CN102501529A - Biaxial drawing polylactic acid compound film with barrier property and preparation method thereof - Google Patents
Biaxial drawing polylactic acid compound film with barrier property and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a biaxial drawing polylactic acid compound film with a barrier property and a preparation method thereof. The compound film comprises two polylactic acid layers and a barrier layer arranged between the two polylactic acid layers, wherein each polylactic acid layer comprises the following components in weight percentage: 75-100 percent of crystalline polylactic acid, 0-5 percent of melt reinforcing agent, 0-5 percent of toughening agent, 0-5 percent of antistatic agent, 0-5 percent of antioxygen, 0-5 percent of slipping agent and 0-5 percent of antiblocking agent, and the barrier layer is fully biodegradable and is provided with a carbon dioxide copolymer with the gas barrier property. According to the preparation method, a multilayer co-extrusion gradual or synchronous biaxial drawing process is adopted. The compound film can be fully biodegradable, has very good oxygen, carbon dioxide and moisture barrier property, higher tensile strength, high puncture resistance and high deflection, and can be used for packages of foods, cosmetics, electronic products, chemicals and the like.
Description
Technical field
The present invention relates to a kind of biaxial stretch-formed PLA laminated film and preparation method of barrier.
Background technology
Many traditional packaging films (like PP, PE, PVC, PET), they have good heat sealability, printing, gold-plated attribute, barrier properties for gases and controlled coefficient of friction, but these materials all do not possess biodegradability, contaminated environment.
Along with the exploitation of full-biodegradable material, biodegradation material is applied in the packaging film gradually, and like polylactic acid membrane (BOPLA film), but the barrier of PLA itself is relatively poor, can not use as barrier material separately.
Chinese patent 200980108671.7 discloses a kind of biodegradation composite oxygen Obstruct membrane; Be made up of at least two supporting layers and the barrier layer that is located between said per two supporting layers, this composite oxygen Obstruct membrane helps prolonging shelf-life, the shelf life of food and medicine etc.; Simultaneously can prevent to cause the advantage of white pollution, but it adopts is that multi-layer co-extruded method prepares, the mechanical performance of film is relatively poor, and the scope of application is restricted.
Summary of the invention
The object of the invention is to provide a kind of to be had better barrier and has the biaxial stretch-formed PLA laminated film of better mechanical performance and the preparation method of this laminated film thereof.
The biaxial stretch-formed PLA laminated film of a kind of barrier of the present invention is characterized in that, is made up of the barrier layer that two polylactic acid layers are middle with being located at two polylactic acid layers; Said polylactic acid layers comprises following component in percentage by weight: crystalline polylactic acid 75%-100%, melt reinforcing agent 0%-5%, flexibilizer 0%-5%; Antistatic additive 0%-5%; Antioxidant 0%-5%, slipping agent 0%-5%, antiblocking agent 0%-5%; Said barrier layer is complete biodegradable and the carbon dioxide copolymer with barrier properties for gases.
In the structure of the biaxial stretch-formed PLA laminated film of above-mentioned barrier; Said polylactic acid layers is the mechanics supporting layer of film; Used PLA is a crystalline polylactic acid; Be two kinds of optical isomers by lactic acid: D-lactic acid or L-lactic acid are the synthetic crystalline homopolymers of raw material, and such PLA fusing point is high, good heat resistance.The preferential PLA of selecting 100,000-300,000 molecular weight of the present invention if component is less, shows practical rerum naturas such as mechanicalness or hear resistance hardly, if too big, melt viscosity can uprise, and shaping processability is poor.Because PLA is a kind of polar polymer, suction easily needs drying before using in addition, needs to keep moisture to be lower than 0.02%.
Can also add some function additives such as melt reinforcing agent, melt flexibilizer, antistatic additive, antiblocking agent, antioxidant, slipping agent etc. in polylactic acid layers.
There is the chain extender of trace can make PLA grafting chain extension to a certain extent in the polylactic acid melt reinforcing agent, improves its heat endurance, better keep molecular weight; Melt flexibilizer can increase the PLA impact strength, reduces the hardness of polylactic acid membrane, increases horizontal degree of widening etc., like the special-purpose acrylic copolymer of PLA; Antistatic additive reduces the surface resistivity of film, can prevent dust, improve the serviceability that unreels performance and film of film, and antistatic additive can adopt existing general antistatic additive commonly used, and it mainly is that amine, ester class or both are composite; Antiblocking agent prevents film blocking, and antiblocking agent can use on the existing general plastic sheeting commonly used, silica for example, calcium carbonate, magnesium carbonate, talcum, titanium dioxide, kaolin and aluminium oxide, polymethyl methacrylate, any of bead etc.; Antioxidant can prevent that polymer is rotten because of oxidation causes, antioxidant can use on the existing general plastic sheeting commonly used, for example Hinered phenols antioxidant, thio-2 acid dibasic acid esters etc.; Slipping agent can make film surface have smooth characteristic, can reduce the coefficient of friction of film, and it is bonding to avoid film to take place, and slipping agent can adopt existing slipping agent commonly used, like oleamide, erucyl amide.
