CN110760167A - Long-acting antibacterial transparent PET master batch, window film and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of PET (polyethylene terephthalate) master batches, and particularly relates to a long-acting antibacterial transparent PET master batch, a window film and a preparation method thereof. The composite material comprises the following raw materials in parts by weight: 50 parts of PET resin, 40-50 parts of special antibacterial agent, 2-6 parts of antioxidant, 1-4 parts of light stabilizer and 1-3 parts of ultraviolet absorbent. The mechanism of the special antibacterial agent of the invention is that: although the softening point of polyacrylonitrile is lower, the melting point is higher, the polyacrylonitrile microspheres can keep better structural integrity in the process of PET melt extrusion, after PET stretching film forming, because the thickness of the polyacrylonitrile microspheres is equivalent to the film thickness, the polyacrylonitrile microspheres are inserted into the BOPET film and exposed in the air, the distribution condition of nano titanium dioxide on the film surface is improved, and the finally prepared film material has the characteristic of long-acting antibiosis without spraying treatment.

Description

A kind of long-acting antibacterial transparent PET masterbatch, window film and preparation method thereof

technical field

The invention relates to the technical field of PET master batches, in particular to a long-acting antibacterial transparent PET master batch, a window film and a preparation method thereof.

Background technique

Polyester polymers are widely used in products such as toys, window films, and packaging materials. With the progress of society, the frequency of use is getting higher and higher, and the types are also increasing. However, these products do not have bacteriostatic function, and are easy to breed or multiply various harmful bacteria, molds, viruses and other microorganisms, becoming a source of public transmission and causing great trouble to people's health.

Nano-titanium dioxide is an emerging antibacterial agent. Nano-titanium dioxide decomposes bacteria under the action of photocatalysis to achieve antibacterial effect. Since the electronic structure of nano-TiO2 is characterized by a valence band filled with TiO ₂ and an empty conduction band, in the system of water and air, nano-TiO2 can be exposed to sunlight, especially ultraviolet rays, when the electron energy reaches or exceeds its band. At the gap energy, electrons can be excited from the valence band to the conduction band, and corresponding holes are generated in the valence band, that is, electron-hole pairs are generated. Under the action of the electric field, the electrons and holes are separated and migrate to the particle surface. At different positions of TiO 2 , a series of reactions occur, and the oxygen dissolved on the surface of TiO ₂ is adsorbed to capture electrons to form O ₂ , and the generated superoxide anion radicals react (oxidize) with most organic substances. At the same time, it can react with the organic matter in the bacteria to generate CO ₂ and H ₂ O; while the holes oxidize the OH and H ₂ O adsorbed on the surface of TiO ₂ to ·OH, ·OH has a strong oxidizing ability and attacks the organic matter. Unsaturated bonds or extraction of H atoms generate new free radicals, triggering a chain reaction that eventually causes bacteria to decompose.

Also due to the characteristics of nano-titanium dioxide absorbing ultraviolet rays, absorbing moisture and air, nano-titanium dioxide is generally coated on the surface of the product through a coating liquid, which can exert better performance. However, from the perspective of production economic benefits, taking window film manufacturers as an example, they need to prepare additional coating materials, coating devices and curing equipment, which is costly, and the film material coating and curing occupies a large area, and the efficiency is relatively high. Low.

Therefore, the development of long-acting antibacterial masterbatch is an urgent technical problem to be solved.

SUMMARY OF THE INVENTION

In order to overcome the shortcomings and deficiencies in the prior art, the purpose of the present invention is to provide a long-acting antibacterial transparent PET master batch, a window film and a preparation method thereof.

The object of the present invention is achieved through the following technical solutions:

A long-acting antibacterial transparent PET master batch, comprising the following raw materials by weight:

Wherein, the special antibacterial agent is obtained by the following steps:

(1) Dissolve 20-30 parts by weight of acrylonitrile in 100 parts by weight of an organic solvent, then add 0.1-0.3 parts by weight of the first initiator, stir and mix, heat up to 40-50 ° C, and react for 2-4h , to obtain the precursor solution;

(2) adding 6-12 parts by weight of nano-titanium dioxide and 0.1-0.2 parts by weight of the second initiator to the precursor solution, stirring and dispersing, heating up to 50-60 ° C, and reacting for 3-5 h to obtain a suspension liquid;

(3) electrostatically spraying the suspension to obtain the special antibacterial agent.

