CN102152579A - Co-extruded and bidirectional-stretched composite film and preparation method thereof - Google Patents

Co-extruded and bidirectional-stretched composite film and preparation method thereof Download PDF

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Publication number
CN102152579A
CN102152579A CN2010105985603A CN201010598560A CN102152579A CN 102152579 A CN102152579 A CN 102152579A CN 2010105985603 A CN2010105985603 A CN 2010105985603A CN 201010598560 A CN201010598560 A CN 201010598560A CN 102152579 A CN102152579 A CN 102152579A
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China
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resin
barrier layer
ethylene
vinyl alcohol
film
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CN2010105985603A
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Chinese (zh)
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林子茂
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福融辉实业(福建)有限公司
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Priority to CN2010105985603A priority Critical patent/CN102152579A/en
Publication of CN102152579A publication Critical patent/CN102152579A/en

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Abstract

The invention discloses a co-extruded and bidirectional-stretched composite film, which has a three-layered structure, namely a homopolymer or copolymer polypropylene resin assistant barrier layer, a homopolymer polypropylene resin assistant barrier layer containing adhesive resin and an ethylene-vinyl alcohol copolymer resin main barrier layer in turn, or a homopolymer polypropylene resin assistant barrier layer, an ethylene-vinyl alcohol copolymer resin main barrier layer and a homopolymer or copolymer polypropylene resin assistant barrier layer containing adhesive resin in turn, wherein the composite film is formed by co-extruding the three-layered structure and then stretching bi-directionally. The composite film provided by the invention has the combined advantages of high stretching intensity and good optical performance of the polypropylene resin layer and the advantage of high barrier property of the ethylene-vinyl alcohol copolymer resin layer, so that a film material with extremely high permeability resistance to oxygen, carbon oxygen, fragrance, smells, aqueous vapor and the like, high toughness and high antistatic property is obtained; the film is thin; the manufacturing cost is low and the yield is high.

Description

A kind of co-extruding biaxial stretched laminated film and preparation method thereof

Technical field

The present invention relates to a kind of environmental protection film, relate in particular to a kind of co-extruding biaxial stretched laminated film of high-intensity high separating performance, the invention still further relates to the preparation method of this laminated film.

Background technology

Multi-layer co-extruded oriented film technology has obtained extensive use.Some multi-layer compound films have appearred in the prior art, with ethylene-vinyl alcohol copolymer resin (EVOH) as main barrier layer.Because EVOH is the crystal polymer thing, fusing point is about 180 ℃, and fusion range is narrow, if carrying out longitudinal stretching post crystallization Du Taigao, and difficulty just when carrying out cross directional stretch once more, and the phenomenon that can turn white of the too high film of degree of crystallinity.Therefore the stretch processes of EVOH film always is the bottleneck in the production.

Patent of invention ZL99809184.7 " producing the method for EVOH/ polyester bistretched film " discloses a kind of plural layers, and it comprises PET, binding agent, EVOH, binding agent, pet layer structure, and it adopts biaxial tension simultaneously to produce.Defectives such as PET is a kind of polyester, and it has the mechanical performance advantages of higher, but also exists hot strength general, and optical property is relatively poor.And, need the redesign corresponding apparatus, the production cost height in order to realize the production of these plural layers.

Patent of invention ZL02105126.7 " manufacture method of ethylene-vinyl alcohol copolymer bidirectiohnal stretched film " discloses and has adopted biaxial tension to make the method for ethylene-vinyl alcohol copolymer film, wherein also disclose the layer that constitutes by EVOH biaxial stretching film and other thermoplastic resins and constituted laminates jointly, but this laminates is that the EVOH pellicular cascade that other thermoplastic resins and biaxial tension obtain is formed, conjugation between each layer is limited, thereby has influence on gas-barrier property, morphological stability and the transparency of laminates.

Summary of the invention

The purpose of this invention is to provide the co-extruding biaxial stretched laminated film that a kind of Film Optics performance is good, have high tensile and barrier.Another object of the present invention provides the preparation method of this laminated film.

