CN112795153A

CN112795153A - Black antibacterial PET film and preparation method thereof

Info

Publication number: CN112795153A
Application number: CN202110048743.6A
Authority: CN
Inventors: 谢珈璐
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-01-14
Filing date: 2021-01-14
Publication date: 2021-05-14

Abstract

The invention provides a black antibacterial agentA PET film and a preparation method thereof belong to the technical field of high polymer materials, and are prepared from the following raw materials by weight: 100 portions of PET resin and 200 portions of TiO₂5-10 parts of/Cu/carbon microspheres, 13-17 parts of chitin/polyhexamethylene guanidine microspheres, 2-5 parts of toughening agent, 1-3 parts of compatilizer, 2-4 parts of carbon fibers, 1-2 parts of ultraviolet-resistant absorbent and 250 parts of cyclohexanone. The preparation method is simple, the raw material source is wide, and the prepared black antibacterial PET film has excellent antibacterial, bacteriostatic, bactericidal and mildew-proof performances, excellent mechanical properties, good flexibility and toughness and wide application prospect.

Description

Black antibacterial PET film and preparation method thereof

Technical Field

The invention relates to the technical field of high polymer materials, and particularly relates to a black antibacterial PET film and a preparation method thereof.

Background

Antimicrobial films include films used on packaging materials and films that are bonded to the surface of the material in the form of a coating. The surface of the packaging film for packaging foods, fruits, vegetables and other nutrient-rich articles is rich in nutrition, the conditions of common storage temperature, humidity and the like are also suitable for the growth of microorganisms, the surface of the packaging film is easily infected with the microorganisms, and the microorganisms are easily migrated to the articles, so that the articles are rotten. If the packaging film is made of antibacterial plastic, the growth of microorganisms can be inhibited, and the propagation of microorganisms on the surface of a packaging material can be prevented, so that the deterioration of articles can be further prevented, and the packaging protection capability of the plastic film can be improved.

Polyester is an abbreviation for thermoplastic polyester containing ester groups. The PET resin can be processed and molded into various bottle containers, sheets and films. Among them, the largest application market of PET resin is flexible packaging composite material, which accounts for about 50% of the total amount. The PET resin is polyethylene terephthalate plastic, commonly called polyester resin, which is a polycondensate of terephthalic acid and ethylene glycol, and is commonly called as thermoplastic polyester or saturated polyester together with PBT, the molecular structure 3 of the PET resin is highly symmetrical and has certain crystal orientation capability, so the PET resin has higher film forming property, has good weather resistance, and in addition, the PET resin has excellent wear and friction resistance, dimensional stability and electrical insulation property, and PET bottles made of the PET have the advantages of high strength, no toxicity, seepage prevention, light weight, high production efficiency and the like, so the PET resin is widely applied, but the PET resin has high transparency, strong light transmittance, slow crystallization speed, poor impact resistance and difficult processing.

In actual production, some products need to be stored in a dark place, and although deep glass bottles and glass sheets can absorb light with most wavelengths in white light to play the roles of keeping out of the light and isolating the light, the deep glass bottles and the glass sheets have a lot of limitations in practical application due to a series of defects of hard and brittle materials, poor wear resistance and the like. Therefore, materials which can resist bacteria and prevent most of light from being emitted and avoid the decomposition of contents by light are continuously developed to meet the requirements of modern markets.

Disclosure of Invention

The invention aims to provide a black antibacterial PET film and a preparation method thereof, the preparation method is simple, the raw material source is wide, and the prepared black antibacterial PET film has excellent antibacterial, bacteriostatic, bactericidal and mildew-proof properties, excellent mechanical properties, good flexibility and toughness and wide application prospect.

