CN108516212A - A kind of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films and preparation method thereof - Google Patents
A kind of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films and preparation method thereof Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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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
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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
- 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
- B32B2307/306—Resistant to heat
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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
- B32B2307/31—Heat sealable
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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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
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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
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
- B32B2307/736—Shrinkable
-
- 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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
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- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The present invention relates to a kind of multi-layer co-extruded low temperature polyolefin to be crosslinked heat shrink films and preparation method thereof, and the heat shrink films are made of the film of outer layer, middle layer and the three-layer co-extruded bonding of internal layer, and the heat shrink films thickness is 10~40 μm, the thickness of the outer layer：The thickness of middle layer：The thickness ratio of internal layer is 1：3~10：1；Raw material is stretched through extrusion molding, crosslinking with radiation, cooling, bi-directional synchronization, vane is cooling, is prepared after post-processing.Product of the present invention not only has the feature of crosslinked products, keep excellent seal performance and low-temperature shrink performance simultaneously, with properties such as the distinctive paracentesis resistance of cross linking membrane, high temperature resistant, rub resistance, anti-loosenings, and keep heat-sealing character and spatial stability, it can be used in the application of hot environment stretched film and shrink film, there is low shrinkage temperature simultaneously, the packaging demand of temperature sensitive packing material can be met.
Description
Technical field
The present invention relates to a kind of heat shrinkable package films, are received more particularly, to a kind of multi-layer co-extruded low temperature polyolefin crosslinking heat
Contracting film and preparation method thereof.
Background technology
With the continuous development of economy and society, environmental protection becomes modern humans' focus of attention with resource problem.Traditional
Wooden package, glass packaging, papery packaging, mental package and fabrics packaging are since it is not recyclable, it is biodegradable not have
Property, waste non-renewable resources, non-anti-extrusion, intolerant to moisture-proof damp proof, the pollution reasons such as environment be gradually eliminated and substituted.
And currently, being heat shrinkable package film (POF) film obtained by raw material is produced through compound extruded, stretch processes using polyolefin
With its light weight, good appearance, environmental protection and energy saving, conducive to packed and transported, it is easy to use the advantages that become gradually replace conventional wooden,
The novel environment friendly packaging material of the packaging materials such as papery, metal, glass, can be widely used in food, drug, daily necessities, style
The outer packings of the extensive stocks such as articles for use, electronic apparatus produces, it can be achieved that the skin packaging of commodity and visual transparent wrapper demand
Simple with technology of the package, at low cost, easy to use, safety and sanitation, production efficiency are high, are more suitable for commodity to bandwagon effect and environmental protection
Energy saving, industrialized production requirement.
Multi-layer co-extruded shrink film is a kind of novel two-way drawing of high shrinkage developed on the basis of POF shrink films in recent years
Stretch shrink film.It is to radiate multi-layer co-extruded shrink film by high-voltage electricity beamlet, makes to crosslink between molecule, by linear chain
Thaumatropy is reticular structure, to make the physical mechanical property of product change.Matched by different in cross linking membrane production
Side's design and degree of cross linking control, can be made the product of different performance requirement, be adapted to different packaging facilities and product packaging.
Major defect is：
Existing market POF films, with linear low density polyethylene (LLDPE) for middle layer, copolymer polypropylene (PP) is interior
Outer layer compound extruded, the heat shrinkable package film (POF films) of biaxial tension co-extrusion technology production is in food, drug, day
The fields such as articles for use are widely applied.POF films are due to excellent performances such as the high grade of transparency, high shrinkages, in flexible package
Field receives favor.But conventional POF films usually require to shrink completely at 110 DEG C or more, many product demand low temperature
Packaging, the starting heat shrink temperature of packing film is excessively high, cannot meet its demand, easily leads to packed article deformation, rotten, mistake
The generation of phenomena such as effect, aging.And higher package temperature has an impact the quality of packing article, such as many cosmetics, food
Product, electronic product and pharmaceuticals industry, all to the heat shrink temperature of packing material, more stringent requirements are proposed, therefore it is not suitable for pair
The packaging of temperature sensitive product, limits its scope of application.
