High-barrier antibacterial anti-ultraviolet BOPET release film and preparation method thereof

Abstract

The invention discloses a high-barrier antibacterial anti-ultraviolet BOPET release film and a preparation method thereof, and belongs to the technical field of high polymer materials. The BOPET release film comprises a BOPET base film layer, a middle layer and a release layer, wherein the middle layer and the release layer are sequentially arranged on the BOPET base film layer; the release layer is prepared from the following components in parts by weight: 60 to 80 parts of polyether modified heptamethyltrisiloxane, 30 to 50 parts of organic silicon modified resin, 5 to 10 parts of a photoinitiator and 1 to 3 parts of an ethylene-vinyl acetate copolymer; the middle layer is prepared from the following components in parts by weight: 80-100 parts of epoxy resin, 60-70 parts of polyethylene glycol terephthalate, 30-40 parts of a blocking agent, 5-15 parts of an ultraviolet absorbent and 5-10 parts of an antibacterial agent. The BOPET release film provided by the invention has high barrier property, antibacterial property and anti-ultraviolet capability, and is moderate in stripping force. Therefore, the BOPET release film has a relatively good application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a high-barrier antibacterial and ultraviolet-proof BOPET release film and a preparation method thereof. Background Art

[0002] BOPET release film is a film made of polyethylene terephthalate (PET) through a biaxial stretching process, and its surface is usually coated with a release agent. This film has good mechanical properties, chemical stability and heat sealing properties, and is widely used in electronics, mobile phones, adhesives, waterproofing, advertising consumables and other fields.

[0003] There are many research reports on BOPET release films in the prior art. For example, Chinese patent application document CN104592848A discloses a BOPET release film and a preparation method thereof. The BOPET release film is based on a BOPET film as a base film, and a release agent layer is coated on the BOPET film; wherein the raw material composition of the release agent layer includes reactant monomers, an initiator and toluene; the reactant monomers include the following components in terms of mass percentage: 10% to 30% of a vinyl-containing silicone monomer; 30% to 50% of acrylic acid; 10% to 25% of methyl acrylate or methyl methacrylate; 8% to 25% of ethyl acrylate or butyl acrylate; 5% to 20% of styrene; and 4% to 10% of isobutyl methacrylate.

[0004] However, the existing BOPET release films still have problems such as large peeling force and single performance. Summary of the invention

[0005] The purpose of the present invention is to provide a high-barrier antibacterial and UV-proof BOPET release film and a preparation method thereof, so as to solve the problems of large peeling force and single performance of the existing BOPET release film.

[0006] In a first aspect, the present invention provides a high-barrier, antibacterial and UV-proof BOPET release film, comprising a BOPET base film layer and an intermediate layer and a release layer sequentially arranged on the BOPET base film layer; the release layer is made of components comprising the following parts by weight: 60-80 parts of polyether-modified heptamethyltrisiloxane, 30-50 parts of silicone-modified resin, 5-10 parts of photoinitiator, and 1-3 parts of ethylene-vinyl acetate copolymer; the intermediate layer is made of components comprising the following parts by weight: 80-100 parts of epoxy resin, 60-70 parts of polyethylene terephthalate, 30-40 parts of barrier agent, 5-15 parts of UV absorber and 5-10 parts of antibacterial agent.

[0007] In the present invention, the inventors have found that in the release layer of the BOPET release film, polyether-modified heptamethyltrisiloxane is used as a base material, and it is cross-linked with a silicone-modified resin under a photoinitiator, so that the release force of the release layer is moderate. In addition, by adding ethylene-vinyl acetate copolymer, on the one hand, the flexibility of the release layer is increased, and at the same time, the release layer is further made to have a moderate peeling force; further, by adding polyethylene terephthalate, a barrier agent, an ultraviolet absorber and an antibacterial agent to the middle layer, the BOPET release film has good barrier properties, antibacterial properties and anti-ultraviolet properties. At the same time, polyethylene terephthalate also has certain barrier properties and anti-ultraviolet properties, which can further enhance the performance of the BOPET release film and solve the problem of the single performance of the traditional BOPET release film.

