CN116001403A - Durable anti-collision PETG heat-shrinkable film and preparation method thereof - Google Patents
Durable anti-collision PETG heat-shrinkable film and preparation method thereof Download PDFInfo
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- CN116001403A CN116001403A CN202211556487.2A CN202211556487A CN116001403A CN 116001403 A CN116001403 A CN 116001403A CN 202211556487 A CN202211556487 A CN 202211556487A CN 116001403 A CN116001403 A CN 116001403A
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Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention discloses a durable collision-resistant PETG heat-shrinkable film which sequentially comprises a printing layer, a core layer and a durable layer, wherein the printing layer mainly comprises NPG modified PET and functional master batch; the core layer mainly comprises PET, PETG and a collision-resistant toughening agent; the durable layer mainly comprises NPG modified PET, scratch resistant agent, functional master batch and lubricant; the invention also discloses a preparation method of the heat-shrinkable film, which comprises the steps of drying and uniformly mixing all the raw materials, and obtaining the heat-shrinkable film through extrusion, melting and plasticizing, die casting, biaxial stretching, cooling and shaping and rolling. The heat-shrinkable film prepared by the method has a three-functional-layer structure, the whole film can integrate the advantages of all functional layers, meanwhile, all the layers of materials are derivatives of PET materials, the polarities are similar, the layering problem is avoided, the operation difficulty of equipment can be reduced, the process flow is reduced, the overall thickness of the film is reduced, and the production cost is reduced.
Description
Technical Field
The invention belongs to the field of heat shrink films, and particularly relates to a durable anti-collision PETG heat shrink film and a preparation method thereof.
Background
The PETG heat shrinkage film is used as an environment-friendly polyester film, has good mechanical strength, barrier property, chemical stability and environmental affinity, is widely used in aspects of beverage packaging, daily chemicals packaging and battery packaging, but most PETG heat shrinkage labels in the current market can be worn and bumped in the transportation and use processes, and the problems of film brittle failure and the like occur during printing, palm closing or label sleeving, so that the printing at the rear end of the film and the normal palm closing are seriously influenced. After the label sleeve label is used on the vessel, collision and friction can be generated between the bottle bodies and the packing box body in the transportation process, and the label surface can be caused to appear knocking marks, breakage and even fracture and fall off after long-time transportation due to poor anti-knocking performance of the label, so that the packaging effect is seriously influenced, and larger loss is caused.
For many packing conditions, the abrasion resistance of the label can be increased by using abrasion-resistant and scratch-resistant ink, but the damage to the label film is directly caused by the collision generated on the corner of the packaging vessel, so that the film is broken, the collision-resistant performance of the film is improved from the root, and the damage problem of the label film in the transportation process can be effectively reduced.
The method for increasing the collision resistance of the film reported in the current literature is to increase wear-resistant ink and coating or compound with other materials. However, the abrasion-resistant ink and the coating can not fundamentally solve the problem of label damage, and after the PETG film is compounded with other materials, the strength of the materials is increased, but the overall materials do not have contractility, so that the problem of incapability of shrinking the label is caused.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides the durable anti-collision PETG heat-shrinkable film and the preparation method thereof, and the prepared heat-shrinkable film can effectively reduce scratches, bruises and the like generated in the process of contacting the film with other objects in the long-distance transportation and use processes, so that the anti-collision performance of the film is improved from the root.
In order to solve the technical problems, the invention adopts the following technical scheme: a durable anti-collision PETG heat shrink film sequentially comprises a printing layer, a core layer and a durable layer; the printing layer mainly comprises NPG modified PET and functional master batch; the core layer mainly comprises PET, PETG and a collision-resistant toughening agent; the durable layer mainly comprises NPG modified PET, scratch resistant agent, functional master batch and lubricant. The mass percentage of the NPG modified PET in the printing layer is 96.0-99.2%, and the mass percentage of the functional master batch is 0.8-4.0%; 60-75% of PETG in the core layer, 5-15% of anti-collision toughening agent and 10-35% of PET; the mass percentage of NPG modified PET in the durable layer is 72.5-85.5%, the mass percentage of PET is 10-15%, the mass percentage of scratch resistant agent is 1.5-2.5%, the mass percentage of functional master batch is 0.8-4.0%, and the mass percentage of lubricant is 2.2-6.0%.
Preferably, the PETG is
S2012, isman GN071 or isman 0603.
Preferably, the PET is middle petrochemical instrumentation chemical fiber BG80, middle petrochemical instrumentation chemical fiber FG600, or source macro polymer YH600.
Further, the scratch resistant agent is transparent powder, nano zinc oxide or nano calcium carbonate.
Preferably, the functional master batch is formed by compounding one or more of silicon dioxide, talcum powder, clay and kaolin with erucamide.
Further, the anti-collision toughening agent is POE-g-GMA (glycidyl methacrylate grafted polypropylene elastomer) or E-MA-GMA (glycidyl methacrylate-containing terpolymer).
