CN113927987A - Full-biodegradable self-adhesive preservative film and preparation method thereof - Google Patents
Full-biodegradable self-adhesive preservative film and preparation method thereof Download PDFInfo
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- CN113927987A CN113927987A CN202111160668.9A CN202111160668A CN113927987A CN 113927987 A CN113927987 A CN 113927987A CN 202111160668 A CN202111160668 A CN 202111160668A CN 113927987 A CN113927987 A CN 113927987A
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Abstract
The invention discloses a full-biodegradable self-adhesive preservative film which adopts a three-layer co-extrusion structure of an outer layer, a middle layer and an inner layer, wherein all the layers are made of full-biodegradable materials, and the whole preservative film has good biodegradability. Compared with the common degradable preservative film, the full-biodegradable self-adhesive preservative film has better self-adhesiveness (shear peel strength) and higher transparency, and can be efficiently and continuously produced without being easily adhered to a roller. The full-biodegradable self-adhesive preservative film has the advantages of low processing temperature, good gas barrier property, capability of being heated by microwave, short production period, no solvent residue, edible product contact and the like, can be composted together with organic garbage such as leftovers and leftovers under proper conditions, can realize full biodegradation in natural environment, and does not pollute the environment. And the paint does not contain VOCs, heavy metals and carcinogenic substances, has no corrosiveness, is pollution-free and is green and friendly. The relative biological decomposition rate is more than or equal to 90 percent. The invention also discloses a preparation method of the self-adhesive preservative film with the whole biological profile.
Description
Technical Field
The invention belongs to the technical field of preservative films, and relates to a full-biodegradable self-adhesive preservative film and a preparation method thereof.
Background
Social sustainable development requires people to develop environmentally friendly materials that are conducive to ecological environments, biodegradable and biocompatible. The traditional preservative film products use polyethylene, polyvinyl chloride and other materials, and are the root cause of white pollution.
Along with the improvement of living standard of people, the safety and convenience of food are highly valued, the environmental awareness of people is continuously strengthened, and the traditional plastic packaging film can not meet the requirements of people on the aspect of vegetable fresh-keeping packaging. With the acceleration of the pace of life of people, the demand of fresh-cut vegetables is increasing. The research and development range of the freshness-retaining packaging is gradually detailed from the original wide application field to the aspects of material proportioning, film manufacturing conditions, performance improvement and the like, particularly on the aspect of film performance, the requirements of freshness-retaining quality and safety of vegetables are forced, and the requirements of the freshness-retaining packaging material on the mechanical performance, permeability, self-adhesiveness and the like of the film are higher and higher.
The degradable preservative film is a functional film with the functions of protection and preservation, which is prepared from degradable raw materials. The film is mainly generated by the mutual crosslinking action among molecules, a layer of barrier is formed on the surface or the internal interface of food, and specific substances can be loaded to improve the functional property of the film while retaining water and regulating internal gas components, so that the film has the characteristics of degradability, no pollution and the like. Degradable preservative films are classified into biodegradable films, environmentally degradable films and photodegradable films according to a degradation mechanism, wherein the biodegradable films are important development directions. The biodegradable film is mainly composed of substances which can be completely decomposed by microorganisms, and can not cause secondary pollution to the environment. The main types of biodegradable films are polylactic acid (PLA), Polycaprolactone (PCL), poly (terephthalic acid)/adipic acid/butylene terephthalate (PBAT), etc. With the increase of environmental protection pressure and the improvement of the yield of the degradable film, the degradable film is expected to become the mainstream of the future preservative film market.
CN112341651A discloses a preparation method of a food preservative film, which mainly comprises konjac glucomannan, ethyl cellulose and sodium alginate, wherein the film forming solution is uniformly coated on the surface of organic glass, and the film is uncovered to obtain the preservative film which is biodegradable but has poor tensile property and self-adhesive property.
CN111890769A discloses an antibacterial composite polylactic acid preservative film material and a preparation method thereof, the antibacterial preservative property is improved by the component modification of a polylactic acid film and the application and bonding process design of a three-layer film structure, but the polylactic acid material has the characteristic of lower impact toughness, and the application of the polylactic acid material in the packaging field is limited. CN112457550A discloses an anti-condensation controlled-atmosphere casting LDPE/POE/PBAT composite film, wherein the LDPE and POE materials are not biodegradable and do not meet the standard of full-biodegradable materials.
CN109401225A discloses a biodegradable plastic wrap and a preparation method thereof, the main raw materials comprise PBAT, modified starch, polylactic acid, aliphatic-aromatic copolyester, methyl hydroxypropyl cellulose ether and other materials with different refractive indexes, the transparency of the formed film is poor, and the polylactic acid and cellulose materials are brittle and hard, and the puncture resistance and self-adhesion of the formed film are poor.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a full-biodegradable self-adhesive preservative film and a production process thereof, so as to solve the defect that the preservative film in the prior art is made of non-degradable materials (such as PE, PVC, PVDC and the like) and cannot be degraded to pollute the environment. The full-biodegradable self-adhesive preservative film disclosed by the invention has good self-adhesion, transparency, elongation at break and puncture resistance. All parts are made of full-biodegradable materials, the whole body has good biodegradability, and composting treatment can be carried out together with organic garbage such as leftovers and the like under a proper condition. Can realize full biodegradation in natural environment after being discarded, and does not pollute the environment. And the paint does not contain VOCs, heavy metals and carcinogenic substances, has no corrosiveness, is pollution-free and is green and friendly. Meets GB/T19277.1 determination of biological decomposition capability required by the material under the controlled composting condition, and the relative biological decomposition rate is more than or equal to 90 percent. In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a full-biodegradable self-adhesive preservative film, which comprises an inner layer, a middle layer and an outer layer;
the inner layer comprises the following components: PBAT-2 and an anti-reflection agent;
the middle layer comprises the following components: PBAT-1 and an anti-reflection agent;
the outer layer comprises the following components: PBAT-1, slipping agent, anti-reflection agent and silicon dioxide microspheres;
each layer of material is formed by screw extrusion and three-layer coextrusion casting.
