CN109720055A - Polyving alcohol/polylactic acid laminated film and preparation method thereof - Google Patents
Polyving alcohol/polylactic acid laminated film and preparation method thereof Download PDFInfo
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- CN109720055A CN109720055A CN201711039309.1A CN201711039309A CN109720055A CN 109720055 A CN109720055 A CN 109720055A CN 201711039309 A CN201711039309 A CN 201711039309A CN 109720055 A CN109720055 A CN 109720055A
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Abstract
The present invention relates to polyvinyl alcohol film fields, and in particular, to polyving alcohol/polylactic acid laminated film and preparation method thereof.The polyving alcohol/polylactic acid laminated film includes polyvinyl alcohol film layer and polylactic acid film layer, wherein the polyvinyl alcohol film layer is formed by polyvinyl alcohol compositions, which contains polyvinyl alcohol, plasticizer, lubricant and optional auxiliary agent；The plasticizer contains component A, component B and component C；The component A is one of glycerine, ethylene glycol, polyethylene glycol and pentaerythrite or a variety of；The component B is one of magnesium chloride, magnesium nitrate, calcium chloride, copper sulphate and sodium acetate or a variety of；The component C is water.The present invention enables to the polyvinyl alcohol of wider alcoholysis degree range to be film-made through biaxial tension, and resulting polyving alcohol/polylactic acid laminated film not only has biodegradable, also has excellent mechanical strength and barrier property.
Description
Technical field
The present invention relates to polyvinyl alcohol film fields, and in particular, to polyving alcohol/polylactic acid laminated film and its preparation
Method.
Background technique
Polyvinyl alcohol (PVA) be a kind of water soluble polymer and industrialized production few in number can
The non-petroleum base high molecular material prepared from natural gas and coal, application range add throughout weaving, food, medicine, building, timber
The fields such as work, papermaking, printing, agricultural, steel, macromolecule chemical industry.The acid and alkali-resistance and organic solvent resistance of PVA is excellent, biology
Compatibility is good, biodegradable, and PVA film has excellent oxygen barrier property, impact flexibility and puncture resistance, but ruler
Very little stability and environmental stability are poor.
Polyvinyl alcohol is because there are polyhydroxy structure, making its intramolecular and intermolecular producing very strong hydrogen on its strand
Key causes its fusing point and decomposition temperature close, is difficult thermoplastic processing, therefore its application is main at present or is based on solwution method work
Skill.Solution casting method is the common method for industrially preparing PVA film, and there is complex steps, film strength difference etc. for the method
Disadvantage.The high production efficiency of biaxial tension method, and obtained thin film mechanics intensity, optical property and the thickness uniformity are more preferably,
But film forming is influenced significantly by process condition fluctuations, film stretch process difficulty is big, has for film raw material higher
It is required that.And due to the particularity of PVA processing, there are no the biaxial tension method process system researchs for PVA.
There are some researchs for PVA plasticising at present, it is desirable to which the plasticity that PVA is improved by the means such as being copolymerized, being blended makes it
It is able to carry out thermoplasticity processing, to reduce its preparation cost, expands its use scope, but the research for thermoplasticity PVA film
Also seldom.It is more at present be all design using melt-processed method prepare PVA film (such as CN106189010A,
CN106189008A, CN101864132A and CN102391598A etc.), but it is all made of the tape casting or blowing prepares film,
Both methods prepares film and comparatively requires raw material and technique all relatively low, and the performance of film is also compared with biaxial tension method
Difference.
CN106189006A proposes to prepare PVA film using biaxial tension method, but its method need to use 95 (mol) %
The PVA raw material of≤alcoholysis degree < 99.9 (mol) %, it is relatively narrow for the applicability of PVA；And the tensile strength of resulting PVA film
It improves limited.
Summary of the invention
The purpose of the present invention is to provide a kind of novel polyving alcohol/polylactic acid laminated films and preparation method thereof, should
Polyving alcohol/polylactic acid laminated film is compound by polyvinyl alcohol film and the extraordinary polylactic acid film of biocompatibility, can
Higher biodegradable is obtained, and also there is excellent mechanical strength and barrier property.
To achieve the goals above, one aspect of the present invention provides a kind of polyving alcohol/polylactic acid laminated film, the THIN COMPOSITE
Film includes polyvinyl alcohol film layer and polylactic acid film layer, wherein the polyvinyl alcohol film layer is by polyvinyl alcohol compositions shape
At the polyvinyl alcohol compositions contain polyvinyl alcohol, plasticizer, lubricant and optional auxiliary agent；The plasticizer contains component
A, component B and component C；The component A is one of glycerine, ethylene glycol, polyethylene glycol and pentaerythrite or a variety of；It is described
Component B is one of magnesium chloride, magnesium nitrate, calcium chloride, copper sulphate and sodium acetate or a variety of；The component C is water.
Second aspect of the present invention provides a kind of preparation method of polyving alcohol/polylactic acid laminated film, which is characterized in that should
Method includes:
(1) polyvinyl alcohol film is provided, the preparation of the polyvinyl alcohol film includes:
(a) first material of polyvinyl alcohol compositions ingredient is provided；The polyvinyl alcohol compositions as determined above
Justice；
(b) first material is subjected to melting extrusion and is cast slab, obtain polyvinyl alcohol slab；
(c) polyvinyl alcohol slab is subjected to biaxial tension to form a film, obtains polyvinyl alcohol film；
(2) polylactic acid film is provided, the preparation of the polylactic acid film includes:
(A) second material containing polylactic acid is provided；
(B) second material is subjected to melting extrusion and is cast slab, obtain polylactic acid slab；
(C) polylactic acid slab is subjected to biaxial tension to form a film, obtains polylactic acid film；
(3) polyvinyl alcohol film and polylactic acid film progress is compound, obtain polyving alcohol/polylactic acid THIN COMPOSITE
Film.
Third aspect present invention provides a kind of polyving alcohol/polylactic acid laminated film prepared by the above method.