Further, the lubricant is one or more of oleamide, erucamide, stearyl alcohol, pentaerythritol and pentaerythritol stearate.
Preferably, the thickness of the durable and collision-resistant PETG heat-shrinkable film is 30-100 μm.
Preferably, the thickness ratio of the printing layer, the core layer and the durable layer is 10:60:30.
the method for preparing the durable and collision-resistant PETG heat-shrinkable film comprises the following steps:
step (1), drying the raw materials in a vacuum dryer to remove water;
step (2), primarily mixing the NPG modified PET and the functional master batch in a mixer according to the mass percentage of 96.0-99.2% and the mass percentage of 0.8-4.0% respectively to serve as mixed raw materials of a printing layer; the PETG, the anti-collision toughening agent and the PET are respectively and primarily mixed in a mixer according to the mass percentage of 60-75%, 5-15% and 10-35% to be used as the mixed raw materials of the core layer; the NPG modified PET, scratch resistant agent, functional master batch and lubricant are respectively mixed in a mixer according to the mass percentage of 72.5-85.5%, 10-15%, 1.5-2.5%, 0.8-4.0% and 2.2-6.0% to be used as the mixed raw materials of the durable layer;
step (3), uniformly mixing the mixed raw materials of all layers in a planetary mixer, wherein the mixing time is not less than 1h, and the mixing temperature is 70 ℃; respectively putting each layer of ingredients into a double-screw extruder according to the mixing area of the core layer and the surface layer for melting and plasticizing, wherein the diameter of a screw is 80mm, the length-diameter ratio of the screw is 32, and the temperature is 260-265 ℃;
step (4), melting and extruding each layer of raw materials after melting and plasticizing through a three-layer composite die head (the die head temperature is 260-280 ℃), cooling into cast sheets in a quenching roller, controlling the ratio of the linear speed of the rotation of the quenching roller to the outflow speed of the melt to be less than or equal to 5 in the quenching process, and controlling the temperature to be 33-37 ℃;
and (5) carrying out biaxial stretching on the cast sheet, wherein the longitudinal stretching conditions are as follows: preheating at 80-90 deg.c, stretching at 80-100 deg.c to reach stretching ratio of 1.2-1.5, longitudinal stretching and cooling at 40-60 deg.c to form; and after the longitudinal stretching is finished, transversely stretching, wherein the conditions of the transverse stretching are as follows: preheating at 90-110 ℃, enabling the stretching multiple to reach 3.5-4.5 at 70-90 ℃, transversely stretching, and cooling and shaping at 80-90 ℃ to obtain the durable and collision-resistant PETG heat-shrinkable film;
and (6) traction rolling, slitting, packaging and obtaining a finished product.
Compared with the prior art, the invention has the following advantages:
(1) The shrink film prepared by the method has a three-functional-layer structure, the whole film can integrate the advantages of all functional layers, meanwhile, all layers of materials are derivatives of PET materials, the polarities are similar, the interlayer adhesion force is strong, the layering problem is avoided, the equipment operation difficulty is reduced, the composite process is reduced, the overall thickness of the film is reduced, and the production cost is reduced;
(2) The three-layer co-extrusion film prepared by the method provided by the invention has the advantages that the surface layer mainly comprises the modified PET material with higher melt index and adopting the NPG modified, CHDM or NPG+CHDM monomer to be added, so that the crystallinity of the printing material is effectively reduced, wherein the addition of the functional master batch is beneficial to increasing the roughness of the printing layer, the corrosion and adhesive force of printing ink can be effectively increased, and the integral printability of the film is improved;
(3) According to the method, a certain PET component is added into the core layer and the durable layer, and the proper stretching ratio is combined with the regulation and control of the stretching process, the shaping temperature of the film is improved, and the like, so that the crystallinity of the film is improved to a certain extent on the premise of keeping the good palm closing performance of the film, the integral tensile strength of the film is effectively improved, the toughening agent mainly improves the integral flexibility of the film in the core layer, and the elongation of the film is effectively increased under the condition that the strength of the film is not reduced, so that the film has the characteristics of toughness and strength in the use process;
(4) The scratch resistant agent and the lubricant are added into the durable layer, so that the molecular arrangement of the polymer can be enhanced, the performance of the polymer is enhanced, the hardness is improved, the auxiliary agent migrates to the surface of the plastic to form uniform particle dispersion, the surface smoothness of the product is improved, the scratch resistant performance is improved, and the transparency of the product is not affected basically;
(5) The film has simple production process and excellent collision resistance, scratch resistance and strength, and the product packed by the film can be kept beautiful for a long time.
Detailed Description
The technical scheme of the invention is further described below in conjunction with the specific embodiments. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure.