Meanwhile common heat-shrinkable film due to thickness it is thicker, intensity and mechanical performance are to be improved, and its frictional force
By force, easily mill is spent, is easily punctured, non-refractory, significantly limits its application in actual production.And pass through crosslinking radiation
Being crosslinked heat shrink films has the advantages such as good excellent mechanical strength, puncture resistance, corrugationless, resistance to relaxation, high-temperature behavior be good.
Chinese patent CN103358560A discloses a kind of producer of multi-layer co-extruded low-temperature shrink Polyolefin Heat Shrinkable Film
Method.With 96~98 parts by weight co-polypropylenes and 2~4 parts by weight bonding-prevention master batchs for upper layer, 95~97 parts by weight of ethylene-pungent
Alkene copolymer, the smooth masterbatch of 2~3.5 parts by weight and 1~1.5 parts by weight antistatic master batch are sandwich layer, respectively through three single screw rods
After extruder squeezes out, pipe is extruded by triple extrusion die head, pipe cooling rear haulage enters drawing oven and carries out several times
Different-thickness oriented film is made in horizontal and vertical stretch, and the method that oriented film takes vane to force rolling after cooling cutting is given birth to
It produces.The invention is formed using specific raw material and production technology, products obtained therefrom can obtain 11~39% at 80~100 DEG C
Percent thermal shrinkage, disclosure satisfy that low temperature be heat-shrinked packing instructions.Although it has preferable shrinking percentage, its mechanical performance phase
It is smaller than the improvement of common heat shrink films, extra package requirement cannot be met.
Chinese patent CN102149768A discloses a kind of crosslinked polymer film, steady with significant heat resistance and space
Qualitative and heat-sealing character, but its film thickness is excessively high.
Invention content
In order to overcome the shortcomings of the prior art, the present invention provides a kind of multi-layer co-extruded with low-temperature shrink effect
Low temperature polyolefin is crosslinked heat shrink films and preparation method thereof, and the heat shrink films produced may be implemented in 80 DEG C~100 DEG C conditions
It is lower to obtain 40% or more shrinking percentage, and the product of different crosslinking degrees can be obtained by the crosslinked approach of electron radiation, meet
While excellent mechanical performance, resistance to play, rub resistance, high temperature resistant require, meet the low-temperature shrink need of temperature sensitivity packing material
It asks.
A kind of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films, the heat shrink films are by outer layer, middle layer and internal layer three
The film that layer co-extrusion bonds is constituted, and the heat shrink films thickness is 10~40 μm, the thickness of the outer layer：The thickness of middle layer：
The thickness ratio of internal layer is 1：3~10：1.
Preferably, the outer layer is made of the raw material of following weight percentage：10~96% polyethylene, 1~4%
Antiplastering aid, wherein the polyethylene is low density polyethylene (LDPE), linear low density polyethylene, medium density polyethylene, extremely-low density are poly-
One or more kinds of mixtures in ethylene.
The preferred oil of SPC 2426H of low density polyethylene (LDPE), Yanshan Petrochemical 1I2A；The linear low density polyethylene is excellent
It is selected as the FP120 of DOW Chemical 2256,2045, NOVA Chemicals；The medium density polyethylene is preferably DOW Chemical
2036, DOW Chemical 2042G；The ultra-low density polyethylene is preferably DOW Chemical 4023,4404；The antiplastering aid is preferably
Bass spy ABPP905, ABPP906, ABPP909.
Preferably, the middle layer is made of the raw material of following weight percentage：10~96% polyethylene, 1~4%
Slipping agent, wherein the polyethylene is low density polyethylene (LDPE), linear low density polyethylene, one in ultra-low density polyethylene
Kind or two or more mixtures；The slipping agent is one kind in oleamide, calcium stearate, silicone.
The preferred oil of SPC 2426H of low density polyethylene (LDPE), Yanshan Petrochemical 1I2A；The linear low density polyethylene is excellent
It is selected as the FP120 of DOW Chemical 2256,2045, NOVA Chemicals；The ultra-low density polyethylene is preferably DOW Chemical
4023、4404。
Preferably, the internal layer raw material composition is identical as outer layer.
