CN106218159B - Packaging material made of a kind of heat shrink films and the heat shrink films - Google Patents
Packaging material made of a kind of heat shrink films and the heat shrink films Download PDFInfo
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- CN106218159B CN106218159B CN201610578810.4A CN201610578810A CN106218159B CN 106218159 B CN106218159 B CN 106218159B CN 201610578810 A CN201610578810 A CN 201610578810A CN 106218159 B CN106218159 B CN 106218159B
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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
- B32B27/32—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
- B32B27/32—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D2565/38—Packaging materials of special type or form
- B65D2565/381—Details of packaging materials of special type or form
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of heat shrink films and utilize packaging material made of the heat shrink films, the heat shrink films are made of internal layer, interlayer and outer layer, by weight percentage, internal layer and outer layer are made of 50~70% mLLDPE, 10~15% LLDPE, 10~15% UHMWPE, 5~10% ethylene propylene copolymer and 5~10% ethylene-alpha-olefin copolymer；The melting means of mLLDPE, LLDPE≤0.6g/10min, the density of mLLDPE, LLDPE, UHMWPE >=0.930g/cm3.Ectonexine is prepared using the mLLDPE and LLDPE that melting means is low, density is big, heat shrink films is made to have both good tensile strength, transparency and index of refraction；UHMWPE and mLLDPE and LLDPE is combined, and three, which acts synergistically, can further improve the tensile strength and toughness of heat shrink films.
Description
Technical field
The present invention relates to a kind of packaging materials, and in particular to a kind of heat shrink films.
Background technology
Heat shrink films good toughness, impact resistance, tear resistance are strong, moisture-proof, shrinking percentage is big, can meet the transparent display of commodity
Etc. functions, it is and cost-effective, become and substitute carton package development trend, be widely used in food, drug, disinfection meal
The outer packing of tool, stationery sports goods, process gift, printed matter, hardware plastic products, telephone set, electronic apparatus etc. various products,
It is especially more applicable in terms of the combined type of anomalistic object article or commodity (boundling) packaging.
The Chinese patent application of 101049749 A of Publication No. CN discloses a kind of high transparent multilaminar polyethylene thermal contraction
Film, the heat shrink films be three-decker, wherein internal layer and outer layer be including mLLDPE (metallocene linear low density polyethylene),
The mixture of LLDPE (linear low density polyethylene (LLDPE)), LDPE (low density polyethylene (LDPE)) and auxiliary agent composition, interlayer LDPE,
The mixture of LLDPE, HDPE (high density polyethylene (HDPE)) composition.Wherein, as mass fraction, in internal layer and outer layer, MLLDPE has 2
~4 parts, LDPE has 3~5 parts, and LLDPE has 2~4 parts, and auxiliary agent has 0.1~0.5 part；In interlayer, LDPE has 5~7 parts, LLDPE
There is 1~3 part, HDPE has 1~3 part.
If polythene material melt index is lower used by existing heat shrink films production man is generally acknowledged that, density is bigger,
Then the mist degree of manufactured heat shrink films bigger (transparency is lower), intensity are bigger；The transparency and intensity of heat shrink films are can not
It gets both.
Simultaneously as current production man preferably considers thermal contraction film strength, mist degree and refractive power to heat shrink films substantially
Rate requires then relatively low (for mist degree generally more than 30%, index of refraction is below 80%), in order to ensure the same of heat shrink films intensity
When reduce the mist degrees transparencies of heat shrink films (improve) of heat shrink films, producing polythene material melt index used in family will
It is low but cannot too low, density it is big but cannot be too big, substantially, the melt index of the polythene material of the selection is about 1g/
10min, density are about 0.918g/cm3。
How to obtain it is a kind of be not only with the high grade of transparency but also with the heat shrink films of high intensity current research emphasis.
The content of the invention
The present invention provides a kind of heat shrink films, which has both transparency and intensity.