The invention provides a durable anti-collision PETG heat-shrinkable film, which sequentially comprises a printing layer, a core layer and a durable layer, wherein the printing layer is arranged on the inner side of a package when the durable anti-collision PETG heat-shrinkable film is used; the printing layer mainly comprises NPG modified PET and functional master batch, and has the main function of printability; the core layer mainly comprises PET, PETG and a collision-resistant toughening agent, and has the main functions of enabling the film to have good contractility and extensibility; the durable layer mainly comprises NPG modified PET, scratch resistant agent, functional master batch and lubricant, and the main functions of the durable layer are collision resistance and wear resistance. The mass percentage of the NPG modified PET in the printing layer is 96.0-99.2%, and the mass percentage of the functional master batch is 0.8-4.0%; in the core layer, the mass percentage of PETG is 60-75%, the mass percentage of the anti-collision toughening agent is 5-15%, and the mass percentage of PET is 10-35%; the mass percentage of the NPG modified PET in the durable layer is 72.5-85.5%, the mass percentage of the PET is 10-15%, the mass percentage of the scratch resistant agent is 1.5-2.5%, the mass percentage of the functional master batch is 0.8-4.0%, and the mass percentage of the lubricant is 2.2-6.0%.
Preferably, the PETG is
S2012, isman GN071 or isman 0603.
Preferably, the PET is middle petrochemical instrumentation chemical fiber BG80, middle petrochemical instrumentation chemical fiber FG600, or source macro polymer YH600.
Further, the scratch resistant agent is transparent powder, nano zinc oxide or nano calcium carbonate.
Preferably, the functional master batch is formed by compounding one or more of silicon dioxide, talcum powder, clay and kaolin with erucamide.
Further, the anti-collision toughening agent is POE-g-GMA (glycidyl methacrylate grafted polypropylene elastomer) or E-MA-GMA (glycidyl methacrylate-containing terpolymer).
Further, the lubricant is one or more of oleamide, erucamide, stearyl alcohol, pentaerythritol and pentaerythritol stearate.
Preferably, the thickness of the durable and collision-resistant PETG heat-shrinkable film is 30-100 μm.
Preferably, the thickness ratio of the printing layer, the core layer and the durable layer is 10:60:30.
the method for preparing the durable and collision-resistant PETG heat-shrinkable film comprises the following steps:
step (1), drying the raw materials in a vacuum dryer to remove water;
step (2), primarily mixing the NPG modified PET and the functional master batch in a mixer according to the mass percentage of 96.0-99.2% and the mass percentage of 0.8-4.0% respectively to serve as mixed raw materials of a printing layer; the PETG, the anti-collision toughening agent and the PET are respectively and primarily mixed in a mixer according to the mass percentage of 60-75%, 5-15% and 10-35% to be used as the mixed raw materials of the core layer; the NPG modified PET, scratch resistant agent, functional master batch and lubricant are respectively mixed in a mixer according to the mass percentage of 72.5-85.5%, 10-15%, 1.5-2.5%, 0.8-4.0% and 2.2-6.0% to be used as the mixed raw materials of the durable layer;
step (3), uniformly mixing the mixed raw materials of all layers in a planetary mixer, wherein the mixing time is not less than 1h, and the mixing temperature is 70 ℃; respectively putting each layer of ingredients into a double-screw extruder according to the mixing area of the core layer and the surface layer for melting and plasticizing, wherein the diameter of a screw is 80mm, the length-diameter ratio of the screw is 32, and the temperature is 260-265 ℃;
step (4), melting and extruding each layer of raw materials after melting and plasticizing through a three-layer composite die head (the die head temperature is 260-280 ℃), cooling into cast sheets in a quenching roller, controlling the ratio of the linear speed of the rotation of the quenching roller to the outflow speed of the melt to be less than or equal to 5 in the quenching process, and controlling the temperature to be 33-37 ℃;
and (5) carrying out biaxial stretching on the cast sheet, wherein the longitudinal stretching conditions are as follows: preheating at 80-90 deg.c, stretching at 80-100 deg.c to reach stretching ratio of 1.2-1.5, longitudinal stretching and cooling at 40-60 deg.c to form; and after the longitudinal stretching is finished, transversely stretching, wherein the conditions of the transverse stretching are as follows: preheating at 90-110 ℃, enabling the stretching multiple to reach 3.5-4.5 at 70-90 ℃, transversely stretching, and cooling and shaping at 80-90 ℃ to obtain the durable and collision-resistant PETG heat-shrinkable film;
and (6) traction rolling, slitting, packaging and obtaining a finished product.