The present invention enables to the polyvinyl alcohol of wider alcoholysis degree range to be film-made through biaxial tension, and resulting polyethylene
Alcohol/polylactic acid laminated film not only has biodegradable, also has excellent mechanical strength and barrier property.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of polyving alcohol/polylactic acid laminated film, which includes that polyvinyl alcohol is thin
Film layer and polylactic acid film layer, wherein the polyvinyl alcohol film layer is formed by polyvinyl alcohol compositions, polyvinyl alcohol combination
Object contains polyvinyl alcohol, plasticizer, lubricant and optional auxiliary agent；The plasticizer contains component A, component B and component C；Institute
Stating component A is one of glycerine, ethylene glycol, polyethylene glycol and pentaerythrite or a variety of；The component B is magnesium chloride, nitre
One of sour magnesium, calcium chloride, copper sulphate and sodium acetate are a variety of；The component C is water.
According to the present invention, the content of the component A, component B and component C can change in a wider range, in order to obtain
It is more conducive to improve the mechanical property and barrier property of polyvinyl alcohol film, and obtains and enable resulting polyvinyl alcohol film
It is enough preferably compound with polylactic acid film, it is preferable that the weight ratio of the component A, component B and component C are 20-500:100:
80-500, preferably 30-300:100:100-300, for example, 50-200:100:120-250,80-150:100:150-200.
According to the present invention, the average molecular weight that the polyethylene glycol in the component A has is preferably 200-400.Described group
Dividing A is preferably one of glycerine, the polyethylene glycol that average molecular weight is 200-400 and pentaerythrite or a variety of.
Preferably, the component B is one of magnesium chloride, magnesium nitrate and calcium chloride or a variety of.
In a preferred embodiment of the invention, the component A is glycerine and/or number-average molecular weight is 200-
400 polyethylene glycol, the component B are magnesium chloride and/or magnesium nitrate；Alternatively, the component A is pentaerythrite, the component B
For calcium chloride.
According to the present invention, in order to obtain mechanical property and the higher polyvinyl alcohol film of barrier property, it is preferable that described poly-
The weight ratio of vinyl alcohol and plasticizer is 100:5-40, preferably 100:10-30, more preferably 100:15-25.Preferably, institute
The weight ratio for stating polyvinyl alcohol and lubricant is 100:0.5-5, preferably 100:1-3.
Wherein, polyvinyl alcohol compositions of the invention are suitable for the polyethylene of wider range alcoholysis degree, the degree of polymerization and partial size
Alcohol, it is preferable that the alcoholysis degree of the polyvinyl alcohol is 80-99mol%, and the degree of polymerization is 1500 or more (preferably 1500-2500),
Partial size is 90-500 μm.The polyvinyl alcohol of low alcoholysis level is also suitable, such as the alcoholysis degree of the polyvinyl alcohol is 80-
90mol%, degree of polymerization 1600-1800, partial size are 100-300 μm.The polyvinyl alcohol of high alcoholysis degree is also suitable, such as institute
The alcoholysis degree for stating polyvinyl alcohol is 95-99mol%, and degree of polymerization 1700-2500, partial size is 320-400 μm.
According to the present invention, the lubricant can be selected from a variety of lubricants, it is preferable that the lubricant is poly-
Glycols lubricant, fluoropolymer series lubricant agent, organic silicon lubricant, fatty alcohol type emollients, fatty acid lubrication
Agent, fatty acid ester type emollients, stearic amide series lubricant agent, fatty acid metal soaps lubricant, alkane and oxidation of alkanes class
One of lubricant and micro-and nano-particles series lubricant agent are a variety of.
Wherein, the polyethylene glycol series lubricant agent for example can be the PEG molecule that average molecular weight is 500-50000,
It can also pass through other chemical modifications or physical modification by sealing end, grafting, crosslinking Treatment.
Wherein, the fluoropolymer series lubricant agent for example can be polytetrafluoroethylene (PTFE), Kynoar, polyhexafluoropropylene
At least one of Deng, or other unimodal or multimodal fluoropolymers and crystallization or hemicrystalline fluoropolymer
Object.
Wherein, the organo-silicic oil can be existing various using carbon, silicon atom as molecular backbone, with methyl, benzene
The oligomer or oligomer of the organic groups such as base, alkoxy, vinyl are the compound of side chain.
Wherein, the fatty alcohol type emollients for example can in soft fat alcohol, tallow alcohol, tallow fatty alcohol etc. extremely
Few one kind.
Wherein, the fatty acid lubricant for example can be with stearic acid and/or 12- hydroxy stearic acid.
Wherein, the fatty acid ester type emollients for example can be butyl stearate, stearic acid list glycerolipid, palmitinic acid ten
At least one of six Arrcostabs, tearyl base ester etc..
Wherein, the stearic amide series lubricant agent for example can be stearic amide, oleamide, erucyl amide, n,
At least one of n- ethylene bis stearic acid amide (EBS) etc..
Wherein, the fatty acid metal soaps lubricant for example can be lead stearate, calcium stearate, magnesium stearate, conjunction
At at least one of calcium acetate etc..
Wherein, the alkane and oxidation of alkanes series lubricant agent for example can for atoleine, solid paraffin, polyethylene wax,
At least one of polypropylene wax, ethylene oxide wax etc..
Wherein, the micro-and nano-particles series lubricant agent for example can be powdered rubber and/or aerosil particles.
According to the present invention, the polyvinyl alcohol compositions can also contain auxiliary agent, and the auxiliary agent can be for polyvinyl alcohol
Other performances of film have a gain effect, and will not stretching film forming to polyvinyl alcohol film, mechanical property and barrier property produce
The additive of raw detrimental effect.The auxiliary agent can be for example one of antioxidant, acid absorbent, antistatic agent and antitack agent
Or it is a variety of.
