CN112743950A - High-temperature-resistant heat shrinkable film and preparation method and application thereof - Google Patents
High-temperature-resistant heat shrinkable film and preparation method and application thereof Download PDFInfo
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- 229920006257 Heat-shrinkable film Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 72
- -1 polyethylene Polymers 0.000 claims abstract description 67
- 239000004698 Polyethylene Substances 0.000 claims abstract description 28
- 229920000573 polyethylene Polymers 0.000 claims abstract description 28
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 37
- 239000000155 melt Substances 0.000 claims description 26
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 24
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 24
- 229920001684 low density polyethylene Polymers 0.000 claims description 23
- 239000004702 low-density polyethylene Substances 0.000 claims description 23
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
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- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 1
- 229920001903 high density polyethylene Polymers 0.000 description 7
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
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- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
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- 101100291930 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MPE1 gene Proteins 0.000 description 1
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- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- B32B2307/732—Dimensional properties
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- C08J2323/04—Homopolymers or copolymers of ethene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
The invention provides a high-temperature-resistant heat-shrinkable film and a preparation method and application thereof, wherein the high-temperature-resistant heat-shrinkable film comprises a first anti-reflection layer, a first heat-shrinkable layer, a temperature-resistant layer, a second heat-shrinkable layer and a second anti-reflection layer which are sequentially arranged; and the combination of polyethylene glycol terephthalate and polyethylene is selected as the main material of the temperature-resistant layer, so that the high-temperature-resistant heat-shrinkable film has excellent high-temperature-resistant non-tacky performance and heat-shrinkable creep effect, can meet the requirement of long-term bundling package at 90-120 ℃, has very good application value, and is suitable for large-scale batch production.
Description
Technical Field
The invention belongs to the technical field of shrink films, and particularly relates to a high-temperature-resistant heat shrink film and a preparation method and application thereof.
Background
A heat shrinkable film is a thermoplastic film that is stretched and oriented during manufacture and heat shrunk during use. The heat shrinkability of films was used as early as 1936, and originally rubber films were primarily used for shrink-wrapping perishable foods. Nowadays, the heat shrinkage technology has been developed to be able to almost use heat shrinkage film to package various commodities, such as food, medicine, sterilized tableware, stationery, craft gift, printed matter, hardware plastic product, telephone, electronic and electrical products, etc. the package can not only satisfy the functions of moisture-proof and dust-proof, touch-proof, transparent display, etc. of the commodities, but also increase the appearance appeal of the products, especially in the aspect of the combined (bundling) package of irregular shaped articles or commodities, but also can be used to replace various paper boxes, not only save the packaging cost, but also meet the packaging trend.
With the widening of the range of use, studies and reports on heat shrinkable films are increasing. CN104354427A discloses a five-layer polyethylene heavy packaging heat shrinkable film and a preparation method thereof, wherein the thickness of the heat shrinkable film is 40-50 μm, and the heat shrinkable film is composed of five layers of films which are co-extruded and bonded, namely an outer layer, a secondary outer layer, a middle layer, a secondary inner layer and an inner layer; the thickness ratio of the outer layer, the secondary outer layer, the middle layer, the secondary inner layer and the inner layer is 1 (1.5-3) to 3-5 (1.5-3)1, preparing a catalyst; the raw materials of the outer layer and the inner layer are all composed of MPE1, LDPE and EVA; the materials of the secondary outer layer and the secondary inner layer are both composed of HDPE and MPE 2; the material of the intermediate layer consists of LDPE, HDPE and MPE 2. The heat shrinkable film saves 20-50% of materials, effectively reduces the production cost, and has better toughness, glossiness, flatness and mechanical properties. CN104416987A discloses a low-thickness polyethylene heat shrinkable film, which has a thickness of 45-50 μm and comprises three layers of co-extruded and bonded films, namely an outer layer, a middle layer and an inner layer; the raw materials of the outer layer comprise metallocene polyethylene, low-density polyethylene and high-density polyethylene with the mass ratio of (3-5) to (2-3) to 2; the middle layer is made of metallocene polyethylene, low-density polyethylene and high-density polyethylene in a mass ratio of 8 (1-2) to (2-3), and the inner layer is made of metallocene polyethylene, low-density polyethylene and high-density polyethylene in a mass ratio of (5-7) to 2: 1. On the basis of keeping good physical and mechanical properties such as thermal shrinkage, tearing strength, tensile strength at break, elongation at break, impact strength and the like, the material is saved by 40-50%, and the cost is effectively reduced. CN104175676A discloses a high-transparency polyethylene shrink film and a film blowing process, which is composed of three layers of films, namely an outer layer, a middle layer and an inner layer; the outer layer is composed of 0-20 wt% of LDPE, 79-99 wt% of MPE and 1-5 wt% of nucleating agent, wherein the melt index of the LDPE of the outer layer is more than or equal to 2g/10min, and the melt index of the MPE is more than or equal to 1g/10 min; the middle layer consists of 60-80 wt% of MDPE, 10-20 wt% of LDPE and 10-20 wt% of HDPE, the melt index of the MDPE in the middle layer is less than or equal to 0.5g/10min, the melt index of the LDPE is less than or equal to 0.5g/10min, and the density of the HDPE is greater than or equal to 0.960g/cm3(ii) a The raw material composition of the inner layer is the same as that of the outer layer. The high-transparency polyethylene shrink film obtained by the invention has the advantages of 7% of haze, more than or equal to 92% of light transmittance, 75% of glossiness, low haze and good glossiness, and when the film is used for printing, printed patterns are more attractive and clear. The above patents all provide a heat shrinkable film having a good shrink creep effect, but the film is easily sticky and damaged when used at a high temperature of 90 to 120 ℃ and the use feeling is impaired.
