CN110509646A - A kind of high anti-puncture curtain coating polyethylene film and preparation method thereof - Google Patents

A kind of high anti-puncture curtain coating polyethylene film and preparation method thereof Download PDF

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Publication number
CN110509646A
CN110509646A CN201910883462.5A CN201910883462A CN110509646A CN 110509646 A CN110509646 A CN 110509646A CN 201910883462 A CN201910883462 A CN 201910883462A CN 110509646 A CN110509646 A CN 110509646A
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parts
layer
hdpe
agent
metallocene
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CN110509646B (en
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李健
王广
陈渊
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Sichuan Hou Cheng Novel Material Co Ltd
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Sichuan Hou Cheng Novel Material Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/043—HDPE, i.e. high density polyethylene
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/046—LDPE, i.e. low density polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
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  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
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Abstract

The present invention provides a kind of high anti-puncture curtain coating polyethylene films and preparation method thereof, which has five-layer structure, and respectively corona layer, puncture resistant layer a, buffer layer, puncture resistant layer b, hot sealing layer form from outside to inside.Metallocene PE content is higher in puncture resistant layer a/b, can provide good puncture resistance；Buffering hdpe layer can provide good underlying strength, POE can increase the toughness and shock resistance energy of buffer layer, mica powder is a kind of shape filler, in buffer layer " multilayer scale " structure with film in parallel is being formed due to melt flows in extrusion process, interface constraint is generated with polyethylene, it is formed together synergistic effect with puncture resistant layer a/ buffer layer/puncture resistant layer b sandwich structure formed, improves the puncture resistance of film entirety.

Description

A kind of high anti-puncture curtain coating polyethylene film and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, more particularly, to packaging film field, more particularly to a kind of highly resistance Pierce through curtain coating polyethylene film and preparation method thereof.
Background technique
It is generally made of corona layer, sandwich layer and hot sealing layer currently, being packed for curtain coating polyethylene film in the market, corona layer is thin Film surface improves surface polarity by sided corona treatment, to meet requirement of the packaging to printing；Sandwich layer mainly provides intensity, property It can determine the puncture and stiffness of film；Hot sealing layer mainly provides heat seal strength in film internal layer.Pass through multiple extruders The compound die head that the film of each layer different formulations composition is passed through to a multiple flow passages, after simple tension, is compounded in by chilling roller Together, compared with the dry laminating film for using binder and solvent to be bonded together plural layers, have speed of production fast, it is raw Production process is simple, and production environment cleaning, high production efficiency is easy to operate, at low cost, no solvent residue, and no diaminotoluene (causes Cancer substance) residual the advantages that, be particularly suitable for sanitary condition and require the fields such as stringent food, Key works Drug packing.
It is sharppointed article for packing material, such as medical needle device, chicken feet prepared food also require packaging film to have good anti-wear Thorn property causes contamination of products to guarantee that packaging will not be destroyed during production and transport.Currently, the method taken mostly passes through Using the high metallocene PE of puncture resistance according to a certain percentage with other resin alloys, after extrusion again with other function layer It is compound, obtain puncture resistant laminated film.
Application No. is CN201510076827.5 to disclose a kind of packaging film of puncture-resistant, including three-layer composite structure, point For outer membrane layer, middle layer film layer and internal layer membrane layer；The raw material group of outer membrane layer becomes high density polyethylene (HDPE)；Middle layer is thin The raw material group of film layer becomes high density polyethylene (HDPE) and metallocene linear-low density polyethylene；The raw material group of internal layer membrane layer becomes cyclopentadienyl Metal linear low density polyethylene (LDPE), low density polyethylene (LDPE) and polyolefin elastomer.The packaging film of the puncture-resistant and traditional five Golden packaging composite film is compared, and has many advantages, such as that excellent in mechanical performance, film surface coefficient of friction are appropriate, is suitable for any automatic packaging Equipment.
A kind of heavy packaging composite film, including three layers: outer layer are disclosed application No. is CN201110377502.2, sandwich layer, Internal layer composition；Outer layer includes metallocene linear polyethylene and low density polyethylene (LDPE), and sandwich layer includes EVA and low density polyethylene (LDPE), interior Layer includes medium density polyethylene and low density polyethylene (LDPE).Metallocene linear polyethylene in outer layer, in the EVA and internal layer of sandwich layer Density polyethylene, mutually synergistic effect ensure that three layers of compound refitting film while having had both better paracentesis resistance and having stretched strong Degree.
