CN115260561A - Anti-counterfeiting transfer film based on PET laser and production process thereof - Google Patents
Anti-counterfeiting transfer film based on PET laser and production process thereof Download PDFInfo
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Abstract
The invention relates to the technical field of anti-counterfeiting transfer films, and particularly discloses a PET (polyethylene terephthalate) -based laser anti-counterfeiting transfer film and a production process thereof, wherein the PET-based film is coated with a laser modified coating agent to form a laser coating; then infiltrating into bentonite modified glue solution to form a modified composite layer; finally, vacuum aluminizing is carried out to form an aluminized layer; the anti-counterfeiting transfer film is obtained. According to the anti-counterfeiting transfer film, the PET base film is coated with the laser modification coating agent to form the laser coating, the laser coating is matched with the bentonite modification glue solution to soak to form the modification composite layer, the coating technology of the PET base film and the bentonite modification glue solution is improved and optimized, and the prepared film product has excellent temperature resistance, thermal shrinkage and mechanical properties; the laser modifying coating agent can form synergistic interaction with the bentonite modifying glue solution, so that the performance of the product is enhanced together, and the use efficiency of the product is improved.
Description
Technical Field
The invention relates to the technical field of anti-counterfeiting transfer films, in particular to a PET laser-based anti-counterfeiting transfer film and a production process thereof.
Background
Since the laser packaging material is put into the market, the application of the laser packaging material in the fields of food, medicines, daily chemical products, cigarettes, wines and the like is rapidly popularized, and the laser packaging material is organically combined with a color printing technology and becomes the foremost technical product in the world printing and packaging industry. With the development of the green and environmental protection requirements in the world, the traditional aluminum foil or plastic composite material is gradually replaced by the environment-friendly laser transfer film which mainly takes BOPP (biaxially-oriented polypropylene) and PET (polyethylene terephthalate) as carrier base films. In contrast, the BOPP transfer film has less excellent overall performance than the PET transfer film, and the recycling rate is not as high as the latter, so the PET transfer film becomes the first choice for development.
The existing anti-counterfeiting transfer film is poor in temperature resistance and easy to shrink thermally, and meanwhile, the mechanical property and the thermal shrinkage property cannot be improved coordinately, so that the use efficiency is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a PET-based laser anti-counterfeiting transfer film and a production process thereof so as to solve the problems in the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a PET-based laser anti-counterfeiting transfer film, which comprises a PET base film, wherein a laser modification coating agent is coated on the PET base film to form a laser coating; then infiltrating into bentonite modified glue solution to form a modified composite layer; finally, vacuum aluminizing is carried out to form an aluminized layer; the anti-counterfeiting transfer film is obtained.
Preferably, the preparation method of the laser modified paint comprises the following steps:
s01: adding 5-10 parts of acrylic resin into 15-20 parts of acetone solvent, then adding 1-4 parts of silane coupling agent, stirring and mixing fully to prepare a coating base material;
s02: adding hydroxyapatite into 2-3 times of sodium alginate solution, stirring and dispersing uniformly, then adding 1-5% lanthanum sulfate and 1-3% hydrochloric acid of the total amount of the sodium alginate solution, stirring and mixing fully, washing with water, and drying to obtain pre-improved hydroxyapatite;
s03: feeding the pre-improved hydroxyapatite into a furnace, calcining the pre-improved hydroxyapatite at the temperature of 300-350 ℃ for 10-20min, then air-cooling the pre-improved hydroxyapatite to room temperature, and ball-milling the pre-improved hydroxyapatite for 1-2h at the rotating speed of 1000-1500r/min to obtain a hydroxyapatite modified material;
s04: stirring and mixing the hydroxyapatite modified material, the chitosan solution and the coating base material according to the weight ratio of 4.
The inventor of the invention finds that the performance of the product is poor because the hydroxyapatite modified material is not added, the performance of the product is poor because the hydroxyapatite modified material is replaced by the hydroxyapatite, the performance of the product also tends to be poor, the preparation method of the hydroxyapatite modified material is different, the performance of the product tends to be poor, and the performance of the product has obvious improvement effect only when the hydroxyapatite modified material prepared by the method is applied to the laser modified paint.