Therefore, the development of a high-temperature resistant heat shrinkable film which is not sticky at high temperature and has a good shrinkage creep effect has practical research value.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-temperature-resistant heat shrinkage film and a preparation method and application thereof, wherein the high-temperature-resistant heat shrinkage film comprises a first anti-reflection layer, a first heat shrinkage layer, a temperature-resistant layer, a second heat shrinkage layer and a second anti-reflection layer which are sequentially arranged; the high-temperature-resistant heat shrinkable film has the advantages that the polyethylene terephthalate and the polyethylene are added to the material of the temperature-resistant layer, so that the high-temperature-resistant heat shrinkable film has high temperature resistance, no stickiness and excellent heat shrinkage effect, and can be packaged and used for a long time at the temperature of 90-120 ℃.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high-temperature-resistant heat-shrinkable film, which comprises a first antireflection layer, a first heat-shrinkable layer, a temperature-resistant layer, a second heat-shrinkable layer and a second antireflection layer, which are sequentially arranged;
the material of the temperature resistant layer comprises a combination of polyethylene terephthalate and polyethylene.
The schematic cross-sectional structure of the high-temperature resistant heat-shrinkable film provided by the invention is shown in fig. 1, wherein 1 represents a first anti-reflection layer, 2 represents a first heat-shrinkable layer, 3 represents a temperature resistant layer, 4 represents a second heat-shrinkable layer, and 5 represents a second anti-reflection layer; firstly, the first antireflection layer 1 and the second antireflection layer 5 are arranged on the outermost side of the high-temperature-resistant heat shrinkage film, so that the high-temperature-resistant heat shrinkage film has good light transmittance and a good antireflection effect; secondly, the first heat-shrinkable layer 2 and the second heat-shrinkable layer 4 are arranged on the secondary outer side of the high-temperature-resistant heat-shrinkable film, so that the shrinkage force of the high-temperature-resistant heat-shrinkable film can be improved, and the shrinkage effect is ensured; and finally, arranging the temperature-resistant layer 3 on the innermost layer of the high-temperature-resistant heat-shrinkable film, and selecting polyethylene terephthalate and polyethylene as main body materials of the temperature-resistant layer, so that the temperature resistance of the high-temperature-resistant heat-shrinkable film can be improved, the high-temperature-resistant heat-shrinkable film has certain heat shrinkability, and the high-temperature-resistant heat-shrinkable film is not sticky and has a good heat shrinkage creep effect at the temperature of 90-120 ℃.
Preferably, the thickness of the high temperature resistant heat shrinkable film is 40 to 100 μm, such as 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm or 95 μm, and specific values therebetween are not exhaustive, and for brevity, the invention is not limited to the specific values included in the range.
Preferably, the content of the polyethylene terephthalate in the material of the temperature-resistant layer is 10-30% by mass, for example 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26% or 28%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the polyethylene terephthalate has a viscosity of 0.6 to 0.8dL/g, such as 0.62dL/g, 0.64dL/g, 0.66dL/g, 0.68dL/g, 0.7dL/g, 0.72dL/g, 0.74dL/g, 0.76dL/g, or 0.78dL/g, and specific values therebetween, not to mention space and for brevity, the invention is not exhaustive of the specific values included in the ranges.
Preferably, the material of the temperature-resistant layer contains 60 to 90% by mass of polyethylene, for example 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76% or 78%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the range.
Preferably, the polyethylene comprises a first metallocene polyethylene and/or a first low density polyethylene.