For achieving the above object, laminated film of the present invention is a three-decker, each layer in regular turn for the auxilliary barrier layer of homopolymerization or COPP resin, contain the auxilliary barrier layer of HOPP resin, the ethylene-vinyl alcohol copolymer resin master barrier layer of binder resin, or being the auxilliary barrier layer of HOPP resin, ethylene-vinyl alcohol copolymer resin master barrier layer, the homopolymerization that contains binder resin or the auxilliary barrier layer of COPP resin, this laminated film is that the three-decker co-extrusion is after the biaxial tension moulding.The molar content of ethene is 32%-40% in the ethylene-vinyl alcohol copolymer resin of the present invention, wherein preferred 38%.

The thickness of laminated film of the present invention is the 20-60 micron.Described ethylene-vinyl alcohol copolymer resin master barrier layer thickness is the 1-5 micron.The longitudinal tensile strength of laminated film of the present invention is greater than 100MPa, and transverse tensile strength is greater than 180MPa, and glossiness is greater than 95%, and the oxygen transit dose is less than 20cm 3/ m 2/ day/bar, vapor transfer rate is less than 10g/m 2/ day.

Homopolymerization or COPP resin are through biaxial tension rear film hot strength height, good in optical property and have certain barrier, in multi-layer co-extrusion two-way stretching homopolymerization or COPP resin thin film layer, introduce the ethylene-vinyl alcohol copolymer resin bed, to obtain a kind of to oxygen, carbon dioxide, fragrance, smell, gas barrier properties such as aqueous vapor are high, good toughness, the thin-film material that has excellent antistatic properties, with respect to other high-resistant diaphragm material, with the ethylene-vinyl alcohol copolymer resin is the co-extruding biaxial stretched laminated film recycling fully of main barrier layer, simultaneously, because of it is by the biaxial tension moulding, it is little to reach the required thickness of equal barrier, low cost of manufacture, output is big.

Binder resin of the present invention is with anhydride modified polypropylene binder resin, and it accounts for the homopolymerization that contains binder resin or the 5-20% of COPP total resin weight.Because ethylene-vinyl alcohol copolymer resin and polypropylene are inconsistent, need select for use usually with the bonding resin of anhydride modified polypropylene as adhesive, thereby guarantee when stretching, can not occur film complete by garland phenomenon and final thin-film barrier layer.

HOPP resin of the present invention, COPP resin, contain binder resin the HOPP resin, contain the functional master batch that contains the 0.2%-20% weight ratio in the COPP resin of binder resin respectively.Described functional master batch is anti-stick masterbatch, the filling master batch that contains 30-70% weight ratio mineral matter, smooth master batch, anti-oxidant masterbatch, the antistatic master batch of connecting.Add certain functional master batch, the laminated film of producing will have function corresponding.

Prepare that the method for laminated film comprises the steps: step 1 among the present invention: the constituent configuration material according to each layer in the laminated film in the claim 1, melt extrude respectively, form three layers of material film; Wherein, the temperature that melt extrudes of ethylene-vinyl alcohol copolymer resin adopts single screw extrusion machine at 200-235 ℃, single screw rod chromium plating, and its full thread draw ratio is 30; Step 2: three layers of material film converge the back coextrusion, form the film sheet at 20-45 ℃ of following Quench casting sheet; In the Quench casting sheet process, when ethylene-vinyl alcohol copolymer resin master barrier layer was outer, it was pasting the roll surface of sharp cooling roll; Step 3: the film sheet carries out longitudinal stretching to the film sheet with the stretch ratio of 3-4 90-135 ℃ of following preheating under 70-130 ℃, again the 130-135 ℃ of Rapid Thermal typing of carrying out less than 10 seconds; Step 4:,, under 150-158 ℃, the film sheet is carried out cross directional stretch with the stretch ratio of 7-9 165-175 ℃ of following preheating to the film sheet behind the longitudinal stretching in the step 3; Step 5: the film after step 4 processing is carried out thermal finalization under 158-160 ℃.Step 6: the film after step 5 handled draws in regular turn, thickness measuring and THICKNESS CONTROL, sided corona treatment, rolling, Ageing Treatment, cut, pack.

