KR20190126890A - Fully biodegradable mulching film to mechanically mulch film - Google Patents

Abstract

The present invention relates to the field of agricultural materials, and more particularly to a fully biodegradable mulching film capable of mechanically mulching the film. The anchovy film is composed of a complete biodegradable resin, an auxiliary for strengthening strength, toughening and light transmitting, and a processing aid; In this case, the addition of the strength enhancing, toughness enhancing, and light-transmitting auxiliary agents may solve the problem of insufficient mechanical strength, easy breakage, and difficult mechanical film mulching in the ultra-thin mulching film; The use of processing aids solves the problem of processing separation of ultra-thin films, and can also solve the problem of low processing efficiency; In addition, by selecting a suitable type of fully biodegradable resin, and using a functional aid, a mulching film that can control the complete bioseparation of ultra-thin ultra-transparent ultra-high strength of 4-6 μm in thickness is developed. Transparency of the mulching film is high, light transmittance> 90%, haze value <13%; The mechanical strength is high, the tensile strength is> 25MPa, and the film strength is applicable to general film mulching machines. Tensile strength, burst tensile and orthogonal tear strength all meet the criteria for mechanically mulching films in PE film mulching. Physical and mechanical performance complies with GB13735-92.

Description

Fully biodegradable mulching film to mechanically mulch film

The present invention relates to the field of agricultural materials, and more particularly to a fully biodegradable mulching film capable of mechanically mulching the film.

Mulching films play a very large role in agricultural production, but most of the plastic films in use today are polyolefin films that are difficult to decompose in a short time, or polyolefin films that do not decompose with addition of starch and photolysis aid. The use of such mulching film materials causes 'white pollution' in the environment, which poses a safety problem for the continuous development of mankind. Fully biodegradable mulching films can be blow molded using fully biodegradable plastics or made by casting processing means, and can be completely decomposed into microorganisms, the resulting end products being carbon dioxide and water, which can be processed naturally. have. Therefore, the fully biodegradable film has a very important development and use value and prospect as an important means to replace the polyolefin products of the prior art and to solve the white pollution of the agricultural field.

At present, companies such as Germany BASF, Japan Mitsubishi, France's Limagrain Group, China's Guangdong Blonde Company, Shandong Medical Co., Ltd. and Hangzhou Bridal Pharmaceutical Co., Ltd. produce mulching film. In addition, the experiment was used to produce crops such as corn, cotton, peanuts, tobacco, garlic, potatoes, and strawberries. However, in general, the thickness of the film is thick, the cost is high, the processing stability after the thickness reduction is low, and the layer is difficult to open; And mechanical performance is poor and mechanical film mulching is impossible; It has a low weather resistance, becomes crispy when exposed to strong light, and has a very fast decomposition cycle. These problems limit the spread and application of fully biodegradable mulching film.

The present invention provides a type of fully biodegradable mulching film that can be mechanically film mulched in order to solve many problems of the prior art. The anchovy film is composed of a complete biodegradable resin, an auxiliary for strengthening strength, toughening and light transmitting, and a processing aid; In this case, the addition of the strength enhancing, toughness enhancing, and light-transmitting auxiliary agents may solve the problem of insufficient mechanical strength, easy breakage, and difficult mechanical film mulching in the ultra-thin mulching film; The use of processing aids solves the problem of processing separation of ultra-thin films, and can also solve the problem of low processing efficiency; In addition, by selecting a suitable type of fully biodegradable resin, and using a functional aid, a mulching film that can control the complete bioseparation of ultra-thin ultra-transparent ultra-high strength of 4-6 μm in thickness is developed. Transparency of the mulching film is high, light transmittance> 90%, haze value <13%; The mechanical strength is high, the tensile strength is> 25MPa, and the film strength can be applied to the general film mulching machine. Tensile strength, burst tensile and orthogonal tear strength all meet the criteria for mechanically mulching films in PE film mulching. Physical and mechanical performance meets the requirements of GB13735-92.

Specific technical solutions of the present invention are as follows.

In a type of fully biodegradable mulching film that can be mechanically film mulched, its main components are calculated by weight and are as follows.

