CN110920188A - Bio-based PTT/PLA heat-shrinkable label film and preparation method thereof - Google Patents
Bio-based PTT/PLA heat-shrinkable label film and preparation method thereof 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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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
- C08J2367/04—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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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
- 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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- Chemical Kinetics & Catalysis (AREA)
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- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
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Abstract
The invention discloses a bio-based PTT/PLA heat-shrinkable label film, which belongs to the technical field of plastic film processing and comprises a core layer and two surface layers respectively covering the upper surface and the lower surface of the core layer, wherein the surface layers are formed by mixing PLA and PLA opening smooth master batches, and the core layer is formed by mixing PLA, PTT and SEBS compatilizers.
Description
Technical Field
The invention belongs to the technical field of plastic film processing, and particularly relates to a bio-based PTT/PLA heat-shrinkable label film and a preparation method thereof.
Background
The heat-shrinkable label film is a base material film of a shrinkable sleeve label of commodities such as container beverages and the like, and is mainly made of PVC (polyvinyl chloride), PS (polystyrene) and PETG (polyethylene terephthalate-1, 4-cyclohexanedimethanol ester) which are petrochemical materials at present.
The label of the shrinkable sleeve label is thin and small in size, a large amount of ink materials are printed on the surface of the label, and although the label made of PVC and PS materials can be recycled after being concentrated and can be used as a raw material of a low-end product for reprocessing and utilization, the label is troublesome to collect and has low industrial recycling value, so that the label of bottles is directly discarded after being used for one time.
The PETG material shrink sleeve label is similar to the PET bottle sheet in material, and can be nominally recycled together with the PET bottle sheet, but is unrealistic in practice. This is because: 1. a large amount of printing ink is arranged on the PETG label, and if the printing ink is recycled, the PET transparent bottle flakes with higher grade are polluted greatly; 2. PETG is a PET modified material. In order to obtain higher shrinkage, the amount of the copolymerized modifying monomer is larger, the material properties of the copolymerized modifying monomer are greatly different from those of PET, and if the copolymerized modifying monomer is recycled, even if the ink pollution problem is not considered, the properties of PET bottle sheets are greatly changed, and the reprocessing and utilization are difficult and troublesome. Therefore, the most practical method of handling the PET bottles requires peeling the PETG label from the PET bottle and then separating the PET bottle from the PET bottle.
Therefore, the label made of the materials basically becomes a hidden disposable plastic product, which not only causes the waste of petrochemical resources, but also brings certain environmental protection pressure.
The bio-based material is from the nature, can be recycled and reused in a natural cycle, can be recycled in a harmless way in the whole life cycle, and is a material which is more environment-friendly and sustainable in development. The bio-based degradable heat-shrinkable label is the direction of industry development and is a main way for solving the resource crisis and environmental protection problems of the current shrinkable sleeve label.
PLA (polylactic acid) is biodegradable and compostable thermoplastic plastic, belongs to aliphatic polyester, is one of the most mature bio-based materials in current industrialization, is prepared from plant resources such as starch, sugar and the like, has very good optical property, physical and mechanical properties and proper high-shrinkage performance compared with the existing petroleum-based plastic, and is an ideal bio-based degradable material for replacing petroleum-based heat-shrinkable label films such as PETG (polyethylene terephthalate glycol) and the like.
However, PLA has the problems of brittleness, poor heat resistance, low melt strength, narrow processing window, large shrinkage force of a shrink film, and the like, and can be better used as a production material of a heat-shrinkable label film only by modifying or adding a corresponding auxiliary agent for further improvement.
PBS (poly butylene succinate), PBAT (poly butylene adipate terephthalate) and the like are commonly used toughening modified materials for PLA materials, but the transparency of the PLA is deteriorated after the PBS is added into the PLA, which does not meet the requirement of the general heat shrinkable label film on high-transparency products; after the PBAT is added, although the influence on the transparency of the PLA is small, the toughness of the PLA can meet the more satisfactory requirement only when the PBAT is added in a larger proportion (more than or equal to 10%), the rigidity of the PLA material is reduced more because a rubber performance chain segment in a PBAT molecular chain has a plasticizing effect on the PLA, the shrinkage rate is reduced to a certain extent after modification, and certain technical problems exist when the modified PBAT is used as a heat shrinkable sleeve label.