The inventor of the invention also finds that the chitosan solution is not added into the product of the invention, and the performance deterioration trend of the product is more obvious than the effect of the product without the hydroxyapatite modifying material; the hydroxyapatite modified material and the chitosan solution prepared by the method are synergistic and cooperated together, and then are further synergistic with the bentonite modified glue solution treatment, so that the heat shrinkage rate, the tensile strength and the elongation at break of the product are obviously improved in a coordinated and integrated manner.
Preferably, the mass fraction of the sodium alginate solution is 10-20%.
Preferably, the silane coupling agent is a coupling agent KH560.
Preferably, the chitosan solution comprises the following raw materials in parts by weight:
10-20 parts of chitosan, 5-10 parts of graphene, 1-3 parts of glycolic acid and 25-35 parts of deionized water.
The inventor of the invention finds that the performance improvement of the product is not obvious compared with the effect of not adding the chitosan solution because the graphene and the glycolic acid are not added in the preparation of the chitosan solution, and the performance improvement of the product is not good when the chitosan solution is added alone;
one of graphene and glycolic acid is not added, the performance improvement of the product is better than the effect of the chitosan solution which is not added, meanwhile, the glycolic acid is not added, the performance improvement trend is enhanced, the effect of the chitosan solution in the product can be obviously improved by adding the graphene, and meanwhile, the glycolic acid plays a synergistic effect and improves the performance effect of the product;
in addition, the graphene is replaced by the flaky talcum powder, and the performance effect of the product is not obviously improved, so that the performance improvement effect of the product is most obvious only by the chitosan aqueous solution prepared by the graphene, the chitosan and the glycolic acid in the invention in a synergistic manner, and the performance improvement effect of the product by other methods is not obvious as that of the chitosan solution prepared by the method in the invention.
Preferably, the preparation method of the bentonite modified glue solution comprises the following steps:
s11: feeding bentonite into deionized water according to the weight ratio of 1;
s12: and (3) adding the bentonite product of the S11 into 3-5 times of ethanol, then adding 10-20% of carboxymethyl cellulose and 25-35% of polyurethane adhesive in total amount of the bentonite, and stirring and mixing uniformly to obtain the bentonite modified adhesive solution.
The inventor of the invention finds that the thermal shrinkage, tensile strength and elongation at break of the product are obviously deteriorated without adding the laser modified coating agent, and meanwhile, the performance of the product also has obvious deterioration trend without adopting bentonite modified glue solution treatment; the performance of the product treated by the laser modified coating agent and the bentonite modified glue solution can be coordinately improved; thereby achieving the effect of coordinated promotion.
Preferably, the pH value of the phosphoric acid buffer solution is 5.5-6.0.
Preferably, the thickness of the laser coating is 3-6um; the thickness of the modified composite layer is 1-3um; the thickness of the aluminum plating layer is 1-2um.
The invention also provides a production process of the PET-based laser anti-counterfeiting transfer film, which comprises the following steps:
the method comprises the following steps: coating a laser modified coating agent on a PET (polyethylene terephthalate) base film, and pressing a laser pattern on a laser coating by using a die press to form the laser coating;
step two: drying at 45-55 deg.C for 1-2h, soaking in bentonite modified glue solution for 1-2h, taking out, irradiating with proton at 100-150W for 20-30min, and finishing irradiation;
step three: preheating at 110-120 deg.C for 20-30min, and pressing under 10-20MPa for 5-10min;
step four: finally, vacuum aluminizing is carried out to form an aluminized layer, and the aluminized layer is rewound and cut into finished products.
Preferably, the infiltration pressure of the bentonite modified glue solution infiltrated is 10-15MPa.