Wherein, the antioxidant for example can be antioxidant 1010, antioxidant 1076, antioxidant 164, irgasfos 168, resist
At least one of oxygen agent 264 etc..The content of the antioxidant can change in a wider range, the institute relative to 100 parts by weight
Polyvinyl alcohol is stated, the content of the antioxidant is preferably 0.1-1 parts by weight.
Wherein, the acid absorbent can be for example at least one of hydrotalcite, calcium stearate, zinc stearate etc..The suction
The content of sour agent can change in a wider range, relative to the polyvinyl alcohol of 100 parts by weight, the content of the acid absorbent
Preferably 0.1-1 parts by weight.
Wherein, the antistatic agent for example can be sweet for ethoxylated alkylamine, ethoxylated alkyl acid amide, monostearate
At least one of grease, sodium alkyl sulfonate etc..The content of the antistatic agent can change in a wider range, relative to 100
The polyvinyl alcohol of parts by weight, the content of the antistatic agent are preferably 0.1-1 parts by weight.
Wherein, the antitack agent for example can be in silica, calcium carbonate, diatomite, talcum powder, glass microballoon etc.
It is at least one.The content of the antitack agent can change in a wider range, relative to the polyvinyl alcohol of 100 parts by weight, institute
The content for stating antitack agent is preferably 0.1-1 parts by weight.
According to the present invention, the polyving alcohol/polylactic acid laminated film further includes polylactic acid film layer, wherein polylactic acid
It (PLA) is a kind of bio-based polymers, it derives from reproducible natural resources, has good biocompatibility and completely life
Biodegradable performance, preferable physical mechanical property and processing performance are suitable for processing injected articles, foamed material, film, fibre
Dimension etc., is mainly used in biological medicine and food packaging applications.PLA film have high strength and modulus, good stability of the dimension, but
It is that oxygen barrier property is very poor.The present invention is compound by the progress of polyving alcohol/polylactic acid film, can both guarantee the excellent of the two
Compatibility, and the performance complement of the two can be made, thus compound composite membrane can have more comprehensively more balanced performance.This
Outside, polyving alcohol/polylactic acid laminated film will have good biodegradable performance, more convenient for the processing of film, more
Safety and environmental protection.Avoid the problems such as recycling problem or incomplete degradation with the Film laminated bring of other type materials.
In accordance with the present invention it is preferred that the polylactic acid film layer is formed by poly (lactic acid) composition, the poly (lactic acid) composition
Contain polylactic acid and modified additive.
Wherein, the polylactic acid can use multiple choices, it is preferable that the molecular weight of the polylactic acid is 100,000-20 ten thousand D
Using the polylactic acid of the molecular weight ranges rupture of membranes problem can will not occur under higher stretching ratio for (dalton), and also
It can guarantee certain processing performance.Such polylactic acid can be obtained by the usual manner of this field, such as can be commercially available product,
It can also be made using the conventional method of this field, there is no particular limitation to this by the present invention.
According to the present invention, the modified additive is preferably polyethylene glycol, polyglycereol, pentaerythrite, stearic acid, stearic acid
One of salt, butyl stearate, glyceryl monostearate, stearic amide, ethylene bis stearamide and oxidic polyethylene or
A variety of, more preferably one of polyethylene glycol, ethylene bis stearamide and glyceryl monostearate or a variety of are further excellent
It is selected as the polyethylene glycol that average molecular weight is 200-20000, preferably 5000-8000.
In accordance with the present invention it is preferred that the polylactic acid and the weight ratio of modified additive are 100:3-6.
According to the present invention, the poly (lactic acid) composition can also containing the additive of polylactic acid film preparation field routine,
Such as can be heat stabilizer, light stabilizer, pigment etc., specific type and additional amount are conventional selection, and the present invention is herein
It repeats no more.
According to the present invention, the polyvinyl alcohol film layer and polylactic acid film in the polyving alcohol/polylactic acid laminated film
The thickness of layer can change in a wider range, it is preferable that the polyvinyl alcohol film layer (single layer) and polylactic acid film layer are (single
Layer) thickness ratio be 1:0.4-0.8.Wherein, the thickness of the polyvinyl alcohol film layer (single layer) for example can be 20-30 μm,
The thickness of the polylactic acid film layer (single layer) for example can be 8-25 μm.The polyvinyl alcohol that the laminated film can be single layer is thin
The polylactic acid film of film and single layer carries out compound obtained laminated film, is also possible to the poly- of multilaminar polyethylene alcohol film and multilayer
Lactic acid film carries out compound obtained laminated film, and preferably sandwich layer is polyvinyl alcohol film layer and upper layer is that polylactic acid is thin
Three layers of laminated film of film.
Second aspect of the present invention provides a kind of preparation method of polyving alcohol/polylactic acid laminated film, which is characterized in that should
Method includes:
(1) polyvinyl alcohol film is provided, the preparation of the polyvinyl alcohol film includes:
(a) first material of polyvinyl alcohol compositions ingredient is provided；The polyvinyl alcohol compositions as determined above
Justice；
(b) first material is subjected to melting extrusion and is cast slab, obtain polyvinyl alcohol slab；
(c) polyvinyl alcohol slab is subjected to biaxial tension to form a film, obtains polyvinyl alcohol film；
(2) polylactic acid film is provided, the preparation of the polylactic acid film includes:
(A) second material containing polylactic acid is provided；
(B) second material is subjected to melting extrusion and is cast slab, obtain polylactic acid slab；
(C) polylactic acid slab is subjected to biaxial tension to form a film, obtains polylactic acid film；
(3) polyvinyl alcohol film and polylactic acid film progress is compound, obtain polyving alcohol/polylactic acid THIN COMPOSITE
Film.
According to the present invention, the polyvinyl alcohol compositions are as described previously, and details are not described herein the present invention.