In the invention, the thickness of the outer layer is as follows: 2-4 μm; preferably, the outer layer is 3 μm thick.
In the present invention, the thickness of the middle layer is: 3-8 μm; preferably, the middle layer is 5 μm thick.
In the invention, the thickness of the inner layer is as follows: 2-4 μm; preferably, the inner layer is 3 μm thick.
In the invention, the outer layer comprises the following components in percentage by mass: PBAT-1: 98-99.75%; a slipping agent: 0.1-0.5%; an anti-reflection agent: 0.05-1.0%; silicon dioxide microspheres: 0.1-0.5%; preferably, the content of each component is as follows: PBAT-1: 99.1 percent; a slipping agent: 0.3 percent; an anti-reflection agent: 0.5 percent; silicon dioxide microspheres: 0.1 percent.
Wherein the PBAT-1 is poly terephthalic acid/adipic acid/butylene terephthalate, and the molecular structure is shown as the following formula (1):
wherein the B unit is specifically-O-CH2CH2CH2CH2-O-，
The unit A is specifically
T unit is specifically referred to
Wherein, in the polymer, the molar proportion of the repeating unit x containing the A unit accounts for 48 to 52 percent of the total sum of the repeating units x and y; preferably, it is 50.5%.
The melt index of the PBAT-1 is 3-5g/10min (test method: ISO 1133; test conditions: 2.16kg, 190 ℃), the melting temperature Tm is 120-135 ℃, the number average molecular weight Mn is 55000-80000, the weight average molecular weight Mw is 130000-170000, the Tg is-28-38 ℃, and the Tc is 30-50 ℃; preferably, the melt index is 4g/10min, the melting temperature Tm is 120 ℃, the number average molecular weight Mn is 68000, the weight average molecular weight Mw is 160000, Tg is-30 ℃ and Tc is 36 ℃.
Wherein the slipping agent is erucamide (molecular formula: C)21H41CONH2) Oleamide (molecular formula: c17H33CONH2) One or a combination of both; when is asThe ratio of erucamide to oleamide is (0.2-0.4%) when the two are mixed: (0.1-0.3%); preferably, it is 0.3%: 0.1 percent.
Wherein the anti-reflection agent is orotic acid (molecular formula: C)5H4N2O4) The molecular structure is shown in the following formula (2):
wherein the average particle size (D50) of the silica microspheres is as follows: 1-5 μm; SiO2 content: not less than 99.7 percent; specific surface area: less than or equal to 12m2(ii)/g; density: not less than 2.21g/cm3(ii) a Circularity: not less than 0.9 (test method: FPIA); preferably, the average particle size is 1 μm.
In the invention, the middle layer comprises the following components: PBAT-1: 99-99.95%; an anti-reflection agent: 0.05 to 1.0 percent; preferably, the content of PBAT-1 is 99.94%, and the content of the anti-reflection agent is 0.06%.
Wherein the PBAT-1 and the anti-reflection agent are defined as the outer layer of the full-biodegradable self-adhesive preservative film.
In the invention, the inner layer comprises the following components: PBAT-2: 99-99.95%; an anti-reflection agent: 0.05 to 1.0 percent; preferably, the content of PBAT-2 is 99.7%, and the content of the anti-reflection agent is 0.3%.
Wherein the definition of the anti-reflection agent is the same as that of the outer layer of the full-biodegradable self-adhesive preservative film.
Wherein the PBAT-2 has the same molecular basic structure as the PBAT-1 formula (1), and the molar proportion of the repeating unit x containing the A unit in the polymer accounts for 55-70% of the sum of the repeating units x and y, and is preferably 62%;
the melt index of the PBAT-2 is 10-1000g/10min (test method: ISO 1133; test conditions: 2.16kg, 190 ℃), the melting temperature Tm is 70-115 ℃, Tg is-55 to-20 ℃, Tc is-20 to 45 ℃, the number average molecular weight Mn is 60000-.
The material adopted by the full-biodegradable self-adhesive preservative film is a copolyester structure in which flexible and rigid molecular chain segments are mutually embedded, so that microorganisms can degrade the preservative film and finally metabolize the preservative film into CO2 and water; compared with a common PBAT material, the material component contained in the inner layer structure has better melt fluidity and stronger Brownian motion of material molecules, so that the material molecules are more strongly diffused to the surface of an adherend by virtue of the Brownian motion, and the self-adhesiveness of the preservative film disclosed by the invention is improved; the full-biodegradable self-adhesive preservative film disclosed by the invention has moderate oxygen and permeability, can effectively prevent the reproduction of anaerobic bacteria, and can block dust and bacteria in the air, so that the preservation period of food is prolonged.