Application No. is CN201410032352.5 to disclose a kind of high-stiffness puncture-resistant PE film, successively include composite layer, Middle layer and hot sealing layer, composite layer include low density polyethylene (LDPE), metallocene linear-low density polyethylene and processing aid；Middle layer Including high density polyethylene (HDPE), metallocene linear-low density polyethylene and processing aid；Hot sealing layer includes low density polyethylene (LDPE), cyclopentadienyl gold Belong to linear low density polyethylene etc., the high-stiffness puncture-resistant low-friction coefficient composite membrane puncture resistance is good, can pack sharp The objects such as bone fishbone, be not susceptible to the case where bag body is punctured.
However, being easy to cause to wear to equipment, and metallocene PE since metallocene PE difficulty of processing is larger Price is higher, also will cause the rising of product cost.
Summary of the invention
Present invention aim to address metallocene dosage in above-mentioned prior art puncture resistant polyethylene film is more, at high cost is asked Topic, providing one kind has high puncturing resistance performance, combines cost, the curtain coating polyethylene film of simple production process and its manufacturer Method.
In order to achieve the above objectives, the technical solution adopted by the present invention are as follows:
A kind of high anti-puncture is cast polyethylene film, and the polyethylene film has five-layer structure, from outside to inside respectively corona Layer, puncture resistant layer a, buffer layer, puncture resistant layer b, hot sealing layer composition, five layers of thickness proportion is (6-8): (3-5): (8-10): (3-5): (4-6),
Wherein, the raw material for preparing of the corona layer is 40-60 parts of low density polyethylene (LDPE) (LDPE) in parts by weight, cyclopentadienyl 30-50 parts of metal polyethylene (mPE), 0.3-0.6 parts of opening agent, 0.3-0.5 parts of slipping agent, 0.1-0.2 parts of antistatic agent；
The raw material for preparing of the puncture resistant layer a is 70-90 parts of metallocene PE (mPE) in parts by weight, highly dense It spends 5-15 parts of polyethylene (HDPE), maleic anhydride is grafted POE 5-15 parts；
The raw material for preparing of the buffer layer is 20-40 parts of high density polyethylene (HDPE) (HDPE), metallocene in parts by weight 10-20 parts of polyethylene (mPE), POE 15-25 parts of maleic anhydride grafting, 25-35 parts of mica powder, 3-5 parts of dispersing agent, coupling agent 1.5-2.5 part；
The raw material for preparing of the puncture resistant layer b is 70-90 parts of metallocene PE (mPE) in parts by weight, highly dense It spends 5-15 parts of polyethylene (HDPE), maleic anhydride is grafted POE 5-15 parts；
The raw material for preparing of the hot sealing layer is 60-80 parts of low density polyethylene (LDPE) (LDPE), metallocene in parts by weight 20-40 parts of polyethylene (mPE), 0.3-0.6 parts of opening agent, 0.3-0.5 parts of slipping agent, 0.1-0.2 parts of antistatic agent.
Preferably, polyethylene film corona layer from outside to inside, puncture resistant layer a, buffer layer, puncture resistant layer b, hot sealing layer Thickness proportion be (7-8): (3-4): (9-10): (3-4): (5-6),
Preferably, the raw material for preparing of the corona layer is 45-55 parts of low density polyethylene (LDPE) (LDPE) in parts by weight, 40-50 parts of metallocene PE (mPE), 0.4-0.5 parts of opening agent, 0.35-0.45 parts of slipping agent, antistatic agent 0.13-0.18 Part；
Preferably, the raw material for preparing of the puncture resistant layer a is metallocene PE (mPE) 75-85 in parts by weight Part, 8-12 parts of high density polyethylene (HDPE) (HDPE), maleic anhydride is grafted POE 8-12 parts；
Preferably, the raw material for preparing of the buffer layer is 25-35 parts of high density polyethylene (HDPE) (HDPE) in parts by weight, 12-18 parts of metallocene PE (mPE), POE 18-22 parts of maleic anhydride grafting, 27-30 parts of mica powder, dispersing agent 3.5-4.5 Part, 1.8-2.2 parts of coupling agent；
Preferably, the raw material for preparing of the puncture resistant layer b is metallocene PE (mPE) 75-85 in parts by weight Part, 8-12 parts of high density polyethylene (HDPE) (HDPE), maleic anhydride is grafted POE 8-12 parts；
Preferably, the raw material for preparing of the hot sealing layer is 65-75 parts of low density polyethylene (LDPE) (LDPE) in parts by weight, 25-35 parts of metallocene PE (mPE), 0.4-0.5 parts of opening agent, 0.35-0.45 parts of slipping agent, antistatic agent 0.13-0.18 Part.