The technical scheme of the invention is realized as follows:

the invention provides a black antibacterial PET film which is prepared from the following raw materials in parts by weight: 100 portions of PET resin and 200 portions of TiO₂5-10 parts of/Cu/carbon microspheres, 13-17 parts of chitin/polyhexamethylene guanidine microspheres, 2-5 parts of toughening agent, 1-3 parts of compatilizer, 2-4 parts of carbon fibers, 1-2 parts of ultraviolet-resistant absorbent and 250 parts of cyclohexanone 120-;

the TiO is₂the/Cu/carbon microsphere is prepared by the following method:

s1, preparation of carbon microspheres: dissolving glucose in water to prepare a clear glucose solution, placing the clear solution at 190 ℃ for reaction for 3-5h while stirring at 170-;

s2, preparing a copper sulfate solution: dissolving blue copperas in water to prepare blue copperas solution;

s3, preparing a tetrabutyl titanate solution: dissolving tetrabutyl titanate in ethanol to prepare tetrabutyl titanate solution;

S4.TiO₂preparation of/Cu/carbon microspheres: adding the carbon microspheres prepared in the step S1 into the tetrabutyl titanate solution prepared in the step S3, uniformly mixing by ultrasonic waves, heating to volatilize ethanol completely, dropwise adding the copper sulfate solution prepared in the step S2, continuously stirring, reacting at 50-70 ℃ for 1-2h after dropwise adding is finished, cooling to room temperature, filtering, sequentially washing with ethanol and water for 2-3 times, and drying to obtain TiO₂a/Cu/carbon microsphere.

As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 120 portions of PET resin and 180 portions of TiO₂6-9 parts of/Cu/carbon microsphere, 14-16 parts of chitin/polyhexamethylene guanidine microsphere, 3-4 parts of toughening agent and 1.5-2.5 parts of compatilizer2.5 to 3.5 portions of carbon fiber, 1.2 to 1.8 portions of ultraviolet-resistant absorbent and 200 portions of cyclohexanone 150-.

As a further improvement of the invention, the mass percent of the glucose solution is 25-40 wt%; the copper sulfate solution accounts for 55-70 wt%; the mass percentage of the tetrabutyl titanate solution is 25-45wt%, and the mass ratio of the carbon microspheres, the tetrabutyl titanate solution and the copper sulfate solution in the step S4 is 100: (17-30): (10-20).

As a further improvement of the invention, the stirring rotation speed is 500-1000r/min, the ultrasonic power is 1000-2000W, the drying temperature is 50-70 ℃, and the drying time is 2-5 h.

As a further improvement of the invention, the chitin/polyhexamethylene guanidine microspheres are prepared by the following method:

s1, preparation of a chitin solution: dissolving chitin powder in acetic acid solution to obtain chitin solution;

s2, preparing a polyhexamethylene guanidine solution: dissolving polyhexamethylene guanidine hydrochloride and a surfactant in water to obtain a polyhexamethylene guanidine solution;

s3, dripping the chitin solution prepared in the step S1 into the polyhexamethylene guanidine solution prepared in the step S2, stirring at room temperature for 2-3h, emulsifying to prepare chitin/polyhexamethylene guanidine microsphere emulsion, and drying to obtain the chitin/polyhexamethylene guanidine microspheres.

As a further improvement of the invention, the mass ratio of the chitin powder, the polyhexamethylene guanidine hydrochloride and the surfactant is 100: (25-45): (2-5), wherein the acetic acid content in the acetic acid solution is 12-20 wt%; the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate and sodium octadecyl benzene sulfonate.

As a further improvement of the invention, the emulsification condition is emulsification for 2-5min at 10000-.

As a further improvement of the present invention, the toughening agent is selected from one or a combination of several of di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate, diisononyl phthalate, diisodecyl phthalate or diethyl phthalate; the compatilizer is selected from one or a combination of more of compatilizers ST-1, ST-2 and ST-8; the ultraviolet resistant absorbent is nano or micron metal oxide or salicylate, benzophenone organic ultraviolet resistant agent.