In the preparation method of the special antibacterial agent of the present invention, acrylonitrile is used to initiate polymerization and nucleation for the first time, and acrylonitrile is used to initiate polymerization for the second time to coat the nano-titanium dioxide on the acrylonitrile core, so that a polypropylene with nano-titanium dioxide distributed on the surface is prepared. The particle size of nitrile microspheres and polyacrylonitrile microspheres is 10-30 μm, which is equivalent to the thickness of the membrane material. The mechanism of the special antibacterial agent of the present invention is: although the softening point of polyacrylonitrile is low, the melting point is high, and the polyacrylonitrile microspheres can maintain good structural integrity in the process of PET melt extrusion, and the PET is stretched to form a film. Then, since the thickness of the polyacrylonitrile microspheres is equivalent to the thickness of the film, the polyacrylonitrile microspheres are interspersed in the BOPET film and exposed to the air to improve the distribution of nano-titanium dioxide on the surface of the film. It also has long-lasting antibacterial properties without the need for spray treatment.

Wherein, the organic solvent is dimethyl sulfoxide.

Wherein, the first initiator and the second initiator are both azobisisobutyronitrile.

Wherein, the particle size of the nano titanium dioxide is 15-25 nm.

Wherein, the spray voltage of the electrostatic spray is 20-30kV, and the spray temperature is 20-30°C.

Wherein, the antioxidant is antioxidant 168 and/or antioxidant 1076.

Wherein, the light stabilizer is bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and/or poly(1-hydroxyethyl-2,2,6 , 6-tetramethyl-4-hydroxypiperidine) succinate.

Wherein, the ultraviolet absorber is 2-cyano 3,3'-diphenyl acrylate-2-ethylhexyl and/or 2-(2-hydroxy-3-tert-butyl-5-methylphenyl) -5-Chlorobenzotriazole.

The above-mentioned long-acting antibacterial transparent PET masterbatch is prepared by the following method: putting each raw material into a twin-screw extruder for melt extrusion, and the extrusion temperature is 230-260°C.

A BOPET window film, comprising the following raw materials in parts by weight:

100 parts of PET resin

Long-lasting antibacterial transparent PET masterbatch 50-70 copies

Functional additives 0.1-10 copies.

The above-mentioned preparation method of a BOPET window film: after melt-mixing the PET resin, the heat insulating master batch and the remaining auxiliary agents, biaxial stretching is performed to form a film to obtain the BOPET window film.

The beneficial effects of the present invention are: in the preparation method of the special antibacterial agent of the present invention, acrylonitrile is used for the first time to initiate polymerization and nucleation, and acrylonitrile is used for the second time to initiate polymerization to coat the nano-titanium dioxide on the acrylonitrile nucleus, so that the nano-sized titanium dioxide is prepared. Titanium dioxide is distributed on the surface of polyacrylonitrile microspheres, and the particle size of the polyacrylonitrile microspheres is 10-30 μm, which is equivalent to the thickness of the membrane material. The mechanism of the special antibacterial agent of the present invention is: although the softening point of polyacrylonitrile is low, the melting point is high, and the polyacrylonitrile microspheres can maintain good structural integrity in the process of PET melt extrusion, and the PET is stretched to form a film. Then, since the thickness of the polyacrylonitrile microspheres is equivalent to the thickness of the film, the polyacrylonitrile microspheres are interspersed in the BOPET film and exposed to the air to improve the distribution of nano-titanium dioxide on the surface of the film. It also has long-lasting antibacterial properties without the need for spray treatment.

Detailed ways

In order to facilitate the understanding of those skilled in the art, the present invention will be further described below with reference to the examples, and the contents mentioned in the embodiments are not intended to limit the present invention.

Example 1

A long-acting antibacterial transparent PET master batch, comprising the following raw materials by weight:

Wherein, the special antibacterial agent is obtained by the following steps:

(1) 20 parts by weight of acrylonitrile was dissolved in 100 parts by weight of an organic solvent, then 0.1 part by weight of the first initiator was added, after stirring and mixing, the temperature was raised to 40° C., and reacted for 2 h to obtain a precursor solution;

(2) adding 6 parts by weight of nano titanium dioxide and 0.1 part by weight of the second initiator to the precursor solution, after stirring and dispersing, heating up to 50° C. and reacting for 3 hours to obtain a suspension;

(3) electrostatically spraying the suspension to obtain the special antibacterial agent.

Wherein, the organic solvent is dimethyl sulfoxide.