Example 1
(1) NPG modified PET (YH 103, source macro polymer) and PETG are processed
S2012), drying the raw materials such as the functional master batch and the like in a vacuum dryer to remove water;
(2) The printing layer, the core layer and the durable layer are respectively proportioned according to the composition proportion and are preliminarily and uniformly mixed in a mixer, wherein:
the printing layer comprises the following components in percentage by mass: NPG modified PET (YH 103, source macromoleclar): functional master batch (50% antiblocking agent SiO) 2 And 50% slipping agent crodamide ER) =96.0%: 4.0%;
the core layer comprises the following components in percentage by mass: PETG [ ]
S2012): bump resistant toughening agent (POE-g-GMA): PET (medium petrochemical instrumentation BG 80) =60%: 15%:25%;
the durable layer comprises the following components in percentage by mass: NPG modified PET (YH 103, source macromoleclar): PET (medium petrochemical instrumentation chemical fiber BG 80): scratch resistance agent (transparent powder): functional master batch (50% antiblocking agent SiO) 2 And 50% of the slip agent crodamide ER): lubricant (pentaerythritol stearate) =72.5%: 15%:2.5%:4.0%:6.0%;
(3) Uniformly mixing all the ingredients in a planetary mixer for at least 1h, controlling the mixing temperature at 70 ℃, putting the ingredients into a double-screw extruder for melt plasticization, wherein the diameter of a screw is 80mm, the length-diameter ratio is 32, and the temperature is 260-265 ℃;
(4) Carrying out melt extrusion on each layer of raw materials after melt plasticization through a three-layer composite die head, wherein the die head temperature is 270 ℃;
(5) And extruding the cast sheet from the melt, controlling the ratio of the linear speed of the rotation of the quenching roller to the melt outflow speed to be less than or equal to 5, and controlling the temperature of the quenching roller to be 33-37 ℃.
(6) And (3) carrying out biaxial stretching on the cast sheet, wherein the longitudinal stretching conditions are as follows: single-point stretching is carried out by an infrared heating mode, after preheating at 85 ℃, the stretching multiple of the single-point stretching reaches 1.5 at 90 ℃, and after longitudinal stretching, cooling and shaping are carried out at 50 ℃; and after the longitudinal stretching is finished, transversely stretching, wherein the conditions of the transverse stretching are as follows: preheating at 100 ℃, enabling the stretching multiple to reach 4.0 at 80 ℃, transversely stretching, and cooling and shaping at 85 ℃ to obtain a durable and collision-resistant PETG heat-shrinkable film;
wherein, the thickness ratio of the printing layer, the core layer and the durable layer is 10:60:30.
example 2
(1) Drying NPG modified PET (YH 103, source macro polymer), PETG (Isman GN 071), functional master batch and other raw materials in a vacuum dryer to remove water;
(2) The printing layer, the core layer and the durable layer are respectively proportioned according to the composition proportion and are preliminarily and uniformly mixed in a mixer, wherein:
the printing layer comprises the following components in percentage by mass: NPG modified PET (YH 103, source macromoleclar): functional master batch (50% antiblocking agent SiO) 2 And 50% slipping agent crodamide ER) =99.2%: 0.8%;
the core layer comprises the following components in percentage by mass: PETG [ ]
S2012): bump resistant toughening agent (E-MA-EMA): PET (medium petrochemical instrumentation FG 600) =75%: 15%:10%;
the durable layer comprises the following components in percentage by mass: NPG modified PET (YH 103, source macromoleclar): PET (medium petrochemical instrumentation chemical fiber BG 80): scratch resistance agent (nano calcium carbonate): functional master batch (50% antiblocking agent SiO) 2 And 50% of the slip agent crodamide ER): lubricant (oleamide) =85.5%: 10%:1.5%:0.8%:2.2%;
(3) Uniformly mixing all the ingredients in a planetary mixer for at least 1h, controlling the mixing temperature at 70 ℃, putting the ingredients into a double-screw extruder for melt plasticization, wherein the diameter of a screw is 80mm, the length-diameter ratio is 32, and the temperature is 260-265 ℃;
(4) Carrying out melt extrusion on each layer of raw materials after melt plasticization through a three-layer composite die head, wherein the die head temperature is 270 ℃;
(5) And extruding the cast sheet from the melt, controlling the ratio of the linear speed of the rotation of the quenching roller to the melt outflow speed to be less than or equal to 5, and controlling the temperature of the quenching roller to be 33-37 ℃.
(6) And (3) carrying out biaxial stretching on the cast sheet, wherein the longitudinal stretching conditions are as follows: single-point stretching is carried out by an infrared heating mode, after preheating at 85 ℃, the stretching multiple of the single-point stretching reaches 1.5 at 90 ℃, and after longitudinal stretching, cooling and shaping are carried out at 50 ℃; and after the longitudinal stretching is finished, transversely stretching, wherein the conditions of the transverse stretching are as follows: preheating at 100 ℃, enabling the stretching multiple to reach 4.0 at 80 ℃, transversely stretching, and cooling and shaping at 85 ℃ to obtain a durable and collision-resistant PETG heat-shrinkable film;
wherein, the thickness ratio of the printing layer, the core layer and the durable layer is 10:60:30.