Because the existence of water can influence its barrier property, therefore when Quench casting sheet, the ethylene-vinyl alcohol copolymer resin bed is placed on the subsides roll surface of sharp cooling roll, or the ethylene-vinyl alcohol copolymer resin bed is placed on the three-layer co-extruded intermediate layer that goes out structure.In addition, because ethylene-vinyl alcohol copolymer resin melt viscosity height, fusion range is narrow, be easy to generate melt and be detained in extrusion, the molecule of the ethylene-vinyl alcohol copolymer resin of delay dehydration can occur, form two keys, produces crosslinked, " gel " phenomenon appears, even carbonization.In order to prevent " gel ", carbonization phenomenon, the preferred draw ratio of the present invention is 30 full thread and screw rod is implemented the single screw extrusion machine that chromium plating is handled that extrusion temperature is controlled at 200-235 ℃.

Adopt above method, promptly can prepare laminated film of the present invention, the production efficiency height need not specialized designs equipment, and existing extruder and stretching-machine can be finished this work, and production cost is low.

Compared with prior art, laminated film of the present invention has had acrylic resin layer hot strength height, the advantage of good in optical property and the high barrier of ethylene-vinyl alcohol copolymer resin bed concurrently, thereby the thin-film material that obtain a kind of, good toughness high, has excellent antistatic properties to gas barrier properties such as oxygen, carbon dioxide, fragrance, smell, aqueous vapors, this film thickness is little, low cost of manufacture, output is big.Can be widely used in packaging fields such as food, dairy produce, beverage, chemical products, chemical reagent, medicine, agricultural chemicals, electronic material, daily necessities, war products.

Description of drawings

The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments:

Fig. 1 is the three-decker schematic diagram of laminated film of the present invention;

Fig. 2 is the three-decker schematic diagram of the another kind of laminated film of the present invention;

Fig. 3 is preparation method's flow chart of the present invention.

The specific embodiment

Below part term is herein further explained:

Term " acrylic resin " is also referred to as PP herein, is a kind of crystalline polymer of compound with regular structure, is the thermoplastic resin of light oyster white pellet, tasteless, nontoxic, light weight.Relative density is 0.90~0.91, is the lightest a kind of in the resins for universal use.

Term " ethylene-vinyl alcohol copolymer resin " is also referred to as EVOH herein, it be by ethylene-vinyl acetate copolymer through saponification or partly-hydrolysed reaction and alcoholysis product.Its ratio is generally the ethene of 20-40 %, and the vinyl alcohol of 60-80 % can be regarded the modifier of polyvinyl alcohol (PVA) as, and its technological process of production is similar to PVA.It is a kind of novel high polymer synthetic material that integrates the barrier properties for gases of polyvinyl processability and vinyl alcohol polymer.

Term " Quench casting sheet " refers to raw material is extruded on the large-scale live-rollers that is sharp cooling roll herein.Sharp cooling roll is a ganoid runner, and handle through chromium plating on its surface, and its inner logical cooling water keeps constant lower temperature (as 25 ℃) to guarantee its surface.When the raw material of fusion is expressed into sharp cooling roll, can be cooled off rapidly, prevented product internal junction crystallization simultaneously.

Shown in Fig. 1 to 2, laminated film of the present invention is a three-decker, each layer in regular turn for the auxilliary barrier layer 1 of homopolymerization or COPP resin, contain the auxilliary barrier layer 2 of HOPP resin, the ethylene-vinyl alcohol copolymer resin master barrier layer 3 of binder resin, or being the auxilliary barrier layer 4 of HOPP resin, ethylene-vinyl alcohol copolymer resin master barrier layer 5, the homopolymerization that contains binder resin or the auxilliary barrier layer 6 of COPP resin, this laminated film is that the three-decker co-extrusion is after the biaxial tension moulding.The molar content of ethene is 32%-40% in the ethylene-vinyl alcohol copolymer resin of the present invention, wherein preferred 38%.

The thickness of laminated film of the present invention is the 20-60 micron.Described ethylene-vinyl alcohol copolymer resin master barrier layer thickness is the 1-5 micron.The longitudinal tensile strength of laminated film of the present invention is greater than 100MPa, and transverse tensile strength is greater than 180MPa, and glossiness is greater than 95%, and the oxygen transit dose is less than 20cm 3/ m 2/ day/bar, vapor transfer rate is less than 10g/m 2/ day.