According to the present invention, the step of preparing polyvinyl alcohol film in (1), step (a) is mainly to provide above-mentioned polyethylene
The mixture of alcohol composition ingredient, in order to which subsequent processing forms polyvinyl alcohol film.Preferably, step (a) includes: elder generation
Polyvinyl alcohol and plasticizer are mixed, lubricant and optional auxiliary agent are then re-introduced into.It is highly preferred that by polyvinyl alcohol and
The condition that plasticizer is mixed includes: that temperature is 50-90 DEG C (preferably 60-80 DEG C), and the time is 0.5-4h (preferably 1-
2h)。
The mixed process, which can be, is first heated to 50-90 DEG C for polyvinyl alcohol, then introduces plasticizer and is 50- in temperature
90 DEG C of mixing 0.5-4h.Introducing for the plasticizer can be by the way of disposably feeding intake, can also be using the side that feed intake step by step
Formula, in order to improve the dispersion effect of plasticizer and polyvinyl alcohol, it is preferred to use the mode to feed intake step by step, it is preferable that the plasticising
Agent is added in 5-60min and is finished.
It according to the present invention,, can be with before adding lubricant and optional auxiliary agent after polyvinyl alcohol and plasticizer being mixed
The mixture of polyvinyl alcohol and plasticizer is first down to room temperature (such as 20-30 DEG C) and adds lubricant and optional auxiliary agent again, and
After be sufficiently mixed, obtain the mixture of above-mentioned composition ingredient.
According to the present invention, before carrying out step (b), the resulting mixture of step (a) can also be subjected to extruding pelletization and (squeezed
The temperature being granulated out is 100-200 DEG C), resulting master batch is used for the operation of step (b)；It is, of course, preferable to directly by step (a)
Resulting mixture carries out the processing of step (b), to reduce loss of material, especially reduces the loss of plasticizer.
According to the present invention, the second material is preferably the mixing of hereinbefore described poly (lactic acid) composition ingredient
Object.The poly (lactic acid) composition is as described previously, and details are not described herein the present invention.
According to the present invention, according to the present invention, the first material is carried out melting extrusion and is cast slab can be with for step (b)
It being carried out in casting machine, the second material is carried out melting extrusion and is cast slab to carry out in casting machine by step (B),
Preferably, in step (b), the temperature of the melting extrusion is 100-200 DEG C (preferably 110-160 DEG C)；The curtain coating slab
Curtain coating chilling roll temperature be 15-50 DEG C (preferably 20-40 DEG C).Preferably, in step (B), the temperature of the melting extrusion
For 150-220 DEG C (preferably 170-200 DEG C)；The curtain coating chilling roll temperature of the curtain coating slab is 30-70 DEG C of (preferably 50-
60℃)。
According to the present invention, the slab die head that the curtain coating slab uses can use single layer die, can also use multilayer
Structure composite die head, using multilayered structure compound tense, can only wherein one layer of (preferably sandwich layer) die head with above-mentioned poly- second is housed
The connection of the extruder hopper of enol composition or poly (lactic acid) composition can obtain the polyvinyl alcohol slab or poly- newborn of single layer in this way
Sour slab.
According to the present invention, in step (c) and step (C), the biaxial tension may include Synchronos method stretching or the method for fractional steps
It stretches.Wherein, the Synchronos method stretching refers to carrying out film longitudinal (MD) simultaneously and laterally (TD) is stretched, the substep farad
It stretches and refers to first carrying out film longitudinal stretching, then carry out film cross directional stretch.
Preferably, in step (c), it includes first preheating polyvinyl alcohol slab that the Synchronos method, which stretches, simultaneously then
MD and TD is carried out to stretch.Preferably, the condition that the Synchronos method stretches includes: that draft temperature is 120-170 DEG C, MD stretching ratio
For 3 times or more (for example, 3-6 times), TD stretching ratio is 3 times or more (for example, 3-6 times), MD rate of extension for 300%/s with
Upper (for example, 300%/s-500%/s), TD rate of extension are 300%/s or more (for example, 300%/s-500%/s)
Preferably, in step (c), the method for fractional steps stretching includes: first to preheat polyvinyl alcohol slab, then advanced
Row MD is stretched, then preheats then progress TD stretching.Preferably, the condition that the method for fractional steps stretches includes: that MD draft temperature is 80-
100 DEG C, TD draft temperature is 120-200 DEG C, and MD stretching ratio is 3 times or more (for example, 3-6 times), and TD stretching ratio is 3 times
(for example, 3-6 times) above, MD rate of extension are 100%/s or more (for example, 100%/s-200%/s), and TD rate of extension is
100%/s or more (for example, 100%/s-200%/s).
Preferably, in step (C), it includes first preheating polylactic acid slab that the Synchronos method, which stretches, then simultaneously into
Row MD and TD are stretched.Preferably, the condition that the Synchronos method stretches includes: that draft temperature is 70-90 DEG C, and MD stretching ratio is 3
Times or more (for example, 3-6 times), TD stretching ratio be 3 times or more (for example, 3-6 times), MD rate of extension be 300%/s or more
(for example, 300%/s-500%/s), TD rate of extension are 300%/s or more (for example, 300%/s-500%/s)
Preferably, in step (C), the method for fractional steps stretching includes: first to preheat polylactic acid slab, is then first carried out
MD is stretched, then preheats then progress TD stretching.Preferably, the condition that the method for fractional steps stretches includes: that MD draft temperature is 50-80
DEG C, TD draft temperature is 70-90 DEG C, and MD stretching ratio is 3 times or more (for example, 3-6 times), and TD stretching ratio is 3 times or more
(for example, 3-6 times), MD rate of extension are 100%/s or more (for example, 100%/s-200%/s), and TD rate of extension is
100%/s or more (for example, 100%/s-200%/s).
According to the present invention, this method can carry out annealing setting processing to the film after stretching, can also be fixed without this
Shape processing, in the case where carrying out setting processing namely this method further includes carrying out after step (c) and/or step (C) to resulting film
Setting of annealing is handled, and the temperature of the middle annealing setting processing of step (c) is preferably 180-200 DEG C, which shapes the time handled
Preferably 5-60s.The temperature of annealing setting processing is preferably 100-140 DEG C in step (C), and the time of annealing setting processing is excellent
It is selected as 5-30s.Carrying out annealing setting processing to the film after stretching can play the role of improving film dimensions stability.It can
To be selected from above-mentioned annealing set conditions each independently.