A kind of heat shrink films are made of internal layer, interlayer and outer layer, by weight percentage, internal layer and outer layer by with
It is lower into being grouped into：50~70% metallocene linear low density polyethylene (hereinafter referred to as mLLDPE), 10~15% line style are low
Density polyethylene (hereinafter referred to as LLDPE), 10~15% ultra-high molecular weight polyethylene (hereinafter referred to as UHMWPE), 5~10%
Ethylene-propylene copolymer, 5~10% ethylene-alpha-olefin copolymer；
The metallocene linear low density polyethylene, the melt index of linear low density polyethylene (LLDPE) are respectively less than and are equal to 0.6g/
10min, the metallocene linear low density polyethylene, linear low density polyethylene (LLDPE), the density of ultra-high molecular weight polyethylene are big
In equal to 0.930g/cm3；In the ethylene-propylene copolymer, the molar content of ethylene-propylene elastomeric is 50~70%,
The molar content of middle ethylene copolymer unit is 20~30%；
The ethylene-alpha-olefin copolymer is the copolymer of ethylene and the alhpa olefin containing 4~8 carbon atoms；And ethylene-α alkene
The melt index of hydrocarbon copolymer, which is respectively less than, is equal to 0.5g/10min, and density is all higher than being equal to 0.920g/cm3, molecular weight distribution is
4.5~7.2.
The present invention creatively prepares outer layer and internal layer using the mLLDPE and LLDPE that melt index is low, density is big so that
Heat shrink films have not only possessed larger tensile strength, also have both good transparency and index of refraction.It is meanwhile of the invention by density
More than or equal to 0.930g/cm3UHMWPE and mLLDPE and LLDPE be combined, three's synergistic effect can further improve hot receipts
The tensile strength and toughness of contracting film.
Also contain ethylene-propylene copolymer in the heat shrink films of the present invention, ethylene-propylene copolymer is the elasticity of indefinite form
Body, therefore there is excellent transparency and toughness, the dosage of LLDPE can not only be reduced by being properly added ethylene-propylene copolymer,
Reduce the production cost of heat shrink films；And the toughness and transparency of heat shrink films are greatly improved, even if subzero 40
Will not occur embrittlement phenomena at DEG C.
Also contain ethylene-alpha-olefin copolymer in the heat shrink films of the present invention, the addition of ethylene-alpha-olefin copolymer can carry
The intensity (such as tearing toughness and impact strength) of high heat shrink films extends the service life of heat shrink films.
Preferably, in the ethylene-propylene copolymer, the molar content of ethylene-propylene elastomeric is 50~70%,
The molar content of middle ethylene copolymer unit is 20~30%.If the molar content of ethylene-propylene elastomeric is excessively high, heat shrink films
Intensity declines；If the molar content of ethylene-propylene elastomeric is too low, the transparency and toughness of heat shrink films are inadequate.Wherein, if
The molar content of ethylene copolymer unit is excessively high, and the glossiness of heat shrink films declines, and index of refraction is low；If mole of ethylene copolymer unit
Content is too low, then ethylene-propylene copolymer and the blending of other components are deteriorated, and the homogeneity for causing heat shrink films is poor, intensity
Decline.
Preferably, the ethylene-alpha-olefin copolymer is the copolymer of ethylene and the alhpa olefin containing 4~8 carbon atoms.
As further preferred, the ethylene-alpha-olefin copolymer is the copolymer of ethylene and hexene or ethylene and octene
Copolymer.During using the ethylene-alpha-olefin copolymer of hexene or octene and vinyl polymerization, the not only tearing toughness of heat shrink films
It can further be promoted with impact strength, and since hexene or octene resin have longer side chain, it can be corresponding
Improve the toughness of heat shrink films in ground.
As further preferred, the melt index of the ethylene-alpha-olefin copolymer, which is respectively less than, is equal to 0.5g/10min, institute
The density for stating ethylene-alpha-olefin copolymer is all higher than being equal to 0.920g/cm3, molecular weight distribution is 4.5~7.2.