The invention further provides a preparation method of the black antibacterial PET film, which comprises the following steps: dissolving PET resin in cyclohexanone, adding toughening agent, carbon fiber and ultraviolet-resistant absorbent, heating to 50-70 deg.C, stirring, mixing, and adding TiO₂The preparation method comprises the following steps of carrying out high-speed shearing dispersion on Cu/carbon microspheres, chitin/polyhexamethylene guanidine microspheres and a compatilizer for 1-2 hours, standing and defoaming to obtain a film forming solution, pouring the film forming solution into a glass mold, uniformly spreading the film forming solution in the glass mold, and drying the glass mold in an electric heating forced air drying oven at 50 ℃ for 5-7 hours to obtain the chitosan/poly (hexamethylene guanidine) composite material.

As a further improvement of the invention, the high-speed shearing rotating speed is 10000-12000 r/min.

The invention has the following beneficial effects: the chitin/polyhexamethylene guanidine microspheres prepared by the invention have the advantages that the guanidino group of the polyhexamethylene guanidine has high activity, so that the polymer is electropositive and can be easily adsorbed by various bacteria and viruses; polyhexamethylene guanidine diffuses through cell membranes and binds to the cytoplasmic membrane, forms a complex with phospholipid bilayers, disrupts osmotic balance and the cytoplasmic membrane, causes cell leakage, and reacts strongly with nucleic acids, thereby inhibiting division of bacterial viruses, and rendering bacteria and viruses incapable of reproduction. Meanwhile, polyhexamethylene guanidine is a polymer, a film which can be formed blocks the breathing channel of microorganism, so that the microorganism is rapidly suffocated, and on the other hand, the molecule of the chitosan contains an active group-NH₂Therefore, it has antibacterial effect on various bacteria under acidic conditionsNH in the chitosan molecule³⁺Combined with anions dissociated from the cell wall, the composite antibacterial microsphere hinders the biosynthesis of the cell wall, prevents the transport of substances inside and outside the cell wall, and thus prevents the mass propagation of bacteria.

The invention also prepares TiO₂The copper sulfate solution is further dripped, not only copper ions are adsorbed on the surface of the carbon microsphere, but also water in the solution can react with tetrabutyl titanate adsorbed on the surface to generate TiO₂Thereby producing TiO₂Cu/carbon microsphere, TiO on carbon microsphere₂The PET film has the advantages that sterilization and bacteriostasis are carried out through photocatalytic reaction, and meanwhile, copper ions are also a good sterilization and bacteriostasis component, so that the antibacterial property of the PET film is obviously improved, bacteria are prevented from being bred on the surface of the PET film after the PET film is prepared into a packaging material, and a good food preservation effect is achieved.

The invention not only adds black TiO₂The carbon fiber can improve the mechanical property of the film material to a certain extent, and simultaneously, the prepared PET film is black, and has the functions of light shielding and light isolation.

The preparation method is simple, the raw material source is wide, and the prepared black antibacterial PET film has excellent antibacterial, bacteriostatic, bactericidal and mildew-proof performances, excellent mechanical properties, good flexibility and toughness and wide application prospect.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 shows TiO prepared in preparation example 2₂SEM image of/Cu/carbon microsphere.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.

Preparation example 1TiO₂Cu/carbon microsphere

The preparation method comprises the following steps:

s1, preparation of carbon microspheres: dissolving glucose in water to prepare a clear 25 wt% glucose solution, placing the clear solution at 170 ℃ for reaction for 3h while stirring, wherein the stirring speed is 500r/min, cooling to room temperature after the reaction is finished, washing for 2 times with water, and drying to obtain black carbon microspheres;

s2, preparing a copper sulfate solution: dissolving blue copperas pentahydrate in water to prepare 55 wt% blue copperas solution;

s3, preparing a tetrabutyl titanate solution: dissolving tetrabutyl titanate in ethanol to prepare a tetrabutyl titanate solution with the weight percent of 25;

S4.TiO₂preparation of/Cu/carbon microspheres: adding 100g of the carbon microspheres prepared in the step S1 into 17g of the tetrabutyl titanate solution prepared in the step S3, ultrasonically mixing uniformly, wherein the ultrasonic power is 1000W, heating to completely volatilize ethanol, dropwise adding 10g of the copper sulfate solution prepared in the step S2, continuously stirring, reacting at 50 ℃ for 1h after dropwise adding, cooling to room temperature, filtering, washing with ethanol and water for 2 times in sequence, drying, wherein the drying temperature is 50 ℃, and the drying time is 2h to obtain TiO₂a/Cu/carbon microsphere.

