CN114953662A - Compostable degradable stretched film composition, compostable degradable stretched film and application of compostable degradable stretched film - Google Patents
Compostable degradable stretched film composition, compostable degradable stretched film and application of compostable degradable stretched film Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
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Abstract
The invention relates to the technical field of compostable and degradable film processing, and discloses a compostable and degradable stretched film composition, a compostable and degradable stretched film and application thereof. The composition comprises a first extruded layer, a skeleton layer and a third extruded layer; the first extrusion layer material, the framework layer material and the third extrusion layer material are the same or different and respectively comprise a full-biodegradable polyester material; the full-biodegradable polyester material comprises one or more of poly (butylene succinate), poly (butylene succinate-co-adipate), poly (butylene terephthalate-co-adipate) and polylactic acid. The compostable and degradable stretched film has higher biological decomposition percentage; in addition, the compostable and degradable stretched film also has excellent physical and mechanical properties.
Description
Technical Field
The invention relates to the technical field of compostable and degradable film processing, in particular to a compostable and degradable stretched film composition, a compostable and degradable stretched film and application thereof.
Background
Stretch films are common packaging materials with excellent performance, and are widely applied to the fields of clothing, cosmetics, food, cigarettes, books, tissues, industry, medicines, electronic protection, coating (glue) and the like.
With the improvement of living standard and consumption ability, the demand and yield of packaging materials increase. Taking the case sealing adhesive tape in the express industry as an example, the number of the case sealing adhesive tape in 2021 year is about 955 hundred million pieces, and the number of the case sealing adhesive tape in the express industry is about 18.7 million tons of BOPP substrate film, calculated by 0.8 meter of case sealing adhesive tape. The waste plastic films are difficult to classify and recycle, and a large amount of waste packaging films are discarded at will and cannot be recycled at present. More and more practical situations are that the waste packaging materials buried in the land can cause soil impoverishment and deterioration, and the yield of crops is reduced or not produced; incineration of waste plastics produces a large amount of CO 2 Toxic gases such as CO and the like and residual heavy metals in ash content aggravate environmental pollution and greenhouse effect; a great deal of research has found that marine life is being endangered by waste packaging materials. Research and development can both take functional and exquisite appearance into consideration, and the packaging sound of compostable degradation is increasing day by day, and the protection of the green earth is urgent.
Therefore, it is of great importance to research and develop compostable degradable stretch films with excellent physical and mechanical properties.
Disclosure of Invention
The invention aims to overcome the defects that the prior art has the defects that the burying of waste packaging materials in the land causes soil impoverishment and deterioration and the yield of crops is reduced or is not produced, and provides a compostable degradable stretched film composition, a compostable degradable stretched film and application thereof, wherein the compostable degradable stretched film has higher biological decomposition percentage; in addition, the compostable and degradable stretched film also has excellent physical and mechanical properties.
In order to achieve the above object, the present invention provides in a first aspect a compostable degradable stretched film composition, wherein the composition comprises a first extruded ply, a carcass ply and a third extruded ply; the first extrusion layer material, the framework layer material and the third extrusion layer material are the same or different and respectively comprise a full-biodegradable polyester material; the full-biodegradable polyester material comprises one or more of poly (butylene succinate), poly (butylene succinate-co-adipate) (PBSA), poly (butylene terephthalate-co-adipate) (PBAT) and polylactic acid.
The invention provides a compostable degradable stretched film, wherein the film comprises a first functional layer, a framework layer and a third functional layer which are sequentially stacked by adopting the composition, wherein the first functional layer is obtained by extruding and stretching a first functional layer material, the framework layer is obtained by extruding and stretching a framework layer material, and the third functional layer is obtained by extruding and stretching a third functional layer material.
In a third aspect, the invention provides a use of the compostable degradable stretched film in one or more of food packaging, commodity packaging, cigarette packaging, book packaging, health product packaging, pharmaceutical box overwrap, adhesive coating, print lamination, plating, functional layer coating and advertising decoration.
By adopting the technical scheme, the compostable degradable stretched film prepared by adopting the full-biodegradable polyester material and the stretching method has excellent physical and mechanical properties; in addition, the compostable degradable stretched film is degraded in a composting environment after being discarded, and finally carbon dioxide, water and humus are generated, so that the aim of enabling the stretched film to enter a natural substance circulation system is fulfilled.
