A kind of polyester film capable of laser engraving and preparation method thereof

Abstract

The present invention relates to the field of polymer materials, and in particular to a polyester film capable of laser engraving and a preparation method thereof, comprising the following steps: preparing polyester resin powder; preparing laser engraving auxiliary agent-carbon nanotubes; using the powder and carbon nanotubes to prepare concentrated masterbatch; adding polyester particles and concentrated masterbatch to an extruder for processing to obtain a polyester film. The present invention obtains a film capable of laser engraving high-blackness graphics by adding grafted amino multi-walled carbon nanotubes and mechanically activated laser engraving auxiliary agents, the grafting reaction improves the laser engraving efficiency, and the surface resistance of the obtained film is less than 109Ω; the obtained film can be laminated and bonded with materials such as PVC, PETG, PC, etc., without the need for glue assistance; during the lamination and carding process of the film, the laminated steel plate will not be adhered. Thus, the problem of poor performance of the existing polyester film is solved.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, and in particular to a laser-engravable polyester film and a preparation method thereof. Background Art

[0002] PETG is a non-crystalline copolyester. Its products are highly transparent and have excellent impact resistance. They are widely used in the market of plates, sheets, high-performance shrink films, bottles and profiles. At present, most of the international card projects are based on PVC and PC materials. However, the environmental disadvantage of PVC is becoming more and more prominent, and the processing of PC materials is difficult, and the requirements for the later card equipment are strict.

[0003] PETG has been recognized by the international market for its high transparency, good gloss, easy printing, environmental advantages, high cost performance, high mechanical strength, and excellent comprehensive performance. Among them, Indian subway cards and Indonesian ID cards are all made of PETG materials. In China, with the promotion of China's second-generation ID cards, PETG card materials are increasingly used.

[0004] Although PETG is widely used, its Vicat softening point is around 68°C, which makes it difficult to be used in high-temperature card fields, such as SIM cards, ETC cards, etc. In addition, PETG has poor laser engraving performance. After adding laser engraving additives, the blackness of the laser engraving is not enough, which limits its use. Summary of the invention

[0005] The purpose of the present invention is to provide a laser-engravable polyester film and a preparation method thereof, aiming to solve the problem of poor performance of existing polyester films.

[0006] To achieve the above object, the present invention provides a method for preparing a laser-engravable polyester film, comprising the following steps:

[0007] preparing polyester resin powder;

[0008] Preparation of laser engraving additive-carbon nanotubes;

[0009] Preparation of concentrated masterbatch using powder and carbon nanotubes;

[0010] The polyester particles and concentrated masterbatch are added to the extruder for processing to obtain polyester film.

[0011] Wherein, in the "preparation of polyester resin powder", the polyester resin powder is 200 mesh powder.

[0012] Among them, in the "preparation of laser engraving additive-carbon nanotube", the following steps are included:

[0013] Laser engraving additives are mechanically activated;

[0014] Add 1 part of ethanol to the mechanically activated laser engraving agent for dilution;

[0015] The aminated multi-walled carbon nanotubes are diluted with an ethanol solvent and then added into the diluted laser engraving agent to obtain the laser engraving agent-carbon nanotubes.

[0016] Among them, in “preparing concentrated masterbatch using powder and carbon nanotubes”, the following steps are included:

[0017] Adding laser engraving additive-carbon nanotubes into the powder and stirring until the ethanol solvent is completely volatilized to obtain a mixture;

[0018] The mixture was added to a granulator for granulation to obtain concentrated masterbatch.

[0019] Among them, the process of “adding polyester particles and concentrated masterbatch into an extruder for processing to obtain a polyester film” includes the following steps:

[0020] Pre-treatment of polyester pellets and concentrated masterbatches;

[0021] The pretreated raw materials are put into an extruder for melt treatment;

[0022] The melt filter filters the raw materials after the melt treatment;

[0023] The melt pump processes and filters the raw materials and transports them to the mold for processing to obtain semi-finished products;

[0024] The three-roll calender cools and shapes the semi-finished product to obtain a polyester film.