PTT (bio-based poly (1, 3-trimethylene terephthalate)) is an important bio-based polyester product in the field of industrial biomaterials, and has the main advantages of not only having the physical properties of PET, including strength, toughness and heat resistance, but also having the processing advantages of PBT, such as low melt temperature, fast crystallization and the like, and simultaneously maintaining the basic advantages of polyester, namely dimensional stability, electrical insulation and chemical resistance, as thermoplastic engineering plastics. The PTT material has good rebound resilience, and if the PTT can be added into the PLA, the toughness of the PLA can be effectively improved, and the problem of larger contraction force of the PLA can be well improved.
Disclosure of Invention
The invention aims to overcome the defects of the technology and provide a bio-based PTT/PLA heat-shrinkable label film and a preparation method thereof, wherein bio-based poly (1, 3-trimethylene glycol terephthalate) (PTT) is used as a modifier of the PLA, and the problems of poor toughness and large shrinkage force of the pure PLA heat-shrinkable label film are solved by utilizing the characteristics of good flexibility and high resilience of the PTT.
In order to achieve the purpose, the invention adopts the technical scheme that: the utility model provides a biological base PTT/PLA heat-shrinkable label membrane, includes the sandwich layer, covers respectively in two surface courses of sandwich layer upper and lower surface, its characterized in that, the surface course comprises PLA and the smooth master batch of PLA opening, the sandwich layer comprises PLA, PTT and SEBS compatilizer.
Further, the mass ratio of PLA to PLA opening smooth master batch in the surface layer is 97-99: 1-3.
Further, the mass ratio of the PLA, the PTT and the SEBS compatilizer in the core layer is 85-90: 8-12: 2-3.
Further, the thickness ratio of the surface layer of the upper surface, the core layer and the surface layer of the lower surface is 1: 8: 1.
further, PLA chooses for use extrusion grade or film level PLA granule, PTT chooses for use the PTT section of big gloss type, SEBS compatibilizer chooses for use industrial grade SEBS compatibilizer.
A preparation method of a bio-based PTT/PLA heat-shrinkable label film is characterized by comprising the following steps:
s1, opening the PLA and the PLA smooth master batch according to the mass ratio of 97-99: 1-3, feeding the mixture into an extruder for plasticizing and melting to form a high-temperature molten polymer, metering the high-temperature molten polymer by a metering pump, conveying the high-temperature molten polymer to a filter for filtering, and feeding the high-temperature molten polymer into a distributor;
s2, mixing PLA, PTT and SEBS compatilizers according to the mass ratio of 85-90: 8-12: 2-3, feeding the mixture into an extruder for plasticizing and melting to form a high-temperature molten polymer, metering the high-temperature molten polymer by a metering pump, conveying the high-temperature molten polymer to a filter for filtering, and feeding the high-temperature molten polymer into a distributor;
and S3, taking the high-temperature molten polymer obtained in the step S1 as a surface layer and the high-temperature molten polymer obtained in the step S2 as a core layer, distributing the surface layer and the core layer through a distributor, conveying the surface layer and the core layer to a die head, performing composite extrusion molding through the die head, attaching the extruded product to a quenching roller, and rapidly cooling the extruded product to form a cast sheet.
And S4, preheating, stretching, sizing and cooling the cast sheet obtained in the step S3 in transverse stretching equipment, and finally, conveying the cast sheet to a winding machine for winding by using a traction roller to obtain the bio-based PTT/PLA heat-shrinkable label film.
And S5, sequentially slitting, inspecting and packaging the bio-based PTT/PLA heat-shrinkable label film obtained in the S4 to obtain a finished product.
Further, the extruder is a parallel twin-screw extruder, and the plasticizing temperature of the extruder is 245-.
Further, the die head is an automatic adjustment coat hanger type single-layer die head, and the extrusion temperature of the die head is 265-270 ℃.
Further, the cold water inlet temperature of the quenching roller is 25-32 ℃.
Further, in the transverse stretching equipment, the preheating temperature is 90-110 ℃, the stretching temperature is 85-95 ℃, the setting temperature is 70-80 ℃, the cooling temperature is 40-45 ℃, and the transverse stretching ratio is 1: 4.8.
the invention has the beneficial effects that: the invention can utilize the prior PETG heat-shrinkable label film production line by a flat film method, does not need to redesign the production line, adopts a PLA blending raw material scheme with different core layers and surface layers, wherein the surface layer adopts a raw material proportioning mode of PLA + bio-based open master batch, the addition of the bio-based open master batch ensures smooth processing of film coiling, subsequent slitting and the like, and the surface layer adopts PLA as a main material, so that the rigidity and good printing performance of the PLA can be better exerted. The core layer adopts a PLA and PTT blending mode, a certain amount of SEBS compatilizer is added for compatibilization, and the good toughness and high resilience of the bio-based polyester PTT material are utilized to improve the toughness of the heat-shrinkable label film and reduce the shrinkage force of the heat-shrinkable label film. The compatibility of PLA and PTT is improved through the SEBS compatilizer, the uniformity of the heat-shrinkable label film is ensured, and the improved PLA performance of the maximum efficiency of PTT is ensured.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is a schematic view of the structure of the heat-shrinkable label film of the present invention.