It is further preferred that polyethylene film corona layer from outside to inside, puncture resistant layer a, buffer layer, puncture resistant layer b, The thickness of hot sealing layer is respectively 15 μm, 8 μm, 20 μm, 8 μm, 12 μm；
It is further preferred that the raw material for preparing of the corona layer is low density polyethylene (LDPE) (LDPE) 50 in parts by weight Part, 49 parts of metallocene PE (mPE), 0.45 part of opening agent, 0.4 part of slipping agent, 0.15 part of antistatic agent；
It is further preferred that the raw material for preparing of the puncture resistant layer a is metallocene PE (mPE) in parts by weight 80 parts, 10 parts of high density polyethylene (HDPE) (HDPE), maleic anhydride is grafted 10 parts of POE；
It is further preferred that the raw material for preparing of the buffer layer is high density polyethylene (HDPE) (HDPE) 30 in parts by weight Part, 15 parts of metallocene PE (mPE), maleic anhydride is grafted 20 parts of POE, 29 parts of mica powder, 4 parts of dispersing agent, 2 parts of coupling agent；
It is further preferred that the raw material for preparing of the puncture resistant layer b is metallocene PE (mPE) in parts by weight 80 parts, 10 parts of high density polyethylene (HDPE) (HDPE), maleic anhydride is grafted 10 parts of POE；
It is further preferred that the raw material for preparing of the hot sealing layer is low density polyethylene (LDPE) (LDPE) 70 in parts by weight Part, 29 parts of metallocene PE (mPE), 0.45 part of opening agent, 0.4 part of slipping agent, 0.15 part of antistatic agent.
Preferably, the low density polyethylene (LDPE) (LDPE) is Tao Shi 150E/310E/312E/352E, South Korea LG One or more of combinations of FB0300, Yanshan Petrochemical LD600, Qilu Petrochemical 2102TN26, oil of SPC Q201；
Preferably, the metallocene PE (mPE) is Exxon Mobil 2005/2010/2010CR/2703hh/ 2705hh/3505hH, DOW Chemical 5100G/5110G/5111G/5230F/5220G/5230G/540G/5401G/5500G, three In well chemistry Evolue SP1510/SP1520/SP1540/V2020H/SP2040/SP2320/SP2510/SP2520/ SP3010 One or more of combinations；
Preferably, the high density polyethylene (HDPE) (HDPE) is Exxon Mobil HTA-08, Tao Shi 35060A, Yanshan Petrochemical 5000S, oil of SPC CH2802, one or more of combinations of Yangtze petrochemical industry 5306J；
Preferably, in the POE Mitsui DF840/940/4085S, Exxon Mobil 3980FL, Tao Shi 8150 One or more of combinations；
Preferably, the opening agent is 8000 mesh of preparing spherical SiO 2；
Preferably, the slipping agent is erucyl amide；
Preferably, the electrostatic agent is Armostat1800；
Preferably, the mica powder specification is 8000 mesh；
Preferably, the dispersing agent is polyvinyl alcohol PEG4000；
Preferably, the coupling agent is DOW CORNING Z-6030；
On the other hand, the present invention provides the preparation method of above-mentioned high anti-puncture curtain coating polyethylene film, the preparation sides Method the following steps are included:
(1) by the low density polyethylene (LDPE) of formulation dosage (LDPE), metallocene PE (mPE), opening agent, slipping agent resists Electrostatic agent is added to the mixer mixing, is subsequently placed in double screw extruder extrusion, enters back into mixing in pressurization internal mixer and obtain electricity The dizzy modified film forming material of layer；
(2) by the metallocene PE of formulation dosage (mPE), high density polyethylene (HDPE) (HDPE), maleic anhydride grafting POE adds Enter in mixing machine and mix, is subsequently placed in double screw extruder extrusion, enters back into mixing in pressurization internal mixer and obtain puncture resistant layer a/ Puncture resistant layer b is modified film forming material；
(3) by the high density polyethylene (HDPE) of formulation dosage (HDPE), metallocene PE (mPE), maleic anhydride is grafted POE, Mica powder, dispersing agent, coupling agent are added to the mixer mixing, are subsequently placed in double screw extruder extrusion, enter back into pressurization mixing Mixing obtains the modified film forming material of buffer layer in machine；
(4) by the low density polyethylene (LDPE) of formulation dosage (LDPE), metallocene PE (mPE), opening agent, slipping agent resists Electrostatic agent is added to the mixer mixing, is subsequently placed in double screw extruder extrusion, enters back into mixing in pressurization internal mixer and obtain heat Sealing is modified film forming material；
(5) the modified film forming material of the corona layer respectively obtained in above-mentioned steps (1), (2), (3), (4), puncture resistant layer a are changed Property film forming material, the modified film forming material of buffer layer, the modified film forming material of puncture resistant layer b, the modified film forming material of hot sealing layer five-layer co-squeezing stream is added Prolong in machine progress coextrusion casting stretching, cooling and shaping obtains the high anti-puncture curtain coating polyethylene film after sided corona treatment.