Drawings
FIG. 1 is a comparative graphical representation of the biodegradation curves of the composting tests of compostable degradable stretch film prepared in example 1 of the invention and reference cellulose;
FIG. 2 is a photograph of a compostable degradable stretched film prepared in example 1 of this invention;
FIG. 3 is a schematic diagram of a process for preparing a compostable degradable stretched film by stretching according to the present invention.
Description of the reference numerals
a-compostable degradable stretched film prepared in example 1 of the invention;
b-reference sample cellulose.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, a first aspect of the present invention provides a compostable degradable stretched film composition, wherein the composition comprises a first extruded ply, a carcass ply, and a third extruded ply; the first extrusion layer material, the framework layer material and the third extrusion layer material are the same or different and respectively comprise a full-biodegradable polyester material; the full-biodegradable polyester material comprises one or more of poly (butylene succinate) (PBS), poly (butylene succinate-co-adipate) (PBSA), poly (butylene terephthalate-co-adipate) (PBAT) and polylactic acid (PLA).
The inventor of the invention finds out through research that: the fully biodegradable polyester material (aliphatic polyester material) adopted by the invention has aliphatic ester bonds, so the film is a copolyester material with small polarity. Generally, biodegradation of polymeric materials is performed through two processes: firstly, microorganisms secrete hydrolytic enzymes to the outside of the body, the hydrolytic enzymes are combined with the surface of the material, and the high molecular chains are cut off by hydrolysis to generate compounds (organic acids, sugars and the like) with small molecular weight less than 500 g/mol; the degraded products are then taken up by the microorganisms and undergo various metabolic pathways to be synthesized into microbial bodies or converted into energy for microbial activities, and finally converted into water and carbon dioxide. The degradation has biophysical and biochemical effects, and is accompanied by other physicochemical effects such as hydrolysis, oxidation, etc., and is a very complex process, which mainly depends on the size and structure of macromolecules, the types of microorganisms, and environmental factors such as temperature, humidity, etc. The chemical structure of the high molecular material directly influences the biodegradability, and generally: aliphatic ester bond, peptide bond > carbamate > aliphatic ether bond > methylene. Various researches show that the length of fragments generated by degradation is in direct proportion to the thickness of a single crystal layer of a high molecular material, copolyester with smaller polarity is easier to degrade by fungi, the degradation effect of bacteria on the high molecular material with high a-amino content is very obvious, and the prepared compostable degradable stretched film has higher biological decomposition percentage. Therefore, the fully biodegradable polyester material adopted by the invention belongs to polar small aliphatic polyester materials, has higher biological decomposition percentage, and is degraded under the composting condition after being discarded, thereby achieving the purpose of environmental protection. In addition, the compostable and degradable stretched film also has excellent physical and mechanical properties.
According to the present invention, it should be noted that, in the present invention, the "fully biodegradable polyester material" may also be referred to as "fully biodegradable polyester material compounding", and the "compounding" specifically refers to a material obtained by feeding the components of the blend in proportion, melting, plasticating, extruding, cooling, and pelletizing in a screw extruder.
According to the present invention, preferably, the all-biodegradable polyester material comprises poly (butylene terephthalate-co-adipate) (PBAT) and/or polylactic acid (PLA).
According to the invention, poly (butylene terephthalate-co-butylene adipate) (PBAT) is a semi-crystalline polymer, belongs to thermoplastic biodegradable plastics, is a copolymer of butylene adipate and butylene terephthalate, combines the excellent degradation performance of aliphatic polyester and the good mechanical property of aromatic polyester, also has excellent biodegradability, and is a degradation material which is very active in the research of the current biodegradable plastics and is best applied in the marketFirstly, performing primary filtration; preferably, the glass transition temperature T of poly (butylene terephthalate-co-adipate) (PBAT) g Has a melting point T of-30 DEG C m 110-120 ℃ and the density of 1.20-1.26g/cm 3 . In the present invention, the poly (butylene terephthalate-co-adipate) (PBAT) is commercially available from Xinjiang blue Shantun river science Co., Ltd, for example, TH801T, melting point 110- 3 A melt index (190 ℃, 2.16kg) of 2.5 to 5; the carboxyl content is less than or equal to 30 mol/t.
In the present invention, "less than or equal to" means both "less than" and "equal to" are included.