The invention also provides a preparation method of the full-biodegradable self-adhesive preservative film, which comprises the following steps:
uniformly mixing a component material PBAT-1, a slipping agent, an anti-reflection agent and silicon dioxide microspheres contained in an outer layer, adding the mixture into a parallel double-screw extruder, melting and blending, air cooling, drying and granulating to prepare outer layer master batches;
the temperatures of the regions 1-7 of the twin-screw extruder in the step (1) are respectively 160-; preferably, the temperatures in zones 1-7 are 165 deg.C, 190 deg.C, 200 deg.C, 220 deg.C, 230 deg.C, 220 deg.C, and the head temperature is 200 deg.C, respectively.
Step (2), uniformly mixing the component material PBAT-1 contained in the middle layer and an anti-reflection agent, adding the mixture into a parallel double-screw extruder, melting and blending, air cooling, drying and granulating to prepare a middle layer master batch;
the temperatures of the regions 1-7 of the twin-screw extruder in the step (2) are respectively 160-; preferably, the temperatures in zones 1-7 are 165 deg.C, 190 deg.C, 230 deg.C, 200 deg.C, respectively, and the head temperature is 190 deg.C.
Step (3), uniformly mixing the component material PBAT-2 contained in the inner layer and the anti-reflection agent, adding the mixture into a parallel double-screw extruder, carrying out melt blending, air cooling, drying and granulating to prepare inner layer master batch;
the temperatures of the regions 1-7 of the twin-screw extruder in the step (3) are respectively 160-; preferably, the temperatures in zones 1-7 are 165 deg.C, 190 deg.C, 230 deg.C, 200 deg.C, respectively, and the head temperature is 170 deg.C.
And (4) respectively feeding the outer layer master batch, the middle layer master batch and the inner layer master batch prepared in the steps (1) to (3) into three single-screw extruders of a three-layer co-extrusion casting device, wherein molten materials of the three screws respectively correspond to the outer layer, the middle layer and the inner layer of the film. And (3) carrying out tape casting on the molten materials formed in the three screws through corresponding T-shaped dies by utilizing a three-layer co-extrusion process. The extruded casting material sequentially passes through a casting roller, a preheating roller, a fixed stretching roller, a cooling roller, a traction roller and a winding roller.
The step (4) is carried out in a drying workshop with the dew point temperature less than or equal to-25 ℃.
In the step (4), the temperatures of the zones 1-7 of the outer layer of the screw extruder are respectively 160-; preferably, the temperatures in zones 1-7 are 165 deg.C, 190 deg.C, 220 deg.C, 190 deg.C, and the head temperature is 175 deg.C, respectively.
In the step (4), the temperatures of the zones 1-7 of the screw extruder in the middle layer are respectively 160-; preferably, the temperatures in zones 1-7 are 165 deg.C, 190 deg.C, 220 deg.C, 190 deg.C, and the head temperature is 170 deg.C, respectively.
In the step (4), the temperatures of the zones 1-7 of the screw extruder in the inner layer are respectively 160-; preferably, the temperatures in zones 1-7 are 145 deg.C, 160 deg.C, 180 deg.C, 200 deg.C, 180 deg.C, and the head temperature is 160 deg.C, respectively.
In the step (4), the temperature of the casting roller is-20-5 ℃, the temperature of the preheating roller is 10-50 ℃, the stretching ratio is 1-5 times, and the temperature of the cooling roller is 10-25 ℃. Preferably, the temperature of the casting roller is-10-5 ℃, the temperature of the preheating roller is 15 ℃, the stretching ratio is 2.5 times, and the temperature of the cooling roller is 15 ℃.
The invention also provides the application of the full-biodegradable self-adhesive preservative film in the fields of food preservation, food packaging, industry and medicine packaging.
The food packaging field comprises the food packaging field of fruits, vegetables, meat, chilled foods and the like.
The full-biodegradable self-adhesive preservative film realizes the functions of preservation, moisture resistance, water resistance, oil resistance, acid resistance and the like in the field of food packaging.
The technical breakthrough of the invention is as follows: (1) the material component contained in the inner layer structure of the invention, PBAT-2 containing PBAT-2 in which the molar proportion of the repeating unit of the A unit accounts for 55% -70% of the total sum of the repeating units x and y, has better melt fluidity and stronger Brownian motion of material molecules compared with the common PBAT material (the molar proportion of the repeating unit of the A unit accounts for 48% -51% of the total sum of the repeating units x and y), so that the material molecules can be more strongly diffused to the surface of an adherend by virtue of the Brownian motion, polar groups or chain links at two interfaces are close to each other, and when the distance between a binder and the adherend molecules reaches the value
In the process, the molecules at the interface generate mutual attraction, so that the distance between the molecules is further shortened, and the contacted objects are mutually adsorbed together by the intermolecular force, thereby improving the self-adhesiveness of the preservative film.