Compared with the prior art, the invention has the following beneficial effects:
according to the anti-counterfeiting transfer film, the PET base film is coated with the laser modification coating agent to form the laser coating, the laser coating is matched with the bentonite modification glue solution to soak to form the modification composite layer, the coating technology of the PET base film and the bentonite modification glue solution is improved and optimized, and the prepared film product has excellent temperature resistance, thermal shrinkage and mechanical properties; the laser modifying coating agent can form synergistic interaction with the bentonite modifying glue solution, so that the performance of the product is enhanced together, and the use efficiency of the product is improved;
the bentonite modified glue solution is prepared by dispersing bentonite in deionized water, modifying and activating with a phosphoric acid buffer solution, the dispersing capacity of the modified bentonite is enhanced, the glue solution prepared from the bentonite modified glue solution, carboxymethyl cellulose and polyurethane adhesive has excellent adhesive bonding strength, and the bentonite lamellar structure is used for alternately blocking and enhancing the stability of the product;
the hydroxyapatite modified material in the laser modified paint is subjected to sodium alginate dispersion through hydroxyapatite, activity modification through hydrochloric acid and lanthanum sulfate, calcination and ball milling, dispersion degree and activity degree enhancement, and then the hydroxyapatite modified material is matched with a paint base material and then dispersed in the paint, so that the hydroxyapatite modified material is highly dispersed in a base film and matched with graphene in a chitosan solution, the thermal shrinkage and mechanical strength performance of the base film are enhanced through the cooperation of the hydroxyapatite modified material and the graphene, and meanwhile, the modified raw material and bentonite in a bentonite modified glue solution are further cooperated to enhance the effect, and the temperature resistance, thermal shrinkage prevention and mechanical strength performance of a product are obviously enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The number average molecular weight distribution of acrylic resin in the raw materials of the product used by the invention is less than 1.2, the product is bead-shaped particle in appearance, the fineness is 20 meshes, the glass transition temperature is 45Tg ℃, the acid value is 16 mgKOH/g, the ring-and-ball conversion point is 120 ℃, the solution viscosity is 280 mPa.s (under the conditions of 40% resin and 60% ethanol), and the weight average molecular weight is 9700Mw; the acrylic resin raw material is purchased and collected from Sanjin pigment Co., ltd, yongyang county;
the crystal structure of the hydroxyapatite is hexagonal structure, the granularity is 10-50um, and the melting point is as follows: 1650 ℃, specific gravity: 3.16g/cm, solubility: 0.4ppm, ca/P1.67, purchased by Sienna Tonze Biotech Co., ltd;
the molecular weight of the chitosan is 1-5 ten thousand, 150-200nm, and the chitosan is purchased from Xian Tongze biological technology limited company;
the graphene is of a sheet structure, the granularity of powder is 100 meshes, the carbon content is 99.5-99.8%, and the graphene is purchased from Xian Tongze biological technology company Limited;
the bentonite has a lamellar structure, the granularity is 200 meshes, and interlayer cations are sodium ions; purchased by siennan zest biotechnology limited;
the polyurethane adhesive meets the standard of a QJLC002-2019 double-component solvent-free polyurethane adhesive; the polyurethane adhesive and the carboxymethyl cellulose are purchased by Qingdao Deda chemical industry Co., ltd;
the PET-based laser anti-counterfeiting transfer film comprises a PET base film, wherein a laser modification coating agent is coated on the PET base film to form a laser coating; then infiltrating into bentonite modified glue solution to form a modified composite layer; finally, vacuum aluminizing is carried out to form an aluminized layer; the anti-counterfeiting transfer film is obtained.
The preparation method of the laser modified paint of the embodiment comprises the following steps:
s01: adding 5-10 parts of acrylic resin into 15-20 parts of acetone solvent, then adding 1-4 parts of silane coupling agent, and stirring and mixing fully to prepare a coating base material;
s02: adding hydroxyapatite into 2-3 times of sodium alginate solution, stirring and dispersing uniformly, then adding 1-5% lanthanum sulfate and 1-3% hydrochloric acid of the total amount of the sodium alginate solution, stirring and mixing fully, washing with water, and drying to obtain pre-improved hydroxyapatite;
s03: feeding the pre-improved hydroxyapatite into a furnace, calcining the pre-improved hydroxyapatite at the temperature of 300-350 ℃ for 10-20min, then air-cooling the pre-improved hydroxyapatite to room temperature, and ball-milling the pre-improved hydroxyapatite for 1-2h at the rotating speed of 1000-1500r/min to obtain a hydroxyapatite modified material;
s04: stirring and mixing the hydroxyapatite modified material, the chitosan solution and the coating base material according to the weight ratio of 4.
