granulating is included.

The blow-molded film grade material obtained by the method described above can be directly formed into an ultrathin film having a thickness of 6 μm or less, and its tensile strength and tear elongation ratio are superior to those of the LLDPE film having the same thickness. It can completely replace PE products, has excellent processing performance, and does not need to be processed by special manufacturing equipment.

In addition to the above film masterbatch, the inventor further provided an ultra-thin fully biodegradable multi-film enhanced toughening and transparency masterbatch. When calculated in parts by weight, as the main component,
65 to 85 parts by weight of polyadipate/terephthalate, 1 to 20 parts by weight of polylactic acid, 10 to 20 parts by weight of reinforcing and toughening agent, 5 to 30 parts by weight of lubricant, 1 to 5 parts by weight of dispersant, and 1 to stabilizer. Including 5 parts by weight.

Among them, polylactic acid and polyadipate/terephthalate are used as a carrier resin, the melt flow rate thereof is 2 to 5 g/10 min, the acid value is less than 15, which is the same standard as polyadipate/terephthalate.

The lubricants and dispersants used above are the same as the candidate substances for the film masterbatch, so the inventor will not repeat them here. The stabilizer is one or two of an ultraviolet absorber and an ultraviolet stabilizer, and the ultraviolet absorber is a low-volatile benzotriazole ultraviolet absorber Tinuvin 234. The UV stabilizer is a sterically hindered amine stabilizer Uvinul (registered trademark) 5050H, which can prevent the photodegradation problem during the process of processing an ultra-thin completely biodegradable film and in the field, and extend the service life. You can

The inventor has also provided a method for producing the masterbatch for enhanced toughness and transparency for mulch film. The manufacturing method is
A step (1) of dissolving a predetermined amount of a strengthening/toughening agent and a dispersant in carbon tetrachloride to disperse and uniformly stirring, and then distilling carbon tetrachloride to obtain a mixture;
The mixture obtained from the step (1), polyadipate/terephthalate, polylactic acid, stabilizer and lubricant were sequentially added to a high speed mixer in parts by weight and stirred at a speed of 700 to 1000 r/min for 10 to 30 minutes. Kneading step (2),
For the ultrathin completely biodegradable film, put the uniformly mixed mixture obtained from step (2) in a twin-screw extruder, extrude under the condition of 135-160° C., air cool and granulate. A step (3) of obtaining an enhanced toughening and transparent masterbatch.

Similarly, the masterbatch may be dispersed by a known physical dispersion method instead of the dispersant. For the specific method, the manufacturing method of the above-mentioned masterbatch for enhancing toughness and transparency for ultrathin biodegradable film may be referred to.

As described above, the masterbatch provided by the present invention is manufactured by using polyadipate/terephthalate and an enhanced toughening/clarifying agent as main materials, and can be processed into not only a film but also a multi-film. It is possible to maintain the smooth processing of thin, completely biodegradable film products, maintain mechanical and optical properties, and use stability, and significantly reduce the cost of raw materials. The production process of this masterbatch is simple and easy to grasp, and the obtained masterbatch has stable properties, has no water content, is completely decomposed, and has good dispersibility. By adding a small amount of the masterbatch of the present invention, an ultra-thin completely biodegradable film product having a size of 6 μm or less can be formed, and it is easy to open the bubbles in the ultra-thin complete film forming process and the processing stability is enhanced. It also has mechanical properties and can be widely applied to film packaging, shopping bags, agricultural mulch film, garbage bags and separate landfills, and composting processing.

(Example 1)
The components of the enhanced toughening and transparent masterbatch for ultrathin completely biodegradable film are as follows, calculated in parts by weight.
Polyadipate/terephthalate 75 parts by weight Hydrophobic nanosilica (particle size 5-10 nm) 20 parts by weight Polymer PMMA microspheres (particle size 2-3 μm) 30 parts by weight Epoxidized soybean oil 1 part by weight

It is produced by the following steps.
Hydrophobic nanosilica and epoxidized soybean oil are dissolved and dispersed in carbon tetrachloride, stirred uniformly, carbon tetrachloride is distilled to obtain mixture 1, and mixture 1, polyadipate/terephthalate and polymer PMMA microspheres are spun at high speed. Put in a mixer one by one, knead at a speed of 700 to 1000 r/min for 10 to 30 minutes to obtain a mixture 2, put the mixture 2 in a twin-screw extruder, extrude under the condition of 135 to 160° C., and air cool. And granulated to obtain a masterbatch with enhanced toughness and transparency for ultrathin completely biodegradable film.