Preparation example 2TiO₂Cu/carbon microsphere

The preparation method comprises the following steps:

s1, preparation of carbon microspheres: dissolving glucose in water to prepare a clear 40wt% glucose solution, placing the clear solution at 190 ℃ for reaction for 5 hours while stirring, wherein the stirring speed is 1000r/min, cooling to room temperature after the reaction is finished, washing with water for 3 times, and drying to obtain black carbon microspheres;

s2, preparing a copper sulfate solution: dissolving blue copperas pentahydrate in water to prepare a 70wt% blue copperas solution;

s3, preparing a tetrabutyl titanate solution: dissolving tetrabutyl titanate in ethanol to prepare a 45wt% tetrabutyl titanate solution;

S4.TiO₂preparation of/Cu/carbon microspheres: adding 100g of the carbon microspheres prepared in the step S1 into 30g of the tetrabutyl titanate solution prepared in the step S3, ultrasonically mixing uniformly at the ultrasonic power of 2000W, heating to volatilize ethanol completely, dropwise adding 20g of the copper sulfate solution prepared in the step S2, continuously stirring, reacting at 70 ℃ for 2 hours after dropwise adding, cooling to room temperature, filtering, washing with ethanol and water for 3 times in sequence, drying at the drying temperature of 70 ℃ for 5 hours to obtain TiO₂The SEM image of the/Cu/carbon microsphere is shown in figure 1.

Comparative preparation example 1

Preparing carbon microspheres: dissolving glucose in water to prepare a clear 40wt% glucose solution, reacting the clear solution at 190 ℃ for 5h while stirring, wherein the stirring speed is 1000r/min, cooling to room temperature after the reaction is finished, washing with water for 3 times, and drying to obtain the black carbon microspheres.

Comparative preparation example 2

Compared with preparation example 2, no copper sulfate solution is added, and other conditions are consistent.

The preparation method comprises the following steps:

s2, preparing a tetrabutyl titanate solution: dissolving tetrabutyl titanate in ethanol to prepare a 45wt% tetrabutyl titanate solution;

S3.TiO₂preparation of carbon microspheres: step 100gS1 adding the carbon microspheres into 30g of tetrabutyl titanate solution prepared in the step S3, ultrasonically mixing uniformly with ultrasonic power of 2000W, heating to volatilize ethanol, dropwise adding 20g of water, continuously stirring, reacting at 70 ℃ for 2h after dropwise adding, cooling to room temperature, filtering, washing with ethanol and water for 3 times in sequence, drying at 70 ℃ for 5h to obtain TiO₂Carbon microsphere.

Comparative preparation example 3

In comparison with preparation example 2, the tetrabutyl titanate solution was not added, and the other conditions were the same.

The preparation method comprises the following steps:

s3, preparing Cu/carbon microspheres: and (3) adding 100g of the carbon microsphere prepared in the step S1 into 20g of the copper sulfate solution prepared in the step S2, continuously stirring, placing at 70 ℃ for reacting for 2h after dropwise adding, cooling to room temperature, filtering, washing with ethanol and water for 3 times in sequence, drying at 70 ℃ for 5h to obtain the Cu/carbon microsphere.