Preferably, the first metallocene polyethylene has a melt index of 0.8 to 1.2g/10min, such as 0.83g/10min, 0.86g/10min, 0.92g/10min, 0.95g/10min, 0.99g/10min, 1.1g/10min, 1.15g/10min or 1.18g/10min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the density of the first metallocene polyethylene0.91 to 0.92g/cm3E.g. 0.911g/cm3、0.912g/cm3、0.913g/cm3、0.914g/cm3、0.915g/cm3、0.916g/cm3、0.917g/cm3、0.918g/cm3Or 0.919g/cm3And the specific values between the foregoing, are not intended to be exhaustive or to limit the invention to the precise values encompassed within the scope, for reasons of brevity and clarity.
Preferably, the first low density polyethylene has a melt index of less than 0.5g/10min, such as 0.4g/10min, 0.3g/10min, 0.2g/10min, 0.1g/10min or 0.05g/10min, and specific values therebetween, not to be taken as space and for brevity, the invention is not exhaustive of the specific values included in the ranges.
Preferably, the mass ratio of the polyethylene terephthalate to the polyethylene is 1 (3-6), such as 1:3.2, 1:3.4, 1:3.6, 1:3.8, 1:4, 1:4.2, 1:4.4, 1:4.6, or 1: 4.8.
According to the preferable technical scheme, when the mass ratio of polyethylene terephthalate to polyethylene in the material of the temperature-resistant layer is 1 (3-6), the high-temperature-resistant heat shrinkable film has excellent temperature resistance, no stickiness and excellent heat shrinkage creep performance; on the one hand, if the content of the polyethylene terephthalate is relatively high, the temperature-resistant layer can be incompatible with the polyethylene terephthalate, so that the overall performance of the heat shrinkable film is reduced; on the other hand, if the content of the polyethylene terephthalate is relatively low, the temperature resistance of the high temperature resistant heat shrinkable film is reduced.
Preferably, the material of the temperature-resistant layer further comprises one or a combination of any two of a compatilizer, a slipping agent or an antioxidant.
Preferably, the content of the compatibilizer in the material of the temperature-resistant layer is 2 to 8% by mass, for example, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, or 7.5%, and specific values therebetween are limited by space and for brevity, and the invention is not exhaustive.
Preferably, the compatibilizer comprises a maleic anhydride grafted ethylene-1-octene copolymer.
Preferably, the material of the temperature-resistant layer contains 0.1-0.5% by mass of the slip agent, such as 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4% or 0.45%, and the specific values therebetween are not limited to the space and for the sake of brevity, and the invention is not exhaustive.
The slipping agent may be selected from Schelman, Germany, CE 505.
Preferably, the antioxidant is contained in the material of the temperature-resistant layer in an amount of 0.1-0.5% by mass, for example 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4% or 0.45%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the range. .
The antioxidant can be selected from Beijing big Dipper, Tiangang AO-B225.
Preferably, the thickness ratio of the temperature resistant layer to the first heat shrinkable layer is 1 (0.4-0.6), such as 1:0.42, 1:0.46, 1:0.48, 1:0.5, 1:0.52, 1:0.54, 1:0.56, or 1: 0.58.
Preferably, the thickness ratio of the temperature resistant layer to the second heat shrinkable layer is 1 (0.4-0.6), such as 1:0.42, 1:0.46, 1:0.48, 1:0.5, 1:0.52, 1:0.54, 1:0.56, or 1: 0.58.
Preferably, the materials of the first and second heat shrink layers each comprise a combination of a second metallocene polyethylene and a second low density polyethylene.
Preferably, the mass percentage content of the second metallocene polyethylene in the material of the first heat-shrinkable layer and the second heat-shrinkable layer is 70 to 95% each independently, for example 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92% or 94%, and specific points therebetween, for reasons of space and brevity, the present invention is not exhaustive of the specific points included in the ranges.
Preferably, the mass percentage content of the second low density polyethylene in the material of the first heat-shrinkable layer and the second heat-shrinkable layer is 10 to 30%, such as 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26% or 28%, respectively, and the specific values therebetween are not limited to the space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the thickness ratio of the temperature resistant layer to the first antireflection layer is 1 (0.2 to 0.3), for example, 1:0.21, 1:0.22, 1:0.23, 1:0.24, 1:0.25, 1:0.26, 1:0.27, 1:0.28, 1:0.29, or the like.
Preferably, the thickness ratio of the temperature resistant layer to the second antireflection layer is 1 (0.2-0.3), for example, 1:0.21, 1:0.22, 1:0.23, 1:0.24, 1:0.25, 1:0.26, 1:0.27, 1:0.28, 1:0.29, or the like.
Preferably, the materials of the first antireflective layer and the second antireflective layer each comprise a combination of a third metallocene polyethylene and a terpolymer polypropylene.