The masterbatch is used to produce an ultrathin ultratransparent fully biodegradable film blow molded film grade material. When calculated in parts by weight, as the main ingredients,
Includes 87 parts by weight of polyadipate/terephthalate, 10 parts by weight of polylactic acid, and 3 parts by weight of masterbatch for strengthening/toughening/permeation for ultra-thin ultra-transparent bright fully biodegradable film.

Among them, the polyadipate/terephthalate is used as a carrier resin, the melt flow rate is 5 g/10 min, and the acid value is less than 15. The melt flow rate of the polylactic acid is 2.5 g/10 min.

The method for producing the ultra-thin ultra-transparent bright fully biodegradable film blow molded film grade material is as follows:

The polyadipate/terephthalate, polylactic acid, and the ultra-thin ultra-transparent enhanced bioreinforcing film-reinforced masterbatch were placed in a high-speed mixer and stirred at a speed of 700 to 1000 r/min for 5 to 8 minutes, and then the above-mentioned process was performed. The uniformly mixed mixture is put into a twin-screw extruder, extruded under the condition of 135 to 160° C., air-cooled and granulated to obtain an ultrathin ultra-transparent completely biodegradable film blow-molded film grade material.

Using the ultra-thin ultra-transparent type fully biodegradable film blow-molded film grade material provided by this example, a film product of 5±1 μm can be molded and stored at room temperature for 12 months while avoiding direct sunlight. When it does, there is no significant change in mechanical properties. The tensile strength is 30 MPa, and the stretching ratio in the machine direction and the transverse direction exceeds 900% in total.

(Example 2)
The components of the enhanced toughening and transparent masterbatch for ultrathin completely biodegradable film are as follows, calculated in parts by weight.
Polyadipate/terephthalate 69 parts by weight Hydrophobic nanosilica (particle size 5-10 nm) 10 parts by weight Aike CE-AZ01 10 parts by weight Silica microspheres (particle size 2-3 μm) 10 parts by weight Epoxidized soybean oil 0.5 parts by weight Organic Silicone diffusion oil 0.5 parts by weight

It is produced by the following steps.
Hydrophobic nanosilica, epoxidized soybean oil and organic silicone diffusion oil are dissolved and dispersed in carbon tetrachloride, stirred uniformly, carbon tetrachloride is distilled to obtain mixture 1, and mixture 1, polyadipate/terephthalate and PO Aike CE to AZ01 and silica microspheres were sequentially put into a high speed mixer and kneaded at a speed of 700 to 1000 r/min for 10 to 30 minutes to obtain a mixture 2, and the mixture 2 was put in a twin-screw extruder and put in a tube. It is extruded under the condition of ~160°C, air-cooled and granulated to obtain an ultra-thin fully biodegradable film enhanced toughening and transparent masterbatch.

The masterbatch is applied to produce an ultrathin ultratransparent fully biodegradable film blow-molded film grade material. When calculated in parts by weight, as the main ingredients,
Includes 85 parts by weight of polyadipate/terephthalate, 10 parts by weight of polylactic acid, and 5 parts by weight of masterbatch for strengthening/toughening/transparency for ultra-thin ultra-transparent completely biodegradable film.

Among them, the polyadipate/terephthalate is used as a carrier resin, the melt flow rate is 5 g/10 min, and the acid value is less than 15. The melt flow rate of the polylactic acid is 2.5 g/10 min.