[0008] In the BOPET release film provided by the present invention, the polyether-modified heptamethyl trisiloxane in the release layer may be, for example, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts or other values ​​within the range, the silicone-modified resin may be, for example, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or other values ​​within the range, the photoinitiator may be, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts or other values ​​within the range, the ethylene-vinyl acetate copolymer may be, for example, 1 part, 2 parts, 3 parts or other values ​​within the range; the epoxy resin in the middle layer may be, for example, It can be 80 parts, 85 parts, 90 parts, 95 parts, 100 parts or other values ​​within this range, the polyethylene terephthalate can be, for example, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts or other values ​​within this range, the barrier can be, for example, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts or other values ​​within this range, the ultraviolet absorber can be, for example, 5 parts, 7 parts, 10 parts, 13 parts, 15 parts or other values ​​within this range, and the antibacterial agent can be, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts or other values ​​within this range.

[0009] In some embodiments, the organosilicon-modified resin includes an organosilicon-modified epoxy resin and an organosilicon-modified acrylic resin, and the mass ratio of the organosilicon-modified epoxy resin to the organosilicon-modified acrylic resin is (1-3):1.

[0010] In the present invention, the inventors further discovered that by mixing the organosilicon-modified epoxy resin and the organosilicon-modified acrylic resin in a specific ratio, the BOPET release film can have a moderate peeling force.

[0011] In some embodiments, the photoinitiator is photoinitiator 1173.

[0012] It can be understood that, in the present invention, the photoinitiator can be conventionally selected according to actual use needs. In the present invention, the photoinitiator is preferably photoinitiator 1173.

[0013] In some embodiments, the barrier agent is selected from at least one of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyethylene naphthalate, and poly(m-xylylene adipamide).

[0014] In some embodiments, the ultraviolet absorber is selected from at least one of 2-hydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-3'-tert-butyl-5'-chlorophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole.

[0015] In some embodiments, the antibacterial agent is selected from at least one of dioctyldimethylammonium chloride, didecyldimethylammonium chloride, ditetradecyldimethylammonium chloride, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, and 1-bromo-3-chloro-5,5-dimethylhydantoin.

[0016] In some embodiments, the thickness of the BOPET base film layer is 30-50 μm, for example, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or other values ​​within the range; the thickness of the intermediate layer is 2-10 μm, for example, 2 μm, 4 μm, 6 μm, 8 μm, 10 μm or other values ​​within the range; the thickness of the release layer is 15-25 μm, for example, 15 μm, 17 μm, 20 μm, 23 μm, 25 μm or other values ​​within the range.

[0017] In a second aspect, the present invention provides a method for preparing a high-barrier, antibacterial and UV-proof BOPET release film as described above, comprising the following steps: S1, mixing epoxy resin, polyethylene terephthalate, a barrier agent, a UV absorber and an antibacterial agent to obtain a mixture; S2, coating the mixture on a BOPET base film layer, and obtaining an intermediate layer after drying; S3, mixing polyether-modified heptamethyltrisiloxane, a silicone-modified resin, a photoinitiator and an ethylene-vinyl acetate copolymer, and coating the mixture on the intermediate layer, and UV-curing to obtain a high-barrier, antibacterial and UV-proof BOPET release film.

[0018] In the present invention, the preparation process is simple, the raw materials are cheap and easily available, and the large-scale industrial preparation of the BOPET release film is convenient.

[0019] In some embodiments, in step S2, the drying temperature is 50-60°C, for example, 50°C, 52°C, 55°C, 57°C, 60°C or other values ​​within the range.

[0020] In some embodiments, in step S3, UV curing includes: an irradiation power of 1500-2000 W, for example, 1500 W, 1600 W, 1700 W, 1800 W, 1900 W, 2000 W or other values ​​within the range; a wavelength of 360-370 nm, for example, 360 nm, 362 nm, 365 nm, 368 nm, 370 nm or other values ​​within the range; an irradiation distance of 20-30 cm, for example, 20 cm, 22 cm, 25 cm, 28 cm, 30 cm or other values ​​within the range; a curing time of 1-3 min, for example, 1 min, 2 min, 3 min or other values ​​within the range.