[0025] Among them, in "pre-treating polyester particles and concentrated masterbatch", the following steps are included:

[0026] Mixing 90 parts of polyester particles with the concentrated masterbatch to obtain a mixed raw material;

[0027] The mixed raw materials are dried.

[0028] In a second aspect, a laser-engravable polyester film is prepared by the method for preparing a laser-engravable polyester film described in the first aspect, and includes 100 parts of a polyester resin, 0.025-0.1 parts of a laser-engraving auxiliary agent, and 0.0001-0.0005 parts of an antistatic agent.

[0029] The present invention discloses a method for preparing a polyester film capable of laser engraving, comprising the following steps: preparing polyester resin powder; preparing laser engraving auxiliary agent-carbon nanotubes; using the powder and carbon nanotubes to prepare concentrated masterbatch; adding polyester particles and concentrated masterbatch to an extruder for processing to obtain a polyester film. The present invention obtains a film capable of laser engraving high-blackness images and texts by adding grafted amino multi-walled carbon nanotubes and mechanically activated laser engraving auxiliary agents. The grafting reaction improves the efficiency of laser engraving, and the surface resistance of the obtained film is less than 109Ω; the obtained film can be laminated and bonded with materials such as PVC, PETG, and PC without the assistance of glue; during the lamination and carding process of the film, the laminated steel plate will not be adhered. The present invention provides a simple and easy preparation method, broadens the application prospects of high-temperature polyester, promotes the process of material functionalization, and has great application prospects. Thus, the problem of poor performance of existing polyester films is solved. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0031] Figure 1 The present invention provides a flow chart of a method for preparing a polyester film capable of being laser engraved.

[0032] Figure 2 This is a flow chart for preparing laser engraving additive-carbon nanotubes.

[0033] Figure 3 This is a flow chart of preparing concentrated masterbatch using powder and carbon nanotubes.

[0034] Figure 4 This is a flow chart of adding polyester particles and concentrated masterbatch into an extruder for processing to obtain polyester film.

[0035] Figure 5 This is a flow chart for pre-processing polyester granules and concentrated masterbatches. DETAILED DESCRIPTION

[0036] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and should not be construed as limiting the present invention.

[0037] See also Figures 1 to 5In a first aspect, the present invention provides a method for preparing a laser-engravable polyester film, comprising the following steps:

[0038] S1 prepares polyester resin powder;

[0039] The polyester resin powder is 200 mesh powder.

[0040] Specifically, select SK's ECOZEN series or EASTMAN's Tritan series polyester resin as raw material, grind 10 parts of polyester resin into 200 mesh powder through a grinder, and adjust the parameters of the grinder to ensure that the particle size of the powder reaches 200 mesh. Purpose This process is to increase the contact area between the polyester resin and subsequent additives and improve mixing uniformity.

[0041] S2 prepares laser engraving additive-carbon nanotubes;

[0042] The laser carving agent is added into a high-speed mixer for high-speed stirring for mechanical activation, 1 part of ethanol is added for dilution, and then the agent is diluted with the amino multi-walled carbon nanotubes through 1 part of ethanol solvent to obtain grafted laser carving agent-carbon nanotubes.

[0043] S21 laser engraving agent for mechanical activation;

[0044] Specifically, a laser engraving agent (at least one of Merck's 8825, 8817, and 8850) is added to a high-speed mixer and stirred at high speed for mechanical activation, which helps to enhance the dispersibility and reactivity of the laser engraving agent in the polyester resin.

[0045] S22 Add 1 part of ethanol to the mechanically activated laser engraving agent for dilution;

[0046] Specifically, 1 part of ethanol is added to the mechanically activated laser engraving auxiliary agent for dilution to reduce its viscosity, so as to facilitate subsequent mixing with the amino-modified multi-walled carbon nanotubes.

