CN110757924B - Heat shrinkable film - Google Patents
Heat shrinkable film Download PDFInfo
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- CN110757924B CN110757924B CN201810823046.1A CN201810823046A CN110757924B CN 110757924 B CN110757924 B CN 110757924B CN 201810823046 A CN201810823046 A CN 201810823046A CN 110757924 B CN110757924 B CN 110757924B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/308—Heat stability
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention belongs to the field of polyolefin films, and particularly relates to a heat shrinkable film composition. The heat shrinkable film composition comprises an inner layer, a middle layer and an outer layer, and is prepared from the following raw materials in percentage by weight: 20-40% of high-density polyethylene; 20-40% of high-pressure polyethylene; 30-60% of medium-density metallocene polyethylene; wherein the medium density metallocene polyethylene is a copolymer of ethylene and alpha-olefin, and has a density of 0.932-0.938g/cm3(ii) a The melt mass flow rate is 0.1-0.8g/10 min. The invention provides a heat shrinkable film composition, which adopts medium-density metallocene polyethylene, changes the entanglement effect among polyethylene molecular chains, improves the retraction rate of high-pressure polyethylene long-chain branches in a formula during heat shrinkage, reduces the heat shrinkage temperature of a film on the basis of reducing the thickness and keeping good mechanical property when being used for producing a heat shrinkable film, saves energy consumption for downstream users and improves the production efficiency.
Description
Technical Field
The invention belongs to the field of polyolefin films, and particularly relates to a heat shrinkable film.
Background
The heat shrinkable film is commonly called as a shrinkable film, and is a film which can be greatly shrunk after being heated, so that the film can tightly wrap an article and can keep the shape of the article for a long time. The heat shrinkable film is designed by adopting the principle of stretching and orienting polymer molecular chains and is formed by a rapid cooling and shaping method. The physical principle is as follows: after the plastic material is heated, plasticized and extruded into a mother film, the polymer is forcibly stretched in the longitudinal and transverse directions between the glass transition temperature and the viscous flow temperature to orient the molecular chains of the polymer in the stretching direction, and then the polymer is rapidly cooled, so that the molecular orientation is frozen. When the film is reheated to the "thawing" temperature, the molecules return to their original state, causing shrinkage, due to stress relaxation caused by molecular motion. The polyethylene heat shrinkable film has high impact strength and high heat sealing strength after processing, is mainly used for packaging heavy articles such as bottled beverages and the like, such as collective packages of wines, pop-top cans, mineral water and the like, and can partially replace carton packages.
Most of polyethylene heat shrinkable films on the market at the beginning are processed and produced by using high-pressure polyethylene alone or blending high-density polyethylene and high-pressure polyethylene, and although the heat shrinkable films have high shrinkability and mechanical properties, the film products are thicker, generally more than 100 mu m, and meanwhile, the transparency is poor, so that the appearance of packaged goods is influenced. With the development of the processing technology of the heat shrinkable film, the thinning and permeability increasing of the heat shrinkable film become new development trends, medium-density metallocene polyethylene gradually becomes one of main raw materials for processing the heat shrinkable film, and through the addition of metallocene polyethylene resin, the mechanical property of the heat shrinkable film is further improved, the thickness of the film is reduced, and meanwhile, the transparency of the film is improved. The shrinkage test method of the heat shrinkable film without adding metallocene polyethylene in the early stage is heating shrinkage at 120 ℃ according to the test method of GB/T13519-92, but after adding the metallocene polyethylene, due to the structural regularity of the metallocene polyethylene, the activity space of high-pressure polyethylene long branched chains during heating shrinkage is limited, so that the shrinkage temperature at 120 ℃ cannot meet the shrinkage requirement, manufacturers usually perform heat shrinkage at 130 ℃, and the heat shrinkage test method in the application No. 201010611980.0 'a polyethylene repackaging heat shrinkable film and the preparation method thereof' is 130 ℃ and 20 s. Meanwhile, the heat shrinkage temperature of the film is increased when the beverage is packaged in the later period, and the energy consumption of beverage production enterprises is increased when the product is packaged.