According to the invention, polylactic acid, also known as polylactide, is produced using starch raw materials proposed by renewable plant resources, such as corn, cassava, etc. The starch raw material is saccharified to obtain glucose, the glucose and certain strains are fermented to prepare high-purity lactic acid, and the polylactic acid with certain molecular weight is synthesized by a chemical synthesis method. The biodegradable plastic has good biodegradability, can be completely degraded by microorganisms in the nature under specific conditions after being used, finally generates carbon dioxide and water, does not pollute the environment, is very beneficial to environmental protection, and is a well-known environment-friendly material; preferably, the polylactic acid (PLA) has a melting range of 100-180 ℃ and a density of 1.24g/cm 3 . The melt index (190 ℃, 2.16kg) is 3-7. In the present invention, the polylactic acid (PLA) is commercially available from Anhui Feng Probiotics group, for example, FY802 having a melting range of 100- 3 The monomer content is less than or equal to 0.3 percent.
According to the invention, the first extrusion layer material also comprises an auxiliary agent B1, and the auxiliary agent B1 comprises a material containing SiO 2 Optionally a blend of a silicone grafted slip agent and poly (butylene terephthalate-co-butylene adipate) (PBAT); based on the total weight of the assistant B1, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 85-99.5 wt%, and SiO is 2 The content of (B) is 0.5-10 wt%The content of the silicone grafted slipping agent is 0-5 wt%; preferably, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 92-98.5 wt% SiO based on the total weight of the assistant B1 2 The content of the silicone grafted slipping agent is 1-5 wt%, and the content of the silicone grafted slipping agent is 0.5-3 wt%; more preferably, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 94-97.5 wt% SiO based on the total weight of the aid B1 2 The content of the silicon grafted slipping agent is 1.5-3.5 wt%, and the content of the silicon grafted slipping agent is 1-2.5 wt%.
According to the invention, the silicone grafted slipping agent is obtained by commercial purchase, is purchased from Hainan Ruiyan high-tech limited company, and has the model number of SL 1002; preferably, the melting point of the silicone grafted slipping agent is 65-70 ℃; the density (25 ℃ C.) was 0.93g/cm 3 (ii) a The volatile matter (105 ℃ multiplied by 2h) is less than or equal to 0.5 percent; TGA (5% weight loss temperature) was 305 ℃ to 310 ℃.
According to the invention, the adjuvant B1 is commercially available as an adjuvant model M6020B1 from Shanghai Ruan Yi New Material science and technology Co., Ltd. in M6020B1, the content of poly (succinic acid-co-butylene adipate) is 95 wt.%, and SiO is contained 2 The content of the silicon grafting slipping agent is 3.5 weight percent, and the content of the silicon grafting slipping agent is 1.5 weight percent.
According to the invention, in the first extruded layer material, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 10-50 wt% and the content of polylactic acid is 50-90 wt% based on the total weight of the fully biodegradable polyester material; preferably, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 10-20 wt% and the content of polylactic acid is 80-90 wt% based on the total weight of the fully biodegradable polyester material.
According to the invention, in the first extrusion layer material, the first extrusion layer material contains a full biodegradable polyester material compound A1 and an auxiliary agent B1, and the weight ratio of the full biodegradable polyester material A1 to the auxiliary agent B1 is (90-99): (1-10), preferably (90-97): 3.
according to the invention, the skeleton layer material also comprises an auxiliary agent B2, and the auxiliary agent B2 comprises an amide slipping agent and/or poly (butylene terephthalate-co-adipate) (PBAT); based on the total weight of the assistant B2, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 95-100 wt%, and the content of the amide slipping agent is 0-5 wt%; preferably, based on the total weight of the assistant B2, the content of poly (butylene terephthalate-co-adipate butylene terephthalate) (PBAT) is 97.5-99.5 wt%, and the content of the amide slipping agent is 0.5-2.5 wt%; more preferably, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 99-99.5 wt% and the content of the amide slipping agent is 0.5-1 wt% based on the total weight of the assistant B2.
According to the invention, the amide slipping agent is one or more of stearic acid amide, erucic acid amide and oleic acid amide; preferably, the amide-type slipping agent is stearic acid amide, and the density is 0.868-0.872g/cm 3 The melting point is 98-108 ℃, the boiling point is 205-251 ℃/12 mmHg. In the present invention, the amide slip agent is commercially available from Shanghai Ruo Yi New Material science and technology, Inc. under model number DS 07.
According to the invention, the aid B2 is commercially available, and is an aid of type M6020B2, made by New materials science and technology Co., Ltd, of Shanghai Ruan Yi, and in M6020B2, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 99 wt%, and the content of the amide type slip agent is 1 wt%.