The total biodegradation resin is 70-98 parts by weight, the strength enhancing and toughness enhancing and light transmitting enhancement adjuvant is 1-8 parts by weight, and the processing aid is 1-3 parts by weight;

Wherein the complete biodegradable resin is one or more of polyadipic acid / polybutylene terephthalate, and polylactic acid, polypropylene carbonate;

Wherein the polyadipic acid / polybutylene terephthalate is a major component and combines with one or more of polylactic acid and polypropylene carbonate; Here, polyadipic acid / polybutylene terephthalate accounts for 85-95% of the complete biodegradable resin.

The fuse flow rate of the polyadipic acid / polybutylene terephthalate is l-2g / 10min, and an acid value <15; Wherein the fuse flow rate of the polylactic acid is 2-5g / 10min, and an acid value <15; Here, the fuse flow rate of the polypropylene carbonate is l-2g / 10min, the acid value <15.

The strength enhancing, toughness strengthening and light-transmitting supplements are one or more of inorganic strength strengthening and toughening and light-transmitting supplements, and organic strength strengthening and toughness-enhancing supplements.

The inorganic strength enhancing, toughening enhancing and light transmitting enhancing aids are selected from drainable nano silicon dioxide; The particle diameter of the drainable nano silicon dioxide is 2-25 nm; The organic strength reinforcement and toughening aids are ARKMA AX-8900 or ADX-1200s resin commercial reagents.

The processing aid is one or more of a polymeric PMMA microballoon and a silicon dioxide microballoon; The particle diameter of the polymer micro balloon is 1-5 μm, and the particle size of the silicon dioxide micro balloon is 1-5 μm.

In the present invention, the inventors mainly use polyadipic acid / polybutylene terephthalate as a complete biodegradable resin, the fuse flow rate is controlled at l-2g / 10min, and the acid value is <15; It is blended with other resins using its good toughness, and the performance is complemented with each other, resulting in a relatively good formability and processability of the film.

Based on the above-mentioned basic components, the inventor provides an ultra-thin ultra-reinforced ultra-transparent fully biodegradable mulching film which can be mechanically film-mulled, the main components of which are calculated by weight as follows.

The total biodegradation resin is 89-98 parts by weight, the auxiliary agent for strength enhancement, toughness enhancement and light transmission enhancement is 1-8 parts by weight, and the processing aid is 1-3 parts by weight.

Among the above-mentioned components, the inventors improve the mechanical and lightcasting performance by improving the amount of the complete biodegradable resin.

Specific steps of the corresponding manufacturing method are as follows.

The complete biodegradable resin, the strength enhancing and toughening and translucent strengthening, and the processing aid are stirred by weight in a high speed mixer for 5-8 min, then placed in a twin screw extruder and extruded at 135-160 ° C. And make a micro balloon and obtain a film blowing material dedicated to the fully biodegradable mulching film. Next, the film blowing material of the fully biodegradable mulching film is film blown in an extruder to obtain an ultra-thin film having a thickness of 4-6 μm. Here, the film blow-up ratio is 1.6-3.6, the gap of the dioripis is 0.8-1.8, the width of the film can be adjusted between 600-4000mm. The above-mentioned parameters strictly limit the gap of the lipolith and the film blow-up ratio, thereby ensuring good performance of the film.

Compared with the prior art, the ultra-thin ultra-strength ultra-transparent fully biodegradable mulching film that can be mechanically film-mulled has the following advantages.

1. The mulching film is 4-6μm thick, thinned mulching film lowers the cost of the unit area of the fully biodegradable mulching film.

2. The mulching film improves the transmittance not only by improving the mechanical performance (tensile strength> 25 MPa, suitable for the criteria of mechanical film mulching) by using an auxiliary agent for strengthening strength, strengthening toughness, and improving light transmittance. . (Light transmittance> 90%, haze value <13%)

3. The mulching film stabilizes the film blowing process by using a microsphere processing aid, and the mulching film becomes smooth and soft when separated processing.

4. The mulching film can be completely decomposed and the product is free of contamination.

In addition, the inventor further provides a fully biodegradable mulching film having ultrathin and weather resistance that can be a kind of mechanical film mulching based on the basic components. The major components are calculated by weight, as follows.