(2) Because the inner layer of the preservative film has strong self-adhesion, the preparation steps of the casting film are carried out in a drying workshop with the dew point temperature less than or equal to minus 25 ℃ in order to facilitate production and processing. Different from the processing temperature (10-50 ℃) of a common casting film, the casting roller temperature in the step of the invention is lower, namely-20-5 ℃, and the lower casting roller temperature can improve the transparency of the film after the film is formed and reduce the roller sticking phenomenon when the film is peeled from the roller surface. In order to prevent the surface of the low-temperature casting roller and the film from forming water mist to influence the glossiness and the transparency of the film in the processing process, the invention adopts a drying workshop with the dew point temperature less than or equal to minus 25 ℃ to process the casting film.
(3) The material components contained in the outer layer, the middle layer and the inner layer structure of the invention are as follows: the permeability-increasing agent is orotic acid. Orotic acid, also known as vitamin B13, is present in the milk of various mammals. Can improve liver function and promote liver cell repair, is a good liver protection medicine, and has good curative effect on icteric liver disease, fatty liver and acute and chronic hepatitis. In addition, it has many new medical functions including treating gout, improving cerebral vascular circulation, strengthening immunity, promoting tissue regeneration and wound healing. In the food and feed industry, the orotic acid is mainly used as a food supplement and added into children's food to benefit the physical development. The additive can be added into feed to promote growth of chicken and increase egg yield. In the cosmetics industry, the orotic acid component is also effective in delaying skin aging.
(4) The anti-reflection effect of the orotic acid on the PBAT-1 and the PBAT-2 in the preservative film has two mechanisms of heterogeneous nucleation and epiphytic crystallization. The PBAT crystallization is mainly formed by the movement of a melt high-molecular chain segment, and the molecular chain needs to have the energy required by the movement, so that the number of formed crystal nuclei of the common PBAT is small, the crystallization space is large, the size of finally formed spherulites is large, the transparent bottom is lower, and the application of the PBAT crystallization in the field of preservative films is influenced. The orotic acid in the invention is used as a heterogeneous crystal nucleus in PBAT, and the main PBAT molecular chain is regularly arranged at the dent formed by the polar part of the orotic acid molecule. The introduction of the permeability-increasing agent orotic acid enables the system to have a large number of heterogeneous crystal nuclei, and the PBAT nucleation efficiency is greatly improved; in addition, the PBAT is attached to the orotic acid surface of the guest crystal for epitaxic crystallization, and the nucleation free energy of the PBAT is reduced on the basis of geometric matching such as the molecular distance, the crystal face distance, the unit cell parameter or the atomic distance and the like between the PBAT and the orotic acid, so that the nucleation efficiency and the crystallization rate of the PBAT are improved. Because the spherulites with limited crystallization space collide with other spherulites before growing up, the size of the formed spherulites is greatly reduced, and finally the transparency of the preservative film is improved and the haze is reduced.
(5) The material components used for the outer layer of the invention comprise: silica microspheres. The higher circularity (more than or equal to 0.9) can improve the melt fluidity of the mixture, thereby improving the mixing uniformity and the processing performance of the material. The average particle size (D50: 1-5 μm) is smaller, and the particles with the size form a composite structure of micron and nanometer protrusions on the surface of the film, so that the surface roughness is increased, and the surface energy required by adhesion of material molecules is increased. After the film is rolled, the outer layer is not easy to be bonded with the inner layer material with high self-adhesiveness, and the uncoiling property of the preservative film is improved.
Based on the technical scheme, the invention has the advantages that:
the fully biodegradable self-adhesive preservative film provided by the invention adopts a three-layer co-extrusion structure of an outer layer, a middle layer and an inner layer, all the materials of all the layers are fully biodegradable materials, the requirement of GB/T19277.1 on the determination of the final required biological decomposition capability of the materials under the controlled composting condition is met, and the relative biological decomposition rate is more than or equal to 90 percent; based on the material and process characteristics, the full-biodegradable self-adhesive preservative film has better self-adhesiveness (shear peel strength) compared with the degradable preservative films such as common PBAT, PLA and the like; the invention has high transparency, is not easy to stick to a roller and can realize high-efficiency continuous production; the materials used in the invention are all biodegradable materials, so that the fully biodegradable self-adhesive preservative film has the advantages of low processing temperature, good gas barrier property, good uncoiling property, capability of microwave heating, short production period, no solvent residue, edible product contact and the like.
Drawings
Fig. 1 is a schematic structural view of the full-biodegradable self-adhesive preservative film disclosed by the invention.
FIG. 2 is a schematic view of the processing process of the full-biodegradable self-adhesive preservative film.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1
A fully biodegradable self-adhesive cling film, comprising: inner layer 1, middle layer 2, outer layer 3.
The thickness of the outer layer is: 2 μm; the thickness of the middle layer is: 4 μm; the thickness of the inner layer is: 2 μm; each layer of material is formed by screw extrusion and three-layer coextrusion casting.
The outer layer comprises the following components: PBAT-1: 99.2 percent; erucamide: 0.3 percent; orotic acid: 0.3 percent; silicon dioxide microspheres: 0.2 percent.
The PBAT-1 has a molar ratio of a repeating unit x comprising an A unit to the total of the repeating units x and y of 50.5%, a melt index of 3.5g/10min, a melting temperature Tm of 120 ℃, a number average molecular weight Mn of 70000 to 75000, a weight average molecular weight Mw of 130000-140000, a Tg of-28 ℃ and a Tc of 45 ℃ in the polymer.