The mass fraction of the sodium alginate solution in the embodiment is 10-20%.
The silane coupling agent of the present example is a coupling agent KH560.
The chitosan solution of the embodiment comprises the following raw materials in parts by weight:
10-20 parts of chitosan, 5-10 parts of graphene, 1-3 parts of glycolic acid and 25-35 parts of deionized water.
The preparation method of the bentonite modified glue solution in the embodiment comprises the following steps:
s11: sending bentonite into deionized water according to a weight ratio of 1;
s12: and (3) adding the bentonite product of the S11 into 3-5 times of ethanol, then adding 10-20% of carboxymethyl cellulose and 25-35% of polyurethane adhesive in total amount of the bentonite, and stirring and mixing uniformly to obtain the bentonite modified adhesive solution.
The pH of the phosphate buffer solution of this example was 5.5-6.0.
The thickness of the laser coating of the embodiment is 3-6um; the thickness of the modified composite layer is 1-3um; the thickness of the aluminum plating layer is 1-2um.
The production process based on the PET laser anti-counterfeiting transfer film comprises the following steps:
the method comprises the following steps: coating a laser modified coating agent on a PET (polyethylene terephthalate) base film, and pressing a laser pattern on a laser coating by using a die press to form the laser coating;
step two: drying at 45-55 deg.C for 1-2h, soaking in bentonite modified glue solution for 1-2h, taking out, irradiating with proton at 100-150W for 20-30min, and finishing irradiation;
step three: preheating at 110-120 deg.C for 20-30min, and pressing under 10-20MPa for 5-10min;
step four: finally, vacuum aluminizing is carried out to form an aluminized layer, and the aluminized layer is rewound and cut into finished products.
The infiltration pressure of the bentonite modified glue solution infiltrated in the embodiment is 10-15MPa.
Example 1.
The anti-counterfeiting transfer film based on the PET comprises a PET base film, wherein a laser modified coating agent is coated on the PET base film to form a laser coating; then soaking the mixture into bentonite modified glue solution to form a modified composite layer; finally, vacuum aluminizing is carried out to form an aluminized layer; the anti-counterfeiting transfer film is obtained.
The preparation method of the laser modified paint of the embodiment comprises the following steps:
s01: adding 50g of acrylic resin into 150g of acetone solvent, then adding 10g of silane coupling agent, and fully stirring and mixing to prepare a coating base material;
s02: adding 10g of hydroxyapatite into 20g of sodium alginate solution, stirring and dispersing uniformly, then adding 2g of lanthanum sulfate and 1g of hydrochloric acid, stirring and mixing fully, then washing with water, and drying to obtain pre-improved hydroxyapatite;
s03: feeding the pre-modified hydroxyapatite into a furnace, calcining the pre-modified hydroxyapatite at 300 ℃ for 10min, then air-cooling the pre-modified hydroxyapatite to room temperature, and ball-milling the pre-modified hydroxyapatite at the rotating speed of 1000r/min for 1h to obtain a hydroxyapatite modified material;
s04: and (3) stirring and mixing 8g of hydroxyapatite modified material, 2g of chitosan solution and 14g of paint base material fully, stirring for 20min at 55 ℃, wherein the stirring speed is 550r/min, and thus obtaining the laser modified paint.
The mass fraction of the sodium alginate solution in this example was 10%.
The silane coupling agent of the present example is a coupling agent KH560.
The chitosan solution of the embodiment comprises the following raw materials in parts by weight:
10g of chitosan, 5g of graphene, 1g of glycolic acid and 25g of deionized water.