The complete biodegradable resin is 70-90 parts by weight, the aid of strength enhancement, toughness enhancement and light transmission enhancement is 1-8 parts by weight, the processing aid is 1-3 parts by weight, and the stability aid is 1-2 parts by weight.

Here, the stability aid is one or more of the ultraviolet stabilizer and the ultraviolet absorber. And the ultraviolet absorbent is Lowball Tinuvin234; The UV stabilizer is a hindered amine stabilizer Uvinul ^® 5050H.

Various main materials and auxiliaries employed in the present invention can be purchased directly from the market, except as otherwise described.

The manufacturing method of the fully biodegradable mulching film having the ultra-thin and weather resistance that can be mechanical film mulching described above is as follows.

(1) Distribute the complete biodegradable resin and the strength, toughness, and light-transmitting aids, stability aids, and processing aids by weight, stirring for 5-8 minutes using a high speed mixer, and then twin screw extruder. And extruded at 135-160 ° C. to make a micro balloon and obtain a dedicated film blowing material for a fully biodegradable mulching film.

(2) The film blowing material of the fully biodegradable mulching film is film blown in an extruder to obtain an ultra-thin film having a thickness of 4-6 μm. Here, the film blow-up ratio is 1.6-3.6, and the gap between the dioripipes is 0.8-1.8.

Compared with the prior art, the fully biodegradable mulching film having ultra-thin and weather resistance that can be mechanical film mulching has the following advantages.

1. The mulching film is 4-6μm thick, thinned mulching film lowers the cost of the unit area of the fully biodegradable mulching film.

2. The mulching film improves the transmittance not only by improving the mechanical performance (tensile strength> 25 MPa, suitable for the criteria of mechanical film mulching) by using an auxiliary agent for strengthening strength, strengthening toughness, and improving light transmittance. . (Light transmittance> 90%, haze value <13%)

3. The mulching film stabilizes the film blowing process by using a microsphere processing aid, and the mulching film becomes smooth and soft when separated processing.

4. The mulching film may be blended with a fully biodegradable resin and a functional aid, combining various thicknesses, and improving weather resistance of the mulching film; The mulching film is sprayed for 2-6 months, completely degradable, and the product is free of contamination.

Example  One

The raw material composition of the ultra-thin ultra-transparent ultra-high strength fully biodegradable mulching film that can be a kind of mechanical film mulching is calculated according to the weight fraction as follows.

Polyadipic acid / polybutylene terephthalate is 90% by weight;

Polylactic acid is 5 parts by weight;

Drainable nano silicon dioxide (particle size 2-25 nm) is 2 parts by weight;

The silicon dioxide micro balloon (particle size 1-4 μm) is 3 parts by weight.

It is manufactured according to the following steps.

Step 1: Place the components in a high speed mixer and stir to mix. There is no need to heat and stir for 5-8 min in a high speed mixer.

Step 2: The well mixed material is introduced into a twin screw extruder through Step 1, extruded at 135-160 ° C. to make a micro balloon and to obtain a dedicated film blowing material of the complete biodegradable film.

Step 3: The film blowing material obtained through step 2 is film blown in an extruder. The film blow-up ratio is 3.6, the gap between the dioripiles is 1.0 mm, the thickness is 0.004 mm, and the width is 4000 mm.

Example 2

The raw material composition of the ultra-thin ultra-transparent ultra-strength fully bio-mulling decomposition film that can be mechanical film mulching is calculated according to the weight fraction as follows.

Polyadipic acid / polybutylene terephthalate is 89% by weight;

Polypropylene carbonate is 5% by weight;

Drainable nano silicon dioxide (particle diameter 2-25 nm) is 4 weight part;

Silicon dioxide micro-balloons (particle size 2-3 μm) were 1 part by weight;

The polymer PMMA microballoons (particle size 2-3 μm) are 1 part by weight.

It is manufactured according to the following steps.

Step 1: Place the components in a high speed mixer and stir to mix. There is no need to heat and stir for 5-8 min in a high speed mixer.