The average particle diameter (D50) of the silica microspheres is as follows: 4.5 μm.
The middle layer comprises the following components: PBAT-1: 99.95 percent; orotic acid: 0.05 percent; wherein the PBAT-1 is the same as the outer layer.
The inner layer comprises the following components: PBAT-2: 99.95 percent; orotic acid: 0.05 percent.
PBAT-2 as described above in which the molar proportion of the repeating unit x comprising the A unit accounts for 70% of the total of the repeating units x and y; the melt index is 25g/10min, the melting temperature Tm is 73 ℃, the Tg is-48 ℃, the Tc is 20 ℃, the number average molecular weight Mn is 60000-65000, and the weight average molecular weight Mw is 130000-140000.
The preparation method of the full-biodegradable self-adhesive preservative film comprises the following specific steps:
uniformly mixing the component materials PBAT-1, erucamide, orotic acid and silicon dioxide microspheres contained in the outer layer, adding the mixture into a parallel double-screw extruder, carrying out melt blending, air cooling, drying and granulating to prepare outer layer master batches; the temperatures of the zones 1-7 of the twin-screw extruder were 165 ℃, 190 ℃, 200 ℃, 220 ℃, 230 ℃, 230 ℃, 220 ℃ and the head temperature was 200 ℃.
Uniformly mixing the component materials PBAT-1 and the orotic acid contained in the middle layer, adding the mixture into a parallel double-screw extruder, melting, blending, air cooling, drying and granulating to prepare middle-layer master batches; the temperatures of the zones 1-7 of the twin-screw extruder were 165 ℃, 190 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 200 ℃ and the head temperature was 190 ℃.
Uniformly mixing the component materials PBAT-2 and the orotic acid contained in the inner layer, adding the mixture into a parallel double-screw extruder, melting, blending, air cooling, drying and granulating to prepare inner layer master batches; the temperatures in zones 1-7 of the twin-screw extruder were 165 deg.C, 190 deg.C, 230 deg.C, 200 deg.C, and the head temperature was 170 deg.C, respectively.
And respectively feeding the prepared outer layer master batch, middle layer master batch and inner layer master batch into three single-screw extruders of a three-layer co-extrusion casting device, wherein molten materials of the three screws respectively correspond to the outer layer, the middle layer and the inner layer of the film. And (3) carrying out tape casting on the molten materials formed in the three screws through corresponding T-shaped dies by utilizing a three-layer co-extrusion process. The extruded casting material sequentially passes through a casting roller, a preheating roller, a fixed stretching roller, a cooling roller, a traction roller and a winding roller. The temperatures of the zones 1-7 of the screw extruder on the outer layer are 165 ℃, 190 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 190 ℃ and the head temperature is 175 ℃. The temperatures of the zones 1-7 of the screw extruder in the middle layer are respectively 165 ℃, 190 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 190 ℃ and the temperature of the machine head is 170 ℃. The temperatures of the zones 1-7 of the screw extruder of the inner layer are respectively 145 ℃, 160 ℃, 180 ℃, 200 ℃, 200 ℃, 180 ℃ and the head temperature is 160 ℃. The casting roll temperature is-10 ℃, the preheating roll temperature is 15 ℃, the stretching ratio is 2.5 times, and the cooling roll temperature is 15 ℃. The steps from co-extrusion casting to rolling are all carried out in a drying workshop with the dew point temperature less than or equal to-25 ℃.
The obtained full-biodegradable self-adhesive preservative film has the water vapor transmission capacity of 654g/m2Day (38 ℃, 90% r.h.), oxygen transmission 0.01616cm3/m2D Pa (38 deg.C), haze 1.9%, self-adhesiveness (shear peel strength) 0.71N/cm2Uncoiling property of 4.1s (test method: GB 10457), elongation at break (MD/TD) of not less than 300%, puncture resistance of 1.5N, and relative biological decomposition rate of not less than 90%.
Example 2
The structure and the process flow of the full-biodegradable self-adhesive preservative film are the same as those of the embodiment 1 of the invention.
The thickness of the outer layer is: 2.5 μm; the thickness of the middle layer is: 3.5 μm; the thickness of the inner layer is: 2 μm; each layer of material is formed by screw extrusion and three-layer coextrusion casting.
The outer layer comprises the following components: PBAT-1: 99.0 percent; oleic acid amide: 0.3 percent; orotic acid: 0.5 percent; silicon dioxide microspheres: 0.2 percent.
The PBAT-1 has a molar ratio of a repeating unit x comprising an A unit to the total of the repeating units x and y of 50.5%, a melt index of 3.5g/10min, a melting temperature Tm of 120 ℃, a number average molecular weight Mn of 70000 to 75000, a weight average molecular weight Mw of 130000-140000, a Tg of-28 ℃ and a Tc of 45 ℃ in the polymer.
The average particle diameter (D50) of the silica microspheres is as follows: 3.5 μm.
The middle layer comprises the following components: PBAT-1: 99.8 percent; orotic acid: 0.2 percent; the PBAT-1 is the same as the outer layer.
The inner layer comprises the following components: PBAT-2: 99.8 percent; orotic acid: 0.2 percent.