In the figure: surface layer 1 and core layer 2.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.
Example 1
Referring to fig. 1-2, a bio-based PTT/PLA heat-shrinkable label film includes a core layer 2, and two surface layers 1 respectively covering the upper and lower surfaces of the core layer 2, wherein the thickness ratio of the surface layer 1 on the upper surface to the surface layer 1 on the lower surface to the surface layer 1 on the core layer 2 is 1: 8: 1; surface course 1 comprises PLA and the smooth master batch of PLA opening, and the quality ratio of PLA in the surface course 1 and the smooth master batch of PLA opening is 97: 3; the core layer 2 is composed of PLA, PTT and SEBS compatilizers, and the mass ratio of the PLA, PTT and SEBS compatilizers in the core layer 2 is 90: 8: 2; wherein, PLA chooses for use and extrudes the PLA granule of level or film level, and PTT chooses for use the PTT section of big light type, and the SEBS compatibilizer chooses for use industrial grade SEBS compatibilizer.
A preparation method of a bio-based PTT/PLA heat-shrinkable label film is characterized by comprising the following steps:
s1, opening the PLA and the PLA smooth master batch according to the mass ratio of 97: 3, feeding the mixture into an extruder for plasticizing and melting to form a high-temperature molten polymer, metering the high-temperature molten polymer by a metering pump, conveying the high-temperature molten polymer to a filter for filtering, and feeding the high-temperature molten polymer into a distributor;
s2, mixing PLA, PTT and SEBS compatilizers according to a mass ratio of 90: 8: 2, feeding the mixture into an extruder for plasticizing and melting to form a high-temperature molten polymer, metering the high-temperature molten polymer by a metering pump, conveying the high-temperature molten polymer to a filter for filtering, and feeding the high-temperature molten polymer into a distributor;
and S3, taking the high-temperature molten polymer obtained in the step S1 as a surface layer and the high-temperature molten polymer obtained in the step S2 as a core layer, distributing the surface layer and the core layer through a distributor, conveying the surface layer and the core layer to a die head, performing composite extrusion molding through the die head, attaching the extruded product to a quenching roller, and rapidly cooling the extruded product to form a cast sheet.
And S4, preheating, stretching, sizing and cooling the cast sheet obtained in the step S3 in transverse stretching equipment, and finally, conveying the cast sheet to a winding machine for winding by using a traction roller to obtain the bio-based PTT/PLA heat-shrinkable label film.
And S5, sequentially slitting, inspecting and packaging the bio-based PTT/PLA heat-shrinkable label film obtained in the S4 to obtain a finished product.
The extruder is a parallel double-screw extruder, and the plasticizing temperature of the extruder is 245-265 ℃; the extrusion temperature of the automatic adjustment coat hanger type single-layer die head is 265-270 ℃; the cold water inlet temperature of the quenching roller is 25-32 ℃; in the transverse stretching equipment, the preheating temperature is 90-110 ℃, the stretching temperature is 85-95 ℃, the setting temperature is 70-80 ℃, the cooling temperature is 40-45 ℃, and the transverse stretching ratio is 1: 4.8.
example 2
Referring to example 1, the remaining characteristics are unchanged, and the mass ratio of the PLA of the surface layer to the PLA opening smooth master batch is 98: 2; the mass ratio of PLA, PTT and SEBS compatilizers of the core layer is 88: 10: 2.
example 3
Referring to example 1, the remaining characteristics are unchanged, and the mass ratio of the PLA of the surface layer to the PLA opening smooth master batch is 99: 1; the mass ratio of PLA, PTT and SEBS compatilizers of the core layer is 85: 12: 3.
the main properties of bio-based PTT/PLA heat shrink label films:
note: the comparative sample was a clear PETG heat shrink label film.
The described embodiments are only some, but not all embodiments of the invention. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.