According to the invention, in the framework layer material, based on the total weight of the fully biodegradable polyester material, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 0-50 wt%, and the content of polylactic acid is 50-100 wt%; preferably, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 0-10 wt% and the content of polylactic acid is 90-100 wt% based on the total weight of the fully biodegradable polyester material.
According to the invention, in the framework layer material, the framework layer material contains a fully biodegradable polyester material compound A2 and an optional auxiliary agent B2, and the weight ratio of the fully biodegradable polyester material A2 to the auxiliary agent B2 is (95-100): (0-5), preferably (95-99): 1.
according to the invention, the third extrusion material also comprises an auxiliary B3, and the auxiliary B3 is SiO 2 And/or poly (butylene terephthalate-co-adipate) (PBAT); based on the total weight of the assistant B3, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 80-99 wt%, and the SiO is 2 In an amount of 1 to 20% by weight; preferably, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 85-98 wt% based on the total weight of the assistant B3, and the SiO is 2 In an amount of 2 to 15% by weight; more preferably, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 90-97 wt% based on the total weight of the assistant B3, and the SiO is 2 Is contained in an amount of 3 to 10% by weight.
According to the invention, SiO 2 For activating silicon microspheres, the median diameter D 50 Is 4.5-5.5 μm, D 90 Is 10-15.5 μm.
According to the invention, the aid B3 is commercially available as an aid M6020B3 from New materials science Co., Ltd, Shanghai No. Yi, with a content of poly (butylene terephthalate-co-butylene adipate) (PBAT) of 95 wt.% in M6020B3, and the SiO is added to the solution 2 Is 5% by weight.
According to the invention, in the third extrusion material, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 0-50 wt% and the content of polylactic acid is 50-100 wt% based on the total weight of the fully biodegradable polyester material; preferably, the content of poly (butylene terephthalate-co-butylene adipate) (PBAT) is 10-15 wt% and the content of polylactic acid is 85-90 wt% based on the total weight of the fully biodegradable polyester material.
According to the invention, in the third extrusion material, the third extrusion layer material contains a fully biodegradable polyester material compound A3 and an optional auxiliary agent B3, and the weight ratio of the fully biodegradable polyester material A3 to the auxiliary agent B3 is (95-99): (1-5), preferably (96-99): 1.
the invention provides a compostable degradable stretched film, wherein the film comprises a first functional layer, a framework layer and a third functional layer which are sequentially stacked by adopting the composition, wherein the first functional layer is obtained by extruding and stretching a first functional layer material, the framework layer is obtained by extruding and stretching a framework layer material, and the third functional layer is obtained by extruding and stretching a third functional layer material.
According to the invention, the compostable and degradable film is produced by coextrusion and stretching. Wherein the stretching comprises one or more of plane extrusion biaxial stretching, plane extrusion uniaxial stretching, tube bubble method biaxial stretching and tube bubble method uniaxial stretching.
In the present invention, the method for producing a compostable degradable stretched film by stretching can be referred to the schematic production flow shown in FIG. 2:
preparing materials:
the content of the compound material A1 is 90-99 wt% based on the total weight of the first extrusion layer material; the content of the B1 is 1-10 wt%;
taking the total weight of the framework layer material as a reference, and taking the content of the compound material A2 as 95-100 wt%; the content of the B2 is 0-5 wt%;
based on the total weight of the third extrusion layer material, the content of the compound A3 is 95-100 wt%; the content of the B3 is 0-5 wt%.
Preparing ingredients: respectively putting the components of the first extrusion layer, the framework layer and the third extrusion layer into respective corresponding low-speed mixers according to the weight percentage, and premixing for 30 minutes;
the material is through stirring, the back suction hopper of mixing of settlement time in the blender, and the material separates the material that probably sneakes into the metal (avoids damaging the extruder) through the metal separator, gets into the crystallization dryer through the rotary valve and carries out drying crystallization.
Plasticating and extruding: and extruding the resins of the first extrusion layer, the framework layer and the third extrusion layer by adopting a plurality of extruders respectively, and reasonably layering the molten resins by a distributor. The temperature of each section of the extruder is 180-285 ℃.