Chinese patent CN107458059A discloses a polyethylene heat shrinkable film, wherein the given resin can also be used for producing a thinned heat shrinkable film, but tests show that the heat shrinkable film prepared by using the resin also needs to reach 130 ℃ to have better heat shrinkage.
Disclosure of Invention
The invention aims to provide a heat shrinkable film, which reduces the heat shrinkage temperature of a film, saves energy consumption for downstream users and improves production efficiency.
The invention relates to a heat shrinkable film, which comprises an inner layer, a middle layer and an outer layer, wherein the inner layer and the outer layer are respectively prepared from the following raw materials in percentage by weight:
20-40% of high-density polyethylene;
20-40% of high-pressure polyethylene;
30-60% of medium-density metallocene polyethylene;
wherein the medium density metallocene polyethylene is a copolymer of ethylene and alpha-olefin, and has a density of 0.932-0.938g/cm3(ii) a The melt mass flow rate is 0.1-0.8g/10 min.
Wherein:
the inner layer is prepared from the following raw materials in percentage by weight: 20-40% of high-density polyethylene, 20-40% of high-pressure polyethylene and 30-60% of medium-density metallocene polyethylene; the middle layer is prepared from the following raw materials in percentage by weight: 0-30% of high-density polyethylene, 0-30% of high-pressure polyethylene and 50-100% of medium-density metallocene polyethylene; the outer layer is prepared from the following raw materials in percentage by weight: 20-40% of high-density polyethylene, 20-40% of high-pressure polyethylene and 30-60% of medium-density metallocene polyethylene.
The density of the high-density polyethylene is 0.938-0.942g/cm3The melt mass flow rate of 21.6kg is 5-10g/10 min.
The density of the high-pressure polyethylene is 0.918-0.926g/cm3The 2.16kg melt mass flow rate is 0.5-2.0g/10 min.
The medium-density metallocene polyethylene is a copolymer of ethylene and 1-hexene, and the density is 0.934-0.937g/cm3(ii) a The melt mass flow rate is 0.4-0.6g/10 min.
The medium-density metallocene polyethylene used in the invention is used for determining the molecular mass fraction of polyethylene with different lamella thicknesses through crystallization thermal classification, in the medium-density metallocene polyethylene, the mass fraction of a crystal fraction with a central value of platelet thickness of 4.94 angstroms is 3.0-4.5%, the mass fraction of a crystal fraction with a central value of platelet thickness of 5.448 angstroms is 3.0-3.5%, the mass fraction of a crystal fraction with a central value of 6.090 angstroms is 4.2-4.5%, the mass fraction of a crystal fraction with a central value of 6.931 angstroms is 4.5-5.4%, the mass fraction of a crystal fraction with a central value of 8.070 angstroms is 8.2-8.6%, the mass fraction of a crystal fraction with a central value of 9.830 angstroms is 15.9-16.8%, the mass fraction of a crystal fraction with a central value of 12.904 angstroms is 38.5-43.1%, and the mass fraction of a crystal fraction with a central value of 16.743 angstroms is 18.2-20.3%.
The molecular weight and the distribution of the medium-density metallocene polyethylene are tested by a gel chromatography permeation method, the weight-average molecular weight is 63000-82000, and the molecular weight distribution is 4.00-4.87.
The medium-density metallocene polyethylene contains an antioxidant and an acid absorbent, wherein the antioxidant is a compound composition of a hindered phenol antioxidant and a phosphite antioxidant, the content of the hindered phenol antioxidant is 300-1500ppm, and the content of the phosphite antioxidant is 300-1500 ppm; the acid absorbent is zinc stearate or calcium stearate, and the content of the acid absorbent is 400-800 ppm.
The hindered phenol antioxidant is antioxidant 1010 or antioxidant 1076, preferably antioxidant 1076. Preferably, the hindered phenol type antioxidant is contained in an amount of 500-600 ppm.