Preferably, in above-mentioned steps (1):
The time mixed in mixing machine is 45min；
The draw ratio of double screw extruder be 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature difference Are as follows: 205 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 220 DEG C, the revolving speed of screw rod are 440r/min；
The time of mixing in mixer is 45min, and the temperature of mixing is 185 DEG C.
Preferably, in above-mentioned steps (2):
The time mixed in mixing machine is 45min；
The draw ratio of double screw extruder be 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature difference Are as follows: 210 DEG C, 225 DEG C, 240 DEG C, 240 DEG C, 225 DEG C, the revolving speed of screw rod are 440r/min；
The time of mixing in mixer is 45min, and the temperature of mixing is 200 DEG C.
Preferably, in above-mentioned steps (3):
The time mixed in mixing machine is 45min；
The draw ratio of double screw extruder be 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature difference Are as follows: 210 DEG C, 220 DEG C, 235 DEG C, 235 DEG C, 220 DEG C, the revolving speed of screw rod are 440r/min；
The time of mixing in mixer is 45min, and the temperature of mixing is 190 DEG C.
Preferably, in above-mentioned steps (4):
The time mixed in mixing machine is 45min；
The draw ratio of double screw extruder be 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature difference Are as follows: 205 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 220 DEG C, the revolving speed of screw rod are 440r/min；
The time of mixing in mixer is 45min, and the temperature of mixing is 185 DEG C.
Preferably, in above-mentioned steps (5):
Co-extruding mould temperature is 240 DEG C, and casting and stretching ratio is 1.1-1.5, and cooling and shaping temperature is 30 DEG C.
Compared with prior art, the present invention has gain effect below:
(1) puncture can be good.Metallocene PE content is higher in puncture resistant layer a/b, can provide good puncture resistant Performance；Buffering hdpe layer can provide good underlying strength, and POE can increase the toughness and shock resistance of buffer layer Can, mica powder is a kind of shape filler, in buffer layer is forming the " multilayer with film in parallel due to melt flows in extrusion process Scale " structure generates interface constraint with polyethylene, and tear failure is along the interface between mica sheet and polyethylene when being impacted It propagates, considerably increases propagation distance, reduce breakdown strength and puncture resistant layer a/ buffer layer/puncture resistant layer b formation Sanming City It controls structure and is formed together synergistic effect, improve the puncture resistance of film entirety.
(2) cost is taken into account.The high density polyethylene (HDPE) (HDPE) and mica powder that part low cost has been used in buffer layer replace The high metallocene PE of cost lattice (mPE) reduces integral material cost while improving puncture energy.
Detailed description of the invention
Fig. 1 is that a kind of high anti-puncture of the present invention is cast polyethylene film schematic diagram；
Wherein, 1-corona layer；2-puncture resistant layer a；3-buffer layers；4-puncture resistant layer b；5-hot sealing layers.
Specific embodiment
Below with reference to specific real mode, present invention is further described in detail, is only to inventive technique in concrete mode The verifying of effect is not exhaustion.