The preparation method of the bentonite modified glue solution in the embodiment comprises the following steps:
s11: sending 100g of bentonite into 600g of deionized water for even dispersion, then adding 30g of phosphoric acid buffer solution, stirring evenly, and washing with water;
s12: adding 50g of bentonite which is a product of S11 into 150g of ethanol, then adding 5g of carboxymethyl cellulose and 12.5g of polyurethane adhesive, and uniformly stirring and mixing to obtain bentonite modified glue solution.
The pH of the phosphate buffer solution of this example was 5.5.
The thickness of the laser coating of the embodiment is 3um; the thickness of the modified composite layer is 1um; the thickness of the aluminum plating layer is 1um.
The production process based on the PET laser anti-counterfeiting transfer film comprises the following steps:
the method comprises the following steps: coating a laser modified coating agent on a PET (polyethylene terephthalate) base film, and pressing a laser pattern on a laser coating by a die press to form the laser coating;
step two: drying at 45 deg.C for 1 hr, soaking in bentonite modified glue solution for 1 hr, taking out, irradiating with proton at 100W for 20min, and finishing irradiation;
step three: preheating at 110 deg.C for 20min, and pressing under 10MPa for 5min;
step four: finally, vacuum aluminizing is carried out to form an aluminized layer, and the aluminized layer is rewound and cut into finished products.
The infiltration pressure of the bentonite modified glue solution infiltrated in the embodiment is 10MPa.
Example 2.
The PET-based laser anti-counterfeiting transfer film comprises a PET base film, wherein a laser modification coating agent is coated on the PET base film to form a laser coating; then soaking the mixture into bentonite modified glue solution to form a modified composite layer; finally, vacuum aluminizing is carried out to form an aluminized layer; the anti-counterfeiting transfer film is obtained.
The preparation method of the laser modified paint of the embodiment comprises the following steps:
s01: adding 100g of acrylic resin into 200g of acetone solvent, then adding 40g of silane coupling agent, and fully stirring and mixing to prepare a coating base material;
s02: adding 10g of hydroxyapatite into 30g of sodium alginate solution, stirring and dispersing uniformly, then adding 1.5g of lanthanum sulfate and 0.9g of hydrochloric acid, stirring and mixing fully, washing with water, and drying to obtain pre-improved hydroxyapatite;
s03: feeding the pre-modified hydroxyapatite into a furnace at 350 ℃ for calcining for 20min, then air-cooling to room temperature, and then ball-milling for 2h at the rotating speed of 1500r/min to obtain a hydroxyapatite modified material;
s04: and (3) stirring and mixing 8g of hydroxyapatite modified material, 2g of chitosan solution and 15g of paint base material fully, stirring for 30min at 65 ℃, wherein the stirring speed is 650r/min, and thus obtaining the laser modified paint.
The mass fraction of the sodium alginate solution in this example was 20%.
The silane coupling agent of the present example is a coupling agent KH560.
The chitosan solution of the embodiment comprises the following raw materials in parts by weight:
20g of chitosan, 10g of graphene, 3g of glycolic acid and 35g of deionized water.
The preparation method of the bentonite modified glue solution in the embodiment comprises the following steps:
s11: sending 100g of bentonite into 600g of deionized water for uniform dispersion, then adding 10g of phosphoric acid buffer solution, uniformly stirring, and washing with water;
s12: adding 50g of bentonite into 250g of ethanol, then adding 10g of carboxymethyl cellulose and 17.5g of polyurethane adhesive, and uniformly stirring and mixing to obtain bentonite modified adhesive solution.
The pH of the phosphate buffer solution of this example was 6.0.
The thickness of the laser coating of the embodiment is 6um; the thickness of the modified composite layer is 3um; the thickness of the aluminum plating layer is 2um.