And (3) flaw-resistant melt filtration: the multiple layers of filter screens are overlapped in sequence, and the melt is extruded out of the filter screen at the outermost layer;
cooling crystallization and sheet setting: extruding the extruded melt by an extruder through a die head, cooling to obtain an unstretched film/sheet with fine spherical crystals and/or flaky crystals, wherein the gap of a die lip is 0.5-2 mm;
longitudinal (traction) stretching and shaping: the total stretching ratio is controlled to be between 1.5 and 5.0; and (3) longitudinal stretching and shaping zone: controlling the temperature at 50-180 ℃;
transverse stretching and shaping: the transverse stretching magnification is between 0.5 and 12; transverse stretching and shaping area: the temperature is controlled at 100 ℃ and 250 ℃;
measuring the thickness: the total thickness of the film was measured.
Corona and winding: corona treatment may or may not be selected depending on the film application. Carrying out corona treatment on the film by a high-frequency electronic discharger, wherein the offline surface tension value is more than or equal to 38-44 mN/m; and (5) winding the film after shaping. The winding device is automatically controlled by a winding surface tension control device so as to achieve the optimal winding effect; production line speed: 50-500 m/min.
Aging, slitting and rolling: standing for 1-2 days at 25 + -5 deg.C and 60% RH to further stabilize size and performance; and cutting out corresponding finished product width specifications.
In a third aspect, the invention provides a use of the compostable degradable stretched film in one or more of food packaging, commodity packaging, cigarette packaging, book packaging, health product packaging, pharmaceutical box overwrap, adhesive coating, print lamination, coatings, functional layer coatings and advertising decorations.
In the following examples and comparative examples:
(1) physical property test sample condition adjustment: the standard environment for sample condition regulation and test is specified in GB/T2918, and the test environment conditions are 23 deg.C + -2 deg.C, relative humidity 50% + -1%, and the sample is pre-treated for 4hr under the conditions.
(2) And (3) testing tensile strength: according to GB/T1004.3 "determination of tensile Properties of plastics part 3: the test was carried out as specified in test conditions for films and sheets.
(3) Controlled composting degradation test: determination of the ultimate aerobic biological decomposition Capacity of materials under controlled composting conditions according to GB/T19277.1-2021 part 1 of the method for determining the carbon dioxide released: the percent biodegradation of the film was tested as specified in general methods.
(4) Film haze test: the test was carried out according to the regulations of GB/T2410-2008 "determination of light transmittance and haze of transparent plastics".
(5) And (3) testing the friction coefficient: the coefficient of friction between the non-corona surface and the non-corona surface was measured according to the specification of GB/T10006 "method for measuring coefficient of friction between plastic film and sheet".
(6) Initial hot tack temperature test: the test is carried out according to the regulations of GB/T34445 and 2017 thermal bonding performance measurement of the thermoplastic plastic and the composite material thereof on the heat sealing surface. A hot tack temperature at which a heat seal strength obtained by a tensile test within 60 seconds after sealing under the set heat seal conditions is 1.5N/15mm or more. Two films with the length of 100mm and the width of 15mm are overlapped together in a contact way by a heat sealing surface, and the films are placed between an upper clamp and a lower clamp of a heat sealing instrument, wherein the clamps are vertical to the film surface. The clamp on the upper side of the heat sealing instrument is a heating sealing cutter, the heating width is 10mm or more, and no high-temperature-resistant adhesive tape is wrapped. The clamp at the lower side of the heat sealing instrument is a silica gel pad, the heating temperature is (50 +/-1) DEG C, and no high-temperature-resistant adhesive tape is wrapped. The conditions set for the heat sealing instrument are as follows: the pressure is 0.2MPa and the time is 0.3 s.
Example 1
This example illustrates the preparation of a compostable degradable stretched film by stretching.
The film was prepared according to the schematic flow chart of the production process of the stretched film shown in FIG. 3, and the components are shown in Table 1.
Preparing materials (weight percentage):
TABLE 1
Preparing ingredients: respectively putting the components of the first extrusion layer, the framework layer and the third extrusion layer into respective corresponding low-speed mixers according to the weight percentage, and premixing for 30 minutes;
the material is through stirring, the back suction hopper of mixing of settlement time in the blender, and the material separates the material that probably sneakes into the metal (avoids damaging the extruder) through the metal separator, gets into the crystallization dryer through the rotary valve and carries out drying crystallization.
Plasticating and extruding: and extruding the resins of the first extrusion layer, the framework layer and the third extrusion layer by adopting a plurality of extruders respectively, and reasonably layering the molten resins by a distributor. The temperature of each section of the extruder is 180-285 ℃.