The PBAT-2 in which the molar proportion of the repeating unit x comprising the A unit is 65% of the sum of the repeating units x and y; the melt index is 20g/10min, the melting temperature Tm is 81 ℃, the Tg is-43 ℃, the Tc is 20 ℃, the number average molecular weight Mn is 60000-65000, and the weight average molecular weight Mw is 140000-155000.
The preparation method of the full-biodegradable self-adhesive preservative film comprises the following specific steps:
uniformly mixing the component materials PBAT-1, oleamide, orotic acid and silicon dioxide microspheres contained in the outer layer, adding the mixture into a parallel double-screw extruder, carrying out melt blending, air cooling, drying and granulating to prepare outer layer master batches; the temperatures of the zones 1-7 of the twin-screw extruder were 165 ℃, 190 ℃, 200 ℃, 220 ℃, 230 ℃, 230 ℃, 220 ℃ and the head temperature was 200 ℃.
Uniformly mixing the component materials PBAT-1 and the orotic acid contained in the middle layer, adding the mixture into a parallel double-screw extruder, melting, blending, air cooling, drying and granulating to prepare middle-layer master batches; the temperatures of the zones 1-7 of the twin-screw extruder were 165 ℃, 190 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 200 ℃ and the head temperature was 190 ℃.
Uniformly mixing the component materials PBAT-2 and the orotic acid contained in the inner layer, adding the mixture into a parallel double-screw extruder, melting, blending, air cooling, drying and granulating to prepare inner layer master batches; the temperatures of the zones 1-7 of the twin-screw extruder were 165 ℃, 190 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 200 ℃ and the head temperature was 180 ℃.
And respectively feeding the prepared outer layer master batch, middle layer master batch and inner layer master batch into three single-screw extruders of a three-layer co-extrusion casting device, wherein molten materials of the three screws respectively correspond to the outer layer, the middle layer and the inner layer of the film. And (3) carrying out tape casting on the molten materials formed in the three screws through corresponding T-shaped dies by utilizing a three-layer co-extrusion process. The extruded casting material sequentially passes through a casting roller, a preheating roller, a fixed stretching roller, a cooling roller, a traction roller and a winding roller. The temperatures of the zones 1-7 of the screw extruder on the outer layer are 165 ℃, 190 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 190 ℃ and the head temperature is 175 ℃. The temperatures of the zones 1-7 of the screw extruder in the middle layer are respectively 165 ℃, 190 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 190 ℃ and the temperature of the machine head is 170 ℃. The temperatures of the zones 1-7 of the screw extruder of the inner layer are respectively 145 ℃, 160 ℃, 180 ℃, 200 ℃, 200 ℃, 200 ℃ and 180 ℃, and the temperature of the machine head is 170 ℃. The casting roll temperature is-5 ℃, the preheating roll temperature is 35 ℃, the stretching ratio is 3 times, and the cooling roll temperature is 15 ℃. The steps from co-extrusion casting to rolling are all carried out in a drying workshop with the dew point temperature less than or equal to-25 ℃.
The obtained full-biodegradable self-adhesive preservative film has the water vapor permeability of 587g/m2Day (38 ℃, 90% r.h.), oxygen transmission 0.01469cm3/m2D Pa (38 deg.C), haze 2.1%, self-adhesiveness (shear peel strength) 0.68N/cm2The uncoiling property is 3.9s, the elongation at break (MD/TD) is more than or equal to 250 percent, the puncture resistance is 1.7N, and the relative biological decomposition rate is more than or equal to 90 percent.
Example 3
The structure and the process flow of the full-biodegradable self-adhesive preservative film are the same as those of the embodiment 1 of the invention.
The thickness of the outer layer is: 2 μm; the thickness of the middle layer is: 5.5 μm; the thickness of the inner layer is: 3 μm; each layer of material is formed by screw extrusion and three-layer coextrusion casting.
The outer layer comprises the following components: PBAT-1: 99.0 percent; oleic acid amide: 0.15 percent; erucamide: 0.15 percent; orotic acid: 0.2 percent; silicon dioxide microspheres: 0.5 percent.
The PBAT-1 has a molar ratio of a repeating unit x comprising an A unit to the total of the repeating units x and y of 50.0%, a melt index of 3.8g/10min, a melting temperature Tm of 115 ℃, a number average molecular weight Mn of 75000 to 80000, a weight average molecular weight Mw of 135000-144000, a Tg of-26 ℃ and a Tc of 48 ℃.
The average particle diameter (D50) of the silica microspheres is as follows: 1.5 μm.
The middle layer comprises the following components: PBAT-1: 99.7 percent; oleic acid amide: 0.15 percent; erucamide: 0.15 percent. The PBAT-1 is the same as the outer layer.
The inner layer comprises the following components: PBAT-2: 99.7 percent; oleic acid amide: 0.15 percent; erucamide: 0.15 percent.
The PBAT-2 in which the molar proportion of the repeating unit x comprising the A unit accounts for 60% of the sum of the repeating units x and y; the melt index is 15g/10min, the melting temperature Tm is 94 ℃, the Tg is-38 ℃, the Tc is 25 ℃, the number average molecular weight Mn is 60000-65000, and the weight average molecular weight Mw is 140000-155000.