Acrylic resin is through biaxial tension rear film hot strength height, good in optical property and have certain barrier, in the multilayer coextruding two-way extension polypropylene resin thin film layer, introduce the ethylene-vinyl alcohol copolymer resin bed, to obtain a kind of to oxygen, carbon dioxide, fragrance, smell, gas barrier properties such as aqueous vapor are high, good toughness, the thin-film material that has excellent antistatic properties, with respect to other high-resistant diaphragm material, with the ethylene-vinyl alcohol copolymer resin is the co-extruding biaxial stretched laminated film recycling fully of main barrier layer, simultaneously, because of it is by the biaxial tension moulding, it is little to reach the required thickness of equal barrier, low cost of manufacture, output is big.

Binder resin of the present invention is with anhydride modified polypropylene binder resin, and it accounts for the homopolymerization that contains binder resin or the 5-20% of COPP total resin weight.Because ethylene-vinyl alcohol copolymer resin and polypropylene are inconsistent, need select for use usually with the bonding resin of anhydride modified polypropylene as adhesive, thereby guarantee when stretching, can not occur film complete by garland phenomenon and final thin-film barrier layer.

HOPP resin of the present invention, COPP resin, contain binder resin the HOPP resin, contain the functional master batch that contains the 0.2%-20% weight ratio in the COPP resin of binder resin respectively.Described functional master batch is anti-stick masterbatch, the filling master batch that contains 30-70% weight ratio mineral matter, smooth master batch, anti-oxidant masterbatch, the antistatic master batch of connecting.Add certain functional master batch, the laminated film of producing will have function corresponding.

As shown in Figure 3, prepare that the method for laminated film comprises the steps: step 1 among the present invention: the constituent configuration material according to each layer in the laminated film in the claim 1, melt extrude respectively, form three layers of material film; Wherein, the temperature that melt extrudes of ethylene-vinyl alcohol copolymer resin is at 200-235 ℃, and adopting draw ratio is 30 full thread and to the single screw extrusion machine of screw rod chromium plating; Step 2: three layers of material film converge the back coextrusion, form the film sheet at 20-45 ℃ of following Quench casting sheet; In the Quench casting sheet process, when ethylene-vinyl alcohol copolymer resin master barrier layer was outer, it was pasting the roll surface of sharp cooling roll; Step 3: the film sheet carries out longitudinal stretching to the film sheet with the stretch ratio of 3-4 90-135 ℃ of following preheating under 70-130 ℃, again the 130-135 ℃ of Rapid Thermal typing of carrying out less than 10 seconds; Step 4:,, under 150-158 ℃, the film sheet is carried out cross directional stretch with the stretch ratio of 7-9 165-175 ℃ of following preheating to the film sheet behind the longitudinal stretching in the step 3; Step 5: the film after step 4 processing is carried out thermal finalization under 158-160 ℃.Step 6: the film after step 5 handled draws in regular turn, thickness measuring and THICKNESS CONTROL, sided corona treatment, rolling, Ageing Treatment, cut, pack.

Embodiment 1:

Laminated film of the present invention is a three-decker, each layer in regular turn for the auxilliary barrier layer 1 of COPP resin, contain the auxilliary barrier layer 2 of HOPP resin, the ethylene-vinyl alcohol copolymer resin master barrier layer 3 of binder resin, this laminated film is that the three-decker co-extrusion is after the biaxial tension moulding.The molar content of ethene is 38% in the ethylene-vinyl alcohol copolymer resin of the present invention.

Binder resin of the present invention is with anhydride modified polypropylene binder resin, and it accounts for 20% of the homopolymerization that contains binder resin or COPP total resin weight.

COPP resin 1 of the present invention, contain the functional master batch that contains the 0.2%-20% weight ratio in the HOPP resin 2 of binder resin respectively.Described functional master batch is the anti-stick masterbatch that connects.

The thickness of laminated film of the present invention is 20 microns.Described ethylene-vinyl alcohol copolymer resin master barrier layer thickness is 1 micron.