example 3
(1) Drying NPG modified PET (YH 103, source macro polymer), PETG (Isman 0603), functional master batch and other raw materials in a vacuum dryer to remove water;
(2) The printing layer, the core layer and the durable layer are respectively proportioned according to the composition proportion and are preliminarily and uniformly mixed in a mixer, wherein:
the printing layer comprises the following components in percentage by mass: NPG modified PET (YH 103, source macromoleclar): functional master batch (50% antiblocking agent SiO) 2 And 50% slipping agent crodamide ER) =98.0%: 2.0%;
the core layer comprises the following components in percentage by mass: PETG [ ]
S2012): bump resistant toughening agent (POE-g-GMA): PET (source macro polymer YH 600) =60%: 5%:35%;
the durable layer comprises the following components in percentage by mass: NPG modified PET (YH 103, source macromoleclar): PET (medium petrochemical instrumentation chemical fiber BG 80): scratch resistance agent (nano zinc oxide): functional master batch (50% antiblocking agent SiO) 2 And 50% of the slip agent crodamide ER): lubricant (oleamide) =72.5%: 15%:2.5%:4.0%:6.0%;
(3) Uniformly mixing all the ingredients in a planetary mixer for at least 1h, controlling the mixing temperature at 70 ℃, putting the ingredients into a double-screw extruder for melt plasticization, wherein the diameter of a screw is 80mm, the length-diameter ratio is 32, and the temperature is 260-265 ℃;
(4) Carrying out melt extrusion on each layer of raw materials after melt plasticization through a three-layer composite die head, wherein the die head temperature is 270 ℃;
(5) And extruding the cast sheet from the melt, controlling the ratio of the linear speed of the rotation of the quenching roller to the melt outflow speed to be less than or equal to 5, and controlling the temperature of the quenching roller to be 33-37 ℃.
(6) And (3) carrying out biaxial stretching on the cast sheet, wherein the longitudinal stretching conditions are as follows: single-point stretching is carried out by an infrared heating mode, after preheating at 85 ℃, the stretching multiple of the single-point stretching reaches 1.5 at 90 ℃, and after longitudinal stretching, cooling and shaping are carried out at 50 ℃; and after the longitudinal stretching is finished, transversely stretching, wherein the conditions of the transverse stretching are as follows: preheating at 100 ℃, enabling the stretching multiple to reach 4.0 at 80 ℃, transversely stretching, and cooling and shaping at 85 ℃ to obtain a durable and collision-resistant PETG heat-shrinkable film;
wherein, the thickness ratio of the printing layer, the core layer and the durable layer is 10:60:30.
example 4
(1) NPG modified PET (YH 103, source macro polymer) and PETG are processed
S2012), drying the raw materials such as the functional master batch and the like in a vacuum dryer to remove water;
(2) The printing layer, the core layer and the durable layer are respectively proportioned according to the composition proportion and are preliminarily and uniformly mixed in a mixer, wherein:
the printing layer comprises the following components in percentage by mass: NPG modified PET (YH 103, source macromoleclar): functional master batch (50% antiblocking agent SiO) 2 And 50% slipping agent crodamide ER) =98.8%: 1.2%;
the core layer comprises the following components in percentage by mass: PETG [ ]
S2012): bump resistant toughening agent (POE-g-GMA): PET (medium petrochemical instrumentation BG 80) =70%: 12%:18%;
the durable layer comprises the following components in percentage by mass: NPG modified PET (YH 103, source macromoleclar): PET (medium petrochemical instrumentation chemical fiber BG 80): scratch resistant agent (transparent powder): functional master batch (50% antiblocking agent SiO) 2 And 50% of the slip agent crodamide ER): lubricant (oleamide) =78.0%: 12%:2.0%:2.8%:5.2%;
(3) Uniformly mixing all the ingredients in a planetary mixer for at least 1h, controlling the mixing temperature at 70 ℃, putting the ingredients into a double-screw extruder for melt plasticization, wherein the diameter of a screw is 80mm, the length-diameter ratio is 32, and the temperature is 260-265 ℃;
(4) Carrying out melt extrusion on each layer of raw materials after melt plasticization through a three-layer composite die head, wherein the die head temperature is 270 ℃;
(5) And extruding the cast sheet from the melt, controlling the ratio of the linear speed of the rotation of the quenching roller to the melt outflow speed to be less than or equal to 5, and controlling the temperature of the quenching roller to be 33-37 ℃.
(6) And (3) carrying out biaxial stretching on the cast sheet, wherein the longitudinal stretching conditions are as follows: single-point stretching is carried out by an infrared heating mode, after preheating at 85 ℃, the stretching multiple of the single-point stretching reaches 1.5 at 90 ℃, and after longitudinal stretching, cooling and shaping are carried out at 50 ℃; and after the longitudinal stretching is finished, transversely stretching, wherein the conditions of the transverse stretching are as follows: preheating at 100 ℃, enabling the stretching multiple to reach 4.0 at 80 ℃, transversely stretching, and cooling and shaping at 85 ℃ to obtain a durable and collision-resistant PETG heat-shrinkable film;
wherein, the thickness ratio of the printing layer, the core layer and the durable layer is 10:60:30.