The method for producing the ultra-thin ultra-transparent completely biodegradable film blow-molded film grade material is as follows.
The polyadipate/terephthalate, polylactic acid, and the ultra-thin ultra-transparent, bright and completely biodegradable film enhanced and toughening/transparent masterbatch were put into a high-speed mixer, and the mixture was stirred at a speed of 700 to 1000 r/min for 5 to 8 minutes, and The uniformly mixed mixture was put in a twin-screw extruder, extruded under the condition of 135 to 160° C., air-cooled and granulated to obtain an ultrathin ultra-transparent completely biodegradable film blow-molded film grade material. ..

The ultra-thin ultra-transparent fully biodegradable film blow molded film grade material provided by this example can be used to mold film products of 5±1 μm. There is no change in mechanical properties when stored at room temperature for 12 months while avoiding direct sunlight. The tensile strength is 35 MPa, and the stretching ratio in the longitudinal and transverse directions exceeds 800% in total.

(Example 3)
The components of the enhanced toughening and transparent masterbatch for ultrathin completely biodegradable film are as follows, calculated in parts by weight.
Polyadipate/terephthalate 68 parts by weight Hydrophobic nanosilica (particle size 10 to 20 nm) 15 parts by weight Arkema AX-8900 5 parts by weight Silica microspheres (particle size 1 μm) 5 parts by weight Organic silicone diffusion oil 2 parts by weight

It is produced by the following steps.
Hydrophobic nanosilica and organosilicone diffusion oil are dissolved and dispersed in carbon tetrachloride, stirred uniformly, carbon tetrachloride is distilled to obtain mixture 1, mixture 1, polyadipate/terephthalate and poly Arkema AX-8900. , Silica microspheres were sequentially put into a high-speed mixer, and kneaded at a speed of 700 to 1000 r/min for 10 to 30 minutes to obtain a mixture 2, and the mixture 2 was put into a twin-screw extruder and heated at a temperature of 135 to 160°C. Under high pressure, air-cooled and granulated to obtain an enhanced thinness toughening and transparency masterbatch for ultrathin fully biodegradable film.

The masterbatch is used to produce an ultrathin ultratransparent fully biodegradable film blow molded film grade material. When calculated in parts by weight, as the main component,
Includes 90 parts by weight of polyadipate/terephthalate, 5 parts by weight of polylactic acid, and 5 parts by weight of masterbatch for strengthening/toughening/permeation for ultra-thin ultra-transparent completely biodegradable film.

Among them, the polyadipate/terephthalate is used as a carrier resin, and its melt flow rate is 5 g/10 min. The melt flow rate of the polylactic acid is 2.5 g/10 min.

The method for producing the ultra-thin ultra-transparent completely biodegradable film blow-molded film grade material is as follows.
The polyadipate/terephthalate, polylactic acid, and the ultra-thin ultra-transparent enhanced bioreinforcing film-reinforced masterbatch were placed in a high-speed mixer and stirred at a speed of 700 to 1000 r/min for 5 to 8 minutes, and then the above-mentioned process was performed. The uniformly mixed mixture is put into a twin-screw extruder, extruded under the condition of 135 to 160° C., air-cooled and granulated to obtain an ultrathin ultra-transparent completely biodegradable film blow-molded film grade material.

The ultra-thin ultra-transparent fully biodegradable film blow molded film grade material provided by this example can be used to mold film products of 5±1 μm. There is no change in the mechanical properties when stored at room temperature for 12 months while avoiding direct sunlight; the tensile strength is 28MPA; the stretching ratio in the longitudinal and transverse directions exceeds 750% in total.

(Example 4)
In the case of applying the enhanced toughening and transparent masterbatch for the ultrathin completely biodegradable film obtained in Example 1 described above to the blow molding of the ultrathin film, there are two types of addition methods. In one, the masterbatch is directly mixed with a blow molding material in an amount of 1 to 20% by weight of an ultrathin film component, put into a blow molding machine and extruded and molded. The other is a method in which the masterbatch is mixed with 1 to 20% by weight of the ultrathin film component together with other components, granulated, put into a blow molding machine, and extruded to be blow molded.