Embodiment 2:

Laminated film of the present invention is a three-decker, each layer in regular turn for the auxilliary barrier layer 1 of HOPP resin, contain the auxilliary barrier layer 2 of HOPP resin, the ethylene-vinyl alcohol copolymer resin master barrier layer 3 of binder resin, this laminated film is that the three-decker co-extrusion is after the biaxial tension moulding.The molar content of ethene is 32% in the ethylene-vinyl alcohol copolymer resin of the present invention.

Binder resin of the present invention is with anhydride modified polypropylene binder resin, and it accounts for 5% of the homopolymerization that contains binder resin or COPP total resin weight.

HOPP resin 1 of the present invention, contain the functional master batch that contains the 0.2%-20% weight ratio in the HOPP resin 2 of binder resin respectively.Described functional master batch is the filling master batch that contains 30-70% weight ratio mineral matter.

The thickness of laminated film of the present invention is 60 microns.Described ethylene-vinyl alcohol copolymer resin master barrier layer thickness is 5 microns.

Embodiment 3:

Laminated film of the present invention is a three-decker, each layer in regular turn for HOPP resin auxilliary barrier layer 4, ethylene-vinyl alcohol copolymer resin master barrier layer 5, contain the auxilliary barrier layer 6 of HOPP resin of binder resin, this laminated film is that the three-decker co-extrusion is after the biaxial tension moulding.The molar content of ethene is 40% in the ethylene-vinyl alcohol copolymer resin of the present invention.

Binder resin of the present invention is with anhydride modified polypropylene binder resin, and it accounts for 15% of the homopolymerization that contains binder resin or COPP total resin weight.

HOPP resin 4 of the present invention, contain the functional master batch that contains the 0.2%-20% weight ratio in the HOPP resin 6 of binder resin respectively.Described functional master batch is a smooth master batch.

The thickness of laminated film of the present invention is 30 microns.Described ethylene-vinyl alcohol copolymer resin master barrier layer thickness is 3 microns.

Embodiment 4

Laminated film of the present invention is a three-decker, each layer in regular turn for HOPP resin auxilliary barrier layer 4, ethylene-vinyl alcohol copolymer resin master barrier layer 5, contain the auxilliary barrier layer 6 of COPP resin of binder resin, this laminated film is that the three-decker co-extrusion is after the biaxial tension moulding.The molar content of ethene is 36% in the ethylene-vinyl alcohol copolymer resin of the present invention.

Binder resin of the present invention is with anhydride modified polypropylene binder resin, and it accounts for 18% of the homopolymerization that contains binder resin or COPP total resin weight.

HOPP resin 4 of the present invention, contain the functional master batch that contains the 0.2%-20% weight ratio in the COPP resin 6 of binder resin respectively.Described functional master batch is an antistatic master batch.

The thickness of laminated film of the present invention is 40 microns.Described ethylene-vinyl alcohol copolymer resin master barrier layer thickness is 2 microns.

Preparation example 1:

Prepare that the method for laminated film comprises the steps: step 1 among the present invention: the constituent configuration material according to each layer in the laminated film in the claim 1, melt extrude respectively, form three layers of material film; Wherein, the temperature that melt extrudes of ethylene-vinyl alcohol copolymer resin is at 200 ℃, and adopting draw ratio is 30 full thread and to the single screw extrusion machine of screw rod chromium plating; Step 2: three layers of material film converge the back coextrusion, form the film sheet at 20 ℃ of following Quench casting sheets; In the Quench casting sheet process, when ethylene-vinyl alcohol copolymer resin master barrier layer was outer, it was pasting the roll surface of sharp cooling roll; Step 3: the film sheet carries out longitudinal stretching to the film sheet with 4 stretch ratio 135 ℃ of following preheatings under 130 ℃, carries out 9 seconds Rapid Thermal typing again under 135 ℃; Step 4:,, under 158 ℃, the film sheet is carried out longitudinal stretching with 7 stretch ratio 165 ℃ of following preheatings to the film sheet behind the longitudinal stretching in the step 3; Step 5: the film after step 4 processing is carried out thermal finalization under 158 ℃.Step 6: the film after step 5 handled draws in regular turn, thickness measuring and THICKNESS CONTROL, sided corona treatment, rolling, Ageing Treatment, cut, pack.