Preferably, by weight percentage, the interlayer includes following component：30~40% low density polyethylene
Alkene, 20~35% high density polyethylene (HDPE), 10~20% linear low density polyethylene (LLDPE), 10~20% metallocene linear are low close
Spend polyethylene；
The melt index of the low density polyethylene (LDPE) is less than or equal to 0.3g/10min, the linear low density polyethylene (LLDPE) and cyclopentadienyl
The melt index of wire-form low density polyethylene (LDPE), which is respectively less than, is equal to 0.6g/10min, the metallocene linear low density polyethylene
It is all higher than being equal to 0.930g/cm with the density of linear low density polyethylene (LLDPE)3。
The present invention adds in suitable mLLDPE on the basis of conventional interlayer formula and helps to improve the anti-of heat shrink films
Tensile strength.
As further preferred, by weight percentage, the interlayer consists of the following compositions：30~40% it is low close
Spend polyethylene, 20~30% high density polyethylene (HDPE), 10~20% metallocene linear low density polyethylene, 10~15% line
Type low density polyethylene (LDPE), 10~15% ultra-high molecular weight polyethylene；
The melt index of the low density polyethylene (LDPE) is less than or equal to 0.3g/10min, the linear low density polyethylene (LLDPE) and cyclopentadienyl
The melt index of wire-form low density polyethylene (LDPE), which is respectively less than, is equal to 0.6g/10min, the poly- second of metallocene linear low density
The density of alkene, linear low density polyethylene (LLDPE) and ultra-high molecular weight polyethylene is all higher than being equal to 0.930g/cm3。
After further adding suitable UHMWPE in the intermediate layer, UHMWPE cooperates with combination with mLLDPE, can be further
Improve the tensile strength and toughness of heat shrink films.
Most preferably, heat shrink films of the invention are made of internal layer, interlayer and outer layer, wherein, by weight percentage,
The internal layer and outer layer consist of the following compositions：65% metallocene linear low density polyethylene, 12% linear, low density
Polyethylene, 11% ultra-high molecular weight polyethylene, 6% ethylene-propylene copolymer, 6% ethylene-alpha-olefin copolymer；
The interlayer consists of the following compositions：37% low density polyethylene (LDPE), 26% high density polyethylene (HDPE), 14%
Metallocene linear low density polyethylene, 13% linear low density polyethylene (LLDPE), 10% ultra-high molecular weight polyethylene；
The melt index of the low density polyethylene (LDPE) is less than or equal to 0.3g/10min, the linear low density polyethylene (LLDPE) and cyclopentadienyl
The melt index of wire-form low density polyethylene (LDPE), which is respectively less than, is equal to 0.6g/10min, the poly- second of metallocene linear low density
Alkene, linear low density polyethylene (LLDPE) and ultra-high molecular weight polyethylene are all higher than being equal to 0.930g/cm3。
Under the formula, for the mist degree of heat shrink films of the present invention up to being 7~9%, tensile strength can up to 32N, index of refraction
Up to 96%, heat sealing strength is up to 42N.
If no special instruction is made, in the present invention, the melt index lower limit of LDPE, mLLDPE and LLDPE refer in this field
The minimum melt index values for LDPE, mLLDPE and the LLDPE that can accomplish；The upper density limit of mLLDPE, LLDPE and UHMWPE refer to
The maximum density values of mLLDPE, LLDPE and the UHMWPE that can accomplish in this field.
Based on the excellent intensity of the heat shrink films, transparency and index of refraction, the present invention also provides received using the heat
Packaging material made of contracting film.