[0021] The beneficial effects of the present invention are as follows: different from the prior art, the present invention adds polyether-modified heptamethyltrisiloxane and silicone-modified resin into the release layer of the BOPET release film, and the two are cross-linked under a photoinitiator, so that the release force of the release layer is moderate. In addition, by adding ethylene-vinyl acetate copolymer, on the one hand, the flexibility of the release layer is increased, and at the same time, the release layer is further made to have moderate peeling force; further, by adding polyethylene terephthalate, a barrier agent, an ultraviolet absorber and an antibacterial agent into the intermediate layer, the BOPET release film has good barrier properties, antibacterial properties and anti-ultraviolet properties. At the same time, polyethylene terephthalate also has certain barrier properties and anti-ultraviolet properties, which can further enhance the performance of the BOPET release film. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a schematic structural diagram of the high barrier antibacterial and UV-proof BOPET release film of the present invention; The reference numerals have the following meanings: 1: release layer; 2: intermediate layer; 3: BOPET base film layer. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] The experimental methods without specific conditions in the examples are usually carried out according to conventional conditions and conditions described in the manual, or according to conditions recommended by the manufacturer. The general equipment, materials, reagents, etc. used are all available from commercial channels unless otherwise specified.

[0025] See also Figure 1, which is a schematic diagram of the structure of the high barrier antibacterial and UV-proof BOPET release film of the present invention. Specifically, the BOPET release film comprises a BOPET base film layer 3 and an intermediate layer 2 and a release layer 1 sequentially arranged on the BOPET base film layer 3.

[0026] Example 1 A high-barrier antibacterial and anti-ultraviolet BOPET release film, comprising a BOPET base film layer 3 and an intermediate layer 2 and a release layer 1 sequentially arranged on the BOPET base film layer 3; The release layer 1 is prepared from the following components in parts by weight: 60 parts of polyether-modified heptamethyltrisiloxane, 30 parts of silicone-modified epoxy resin, 20 parts of silicone-modified acrylic resin, 5 parts of photoinitiator 1173, and 3 parts of ethylene-vinyl acetate copolymer; The intermediate layer 2 is made of components including the following parts by weight: 80 parts of epoxy resin, 70 parts of polyethylene terephthalate, 40 parts of polyvinyl alcohol, 5 parts of 2-hydroxy-4-methoxybenzophenone and 5 parts of dioctyldimethylammonium chloride.

[0027] The preparation method of the high-barrier antibacterial and UV-proof BOPET release film comprises the following steps: S1, mixing epoxy resin, polyethylene terephthalate, polyvinyl alcohol, 2-hydroxy-4-methoxybenzophenone and dioctyldimethylammonium chloride to obtain a mixture; S2, coating the mixture on a BOPET base film layer 3 with a thickness of 20 μm, and drying at a temperature of 50° C. to obtain an intermediate layer 2 with a thickness of 5 μm; S3. Mix polyether-modified heptamethyltrisiloxane, silicone-modified epoxy resin, silicone-modified acrylic resin, photoinitiator 1173, and ethylene-vinyl acetate copolymer, and apply them on the intermediate layer 2. Curing for 3 minutes under the conditions of irradiation power of 1500 W, wavelength of 370 nm, and irradiation distance of 30 cm to obtain a high-barrier, antibacterial and UV-proof BOPET release film, wherein the thickness of the release layer is 20 μm.

[0028] Example 2 A high-barrier antibacterial and anti-ultraviolet BOPET release film, comprising a BOPET base film layer 3 and an intermediate layer 2 and a release layer 1 sequentially arranged on the BOPET base film layer 3; The release layer 1 is prepared from the following components in parts by weight: 70 parts of polyether-modified heptamethyltrisiloxane, 28 parts of silicone-modified epoxy resin, 12 parts of silicone-modified acrylic resin, 8 parts of photoinitiator 1173, and 2 parts of ethylene-vinyl acetate copolymer; The intermediate layer 2 is made of the following components in parts by weight: 90 parts of epoxy resin, 65 parts of polyethylene terephthalate, 35 parts of ethylene-vinyl alcohol copolymer, 10 parts of 2-(2'-hydroxy-3'-tert-butyl-5'-chlorophenyl)-5-chlorobenzotriazole and 8 parts of ditetradecyl dimethyl ammonium chloride.

[0029] The preparation method of the high-barrier antibacterial and UV-proof BOPET release film comprises the following steps: S1, mixing epoxy resin, polyethylene terephthalate, ethylene-vinyl alcohol copolymer, 2-(2'-hydroxy-3'-tert-butyl-5'-chlorophenyl)-5-chlorobenzotriazole and ditetradecyl dimethyl ammonium chloride to obtain a mixture; S2, coating the mixture on a BOPET base film layer 3 with a thickness of 40 μm, and drying at a temperature of 55° C. to obtain an intermediate layer 2 with a thickness of 5 μm; S3. Mix polyether-modified heptamethyltrisiloxane, silicone-modified epoxy resin, silicone-modified acrylic resin, photoinitiator 1173, and ethylene-vinyl acetate copolymer, and apply them on the intermediate layer 2. Curing for 2 minutes under the conditions of irradiation power of 1800 W, wavelength of 365 nm, and irradiation distance of 25 cm to obtain a high-barrier, antibacterial and UV-proof BOPET release film, wherein the thickness of the release layer is 20 μm.