example 5
(1) NPG modified PET (YH 103, source macro polymer) and PETG are processed
S2012), drying the raw materials such as the functional master batch and the like in a vacuum dryer to remove water;
(2) Each layer of the ABC three-layer structure is respectively proportioned according to the composition proportion, and the proportioned materials are preliminarily and uniformly mixed in a mixer, wherein:
the printing layer comprises the following components in percentage by mass: NPG modified PET (YH 103, source macromoleclar): functional master batch (50% antiblocking agent SiO) 2 And 50% slipping agent crodamide ER) =98.8%: 1.2%;
the core isThe layer comprises the following components in percentage by mass: PETG [ ]
S2012): bump resistant toughening agent (POE-g-GMA): PET (medium petrochemical instrumentation BG 80) =70%: 12%:18%;
the durable layer comprises the following components in percentage by mass: NPG modified PET (YH 103, source macromoleclar): PET (medium petrochemical instrumentation chemical fiber BG 80): scratch resistance agent (transparent powder): functional master batch (50% antiblocking agent SiO) 2 And 50% of the slip agent crodamide ER): lubricant (oleamide) =78.0%: 12%:2.0%:2.8%:5.2%;
(3) Uniformly mixing all the ingredients in a planetary mixer for at least 1h, controlling the mixing temperature at 70 ℃, putting the ingredients into a double-screw extruder for melt plasticization, wherein the diameter of a screw is 80mm, the length-diameter ratio is 32, and the temperature is 260-265 ℃;
(4) Carrying out melt extrusion on each layer of raw materials after melt plasticization through a three-layer composite die head, wherein the die head temperature is 270 ℃;
(5) And extruding the cast sheet from the melt, controlling the ratio of the linear speed of the rotation of the quenching roller to the melt outflow speed to be less than or equal to 5, and controlling the temperature of the quenching roller to be 33-37 ℃.
(6) And (3) carrying out biaxial stretching on the cast sheet, wherein the longitudinal stretching conditions are as follows: single-point stretching is carried out by an infrared heating mode, after preheating at 85 ℃, the stretching multiple of the single-point stretching reaches 1.5 at 90 ℃, and after longitudinal stretching, cooling and shaping are carried out at 50 ℃; and after the longitudinal stretching is finished, transversely stretching, wherein the conditions of the transverse stretching are as follows: preheating at 100 ℃, enabling the stretching multiple to reach 4.0 at 80 ℃, transversely stretching, and cooling and shaping at 85 ℃ to obtain a durable and collision-resistant PETG heat-shrinkable film;
wherein, the thickness ratio of the printing layer, the core layer and the durable layer is 10:60:30.
comparative example 1
The core layer in this comparative example comprises the following components in mass percent: PETG [ ]
S2012): PET (medium petrochemical instrumentation BG 80) =82%: 18%; the other components were the same as in example 4, and the preparation method was the same as in example 4.
Comparative example 2
The core layer in this comparative example comprises the following components in mass percent: PETG [ ]
S2012): bump resistant toughening agent (POE-g-GMA) =88%: 12%; the other components were the same as in example 4, and the preparation method was the same as in example 4.
Comparative example 3
The core layer in this comparative example comprises the following components in mass percent: PET (medium petrochemical instrumentation chemical fiber BG 80): bump resistant toughening agent (POE-g-GMA) =85%: 15%; the other components were the same as in example 4, and the preparation method was the same as in example 4.
Comparative example 4
The durable layer in this comparative example comprises the following components in mass percent: NPG modified PET (YH 103, source macromoleclar): PET (medium petrochemical instrumentation chemical fiber BG 80): scratch resistance agent (transparent powder): functional master batch (50% antiblocking agent SiO) 2 And 50% slipping agent crodamide ER) =83.2%: 12%:2.0%:2.8% and the other components were the same as in example 4, and the preparation was the same as in example 4.
Comparative example 5
The durable layer in this comparative example comprises the following components in mass percent: NPG modified PET (YH 103, source macromoleclar): PET (medium petrochemical instrumentation chemical fiber BG 80): functional master batch (50% antiblocking agent SiO) 2 And 50% of the slip agent crodamide ER): lubricant (oleamide) =80.0%: 12%:2.8%:5.2% other components were identical to those of example 4 and the preparation was identical to that of example 4.
Comparative example 6
The durable layer described in this comparative example comprises the following components in mass percent: NPG modified PET (YH 103, source macromoleclar): PET (medium petrochemical instrumentation chemical fiber BG 80): scratch resistance agent (transparent powder): lubricant (oleamide) =80.8%: 12%:2.0%:5.2% other components were identical to those of example 4 and the preparation was identical to that of example 4.
Comparative example 7
The durable layer described in this comparative example comprises the following components in mass percent: NPG modified PET (YH 103, source macromoleclar): scratch resistance agent (transparent powder): functional master batch (50% antiblocking agent SiO) 2 And 50% of the slip agent crodamide ER): lubricant (oleamide) =90.0%: 2.0%:2.8%:5.2% other components were identical to those of example 4 and the preparation was identical to that of example 4.
Comparative example 8
The durable layer described in this comparative example comprises the following components in mass percent: NPG modified PET (YH 103, source macromoleclar): functional master batch (50% antiblocking agent SiO) 2 And 50% slipping agent crodamide ER) =97.2%: 2.8% and the other components were the same as in example 4, and the preparation was the same as in example 4.