(Application Example 1)
Ingredients and amount added (parts by weight)
PBAT 90 parts by weight PLA 5 parts by weight Enhanced super-tough and translucent masterbatch for ultra-thin fully biodegradable film produced in Example 1
5 parts by weight

The manufacturing process is to weigh each raw material by the above-mentioned blending method, put it in a high speed mixer, and stir for 5 minutes. After uniformly mixing, the mixture is extruded by a twin-screw extruder and granulated. The mixture is put in a hopper of a blow molding machine, blow-molded into a uniform cylindrical film (having a thickness of 4 to 6 μm), cut and wound to produce an ultrathin completely biodegradable film.

(Application Example 2)
Ingredients and amount added (parts by weight)
PBAT 92 parts by weight PPC 5 parts by weight Enhanced thinning and strengthening transparency masterbatch for the ultrathin fully biodegradable film produced in Example 1
3 parts by weight

The manufacturing process is to weigh each raw material by the above-mentioned blending method, put it in a high speed mixer, and stir for 5 minutes. After mixing evenly, put the mixture in the hopper of blow molding machine, blow mold into a uniform cylindrical film (if the thickness is 4 to 6 μm), cut and wind to obtain ultrathin complete biodegradability. Produce a film.

GB/T1040.3 Third Part of Plastic Tensile Property Measurements: The conditions for testing films and sheets were a pulling speed of 200 mm/min, and the properties of the resulting films are as shown in the table below. The comparative example is a film produced by adopting an equivalent resin and adding no strengthening/toughening/transparency masterbatch for an ultrathin completely biodegradable film.

+: The opening property is good and the film cannot be cut. +-: Openable, but the film is easily cut. --: The film is difficult to open and the film is easily cut.

As can be confirmed from the above, the ultrathin fully biodegradable film produced by using the enhanced thinning/toughening/transparency masterbatch for the ultrathin fully biodegradable film produced by the present invention has a light transmittance and a tensile strength. In addition, the tear stretch ratio is superior to that of a fully biodegradable film having a large thickness, and also has good processability.

(Example 5)
GB/T 1040.3 This is the third part of the measurement of plastic tensile properties. The conditions of the film and sheet test are as follows: the pulling speed is 200 mm/min, and the properties of the films obtained by using the blow-molded film grade materials in Examples 1 to 3 are as shown in the table below.
The comparative example is an LLDPE film having the same thickness.

As can be confirmed from the above, the ultrathin completely biodegradable film formed by using the blow-molded film grade material produced according to the present invention has good light transmittance, and has the same tensile strength and tear stretch ratio as LLDPE. Better than film, it can completely replace PE film. It also has good processing performance and does not need to be manufactured with special processing equipment. The film products manufactured using the resin of the present invention have good stability at room temperature, can be stored for 12 months without direct sunlight, and have excellent mechanical properties. They are film packaging, shopping bags, waste landfills, and composting. Can be widely used for processing.

(Example 7)
The components of the enhanced toughening and transparent masterbatch for ultrathin fully biodegradable mulch film are as follows, calculated in parts by weight.
Polyadipate/terephthalate 67 parts by weight Polylactic acid 1 part by weight Hydrophobic nanosilica (particle size 5-10 nm) 20 parts by weight Polymer PMMA microspheres (particle size 2-3 μm) 10 parts by weight Epoxidized soybean oil 2 parts by weight UV absorber Tinuvin 234 1 part by weight

It is produced by the following steps.
Hydrophobic nanosilica and epoxidized soybean oil are dissolved and dispersed in carbon tetrachloride, stirred uniformly, carbon tetrachloride is distilled to obtain mixture 1, and mixture 1, polyadipate/terephthalate, polylactic acid, UV absorption The agent Tinuvin 234 and the polymer PMMA microspheres were sequentially charged into a high-speed mixer and kneaded at a speed of 700 to 1000 r/min for 10 to 30 minutes to obtain a mixture 2, and the mixture 2 was put into a twin-screw extruder and heated to 135-135. It is extruded under the condition of 160° C., air-cooled and granulated to obtain an ultra-thin fully biodegradable reinforced multi-film enhanced toughening and transparent masterbatch.