The production process based on the PET laser anti-counterfeiting transfer film comprises the following steps:
the method comprises the following steps: coating a laser modified coating agent on a PET (polyethylene terephthalate) base film, and pressing a laser pattern on a laser coating by using a die press to form the laser coating;
step two: drying at 55 deg.C for 2h, soaking in bentonite modified glue solution for 2h, taking out, irradiating with proton at 150W for 30min, and finishing irradiation;
step three: preheating at 120 deg.C for 30min, and pressing under 20MPa for 5-10min;
step four: finally, vacuum aluminizing is carried out to form an aluminized layer, and the aluminized layer is rewound and cut into finished products.
The infiltration pressure of the bentonite modified glue solution infiltrated in the embodiment is 15MPa.
Example 3.
The PET-based laser anti-counterfeiting transfer film comprises a PET base film, wherein a laser modification coating agent is coated on the PET base film to form a laser coating; then soaking the mixture into bentonite modified glue solution to form a modified composite layer; finally, vacuum aluminizing is carried out to form an aluminized layer; the anti-counterfeiting transfer film is obtained.
The preparation method of the laser modified paint of the embodiment comprises the following steps:
s01: adding 75g of acrylic resin into 175g of acetone solvent, then adding 25g of silane coupling agent, and fully stirring and mixing to prepare a coating base material;
s02: adding 10g of hydroxyapatite into 25g of sodium alginate solution, stirring and dispersing uniformly, then adding 7.5g of lanthanum sulfate and 5g of hydrochloric acid, stirring and mixing fully, then washing with water and drying to obtain pre-improved hydroxyapatite;
s03: feeding the pre-modified hydroxyapatite into a calcining furnace at 325 ℃ for calcining for 15min, then air-cooling to room temperature, and ball-milling for 1.5h at the rotating speed of 1250r/min to obtain a hydroxyapatite modified material;
s04: and (3) stirring and mixing 8g of hydroxyapatite modified material, 2g of chitosan solution and 14g of coating base material fully, stirring for 25min at the temperature of 60 ℃, and stirring at the rotating speed of 600r/min to obtain the laser modified coating.
The mass fraction of the sodium alginate solution in this example was 15%.
The silane coupling agent of the present example is a coupling agent KH560.
The chitosan solution of the embodiment comprises the following raw materials in parts by weight:
15g of chitosan, 7.5g of graphene, 2g of glycolic acid and 30g of deionized water.
The preparation method of the bentonite modified glue solution in the embodiment comprises the following steps:
s11: sending 100g of bentonite into 600g of deionized water for uniform dispersion, then adding 45g of phosphoric acid buffer solution, uniformly stirring, and washing with water;
s12: adding 50g of S11 bentonite into 200g of ethanol, then adding 7.5g of carboxymethyl cellulose and 15g of polyurethane adhesive, and uniformly stirring and mixing to obtain bentonite modified glue solution.
The pH of the phosphate buffer solution of this example was 5.7.
The thickness of the laser coating of the embodiment is 4.5um; the thickness of the modified composite layer is 2um; the thickness of the aluminum plating layer is 1.5um.
The production process based on the PET laser anti-counterfeiting transfer film comprises the following steps:
the method comprises the following steps: coating a laser modified coating agent on a PET (polyethylene terephthalate) base film, and pressing a laser pattern on a laser coating by using a die press to form the laser coating;
step two: then drying at 50 ℃ for 1.5h, then soaking into bentonite modified glue solution for 1.5h, taking out, irradiating for 25min by protons under the power of 120W, and ending the irradiation;
step three: preheating at 115 deg.C for 25min, and pressing under 15MPa for 7.5min;
step four: finally, vacuum aluminizing is carried out to form an aluminized layer, and the aluminized layer is rewound and cut into finished products.
The infiltration pressure of the bentonite-modified colloidal solution infiltrated in this example was 12.5MPa.
Comparative example 1.
The difference from the example 3 is that no laser modifying coating agent is added.
Comparative example 2.
The difference from the embodiment 3 is that hydroxyapatite modifying material is not added in the preparation of the laser modifying coating agent.
Comparative example 3.
Different from the embodiment 3, the hydroxyapatite is adopted to replace the hydroxyapatite in the preparation of the hydroxyapatite modified material.