A kind of high anti-puncture of embodiment 1 is cast polyethylene film
As shown in Figure 1, high anti-puncture is cast polyethylene film, including five-layer structure, it is followed successively by corona layer 1 from outside to inside, resists It punctures layer a2, buffer layer 3, puncture resistant layer b4, hot sealing layer 5 to form, each thickness degree and composition are as follows:
Embodiment 1 Corona layer Puncture resistant layer a Buffer layer Puncture resistant layer b Hot sealing layer
Each thickness degree μm 15 8 20 8 12
Each layer component weight ratio
Tao Shi 150E (LDPE) 50 70
Tao Shi 35060A (HDPE) 10 30 10
Tao Shi 5500G (mPE) 49 80 15 80 29
8150 POE of Tao Shi 10 20 10
Opening agent spherical SiO28000 mesh 0.45 0.45
Slipping agent erucyl amide 0.4 0.4
Electrostatic agent is Armostat1800 0.15 0.15
8000 mesh of mica powder 29
Polyvinyl alcohol PEG4000 4
Coupling agent DOW CORNING Z-6030 2
Preparation method the following steps are included:
(1) by the low density polyethylene (LDPE) of formulation dosage (LDPE), metallocene PE (mPE), opening agent, slipping agent resists Electrostatic agent is added to the mixer mixing 45min, is subsequently placed in double screw extruder extrusion, and the draw ratio of double screw extruder is 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature be respectively as follows: 205 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 220 DEG C, the revolving speed of screw rod is 440r/min, enters back into mixing in pressurization internal mixer, and the time of mixing is 45min, the temperature of mixing It is 185 DEG C, obtains the modified film forming material of corona layer.
(2) by the metallocene PE of formulation dosage (mPE), high density polyethylene (HDPE) (HDPE), maleic anhydride grafting POE adds Entering and mix 20min in mixing machine, is subsequently placed in double screw extruder extrusion, the draw ratio of double screw extruder is 44, conveying section, Melt zone, mixing section, exhaust section, homogenizing zone temperature be respectively as follows: 210 DEG C, 225 DEG C, 240 DEG C, 240 DEG C, 225 DEG C, screw rod Revolving speed be 440r/min, enter back into mixing in pressurization internal mixer, the time of the mixing in mixer is 45min, the temperature of mixing Degree is 200 DEG C, obtains the modified film forming material of puncture resistant layer a/ puncture resistant layer b；
(3) by the high density polyethylene (HDPE) of formulation dosage (HDPE), metallocene PE (mPE), maleic anhydride is grafted POE, Mica powder, dispersing agent, coupling agent are added to the mixer mixing 20min, are subsequently placed in double screw extruder extrusion, twin-screw extrusion The draw ratio of machine be 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature be respectively as follows: 210 DEG C, 220 DEG C, 235 DEG C, 235 DEG C, 220 DEG C, the revolving speed of screw rod is 440r/min, enters back into mixing in pressurization internal mixer, and the time of mixing is 45min, the temperature of mixing are 190 DEG C, obtain the modified film forming material of buffer layer；
(4) by the low density polyethylene (LDPE) of formulation dosage (LDPE), metallocene PE (mPE), opening agent, slipping agent resists Electrostatic agent is added to the mixer mixing 45min, is subsequently placed in double screw extruder extrusion, and the draw ratio of double screw extruder is 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature be respectively as follows: 205 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 220 DEG C, the revolving speed of screw rod is 440r/min, enters back into mixing in pressurization internal mixer, and the time of the mixing in mixer is 45min, The temperature of mixing is 185 DEG C, obtains the modified film forming material of hot sealing layer；
(5) the modified film forming material of the corona layer respectively obtained in above-mentioned steps (1), (2), (3), (4), puncture resistant layer a are changed Property film forming material, the modified film forming material of buffer layer, the modified film forming material of puncture resistant layer b, the modified film forming material of hot sealing layer five-layer co-squeezing stream is added Prolong progress coextrusion casting stretching in machine, co-extruding mould temperature is 240 DEG C, and casting and stretching ratio is 1.7, and cooling and shaping temperature is 30 DEG C, the high anti-puncture curtain coating polyethylene film is obtained after sided corona treatment.
A kind of high anti-puncture of embodiment 2 is cast polyethylene film
As shown in Figure 1, high anti-puncture is cast polyethylene film, including five-layer structure, it is followed successively by corona layer 1 from outside to inside, resists It punctures layer a2, buffer layer 3, puncture resistant layer b4, hot sealing layer 5 to form, each thickness degree and composition are as follows:
Preparation method is same as Example 1.
A kind of high anti-puncture of embodiment 3 is cast polyethylene film
As shown in Figure 1, high anti-puncture is cast polyethylene film, including five-layer structure, it is followed successively by corona layer 1 from outside to inside, resists It punctures layer a2, buffer layer 3, puncture resistant layer b4, hot sealing layer 5 to form, each thickness degree and composition are as follows:
Embodiment 3 Corona layer Puncture resistant layer a Buffer layer Puncture resistant layer b Hot sealing layer
Each thickness degree μm 16 7 20 7 13
Each layer component weight ratio
Oil of SPC Q201 (LDPE) 60 75
Oil of SPC CH2802 (HDPE) 15 25 10
Tao Shi 5500G (mPE) 39 70 20 80 24
8150 POE of Tao Shi 15 20 10
Opening agent spherical SiO28000 mesh 0.45 0.45
Slipping agent erucyl amide 0.4 0.4
Electrostatic agent is Armostat1800 0.15 0.15
8000 mesh of mica powder 29
Polyvinyl alcohol PEG4000 4
Coupling agent DOW CORNING Z-6030 2
Preparation method is same as Example 1.