(Example 8)
The components of the enhanced toughening and transparent masterbatch for ultrathin fully biodegradable mulch film are as follows, calculated in parts by weight.
Polyadipate/terephthalate 69 parts by weight Polylactic acid 10 parts by weight Hydrophobic nanosilica (particle size 15 to 25 nm) 10 parts by weight Aike CE-AZ01 10 parts by weight Silica microspheres (particle size 2 to 3 μm) 5 parts by weight Organic silicone diffusion oil 1 Parts by weight UV absorber Tinuvin 234 2.5 parts by weight UV stabilizer Uvinul® 5050H 2.5 parts by weight

It is produced by the following steps.
Hydrophobic nanosilica and organic silicone diffusion oil are dissolved and dispersed in carbon tetrachloride, uniformly stirred, carbon tetrachloride is distilled to obtain mixture 1, and mixture 1, polyadipate/terephthalate, polylactic acid, Aike CE ~AZ01, UV absorber Tinuvin 234, UV stabilizer Uvinul (registered trademark) 5050H, and silica microspheres are sequentially put into a high-speed mixer, and stirred and kneaded at a speed of 700 to 1000 r/min for 10 to 30 minutes to obtain a mixture. 2, the mixture 2 was put into a twin-screw extruder, extruded under the condition of 135 to 160° C., air-cooled and granulated, and an ultrathin fully biodegradable multi-film enhanced toughening and transparency master. Get a batch.

(Example 9)
The components of the enhanced toughening and transparent masterbatch for ultrathin fully biodegradable mulch film are as follows, calculated in parts by weight.
Polyadipate/terephthalate 85 parts by weight Polylactic acid 20 parts by weight Hydrophobic nanosilica (particle size 10 to 20 nm) 10 parts by weight Arkema AX-8900 10 parts by weight Silica microspheres (particle size 1 μm) 1 part by weight UV stabilizer Uvinul (registered trademark) ) 5050H 2.5 parts by weight Organic silicone diffusion oil 1.5 parts by weight

It is obtained by manufacturing as follows.
Hydrophobic nanosilica and organic silicone diffusion oil are dissolved and dispersed in carbon tetrachloride, uniformly stirred, carbon tetrachloride is distilled to obtain mixture 1, and mixture 1, polyadipate/terephthalate, UV stabilizer Uvinul( (Registered trademark) 5050H, Arkema AX-8900 and silica microspheres are sequentially put in a high-speed mixer, stirred at a speed of 700-1000 r/min for 10-30 minutes to knead to obtain a mixture 2, and a mixture 2 is mixed. It is put into a shaft extruder, extruded under the condition of 135 to 160° C., air-cooled and granulated to obtain an ultrathin fully biodegradable reinforced multi-film enhanced toughening and transparent masterbatch.

(Example 10)
There are mainly two types of addition methods for using the ultrathin fully biodegradable multi-film enhanced and toughening/permeable masterbatch of the present invention for blow molding of ultra-thin multi-film. One is to directly mix the masterbatch with blow-molded film grade material at 1 to 5% by weight of the ultrathin mulch film component, put it in a blow molding machine and extrude it. The other is to mix the masterbatch with other components in an amount of 1 to 5% by weight of the ultrathin mulch film component and granulate it, and then put it into a blow molding machine and extrude it.

(Application Example 3)
Ingredients and amounts (parts by weight)
90 parts by weight of PBAT 5 parts by weight of PLA 5 parts by weight of masterbatch with enhanced toughness and transparency for ultra-thin fully biodegradable mulch film manufactured in Example 7

The manufacturing process is to weigh each raw material by the above-mentioned blending method, put it in a high speed mixer, and stir for 5 minutes. After uniformly mixing, the mixture is extruded by a twin-screw extruder and granulated. The mixture is placed in the hopper of a blow molding machine, blow molded into a uniform cylindrical mulch film (if the thickness is 4-5 μm), cut and wound to produce an ultrathin fully biodegradable mulch film. Get it.