Barrier layer according to the invention is complete biodegradable and the carbon dioxide copolymer with barrier properties for gases.Can select carbon dioxide epoxy propane copolymer or carbon dioxide ethylene oxide copolymer, the preferably carbon dioxide epoxy propane copolymer is propylene carbonate (PPC).PPC is with carbon dioxide and propylene oxide feedstock, adopts the synthetic a kind of novel complete biodegradable environment-friendly materials of rare-earth ternary catalyst.This material molecule segment is soft, is prone to decompose, and good biocompatibility, and have utmost point low oxygen, carbon dioxide transmitance, can be widely used in packaging material.
For heat endurance and the flowability that improves PPC, can use maleic anhydride graft PPC modification; Can add natural inorganic or organic filler blending and modifying, for example starch, natural fiber, calcium carbonate, silica, imvite and vermiculite etc.; Also can add the biodegradable polymer blending modification, like poly-succinic fourth diester (PBS), polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), poly butyric ester, poly-epsilon-caprolactone (PCL), PHA (PHA) etc.
The biaxial stretch-formed PLA laminated film of barrier of the present invention, gross thickness be at 20 μ m-120 μ m, and outer layer thickness is at 2 μ m-118 μ m, barrier layer thickness 2 μ m-116 μ m.
The biaxial stretch-formed PLA laminated film of barrier of the present invention can also add hot sealing layer again outside polylactic acid layers, also can add the metal receiving layer again, and the metal receiving layer is outer can to add aluminium coated etc.
Above-mentioned hot sealing layer, the used PLA of metal receiving layer are the amorphism PLA; Be to be raw material with D-lactic acid and L-lactic acid, both ratios synthetic random copolymer between 80:20～20:80, such PLA fusing point is low; Hear resistance is relatively poor, is applicable to hot sealing layer, the metal receiving layer of film.
Also can add some function additives such as melt reinforcing agent, melt flexibilizer, antistatic additive, antiblocking agent, antioxidant etc. at hot sealing layer and metal receiving layer.
The employed all material of laminated film provided by the present invention all is totally biodegradables, has effectively prevented white pollution, avoids the toxic solvent contaminated environment, is a kind of high-performance environmentally-friendly product; Carbon dioxide copolymer with efficient barrier makes this laminated film have the fabulous barrier to oxygen, carbon dioxide, moisture as barrier layer.
A kind of preparation method of biaxial stretch-formed PLA laminated film of barrier, be made up of following steps:
A. prepare burden: two polylactic acid layers comprise following component in percentage by weight: crystalline polylactic acid 75%-100%, melt reinforcing agent 0%-5%, flexibilizer 0%-5%, antistatic additive 0%-5%, antioxidant 0%-5%, slipping agent 0%-5%, antiblocking agent 0%-5%; Barrier layer: complete biodegradable also has the carbon dioxide copolymer 100% of barrier properties for gases;
B. plasticizing: will prepare burden adds corresponding extruder respectively and between 150 ℃-230 ℃, carries out fusion, plasticizing; Melt confluxes in T type or rack type die through filtering and metering, is evenly distributed to film lip each point; Form melt films, die head temperature is between 160 ℃-230 ℃;
C. cast sheet: cool off on the sharp cooling roll surface of melt films between 15 ℃-50 ℃, forms diaphragm;
D. stretch one by one: diaphragm after preheating between 40 ℃-90 ℃, longitudinal stretching between 40 ℃-90 ℃, thermal finalization between 20 ℃-90 ℃; Draw ratio is 1-5 times; Film behind the longitudinal stretching after preheating between 40 ℃-120 ℃, cross directional stretch between 40 ℃-120 ℃, thermal finalization between 50 ℃-160 ℃, draw ratio be 2-7 doubly;