According to the present invention, this method can also include that resulting polyvinyl alcohol film and/or polylactic acid film are carried out surface
Sided corona treatment, cutting edge and winding processing, surface corona processing, cutting edge and winding processing are the operation of this field routine, this hair
It is bright that this, there is no particular limitation.
According to the present invention, in step (3) that the polyvinyl alcohol film and polylactic acid film progress is compound, it can be obtained poly-
Vinyl alcohol/polylactic acid laminated film.It may include that will first gather that polyvinyl alcohol film and polylactic acid film, which are carried out compound process,
Alcohol film and polylactic acid film are compound to obtain polyving alcohol/polylactic acid by laminating machine progress gluing, drying and hot pressing
Film.The polylactic acid film of polyvinyl alcohol film and single layer that the laminated film can be single layer carries out compound obtained THIN COMPOSITE
Film, the polylactic acid film for being also possible to multilaminar polyethylene alcohol film and multilayer carry out compound obtained laminated film, preferably core
Layer is polyvinyl alcohol film layer and upper layer is three layers of laminated film of polylactic acid film.Preferably, the polyvinyl alcohol is thin
The thickness ratio of film layer (single layer) and polylactic acid film layer (single layer) is 1:0.4-0.8.Wherein, the polyvinyl alcohol film layer is (single
Layer) thickness for example can be 20-30 μm, the thickness of the polylactic acid film layer (single layer) for example can be 8-25 μm.
Third aspect present invention provides a kind of polyving alcohol/polylactic acid laminated film prepared by the above method.
The resulting polyving alcohol/polylactic acid laminated film of the present invention has biodegradable, mechanics also with higher
Performance and barrier property, the MD tensile strength of the polyving alcohol/polylactic acid laminated film for example can be 80MPa or more, special
It is not 90MPa or more, preferably 100MPa or more, more preferably 100-180MPa；TD tensile strength for example can be 100MPa
More than, especially 120MPa or more, preferably 140MPa or more, more preferably 145-200MPa；Oxygen transmission rate for example can be
2.6cc·mil/m2It is hereinafter, preferably 2.5ccmil/m2It is hereinafter, more preferably 0.1-2.4ccmil/m2·
It.
Polyving alcohol/polylactic acid THIN COMPOSITE resulting for the polyvinyl alcohol of higher alcoholysis degree (for example, 95-99mol%)
For film, the MD tensile strength of the polyving alcohol/polylactic acid laminated film is 130MPa or more, preferably 150-170MPa；
TD tensile strength is 150MPa or more, preferably 160-200MPa；Oxygen transmission rate for example can be 2.2ccmil/m2It with
Under, preferably 0.3-2.2ccmil/m2It.
For the resulting polyving alcohol/polylactic acid THIN COMPOSITE of polyvinyl alcohol compared with low alcoholysis level (for example, 80-90mol%)
For film, the MD tensile strength of the polyving alcohol/polylactic acid laminated film for example can be 80MPa or more, especially 90MPa
More than, preferably 100MPa or more, more preferably 100-120MPa；TD tensile strength for example can be 100MPa or more, especially
It is 120MPa or more, preferably 140MPa or more, more preferably 145-155MPa；Oxygen transmission rate for example can be 2.6ccmil/
m2It is hereinafter, preferably 1.1-2.5ccmil/m2It.
The present invention will be described in detail by way of examples below.
In following example:
PEG200 is to recover the polyethylene glycol that the average molecular weight of fine chemistry industry research institute is 200 purchased from Tianjin.
PEG400 is to recover the polyethylene glycol that the average molecular weight of fine chemistry industry research institute is 400 purchased from Tianjin.
Tensile strength, elongation at break and the tensile modulus of elasticity of polyvinyl alcohol film are according to GB/T1040.3-2006
Specified in method measure；
The oxygen transmission rate of polyvinyl alcohol film is that the method according to specified in GB/T 19789-2005 (coulomb method) measures.
Plasticizer preparation example
By according to the formula in table 1, component A, component B and component C are proportionally mixed, corresponding plasticizer is obtained.
Table 1
Note: the above component A and component B is measured with the pure material of substance listed in table.
Embodiment 1
The present embodiment is for illustrating polyving alcohol/polylactic acid laminated film and preparation method thereof of the invention.
(1) preparation of polyvinyl alcohol film:
(a) by 100 weight account polyethylene alcohol, (alcoholysis degree 88mol%, the degree of polymerization 1700, are purchased from Shanxi three by 180 μm of partial size
Dimension group company) 60 DEG C are warming up to, the plasticizer E1 (finishing in 30min) of 15 parts by weight is gradually added dropwise；After finishing, temperature is protected
It holds and is stirred 1h at 50 DEG C.After naturally cooling to 30 DEG C, the Kynoar lubricant that 1 parts by weight are added is (public purchased from 3M
Take charge of the FX5911 trade mark) and 0.25 parts by weight antioxidant 1010 (purchased from Switzerland's vapour bar chemistry (China) Co., Ltd, the same below),
Polyvinyl alcohol compositions are obtained after mixing；
(b) polyvinyl alcohol compositions made from step (a) are added to the model LCR400's of Labtech company, Sweden
Melting extrusion is carried out in the sandwich layer extruder of multilayer extrusion casting machine and is cast slab, and the temperature that each section of melting extrusion is 110-
160 DEG C, curtain coating chilling roll temperature is 25 DEG C, thus obtains monolayer polyethylene alcohol slab；
(c) above-mentioned polyvinyl alcohol slab is put into the stretching clamp of film biaxial tension equipment, using two-way substep
Stretch film comprising: first polyvinyl alcohol slab is preheated, then first carries out MD stretching, then preheats then progress TD drawing
It stretches；Its condition includes: that the preceding preheating temperature of MD stretching is 90 DEG C, and MD draft temperature is 90 DEG C, and 3 times of MD stretching ratio, film MD is drawn
Stretching rate is 100%/s；Preheating temperature is 140 DEG C before TD is stretched, and TD draft temperature is 140 DEG C, and TD stretching ratio is 4 times, thin
Film TD rate of extension is 100%/s；Then the resulting film of biaxial tension is subjected to annealing setting processing 10s at 180 DEG C, obtained
The polyvinyl alcohol film for being 25 μm to average thickness.