Compared with prior art, beneficial effects of the present invention are：
(1) present invention creatively prepares outer layer and internal layer using the mLLDPE and LLDPE that melt index is low, density is big,
So that heat shrink films have not only possessed larger tensile strength, good transparency and index of refraction are also had both.Meanwhile the present invention will
Density is more than or equal to 0.930g/cm3UHMWPE and mLLDPE and LLDPE be combined, three's synergistic effect can further improve
The tensile strength and toughness of heat shrink films；
(2) ethylene-propylene copolymer is also contained in heat shrink films of the invention, ethylene-propylene copolymer is indefinite form
Elastomer, therefore with excellent transparency and toughness, being properly added ethylene-propylene copolymer can not only reduce LLDPE's
Dosage reduces the production cost of heat shrink films；And the toughness and transparency of heat shrink films are greatly improved, even if zero
Embrittlement phenomena will not occur at lower 40 DEG C；
(3) ethylene-alpha-olefin copolymer, the addition energy of ethylene-alpha-olefin copolymer are also contained in heat shrink films of the invention
Thermal contraction film strength (such as tearing toughness and impact strength) is enough improved, extends the service life of heat shrink films；
(4) in heat shrink films of the invention without using auxiliary agent, ingredient is simple.
Specific embodiment
Specific embodiment is set forth below to be described in further detail technical scheme.
Embodiment 1
A kind of heat shrink films of the present embodiment, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：65% mLLDPE, 12% LLDPE, 11% UHMWPE, 6% ethylene-propylene are total to
Polymers, 6% ethylene-hexene co-polymers；
Interlayer consists of the following compositions：37% LDPE, 26% HDPE, 14% mLLDPE, 13% LLDPE,
10% UHMWPE；
Wherein, the melt index 0.2g/10min of mLLDPE, density 0.942g/cm3；
The melt index of LLDPE is 0.5g/10min, density 0.930g/cm3；
The density of UHMWPE is 0.935g/cm3；
The melt index of LDPE is 0.3g/10min；
The molar content of ethylene-propylene elastomeric is 60% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 25%, and the molar content of copolymerized units of propylene is 35%；
The melt index of ethylene-hexene co-polymers is 0.4g/10min, density 0.920g/cm3, molecular weight distribution is
6.6。
The preparation method of the heat shrink films is：
(1) internal layer, outer layer and the raw material in interlayer are weighed respectively by default weight percent；
(2) after each mixing internal layer, outer layer and the raw material in interlayer, it is respectively put into plastics processing mill, is heated at 170 DEG C
15min, the hot material being plasticized；
(3) hot material for being plasticized three layers is squeezed out on three single screw extrusion machines, squeezed by triple extrusion die head respectively
Go out into pipe, co-extrusion die head temperature is 205 DEG C, is molded by blow extrusion, overtemperature is automatically air-cooled, obtains heat shrink films.
Embodiment 2
A kind of heat shrink films of the present embodiment, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：50% mLLDPE, 15% LLDPE, 15% UHMWPE, 10% ethylene-propylene
Copolymer, 10% ethylene-octene hydrocarbon copolymer；
Interlayer consists of the following compositions：40% LDPE, 20% HDPE, 10% mLLDPE, 15% LLDPE,
15% UHMWPE；
Wherein, the melt index 0.6g/10min of mLLDPE, density 0.932g/cm3；
The melt index of LLDPE is 0.2g/10min, density 0.953g/cm3；
The density of UHMWPE is 0.947g/cm3；
The melt index of LDPE is 0.2g/10min；
The molar content of ethylene-propylene elastomeric is 70% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 30%, and the molar content of copolymerized units of propylene is 40%；
The melt index of ethylene-octene copolymer is 0.3g/10min, density 0.938g/cm3, molecular weight distribution is
4.5。
The preparation method of the heat shrink films is the same as embodiment 1.
Embodiment 3
A kind of heat shrink films of the present embodiment, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：70% mLLDPE, 10% LLDPE, 10% UHMWPE, 5% ethylene-propylene are total to
Polymers, 5% Ethylene/Butylene hydrocarbon copolymer；
Interlayer consists of the following compositions：30% LDPE, 30% HDPE, 20% mLLDPE, 10% LLDPE,
10% UHMWPE；
Wherein, the melt index 0.4g/10min of mLLDPE, density 0.964g/cm3；
The melt index of LLDPE is 0.4g/10min, density 0.935g/cm3；
The density of UHMWPE is 0.954g/cm3；
The melt index of LDPE is 0.1g/10min；
The molar content of ethylene-propylene elastomeric is 50% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 20%, and the molar content of copolymerized units of propylene is 30%；
The melt index of ethylene-butene copolymer is 0.5g/10min, density 0.961g/cm3, molecular weight distribution is
7.2。
The preparation method of the heat shrink films is the same as embodiment 1.