Comparative example 4.
Different from the example 3, the hydroxyapatite modified material is not treated by S03 in the preparation process.
Comparative example 5.
Different from the embodiment 3, lanthanum sulfate and hydrochloric acid are not added in the preparation of the hydroxyapatite modified material.
Comparative example 6.
The difference from the embodiment 3 is that the chitosan solution is not added in the preparation of the laser modified paint.
Comparative example 7.
Different from the example 3, the bentonite modified glue solution is not adopted for treatment.
The results of the performance measurements of examples 1 to 3 and comparative examples 1 to 7 are as follows
Taking a film material with the size of 10cm by 10cm, testing the size of the film material, and marking the size as S0, clamping the film material in a book, placing the book in a constant-temperature oven at 85 ℃, starting timing after the temperature returns to 85 ℃, taking out the film material after 30min, cooling to room temperature, testing the size of the film material, and marking the size as S1, wherein the thermal shrinkage rate of the film material is (S0-S1)/S0-100%;
detecting the tensile strength performance according to the GB/T25255-2010 standard; the elongation at break is tested by a film tensile tester, and the numerical value is recorded;
from examples 1-3 and comparative examples 1-7, the product of example 3 of the present invention has excellent heat shrinkage, tensile strength and elongation at break, and the heat shrinkage and mechanical strength properties have synergistic improvement;
compared with the comparative examples 1-7 and the example 3, the laser modified coating agent is not added, the heat shrinkage rate, the tensile strength and the elongation at break of the product are obviously reduced, and the bentonite modified glue solution is not adopted for treatment, so that the performance of the product also has a trend of obviously reducing; the performance of the product treated by the laser modified coating agent and the bentonite modified glue solution can be coordinately improved; the coordinated type enhancing effect is achieved;
compared with the comparative examples 2-5, the performance of the product is poor because the hydroxyapatite modified material is not added, meanwhile, the hydroxyapatite modified material is replaced by hydroxyapatite, the performance also has a tendency of deterioration, and the performance of the product has a tendency of deterioration because the preparation methods of the hydroxyapatite modified material are different, and only when the hydroxyapatite modified material prepared by the method is applied to the laser modified paint, the performance of the product has a remarkable improvement effect;
as can be seen from comparative examples 2-6 and example 3, the chitosan solution is not added into the product, and the performance deterioration trend of the product is more obvious than the effect of the product without the hydroxyapatite modifying material; the hydroxyapatite modified material and the chitosan solution prepared by the method of the invention are synergistic and cooperated together to assist, and are further synergistic with the bentonite modified glue solution treatment, and the thermal shrinkage rate, the tensile strength and the elongation at break of the product are obviously improved in a coordinated and integrated manner.
The invention further researches the product performance by the chitosan solution
Experimental example 1.
The chitosan solution was the same as example 3 except that graphene and glycolic acid were not added.
Experimental example 2.
The only difference was that no graphene was added to the chitosan solution, as in example 3.
Experimental example 3.
The chitosan solution was not added glycolic acid, as in example 3, except that the solution was not added.
Experimental example 4.
The same as in example 3, except that the graphene was replaced with platy talc.
As can be seen from the experimental examples 1-4, the performance improvement of the product is not obvious compared with the effect of not adding the chitosan solution because graphene and glycolic acid are not added in the preparation of the chitosan solution, and the performance improvement effect of singly adding the chitosan product is not good; one of graphene and glycolic acid is not added, the performance improvement of the product is better than the effect of the chitosan solution which is not added, meanwhile, the glycolic acid is not added, the performance improvement trend is enhanced, the effect of the chitosan solution in the product can be obviously improved by adding the graphene, and meanwhile, the glycolic acid plays a synergistic effect and improves the performance effect of the product; in addition, the graphene is replaced by the flaky talcum powder, and the performance effect of the product is not obviously improved, so that the performance improvement effect of the product is most obvious only by the chitosan aqueous solution prepared by the graphene, the chitosan and the glycolic acid in the invention in a synergistic manner, and the performance improvement effect of the product by other methods is not as obvious as that of the chitosan solution prepared by the method in the invention.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The PET-based laser anti-counterfeiting transfer film comprises a PET base film and is characterized in that a laser modifying coating agent is coated on the PET base film to form a laser coating; then soaking the mixture into bentonite modified glue solution to form a modified composite layer; finally, vacuum aluminizing is carried out to form an aluminized layer; the anti-counterfeiting transfer film is obtained.