According to the preferable technical scheme, the third metallocene polyethylene and the third metallocene polyethylene are selected as materials of the first anti-reflection layer and the second anti-reflection layer, the third metallocene polyethylene and the fourth metallocene polyethylene can effectively break crystals of the first anti-reflection layer and the second anti-reflection layer to form a transparent layer, and the high-temperature-resistant heat shrinkage film can have high light transmittance.
Preferably, the third metallocene polyethylene content in the materials of the first anti-reflection layer and the second anti-reflection layer is 30-90%, such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, independently of each other, and specific values therebetween are not exhaustive for brevity and clarity.
Preferably, the melt index of the third metallocene polyethylene is 0.4-2 g/10min, such as 0.42g/10min, 0.44g/10min, 0.46g/10min, 0.48g/10min, 0.5g/10min, 0.52g/10min, 0.54g/10min, 0.56g/10min, 0.58g/10min, 0.7g/10min, 0.9g/10min, 1.1g/10min, 1.3g/10min, 1.5g/10min, 1.7g/10min or 1.9g/10min, respectively, and the specific values therebetween are limited in space and for the sake of brevity, and the specific values included in the range are not enumerated herein.
Preferably, the density of the third metallocene polyethylene is 0.91-0.93 g/cm3E.g. 0.911g/cm3、0.912g/cm3、0.913g/cm3、0.914g/cm3、0.915g/cm3、0.916g/cm3、0.917g/cm3、0.918g/cm3Or 0.919g/cm3And the specific values between the foregoing, are not intended to be exhaustive or to limit the invention to the precise values encompassed within the scope, for reasons of brevity and clarity.
Preferably, the content of the terpolypropylene in the materials of the first anti-reflection layer and the second anti-reflection layer is 10-25%, for example, 5%, 10%, 12%, 20% or 25%, independently, and specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive list of the specific values included in the range.
Preferably, the melt index of the terpolymer polypropylene is 3-5 g/10min, such as 3.2g/10min, 3.4g/10min, 3.6g/10min, 3.8g/10min, 4g/10min, 4.2g/10min, 4.4g/10min, 4.6g/10min or 4.8g/10min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the density of the ternary copolymerized polypropylene is 0.9-0.94 g/cm3For example 0.905g/cm3、0.909g/cm3、0.912g/cm3、0.915g/cm3、0.918g/cm3、0.921g/cm3、0.925g/cm3、0.928g/cm3、0.93g/cm3、0.935g/cm3Or 0.939g/cm3And the specific values between the foregoing, are not intended to be exhaustive or to limit the invention to the precise values encompassed within the scope, for reasons of brevity and clarity.
In a second aspect, the present invention provides a method for preparing a high temperature resistant heat shrinkable film according to the first aspect, the method comprising: and extruding, granulating and blowing the material of the first anti-reflection layer, the material of the first heat shrinkage layer, the material of the temperature-resistant layer, the material of the second heat shrinkage layer and the material of the second anti-reflection layer to obtain the high-temperature-resistant heat shrinkage film.
Preferably, the extrusion is performed by a single screw extruder.
Preferably, the single screw extruder has a length to diameter ratio of 20 to 25, such as 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, or 24.5, and specific values therebetween, not to be construed as limiting the disclosure and for the sake of brevity, the invention is not exhaustive of the specific values included in the recited ranges.
Preferably, the granulation temperature is 230-270 ℃, such as 232 ℃, 236 ℃, 239 ℃, 241 ℃, 246 ℃, 249 ℃, 251 ℃, 256 ℃ or 259 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the range.
Preferably, the preparation method comprises: and extruding the material of the first anti-reflection layer, the material of the first heat shrinkage layer, the material of the temperature-resistant layer, the material of the second heat shrinkage layer and the material of the second anti-reflection layer by a single-screw extruder with the length-diameter ratio of 20-25, granulating at 230-270 ℃, and blowing to obtain the high-temperature-resistant heat shrinkage film.
In a third aspect, the present invention provides a use of a heat resistant and heat shrinkable film according to the first aspect in the outer packaging of an article.
Compared with the prior art, the invention has the following beneficial effects:
according to the high-temperature-resistant heat-shrinkable film provided by the invention, the first anti-reflection layer, the first heat-shrinkable layer, the temperature-resistant layer, the second heat-shrinkable layer and the second anti-reflection layer are sequentially arranged, and the combination of polyethylene terephthalate and polyethylene is selected as a main material of the temperature-resistant layer, so that the high-temperature-resistant heat-shrinkable film has excellent high-temperature-resistant non-tacky performance and excellent heat-shrinkable creep effect; specifically, the high-temperature-resistant heat-shrinkable film provided by the invention has the elongation ratio of only 1.1-20 at 80 ℃, the elongation ratio of 5.3-60 at 120 ℃, the bonding temperature of 125-140 ℃, and the elongation ratios at 80 ℃ and 120 ℃ are greatly reduced compared with the heat-shrinkable film in the prior art, so that the high-temperature-resistant heat-shrinkable film provided by the invention has excellent high-temperature resistance; the long-term bundling package use under the condition of 90-120 ℃ can be met; the high-temperature-resistant heat-shrinkable film has excellent mechanical properties, the transverse tensile strength is 38-47 MPa, and the longitudinal tensile strength is 44-53 MPa; the preparation method of the high-temperature-resistant heat shrinkable film is simple, convenient to operate, wide in application range and suitable for large-scale batch production.