A kind of preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films, includes the following steps：
(1) extrusion molding：The raw material of outer layer, middle layer, internal layer is uniformly mixed by weight percentage respectively, by each
Hopper is sent to the extruder of three-layer co-extruded unit；
(2) crosslinking with radiation：The master slice that previous step is obtained carries out irradiation processing；
(3) cooling：After the female film of crosslinking is formed just periosteum by co-extrusion die head, quenching process is carried out by cooling water；
(4) bi-directional synchronization stretches：After female film passes through stretching furnace, startup preheating furnace, stretching furnace heat it, then open
Beginning froths, and is longitudinally, laterally stretched simultaneously to film progress；
(5) vane cools down：Vacuolar membrane enters the cooling of air cooling area after biaxial tension；
(6) it post-processes：Film bubble after cooling first uses hot 30~80 DEG C of rollers to after point splitting, carrying out cold and hot roller processing, then
Handled using 15~40 DEG C of chilling rollers, then wound, cure after cut doubling packaging and storage.
Preferably, in step (1), the three-layer co-extruded unit is made of single screw extrusion machine, extruder temperature 160~
220 DEG C, die head is heated by Electrothermal ring, is squeezed out using three stackings plus the structure type of co-extrusion, including three sections of temperature control regions
Mold lip gap is 1.4~1.8mm.
Preferably, in step (2), the irradiation electric current that irradiation processing uses irradiates voltage 1MV, electronics for 10~30mA
The harness number of plies is bilayer.
Preferably, in step (3), about 10~20 DEG C of the temperature of cooling water；In step (4), draft temperature be 100~
110 DEG C, during frothing, draw ratio longitudinally, laterally is respectively 5~6,5~6.5.
Preferably, in step (5), air cooling area has three vanes altogether, and the wind for blowing to the vane of film bubble need by
Cooling water cooling, the air quantity of each vane can be adjusted by the air door of wind turbine；Air door wherein by adjusting the first vane
Size adjusts film bubble position.
Preferably, the outer layer is made of the raw material of following weight percentage：10~96% polyethylene, 1~4%
Antiplastering aid, wherein the polyethylene is low density polyethylene (LDPE), linear low density polyethylene, medium density polyethylene, extremely-low density are poly-
One or more kinds of mixtures in ethylene；The middle layer is made of the raw material of following weight percentage：10~
96% polyethylene, 1~4% slipping agent, wherein the polyethylene is low density polyethylene (LDPE), linear low density polyethylene, surpasses
One or more kinds of mixtures in low density polyethylene (LDPE)；The slipping agent is in oleamide, calcium stearate, silicone
One kind；The internal layer raw material composition is identical as outer layer.
Product of the present invention not only has the feature of crosslinked products, while keeping excellent seal performance and low-temperature shrink performance,
With properties such as the distinctive paracentesis resistance of cross linking membrane, high temperature resistant, rub resistance, anti-loosenings, and keep heat-sealing character and spatial stability
Property, it can be used in the application of hot environment stretched film and shrink film, while there is low shrinkage temperature, can meet temperature sensitive
The packaging demand of packing material.
Specific implementation mode
The present invention is further explained in the light of specific embodiments, but invention which is intended to be protected is not limited to
This.
Embodiment 1
A kind of multi-layer co-extruded low temperature polyolefin is crosslinked heat shrink films, the heat-shrinkable film by three-layer co-extruded bonding film
It constitutes, i.e. outer layer, middle layer and internal layer；
The outer layer is by the FP120 of NOVA Chemicals of mass fraction 15%, the DOW Chemical of mass fraction 81%
2036,4% ABPP905 compositions,
The middle layer is made of the oleamide that weight percent is 97% DOW Chemical 2256,3%,
The internal layer is identical as outer layer composition,
Wherein, the thickness of the outer layer：The thickness of middle layer：The ratio between thickness of internal layer is 1：4：1.