Wherein, the first initiator and the second initiator are both azobisisobutyronitrile.

Wherein, the particle size of the nano titanium dioxide is 15nm.

Wherein, the spray voltage of the electrostatic spray is 20kV, and the spray temperature is 20°C.

Wherein, the antioxidant is antioxidant 168.

Wherein, the light stabilizer is bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate.

Wherein, the ultraviolet absorber is 2-cyano-3,3'-diphenylacrylate-2-ethylhexyl.

A BOPET window film, comprising the following raw materials in parts by weight:

100 parts of PET resin

Long-lasting antibacterial transparent PET masterbatch 50 parts

0.1 part of functional additives;

The functional auxiliary is antioxidant 1010.

The above-mentioned preparation method of a BOPET window film: after melt-mixing the PET resin, the heat insulating master batch and the remaining auxiliary agents, biaxial stretching is performed to form a film to obtain the BOPET window film.

Example 2

A long-acting antibacterial transparent PET master batch, comprising the following raw materials by weight:

Wherein, the special antibacterial agent is obtained by the following steps:

(1) 20-30 parts by weight of acrylonitrile is dissolved in 100 parts by weight of organic solvent, then 0.3 parts by weight of the first initiator is added, after stirring and mixing, the temperature is raised to 50 ° C, and the reaction is performed for 4h to obtain a precursor solution;

(2) adding 12 parts by weight of nano-titanium dioxide and 0.2 parts by weight of the second initiator to the precursor solution, stirring and dispersing, heating up to 60° C., and reacting for 5 hours to obtain a suspension;

(3) electrostatically spraying the suspension to obtain the special antibacterial agent.

Wherein, the organic solvent is dimethyl sulfoxide.

Wherein, the first initiator and the second initiator are both azobisisobutyronitrile.

Wherein, the particle size of the nano titanium dioxide is 25 nm.

Wherein, the spray voltage of the electrostatic spray is 30kV, and the spray temperature is 30°C.

Wherein, the antioxidant is antioxidant 1076.

Wherein, the light stabilizer is poly(1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine)succinate.

Wherein, the ultraviolet absorber is 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole.

A BOPET window film, comprising the following raw materials in parts by weight:

100 parts of PET resin

Long-lasting antibacterial transparent PET masterbatch 70 parts

10 functional additives;

The functional additives are antistatic agents, lubricants and antioxidants

The above-mentioned preparation method of a BOPET window film: after melt-mixing the PET resin, the heat insulating master batch and the remaining auxiliary agents, biaxial stretching is performed to form a film to obtain the BOPET window film.

Example 3

A long-acting antibacterial transparent PET master batch, comprising the following raw materials by weight:

Wherein, the special antibacterial agent is obtained by the following steps:

(1) 25 parts by weight of acrylonitrile was dissolved in 100 parts by weight of an organic solvent, then 0.2 parts by weight of the first initiator was added, after stirring and mixing, the temperature was raised to 45° C. and reacted for 3h to obtain a precursor solution;

(2) adding 9 parts by weight of nano-titanium dioxide and 0.15 parts by weight of the second initiator to the precursor solution, after stirring and dispersing, heating up to 55° C. and reacting for 4 hours to obtain a suspension;

(3) electrostatically spraying the suspension to obtain the special antibacterial agent.

Wherein, the organic solvent is dimethyl sulfoxide.

Wherein, the first initiator and the second initiator are both azobisisobutyronitrile.

Wherein, the particle size of the nano titanium dioxide is 20 nm.

Wherein, the spray voltage of the electrostatic spray is 25kV, and the spray temperature is 25°C.

Wherein, the antioxidant is composed of antioxidant 168 and antioxidant 1076 in a weight ratio of 1:1.

Wherein, the light stabilizer is composed of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and poly(1-hydroxyethyl-2,2,6,6 -Tetramethyl-4-hydroxypiperidine)succinate is composed in a weight ratio of 1:1.

Wherein, the ultraviolet absorber is composed of 2-cyano 3,3'-diphenyl acrylate-2-ethylhexyl and 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5 -Chlorobenzotriazoles are composed in a weight ratio of 1:1.

A BOPET window film, comprising the following raw materials in parts by weight:

100 parts of PET resin

Long-lasting antibacterial transparent PET masterbatch 60 parts

Functional Auxiliary 0.1 part

The functional auxiliary is antioxidant 1010.