G. corona or flame treatment;
H. rolling.
The present invention also provides other a kind of preparation method, and this method is made up of following steps successively:
A. prepare burden: wherein two polylactic acid layers comprise following component in percentage by weight: crystalline polylactic acid 75%-100%, melt reinforcing agent 0%-5%, flexibilizer 0%-5%, antistatic additive 0%-5%, antioxidant 0%-5%, slipping agent 0%-5%, antiblocking agent 0%-5%; Barrier layer is complete biodegradable and the carbon dioxide copolymer 100% with barrier properties for gases;
B. plasticizing: will prepare burden adds corresponding extruder respectively and between 150 ℃-230 ℃, carries out fusion, plasticizing; Melt confluxes in T type or rack type die through filtering and metering, is evenly distributed to film lip each point; Form melt films, die head temperature is between 160 ℃-230 ℃;
C. cast sheet: cool off on the sharp cooling roll surface of melt films between 15 ℃-50 ℃, forms diaphragm;
D. synchro-draw: diaphragm carries out vertical, horizontal simultaneously and stretches after preheating between 40 ℃-120 ℃ between 40 ℃-120 ℃, thermal finalization between 50 ℃-160 ℃, and total draw ratio is 6-25 times;
E. corona or flame treatment;
F. rolling.
What preparation method of composite film of the present invention adopted is one by one multi-layer co-extruded or biaxial stretch-formed in the same way technology.Batching is carried out fusion, plasticizing by different extruders respectively between 150-230 ℃, melt-flow becomes melt films through T type or rack type die; Melt films is cooled off on slab roller and is formed diaphragm, even compact is arranged contacts in order to guarantee diaphragm and slab roller, can use electrostatic adsorption device, and according to the demand of different product, chilling temperature can be provided with between 15 ℃-50 ℃.
The present invention can adopt one by one biaxial stretch-formed method or synchronous twin shaft drawing process; In biaxial stretch-formed preparation film one by one; Diaphragm earlier gets into longitudinal tensile fixture through deflector roll, longitudinal tensile fixture by preheating roller tube, stretching roller, shaping roller tube, wear chip system, heating system, rotation system etc. and form.Evenly preheating in the scope of diaphragm between 40-90 ℃ makes diaphragm softening, reaches draft temperature, on the draw roll of one or more groups different rates, carries out longitudinal stretching, and draft temperature is between 40-90 ℃; Cooling between 20-90 ℃ increases film dimensions stability.Diaphragm gets into the cross directional stretch device through guide roller then, and lateral means comprises four sections of preheating, stretching, typing and coolings.Diaphragm by 2 in the same way, the motion of synchronous chain folder, preheating between 40-120 ℃, cross directional stretch between 40-120 ℃, thermal finalization between 50-160 ℃, thermal finalization mainly are to eliminate internal stress, increase degree of crystallinity, increase film dimensions stability.
In synchronous biaxial stretch-formed preparation film, diaphragm will be clamped motion by the chain in the stretching device, through preheating, stretching, typing, heat treatment four districts, carry out vertical and horizontal earlier and will stretch simultaneously, and the stretch rate of both direction is close, then through thermal finalization and heat treatment.Draft temperature is between 40 ℃-120 ℃, and thermal finalization is between 50 ℃-160 ℃, and the film of this prepared has harmonious preferably.
As stretching condition, can be doubly along longitudinal stretching 1-5, cross directional stretch 2-7 doubly considers that from the intensity and the thickness and precision aspect of film need take all factors into consideration longitudinal stretching multiple and cross directional stretch multiple, general preferred stretching general times is 6-25 times in addition.
In addition, in biaxial stretch-formed technology, draft temperature and draw ratio be not in being provided with scope the time, and resulting film thickness precision significantly reduces, and particularly after stretching, carries out in the heat treated film, and this tendency is more remarkable.Film printing or with the compound secondary operations of other films in, the serious uneven of product thickness can produce open defects such as wrinkle, waveform.
Corona treatment plant or flame treatment device are the parts in traction rolling zone, and corona treatment mainly is to improve the wetting tension of film surface, help the downstream processing such as printing, heat-sealing on the film surface.
The above-mentioned laminated film that processes through after drawing, to taking-up equipment, can be prepared the biaxial stretch-formed PLA laminated film of barrier according to the production requirement rolling.
The preparation method of laminated film of the present invention, production technology is simple, has practiced thrift cost; Adopt biaxial stretch-formed one by one method or synchronous twin shaft drawing process; Control draft temperature and draw ratio are in particular range; The laminated film for preparing is had than high-tensile, punctured resistance, high-stiffness; Also have twist together preferably retentivity and wetting tension persistence, and its thickness is even, thickness and precision is higher.
The specific embodiment
Through the specific embodiment the present invention is described below, but following embodiment is not to qualification of the present invention.