(2) preparation of polylactic acid film:
(A) by 100 parts by weight polylactic acid (the model 3051D purchased from natural works company, the U.S.) and 4 parts by weight
Polyethylene glycol (average molecular weight purchased from Chinese medicines group company is 6000), which is sent, is stirred mixing 1min into high-speed mixer,
Obtain poly (lactic acid) composition；
(B) poly (lactic acid) composition made from step (A) is added to the more of the model LCR400 of Labtech company, Sweden
Melting extrusion is carried out in the sandwich layer extruder of layer extrusion casting machine and is cast slab, and the temperature that each section of melting extrusion is 170-200
DEG C, curtain coating chilling roll temperature is 50 DEG C, thus obtains single layer polylactic acid slab；
(C) above-mentioned polylactic acid slab is put into the stretching clamp of film biaxial tension equipment, is drawn using two-way substep
Stretch film comprising: first polylactic acid slab is preheated, then first carries out MD stretching, then preheats then progress TD stretching；Its
Condition include: MD stretch before preheating temperature be 65 DEG C, MD draft temperature be 65 DEG C, 3 times of MD stretching ratio, film MD rate of extension
For 100%/s；Preheating temperature is 83 DEG C before TD is stretched, and TD draft temperature is 83 DEG C, and TD stretching ratio is 4 times, and film TD is stretched
Rate is 100%/s；Then the resulting film of biaxial tension is subjected to annealing setting processing 15s at 120 DEG C, obtains average thickness
The polylactic acid film that degree is 15 μm.
(3) prepared by laminated film:
Above-mentioned prepared polyvinyl alcohol film and polylactic acid film are obtained by laminating machine by gluing, drying and hot pressing
Sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film, (poly- with a thickness of 55 μm
The thickness ratio of alcohol film layer and single layer polylactic acid film layer is 1:0.6).Gained laminated film performance is as shown in table 2.
Embodiment 2
The present embodiment is for illustrating polyving alcohol/polylactic acid laminated film and preparation method thereof of the invention.
(1) preparation of polyvinyl alcohol film:
(a) by 100 weight account polyethylene alcohol, (alcoholysis degree 85mol%, the degree of polymerization 1500, are purchased from Shanxi three by 200 μm of partial size
Dimension group company) 70 DEG C are warming up to, the plasticizer E2 (finishing in 25min) of 20 parts by weight is gradually added dropwise；After finishing, temperature is protected
It holds and is stirred 1.5h at 60 DEG C.After naturally cooling to 30 DEG C, the polyethylene glycol lubricant that 2 parts by weight are added (is purchased from Switzerland
Clariant Corporation, average molecular weight 10000), the irgasfos 168 (purchases of the antioxidant 1010 of 0.15 parts by weight and 0.25 parts by weight
From Switzerland vapour bar chemistry (China) Co., Ltd), polyvinyl alcohol compositions are obtained after mixing；
(b) polyvinyl alcohol compositions made from step (a) are added to the model LCR400's of Labtech company, Sweden
Melting extrusion is carried out in the sandwich layer extruder of multilayer extrusion casting machine and is cast slab, and the temperature that each section of melting extrusion is 110-
160 DEG C, curtain coating chilling roll temperature is 20 DEG C, thus obtains monolayer polyethylene alcohol slab；
(c) above-mentioned polyvinyl alcohol slab is put into the stretching clamp of film biaxial tension equipment, using two-way substep
Stretch film comprising: first polyvinyl alcohol slab is preheated, then first carries out MD stretching, then preheats then progress TD drawing
It stretches；Its condition include: MD stretch before preheating temperature be 100 DEG C, MD draft temperature be 100 DEG C, 4 times of MD stretching ratio, film MD
Rate of extension is 100%/s；Preheating temperature is 135 DEG C before TD is stretched, and TD draft temperature is 135 DEG C, and TD stretching ratio is 5 times,
Film TD rate of extension is 150%/s；The resulting film of biaxial tension is then subjected to annealing setting processing 8s at 200 DEG C,
Obtain the film that average thickness is 25 μm.
(2) preparation of polylactic acid film:
(A) by 100 parts by weight polylactic acid (the model 4032D purchased from natural works company, the U.S.) and 5 parts by weight
Polyethylene glycol (average molecular weight purchased from Chinese medicines group company is 5000), which is sent, is stirred mixing 1min into high-speed mixer,
Obtain poly (lactic acid) composition；
(B) poly (lactic acid) composition made from step (A) is added to the more of the model LCR400 of Labtech company, Sweden
Melting extrusion is carried out in the sandwich layer extruder of layer extrusion casting machine and is cast slab, and the temperature that each section of melting extrusion is 170-200
DEG C, curtain coating chilling roll temperature is 40 DEG C, thus obtains single layer polylactic acid slab；
(C) above-mentioned polylactic acid slab is put into the stretching clamp of film biaxial tension equipment, is drawn using two-way substep
Stretch film comprising: first polylactic acid slab is preheated, then first carries out MD stretching, then preheats then progress TD stretching；Its
Condition include: MD stretch before preheating temperature be 60 DEG C, MD draft temperature be 60 DEG C, 3 times of MD stretching ratio, film MD rate of extension
For 100%/s；Preheating temperature is 90 DEG C before TD is stretched, and TD draft temperature is 90 DEG C, and TD stretching ratio is 4 times, and film TD is stretched
Rate is 100%/s；Then the resulting film of biaxial tension is subjected to annealing setting processing 10s at 130 DEG C, obtains average thickness
The polylactic acid film that degree is 15 μm.