Step 2: The mixed material is introduced into the twin screw extruder through Step 1, extruded at 135-160 ° C. to make a micro-balloon, and obtain a dedicated film blowing material of the complete biodegradable anchovy film.

Step 3: The film blowing material obtained in step 2 is film blown in an extruder. The film blow-up ratio is 2.3, the gap between the diodes is 1.0 mm, the thickness is 0.006 mm, and the width is 900 mm.

Example 3

The raw material composition of the ultra-thin, ultra-transparent, ultra-high strength biodegradable film that can be mechanically filmed is calculated by weight:

Polyadipic acid / polybutylene terephthalate is 85% by weight;

Polylactic acid is 5 parts by weight;

Polypropylene carbonate is 5% by weight;

Drainable nano silicon dioxide (particle diameter 2-25 nm) is 2 parts by weight;

Silicon dioxide micro balloons (particle size 2-3 mu m) were 3 parts by weight;

It is manufactured according to the following steps.

Step 1: Place the components in a high speed mixer and stir to mix. There is no need to heat and stir for 5-8 min in a high speed mixer.

Step 2: The well mixed material is introduced into the twin screw extruder through Step 1, extruded at 135-160 ° C. to make a micro balloon and to obtain a dedicated film blowing material of the fully biodegradable mulching film.

Step 3: The film blowing material obtained in step 2 is film blown in an extruder. The film blow-up ratio is 1.6, the gap between the dioripipes is 0.8 mm, the thickness is 0.005 mm, and the width is 900 mm.

Experimental Example 1

Tensile rate is 200mm / min according to the measurement result of tensile property of GB13735-92 plastic. The performance of the obtained ultra-thin super strong ultra-transparent fully biodegradable mulching film is shown in Table 1.

Example 1 Example 2 Example 3 Thickness (μm) 4 6 5 Light transmittance (%) 91.9 90.5 90.0 Haze value 11.0 12.4 12.6 Tensile Strength (MPa) 28 28 26 Sum of transverse elongation and longitudinal elongation (%) 900 856 820 Right angle tear strength (N / mm) 120 115 109 Separation of film mulching Separation Smooth and soft so the film does not tear Separation Smooth and soft so the film does not tear Separation Smooth and soft so the film does not tear

The ultra-thin ultra-transparent ultra-high strength biodegradable mulching film made of the present invention through the decomposition experiment of ultra-thin ultra-transparent ultra-high strength fully biodegradable mulching film has a high transparency, a light transmittance of> 90%, and a haze value of <13. %ego; The mechanical strength is high, the tensile strength is> 25 MPa, and the film film can be mechanically filmed using a general film mulching machine. Film mulching cultivation of wintering garlic can meet garlic's six-month growing demand. In addition, the mulching film may be completely decomposed.

Example 4

The raw material composition of the fully biodegradable mulching film having ultra-thin and weather resistance that can be mechanical film mulching is calculated by weight.

Polyadipic acid / polybutylene terephthalate is 88.7 parts by weight;

Polylactic acid is 5 parts by weight;

Drainable nano silicon dioxide (particle size 2-25 nm) is 2 parts by weight;

Silicon dioxide micro-balloons (particle size: 1 μm) were 3 parts by weight;

Ultraviolet absorbent Tinuvin234 is 1.5 weight part;

It is manufactured according to the following steps.

Step 1: Place the components in a high speed mixer and stir to mix. There is no need to heat and stir for 5-8 min in a high speed mixer.

Step 2: The well mixed material is introduced into the twin screw extruder through Step 1, extruded at 135-160 ° C. to make a micro balloon and to obtain a dedicated film blowing material of the complete biodegradable mulching film.

Step 3: The film blowing material obtained in step 2 is film blown in an extruder. The film blow-up ratio is 3.6, the gap between the dioripiles is 0.8 mm, the thickness is 0.004 mm and the width is 2000 mm.

Example 5

The raw material composition of the fully biodegradable mulching film having ultra-thin and weather resistance that can be mechanical film mulching is calculated by weight.