Embodiment 4
A kind of heat shrink films of the present embodiment, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：70% mLLDPE, 10% LLDPE, 10% UHMWPE, 5% ethylene-propylene are total to
Polymers, 5% ethylene-pentene hydrocarbon copolymer；
Interlayer consists of the following compositions：30% LDPE, 35% HDPE, 20% mLLDPE, 15% LLDPE；
Wherein, the melt index 0.2g/10min of mLLDPE, density 0.930g/cm3；
The melt index of LLDPE is 0.6g/10min, density 0.946g/cm3；
The density of UHMWPE is 0.961g/cm3；
The melt index of LDPE is 0.3g/10min；
The molar content of ethylene-propylene elastomeric is 58% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 20%, and the molar content of copolymerized units of propylene is 38%；
The melt index of ethylene-pentene copolymers is 0.2g/10min, density 0.941g/cm3, molecular weight distribution is
5.7。
The preparation method of the heat shrink films is the same as embodiment 1.
Comparative example 1
A kind of heat shrink films of this comparative example, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：69% mLLDPE, 15% LLDPE, 8% ethylene-propylene copolymer, 8% second
Alkene-hexene copolymer；
Interlayer consists of the following compositions：37% LDPE, 26% HDPE, 14% mLLDPE, 13% LLDPE,
10% UHMWPE；
Wherein, the melt index 0.2g/10min of mLLDPE, density 0.942g/cm3；
The melt index of LLDPE is 0.5g/10min, density 0.930g/cm3；
The melt index of LDPE is 0.3g/10min；
The molar content of ethylene-propylene elastomeric is 60% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 25%, and the molar content of copolymerized units of propylene is 35%；
The melt index of ethylene-hexene co-polymers is 0.4g/10min, density 0.920g/cm3, molecular weight distribution is
6.6。
The preparation method of the heat shrink films is the same as embodiment 1.
Comparative example 2
A kind of heat shrink films of this comparative example, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：65% mLLDPE, 15% LLDPE, 10% UHMWPE, 10% polyethylene-hexene
Copolymer；
Interlayer consists of the following compositions：37% LDPE, 26% HDPE, 14% mLLDPE, 13% LLDPE,
10% UHMWPE；
Wherein, the melt index 0.2g/10min of mLLDPE, density 0.942g/cm3；
The melt index of LLDPE is 0.5g/10min, density 0.930g/cm3；
The density of UHMWPE is 0.935g/cm3；
The melt index of LDPE is 0.3g/10min；
The melt index of ethylene-hexene co-polymers is 0.4g/10min, density 0.920g/cm3, molecular weight distribution is
6.6。
The preparation method of the heat shrink films is the same as embodiment 1.
Comparative example 3
A kind of heat shrink films of this comparative example, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：65% mLLDPE, 15% LLDPE, 10% UHMWPE, 10% ethylene-propylene
Copolymer；
Interlayer consists of the following compositions：37% LDPE, 26% HDPE, 14% mLLDPE, 13% LLDPE,
10% UHMWPE；
Wherein, the melt index 0.2g/10min of mLLDPE, density 0.942g/cm3；
The melt index of LLDPE is 0.5g/10min, density 0.930g/cm3；
The density of UHMWPE is 0.935g/cm3；
The melt index of LDPE is 0.3g/10min；
The molar content of ethylene-propylene elastomeric is 60% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 25%, and the molar content of copolymerized units of propylene is 35%.
The preparation method of the heat shrink films is the same as embodiment 1.