Preparation example 3 chitin/polyhexamethylene guanidine microspheres

The preparation method comprises the following steps:

s1, preparation of a chitin solution: dissolving 100g of chitin powder in 100mL of 12 wt% acetic acid solution to obtain chitin solution;

s2, preparing a polyhexamethylene guanidine solution: dissolving 25g of polyhexamethylene guanidine hydrochloride and 2g of sodium hexadecylbenzene sulfonate in 50mL of water to obtain a polyhexamethylene guanidine solution;

s3, dripping the chitin solution prepared in the step S1 into the polyhexamethylene guanidine solution prepared in the step S2, stirring at room temperature for 2 hours, emulsifying at the rotating speed of 10000r/min for 2 minutes to prepare chitin/polyhexamethylene guanidine microsphere emulsion, and drying at 50 ℃ for 2 hours to obtain the chitin/polyhexamethylene guanidine microsphere.

Preparation example 4 chitin/polyhexamethylene guanidine microspheres

The preparation method comprises the following steps:

s1, preparation of a chitin solution: dissolving 100g of chitin powder in 100mL of 20wt% acetic acid solution to obtain chitin solution;

s2, preparing a polyhexamethylene guanidine solution: dissolving 25-45g of polyhexamethylene guanidine hydrochloride and 5g of sodium dodecyl benzene sulfonate in 50mL of water to obtain a polyhexamethylene guanidine solution;

s3, dripping the chitin solution prepared in the step S1 into the polyhexamethylene guanidine solution prepared in the step S2, stirring at room temperature for 3 hours, emulsifying at the rotating speed of 20000r/min for 5 minutes to prepare chitin/polyhexamethylene guanidine microsphere emulsion, and drying at 70 ℃ for 5 hours to obtain the chitin/polyhexamethylene guanidine microsphere.

Example 1

The raw materials comprise the following components in parts by weight: PET resin 100 parts, TiO produced in production example 1₂5 parts of/Cu/carbon microspheres, 13 parts of chitin/polyhexamethylene guanidine microspheres prepared in preparation example 3, 2 parts of di (2-ethylhexyl) phthalate, 21 parts of a compatilizer ST, 2 parts of carbon fibers, 1 part of nano copper and 120 parts of cyclohexanone.

The method comprises the following steps: dissolving PET resin in cyclohexanone, adding di (2-ethylhexyl) phthalate, carbon fiber and nano copper, heating to 50 deg.C, stirring, mixing, adding TiO₂The preparation method comprises the following steps of carrying out high-speed shearing dispersion on Cu/carbon microspheres, chitin/polyhexamethylene guanidine microspheres and a compatilizer ST-2 for 1h at a high-speed shearing rotation speed of 10000r/min, standing and defoaming to obtain a film forming solution, pouring the film forming solution into a glass mold, uniformly spreading the film forming solution in the glass mold, and drying the glass mold in an electric heating forced air drying oven at 50 ℃ for 5h to obtain the chitosan/polyhexamethylene guanidine microsphere/chitosan/.

Example 2

The raw materials comprise the following components in parts by weight: PET resin 200 parts, TiO produced in production example 1₂10 parts of/Cu/carbon microspheres, 17 parts of chitin/polyhexamethylene guanidine microspheres prepared in preparation example 3, 5 parts of di-sec-octyl phthalate and compatilizer ST-83 parts of carbon fiber, 4 parts of methyl salicylate and 250 parts of cyclohexanone.

The method comprises the following steps: dissolving PET resin in cyclohexanone, adding di-sec-octyl phthalate, carbon fiber and methyl salicylate, heating to 70 ℃, stirring and mixing uniformly, adding TiO₂The preparation method comprises the following steps of carrying out high-speed shearing dispersion on Cu/carbon microspheres, chitin/polyhexamethylene guanidine microspheres and a compatilizer ST-8 for 2 hours at a high-speed shearing rotation speed of 12000r/min, standing and defoaming to obtain a film forming solution, pouring and uniformly spreading the film forming solution in a glass mold, and drying the glass mold in an electric heating forced air drying oven at 50 ℃ for 7 hours to obtain the chitosan/polyhexamethylene guanidine microsphere.