Drawings
Fig. 1 is a schematic cross-sectional structure diagram of a high temperature resistant heat shrinkable film provided by the invention, wherein 1-a first antireflection layer, 2-a first heat shrinkable layer, 3-a temperature resistant layer, 4-a second heat shrinkable layer, and 5-a second antireflection layer.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A high-temperature resistant heat shrinkage film is 70 mu m thick, the schematic cross-sectional structure of the film is shown in figure 1, and the film comprises a first anti-reflection layer 1, a first heat shrinkage layer 2, a temperature resistant layer 3, a second heat shrinkage layer 4 and a second anti-reflection layer 5 which are sequentially arranged, wherein the thickness ratio of the first anti-reflection layer 1 to the second anti-reflection layer 2 to the temperature resistant layer 3 is 0.25:0.5:1:0.5: 0.25;
wherein the first antireflection layer 1 comprises 80 mass percent of metallocene polyethylene (the melt index is 1.3g/10min, and the density is 0.927 g/cm)3) And 20 percent by mass of ternary copolymer polypropylene (the melt index is 4g/10min, the density is 0.92 g/cm)3) (ii) a The first heat-shrinkable layer 2 comprises 90% by mass of metallocene polyethylene (melt index of 0.2g/10min, density of 0.940 g/cm)3) And 10% by mass of low-density polyethylene (melt index of 0.5g/10min, density of 0.916 g/cm)3) (ii) a The temperature-resistant layer 3 comprises 20 mass percent of polyethylene terephthalate (viscosity is 0.7dL/g) and 75 mass percent of polyethylene (melt index is 1g/10 m)in, density of 0.915g/cm3) 4.5 percent by mass of maleic anhydride grafted ethylene-1-octene copolymer, 0.25 percent by mass of slipping agent (CE 505, Germany schulman) and 0.25 percent by mass of antioxidant (Tiangang AO-B225, Beijing Tiangang); the second heat-shrinkable layer 4 comprises 90% by mass of metallocene polyethylene (melt index of 0.2g/10min, density of 0.940 g/cm)3) And 10% by mass of low-density polyethylene (melt index of 0.5g/10min, density of 0.916 g/cm)3) (ii) a The second anti-reflection layer 5 comprises 80 mass percent of metallocene polyethylene (the melt index is 1.3g/10min, and the density is 0.927 g/cm)3) And 20 percent by mass of ternary copolymer polypropylene (the melt index is 4g/10min, the density is 0.92 g/cm)3)；
The preparation method comprises the following steps: and extruding the material of the first anti-reflection layer, the material of the first heat shrinkage layer, the material of the temperature-resistant layer, the material of the second heat shrinkage layer and the material of the second anti-reflection layer by a single-screw extruder with the length-diameter ratio of 22, granulating at 240 ℃, and blowing to obtain the high-temperature-resistant heat shrinkage film.
Example 2
A high-temperature-resistant heat shrinkage film is 40 mu m thick, has the same cross-sectional structure as that of example 1, and comprises a first anti-reflection layer, a first heat shrinkage layer, a temperature-resistant layer, a second heat shrinkage layer and a second anti-reflection layer which are sequentially arranged, wherein the thickness ratio of the first anti-reflection layer to the second anti-reflection layer is 0.2:0.4:1:0.4: 0.2;
wherein the first antireflection layer comprises 75 mass percent of metallocene polyethylene (the melt index is 0.5g/10min, and the density is 0.916 g/cm)3) And 25 percent by mass of ternary copolymerized polypropylene (the melt index is 3g/10min, the density is 0.9 g/cm)3) (ii) a The first heat-shrinkable layer comprises 95 mass percent of metallocene polyethylene (the melt index is 0.5g/10min, and the density is 0.945 g/cm)3) And 5% by mass of low density polyethylene (melt index of 0.2g/10min, density of 0.916 g/cm)3) (ii) a The temperature resistant layer comprises 15 percent by mass of polyethylene terephthalate (viscosity is 0.6dL/g) and 80 percent by mass of polyethylene (melt index is 0)8g/10min, density 0.91g/cm3) 4.6 percent by mass of maleic anhydride grafted ethylene-1-octene copolymer, 0.2 percent by mass of slipping agent (CE 505, Germany) and 0.2 percent by mass of antioxidant (Tiangang AO-B225, Beijing Tiangang); the second heat-shrinkable layer comprises 95 mass percent of metallocene polyethylene (melt index of 0.5g/10min, density of 0.945 g/cm)3) And 5% by mass of low density polyethylene (melt index of 0.2g/10min, density of 0.916 g/cm)3) (ii) a The second anti-reflection layer comprises 75 mass percent of metallocene polyethylene (the melt index is 05g/10min, and the density is 0.916 g/cm)3) And 25 percent by mass of ternary copolymerized polypropylene (the melt index is 3g/10min, the density is 0.9 g/cm)3)；
The preparation method comprises the following steps: and extruding the material of the first anti-reflection layer, the material of the first heat-shrinkable layer, the material of the temperature-resistant layer, the material of the second heat-shrinkable layer and the material of the second anti-reflection layer by a single-screw extruder with the length-diameter ratio of 23, granulating at 230 ℃, and blowing to obtain the high-temperature-resistant heat-shrinkable film.