A kind of preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films, includes the following steps：
(1) extrusion molding：The raw material of outer layer, middle layer, internal layer is uniformly mixed by weight percentage respectively, by each
Hopper is sent to the extruder of three-layer co-extruded unit；The three-layer co-extruded unit is made of single screw extrusion machine, extruder temperature 180
DEG C, die head is heated, extrusion die using three stackings plus the structure type of co-extrusion, including three sections of temperature control regions by Electrothermal ring
Having die lip gap is：1.5mm；
(2) crosslinking with radiation：The master slice that previous step is obtained carries out irradiation processing, and polymer molecule is tied under effect of irradiation
Structure changes, and C-C keys is made to generate crosslinking；Used irradiation electric current is 10mA, electron-beam voltage 1MV, the wire harnesses number of plies
For bilayer；
(3) cooling：After the female film of crosslinking is formed just periosteum by co-extrusion die head, quenching process is carried out by cooling water, it is cold
But 15 DEG C of the temperature of water；
(4) bi-directional synchronization stretches：After female film passes through stretching furnace, start preheating furnace, stretching furnace heats it, stretching temperature
Degree is 105 DEG C, then starts to froth, and is longitudinally, laterally stretched simultaneously to film progress, draw ratio longitudinally, laterally takes 5.8 respectively
With 6；
(5) vane cools down：Vacuolar membrane enters air cooling area after biaxial tension, altogether three vanes, and blows to the vane of film bubble
Wind need to cool down through supercooled water, the air quantity of each vane can be adjusted by the air door of wind turbine；Wherein by adjusting the
The air door size of one vane can make film bubble be in optimum position；
(6) it post-processes：Vane film bubble after cooling first uses 65 DEG C of hot-rollings to after point splitting, carrying out cold and hot roller processing, then
It is handled using 20 DEG C of chilling rollers, can effectively eliminate film internal stress, prevent contraction, creeping phenomenon that later stage film is likely to occur, then
It is wound, doubling packaging and storage is cut after solidification.
Embodiment 2
A kind of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films, it is total by three layers that the low temperature polyolefin is heat-shrinked cross linking membrane
The film for squeezing bonding is constituted, i.e. outer layer, middle layer and internal layer；
The outer layer is made of the ABPP905 of the Tao Shi 4023,4% of 40% DOW Chemical 2045,56% of mass fraction,
The middle layer by weight percent be 47% DOW Chemical 2256, mass fraction 50% DOW Chemical 4023,
3% oleamide composition,
The internal layer is identical as outer layer composition,
Wherein, the thickness of the outer layer：The thickness of middle layer：The ratio between thickness of internal layer is 1：4：1.
A kind of filming technology of crosslinked at low temperature Polyolefin Heat Shrinkable Film, includes the following steps：
(1) extrusion molding：The raw material of outer layer, middle layer, internal layer is uniformly mixed by weight percentage respectively, by each
Hopper is sent to the extruder of three-layer co-extruded unit；The three-layer co-extruded unit is made of single screw extrusion machine, extruder temperature 200
DEG C, die head is heated, extrusion die using three stackings plus the structure type of co-extrusion, including three sections of temperature control regions by Electrothermal ring
Having die lip gap is：1.5mm；
(2) crosslinking with radiation：The master slice that previous step is obtained carries out irradiation processing, and used irradiation electric current is 15mA,
Voltage 1MV is irradiated, the wire harnesses number of plies is bilayer；
(3) cooling：After the female film of crosslinking is formed just periosteum by co-extrusion die head, quenching process is carried out by cooling water, it is cold
But 10 DEG C of the temperature of water；
(4) bi-directional synchronization stretches：After female film passes through stretching furnace, start preheating furnace, stretching furnace heats it, stretching temperature
Degree is 102 DEG C, then starts to froth, and is longitudinally, laterally stretched simultaneously to film progress, draw ratio longitudinally, laterally takes 5.5 respectively
With 5.8；
(5) vane cools down：Vacuolar membrane enters air cooling area after biaxial tension, altogether three vanes, and blows to the vane of film bubble
Wind need to cool down through supercooled water, the air quantity of each vane can be adjusted by the air door of wind turbine；Wherein by adjusting the
The air door size of one vane can make film bubble be in optimum position；
(6) it post-processes：Vane film bubble after cooling first uses 55 DEG C of hot-rollings to after point splitting, carrying out cold and hot roller processing, then
It is handled using 30 DEG C of chilling rollers, can effectively eliminate film internal stress, prevent contraction, creeping phenomenon that later stage film is likely to occur, then
It is wound, doubling packaging and storage is cut after solidification.