Polyadipic acid / polybutylene terephthalate is 88.2 parts by weight;

Polypropylene carbonate is 5% by weight;

Drainable nano silicon dioxide (particle diameter 2-25 nm) is 4 weight part;

The silicon dioxide micro balloon (particle size 2-3 mu m) was 1 part by weight;

The polymer PMMA microballoons (particle size 2-3 μm) were 1 part by weight;

UV stabilizer Uvinul ^® 5050H is 0.5% by weight;

Ultraviolet absorbent Tinuvin234 is 0.5 weight part;

It is manufactured according to the following steps.

Step 1: Place the components in a high speed mixer and stir to mix. There is no need to heat and stir for 5-8 min in a high speed mixer.

Step 2: The well mixed material is introduced into the twin screw extruder through Step 1, extruded at 135-160 ° C. to make a micro balloon and to obtain a dedicated film blowing material of the fully biodegradable mulching film.

Step 3: The film blowing material obtained in step 2 is film blown in an extruder. The film blow-up ratio is 2.3, the gap between the diodes is 1.0 mm, the thickness is 0.006 mm, and the width is 900 mm.

Example 6

The raw material composition of the fully biodegradable mulching film having ultra-thin and weather resistance that can be mechanical film mulching is calculated by weight.

Polyadipic acid / polybutylene terephthalate is 84.2 parts by weight;

Polylactic acid is 5 parts by weight;

Polypropylene carbonate is 5% by weight;

Drainable nano silicon dioxide (particle diameter 2-25 nm) is 2 parts by weight;

Silicon dioxide micro balloons (particle size 2-3 mu m) were 3 parts by weight;

UV stabilizer Uvinul ^® 5050H is 0.5% by weight;

Ultraviolet absorbent Tinuvin234 is 0.5 weight part;

It is manufactured according to the following steps.

Step 1: Place the components in a high speed mixer and stir to mix. There is no need to heat and stir for 5-8 min in a high speed mixer.

Step 2: The well mixed material is introduced into the twin screw extruder through Step 1, extruded at 135-160 ° C. to make a micro balloon and to obtain a dedicated film blowing material of the fully biodegradable mulching film.

Step 3: The film blowing material obtained in step 2 is film blown in an extruder. The film blow-up ratio is 1.6, and the gap between the diodes is 0.8. The thickness is 0.005 mm and the width is 900 mm.

Experimental Example 2

Tensile rate is 200mm / min according to the measurement result of tensile property of GB13735-92 plastic. The mechanical properties of the obtained film, the ultra-biodegradable mulching film having ultra-thin and weather resistance can be shown in Table 2 below.

Example 4 Example 5 Example 6 Thickness (μm) 4 6 5 Light transmittance (%) 91.5 90.2 90.8 Haze value 11.7 12.5 12.0 Tensile Strength (MPa) 28 26 26 Sum of transverse elongation and longitudinal elongation (%) 900 854 800 Right angle tear strength (N / mm) 110 107 99 Separation of film mulching Separation Smooth and soft so the film does not tear Separation Smooth and soft so the film does not tear Separation Smooth and soft so the film does not tear

Ultra-thin ultra-transparent ultra-high strength biodegradable mulching film made by the present invention through the decomposition experiment of the 4-6μm thick mechanical film can be a fully biodegradable mulching film having ultra-thin and weather resistance that can be mulched high transparency, light transmittance> 90 %, Haze value <13%; The mechanical strength is high, the tensile strength is> 25 MPa, and the film film can be mechanically filmed using a general film mulching machine. Film mulching cultivation of wintering garlic can meet garlic's six-month growing demand. The film can also be completely degraded.