The preparation method of the full-biodegradable self-adhesive preservative film comprises the following specific steps:
uniformly mixing the component materials PBAT-1, erucamide, oleamide, orotic acid and silicon dioxide microspheres contained in the outer layer, adding the mixture into a parallel double-screw extruder, carrying out melt blending, air cooling, drying and granulating to prepare outer layer master batches; the temperatures of the zones 1-7 of the twin-screw extruder were 165 ℃, 190 ℃, 200 ℃, 220 ℃, 230 ℃, 230 ℃, 220 ℃ and the head temperature was 200 ℃.
Uniformly mixing the component materials PBAT-1 and the orotic acid contained in the middle layer, adding the mixture into a parallel double-screw extruder, melting, blending, air cooling, drying and granulating to prepare middle-layer master batches; the temperatures of the zones 1-7 of the twin-screw extruder were 165 ℃, 190 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 200 ℃ and the head temperature was 190 ℃.
Uniformly mixing the component materials PBAT-2 and the orotic acid contained in the inner layer, adding the mixture into a parallel double-screw extruder, melting, blending, air cooling, drying and granulating to prepare inner layer master batches; the temperatures of the zones 1-7 of the twin-screw extruder were 165 ℃, 190 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 200 ℃ and the head temperature was 190 ℃.
And respectively feeding the prepared outer layer master batch, middle layer master batch and inner layer master batch into three single-screw extruders of a three-layer co-extrusion casting device, wherein molten materials of the three screws respectively correspond to the outer layer, the middle layer and the inner layer of the film. And (3) carrying out tape casting on the molten materials formed in the three screws through corresponding T-shaped dies by utilizing a three-layer co-extrusion process. The extruded casting material sequentially passes through a casting roller, a preheating roller, a fixed stretching roller, a cooling roller, a traction roller and a winding roller. The temperatures of the zones 1-7 of the screw extruder on the outer layer are 165 ℃, 190 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 190 ℃ and the head temperature is 175 ℃. The temperatures of the zones 1-7 of the screw extruder in the middle layer are respectively 165 ℃, 190 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 190 ℃ and the temperature of the machine head is 170 ℃. The temperatures of the zones 1-7 of the screw extruder of the inner layer are respectively 145 ℃, 160 ℃, 180 ℃, 200 ℃, 200 ℃, 200 ℃ and 180 ℃, and the temperature of the machine head is 190 ℃. The casting roll temperature is-5 ℃, the preheating roll temperature is 55 ℃, the stretching ratio is 4 times, and the cooling roll temperature is 15 ℃. The steps from co-extrusion casting to rolling are all carried out in a drying workshop with the dew point temperature less than or equal to-25 ℃.
The water vapor transmission capacity of the obtained full-biodegradable self-adhesive preservative film is 604g/m2Day (38 ℃, 90% r.h.), oxygen transmission 0.01534cm3/m2D Pa (38 deg.C), haze 1.7%, self-adhesiveness (shear peel strength) 0.64N/cm2The uncoiling property is 4.4s, the elongation at break (MD/TD) is more than or equal to 200 percent, the puncture resistance is 2.0N, and the relative biological decomposition rate is more than or equal to 90 percent.
Comparative examples 1 to 6
The structure and the process flow of the full-biodegradable self-adhesive preservative film are the same as those of the embodiment 1 of the invention.
The contents and performance parameters of the components are shown in the following table 1:
TABLE 1
*The "x%" in the composition of the inner layer, the middle layer and the outer layer represents: the molar proportion of repeating units x comprising a units in the PBAT polymer is a percentage of the sum of repeating units x and y; the content of the anti-reflection agent, the content of the silicon dioxide microspheres and the content of the components of the similar substitute materials in the surface are all 0.3 percent under the unspecified condition; the test methods of the performance parameters all adopt GB 10457-2009.
Compared with the example 1 of the invention, the comparative examples 1, 2 and 3 have higher haze (7.5%) because the anti-reflection agent (orotic acid) used in the invention is not adopted in the preparation process; comparative examples 4 and 5 the products obtained were poor in self-adhesion (0.46N/cm) or in uncoiling (6.5s) because the silica microspheres used in the present invention were not used in the preparation process; in the preparation process of the comparative example 6, the low-temperature (-20-5 ℃) casting process is not adopted, so that the haze of the obtained product is large (5.1%).
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, which is set forth in the following claims.
Claims (13)
1. The full-biodegradable self-adhesive preservative film is characterized by comprising an inner layer (1), a middle layer (2) and an outer layer (3);
the inner layer comprises the following components: PBAT-2 and an anti-reflection agent;
the middle layer comprises the following components: PBAT-1 and an anti-reflection agent;
the outer layer comprises the following components: PBAT-1, slipping agent, anti-reflection agent and silicon dioxide microspheres.
2. The fully biodegradable self-adhesive preservative film according to claim 1, wherein the thickness of the outer layer is as follows: 2-4 μm; the thickness of the middle layer is as follows: 3-8 μm; the thickness of the inner layer is as follows: 2-4 μm; the inner layer, the middle layer and the outer layer are all formed by screw extrusion and three-layer coextrusion casting.