Embodiment 3
A kind of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films, it is total by three layers that the low temperature polyolefin is heat-shrinked cross linking membrane
The film for squeezing bonding is constituted, i.e. outer layer, middle layer and internal layer；
The outer layer by mass fraction 20% Yanshan Petrochemical 1I2A, the 2036 of 20%, 4% ABPP906 form,
The FP120 for the NOVA Chemicals that the middle layer is 15% by weight percent, 82% oil of SPC
2426H, 3% silicone composition,
The internal layer is identical as outer layer composition,
Wherein, the thickness of the outer layer：The thickness of middle layer：The ratio between thickness of internal layer is 1：6：1.
A kind of preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films, includes the following steps：
(1) extrusion molding：Three layers of raw material are uniformly mixed by weight percentage respectively, 210 DEG C of extruder temperature, extrusion die
Having die lip gap is：1.5mm；
(2) crosslinking with radiation：The master slice that previous step is obtained carries out irradiation processing, and used irradiation electric current is 20mA,
Spoke voltage is 1MV, and the wire harnesses number of plies is bilayer；
(3) cooling：After the female film of crosslinking is formed just periosteum by co-extrusion die head, quenching process is carried out by cooling water, it is cold
But 15 DEG C of the temperature of water；
(4) bi-directional synchronization stretches：Draft temperature is 100 DEG C, starts to froth, and longitudinally, laterally stretches, indulges simultaneously to film progress
5.8 and 6 are taken respectively to, lateral draw ratio；
(5) vane cools down：Vacuolar membrane enters air cooling area after biaxial tension, altogether three vanes, and blows to the vane of film bubble
Wind need to cool down through supercooled water, the air quantity of each vane can be adjusted by the air door of wind turbine；Wherein by adjusting the
The air door size of one vane can make film bubble be in optimum position；
(6) it post-processes：Vane film bubble after cooling first uses 45 DEG C of hot-rollings to after point splitting, carrying out cold and hot roller processing, then
It is handled using 25 DEG C of chilling rollers, doubling packaging and storage is cut after solidification.
Embodiment 4
A kind of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films, it is total by three layers that the low temperature polyolefin is heat-shrinked cross linking membrane
The film for squeezing bonding is constituted, i.e. outer layer, middle layer and internal layer；
The outer layer by 67% DOW Chemical 2045,30% of mass fraction DOW Chemical 2042G and 4% ABPP905
Composition,
The middle layer is made of the silicone of the DOW Chemical 4404,3% of weight percent 97%,
The internal layer is identical as outer layer composition,
Wherein, the thickness of the outer layer：The thickness of middle layer：The ratio between thickness of internal layer is 1：9：1.
A kind of preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films, with embodiment 2.
Embodiment 5
A kind of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films, it is total by three layers that the low temperature polyolefin is heat-shrinked cross linking membrane
The film for squeezing bonding is constituted, i.e. outer layer, middle layer and internal layer；
The outer layer is made of the ABPP905 of 96% DOW Chemical 2256,4% of mass fraction,
The middle layer by weight percent 27% 2045,70% DOW Chemical 2426H of DOW Chemical, 3% silicon
Ketone forms,
The internal layer is identical as outer layer composition,
Wherein, the thickness of the outer layer：The thickness of middle layer：The ratio between thickness of internal layer is 1：4：1；
A kind of preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films, with embodiment 2.