A kind of high anti-puncture of embodiment 4 is cast polyethylene film
As shown in Figure 1, high anti-puncture is cast polyethylene film, including five-layer structure, it is followed successively by corona layer 1 from outside to inside, resists It punctures layer a2, buffer layer 3, puncture resistant layer b4, hot sealing layer 5 to form, each thickness degree and composition are as follows:
Embodiment 4 Corona layer Puncture resistant layer a Buffer layer Puncture resistant layer b Hot sealing layer
Each thickness degree μm 15 8 20 8 12
Each layer component weight ratio
Tao Shi 150E (LDPE) 60 70
Tao Shi 35060A (HDPE) 10 30 10
Exxon Mobil 3505hH (mPE) 39 80 15 80 29
Exxon Mobil 3980FL POE 10 20 10
Opening agent spherical SiO28000 mesh 0.45 0.45
Slipping agent erucyl amide 0.4 0.4
Electrostatic agent is Armostat1800 0.15 0.15
8000 mesh of mica powder 29
Polyvinyl alcohol PEG4000 4
Coupling agent DOW CORNING Z-6030 2
Preparation method is same as Example 1.
Comparative example
High anti-puncture is cast polyethylene film, including three-decker, is followed successively by corona layer, sandwich layer, hot sealing layer from outside to inside, in Between sandwich layer as the puncture resistant layer a/b component of embodiment 4, with a thickness of puncture resistant layer a, buffer layer, puncture resistant layer in embodiment 4 The sum of b, each thickness degree and composition are as follows:
Production method is the same as step (1), (2), (4), (5) in embodiment 1.
Example 1-4 and the polyethylene film of comparative example preparation carry out anti-puncture intensity, dart impact and tensile strength and survey Examination.Wherein, film anti-puncture intensity method according to specified in GB/T10004-2008 is measured, and dart impact passes through GB/ T9639.1-2008 plastic film and the free dart method of thin slice shock resistance test method are measured, and tensile strength surveys basis GB/T1040.3-2006 is tested, as a result such as table 1:
1 embodiment 1-4 of table and comparative example test data
It can be seen that in the case where condition of equivalent thickness by above-mentioned test result, with comparative example three-decker polyethylene film It compares, five layers high anti-puncture provided by the invention is cast polyethylene film in holding tensile strength while same level, not only The puncture strength of film improves 25%-33%, and dart impact improves 18%-32%, and reduces metallocene PE (mPE) dosage has taken into account the production cost of product.

Claims (10)

1. a kind of high anti-puncture is cast polyethylene film, it is characterised in that: the polyethylene film has five-layer structure, divides from outside to inside Not Wei corona layer, puncture resistant layer a, buffer layer, puncture resistant layer b, hot sealing layer composition, five layers of thickness proportion is (6-8): (3-5): (8-10): (3-5): (4-6),
The raw material for preparing of the corona layer is 40-60 parts of low density polyethylene (LDPE) (LDPE), the poly- second of metallocene in parts by weight 30-50 parts of alkene (mPE), 0.3-0.6 parts of opening agent, 0.3-0.5 parts of slipping agent, 0.1-0.2 parts of antistatic agent；
The raw material for preparing of the puncture resistant layer a is 70-90 parts of metallocene PE (mPE) in parts by weight, and high density is poly- 5-15 parts of ethylene (HDPE), maleic anhydride are grafted POE 5-15 parts；
The raw material for preparing of the buffer layer is 20-40 parts of high density polyethylene (HDPE) (HDPE), the poly- second of metallocene in parts by weight 10-20 parts of alkene (mPE), POE 15-25 parts of maleic anhydride grafting, 25-35 parts of mica powder, 3-5 parts of dispersing agent, coupling agent 1.5- 2.5 part；
The raw material for preparing of the puncture resistant layer b is 70-90 parts of metallocene PE (mPE) in parts by weight, and high density is poly- 5-15 parts of ethylene (HDPE), maleic anhydride are grafted POE 5-15 parts；
The raw material for preparing of the hot sealing layer is 60-80 parts of low density polyethylene (LDPE) (LDPE), the poly- second of metallocene in parts by weight 20-40 parts of alkene (mPE), 0.3-0.6 parts of opening agent, 0.3-0.5 parts of slipping agent, 0.1-0.2 parts of antistatic agent.