Comparative example 4
A kind of heat shrink films of this comparative example, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：65% mLLDPE, 12% LLDPE, 11% UHMWPE, 6% ethylene-propylene are total to
Polymers, 6% ethylene-hexene co-polymers；
Interlayer consists of the following compositions：37% LDPE, 26% HDPE, 14% mLLDPE, 13% LLDPE,
10% UHMWPE；
Wherein, the melt index 0.2g/10min of mLLDPE, density 0.942g/cm3；
The melt index of LLDPE is 0.5g/10min, density 0.930g/cm3；
The density of UHMWPE is 0.935g/cm3；
The melt index of LDPE is 0.3g/10min；
The molar content of ethylene-propylene elastomeric is 40% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 15%, and the molar content of copolymerized units of propylene is 25%；
The melt index of ethylene-hexene co-polymers is 0.4g/10min, density 0.920g/cm3, molecular weight distribution is
6.6。
Comparative example 5
A kind of heat shrink films of this comparative example, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：65% mLLDPE, 12% LLDPE, 11% UHMWPE, 6% ethylene-propylene are total to
Polymers, 6% ethylene-hexene co-polymers；
Interlayer consists of the following compositions：37% LDPE, 26% HDPE, 14% mLLDPE, 13% LLDPE,
10% UHMWPE；
Wherein, the melt index 0.2g/10min of mLLDPE, density 0.942g/cm3；
The melt index of LLDPE is 0.5g/10min, density 0.930g/cm3；
The density of UHMWPE is 0.935g/cm3；
The melt index of LDPE is 0.3g/10min；
The molar content of ethylene-propylene elastomeric is 80% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 35%, and the molar content of copolymerized units of propylene is 45%；
The melt index of ethylene-hexene co-polymers is 0.4g/10min, density 0.920g/cm3, molecular weight distribution is
6.6。
Comparative example 6
A kind of heat shrink films of this comparative example, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：65% mLLDPE, 12% LLDPE, 11% UHMWPE, 6% ethylene-propylene are total to
Polymers, 6% ethylene-hexene co-polymers；
Interlayer consists of the following compositions：37% LDPE, 26% HDPE, 14% mLLDPE, 13% LLDPE,
10% UHMWPE；
Wherein, the melt index 0.2g/10min of mLLDPE, density 0.942g/cm3；
The melt index of LLDPE is 0.5g/10min, density 0.930g/cm3；
The density of UHMWPE is 0.935g/cm3；
The melt index of LDPE is 0.3g/10min；
The molar content of ethylene-propylene elastomeric is 60% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 25%, and the molar content of copolymerized units of propylene is 35%；
The melt index of ethylene-hexene co-polymers is 0.6g/10min, density 0.910g/cm3, molecular weight distribution 4.
Comparative example 7
A kind of heat shrink films of this comparative example, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：65% mLLDPE, 12% LLDPE, 11% UHMWPE, 6% ethylene-propylene are total to
Polymers, 6% ethylene-hexene co-polymers；
Interlayer consists of the following compositions：37% LDPE, 26% HDPE, 14% mLLDPE, 13% LLDPE,
10% UHMWPE；
Wherein, the melt index 0.2g/10min of mLLDPE, density 0.942g/cm3；
The melt index of LLDPE is 0.5g/10min, density 0.930g/cm3；
The density of UHMWPE is 0.935g/cm3；
The melt index of LDPE is 0.3g/10min；
The molar content of ethylene-propylene elastomeric is 60% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 25%, and the molar content of copolymerized units of propylene is 35%；
The melt index of ethylene-hexene co-polymers is 0.7g/10min, density 0.904g/cm3, molecular weight distribution is
7.5。
Comparative example 8
A kind of heat shrink films of this comparative example, are made of internal layer, interlayer and outer layer, wherein, by weight percentage, internal layer
It is consisted of the following compositions with outer layer：65% mLLDPE, 12% LLDPE, 11% UHMWPE, 6% ethylene-propylene are total to
Polymers, 6% ethylene-hexene co-polymers；
Interlayer consists of the following compositions：37% LDPE, 26% HDPE, 14% mLLDPE, 13% LLDPE,
10% UHMWPE；
Wherein, the melt index 0.8g/10min of mLLDPE, density 0.924g/cm3；
The melt index of LLDPE is 1.0g/10min, density 0.918g/cm3；
The density of UHMWPE is 0.935g/cm3；
The melt index of LDPE is 0.5g/10min；
The molar content of ethylene-propylene elastomeric is 60% in ethylene-propylene copolymer, wherein, ethylene copolymer unit
Molar content is 25%, and the molar content of copolymerized units of propylene is 35%；
The melt index of ethylene-hexene co-polymers is 0.6g/10min, density 0.910g/cm3, molecular weight distribution 4.