Low-temperature shrink performance
It is evaluated according to shrinking percentage at different temperatures, the test method of percent thermal shrinkage is to cut 100mm × 100mm
3 pieces of the sample of (± 0.1mm) respectively draws a graticule in sample vertical, horizontal, and indicates vertical, horizontal.Sample is kept flat into metal
On frame, immerses in the thermostatic medium of set temperature ± 2 DEG C rapidly, taken out after 10s, immerse in spare room temperature water-bath, wait trying
It is taken out after sample cooling, horizontal rest.Then vertical, horizontal graticule size is measured, 0.5mm is accurate to.
It is calculated by formula (1)：
T=100 (L0-L)/L0 (1)
In formula：T-percent thermal shrinkage, %；L0The length of sample graticule before-heating, unit are millimeter (mm)；After L-heating
The length of sample graticule, unit are millimeter (mm).Test result is indicated with the arithmetic mean of instantaneous value of 3 pieces of specimen test results, is retained
One decimal, 100 DEG C primary with 120 DEG C of each tests.
Heat sealing strength is tested
The consistent sample of vertical, horizontal is sealed.Heat seal condition：140 ± 5 DEG C, pressure 0.18Mpa of temperature, time
For 1S, heat-sealing form is to melt disconnected envelope.Using long strip type sample, the wide 15mm ± 0.1mm of sample.
Test provides that progress heat seal strength experiment, tensile speed are 250mm/min ± 50mm/min according to QB/T2358.Knot
Fruit is averaged, unit N, retains a decimal.
Mist degree
It provides to carry out by GB/T2410.
Glossiness
It provides to carry out by GB/T8807.
Tensile strength and elongation at break
It is carried out by the regulation of GB/T1040.3.Using long strip type sample, sample long 150mm, wide 10mm ± 0.1mm, fixture
Spacing is 100mm, and tensile speed is 100mm/min ± 10mm/min.Results are averaged, retains integer.
Tear-resistant intensity
It is carried out by the regulation of GB/T16578.2.Results are averaged, retains a decimal.
Degree of cross linking characterizing method is characterized using melt flow rate (MFR) (MFI), and MFI values are bigger under certain condition, material
Melt flowability it is more excellent, i.e., the degree of cross linking is smaller, MFI test according to ASTM D1238 standards carry out, wherein normal film survey
Examination is tested under load 2.16Kg according to 190 DEG C；The test of cross linking membrane under 230 DEG C, load 10Kg according to being tested.
The following table 1 for the film performance index that is obtained according to the structural parameters of the embodiment of the present invention 1 to 5 with sell on the market
Film performance index comparison.
Table 1
As it can be seen from table 1 the embodiment of the present invention 1 to 5 obtained matt film of embodiment at the same temperature, show ratio
Common heat shrink films have higher percent thermal shrinkage, and can keep excellent heat seal strength and optical property simultaneously, in addition, this hair
The degree of cross linking of the heat shrink films of bright acquisition can be compared according to the MFI values of product.MFI values are bigger, represent the melting stream of product
Dynamic property is poorer, and the degree of cross linking is higher, it is seen then that compared with common heat shrink films, MFI reduces the heat shrink films that the present invention obtains, crosslinking
Degree increases, and by the debugging of irradiation apparatus, can control the variation of the degree of cross linking, to obtain having the Low Temperature Thermal of cross-linking effect to receive
The polyolefin film of contracting excellent effect.
According to heat shrink films made of above-described embodiment and its manufacturing process due to being obtained by electron beam crosslinking
Cross-linking effect has very outstanding shrinking percentage, and seals performance more securely, lasting, shrinkage temperature range is wider, excellent
Adapt to any package packing machine.
This time disclosed embodiment can consider to be to illustrate in all respects, not in any way limiting.The scope of the present invention
Do not illustrated to be limited by the above embodiment, only shown in the range by claims, and includes having with right
There are all deformations in the same meaning and right.
Claims (10)
1. a kind of multi-layer co-extruded low temperature polyolefin is crosslinked heat shrink films, it is characterised in that：The heat shrink films are by outer layer, middle layer
It is constituted with the film of the three-layer co-extruded bonding of internal layer, the heat shrink films thickness is 10~40 μm, the thickness of the outer layer：Middle layer
Thickness：The thickness ratio of internal layer is 1：3~10：1.