[0047] S23 dilutes the amino-modified multi-walled carbon nanotubes with an ethanol solvent, and then adds the diluted laser engraving agent to obtain the laser engraving agent-carbon nanotubes.

[0048] Specifically, the aminated multi-walled carbon nanotubes (MWCNTs-NH2, outer diameter 8-15 nanometers, length ≤ 20 μm) are diluted with another portion of ethanol solvent and then slowly added to the diluted laser engraving agent. Under high-speed stirring, the aminated multi-walled carbon nanotubes and the laser engraving agent undergo a grafting reaction. The grafting reaction improves the laser engraving efficiency and gives the film antistatic properties.

[0049] S3 uses powder and carbon nanotubes to prepare concentrated masterbatch;

[0050] S31 adding a laser engraving auxiliary agent - carbon nanotubes to the powder and stirring until the ethanol solvent is completely volatilized to obtain a mixture;

[0051] Specifically, the grafted mixture is stirred continuously under high-speed stirring until the ethanol solvent is completely volatilized, and then the obtained mixture is dried to remove residual water and solvent.

[0052] S32 adds the mixture into a granulator for granulation to obtain concentrated masterbatch.

[0053] Specifically, the dried grafted laser engraving agent-carbon nanotube mixture is added to the ground polyester resin powder. The two are fully mixed under high-speed stirring. The mixed powder is then added to a twin-screw granulator for granulation.

[0054] S4 adds the polyester particles and the concentrated masterbatch into an extruder for processing to obtain a polyester film.

[0055] S41 pre-treats polyester pellets and concentrated masterbatches;

[0056] S411: mixing 90 parts of polyester particles with the concentrated masterbatch to obtain a mixed raw material;

[0057] Specifically, 90 parts of polyester particles are uniformly mixed with the concentrated functional masterbatch prepared above.

[0058] S412 dries the mixed raw materials.

[0059] Specifically, the mixed raw materials are dried by air blast at 80° C. for 4 hours to ensure that the moisture content in the raw materials is less than 100 PPM, thereby preventing bubbles and defects from appearing in the film during processing.

[0060] S42 puts the pretreated raw materials into an extruder for melt processing;

[0061] Specifically, the polyester resin and concentrated masterbatch that have been dried and mixed uniformly are put into an extruder. The extruder melts and mixes the raw materials uniformly through heating and shearing. The temperature of the extruder is usually controlled between 190-240°C.

[0062] S43 melt filter filters the raw materials after melting treatment;

[0063] Specifically, the melted raw materials are filtered through a melt filter to remove impurities and incompletely melted particles. The temperature of the melt filter is usually slightly higher than the temperature of the extruder to ensure that the melt can flow smoothly and avoid filter clogging. The temperature of the filter is usually controlled between 220-235°C.

[0064] The S44 melt pump processes and filters the raw materials and transports them to the mold for processing to obtain semi-finished products;

[0065] Specifically, the filtered melt is transported by a melt pump. The melt pump can provide stable pressure and flow to ensure that the melt can enter the mold evenly and continuously. In the mold, it is molded into the required shape and thickness to form a semi-finished polyester film. The temperature of the mold is usually controlled between 230-240℃.

[0066] The S45 three-roll calender cools and shapes the semi-finished product to obtain polyester film.

[0067] Specifically, the semi-finished product coming out of the mold is cooled and shaped by a three-roll calender. By adjusting the temperature and pressure of the rollers, the flatness and glossiness of the polyester film can be controlled. As the semi-finished product cools and solidifies, a polyester film is finally obtained. The temperature of the three-roll calender is usually controlled between 20-50℃ to ensure that the film can be quickly cooled and shaped.