[0030] Example 3 A high-barrier antibacterial and anti-ultraviolet BOPET release film, comprising a BOPET base film layer 3 and an intermediate layer 2 and a release layer 1 sequentially arranged on the BOPET base film layer 3; The release layer 1 is prepared from the following components in parts by weight: 80 parts of polyether-modified heptamethyltrisiloxane, 20 parts of silicone-modified epoxy resin, 10 parts of silicone-modified acrylic resin, 10 parts of photoinitiator 1173, and 1 part of ethylene-vinyl acetate copolymer; The intermediate layer 2 is made of the following components in parts by weight: 100 parts of epoxy resin, 60 parts of polyethylene terephthalate, 30 parts of polyethylene naphthalate, 15 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and 10 parts of 1,3-dibromo-5,5-dimethylhydantoin.

[0031] The preparation method of the high-barrier antibacterial and UV-proof BOPET release film comprises the following steps: S1, mixing epoxy resin, polyethylene terephthalate, polyethylene naphthalate, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and 1,3-dibromo-5,5-dimethylhydantoin to obtain a mixture; S2, coating the mixture on a BOPET base film layer 3 with a thickness of 40 μm, and drying at a temperature of 60° C. to obtain an intermediate layer 2 with a thickness of 5 μm; S3. Mix polyether-modified heptamethyltrisiloxane, silicone-modified epoxy resin, silicone-modified acrylic resin, photoinitiator 1173, and ethylene-vinyl acetate copolymer, and apply them on the intermediate layer 2. Curing for 1 minute under the conditions of irradiation power of 2000 W, wavelength of 360 nm, and irradiation distance of 20 cm to obtain a high-barrier, antibacterial and UV-proof BOPET release film, wherein the thickness of the release layer is 20 μm.

[0032] Comparative Example 1 The components and preparation method of the high barrier, antibacterial and UV-proof BOPET release film in this comparative example are basically the same as those in Example 1, except that, in the release layer 1, the organosilicon-modified epoxy resin is replaced by an equal amount of organosilicon-modified acrylic resin.

[0033] Comparative Example 2 The components and preparation method of the high barrier, antibacterial and UV-proof BOPET release film in this comparative example are basically the same as those in Example 1, except that, in the release layer 1, the organosilicon-modified acrylic resin is replaced by an equal amount of organosilicon-modified epoxy resin.

[0034] Comparative Example 3 The components and preparation method of the high barrier, antibacterial and UV-proof BOPET release film in this comparative example are basically the same as those in Example 1, except that no ethylene-vinyl acetate copolymer is added to the release layer 1.

[0035] Comparative Example 4 The components and preparation method of the high barrier antibacterial and UV-proof BOPET release film in this comparative example are basically the same as those in Example 1, except that polyethylene terephthalate is not added to the intermediate layer 2 .

[0036] Performance Testing The performance of the high barrier antibacterial and UV-proof BOPET release films prepared in Examples 1-3 and Comparative Examples 1-4 was tested. Among them, the peeling force test: the method in GB / T 25256-2010 was adopted, and the TESA7457 standard tape was used for testing; the oxygen permeability test: the test was carried out with reference to the method in GB / T19789-2005; the water permeability test: the hydrostatic pressure method was adopted, 1000mm water column; the UV blocking rate test: the UV energy before and after the UV rays passed through the BOPET release film was tested, and the UV blocking rate was calculated; the Staphylococcus aureus inhibition rate: the test was carried out using the method in GB / T31402-2015 standard. The test results are shown in Table 1 below.

[0037] Table 1 Performance test results of high barrier antibacterial and UV-resistant BOPET release film

[0038] It can be seen from Table 1 that the BOPET release films prepared in Examples 1-3 of the present invention have moderate peeling force, good barrier properties, UV protection properties and antibacterial properties.