Comparative example 9
In this example, the cast sheet was transversely stretched under the following conditions: the stretching ratio was 3.0. The components were the same as in example 4 and the preparation was the same as in example 4.
Comparative example 10
In this example, the cast sheet was subjected to longitudinal stretching under the following conditions: the stretching ratio was 1.0. The components were the same as in example 4 and the preparation was the same as in example 4.
Comparative example 11
In this example, the cast sheet was transversely stretched under the following conditions: preheating at 100deg.C, and stretching at 80deg.C to 4.0; cooling and shaping at 70 ℃ after transverse stretching; the components were the same as in example 4 and the preparation was the same as in example 4.
Comparative example 12
In this example, the cast sheet was transversely stretched under the following conditions: preheating at 100 ℃, and enabling the stretching multiplying power to reach 4.0 times at 80 ℃; cooling and shaping at 100 ℃ after transverse stretching; the components were the same as in example 4 and the preparation was the same as in example 4.
The durable and collision-resistant PETG heat-shrinkable films prepared in examples 1 to 5 and comparative examples 1 to 12 were respectively tested for indexes such as thickness, tensile strength, elongation at break, palm closing performance, collision resistance, shrinkage, haze and the like, wherein the tensile strength and the elongation at break were carried out by referring to the GB/T1040.3 method; the determination of the light transmittance and the haze is carried out according to the related method of GB/T2410-2008; the method for testing the anti-collision performance comprises the steps of shrinking the film on the bottle, putting the bottle into a paper box, shaking for 5min, observing the collision marks on the surface of the heat-shrinkable film on the bottle body, and recording the number, wherein the number is large, so that the anti-collision performance is poor, and otherwise, the anti-collision performance is good; the wear resistance test adopts a certain method to rub the surface, the haze value is measured by measuring the haze change by an instrument, and the haze value is used as a comparison basis of the wear resistance effect, and the method comprises the following steps: after the haze of the sample film is measured, the sample film is stuck to a small steel closure for testing friction, the sample film is placed on a clean glass surface for testing, a weight with a certain weight (2 KG) is pressed, the sample film is pulled for 5 times towards the same direction, the haze of the middle part of the test is taken down, the measured haze is stuck to the small closure, the haze is recorded after the haze is measured for 5 times (10 times are accumulated) according to the mode, and the haze is recorded for 15 times after the haze is measured for 5 times. And the numerical values are recorded, and the haze value change is relatively small and the abrasion resistance effect is relatively good under the same test condition. The test results are shown in Table 1.
TABLE 1 Performance of durable anti-bump PETG Heat shrink films
As can be seen from Table 1, according to comparative examples 1 to 4 and comparative example 1, when the core layer is made of (5% -15%) anti-collision toughening agent (POE-g-GMA), the elongation at break is increased, which indicates that the overall toughness of the film is improved, and the number of the knocks easily generated after the bodies of the film collide with each other in the simulated transportation environment is reduced, so that the effect of improving the anti-collision effect of the film is achieved.
In example 4, when PET was not added to the core layer and the durable layer, the elongation at break was high, which means that the toughness was good, but the tensile strength was insufficient, and when the film strength was insufficient, scratches were easily formed on the film surface, the appearance of the film for printing and the like was impaired, and the defects due to the scratches were easily caused to the occurrence of cracks in the film, as compared with comparative example 2 and comparative example 7.
Compared with comparative example 3, in example 4, when PETG is not added to the core layer, the tensile strength of the whole film is greatly improved, but the elongation at break of the film is reduced more, the core layer mainly comprises PET and a collision-resistant toughening agent, the crystallinity of the film is too high, so that the film basically loses heat shrinkage, the original haze of the film is too high, printing (inner printing) is not facilitated, and the use effect of the film is reduced.
Compared with comparative examples 4, 5 and 6, when the durable layer does not contain one of scratch resistant agent, lubricant or functional master batch, the haze of the film is improved more after friction, which indicates that the overall scratch and scratch resistant effect of the film is poor, the requirement of the film on durability and collision resistance cannot be met, and the packaging effect is affected.
Example 4 compared to comparative example 8, when the durable layer did not contain a combination of PET, scratch resistance agent, and lubricant, the haze of the film after rubbing was greatly improved, and the crashworthiness of the film after the simulated transportation test was greatly reduced, both differing significantly from the examples.
Example 4 when the transverse stretching ratio was not properly selected in the process used, the crystallinity orientation degree of the film was low, resulting in insufficient overall strength of the film, compared with comparative example 9.
Example 4 compared with comparative example 10, when the process used was not performed with longitudinal stretching and only 4 times of transverse stretching was used, the film was too high in transverse orientation degree and crystallinity, resulting in the phenomena of slightly high initial haze of the film and weak six-ring palm of the film, affecting the use of back-end palm-fitting agent overprinting.