[0068] Example 1

[0069] Polyester resin (YF300) ECOZEN 100 copies Laser carving additive 8817 0.025 Aminated multi-walled carbon nanotubes 0.0001 copy

[0070] 10 parts of polyester resin are ground into 200 mesh powder by a grinder, the laser engraving agent is added into a high-speed mixer for high-speed stirring for mechanical activation, 1 part of ethanol is added for dilution, and then it is diluted and mixed with amino multi-walled carbon nanotubes by 1 part of ethanol solvent to obtain grafted laser engraving agent-carbon nanotubes, which are added into polyester powder and stirred at high speed until the solvent is completely volatilized, and the mixed powder is added into a twin-screw granulator for granulation to obtain concentrated functional masterbatch.

[0071] 1) Mix the components evenly according to the ratio of polyester resin: concentrated functional masterbatch 90:10, and dry them at 80℃ for 4 hours to ensure that the moisture content is less than 100PPM;

[0072] 2) The dried raw materials are put into an extruder, cooled and shaped through a melt filter, a melt pump, a mold, and a three-roll calender to obtain a high-temperature polyester film.

[0073] In step 2), the process temperatures are 190°C for the extruder, 220°C for the filter, 230°C for the melt pump, 230°C for the mold, and 30°C for the three-roll calender.

[0074] Comparative Example

[0075] The method for preparing the high temperature polyester film comprises the following steps:

[0076] Polyester resin (YF300) ECOZEN 100 copies Laser carving additive 8817 0.025 Aminated multi-walled carbon nanotubes 0.0001 copy

[0077] 1) Mix all components evenly according to the proportion, dry at 110℃ for 4 hours, and ensure that the moisture content is less than 100PPM;

[0078] 2) The dried raw materials are put into an extruder, and are cooled and shaped through a melt filter, a melt pump, a mold, and a three-roll calender to obtain an antistatic ABS smart card substrate.

[0079] In step 2), the process temperatures are 190°C for the extruder, 220°C for the filter, 230°C for the melt pump, 230°C for the mold, and 30°C for the three-roll calender.

[0080] Example 2

[0081] Polyester resin (T95) ECOZEN 100 copies Laser carving additive 8825 0.025 Aminated multi-walled carbon nanotubes 0.0005 copies

[0082] 10 parts of polyester resin are ground into 200 mesh powder by a grinder, the laser engraving agent is added into a high-speed mixer for high-speed stirring for mechanical activation, 1 part of ethanol is added for dilution, and then it is diluted and mixed with amino multi-walled carbon nanotubes by 1 part of ethanol solvent to obtain grafted laser engraving agent-carbon nanotubes, which are added into polyester powder and stirred at high speed until the solvent is completely volatilized, and the mixed powder is added into a twin-screw granulator for granulation to obtain concentrated functional masterbatch.

[0083] 1) Mix the components evenly according to the ratio of polyester resin: concentrated functional masterbatch 90:10, and dry them at 80℃ for 4 hours to ensure that the moisture content is less than 100PPM;

[0084] 2) The dried raw materials are put into an extruder, cooled and shaped through a melt filter, a melt pump, a mold, and a three-roll calender to obtain a high-temperature polyester film.

[0085] In step 2), the process temperatures are 190°C for the extruder, 220°C for the filter, 230°C for the melt pump, 230°C for the mold, and 30°C for the three-roll calender.

[0086] Example 3

[0087] Polyester resin (YF400) ECOZEN 100 copies Laser carving additive 8817 0.1 part Aminated multi-walled carbon nanotubes 0.0001 copy

[0088] 10 parts of polyester resin are ground into 200 mesh powder by a grinder, the laser engraving agent is added into a high-speed mixer for high-speed stirring for mechanical activation, 1 part of ethanol is added for dilution, and then it is diluted and mixed with amino multi-walled carbon nanotubes by 1 part of ethanol solvent to obtain grafted laser engraving agent-carbon nanotubes, which are added into polyester powder and stirred at high speed until the solvent is completely volatilized, and the mixed powder is added into a twin-screw granulator for granulation to obtain concentrated functional masterbatch.