(Application Example 4)
Ingredients and amount added (parts by weight)
92 parts by weight of PBAT 5 parts by weight of PPC 3 parts by weight of masterbatch with enhanced toughness and transparency for ultra-thin fully biodegradable mulch film manufactured in Example 7

The manufacturing process is to weigh each raw material by the above-mentioned blending method, put it in a high speed mixer, and stir for 5 minutes. After uniformly mixing, the mixture is put into a hopper of a blow molding machine, blow-molded into a uniform cylindrical multi-film (having a thickness of 4 to 5 μm, a width of 90 to 200 cm), cutting and winding. Obtained by taking ultra thin thin biodegradable mulch film.

GB/T1040.3 PLASTICHIK THICK PATTERN 3rd Part of Measurement of Tensile Properties: The conditions of the film and sheet tests were a tensile speed of 200 mm/min, and the respective properties of the obtained film are as shown in the table below. The comparative example is a mulch film produced by using an equivalent resin and adding no masterbatch for enhancing toughness and transparency for ultrathin completely biodegradable films.

+: The opening property is good and the film cannot be cut. +-: Openable, but the film is easily cut. --: The film is difficult to open and the film is easily cut.

As can be confirmed from the above, the ultrathin fully biodegradable mulch film produced by using the ultra-thin fully biodegradable mulch film enhanced strengthening/transparency masterbatch produced by the present invention has a light transmittance, It has superior tensile strength and tear draw ratio to the fully biodegradable mulch film with high thickness, and also has good processability.

Claims (10)