3. The full-biodegradable self-adhesive preservative film according to claim 1, wherein the outer layer comprises the following components in percentage by mass: PBAT-1: 98-99.75%; a slipping agent: 0.1-0.5%; an anti-reflection agent: 0.05-1.0%; silicon dioxide microspheres: 0.1 to 0.5 percent.
4. The fully biodegradable self-adhesive preservative film according to claim 3, wherein the PBAT-1 is poly (terephthalic acid)/adipic acid/butylene terephthalate, and the molecular structure is shown as the following formula (1):
wherein, in the PBAT-1, the molar proportion of the repeating unit x containing the A unit accounts for 48 to 52 percent of the sum of the repeating units x and y;
and/or the PBAT-1 has a melt index of 3-5g/10min, a melting temperature Tm of 120-135 ℃, a number average molecular weight Mn of 55000-80000, a weight average molecular weight Mw of 130000-170000, Tg of-28-38 ℃ and Tc of 30-50 ℃;
and/or the slipping agent is erucamide, oleamide, one or the combination of two of the erucamide and the oleamide;
and/or the anti-reflection agent is orotic acid, and the molecular structure is shown as the following formula (2):
and/or the average particle size D50 of the silica microspheres is as follows: 1-5 μm; SiO2 content: not less than 99.7 percent; specific surface area: less than or equal to 12m2(ii)/g; density: not less than 2.21g/cm3(ii) a Circularity: not less than 0.9.
5. The fully biodegradable self-adhesive preservative film according to claim 1, wherein the middle layer comprises the following components: PBAT-1: 99-99.95%; an anti-reflection agent: 0.05-1.0 percent.
6. The fully biodegradable self-adhesive cling film of claim 5, wherein said PBAT-1 is as set forth in claim 4;
and/or the antireflection agent is as shown in claim 4.
7. The fully biodegradable self-adhesive preservative film according to claim 1, wherein the inner layer comprises the following components: PBAT-2: 99-99.95%; an anti-reflection agent: 0.05-1.0 percent.
8. The fully biodegradable self-adhesive preservative film according to claim 7, wherein the anti-reflection agent is as shown in claim 4;
and/or, the PBAT-2 is poly (terephthalic acid)/adipic acid/butylene terephthalate; in the polymer, the molar proportion of a repeating unit x containing an A unit accounts for 55-70% of the sum of the repeating units x and y;
the melt index of PBAT-2 is 10-1000g/10min, the melting temperature Tm is 70-115 ℃, the Tg is-55 to-20 ℃, the Tc is-20-45 ℃, the number average molecular weight Mn is 60000-80000, and the weight average molecular weight Mw is 130000-170000.
The molecular structure of PBAT-2 is shown as the following formula (1):
9. a method for preparing the full-biodegradable self-adhesive preservative film according to any one of claims 1 to 8, wherein the method comprises the following steps:
uniformly mixing a component material PBAT-1, a slipping agent, an anti-reflection agent and silicon dioxide microspheres contained in an outer layer, adding the mixture into a parallel double-screw extruder, melting and blending, air cooling, drying and granulating to prepare outer layer master batches;
step (2), uniformly mixing the component material PBAT-1 contained in the middle layer and an anti-reflection agent, adding the mixture into a parallel double-screw extruder, melting and blending, air cooling, drying and granulating to prepare a middle layer master batch;
step (3), uniformly mixing the component material PBAT-2 contained in the inner layer and the anti-reflection agent, adding the mixture into a parallel double-screw extruder, carrying out melt blending, air cooling, drying and granulating to prepare inner layer master batch;
step (4), respectively feeding the outer layer master batch, the middle layer master batch and the inner layer master batch prepared in the steps (1) to (3) into three single-screw extruders of a three-layer co-extrusion casting device, wherein molten materials of the three screws respectively correspond to the outer layer, the middle layer and the inner layer of the film; carrying out tape casting on the molten materials formed in the three screws through corresponding T-shaped dies by utilizing a three-layer co-extrusion process; and extruding the casting material to sequentially pass through a casting roller, a preheating roller, a fixed stretching roller, a cooling roller, a traction roller and a winding roller to obtain the prepared full-biodegradable self-adhesive preservative film.
10. The method as claimed in claim 9, wherein in the step (1), the temperatures of the regions 1-7 of the twin-screw extruder are respectively 160-;
and/or, in the step (2), the temperatures of the zones 1-7 of the double-screw extruder are respectively 160-;
and/or, in the step (3), the temperatures of the zones 1-7 of the twin-screw extruder are respectively 160-.
11. The method as claimed in claim 9, wherein in the step (4), the temperatures of the zones 1-7 of the outer layer screw extruder are respectively 160-; the temperatures of the zones 1-7 of the middle layer screw extruder are respectively 160-; the temperatures of the zones 1-7 of the inner layer screw extruder are respectively 120-; the temperature of the casting roller is-20-5 ℃; the temperature of the preheating roller is 10-50 ℃, and the stretching ratio is 1-5 times; the temperature of the cooling roller is 10-25 ℃.
12. The process according to claim 9, wherein the step (4) is carried out in a drying plant having a dew point temperature of ≦ 25 ℃.
13. Use of the fully biodegradable self-adhesive cling film as claimed in any one of claims 1-8 in the fields of food preservation, food packaging, industry, pharmaceutical packaging.
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