The above-mentioned preparation method of a BOPET window film: after melt-mixing the PET resin, the heat insulating master batch and the remaining auxiliary agents, biaxial stretching is performed to form a film to obtain the BOPET window film.

Comparative Example 1

This comparative example is a commercially available conventional BOPET film, and a commercially available conventional nano titanium dioxide coating is coated on the film.

Comparative Example 2

The difference between this comparative example and Example 3 is:

Described antibacterial PET master batch comprises the raw material of following parts by weight:

The films of Example 3, Comparative Example 1 and Comparative Example 2 were tested for tensile strength, elongation at break and antibacterial rate according to GB/T13022 and GB/T 21866, wherein the tensile strength and elongation at break of Comparative Example 2 were tested. What is tested is the BOPET film made directly by the described antibacterial PET master batch, and the test results are shown in the following table:

Tensile strength (MPa) Elongation at break (%) Antibacterial rate (%) Example 3 113 470 90 Comparative Example 1 127 420 93 Comparative Example 2 132 560 84

In terms of the performance of antibacterial properties, it is still the best choice to directly apply the nano-silica coating, but the BOPET film of the present invention can also achieve an antibacterial rate of 90%, and the antibacterial properties are also relatively good; In terms of strength, the commercially available BOPET film is not modified with antibacterial agents, so the mechanical properties are kept well, and the tensile strength and elongation at break have good performance. The integrity of the structure will inevitably form stress concentration points on the film, so the tensile strength is the worst; from the performance of elongation at break, the toughness of the finished film in Comparative Example 1 is reduced due to the mixing of a large amount of nano-titania. , so the elongation at break is the worst, not as good as the BOPET film of the present invention.

The above-mentioned embodiment is a preferred implementation scheme of the present invention. In addition, the present invention can also be implemented in other ways, and any obvious replacements are within the protection scope of the present invention without departing from the concept of the present invention.

Claims (10)

1. A long-acting antibacterial transparent PET master batch is characterized in that: the composite material comprises the following raw materials in parts by weight:

wherein, the special antibacterial agent is prepared by the following steps:

(1) dissolving 20-30 parts by weight of acrylonitrile in 100 parts by weight of organic solvent, then adding 0.1-0.3 part by weight of first initiator, stirring and mixing, heating to 40-50 ℃, and reacting for 2-4h to obtain precursor solution;

(2) adding 6-12 parts by weight of nano titanium dioxide and 0.1-0.2 part by weight of second initiator into the precursor solution, stirring and dispersing, heating to 50-60 ℃, and reacting for 3-5 hours to obtain a suspension;

(3) and carrying out electrostatic spraying on the suspension to obtain the special antibacterial agent.

2. The long-acting antibacterial transparent PET master batch according to claim 1, characterized in that: the organic solvent is dimethyl sulfoxide.

3. The long-acting antibacterial transparent PET master batch according to claim 1, characterized in that: the first initiator and the second initiator are both azobisisobutyronitrile.

4. The long-acting antibacterial transparent PET master batch according to claim 1, characterized in that: the particle size of the nano titanium dioxide is 15-25 nm.

5. The long-acting antibacterial transparent PET master batch according to claim 1, characterized in that: the spraying voltage of the electrostatic spraying is 20-30kV, and the spraying temperature is 20-30 ℃.

6. The long-acting antibacterial transparent PET master batch according to claim 1, characterized in that: the antioxidant is antioxidant 168 and/or antioxidant 1076.

7. The long-acting antibacterial transparent PET master batch according to claim 1, characterized in that: the light stabilizer is bis (1, 2,2,6, 6-pentamethyl-4-piperidyl) sebacate and/or poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate.

8. The long-acting antibacterial transparent PET master batch according to claim 1, characterized in that: the ultraviolet absorbent is 2-cyano-3, 3' -diphenylacrylic acid-2-ethylhexyl ester and/or 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole.

9. A BOPET window film is characterized in that: the composite material comprises the following raw materials in parts by weight:

100 parts of PET resin

50-70 parts of long-acting antibacterial transparent PET master batch

0.1-10 parts of functional auxiliary agent;

the long-acting antibacterial transparent PET master batch is the long-acting antibacterial transparent PET master batch according to any one of claims 1 to 8.

10. The method of making a BOPET window film of claim 9, wherein: and melting and mixing the PET resin, the heat-insulating master batch and the rest of auxiliary agents, and performing biaxial tension film forming to obtain the BOPET window film.