2. a kind of high anti-puncture is cast polyethylene film, it is characterised in that: the polyethylene film has five-layer structure, divides from outside to inside Not Wei corona layer, puncture resistant layer a, buffer layer, puncture resistant layer b, hot sealing layer composition, five layers of thickness proportion is (7-8): (3-4): (9-10): (3-4): (5-6),
The raw material for preparing of the corona layer is 45-55 parts of low density polyethylene (LDPE) (LDPE), the poly- second of metallocene in parts by weight 40-50 parts of alkene (mPE), 0.4-0.5 parts of opening agent, 0.35-0.45 parts of slipping agent, 0.13-0.18 parts of antistatic agent；
The raw material for preparing of the puncture resistant layer a is 75-85 parts of metallocene PE (mPE) in parts by weight, and high density is poly- 8-12 parts of ethylene (HDPE), maleic anhydride are grafted POE 8-12 parts；
The raw material for preparing of the buffer layer is 25-35 parts of high density polyethylene (HDPE) (HDPE), the poly- second of metallocene in parts by weight 12-18 parts of alkene (mPE), POE 18-22 parts of maleic anhydride grafting, 27-30 parts of mica powder, 3.5-4.5 parts of dispersing agent, coupling agent 1.8-2.2 part；
The raw material for preparing of the puncture resistant layer b is 75-85 parts of metallocene PE (mPE) in parts by weight, and high density is poly- 8-12 parts of ethylene (HDPE), maleic anhydride are grafted POE 8-12 parts；
The raw material for preparing of the hot sealing layer is 65-75 parts of low density polyethylene (LDPE) (LDPE), the poly- second of metallocene in parts by weight 25-35 parts of alkene (mPE), 0.4-0.5 parts of opening agent, 0.35-0.45 parts of slipping agent, 0.13-0.18 parts of antistatic agent.
3. a kind of high anti-puncture is cast polyethylene film, it is characterised in that: the polyethylene film has five-layer structure, divides from outside to inside Not Wei corona layer, puncture resistant layer a, buffer layer, puncture resistant layer b, hot sealing layer composition, five layers of thickness proportion is 15 μm, 8 μm, 20 μ M, 8 μm, 12 μm；
The raw material for preparing of the corona layer is 50 parts of low density polyethylene (LDPE) (LDPE), metallocene PE (m in parts by weight PE) 49 parts, 0.45 part of opening agent, 0.4 part of slipping agent, 0.15 part of antistatic agent；
The raw material for preparing of the puncture resistant layer a is 80 parts of metallocene PE (mPE), high density polyethylene (HDPE) in parts by weight (HDPE) 10 parts, maleic anhydride is grafted 10 parts of POE；
The raw material for preparing of the buffer layer is 30 parts of high density polyethylene (HDPE) (HDPE), metallocene PE (m in parts by weight PE) 15 parts, maleic anhydride is grafted 20 parts of POE, 29 parts of mica powder, 4 parts of dispersing agent, 2 parts of coupling agent；
The raw material for preparing of the puncture resistant layer b is 80 parts of metallocene PE (mPE), high density polyethylene (HDPE) in parts by weight (HDPE) 10 parts, maleic anhydride is grafted 10 parts of POE；
The raw material for preparing of the hot sealing layer is 70 parts of low density polyethylene (LDPE) (LDPE), metallocene PE in parts by weight (mPE) 29 parts, 0.45 part of opening agent, 0.4 part of slipping agent, 0.15 part of antistatic agent.
4. high anti-puncture as claimed in any one of claims 1-3 is cast polyethylene film, it is characterised in that:
The low density polyethylene (LDPE) (LDPE) is Tao Shi 150E/310E/312E/352E, South Korea LG FB0300, Yanshan Petrochemical One or more of combinations of LD600, Qilu Petrochemical 2102TN26, oil of SPC Q201；
The metallocene PE (mPE) is Exxon Mobil 2005/2010/2010CR/2703hh/2705hh/3505hH, DOW Chemical 5100G/5110G/5111G/5230F/5220G/5230G/540G/5401G/5500G, Mitsui Chemicals Evolue One or more of SP1510/SP1520/SP1540/V2020H/SP2040/SP2320/SP2510/SP2520/ SP3010 Combination；
The high density polyethylene (HDPE) (HDPE) is Exxon Mobil HTA-08, Tao Shi 35060A, Yanshan Petrochemical 5000S, Shanghai One or more of combinations of petrochemical industry CH2802, Yangtze petrochemical industry 5306J；
The POE Mitsui DF840/940/4085S, one or more of Exxon Mobil 3980FL, Tao Shi 8150 Combination；
The opening agent is 8000 mesh of preparing spherical SiO 2；
The slipping agent is erucyl amide；
The electrostatic agent is Armostat1800；
The mica powder specification is 8000 mesh；
The dispersing agent is polyvinyl alcohol PEG4000；
The coupling agent is DOW CORNING Z-6030.