[0089] 1) Mix the components evenly according to the ratio of polyester resin: concentrated functional masterbatch 90:10, and dry them at 80℃ for 4 hours to ensure that the moisture content is less than 100PPM;

[0090] 2) The dried raw materials are put into an extruder, cooled and shaped through a melt filter, a melt pump, a mold, and a three-roll calender to obtain a high-temperature polyester film.

[0091] In step 2), the process temperatures are 190°C for the extruder, 220°C for the filter, 230°C for the melt pump, 240°C for the mold, and 20°C for the three-roll calender.

[0092] Example 4

[0093] Polyester resin (TX1001) Tritan 100 copies Laser carving additive 8850 0.025 Aminated multi-walled carbon nanotubes 0.0001 copy

[0094] 10 parts of polyester resin are ground into 200 mesh powder by a grinder, the laser engraving agent is added into a high-speed mixer for high-speed stirring for mechanical activation, 1 part of ethanol is added for dilution, and then it is diluted and mixed with amino multi-walled carbon nanotubes by 1 part of ethanol solvent to obtain grafted laser engraving agent-carbon nanotubes, which are added into polyester powder and stirred at high speed until the solvent is completely volatilized, and the mixed powder is added into a twin-screw granulator for granulation to obtain concentrated functional masterbatch.

[0095] 1) Mix the components evenly according to the ratio of polyester resin: concentrated functional masterbatch 90:10, and dry them at 80℃ for 4 hours to ensure that the moisture content is less than 100PPM;

[0096] 2) The dried raw materials are put into an extruder, cooled and shaped through a melt filter, a melt pump, a mold, and a three-roll calender to obtain a high-temperature polyester film.

[0097] In step 2), the process temperatures are 190°C for the extruder, 240°C for the filter, 240°C for the melt pump, 240°C for the mold, and 50°C for the three-roll calender.

[0098] Example 5

[0099] Polyester resin (TX1001) Tritan 100 copies Laser carving additive 8817 0.025 Aminated multi-walled carbon nanotubes 0.0005 copies

[0100] 10 parts of polyester resin are ground into 200 mesh powder by a grinder, the laser engraving agent is added into a high-speed mixer for high-speed stirring for mechanical activation, 1 part of ethanol is added for dilution, and then it is diluted and mixed with amino multi-walled carbon nanotubes by 1 part of ethanol solvent to obtain grafted laser engraving agent-carbon nanotubes, which are added into polyester powder and stirred at high speed until the solvent is completely volatilized, and the mixed powder is added into a twin-screw granulator for granulation to obtain concentrated functional masterbatch.

[0101] 1) Mix the components evenly according to the ratio of polyester resin: concentrated functional masterbatch 90:10, and dry them at 80℃ for 4 hours to ensure that the moisture content is less than 100PPM;

[0102] 2) The dried raw materials are put into an extruder, cooled and shaped through a melt filter, a melt pump, a mold, and a three-roll calender to obtain a high-temperature polyester film.

[0103] In step 2), the process temperatures are 190°C for the extruder, 240°C for the filter, 240°C for the melt pump, 240°C for the mold, and 50°C for the three-roll calender.

[0104] The laser-engravable polyester films obtained in Examples 1-5 and the comparative example were subjected to laser engraving verification, Vicat softening point temperature test, lamination test and surface resistance test. The test found that the present invention obtained a high-temperature resistant polyester film, the laser engraving performance of the polyester film was significantly improved, the laser engraving blackness of the material was much lower than that of PETG (PETG laser engraving was yellowish), the addition of carbon nanotubes had an obvious antistatic effect, and the surface resistance was reduced to 10 9 Ω, by comparing Example 1 with the comparative example, it is shown that the grafted laser engraving auxiliary agent - carbon nanotubes improves the laser engraving efficiency and blackness; through the lamination test, it is verified that the patented film has a non-stick steel plate and can be firmly bonded to PC / PETG / PVC materials, and can completely replace traditional card-based materials such as PVC and PETG.