Preparation example 2:

Prepare that the method for laminated film comprises the steps: step 1 among the present invention: the constituent configuration material according to each layer in the laminated film in the claim 1, melt extrude respectively, form three layers of material film; Wherein, the temperature that melt extrudes of ethylene-vinyl alcohol copolymer resin is at 235 ℃, and adopting draw ratio is 30 full thread and to the single screw extrusion machine of screw rod chromium plating; Step 2: three layers of material film converge the back coextrusion, form the film sheet at 45 ℃ of following Quench casting sheets; In the Quench casting sheet process, when ethylene-vinyl alcohol copolymer resin master barrier layer was outer, it was pasting the roll surface of sharp cooling roll; Step 3: the film sheet carries out longitudinal stretching to the film sheet with 3 stretch ratio 90 ℃ of following preheatings under 70 ℃, carries out 6 seconds Rapid Thermal typing again under 130 ℃; Step 4:,, under 150 ℃, the film sheet is carried out cross directional stretch with 8 stretch ratio 175 ℃ of following preheatings to the film sheet behind the longitudinal stretching in the step 3; Step 5: the film after step 4 processing is carried out thermal finalization under 160 ℃.Step 6: the film after step 5 handled draws in regular turn, thickness measuring and THICKNESS CONTROL, sided corona treatment, rolling, Ageing Treatment, cut, pack.

Preparation example 3:

Prepare that the method for laminated film comprises the steps: step 1 among the present invention: the constituent configuration material according to each layer in the laminated film in the claim 1, melt extrude respectively, form three layers of material film; Wherein, the temperature that melt extrudes of ethylene-vinyl alcohol copolymer resin is at 215 ℃, and adopting draw ratio is 30 full thread and to the single screw extrusion machine of screw rod chromium plating; Step 2: three layers of material film converge the back coextrusion, form the film sheet at 30 ℃ of following Quench casting sheets; In the Quench casting sheet process, when ethylene-vinyl alcohol copolymer resin master barrier layer was outer, it was pasting the roll surface of sharp cooling roll; Step 3: the film sheet carries out longitudinal stretching to the film sheet with 3.5 stretch ratio 115 ℃ of following preheatings under 100 ℃, carries out 6 seconds Rapid Thermal typing again under 133 ℃; Step 4:,, under 154 ℃, the film sheet is carried out cross directional stretch with 9 stretch ratio 170 ℃ of following preheatings to the film sheet behind the longitudinal stretching in the step 3; Step 5: the film after step 4 processing is carried out thermal finalization under 160 ℃.Step 6: the film after step 5 handled draws in regular turn, thickness measuring and THICKNESS CONTROL, sided corona treatment, rolling, Ageing Treatment, cut, pack.

Preparation example 4:

Prepare that the method for laminated film comprises the steps: step 1 among the present invention: the constituent configuration material according to each layer in the laminated film in the claim 1, melt extrude respectively, form three layers of material film; Wherein, the temperature that melt extrudes of ethylene-vinyl alcohol copolymer resin is below 225 ℃, and adopting draw ratio is 30 full thread and to the single screw extrusion machine of screw rod chromium plating; Step 2: three layers of material film converge the back coextrusion, form the film sheet at 35 ℃ of following Quench casting sheets; In the Quench casting sheet process, when ethylene-vinyl alcohol copolymer resin master barrier layer was outer, it was pasting the roll surface of sharp cooling roll; Step 3: the film sheet carries out longitudinal stretching to the film sheet with 3.5 stretch ratio 120 ℃ of following preheatings under 115 ℃, carries out 8 seconds Rapid Thermal typing again under 135 ℃; Step 4:,, under 156 ℃, the film sheet is carried out cross directional stretch with 7.5 stretch ratio 168 ℃ of following preheatings to the film sheet behind the longitudinal stretching in the step 3; Step 5: the film after step 4 processing is carried out thermal finalization under 160 ℃.Step 6: the film after step 5 handled draws in regular turn, thickness measuring and THICKNESS CONTROL, sided corona treatment, rolling, Ageing Treatment, cut, pack.