Detect example
Examples 1 to 4, the physical property of each heat shrink films made from comparative example 1~8 are investigated respectively, and investigation the results are shown in Table
1。
The physical property of 1~8 each heat shrink films of 1 Examples 1 to 4 of table and comparative example
By table 1 as it can be seen that when internal layer and outer layer missing UHMWPE (comparative example 1), missing ethylene-propylene copolymer (comparative example
2) when, increase (i.e. transparency declines), tensile strength and percent thermal shrinkage of the mist degrees of heat shrink films is declined；Work as internal layer
When lacking ethylene-alpha-olefin copolymer (comparative example 3) with outer layer, the tensile strength of heat shrink films declines；When second in internal layer and outer layer
During molar content too low (comparative example 4) of alkene-propylene copolymer, the mist degree of heat shrink films improves, and percent thermal shrinkage declines；Work as internal layer
When (comparative example 5) excessively high with the molar content of ethylene-propylene copolymer in outer layer, the tensile strength of heat shrink films declines；When interior
Melt index, density and the molecular weight distribution of ethylene-alpha-olefin copolymer are not suitable for (comparative example 6 and comparative example 7) in layer and outer layer
When, the tensile strength and percent thermal shrinkage of heat shrink films decline；When the melt index mistake of mLLDPE and LLDPE in internal layer and outer layer
It is high, density is too low, during melt index excessively high (comparative example 8) of LDPE, the mist degree of heat shrink films greatly improves；When in the intermediate layer
After lacking UHMWPE (embodiment 4), the tensile strength and percent thermal shrinkage of heat shrink films are declined.
Claims (6)
1. a kind of heat shrink films are made of internal layer, interlayer and outer layer, which is characterized in that by weight percentage, the internal layer
It is consisted of the following compositions with outer layer：50~70% metallocene linear low density polyethylene, 10~15% linear, low density
Polyethylene, 10~15% ultra-high molecular weight polyethylene, 5~10% ethylene-propylene copolymer, 5~10% ethylene-α alkene
Hydrocarbon copolymer；
The metallocene linear low density polyethylene, the melt index of linear low density polyethylene (LLDPE) are respectively less than and are equal to 0.6g/
10min, the metallocene linear low density polyethylene, linear low density polyethylene (LLDPE), the density of ultra-high molecular weight polyethylene are big
In equal to 0.930g/cm3；
In the ethylene-propylene copolymer, the molar content of ethylene-propylene elastomeric is 50~70%, wherein ethylene copolymer list
The molar content of member is 20~30%；
The ethylene-alpha-olefin copolymer is the copolymer of ethylene and the alhpa olefin containing 4~8 carbon atoms；And ethylene-alpha-olefin is total to
The melt index of polymers, which is respectively less than, is equal to 0.5g/10min, and density is all higher than being equal to 0.920g/cm3, molecular weight distribution for 4.5~
7.2。
2. heat shrink films as described in claim 1, which is characterized in that the ethylene-alpha-olefin copolymer is ethylene and hexene
The copolymer of copolymer or ethylene and octene.