(3) prepared by laminated film:
Above-mentioned prepared polyvinyl alcohol film and polylactic acid film are obtained by laminating machine by gluing, drying and hot pressing
Sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film, (poly- with a thickness of 55 μm
The thickness ratio of alcohol film layer and single layer polylactic acid film layer is 1:0.6).Gained laminated film performance is as shown in table 2.
Embodiment 3
The present embodiment is for illustrating polyving alcohol/polylactic acid laminated film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that:
Step (a): using 25 parts by weight plasticizer E3 replace E1, lubricant using 1 parts by weight stearic acid list
Glyceride (is purchased from 163 trade mark of standing grain major company Atmer)；
Step (c): preheating temperature is 145 DEG C before TD is stretched, and TD draft temperature is 145 DEG C；
Finally obtain that sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；
Gained laminated film performance is as shown in table 2.
Embodiment 4-11
The present embodiment is for illustrating polyving alcohol/polylactic acid laminated film and preparation method thereof of the invention.
According to method described in embodiment 1, unlike, the plasticizer E4-E11 for the parts by weight such as being respectively adopted replaces E1,
Finally obtain that sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；Gained is compound
Film performance is as shown in table 2.
Embodiment 12
The present embodiment is for illustrating polyving alcohol/polylactic acid laminated film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, the dosage of the plasticizer is 5 parts by weight；
Finally obtain that sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；
Gained laminated film performance is as shown in table 2.
Embodiment 13
The present embodiment is for illustrating polyving alcohol/polylactic acid laminated film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, the dosage of the plasticizer is 35 parts by weight；
Finally obtain that sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；
Gained laminated film performance is as shown in table 2.
Embodiment 14
The present embodiment is for illustrating polyving alcohol/polylactic acid laminated film and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that:
Step (c) replaces method of fractional steps biaxial tension namely the behaviour of the Synchronos method biaxial tension using Synchronos method biaxial tension
Work includes: first to preheat polyvinyl alcohol slab, then carries out MD simultaneously and stretches and TD stretching；Its condition includes: preheating temperature
Degree is 130 DEG C, and draft temperature is 130 DEG C, and 3.5 times of MD stretching ratio, MD rate of extension is 300%/s, and TD stretching ratio is 3.5
Times, TD rate of extension is 400%/s；
Step (C) replaces method of fractional steps biaxial tension namely the behaviour of the Synchronos method biaxial tension using Synchronos method biaxial tension
Work includes: first to preheat polylactic acid slab, then carries out MD simultaneously and stretches and TD stretching；Its condition includes: preheating temperature
It is 83 DEG C, draft temperature is 83 DEG C, and 4 times of MD stretching ratio, MD rate of extension is 300%/s, and TD stretching ratio is 4 times, and TD is drawn
Stretching rate is 300%/s；
Finally obtain that sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；
Gained laminated film performance is as shown in table 2.
Embodiment 15
The present embodiment is for illustrating polyving alcohol/polylactic acid laminated film and preparation method thereof of the invention.
According to method as described in example 4, unlike, using the alcoholysis degree 99mol%, poly- purchased from Ningxia Neng Hua company
Right 2000 and 360 μm of partial size polyvinyl alcohol replace embodiment 4 in polyvinyl alcohol.
Finally obtain that sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；
Gained laminated film performance is as shown in table 2.
Embodiment 16
The present embodiment is for illustrating polyving alcohol/polylactic acid laminated film and preparation method thereof of the invention.
According to method described in embodiment 15, the difference is that:
Step (c) replaces method of fractional steps biaxial tension namely the behaviour of the Synchronos method biaxial tension using Synchronos method biaxial tension
Work includes: first to preheat polyvinyl alcohol slab, then carries out MD simultaneously and stretches and TD stretching；Its condition includes: preheating temperature
Degree is 160 DEG C, and draft temperature is 160 DEG C, and 3.5 times of MD stretching ratio, MD rate of extension is 300%/s, and TD stretching ratio is 3.5
Times, TD rate of extension is 400%/s；
Step (C) replaces method of fractional steps biaxial tension namely the behaviour of the Synchronos method biaxial tension using Synchronos method biaxial tension
Work includes: first to preheat polylactic acid slab, then carries out MD simultaneously and stretches and TD stretching；Its condition includes: preheating temperature
It is 83 DEG C, draft temperature is 83 DEG C, and 4 times of MD stretching ratio, MD rate of extension is 300%/s, and TD stretching ratio is 4 times, and TD is drawn
Stretching rate is 300%/s；
Finally obtain that sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；
Gained laminated film performance is as shown in table 2.
Embodiment 17
The present embodiment is for illustrating polyving alcohol/polylactic acid laminated film and preparation method thereof of the invention.
According to method described in embodiment 16, the difference is that, using the alcoholysis degree for being purchased from middle petrochemical industry Sichuan vinylon plant
97mol%, the degree of polymerization 1800 and 360 μm of partial size of polyvinyl alcohol replace the polyvinyl alcohol in embodiment 16.
Finally obtain that sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；
Gained laminated film performance is as shown in table 2.
Comparative example 1-5
According to method described in embodiment 1, unlike, the plasticizer DE1-DE5 for the parts by weight such as being respectively adopted replaces E1,
Rupture of membranes occurs in biaxial orientation process for comparative example 1-3, can not stretch, and is unable to get respective films, and comparative example 4-5 is finally obtained
Sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；Gained laminated film performance
As shown in table 2.
Comparative example 6-7
According to method described in embodiment 15, unlike, the plasticizer DE4-DE5 for the parts by weight such as being respectively adopted is replaced
E4, finally obtains that sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；Gained
Laminated film performance is as shown in table 2.