2. The PET-based laser anti-counterfeiting transfer film according to claim 1, wherein the laser modification paint is prepared by the following steps:
s01: adding 5-10 parts of acrylic resin into 15-20 parts of acetone solvent, then adding 1-4 parts of silane coupling agent, and stirring and mixing fully to prepare a coating base material;
s02: adding hydroxyapatite into 2-3 times of sodium alginate solution, stirring and dispersing uniformly, then adding lanthanum sulfate accounting for 1-5% of the total amount of the sodium alginate solution and hydrochloric acid accounting for 1-3% of the total amount of the sodium alginate solution, stirring and mixing fully, washing with water, and drying to obtain pre-improved hydroxyapatite;
s03: feeding the pre-modified hydroxyapatite into a furnace, calcining the pre-modified hydroxyapatite at 300-350 ℃ for 10-20min, then air-cooling the pre-modified hydroxyapatite to room temperature, and ball-milling the pre-modified hydroxyapatite at the rotating speed of 1000-1500r/min for 1-2h to obtain a hydroxyapatite modified material;
s04: stirring and mixing the hydroxyapatite modified material, the chitosan solution and the coating base material fully according to a weight ratio of 4.
3. The PET-based laser anti-counterfeiting transfer film according to claim 2, wherein the mass fraction of the sodium alginate solution is 10-20%.
4. The PET-based laser anti-counterfeiting transfer film according to claim 2, wherein the silane coupling agent is KH560.
5. The PET-based laser anti-counterfeiting transfer film according to claim 2, wherein the chitosan solution comprises the following raw materials in parts by weight:
10-20 parts of chitosan, 5-10 parts of graphene, 1-3 parts of glycolic acid and 25-35 parts of deionized water.
6. The PET-based laser anti-counterfeiting transfer film according to claim 1, wherein the preparation method of the bentonite modified glue solution comprises the following steps:
s11: feeding bentonite into deionized water according to the weight ratio of 1;
s12: and (3) adding the bentonite product of S11 into 3-5 times of ethanol, then adding 10-20% of carboxymethyl cellulose and 25-35% of polyurethane adhesive in total amount of bentonite, and uniformly stirring and mixing to obtain the bentonite modification adhesive solution.
7. The PET-based laser anti-counterfeiting transfer film according to claim 5, wherein the pH value of the phosphoric acid buffer solution is 5.5-6.0.
8. The PET-based laser anti-counterfeiting transfer film according to claim 1, wherein the laser coating layer has a thickness of 3-6um; the thickness of the modified composite layer is 1-3um; the thickness of the aluminum plating layer is 1-2um.
9. The production process of the PET-based laser anti-counterfeiting transfer film according to any one of claims 1 to 8, which comprises the following steps:
the method comprises the following steps: coating a laser modified coating agent on a PET (polyethylene terephthalate) base film, and pressing a laser pattern on a laser coating by a die press to form the laser coating;
step two: drying at 45-55 deg.C for 1-2h, soaking in bentonite modified glue solution for 1-2h, taking out, irradiating with proton at 100-150W for 20-30min, and finishing irradiation;
step three: preheating at 110-120 deg.C for 20-30min, and pressing under 10-20MPa for 5-10min;
step four: finally, vacuum aluminizing is carried out to form an aluminized layer, and the aluminized layer is rewound and cut into finished products.
10. The production process based on the PET laser anti-counterfeiting transfer film according to claim 9, wherein the infiltration pressure for infiltrating into the bentonite modified glue solution is 10-15MPa.
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