And (3) flaw-resistant melt filtration: the multiple layers of filter screens are overlapped in sequence, and the melt is extruded out of the filter screen at the outermost layer;
cooling crystallization and sheet setting: extruding the extruded melt by an extruder through a die head, cooling by water bath of a water tank to form an unstretched film/sheet with fine spherulites and/or sheet crystals, wherein the gap of a die lip is 0.5-2mm, and introducing softened cooling water into a cold drum to ensure that the surface temperature of the cold drum reaches 20-25 ℃;
longitudinal (traction) stretching and shaping: double-stage stretching, wherein the total stretching ratio is controlled to be 1.5-5.0; and (3) longitudinal stretching and shaping zone: controlling the temperature at 50-180 ℃;
transverse stretching and shaping: the transverse stretching magnification is between 0.5 and 12; transverse stretching and shaping area: the temperature is controlled at 150 ℃ and 250 ℃;
measuring the thickness: the total thickness of the film was measured.
Corona and winding: corona treatment may or may not be selected depending on the film application. Carrying out corona treatment on the film by a high-frequency electronic discharger, wherein the offline surface tension value is more than or equal to 38-44 mN/m; and (5) winding the film after shaping. The winding device is automatically controlled by a winding surface tension control device so as to achieve the optimal winding effect; production line speed: 400-480 m/min.
Aging, slitting and rolling: standing for 2 days at the temperature of 25 +/-5 ℃ and the temperature of 60% RH, and further stabilizing the size and the performance; and cutting out corresponding finished product width specifications.
The compostable degradable stretched film prepared was subjected to a degradation test under controlled composting conditions, and the results are shown in the attached part.
Fig. 2 is a photograph of a compostable degradable stretched film prepared in example 1, which is a photograph of the film before testing, which degrades into fragments after composting.
Example 2
A compostable degradable stretched film was prepared in the same manner as in example 1 except that: the stock preparation was different, as shown in table 2 specifically:
preparing materials (weight percentage):
TABLE 2
Example 3
A compostable degradable stretched film was prepared in the same manner as in example 1 except that: preparing materials differently; specifically as shown in table 3:
preparing materials (weight percentage):
TABLE 3
Example 4
A compostable degradable stretched film was prepared in the same manner as in example 1 except that: the stock preparation is different. Specifically as shown in table 4:
preparing materials (weight percentage):
TABLE 4
Example 5
A compostable degradable stretched film was prepared in the same manner as in example 1 except that: preparing materials differently; specifically as shown in table 5:
preparing materials (weight percentage):
TABLE 5
Example 6
A compostable degradable stretched film was prepared in the same manner as in example 1 except that: preparing materials differently; specifically as shown in table 6:
preparing materials (weight percentage):
TABLE 6
Example 7
A compostable degradable stretched film was prepared in the same manner as in example 1 except that: preparing materials differently; specifically as shown in table 7:
preparing materials (weight percentage):
TABLE 7
Comparative example 1
A compostable degradable stretched film was prepared in the same manner as in example 1 except that: the stock preparation is different. Specifically as shown in table 8:
preparing materials (weight percentage):
TABLE 8
Comparative example 2
A compostable degradable stretched film was prepared in the same manner as in example 1 except that: the stock preparation is different. Specifically as shown in table 9:
preparing materials (weight percentage):
TABLE 9
Comparative example 3
A compostable degradable stretched film was prepared in the same manner as in example 1 except that: the stock preparation is different. Specifically as shown in table 10:
preparing materials (weight percentage):
watch 10
Test example 1
The compostable degradable stretched films prepared according to examples 1 to 7 of the invention and comparative examples 1 to 3 were subjected to the determination of the final aerobic biodegradability of the material under controlled composting conditions according to GB/T19277.1-2011/ISO 14855-1:2005, part I of the method for determining the carbon dioxide released: general method for testing the biological decomposition percentage of the film, the sample is detected in the center of the antibacterial material detection of the research institute of physical and chemical technology of Chinese academy of sciences.
Description of the samples: compostable degradable stretched films prepared in examples 1 to 7 and comparative examples 1 to 3 were prepared into plastic film bags having an organic carbon content of 53.44%. The reference material was thin layer chromatography grade cellulose (TLC), white powder, particle size 20 μm, organic carbon content 43.76%.
Other descriptions: the composting adopts a vermiculite method. After activating the special compost strain, inoculating the activated special compost strain to vermiculite, activating for 72 hours, and then starting composting. The date of composting was from 04/19/2021 to 08/12/2021.
The test data are shown in table 11 below.