Experimental example 1:

Laminated film of the present invention is a three-decker, and each layer wherein adds 2% the anti-stick masterbatch that connects in regular turn for selecting the F280S trade mark polypropylene resin of Kingsoft, Shanghai petrochemical industry for use; 15% Bynel 50E571(binder resin) and 85% F280S; Ethylene-vinyl alcohol copolymer resin ET3803;

The properties of product that the present invention obtained are as shown in table 1 after testing.

Table 1 is the co-extruding biaxial stretched laminated film testing result of main barrier layer with EVOH

Experimental example 2:

Laminated film of the present invention is a three-decker, and each layer wherein adds 2% the anti-stick masterbatch that connects in regular turn for selecting the KS407 trade mark COPP resin of Ineos for use; 15% Bynel 50E571(binder resin) and 85% F280S; Ethylene-vinyl alcohol copolymer resin ET3803; The thickness of COPP tree resin layer is 1 μ m.

According to a conventional method laminated film is prepared as the heat-sealing type product, the properties of product that obtained are as shown in table 2 after testing.

Table 2 is the co-extruding biaxial stretched laminated film heat-sealing type sample detection result of main barrier layer with EVOH

Experimental example 3:

Laminated film of the present invention is a three-decker, and each layer wherein adds 2% the anti-stick masterbatch that connects in regular turn for selecting the F280S trade mark polypropylene resin of Kingsoft, Shanghai petrochemical industry for use; 15% Bynel 50E571(binder resin), 17% white mineral filling master batch, 68% F280S; Ethylene-vinyl alcohol copolymer resin ET3803;

According to a conventional method laminated film is prepared as opaque type product, the properties of product that obtained are as shown in table 3 after testing.

Table 3 is the opaque type sample detection of the co-extruding biaxial stretched laminated film result of main barrier layer with EVOH

Experimental example 4:

Laminated film of the present invention is a three-decker, and each layer wherein adds 2% the anti-stick masterbatch that connects in regular turn for selecting the KS407 trade mark COPP resin of Ineos for use; 15% Bynel 50E571(binder resin), 17% white mineral filling master batch, 68% F280S; Ethylene-vinyl alcohol copolymer resin ET3803; The thickness of COPP tree resin layer is 1 μ m.

According to a conventional method laminated film is prepared as the opaque type product of heat-sealing, the properties of product that obtained are as shown in table 4 after testing.

Table 4 is the opaque sample detection result of co-extruding biaxial stretched laminated film heat-sealing type of main barrier layer with EVOH

The prepared laminated film of the present invention can be widely used in packaging fields such as food, dairy produce, beverage, chemical products, chemical reagent, medicine, agricultural chemicals, electronic material, daily necessities, war products.Be not limited in the foregoing description; technical staff for this area and biaxially oriented film industry; among specification of the present invention and the embodiment the present invention being improved is thing easily, but all should be within protection scope of the present invention under the situation of invention main body that does not deviate from claim and scope.

Claims (11)