Example 3
A high-temperature-resistant heat shrinkage film is 100 mu m thick, has the same cross-sectional structure as that of example 1, and comprises a first anti-reflection layer, a first heat shrinkage layer, a temperature-resistant layer, a second heat shrinkage layer and a second anti-reflection layer which are sequentially arranged, wherein the thickness ratio of the first anti-reflection layer to the second anti-reflection layer is 0.3:0.5:1:0.5: 0.32;
wherein the first antireflection layer comprises 90 wt% of metallocene polyethylene (melt index of 0.3g/10min, density of 0.92 g/cm)3) And 10 percent by mass of ternary copolymer polypropylene (the melt index is 5g/10min, the density is 0.94 g/cm)3) (ii) a The first heat-shrinkable layer comprises 80 mass percent of metallocene polyethylene (the melt index is 0.5g/10min, and the density is 0.935 g/cm)3) And 20% by mass of low density polyethylene (melt index of 0.8g/10min, density of 0.91 g/cm)3) (ii) a The temperature resistant layer comprises 20 mass percent of polyethylene terephthalate (viscosity is 0.6dL/g) and 75 mass percent of polyethylene (melt index is0.8g/10min, density 0.91g/cm3) 4 percent by mass of maleic anhydride grafted ethylene-1-octene copolymer, 0.5 percent by mass of slipping agent (Germany Schulmann, CE505) and 0.5 percent by mass of antioxidant (Beijing Tiangang, Tiangang AO-B225); the second heat-shrinkable layer comprises 80 mass percent of metallocene polyethylene (the melt index is 0.5g/10min, and the density is 0.935 g/cm)3) And 20% by mass of low density polyethylene (melt index of 0.8g/10min, density of 0.91 g/cm)3) (ii) a The second anti-reflection layer comprises 90 mass percent of metallocene polyethylene (the melt index is 0.3g/10min, and the density is 0.92 g/cm)3) And 10 percent by mass of ternary copolymer polypropylene (the melt index is 5g/10min, the density is 0.94 g/cm)3)；
The preparation method comprises the following steps: and extruding the material of the first anti-reflection layer, the material of the first heat shrinkage layer, the material of the temperature-resistant layer, the material of the second heat shrinkage layer and the material of the second anti-reflection layer by a single-screw extruder with the length-diameter ratio of 25, granulating at 270 ℃, and blowing to obtain the high-temperature-resistant heat shrinkage film.
Example 4
The high-temperature-resistant heat shrinkable film is different from the high-temperature-resistant heat shrinkable film in example 1 in that the weight percentage of polyethylene terephthalate in the high-temperature-resistant layer is 10%, the weight percentage of polyethylene is 85%, and other components, structures and preparation methods are the same as those in example 1.
Example 5
The high-temperature-resistant heat shrinkable film is different from the high-temperature-resistant heat shrinkable film in example 1 in that the weight percentage of polyethylene terephthalate in the high-temperature-resistant layer is 25%, the weight percentage of polyethylene in the high-temperature-resistant layer is 70%, and other components, structures and preparation methods are the same as those in example 1.
Example 6
The high-temperature-resistant heat shrinkable film is different from the high-temperature-resistant heat shrinkable film in example 1 in that the metallocene polyethylene in the first antireflection layer accounts for 100% by mass, the terpolymer polypropylene is not added, and other components, structures and preparation methods are the same as those in example 1.
Example 7
The high-temperature-resistant heat-shrinkable film is different from the high-temperature-resistant heat-shrinkable film in example 1 in that the metallocene polyethylene in the second antireflection layer accounts for 100% by mass, the terpolymer polypropylene is not added, and other components, structures and preparation methods are the same as those in example 1.