Embodiment 1
A kind of biaxial stretch-formed PLA laminated film of barrier comprises the barrier layer that two polylactic acid layers are middle with being located at two polylactic acid layers, and total film thickness is 40 μ m, and polylactic acid layers thickness is 15 μ m, and barrier layer thickness is 10 μ m.This each layer of film comprises following composition by weight percentage, two polylactic acid layers: crystalline polylactic acid 85%, melt reinforcing agent 3%, flexibilizer 2%, antistatic additive 2%, antioxidant 2%, slipping agent 3%, antiblocking agent 3%; Barrier layer: the inorganic modified thing 100% of poly (propylene carbonate).
The preparation method of this PLA laminated film may further comprise the steps:
To be placed on respectively in the hopper of corresponding separately three extruders through three layers of batching of online drying, suitable temperature (PLA is provided with temperature and is no more than 230 ℃, and the poly (propylene carbonate) modifier is provided with temperature and is no more than 180 ℃) is set; Polymer carries out fusion, plasticizing; Melt confluxes in die head (T type or clothes hanger type) lining through filtering and metering, is evenly distributed to film lip each point; Form melt films, die head temperature is arranged between 160 ℃-230 ℃;
Melt films is cooled off on 15 ℃-50 ℃ sharp cooling roll surface, forms diaphragm;
Then diaphragm is carried out one by one or synchro-draw technology: in biaxial stretch-formed technology one by one; Diaphragm elder generation longitudinal stretching, preheat temperature is set between 40 ℃-90, and draft temperature is set between 40 ℃-90 ℃; Thermal finalization is set between 20 ℃-90 ℃, and draw ratio is 1-5 times; Carry out cross directional stretch then, preheat temperature is set in 40 ℃-120 ℃, and draft temperature is set in 40-120 ℃, and heat setting temperature is set in 50 ℃-160 ℃, and draw ratio is 2-7 times; In synchronous twin shaft drawing process, the diaphragm preheat temperature is set between 40 ℃-120 ℃, between 40 ℃-120 ℃, carries out vertical, horizontal simultaneously and stretches, and between 50 ℃-160 ℃, carries out thermal finalization, and vertical, horizontal stretching general times is 6-25 times;
Film carries out corona treatment, traction, rolling.
Adopt the present embodiment manufactured thin film, have fabulously, have, also have twist together preferably retentivity and wetting tension persistence than high-tensile, punctured resistance, high-stiffness to oxygen and carbon dioxide barrier.
Embodiment 2
A kind of biaxial stretch-formed PLA laminated film of barrier comprises four-layer structure, is made up of hot sealing layer, polylactic acid layers, barrier layer and polylactic acid layers successively, and total film thickness is 50 μ m, and hot sealing layer is 3 μ m, and polylactic acid layers is 18 μ m, and barrier layer is 11 μ m.This each layer of film comprises following composition by weight percentage, two polylactic acid layers: crystalline polylactic acid 86%, melt reinforcing agent 2%, flexibilizer 3%, antistatic additive 2%, antioxidant 3%, slipping agent 1%, antiblocking agent 3%; Barrier layer: the inorganic modified thing 100% of poly (propylene carbonate); Hot sealing layer: noncrystalline PLA 95%, antitack agent 3%, antioxidant 2%.
The preparation method of this PLA laminated film compares with embodiment 1, is used for fusion, plastifies the hot sealing layer batching that has more except that having more an extruder, and all the other steps are with embodiment 1.
Compare with embodiment 1, film has added hot sealing layer, makes film have the envelope performance that temperature is low, heat seal strength is high.
Embodiment 3
A kind of biaxial stretch-formed PLA laminated film of barrier comprises five-layer structure, is made up of hot sealing layer, polylactic acid layers, barrier layer, metal receiving layer and aluminium coated successively.Total film thickness is at 60 μ m, and hot sealing layer is 3 μ m, and skin is 35 μ m, and barrier layer is 20 μ m, metal receiving layer 2 μ m.This each layer of film comprises following composition, skin by weight percentage: crystalline polylactic acid 75%, and melt reinforcing agent 5%, flexibilizer 5%, antistatic 4%, antioxidant 4%, slipping agent 3%, antiblocking agent 4%; Barrier layer: the inorganic modified thing 100% of poly (propylene carbonate); Hot sealing layer: amorphism PLA 96%, antitack agent 2%, antioxidant 2%; Metal receiving layer: amorphism PLA 95%, antitack agent 3%, antioxidant 2%.
The preparation method of this PLA laminated film is used for fusion, plastifies the metal receiving layer batching that has more except that having more an extruder, and all the other steps are with embodiment 2, and in addition, when aluminizing, vacuum pressure is arranged on 10
3Mbar, thickness is at the 300-500 dust.