3. heat shrink films as claimed in claim 1 or 2, which is characterized in that by weight percentage, the interlayer include with
Lower ingredient：30~40% low density polyethylene (LDPE), 20~35% high density polyethylene (HDPE), 10~15% poly- second of linear, low density
Alkene, 10~20% metallocene linear low density polyethylene；
The melt index of the low density polyethylene (LDPE) is less than or equal to 0.3g/10min, the linear low density polyethylene (LLDPE) and metallocene
The melt index of linear low density polyethylene (LLDPE), which is respectively less than, is equal to 0.6g/10min, the metallocene linear low density polyethylene and line
Type low density polyethylene (LDPE) is all higher than being equal to 0.930g/cm3。
4. heat shrink films as claimed in claim 3, which is characterized in that by weight percentage, the interlayer by below into
It is grouped into：30~40% low density polyethylene (LDPE), 20~30% high density polyethylene (HDPE), 10~20% metallocene linear are low close
Spend polyethylene, 10~15% linear low density polyethylene (LLDPE), 10~15% ultra-high molecular weight polyethylene；
The melt index of the low density polyethylene (LDPE) is less than or equal to 0.3g/10min, the linear low density polyethylene (LLDPE) and metallocene
The melt index of linear low density polyethylene (LLDPE), which is respectively less than, is equal to 0.6g/10min, the metallocene linear low density polyethylene, line
The density of type low density polyethylene (LDPE) and ultra-high molecular weight polyethylene is all higher than being equal to 0.930g/cm3。
5. heat shrink films as claimed in claim 1 or 2, which is characterized in that by weight percentage, the internal layer and outer layer are equal
It consists of the following compositions：65% metallocene linear low density polyethylene, 12% linear low density polyethylene (LLDPE), 11% superelevation
Molecular weight polyethylene, 6% ethylene-propylene copolymer, 6% ethylene-alpha-olefin copolymer；
The interlayer consists of the following compositions：37% low density polyethylene (LDPE), 26% high density polyethylene (HDPE), 14% cyclopentadienyl gold
Belong to linear low density polyethylene (LLDPE), 13% linear low density polyethylene (LLDPE), 10% ultra-high molecular weight polyethylene；
The melt index of the low density polyethylene (LDPE) is less than or equal to 0.3g/10min, the linear low density polyethylene (LLDPE) and metallocene
The melt index of linear low density polyethylene (LLDPE), which is respectively less than, is equal to 0.6g/10min, the metallocene linear low density polyethylene, line
The density of type low density polyethylene (LDPE) and ultra-high molecular weight polyethylene is all higher than being equal to 0.930g/cm3。
6. utilize packaging material made of heat shrink films as claimed in claim 1 or 2.
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| CN107443847A (en) * | 2017-09-14 | 2017-12-08 | 安徽蓝韵包装有限公司 | Food packaging no white casse is without floating object polyethylene film and preparation method thereof |
| TWI755577B (en) * | 2017-12-26 | 2022-02-21 | 日商迪愛生股份有限公司 | Laminated films and food packaging bags |
| CN110181911A (en) * | 2019-06-27 | 2019-08-30 | 常州工程职业技术学院 | A kind of multi-layer co-extruded polyethylene torsion film of simple tension |
| CN117246018B (en) * | 2023-10-25 | 2024-04-12 | 沧州市鑫峰塑料有限公司 | PE heat-shrinkable film and preparation method thereof |
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| JPH08323939A (en) * | 1995-06-01 | 1996-12-10 | Toyobo Co Ltd | Heat-sealable laminate film for paper container, and laminate product and container using the same |
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| CN1198706A (en) * | 1995-10-06 | 1998-11-11 | 陶氏化学公司 | Novel pouches for packaging flowable materials |
| CN102126323A (en) * | 2011-01-17 | 2011-07-20 | 吴卓彬 | Multilayer thermal shrinkage film |
| CN102431258A (en) * | 2011-09-01 | 2012-05-02 | 广州市得力仕食品包装有限公司 | Multilayer heat shrinkage film |
| CN105733066A (en) * | 2014-12-08 | 2016-07-06 | 中国石油天然气股份有限公司 | Special-purposed material used for preparing heat shrink film, and preparation method thereof |
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