Example 3

The raw materials comprise the following components in parts by weight: PET resin 120 parts, TiO produced in production example 2₂6 parts of/Cu/carbon microspheres, 14 parts of chitin/polyhexamethylene guanidine microspheres prepared in preparation example 4, 3 parts of di (2-ethylhexyl) phthalate, 21.5 parts of a compatilizer ST, 2.5 parts of carbon fibers, 1.2 parts of nano copper and 150 parts of cyclohexanone.

The method comprises the following steps: dissolving PET resin in cyclohexanone, adding di (2-ethylhexyl) phthalate, carbon fiber and nano copper, heating to 55 deg.C, stirring, mixing, and adding TiO₂The preparation method comprises the following steps of carrying out high-speed shearing dispersion on Cu/carbon microspheres, chitin/polyhexamethylene guanidine microspheres and a compatilizer ST-2 for 1h at a high-speed shearing rotation speed of 10500r/min, standing and defoaming to obtain a film forming solution, pouring and uniformly spreading the film forming solution in a glass mold, and drying the glass mold in an electric heating forced air drying oven at 50 ℃ for 6h to obtain the chitosan/polyhexamethylene guanidine microsphere.

Example 4

The raw materials comprise the following components in parts by weight: PET resin 180 parts, TiO produced in production example 2₂9 parts of/Cu/carbon microspheres, 16 parts of chitin/polyhexamethylene guanidine microspheres prepared in preparation example 4, 4 parts of dibutyl phthalate, 12.5 parts of compatilizer ST-5, 3.5 parts of carbon fibers, 1.8 parts of methyl salicylate and 200 parts of cyclohexanone.

The method comprises the following steps: dissolving PET resin in cyclohexanone, adding dibutyl phthalate, carbon fiber and methyl salicylate, heating to 65 deg.C, stirring, mixing, and adding TiO₂Cu/carbon microsphere, chitin/polyhexamethylene guanidine microsphere and compatilizer ST-1, high-speed shearingCutting and dispersing for 2h, carrying out high-speed shearing at the rotating speed of 11500r/min, standing and defoaming to obtain a film forming solution, pouring and uniformly spreading the film forming solution in a glass mold, and drying in an electric heating forced air drying oven at 50 ℃ for 6h to obtain the film forming solution.

Example 5

The raw materials comprise the following components in parts by weight: 150 parts of PET resin and TiO prepared in preparation example 2₂7 parts of/Cu/carbon microspheres, 15 parts of chitin/polyhexamethylene guanidine microspheres prepared in preparation example 4, 3.5 parts of di (2-ethylhexyl) phthalate, 12 parts of compatilizer ST-12 parts, 3 parts of carbon fibers, 1.6 parts of benzophenone and 170 parts of cyclohexanone.

The method comprises the following steps: dissolving PET resin in cyclohexanone, adding di (2-ethylhexyl) phthalate, carbon fiber and benzophenone, heating to 60 deg.C, stirring, mixing, adding TiO₂The preparation method comprises the following steps of carrying out high-speed shearing dispersion on Cu/carbon microspheres, chitin/polyhexamethylene guanidine microspheres and a compatilizer ST-1 for 1.5h at a high-speed shearing rotation speed of 11000r/min, standing and defoaming to obtain a film forming solution, pouring the film forming solution into a glass mold, uniformly spreading the film forming solution in the glass mold, and drying the glass mold in an electric heating air blowing drying oven at 50 ℃ for 6h to obtain the chitosan/polyhexamethylene guanidine microsphere/polyethylene guanidine.

Comparative example 1

Preparation of TiO from example 2 in comparison with example 5₂the/Cu/carbon microspheres were replaced with the carbon microspheres prepared in comparative preparation example 1, and the other conditions were the same.

Comparative example 2

Preparation of TiO from example 2 in comparison with example 5₂Replacement of/Cu/carbon microspheres with TiO from comparative preparation 2₂Carbon microsphere, other conditions were the same.

Comparative example 3

Preparation of TiO from example 2 in comparison with example 5₂the/Cu/carbon microspheres were replaced with the Cu/carbon microspheres prepared in comparative preparation example 2, and the other conditions were the same.