2. multi-layer co-extruded low temperature polyolefin according to claim 1 is crosslinked heat shrink films, it is characterised in that：The outer layer by
The raw material of following weight percentage forms：10~96% polyethylene, 1~4% antiplastering aid, wherein the polyethylene is low
It is one or more kinds of in density polyethylene, linear low density polyethylene, medium density polyethylene, ultra-low density polyethylene
Mixture.
3. multi-layer co-extruded low temperature polyolefin according to claim 1 is crosslinked heat shrink films, it is characterised in that：The middle layer
It is made of the raw material of following weight percentage：10~96% polyethylene, 1~4% slipping agent, wherein the polyethylene is
One or more kinds of mixtures in low density polyethylene (LDPE), linear low density polyethylene, ultra-low density polyethylene；It is described
Slipping agent is one kind in oleamide, calcium stearate, silicone.
4. multi-layer co-extruded low temperature polyolefin according to claim 3 is crosslinked heat shrink films, it is characterised in that：The internal layer is former
Material composition is identical as outer layer.
5. the preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films described in a kind of claim 1, it is characterised in that packet
Include following step：
(1) extrusion molding：The raw material of outer layer, middle layer, internal layer is uniformly mixed by weight percentage respectively, passes through each hopper
It is sent to the extruder of three-layer co-extruded unit；
(2) crosslinking with radiation：The master slice that previous step is obtained carries out irradiation processing；
(3) cooling：After the female film of crosslinking is formed just periosteum by co-extrusion die head, quenching process is carried out by cooling water；
(4) bi-directional synchronization stretches：After female film passes through stretching furnace, startup preheating furnace, stretching furnace heat it, then start to blow
Bubble longitudinally, laterally stretches film progress simultaneously；
(5) vane cools down：Vacuolar membrane enters the cooling of air cooling area after biaxial tension；
(6) it post-processes：Film bubble after cooling first uses 30~80 DEG C of hot-rollings, reuses to after point splitting, carrying out cold and hot roller processing
The processing of 15~40 DEG C of chilling rollers, then wound, cure after cut doubling packaging and storage.
6. the preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films according to claim 5, it is characterised in that：Step
Suddenly in (1), the three-layer co-extruded unit is made of single screw extrusion machine, 160~220 DEG C of extruder temperature, and die head uses three layers
It is superimposed the structure type of co-extrusion, including three sections of temperature control regions, is heated by Electrothermal ring, extrusion die die lip gap is 1.4
~1.8mm.
7. the preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films according to claim 5, it is characterised in that：Step
Suddenly in (2), the irradiation electric current that irradiation processing uses irradiates voltage 1MV for 10~30mA, and the wire harnesses number of plies is bilayer.
8. the preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films according to claim 5, it is characterised in that：Step
Suddenly in (3), about 10~20 DEG C of the temperature of cooling water；In step (4), draft temperature is 100~110 DEG C, during frothing, is indulged
It is respectively 5~6,5~6.5 to, lateral draw ratio.
9. the preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films according to claim 5, it is characterised in that：Step
Suddenly in (5), air cooling area has three vanes altogether, and the wind for blowing to the vane of film bubble needs to cool down through supercooled water, each vane
Air quantity can be adjusted by the air door of wind turbine；Wherein by adjusting the air door size of the first vane, film bubble position is adjusted.
10. the preparation method of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films according to claim 5, it is characterised in that：
The outer layer is made of the raw material of following weight percentage：10~96% polyethylene, 1~4% antiplastering aid, wherein described
Polyethylene be low density polyethylene (LDPE), linear low density polyethylene, medium density polyethylene, one kind in ultra-low density polyethylene or
Two or more mixtures；The middle layer is made of the raw material of following weight percentage：10~96% polyethylene, 1~4%
Slipping agent, wherein the polyethylene is low density polyethylene (LDPE), linear low density polyethylene, one in ultra-low density polyethylene
Kind or two or more mixtures；The slipping agent is one kind in oleamide, calcium stearate, silicone；The internal layer is former
Material composition is identical as outer layer.
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Application publication date: 20180911 |