Claims (10)
1. The utility model provides a biological base PTT/PLA heat-shrinkable label membrane, includes the sandwich layer, covers respectively in two surface courses of sandwich layer upper and lower surface, its characterized in that, the surface course comprises PLA and the smooth master batch of PLA opening, the sandwich layer comprises PLA, PTT and SEBS compatilizer.
2. The bio-based PTT/PLA heat-shrinkable label film according to claim 1, wherein the mass ratio of PLA to PLA opening-smooth master batch in the face layer is 97-99: 1-3.
3. The bio-based PTT/PLA heat-shrinkable label film according to claim 1, wherein the mass ratio of the PLA, the PTT and the SEBS compatibilizer in the core layer is 85-90: 8-12: 2-3.
4. The bio-based PTT/PLA heat-shrinkable label film according to claim 1, wherein the ratio of the thickness of the top surface facing, core layer and bottom surface facing is 1: 8: 1.
5. the bio-based PTT/PLA heat-shrinkable label film as claimed in claim 1, wherein the PLA is selected from PLA granules of extrusion grade or film grade, the PTT is selected from PTT slices of bright type without addition of opening smooth master batch, and the SEBS compatibilizer is selected from industrial SEBS compatibilizer.
6. A preparation method of a bio-based PTT/PLA heat-shrinkable label film is characterized by comprising the following steps:
s1, opening the PLA and the PLA smooth master batch according to the mass ratio of 97-99: 1-3, feeding the mixture into an extruder for plasticizing and melting to form a high-temperature molten polymer, metering the high-temperature molten polymer by a metering pump, conveying the high-temperature molten polymer to a filter for filtering, and feeding the high-temperature molten polymer into a distributor;
s2, mixing PLA, PTT and SEBS compatilizers according to the mass ratio of 85-90: 8-12: 2-3, feeding the mixture into an extruder for plasticizing and melting to form a high-temperature molten polymer, metering the high-temperature molten polymer by a metering pump, conveying the high-temperature molten polymer to a filter for filtering, and feeding the high-temperature molten polymer into a distributor;
s3, taking the high-temperature molten polymer obtained in the step S1 as a surface layer and the high-temperature molten polymer obtained in the step S2 as a core layer, distributing and conveying the surface layer and the core layer to a die head through a distributor, carrying out composite extrusion molding through the die head, attaching an extruded product to a quenching roller, and rapidly cooling the extruded product to form a cast sheet;
s4, preheating, stretching, sizing and cooling the cast sheet obtained in the step S3 in transverse stretching equipment, and finally, sending the cast sheet to a winding machine for winding by a traction roller to obtain the bio-based PTT/PLA heat-shrinkable label film;
and S5, sequentially slitting, inspecting and packaging the bio-based PTT/PLA heat-shrinkable label film obtained in the S4 to obtain a finished product.
7. The method for preparing the bio-based PTT/PLA heat-shrinkable label film as claimed in claim 6, wherein the extruder is a parallel twin-screw extruder, and the plasticizing temperature of the extruder is 245-265 ℃.
8. The method for preparing a bio-based PTT/PLA heat-shrinkable label film as claimed in claim 6, wherein the die head is a self-adjusting coat hanger type single-layer die head, and the extrusion temperature of the die head is 265 ℃ and 270 ℃.
9. The method for preparing a bio-based PTT/PLA heat-shrinkable label film as claimed in claim 6, wherein the chilled water inlet temperature of the chill roll is 25-32 ℃.
10. The method for preparing a bio-based PTT/PLA heat-shrinkable label film as claimed in claim 6, wherein in the transverse stretching device, the preheating temperature is 90-110 ℃, the stretching temperature is 85-95 ℃, the setting temperature is 70-80 ℃, the cooling temperature is 40-45 ℃, and the transverse stretching ratio is 1: 4.8.
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| CN112457638A (en) * | 2020-11-13 | 2021-03-09 | 南通大学 | Stereo polylactic acid/PTT biomass plastic and preparation method and application thereof |
| CN112721366A (en) * | 2020-12-23 | 2021-04-30 | 江苏光辉包装材料有限公司 | Low-density, low-shrinkage force and scratch-resistant heat-shrinkable label film and preparation method thereof |
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| CN112721366B (en) * | 2020-12-23 | 2022-07-19 | 江苏光辉包装材料有限公司 | Low-density, low-shrinkage force and scratch-resistant heat-shrinkable label film and preparation method thereof |
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