Comparative example 1
A heat shrinkable film, which is different from example 1 in that the weight percentage of polyethylene terephthalate in the heat resistant layer is 95%, polyethylene is not added, and other components, structures and preparation methods are the same as those of example 1.
Comparative example 2
A heat shrinkable film, which is different from example 1 in that the polyethylene content in the heat resistant layer is 95% by mass, polyethylene terephthalate is not added, and the other components, structure and preparation method are the same as those of example 1.
And (3) performance testing:
(1) elongation ratio at different temperatures: the sample was cut into a 10mm × 10cm strip, held by a clip, and a 200g weight was hung thereunder, and the strip was heated in a constant temperature oven at 80 ℃ and 120 ℃ for 14 days to measure the elongation ratio of the strip.
(2) Bonding temperature: using a five-point heat sealer, at 2 atmospheres and a dwell time of 5 seconds, the temperature was increased from 120 ℃ and 2 ℃ until the bonding temperature was reached.
(3) Tensile strength: the test was carried out according to GBT13519-2016 polyethylene shrink film for packaging.
Test pieces of the shrink films obtained in examples 1 to 7 and comparative examples 1 and 2 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1:
the high-temperature-resistant heat shrinkable film provided by the invention has smaller elongation at high temperature, which shows that the film has better high-temperature resistance; the non-stick temperature is higher, which shows that the non-stick performance is good, the tensile strength is higher, and the mechanical property is better.
Specifically, the high-temperature resistant heat shrinkable films obtained in examples 1 to 7 have an elongation ratio of only 1.1 to 20 at 80 ℃, an elongation ratio of 5.3 to 60 at 120 ℃, a bonding temperature of 125 to 140 ℃, a transverse tensile strength of 38 to 47MPa, and a longitudinal tensile strength of 44 to 53 MPa; compared with the heat shrinkable films obtained in comparative examples 1 and 2, the elongation ratios at 80 ℃ and 120 ℃ are greatly reduced, and the high-temperature resistant heat shrinkable film provided by the invention is proved to have excellent high-temperature resistance; and the transverse tensile strength and the longitudinal tensile strength are reduced, which proves that the heat shrinkable film with excellent mechanical property and high temperature resistance is obtained by adding the combination of polyethylene terephthalate and polyethylene in a specific part into the heat-resistant layer.
Further, comparing example 1, example 4 and example 5, we found that the heat shrinkable films obtained in examples 4 and 5 have higher elongation ratios at 80 ℃ and 120 ℃ than those of example 1 and lower tensile strengths in both the machine direction and the transverse direction than those of example 1; this shows that controlling the ratio of polyethylene terephthalate to polyethylene in the temperature resistant layer within a specific range can further improve the temperature resistance of the obtained high temperature resistant heat shrinkable film, and can improve the mechanical properties of the high temperature resistant heat shrinkable film.
Further, comparing example 1, example 6 and example 7, we found that the bonding temperature of the high temperature resistant heat shrinkable films obtained in examples 6 and 7 is reduced, which indicates that the addition of the terpolypropylene to the anti-reflection layer is beneficial to improving the non-sticky property of the high temperature resistant composite film.
The applicant states that the present invention is illustrated by the above examples to provide a high temperature resistant heat shrinkable film and a method for making and using the same, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. The high-temperature-resistant heat-shrinkable film is characterized by comprising a first antireflection layer, a first heat-shrinkable layer, a temperature-resistant layer, a second heat-shrinkable layer and a second antireflection layer which are sequentially arranged;
the material of the temperature resistant layer comprises a combination of polyethylene terephthalate and polyethylene.
2. The high-temperature-resistant heat-shrinkable film of claim 1, wherein the thickness of the high-temperature-resistant heat-shrinkable film is 40 to 100 μm.
3. The high-temperature-resistant heat shrinkable film of claim 1 or 2, wherein the material of the temperature-resistant layer comprises 10-30% by mass of polyethylene terephthalate;
preferably, the viscosity of the polyethylene terephthalate is 0.6-0.8 dL/g;
preferably, the mass percentage of the polyethylene in the material of the temperature-resistant layer is 60-90%;
preferably, the polyethylene comprises a first metallocene polyethylene and/or a first low density polyethylene;
preferably, the first metallocene polyethylene has a melt index of 0.8 to 1.2g/10 min;
preferably, the density of the first metallocene polyethylene is 0.91-0.92 g/cm3；
Preferably, the first low density polyethylene has a melt index of less than 0.5g/10 min;
preferably, the mass ratio of the polyethylene terephthalate to the polyethylene is 1 (3-6).