Compare with embodiment 2, film has added aluminium coated, makes film have the performance of extremely excellent obstruct steam, oxygen, carbon dioxide.
Claims (8)
1. the biaxial stretch-formed PLA laminated film of a barrier is characterized in that, is made up of the barrier layer that two polylactic acid layers are middle with being located at two polylactic acid layers; Said polylactic acid layers comprises following component in percentage by weight: crystalline polylactic acid 75%-100%, melt reinforcing agent 0%-5%, flexibilizer 0%-5%; Antistatic additive 0%-5%; Antioxidant 0%-5%, slipping agent 0%-5%, antiblocking agent 0%-5%; Said barrier layer is complete biodegradable and the carbon dioxide copolymer with barrier properties for gases.
2. the biaxial stretch-formed PLA laminated film of a kind of barrier according to claim 1 is characterized in that, the molecular weight of said crystalline polylactic acid is 100,000-300,000, water content＜0.02%.
3. the biaxial stretch-formed PLA laminated film of a kind of barrier according to claim 1 is characterized in that, said complete biodegradable and the carbon dioxide copolymer with barrier properties for gases are propylene carbonate PPC.
4. the biaxial stretch-formed PLA laminated film of a kind of barrier according to claim 1 is characterized in that, the polylactic acid layers of said laminated film is outer can add hot sealing layer and/or metal receiving layer.
5. the biaxial stretch-formed PLA laminated film of a kind of barrier according to claim 4 is characterized in that, said metal receiving layer is outer can to add aluminium coated.
6. the biaxial stretch-formed PLA laminated film of a kind of barrier according to claim 1 is characterized in that, the gross thickness of said laminated film is 20 μ m-120 μ m, and outer layer thickness is 2 μ m-118 μ m, and barrier layer thickness is 2 μ m-116 μ m.
7. the preparation method of the biaxial stretch-formed PLA laminated film of a kind of barrier according to claim 1 is characterized in that, this method is made up of following steps successively:
A. prepare burden: wherein two polylactic acid layers comprise following component in percentage by weight: crystalline polylactic acid 75%-100%, melt reinforcing agent 0%-5%, flexibilizer 0%-5%, antistatic additive 0%-5%, antioxidant 0%-5%, slipping agent 0%-5%, antiblocking agent 0%-5%; Barrier layer is complete biodegradable and the carbon dioxide copolymer 100% with barrier properties for gases;
B. plasticizing: will prepare burden adds corresponding extruder respectively and between 150 ℃-230 ℃, carries out fusion, plasticizing; Melt confluxes in T type or rack type die through filtering and metering, is evenly distributed to film lip each point; Form melt films, die head temperature is between 160 ℃-230 ℃;
C. cast sheet: cool off on the sharp cooling roll surface of melt films between 15 ℃-50 ℃, forms diaphragm;
D. stretch one by one: diaphragm is after preheating between 40 ℃-90 ℃, and longitudinal stretching between 40 ℃-90 ℃, draw ratio are 1-5 times; Thermal finalization between 20 ℃-90 ℃; Film behind the longitudinal stretching is after preheating between 40 ℃-120 ℃, and cross directional stretch between 40 ℃-120 ℃, draw ratio are 2-7 times; Thermal finalization between 50 ℃-160 ℃;
E. corona or flame treatment;
F. rolling.
8. the preparation method of the biaxial stretch-formed PLA laminated film of a kind of barrier according to claim 1 is characterized in that, this method is made up of following steps successively:
A. prepare burden: wherein two polylactic acid layers comprise following component in percentage by weight: crystalline polylactic acid 75%-100%, melt reinforcing agent 0%-5%, flexibilizer 0%-5%, antistatic additive 0%-5%, antioxidant 0%-5%, slipping agent 0%-5%, antiblocking agent 0%-5%; Barrier layer is complete biodegradable and the carbon dioxide copolymer 100% with barrier properties for gases;
B. plasticizing: will prepare burden adds corresponding extruder respectively and between 150 ℃-230 ℃, carries out fusion, plasticizing; Melt confluxes in T type or rack type die through filtering and metering, is evenly distributed to film lip each point; Form melt films, die head temperature is between 160 ℃-230 ℃;
C. cast sheet: cool off on the sharp cooling roll surface of melt films between 15 ℃-50 ℃, forms diaphragm;
D. synchro-draw: diaphragm carries out vertical, horizontal simultaneously and stretches after preheating between 40 ℃-120 ℃ between 40 ℃-120 ℃, thermal finalization between 50 ℃-160 ℃, and total draw ratio is 6-25 times;
E. corona or flame treatment;
F. rolling.
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