5. the high anti-puncture as described in any one of claim 1-3 is cast polyethylene film, it is characterised in that: including following step It is rapid:
(1) by the low density polyethylene (LDPE) of formulation dosage (LDPE), metallocene PE (mPE), opening agent, slipping agent is antistatic Agent is added to the mixer mixing, is subsequently placed in double screw extruder extrusion, enters back into mixing in pressurization internal mixer and obtain corona layer Modified film forming material；
(2) by the metallocene PE of formulation dosage (mPE), high density polyethylene (HDPE) (HDPE), it is mixed that maleic anhydride is grafted POE addition It is mixed in conjunction machine, is subsequently placed in double screw extruder extrusion, entered back into mixing in pressurization internal mixer and obtain that puncture resistant layer a/ is anti-to be worn Pierce the modified film forming material of layer b；
(3) by the high density polyethylene (HDPE) of formulation dosage (HDPE), metallocene PE (mPE), maleic anhydride grafting POE, mica Powder, dispersing agent, coupling agent are added to the mixer mixing, are subsequently placed in double screw extruder extrusion, enter back into pressurization internal mixer Mixing obtains the modified film forming material of buffer layer；
(4) by the low density polyethylene (LDPE) of formulation dosage (LDPE), metallocene PE (mPE), opening agent, slipping agent is antistatic Agent is added to the mixer mixing, is subsequently placed in double screw extruder extrusion, enters back into mixing in pressurization internal mixer and obtain hot sealing layer Modified film forming material；
(5) the modified film forming material of the corona layer respectively obtained in above-mentioned steps (1), (2), (3), (4), puncture resistant layer a are modified to Five-layer co-squeezing casting machine is added in the modified film forming material of coating materials, buffer layer, the modified film forming material of puncture resistant layer b, the modified film forming material of hot sealing layer Middle progress coextrusion casting stretching, cooling and shaping obtain the high anti-puncture curtain coating polyethylene film after sided corona treatment.
6. preparation method as described in claim 5, it is characterised in that: in the step (1):
The time mixed in mixing machine is 45min；
The draw ratio of double screw extruder be 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature be respectively as follows: 205 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 220 DEG C, the revolving speed of screw rod are 440r/min；
The time of mixing in mixer is 45min, and the temperature of mixing is 185 DEG C.
7. preparation method as described in claim 5, it is characterised in that: in the step (2):
The time mixed in mixing machine is 45min；
The draw ratio of double screw extruder be 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature be respectively as follows: 210 DEG C, 225 DEG C, 240 DEG C, 240 DEG C, 225 DEG C, the revolving speed of screw rod are 440r/min；
The time of mixing in mixer is 45min, and the temperature of mixing is 200 DEG C.
8. preparation method as described in claim 5, it is characterised in that: in the step (3):
The time mixed in mixing machine is 45min；
The draw ratio of double screw extruder be 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature be respectively as follows: 210 DEG C, 220 DEG C, 235 DEG C, 235 DEG C, 220 DEG C, the revolving speed of screw rod are 440r/min；
The time of mixing in mixer is 45min, and the temperature of mixing is 190 DEG C.
9. preparation method as described in claim 5, it is characterised in that: in the step (4):
The time mixed in mixing machine is 45min；
The draw ratio of double screw extruder be 44, conveying section, melt zone, mixing section, exhaust section, homogenizing zone temperature be respectively as follows: 205 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 220 DEG C, the revolving speed of screw rod are 440r/min；
The time of mixing in mixer is 45min, and the temperature of mixing is 185 DEG C.
10. preparation method as described in claim 5, it is characterised in that: in the step (5):
Co-extruding mould temperature is 240 DEG C, and casting and stretching ratio is 1.1-1.5, and cooling and shaping temperature is 30 DEG C.
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