4. The high-temperature-resistant heat shrinkable film of any one of claims 1 to 3, wherein the material of the temperature-resistant layer further comprises one or a combination of any two of a compatilizer, a slipping agent or an antioxidant;
preferably, the mass percentage of the compatilizer in the material of the temperature-resistant layer is 2-8%;
preferably, the compatibilizer comprises a maleic anhydride grafted ethylene-1-octene copolymer;
preferably, the mass percentage content of the slipping agent in the material of the temperature-resistant layer is 0.1-0.5%;
preferably, the mass percentage of the antioxidant in the material of the temperature-resistant layer is 0.1-0.5%.
5. The high temperature resistant heat shrinkable film of any one of claims 1 to 4, wherein the thickness ratio of the temperature resistant layer to the first heat shrinkable layer is 1 (0.4 to 0.6);
preferably, the thickness ratio of the temperature-resistant layer to the second heat-shrinkable layer is 1 (0.4-0.6);
preferably, the materials of the first and second heat-shrinkable layers each comprise a combination of a second metallocene polyethylene and a second low density polyethylene;
preferably, the mass percentage content of the second metallocene polyethylene in the materials of the first heat-shrinkable layer and the second heat-shrinkable layer is 70-95% respectively and independently;
preferably, the mass percentage of the second low-density polyethylene in the materials of the first heat-shrinkable layer and the second heat-shrinkable layer is 10-30% respectively and independently.
6. The high-temperature-resistant heat shrinkable film according to any one of claims 1 to 5, wherein the thickness ratio of the temperature-resistant layer to the first antireflection layer is 1 (0.2 to 0.3);
preferably, the thickness ratio of the temperature-resistant layer to the second antireflection layer is 1 (0.2-0.3);
preferably, the materials of the first antireflection layer and the second antireflection layer both comprise a combination of third metallocene polyethylene and terpolymer polypropylene;
preferably, the content of the third metallocene polyethylene in the materials of the first antireflection layer and the second antireflection layer is 30-90% independently;
preferably, the melt indexes of the third metallocene polyethylenes are each independently 0.4 to 2g/10 min;
preferably, the density of the third metallocene polyethylene is 0.91-0.93 g/cm3；
Preferably, the content of the ternary copolymer polypropylene in the materials of the first anti-reflection layer and the second anti-reflection layer is 10-25% independently;
preferably, the melt indexes of the ternary copolymerized polypropylene are respectively and independently 3-5 g/10 min;
preferably, the density of the ternary copolymerized polypropylene is 0.9-0.94 g/cm3。
7. A preparation method of the high temperature resistant heat shrinkable film as claimed in any one of claims 1 to 6, wherein the preparation method comprises the following steps: and extruding, granulating and blowing the material of the first anti-reflection layer, the material of the first heat shrinkage layer, the material of the temperature-resistant layer, the material of the second heat shrinkage layer and the material of the second anti-reflection layer to obtain the high-temperature-resistant heat shrinkage film.
8. The production method according to claim 7, wherein the extrusion is performed by a single screw extruder;
preferably, the length-diameter ratio of the single-screw extruder is 20-25;
preferably, the temperature of the granulation is 230-270 ℃.
9. The production method according to claim 7 or 8, characterized by comprising: and extruding the material of the first anti-reflection layer, the material of the first heat shrinkage layer, the material of the temperature-resistant layer, the material of the second heat shrinkage layer and the material of the second anti-reflection layer by a single-screw extruder with the length-diameter ratio of 20-25, granulating at 230-270 ℃, and blowing to obtain the high-temperature-resistant heat shrinkage film.
10. Use of a high temperature resistant heat shrinkable film of any one of claims 1 to 6 in the outer packaging of articles.
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| CN103009753A (en) * | 2012-12-26 | 2013-04-03 | 郦国强 | Polyethylene terephthalate (PET) extrusion composite material for sealing aseptic packages and preparation method thereof |
| CN107892769A (en) * | 2017-11-20 | 2018-04-10 | 东莞市星华包装材料有限公司 | The preparation method and stretched film of a kind of stretched film |
| CN108608702A (en) * | 2018-04-08 | 2018-10-02 | 无锡市太平洋新材料股份有限公司 | A kind of heat shrink films and preparation method thereof |
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2020
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103009753A (en) * | 2012-12-26 | 2013-04-03 | 郦国强 | Polyethylene terephthalate (PET) extrusion composite material for sealing aseptic packages and preparation method thereof |
| CN107892769A (en) * | 2017-11-20 | 2018-04-10 | 东莞市星华包装材料有限公司 | The preparation method and stretched film of a kind of stretched film |
| CN108608702A (en) * | 2018-04-08 | 2018-10-02 | 无锡市太平洋新材料股份有限公司 | A kind of heat shrink films and preparation method thereof |
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Application publication date: 20210504 |