Claims (10)

The major components are calculated by weight and are as follows;
The complete biodegradable resin is 70-98 parts by weight, the auxiliary agent for strength enhancement, toughness enhancement and light transmission enhancement is 1-8 parts by weight, and the processing aid is 1-3 parts by weight;
The fully biodegradable resin is one or more of polyadipic acid / polybutylene terephthalate, polylactic acid, polypropylene carbonate, and polyadipic acid / polybutylene terephthalate is 85-95 wt% of the total biodegradable resin. Occupies;
The strength enhancing, toughness enhancing and light transmitting enhancing aids are inorganic supplementing and toughening enhancing and light transmitting enhancing aids or one or more of organic strength enhancing and toughening enhancing auxiliary;
The processing aid is one or more of a polymeric PMMA microballoon or a silicon dioxide microballoon;
A mechanical film that can be mulched fully biodegradable mulching film, characterized in that it comprises the component. The method of claim 1,
The inorganic strength enhancing and toughening enhancing and light transmitting enhancing aids are selected from drainable nano silicon dioxide;
The particle diameter of the drainable nano silicon dioxide is 2-25 nm;
The organic strength reinforcement and toughness-enhancing adjuvant is Arkema AX-8900 or ADX-1200s resin commercial reagents, characterized in that the film can be fully biodegradable mulching film. The method of claim 1,
The particle diameter of the polymer micro-balloon is 1-5 탆;
Particle diameter of the silicon dioxide fine balloon is a mechanical film mulching complete biodegradable film, characterized in that 1-5㎛. The method of claim 1,
The fuse flow rate of the polyadipic acid / polybutylene terephthalate is l-2g / 10min, and an acid value <15;
The fuse flow rate of the polylactic acid is 2-5g / 10min, and an acid value <15;
The fuse flow rate of the polypropylene carbonate is l-2g / 10min, the acid value <15 is a fully biodegradable mulching film that can be mechanical film. The main components are calculated by weight, as follows:
Complete biodegradable resin is 89-98 weight parts;
Supplements for strength enhancement, toughness enhancement and light transmission enhancement are 1 to 8 parts by weight;
Processing aids are 1-3 weight parts;
Mechanical film, ultra-thin ultra-transparent ultra-high strength full biodegradable mulching film, characterized in that it comprises a component. The complete biodegradable resin, the strength and toughness enhancement and light transmission enhancement and processing aids are stirred for 5-8 minutes in a high speed mixer according to the weight, and the mixed material is put into a twin screw extruder. When extruded to form a fine balloon and to obtain a dedicated film blowing material of the fully biodegradable mulching film;
Next, the film blowing material of the fully biodegradable mulching film was film blown in an extruder, to obtain an ultra-thin film having a thickness of 4-6 μm;
Here, the blow-up ratio of the film is 1.6-3.6, the gap of the diorifice is 0.8-1.8, and the width of the film can be adjusted between 600-4000mm;
The method of claim 5, wherein the mechanical film of the ultra-thin ultra-transparent ultra-high strength fully biodegradable mulching film comprising a. The major components are calculated by weight, as follows;
Complete biodegradable resin is 70-90 wt%;
Supplements for strength enhancement, toughness enhancement and light transmission enhancement are 1 to 8 parts by weight;
Processing aids are 1-3 weight parts;
Stability aid is 1-2 parts by weight;
Fully biodegradable mulching film having ultra-thin and weather resistance that can be mechanical film mulching, characterized in that it comprises the component. The method of claim 7, wherein
The stability aid is a UV stabilizer or one or more of the ultraviolet absorber mechanical film, characterized in that the ultra-biodegradable mulching film having ultra-thin and weather resistance. The method of claim 8,
The ultraviolet absorbent is a low-ball benzotria ultraviolet absorbent Tinuvin234;
The UV stabilizer is a hindered amine stabilizer Uvinul ^® 5050H mechanical film, characterized in that the ultra-biodegradable mulching film having ultra-thin and weather resistance. (1) Calculate complete biodegradable resins, strength and toughness and light-transmitting aids, stability aids, and processing aids by weight, stir for 5-8 min in a high speed mixer, and mix well-mixed materials in a twin screw extruder. Injecting, extruding when brought to 135-160 ° C. to make a micro-balloon and to obtain a dedicated film blowing material of the complete biodegradable mulching film;
(2) film blowing material of the fully biodegradable mulching film by film blowing in an extruder, to obtain an ultra-thin film having a thickness of 4-6 μm;
Here, the blow up ratio of the film is 1.6-3.6, and the gap of the diorifices is 0.8-1.8;
Method for producing a fully biodegradable mulching film having ultra-thin and weather resistance of the mechanical film can be mulched, characterized in that it comprises a.