The phosphite antioxidant is antioxidant 168 or antioxidant TNP, preferably antioxidant TNP. Preferably, the phosphite antioxidant is present in an amount of 500-800 ppm.
Preferably, the acid scavenger is present in an amount of 500 ppm. The acid scavenger is preferably zinc stearate.
Preferably, the adding mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1:1-1:1.5, preferably 1:1.
Preferably, the medium-density metallocene polyethylene is F3306S, a product commercially available from Zibonew plasticator Ltd.
The invention has the following beneficial effects:
the invention provides a heat shrinkable film, which adopts medium-density metallocene polyethylene, changes the entanglement effect among polyethylene molecular chains, improves the retraction rate of high-pressure polyethylene long-chain branches in a formula during heat shrinkage, reduces the heat shrinkage temperature of a film on the basis of reducing the thickness and keeping good mechanical property when being used for producing the heat shrinkable film, saves energy consumption for downstream users and improves the production efficiency.
Detailed Description
The present invention is further described below with reference to examples.
The starting materials used in the examples are all commercially available except where otherwise indicated.
The medium density metallocene polyethylene mPE1, a copolymer of ethylene and 1-hexene, used in the examples of the invention, had a melt index of 2.16kg of 0.5g/10 mm and a density of 0.936g/cm3500ppm of antioxidant 1076, 500ppm of antioxidant 168 and 500ppm of zinc stearate.
The medium-density metallocene polyethylene used was F3306S, a product commercially available from Zibo New plasticator Ltd.
The medium density metallocene polyethylene mPE2, commercially available, used in the comparative example, a copolymer of ethylene and 1-hexene, 2.16kg melt index 0.5g/10 mm, density 0.935g/cm3。
Table 1 shows the crystalline thermal grading different crystalline fraction contents of two medium density metallocene polyethylenes applied in examples and comparative examples.
TABLE 1 lower fraction content of crystallization thermal classification crystallization temperature%
Table 2 shows the molecular weights and their distributions of two medium density metallocene polyethylene resins used in the examples and comparative examples.
TABLE 2 molecular weights and distributions thereof
| Item | mPE1 | mPE2 |
| Weight average molecular weight | 70262 | 50024 |
| Molecular weight distribution | 4.37 | 3.21 |
Heat shrinkable films were prepared using mPE1 and mPE2, respectively, according to the formulations in Table 3, with a film thickness of 60 μm and a ratio of inner, middle and outer layers of 1:1: 1.
TABLE 3 Heat shrink film formulation
Table 4 shows the comparison of the properties of the heat shrinkable films processed using examples and comparative examples.
TABLE 4 Heat shrink film Properties
TABLE 5 film Heat shrinkage at 125 ℃
Claims (4)
1. A heat shrinkable film comprises an inner layer, a middle layer and an outer layer, and is characterized in that: the inner layer and the outer layer are both prepared from the following raw materials in percentage by weight: 20-40% of high-density polyethylene, 20-40% of high-pressure polyethylene and 30-60% of medium-density metallocene polyethylene; the middle layer is prepared from the following raw materials in percentage by weight: 0-30% of high-density polyethylene, 0-30% of high-pressure polyethylene and 50-100% of medium-density metallocene polyethylene;
the high density polyethylene has a density of 0.938 to 0.942g/cm3The mass flow rate of 21.6kg melt is 5-10g/10 min;
the density of the high-pressure polyethylene is 0.918-0.926g/cm3The mass flow rate of the 2.16kg melt is 0.5-2.0g/10 min;
the medium density metallocene polyethylene is a copolymer of ethylene and 1-hexene, and has a density of 0.932-0.938g/cm3(ii) a The mass flow rate of the melt is 0.1-0.8g/10 min;