Comparative example 4

Compared with the embodiment 5, the chitin/polyhexamethylene guanidine microspheres prepared in the preparation 4 are replaced by chitin, and other conditions are consistent.

Comparative example 5

Compared with the embodiment 5, the chitin/polyhexamethylene guanidine microspheres prepared in the preparation example 4 are replaced by polyhexamethylene guanidine hydrochloride, and other conditions are consistent.

Test example 1

The black antibacterial PET films obtained in examples 1 to 5 and comparative examples 1 to 5, and the commercially available PET film were subjected to performance tests, and the results are shown in table 1.

TABLE 1

As can be seen from the above table, the black antibacterial PET film prepared by the invention has good comprehensive performance.

Test example 2 antibacterial property test

Test objects: black antibacterial PET films obtained in examples 1 to 5 and comparative examples 1 to 5, and commercially available PET films.

1. Antibacterial activity against Escherichia coli and Staphylococcus aureus

Testing is carried out according to a test method 1 pasting method of standard GB21551.2-2010, and bacteria for detection: escherichia coli; staphylococcus aureus bacteria; candida albicans; each example and comparative example was tested in parallel for 5 and averaged. The results are shown in Table 2.

TABLE 2

2. Inhibition rate to mould

The test was carried out according to the test method of Standard QB/T2591 (2003) with the following bacteria: aspergillus niger, Aspergillus terreus, Chaetomium globosum, 5 per example and comparative example were tested in parallel and averaged. The results are shown in Table 3.

TABLE 3

As can be seen from the above table, the black antibacterial PET film prepared by the invention has good antibacterial, bacteriostatic and mildewproof effects.

Compared with the prior art, the chitin/polyhexamethylene guanidine microspheres prepared by the invention have the advantages that the guanidino group of the polyhexamethylene guanidine has high activity, so that the polymer is electropositive and can be easily adsorbed by various bacteria and viruses; polyhexamethylene guanidine diffuses through cell membranes and binds to the cytoplasmic membrane, forms a complex with phospholipid bilayers, disrupts osmotic balance and the cytoplasmic membrane, causes cell leakage, and reacts strongly with nucleic acids, thereby inhibiting division of bacterial viruses, and rendering bacteria and viruses incapable of reproduction. Meanwhile, polyhexamethylene guanidine is a polymer, a film which can be formed blocks the breathing channel of microorganism, so that the microorganism is rapidly suffocated, and on the other hand, the molecule of the chitosan contains an active group-NH₂Therefore, the chitosan has antibacterial capability to various bacteria, and NH in chitosan molecules under acidic conditions³⁺Combined with anions dissociated from the cell wall, the composite antibacterial microsphere hinders the biosynthesis of the cell wall, prevents the transport of substances inside and outside the cell wall, and thus prevents the mass propagation of bacteria.

The invention is notWith addition of only black TiO₂The carbon fiber can improve the mechanical property of the film material to a certain extent, and simultaneously, the prepared PET film is black, and has the functions of light shielding and light isolation.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. The black antibacterial PET film is characterized by being prepared from the following raw materials in parts by weight: 100 portions of PET resin and 200 portions of TiO₂5-10 parts of/Cu/carbon microspheres, 13-17 parts of chitin/polyhexamethylene guanidine microspheres, 2-5 parts of toughening agent, 1-3 parts of compatilizer, 2-4 parts of carbon fibers, 1-2 parts of ultraviolet-resistant absorbent and 250 parts of cyclohexanone 120-;

the TiO is₂the/Cu/carbon microsphere is prepared by the following method:

s2 preparation of copper sulfate solution: dissolving blue copperas in water to prepare blue copperas solution;

s3 preparation of tetrabutyl titanate solution: dissolving tetrabutyl titanate in ethanol to prepare tetrabutyl titanate solution;

S4. TiO₂preparation of/Cu/carbon microspheres: adding the carbon microspheres prepared in the step S1 into the tetrabutyl titanate solution prepared in the step S3, uniformly mixing by ultrasonic waves, heating to completely volatilize ethanol, dropwise adding the copper sulfate solution prepared in the step S2, continuously stirring, and dropwise addingAfter the reaction is finished, the mixture is placed at 50-70 ℃ for reaction for 1-2h, cooled to room temperature, filtered, washed by ethanol and water for 2-3 times in sequence, and dried to obtain TiO₂a/Cu/carbon microsphere.