TABLE 11
Remarking: at 112 days, the relative biological decomposition percentage of the sample to be detected is the biological decomposition percentage of the sample to be detected divided by the biological decomposition percentage of the reference (cellulose), and the relative biological decomposition percentage of the sample to be detected is 100 percent
It can be seen that the percentage of biodegradation at 112 days of the compostable, degradable, stretched film prepared in example 1 was 90.6%.
In addition, FIG. 1 is a comparative graphical representation of the biodegradation curves of the composting tests of the compostable degradable stretch film prepared in example 1 of the invention and the cellulose of the reference sample; wherein "a" represents the compostable degradable stretched film prepared in example 1 of the present invention, and "b" represents the reference cellulose; as can be seen from fig. 1: the degradation trend of example 1 is consistent with that of the reference sample, and the relative biological decomposition percentage of 112 days is over 90 percent, which meets the requirements of national standard and international standard.
Test example 2
Physical property tests were conducted on the compostable degradable stretched films prepared in examples 1 to 7 of the present invention and comparative examples 1 to 3, and the physical property test data are shown in the following table 12.
TABLE 12
Remarks 1: the standard environment for sample condition regulation and test is specified in GB/T2918, and the test environment conditions are 23 deg.C + -2 deg.C, relative humidity 50% + -1%, and the sample is pre-treated for 4hr under the conditions.
In the present invention: under the conditions of specific process conditions and proper formula proportion, the compostable degradable stretched film prepared by the stretching method has excellent tensile strength, high transparency, low heat sealing temperature and higher heat sealing strength.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A compostable degradable stretched film composition comprising a first extruded ply, a backbone ply, and a third extruded ply; the first extrusion layer material, the framework layer material and the third extrusion layer material are the same or different and respectively comprise a full-biodegradable polyester material;
the full-biodegradable polyester material comprises one or more of poly (butylene succinate), poly (butylene succinate-co-adipate), poly (butylene terephthalate-co-adipate) and polylactic acid.
2. The composition of claim 1, wherein the fully biodegradable polyester material is poly (butylene terephthalate-co-adipate) and/or polylactic acid.
3. The composition of claim 1 or 2, wherein the first extruded layer further comprises coagent B1, and the coagent B1 comprises SiO-containing 2 Optionally a silicone grafted slip agent and poly (butylene terephthalate-co-adipate) blend;
and/or, based on the total weight of the assistant B1, the content of poly (butylene terephthalate-co-butylene adipate) is 85-99.5 wt%, and SiO is 2 The content of the silicon grafted slipping agent is 0.5-10 wt%, and the content of the silicon grafted slipping agent is 0-5 wt%;
preferably, the content of the poly (butylene terephthalate-co-adipate) is 92-98.5 wt% based on the total weight of the assistant B1, and SiO is 2 The content of the silicone grafted slipping agent is 1-5 wt%, and the content of the silicone grafted slipping agent is 0.5-3 wt%;
more preferably, the content of poly (butylene terephthalate-co-adipate) is 94-97.5 wt% of SiO based on the total weight of the assistant B1 2 The content of the silicone grafted slipping agent is 1.5-3.5 wt%, and the content of the silicone grafted slipping agent is 1-2.5 wt%.
4. The composition of claim 1 or 2, wherein the backbone layer further comprises coagent B2, and the coagent B2 comprises an optional amide slip agent and/or poly (butylene terephthalate-co-adipate);
and/or, based on the total weight of the assistant B2, the content of poly (butylene terephthalate-co-butylene adipate) is 95-100 wt%, and the content of the amide slipping agent is 0-5 wt%;
preferably, based on the total weight of the assistant B2, the content of poly (butylene terephthalate-co-adipate) is 97.5-99.5 wt%, and the content of the amide slipping agent is 0.5-2.5 wt%;
more preferably, the content of poly (butylene terephthalate-co-adipate) is 99-99.5 wt% and the content of the amide slipping agent is 0.5-1 wt% based on the total weight of the auxiliary B2.
5. The composition of claim 1 or 2, wherein the third extrudate further comprises coagent B3, and the coagent B3 comprises SiO 2 And/or poly (butylene terephthalate-co-adipate);
and/or the content of poly (butylene terephthalate-co-adipate) is 80 to 99 weight percent based on the total weight of the additive B3, and the SiO is 2 In an amount of 1 to 20% by weight;
preferably, the content of the poly (butylene terephthalate-co-butylene adipate) is 85-98 wt% based on the total weight of the assistant B3, and the SiO is 2 In an amount of 2 to 15% by weight;
more preferably, the content of poly (butylene terephthalate-co-adipate) is 90-97 wt% based on the total weight of the assistant B3, and the SiO is 2 Is contained in an amount of 3 to 10% by weight.