the medium-density metallocene polyethylene contains an antioxidant and an acid-absorbing agent, wherein the antioxidant is a compound composition of a hindered phenol antioxidant and a phosphite antioxidant, the content of the hindered phenol antioxidant is 300-1500ppm, and the content of the phosphite antioxidant is 300-1500 ppm; the acid absorbent is zinc stearate or calcium stearate, and the content of the acid absorbent is 400-800 ppm;
the weight average molecular weight of the medium-density metallocene polyethylene is 63000-82000, and the molecular weight distribution is 4.00-4.87;
in the medium-density metallocene polyethylene, the mass fraction of a crystal fraction with a central value of platelet thickness of 4.940 angstroms is 3.0-4.5%, the mass fraction of a crystal fraction with a central value of platelet thickness of 5.448 angstroms is 3.0-3.5%, the mass fraction of a crystal fraction with a central value of 6.090 angstroms is 4.2-4.5%, the mass fraction of a crystal fraction with a central value of 6.931 angstroms is 4.5-5.4%, the mass fraction of a crystal fraction with a central value of 8.070 angstroms is 8.2-8.6%, the mass fraction of a crystal fraction with a central value of 9.830 angstroms is 15.9-16.8%, the mass fraction of a crystal fraction with a central value of 12.904 angstroms is 38.5-43.1%, and the mass fraction of a crystal fraction with a central value of 16.743 angstroms is 18.2-20.3%.
2. The heat shrinkable film of claim 1, characterized in thatCharacterized in that: the medium-density metallocene polyethylene is a copolymer of ethylene and 1-hexene, and the density is 0.934-0.937g/cm3The melt mass flow rate is 0.4-0.6g/10 min.
3. The heat shrinkable film of claim 1, wherein: the hindered phenol antioxidant is an antioxidant 1010 or an antioxidant 1076, and the phosphite antioxidant is an antioxidant 168 or an antioxidant TNP.
4. The heat shrinkable film of claim 1, wherein: the medium-density metallocene polyethylene is F3306S.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810823046.1A CN110757924B (en) | 2018-07-25 | 2018-07-25 | Heat shrinkable film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810823046.1A CN110757924B (en) | 2018-07-25 | 2018-07-25 | Heat shrinkable film |
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| CN110757924A CN110757924A (en) | 2020-02-07 |
| CN110757924B true CN110757924B (en) | 2022-04-08 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173160A (en) * | 2010-12-29 | 2011-09-07 | 东莞市正新包装制品有限公司 | Heavy-duty thermal shrinkage polyethylene film and preparation method thereof |
| CN104311949A (en) * | 2014-10-11 | 2015-01-28 | 中国石油化工股份有限公司 | High-strength polyethylene material for preparing heat shrinkable film, and preparation method of high-strength polyethylene material |
| CN104416987A (en) * | 2013-08-30 | 2015-03-18 | 东莞市正新包装制品有限公司 | Low-thickness polyethylene heat shrinkable film |
| CN104608443A (en) * | 2014-11-26 | 2015-05-13 | 界首市天鸿包装材料有限公司 | Processing technology for heat shrinkable film |
| CN107458059A (en) * | 2016-06-03 | 2017-12-12 | 中国石油化工股份有限公司 | A kind of polyethylene heat-shrinkage film |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173160A (en) * | 2010-12-29 | 2011-09-07 | 东莞市正新包装制品有限公司 | Heavy-duty thermal shrinkage polyethylene film and preparation method thereof |
| CN104416987A (en) * | 2013-08-30 | 2015-03-18 | 东莞市正新包装制品有限公司 | Low-thickness polyethylene heat shrinkable film |
| CN104311949A (en) * | 2014-10-11 | 2015-01-28 | 中国石油化工股份有限公司 | High-strength polyethylene material for preparing heat shrinkable film, and preparation method of high-strength polyethylene material |
| CN104608443A (en) * | 2014-11-26 | 2015-05-13 | 界首市天鸿包装材料有限公司 | Processing technology for heat shrinkable film |
| CN107458059A (en) * | 2016-06-03 | 2017-12-12 | 中国石油化工股份有限公司 | A kind of polyethylene heat-shrinkage film |
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