An enhanced toughening and transparent masterbatch,
When calculated in terms of parts by weight, the main components include polyadipate/terephthalate 65 to 88 parts by weight and an enhanced toughening/thickening agent 10 to 20 parts by weight.
An enhanced toughening and transparent masterbatch characterized by the following. The melt flow rate of the polyadipate/terephthalate is 2 to 5 g/10 min, the acid value is less than 15, and the enhanced toughening agent is an inorganic enhanced toughening agent or an organic enhanced toughening agent. One or more of
The enhanced toughening and transparent masterbatch according to claim 1, wherein The inorganic enhanced toughening agent is selected from hydrophobic nanosilica, the particle size of the hydrophobic nanosilica is 5 to 25 nmx, and the organic enhanced toughening agent is Arkema AX-8900, ADX to 1200s resin compatibilization. Agent or one or more of Hangzhou Aike CE to AZ01 compatibilizer,
The enhanced toughening and transparent masterbatch according to claim 1, wherein A masterbatch with enhanced toughness and transparency for ultra-thin fully biodegradable film,
Main components include 65 to 88 parts by weight of polyadipate/terephthalate, 10 to 20 parts by weight of reinforcing and toughening agent, 0.5 to 30 parts by weight of lubricant, and 1 to 5 parts by weight of dispersant,
The melt flow rate of the polyadipate/terephthalate is 2-5 g/10 min, the acid value is less than 15, and the lubricant is one or two of polymer PMMA microspheres or silica microspheres, The dispersant is one or two selected from epoxidized soybean oil or organic silicone diffusion oil,
A masterbatch with enhanced toughness and transparency for ultra-thin completely biodegradable films. A method for producing an enhanced toughening and transparent masterbatch for an ultra-thin completely biodegradable film,
A step (1) of dissolving a predetermined amount of a strengthening/toughening agent and a dispersant in carbon tetrachloride to disperse and uniformly stirring, and distilling carbon tetrachloride to obtain a mixture;
A step (2) in which the mixture obtained from the step (1), polyadipate/butylene terephthalate, and a lubricant are sequentially put in a high-speed mixer in parts by weight and kneaded for 10 to 30 minutes;
The homogeneously mixed mixture obtained from the step (2) is put into a twin-screw extruder, extruded under the condition of 135 to 160° C., air-cooled and granulated to enhance the ultrathin completely biodegradable film. A step (3) of obtaining a toughening and transparent masterbatch,
A method for producing an enhanced toughening and transparent masterbatch for an ultra-thin completely biodegradable film, which is characterized by the above. An ultra-thin fully biodegradable multi-film enhanced toughening and transparent masterbatch,
When calculated in terms of parts by weight, the main components are polyadipate/terephthalate 65 to 85 parts by weight, polylactic acid 1 to 20 parts by weight, an enhanced toughening and transparent agent 10 to 20 parts by weight, a lubricant 0.5 to 30 parts by weight, 1 to 5 parts by weight of a dispersant and 1 to 5 parts by weight of a stabilizer,
The polyadipate/terephthalate has a melt flow rate of 2 to 5 g/10 min and an acid value of less than 15, and the polylactic acid has a melt flow rate of 2 to 5 g/10 min and an acid value of less than 15. And the lubricant is one or two of polymer PMMA microspheres or silica microspheres, and the dispersant is one or two selected from epoxidized soybean oil or organic silicone diffusion oil, and The stabilizer is one or two of an ultraviolet absorber or an ultraviolet stabilizer,
An ultra-thin fully biodegradable multi-film enhanced and toughened and transparent masterbatch. The UV absorber is a low-volatile benzotriazole-based UV absorber Tinuvin 234, and the UV stabilizer is a sterically hindered amine stabilizer Uvinul® 5050H,
The enhanced thinning/toughening/transparency masterbatch for an ultrathin completely biodegradable mulch film according to claim 6. A method for producing an enhanced toughening and transparent masterbatch for ultrathin completely biodegradable mulch film,
Obtained from step (1) and step (1) in which a predetermined amount of the strengthening/toughening agent and dispersant are dissolved and dispersed in carbon tetrachloride, and after uniformly stirring, carbon tetrachloride is distilled to obtain a mixture. And the step (2) in which the mixture, polyadipate/butylene terephthalate, polylactic acid, stabilizer and lubricant are sequentially added to a high-speed mixer in parts by weight and stirred at a speed of 700 to 1000 r/min for 10 to 30 minutes. ,
For the ultrathin fully biodegradable mulch film, put the uniformly mixed mixture obtained from step (2) into a twin-screw extruder, extrude under conditions of 135-160°C, air cool and granulate. And (3) obtaining an enhanced toughening and transparent masterbatch.
A method for producing a masterbatch having enhanced toughness and transparency for an ultra-thin completely biodegradable mulch film, which is characterized by the above. An ultra-thin ultra-transparent fully biodegradable film blow molding film grade material manufactured by applying an enhanced toughening and transparency masterbatch for ultra-thin fully biodegradable film,
Calculated in parts by weight, the main components are polyadipate/terephthalate 80 to 90 parts by weight, polylactic acid 0.5 to 20 parts by weight, ultra-thin fully biodegradable film enhanced toughening and transparency masterbatch 1 to 5 parts by weight. Including parts,
The carrier resin is polyadipate/terephthalate, the melt flow rate is 2 to 5 g/10 min, the acid value is less than 15, and the melt flow rate of the polylactic acid is 2 to 5 g/10 min.
Ultra-thin ultra-transparent fully biodegradable film blow-molded film grade material manufactured by applying an enhanced toughening/transparency masterbatch for ultra-thin fully biodegradable film. A method for producing an ultra-thin ultra-transparent fully biodegradable film blow-molded film grade material produced by applying an enhanced toughening and transparency masterbatch for ultrathin fully biodegradable film,
A step of adding polyadipate/butylene terephthalate, polylactic acid, and an ultra-thin ultra-transparent type fully enhanced biodegradable film enhanced toughening/transparency masterbatch into a high-speed mixer and stirring at a speed of 700 to 1000 r/min for 5 to 8 minutes (1 )When,
A step (2) in which the above-mentioned homogeneously mixed mixture is put into a twin-screw extruder, extruded under the condition of 135 to 160° C., air-cooled and granulated to obtain.
A method for producing an ultra-thin ultra-transparent fully biodegradable film blow-molded film grade material produced by applying an enhanced toughening/transparency masterbatch for an ultrathin fully biodegradable film.