Example 4 compared with comparative example 11 and comparative example 12, when the setting temperature in the transverse stretching of the process used (comparative example 11-70 ℃) is low, the crystallinity of the film is low, the impact resistance and scratch resistance effects are general, and when the setting temperature in the transverse stretching of the process used (comparative example 11-100 ℃) is high, the film is excessively crystallized, so that the phenomena of slightly high initial haze of the film and infirm six-ring palm closing of the film occur, and the use of the back end palm closing agent overprinting is affected.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The durable anti-collision PETG heat-shrinkable film sequentially comprises a printing layer, a core layer and a durable layer, and is characterized in that the printing layer mainly comprises NPG modified PET and functional master batch; the core layer mainly comprises PET, PETG and a collision-resistant toughening agent; the durable layer mainly comprises NPG modified PET, scratch resistant agent, functional master batch and lubricant; the mass percentage of the NPG modified PET in the printing layer is 96.0-99.2%, and the mass percentage of the functional master batch is 0.8-4.0%; 60-75% of PETG in the core layer, 5-15% of anti-collision toughening agent and 10-35% of PET; the mass percentage of NPG modified PET in the durable layer is 72.5-85.5%, the mass percentage of PET is 10-15%, the mass percentage of scratch resistant agent is 1.5-2.5%, the mass percentage of functional master batch is 0.8-4.0%, and the mass percentage of lubricant is 2.2-6.0%.
2. The durable and collision-resistant PETG heat-shrinkable film of claim 1, wherein said PETG is
S2012, isman GN071 or isman 0603.
3. The durable and collision-resistant PETG heat-shrinkable film of claim 1, wherein the PET is middle petrochemical instrumentation BG80, middle petrochemical instrumentation FG600, or source macro polymer YH600.
4. The durable and collision-resistant PETG heat-shrinkable film of claim 1, wherein the scratch-resistant agent is transparent powder, nano zinc oxide or nano calcium carbonate.
5. The durable and collision-resistant PETG heat-shrinkable film of claim 1, wherein the functional master batch is formed by compounding one or more of silicon dioxide, talcum powder, clay and kaolin with erucamide.
6. The durable and collision-resistant PETG heat-shrinkable film of claim 1, wherein the collision-resistant toughening agent is POE-g-GMA or E-MA-GMA.
7. A durable bump resistant PETG heat shrink film according to claim 1, wherein the lubricant is one or more of oleamide, erucamide, stearyl alcohol, pentaerythritol stearate.
8. The durable and collision-resistant PETG heat-shrinkable film according to claim 1, wherein the thickness of the durable and collision-resistant PETG heat-shrinkable film is 30-100 μm.
9. The durable bump resistant PETG heat shrink film of claim 1, wherein the thickness ratio of the print layer, core layer and durable layer is 10:60:30.
10. the method for preparing the durable and collision-resistant PETG heat-shrinkable film is characterized by comprising the following steps:
step (1), drying the raw materials in a vacuum dryer to remove water;
step (2), primarily mixing the NPG modified PET and the functional master batch in a mixer according to the mass percentage of 96.0-99.2% and the mass percentage of 0.8-4.0% respectively to serve as mixed raw materials of a printing layer; the PETG, the anti-collision toughening agent and the PET are respectively and primarily mixed in a mixer according to the mass percentage of 60-75%, 5-15% and 10-35% to be used as the mixed raw materials of the core layer; the NPG modified PET, scratch resistant agent, functional master batch and lubricant are respectively mixed in a mixer according to the mass percentage of 72.5-85.5%, 10-15%, 1.5-2.5%, 0.8-4.0% and 2.2-6.0% to be used as the mixed raw materials of the durable layer;
step (3), uniformly mixing the mixed raw materials of all layers in a planetary mixer, wherein the mixing time is not less than 1h, and the mixing temperature is 70 ℃; respectively putting each layer of ingredients into a double-screw extruder according to the mixing area of the core layer and the surface layer for melting and plasticizing, wherein the diameter of a screw is 80mm, the length-diameter ratio of the screw is 32, and the temperature is 260-265 ℃;
step (4), melting and extruding each layer of raw materials after melting and plasticizing through a three-layer composite die head (the die head temperature is 260-280 ℃), cooling into cast sheets in a quenching roller, controlling the ratio of the linear speed of the rotation of the quenching roller to the outflow speed of the melt to be less than or equal to 5 in the quenching process, and controlling the temperature to be 33-37 ℃;
and (5) carrying out biaxial stretching on the cast sheet, wherein the longitudinal stretching conditions are as follows: preheating at 80-90 deg.c, stretching at 80-100 deg.c to reach stretching ratio of 1.2-1.5, longitudinal stretching and cooling at 40-60 deg.c to form; and after the longitudinal stretching is finished, transversely stretching, wherein the conditions of the transverse stretching are as follows: preheating at 90-110 ℃, enabling the stretching multiple to reach 3.5-4.5 at 70-90 ℃, transversely stretching, and cooling and shaping at 80-90 ℃ to obtain the durable and collision-resistant PETG heat-shrinkable film;
and (6) traction rolling, slitting, packaging and obtaining a finished product.
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