[0105] Table 1 Polyester film substrate performance test

[0106]

[0107] In a second aspect, a laser-engravable polyester film is prepared by the method for preparing a laser-engravable polyester film described in the first aspect, and includes 100 parts of a polyester resin, 0.025-0.1 parts of a laser-engraving auxiliary agent, and 0.0001-0.0005 parts of an antistatic agent.

[0108] 1. The present invention obtains a high-temperature polyester film by using ECOZEN and Tritan series polyesters; by adding grafted amino multi-walled carbon nanotubes and mechanically activated laser engraving additives, a film that can be laser engraved with high-blackness images is obtained, the grafting reaction improves the laser laser engraving efficiency, and the surface resistance of the obtained film is less than 109Ω; the obtained film can be laminated and bonded with materials such as PVC, PETG, PC, etc., without the assistance of glue; during the lamination and carding process of the film, the laminated steel plate will not stick.

[0109] 2. The present invention provides a simple and easy preparation method, which broadens the application prospects of high-temperature polyester, promotes the process of material functionalization, and has great application prospects.

[0110] The above disclosure is only a preferred embodiment of a laser-engravable polyester film and a preparation method thereof of the present invention. Of course, this cannot be used to limit the scope of rights of the present invention. Ordinary technicians in this field can understand that all or part of the processes of the above embodiments and equivalent changes made according to the claims of the present invention still fall within the scope of the invention.

Claims

1. A method for preparing a polyester film capable of being laser engraved, characterized in that: The following steps are involved: preparing polyester resin powder; Preparation of laser engraving additive-carbon nanotubes; Preparation of concentrated masterbatch using powder and carbon nanotubes; The polyester particles and concentrated masterbatch are added to the extruder for processing to obtain polyester film.

2. The method for preparing a polyester film capable of laser engraving according to claim 1, characterized in that: In the "preparation of polyester resin powder", the polyester resin powder is a 200 mesh powder.

3. The method for preparing a polyester film capable of laser engraving according to claim 1, characterized in that: In "preparing laser engraving additive-carbon nanotube", the following steps are included: Laser engraving additives are mechanically activated; Add 1 part of ethanol to the mechanically activated laser engraving agent for dilution; The aminated multi-walled carbon nanotubes are diluted with an ethanol solvent and then added into the diluted laser engraving agent to obtain the laser engraving agent-carbon nanotubes.

4. The method for preparing a polyester film capable of laser engraving according to claim 1, characterized in that: In "Preparation of concentrated masterbatch using powder and carbon nanotubes", the following steps are included: Adding laser engraving additive-carbon nanotubes into the powder and stirring until the ethanol solvent is completely volatilized to obtain a mixture; The mixture was added to a granulator for granulation to obtain concentrated masterbatch.

5. The method for preparing a polyester film capable of laser engraving according to claim 1, characterized in that: In "adding polyester particles and concentrated masterbatch to an extruder and processing them to obtain a polyester film", the following steps are included: Pre-treatment of polyester pellets and concentrated masterbatches; The pretreated raw materials are put into an extruder for melt treatment; The melt filter filters the raw materials after the melt treatment; The melt pump processes and filters the raw materials and transports them to the mold for processing to obtain semi-finished products; The three-roll calender cools and shapes the semi-finished product to obtain a polyester film.

6. The method for preparing a polyester film capable of laser engraving according to claim 5, characterized in that: In "pre-treatment of polyester pellets and concentrated masterbatch", the following steps are included: Mixing 90 parts of polyester particles with the concentrated masterbatch to obtain a mixed raw material; The mixed raw materials are dried.

7. A laser-engravable polyester film, prepared by the method for preparing a laser-engravable polyester film according to any one of claims 1 to 6, characterized in that: The invention comprises 100 parts of polyester resin, 0.025-0.1 parts of laser engraving auxiliary agent and 0.0001-0.0005 parts of antistatic agent.

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