2. The black antibacterial PET film according to claim 1, which is prepared from the following raw materials in parts by weight: 120 portions of PET resin and 180 portions of TiO₂6-9 parts of/Cu/carbon microspheres, 14-16 parts of chitin/polyhexamethylene guanidine microspheres, 3-4 parts of toughening agent, 1.5-2.5 parts of compatilizer, 2.5-3.5 parts of carbon fibers, 1.2-1.8 parts of ultraviolet-resistant absorbent and 200 parts of cyclohexanone 150-.

3. The black antibacterial PET film according to claim 1, wherein the glucose solution is 25-40 wt%; the copper sulfate solution accounts for 55-70 wt%; the mass percentage of the tetrabutyl titanate solution is 25-45wt%, and the mass ratio of the carbon microspheres, the tetrabutyl titanate solution and the copper sulfate solution in the step S4 is 100: (17-30): (10-20).

4. The black antibacterial PET film as claimed in claim 1, wherein the stirring speed is 500-1000r/min, the ultrasonic power is 1000-2000W, the drying temperature is 50-70 ℃, and the drying time is 2-5 h.

5. The black antibacterial PET film according to claim 1, wherein the chitin/polyhexamethylene guanidine microspheres are prepared by the following method:

s1 preparation of chitin solution: dissolving chitin powder in acetic acid solution to obtain chitin solution;

s2 preparation of polyhexamethylene guanidine solution: dissolving polyhexamethylene guanidine hydrochloride and a surfactant in water to obtain a polyhexamethylene guanidine solution;

s3, dripping the chitin solution prepared in the step S1 into the polyhexamethylene guanidine solution prepared in the step S2, stirring at room temperature for 2-3 hours, emulsifying to prepare chitin/polyhexamethylene guanidine microsphere emulsion, and drying to obtain the chitin/polyhexamethylene guanidine microspheres.

6. The black antibacterial PET film as claimed in claim 5, wherein the mass ratio of the chitin powder, the polyhexamethylene guanidine hydrochloride and the surfactant is 100: (25-45): (2-5), wherein the acetic acid content in the acetic acid solution is 12-20 wt%; the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate and sodium octadecyl benzene sulfonate.

7. The black antibacterial PET film as claimed in claim 5, wherein the emulsification condition is emulsification at 10000-.

8. The black antimicrobial PET film according to claim 1, wherein the toughening agent is selected from one or a combination of di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl phthalate, diisononyl phthalate, diisodecyl phthalate, or diethyl phthalate; the compatilizer is selected from one or a combination of more of compatilizers ST-1, ST-2 and ST-8; the ultraviolet resistant absorbent is nano or micron metal oxide or salicylate, benzophenone organic ultraviolet resistant agent.

9. A method for preparing the black antibacterial PET film according to any one of claims 1 to 8, comprising the steps of: dissolving PET resin in cyclohexanone, adding toughening agent, carbon fiber and ultraviolet-resistant absorbent, heating to 50-70 deg.C, stirring, mixing, and adding TiO₂Cu/carbon microsphere, chitin/polyhexamethylene guanidine microsphere and compatilizer, high speedShearing and dispersing for 1-2h, standing and defoaming to obtain a film forming solution, pouring the film forming solution into a glass mold, uniformly spreading the film forming solution in the glass mold, and drying the glass mold in an electric heating forced air drying oven at 50 ℃ for 5-7h to obtain the glass ceramic.

10. The method as claimed in claim 9, wherein the high shear rate is 10000-12000 r/min.