6. The composition of any one of claims 1-3, wherein in the first extruded layer, the poly (butylene terephthalate-co-adipate) is present in an amount of 10-50 wt.%, and the polylactic acid is present in an amount of 50-90 wt.%, based on the total weight of the fully biodegradable polyester material;
preferably, the content of poly (butylene terephthalate-co-adipate) is 10-20 wt% and the content of polylactic acid is 80-90 wt% based on the total weight of the fully biodegradable polyester material;
and/or in the first extrusion layer material, the weight ratio of the fully biodegradable polyester material to the auxiliary agent B1 is (90-99): (1-10).
7. The composition of any of claims 1-2 and 4, wherein the backbone layer comprises poly (butylene terephthalate-co-adipate) in an amount of 0-50 wt.% and polylactic acid in an amount of 50-100 wt.%, based on the total weight of the fully biodegradable polyester material;
preferably, the content of poly (butylene succinate-co-adipate) is 0-10 wt% and the content of polylactic acid is 90-100 wt% based on the total weight of the fully biodegradable polyester material;
and/or in the framework layer material, the weight ratio of the fully biodegradable polyester material to the auxiliary agent B2 is (95-100): (0-5).
8. The composition of any of claims 1-2 and 5, wherein in the third extrudate the poly (butylene terephthalate-co-adipate) is present in an amount of 0-50 wt% and the polylactic acid is present in an amount of 50-100 wt%, based on the total weight of the fully biodegradable polyester material;
preferably, the content of poly (butylene terephthalate-co-adipate) is 10-15 wt% and the content of polylactic acid is 85-90 wt% based on the total weight of the fully biodegradable polyester material;
and/or in the third extrusion material, the weight ratio of the fully biodegradable polyester material to the auxiliary agent B3 is (90-99): (1-5).
9. The composition as in any one of claims 1-9, wherein the silicone grafted slip agent has a melting point of 65-70 ℃;
and/or the amide-type slipping agent is selected from one or more of stearic acid amide, erucamide and oleamide.
10. A compostable degradable stretched film comprising a first functional layer, a skeleton layer and a third functional layer sequentially stacked by using the composition of any one of claims 1 to 9, wherein the first functional layer is obtained by extrusion-stretching of a first functional layer material, the skeleton layer is obtained by extrusion-stretching of a skeleton layer material, and the third functional layer is obtained by extrusion-stretching of a third functional layer material.
11. Use of the compostable, degradable, stretched film of claim 10 in one or more of food packaging, consumer chemical packaging, cigarette packaging, book packaging, health care packaging, pharmaceutical case overwrap, adhesive coating, print lamination, coatings, functional layer coatings, and advertising.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937178A (en) * | 2014-05-06 | 2014-07-23 | 宁波家塑生物材料科技有限公司 | Poly(butylene tertephehalate-co-butanediol adipate)/starch-based full biodegrade composite material and preparation method thereof |
| CN211710265U (en) * | 2019-11-25 | 2020-10-20 | 东莞全球环保科技有限公司 | Degradable film compounded by compostable degradable material and paper |
| CN113500769A (en) * | 2021-07-23 | 2021-10-15 | 厦门长塑实业有限公司 | Biodegradable biaxially oriented composite film and preparation method and application thereof |
| CN114407471A (en) * | 2022-01-24 | 2022-04-29 | 珠海横琴辉泽丰包装科技有限公司 | Three-layer co-extrusion biodegradable automatic packaging film material and manufacturing method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937178A (en) * | 2014-05-06 | 2014-07-23 | 宁波家塑生物材料科技有限公司 | Poly(butylene tertephehalate-co-butanediol adipate)/starch-based full biodegrade composite material and preparation method thereof |
| CN211710265U (en) * | 2019-11-25 | 2020-10-20 | 东莞全球环保科技有限公司 | Degradable film compounded by compostable degradable material and paper |
| CN113500769A (en) * | 2021-07-23 | 2021-10-15 | 厦门长塑实业有限公司 | Biodegradable biaxially oriented composite film and preparation method and application thereof |
| CN114407471A (en) * | 2022-01-24 | 2022-04-29 | 珠海横琴辉泽丰包装科技有限公司 | Three-layer co-extrusion biodegradable automatic packaging film material and manufacturing method thereof |
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