1. co-extruding biaxial stretched laminated film, it is characterized in that: this laminated film is a three-decker, each layer in regular turn for the auxilliary barrier layer of homopolymerization or COPP resin, contain the auxilliary barrier layer of HOPP resin, the ethylene-vinyl alcohol copolymer resin master barrier layer of binder resin, or being the auxilliary barrier layer of HOPP resin, ethylene-vinyl alcohol copolymer resin master barrier layer, the homopolymerization that contains binder resin or the auxilliary barrier layer of COPP resin, this laminated film is that the three-decker co-extrusion is after the biaxial tension moulding.
2. a kind of co-extruding biaxial stretched laminated film according to claim 1 is characterized in that: the molar content of ethene is 32%-40% in the described ethylene-vinyl alcohol copolymer resin.
3. a kind of co-extruding biaxial stretched laminated film according to claim 2 is characterized in that: the molar content of ethene is 38% in the described ethylene-vinyl alcohol copolymer resin.
4. a kind of co-extruding biaxial stretched laminated film according to claim 1 is characterized in that: described HOPP resin or COPP resin, contain the HOPP resin of binder resin or contain the functional master batch that contains the 0.2%-20% weight ratio in the COPP resin of binder resin respectively.
5. a kind of co-extrusion double stretching laminated film according to claim 4 is characterized in that: described functional master batch is anti-stick masterbatch, the filling master batch that contains 30-70% weight ratio mineral matter, smooth master batch, anti-oxidant masterbatch, the antistatic master batch of connecting.
6. a kind of co-extruding biaxial stretched laminated film according to claim 1 is characterized in that: described binder resin is for anhydride modified polypropylene binder resin, and it accounts for the homopolymerization that contains binder resin or the 5-20% of COPP total resin weight.
7. a kind of co-extruding biaxial stretched laminated film according to claim 1 is characterized in that: described ethylene-vinyl alcohol copolymer resin master barrier layer thickness is the 1-5 micron.
8. method for preparing the described laminated film of claim 1 to 7, it is characterized in that: described method comprises the steps:
Step 1: the constituent configuration material according to each layer in the laminated film, melt extrude respectively, form three layers of material film;
Step 2: three layers of material film converge the back coextrusion, form the film sheet at 20-45 ℃ of following Quench casting sheet; In the Quench casting sheet process, when ethylene-vinyl alcohol copolymer resin master barrier layer was outer, it was pasting the roll surface of sharp cooling roll;
Step 3: the film sheet carries out longitudinal stretching to the film sheet with the stretch ratio of 3-4 90-135 ℃ of following preheating under 70-130 ℃, again the 130-135 ℃ of Rapid Thermal typing of carrying out less than 10 seconds;
Step 4:,, under 150-158 ℃, the film sheet is carried out cross directional stretch with the stretch ratio of 7-9 165-175 ℃ of following preheating to the film sheet behind the longitudinal stretching in the step 3;
Step 5: the film after step 4 processing is carried out thermal finalization at 158-160 ℃.
9. preparation method according to claim 8 is characterized in that: the temperature that melt extrudes of ethylene-vinyl alcohol copolymer resin is at 200-235 ℃ in the step 1.
10. preparation method according to claim 8 is characterized in that: in the step 1 the ethylene-vinyl alcohol copolymer resin melt extrude the employing single screw extrusion machine, single screw rod chromium plating, its full thread draw ratio is 30.
11. preparation method according to claim 8 is characterized in that: described method also comprises the steps:
Step 6: the film after step 5 handled draws in regular turn, thickness measuring and THICKNESS CONTROL, sided corona treatment, rolling, Ageing Treatment, cut, pack.
CN2010105985603A 2010-12-21 2010-12-21 Co-extruded and bidirectional-stretched composite film and preparation method thereof CN102152579A (en)

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CN107351496A (en) * 2017-07-17 2017-11-17 安徽国风塑业股份有限公司 A kind of high-barrier type biaxial tension co-extrusion film and preparation method

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CN102825876A (en) * 2012-08-31 2012-12-19 河南李烨包装科技有限公司 Composite base material used for packaging bubble cap, production method and application
CN102825876B (en) * 2012-08-31 2014-08-13 河南李烨包装科技有限公司 Composite base material used for packaging bubble cap, production method and application
CN102873950A (en) * 2012-09-21 2013-01-16 海南赛诺实业有限公司 High-surface-energy double-direction stretching polypropylene thin film and manufacturing method thereof
CN102941719A (en) * 2012-10-25 2013-02-27 海南赛诺实业有限公司 High oxygen barrier biaxially oriented polypropylene film and preparation method thereof
CN105793937A (en) * 2013-12-03 2016-07-20 Abb技术有限公司 Multi-layered dielectric polymer material, capacitor, use of the material and formation method thereof
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CN107351496A (en) * 2017-07-17 2017-11-17 安徽国风塑业股份有限公司 A kind of high-barrier type biaxial tension co-extrusion film and preparation method
CN107351496B (en) * 2017-07-17 2019-06-07 安徽国风塑业股份有限公司 A kind of high-barrier type biaxial tension co-extrusion film and preparation method

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