[0039] Comparative Examples 1 and 2 contain only one of the silicone-modified epoxy resin and the silicone-modified acrylic resin. The results show that the peeling force of the prepared BOPET release film is significantly increased. The results show that the silicone-modified epoxy resin and the silicone-modified acrylic resin have a synergistic effect and can reduce the peeling force of the BOPET release film to a moderate range.

[0040] In Comparative Example 3, no ethylene-vinyl acetate copolymer was added. It was found that the peeling force of the prepared BOPET release film was increased to a certain extent. The results showed that after adding ethylene-vinyl acetate copolymer, the release layer further had a moderate peeling force.

[0041] In Comparative Example 4, polyethylene terephthalate was not added. The results showed that the barrier properties and UV protection properties of the prepared BOPET release film were both reduced to a certain extent. The results showed that polyethylene terephthalate can further enhance the barrier properties and UV protection properties of the BOPET release film.

[0042] In summary, the BOPET release film of the present invention has moderate peeling force, good barrier property, UV protection property and antibacterial property.

[0043] It should be noted that the above embodiments all belong to the same inventive concept, and the description of each embodiment has its own focus. For matters that are not described in detail in some embodiments, reference may be made to the description in other embodiments.

[0044] The above-mentioned embodiments only express the implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A high barrier antibacterial and UV-proof BOPET release film, characterized in that: It comprises a BOPET base film layer, and an intermediate layer and a release layer which are sequentially arranged on the BOPET base film layer; The release layer is made of the following components in parts by weight: 60-80 parts of polyether-modified heptamethyltrisiloxane, 30-50 parts of organosilicon-modified resin, 5-10 parts of photoinitiator, and 1-3 parts of ethylene-vinyl acetate copolymer; The intermediate layer is made of the following components in parts by weight: 80-100 parts of epoxy resin, 60-70 parts of polyethylene terephthalate, 30-40 parts of barrier agent, 5-15 parts of ultraviolet absorber and 5-10 parts of antibacterial agent.

2. The high barrier antibacterial and UV-proof BOPET release film according to claim 1, characterized in that: The organosilicon-modified resin includes an organosilicon-modified epoxy resin and an organosilicon-modified acrylic resin, and the mass ratio of the organosilicon-modified epoxy resin to the organosilicon-modified acrylic resin is (1-3):

1.

3. The high barrier antibacterial and UV-proof BOPET release film according to claim 1, characterized in that: The photoinitiator is photoinitiator 1173.

4. The high barrier antibacterial and UV-proof BOPET release film according to claim 1, characterized in that: The barrier agent is selected from at least one of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyethylene naphthalate, and poly(m-xylylene adipamide).

5. The high barrier antibacterial and UV-proof BOPET release film according to claim 1, characterized in that: The ultraviolet absorber is selected from at least one of 2-hydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-3'-tert-butyl-5'-chlorophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole.

6. The high barrier antibacterial and UV-proof BOPET release film according to claim 1, characterized in that: The antibacterial agent is selected from at least one of dioctyldimethylammonium chloride, didecyldimethylammonium chloride, ditetradecyldimethylammonium chloride, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin and 1-bromo-3-chloro-5,5-dimethylhydantoin.

7. The high barrier antibacterial and UV-proof BOPET release film according to claim 1, characterized in that: The thickness of the BOPET base film layer is 30-50 μm, the thickness of the intermediate layer is 2-10 μm, and the thickness of the release layer is 15-25 μm.

8. A method for preparing a high barrier, antibacterial and UV-proof BOPET release film as claimed in any one of claims 1 to 7, characterized in that: The steps include: S1, mixing epoxy resin, polyethylene terephthalate, a barrier agent, an ultraviolet absorber and an antibacterial agent to obtain a mixture; S2, coating the mixture on the BOPET base film layer, and obtaining an intermediate layer after drying; S3, mixing polyether-modified heptamethyltrisiloxane, silicone-modified resin, photoinitiator and ethylene-vinyl acetate copolymer, coating the mixture on the intermediate layer, and subjecting the mixture to UV curing to obtain a high-barrier antibacterial and UV-proof BOPET release film.

9. The preparation method according to claim 8, characterized in that: In step S2, the drying temperature is 50-60°C.

10. The preparation method according to claim 8, characterized in that: In step S3, the ultraviolet curing includes: irradiation power of 1500-2000W, wavelength of 360-370nm, irradiation distance of 20-30cm, and curing time of 1-3min.

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