Comparative example 8
According to method described in embodiment 1, the difference is that, step (b) adds polyvinyl alcohol compositions made from step (a)
Enter in the sandwich layer extruder of the multilayer extrusion casting machine of the model LCR400 to Labtech company, Sweden and carries out melting extrusion simultaneously
Direct casting film-forming, the temperature that each section of melting extrusion are 110-160 DEG C, and curtain coating chilling roll temperature is 25 DEG C, are thus directly obtained
The curtain coating polyvinyl alcohol film that average thickness is 25 μm；The polyvinyl alcohol film and polylactic acid film progress is compound, final
To sandwich layer be polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；Gained THIN COMPOSITE film property
It can be as shown in table 2.
Comparative example 9
According to method described in embodiment 1, the difference is that, this comparative example uses the upper blowing method of DR.COLLIN company, Germany
Film blowing device extrusion and blow molding obtains polyvinyl alcohol film, and specific method is by polyvinyl alcohol compositions made from step (1)
It is added in the hopper of upper blowing method film blowing device extruder, raw material is after the abundant fusion plastification of extruder, by the annular mouth of head
Melt membrane tube is made in mould extrusion, after through compressed air inflation (blow-up ratio be 2.5 times), and it is poly- after vane is cooling blow molding to be made
Alcohol film, film are the single layer structure that average thickness is 25 μm；The polyvinyl alcohol film and polylactic acid film are answered
It closes, finally obtains that sandwich layer is polyvinyl alcohol film layer and upper layer is the three-decker laminated film of polylactic acid film；Gained
Laminated film performance is as shown in table 2.
Table 2
It can be seen that by the data of table 2 using plasticizer provided in the present invention, enable to wider alcoholysis degree range
Polyvinyl alcohol be film-made through biaxial tension, the polyvinyl alcohol biaxially oriented film and polylactic acid film have good compatibility,
Resulting polyving alcohol/polylactic acid laminated film is prepared with high-strength and high every property.Wherein, especially under preferred proportion,
MD and TD to tensile strength in 100MPa or more, oxygen transmission rate is 2.5ccmil/m2It is following.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (17)
1. a kind of polyving alcohol/polylactic acid laminated film, which is characterized in that the laminated film includes polyvinyl alcohol film layer and gathers
Lactic acid film layer, wherein the polyvinyl alcohol film layer is formed by polyvinyl alcohol compositions, which contains poly-
Vinyl alcohol, plasticizer, lubricant and optional auxiliary agent；The plasticizer contains component A, component B and component C；The component A is
One of glycerine, ethylene glycol, polyethylene glycol and pentaerythrite are a variety of；The component B is magnesium chloride, magnesium nitrate, chlorination
One of calcium, copper sulphate and sodium acetate are a variety of；The component C is water.
2. laminated film according to claim 1, wherein the weight ratio of the component A, component B and component C are 20-
500:100:80-500, preferably 30-300:100:100-300.
3. laminated film according to claim 1 or 2, wherein the component A is glycerine, average molecular weight 200-
One of 400 polyethylene glycol and pentaerythrite are a variety of；
The component B is one of magnesium chloride, magnesium nitrate and calcium chloride or a variety of.
4. laminated film described in any one of -3 according to claim 1, wherein described in the polyvinyl alcohol compositions
The weight ratio of polyvinyl alcohol and plasticizer is 100:5-40, preferably 100:10-30, more preferably 100:15-25；
Preferably, the weight ratio of the polyvinyl alcohol and lubricant is 100:0.5-5, preferably 100:1-3.
5. laminated film described in any one of -4 according to claim 1, wherein described in the polyvinyl alcohol compositions
The alcoholysis degree of polyvinyl alcohol is 80-99mol%, and the degree of polymerization is 1500 or more, and partial size is 90-500 μm；
Preferably, the alcoholysis degree of the polyvinyl alcohol is 80-90mol%, and degree of polymerization 1600-1800, partial size is 100-300 μ
m；
Preferably, the alcoholysis degree of the polyvinyl alcohol is 95-99mol%, and degree of polymerization 1700-2500, partial size is 320-400 μ
m。
6. laminated film described in any one of -5 according to claim 1, wherein the lubricant is polyethylene glycols lubrication
Agent, fluoropolymer series lubricant agent, organic silicon lubricant, fatty alcohol type emollients, fatty acid lubricant, fatty acid ester
Lubricant, stearic amide series lubricant agent, fatty acid metal soaps lubricant, alkane and oxidation of alkanes series lubricant agent and micro-nano
One of particle series lubricant agent is a variety of.
7. laminated film described in any one of -6 according to claim 1, wherein described in the polyvinyl alcohol compositions
Auxiliary agent is one of antioxidant, acid absorbent, antistatic agent and antitack agent or a variety of.
8. laminated film according to any one of claims 1-7, wherein the polylactic acid film layer is by polylactic acid group
It closes object to be formed, the poly (lactic acid) composition contains polylactic acid and modified additive；
Wherein, the molecular weight of the polylactic acid is 100,000-20 ten thousand D；
The modified additive is polyethylene glycol, polyglycereol, pentaerythrite, stearic acid, stearate, butyl stearate, stearic acid
One of monoglyceride, stearic amide, ethylene bis stearamide and oxidic polyethylene are a variety of, preferably polyethylene glycol,
One of ethylene bis stearamide and glyceryl monostearate are a variety of, and more preferably average molecular weight is 200-20000's
Polyethylene glycol；
Preferably, the polylactic acid and the weight ratio of modified additive are 100:3-6.
9. laminated film described in any one of -8 according to claim 1, wherein the polyvinyl alcohol film layer and polylactic acid
The thickness ratio of film layer is 1:0.4-0.8.
10. a kind of preparation method of polyving alcohol/polylactic acid laminated film, which is characterized in that this method comprises:
(1) polyvinyl alcohol film is provided, the preparation of the polyvinyl alcohol film includes:
(a) first material of polyvinyl alcohol compositions ingredient is provided；In the polyvinyl alcohol compositions such as claim 1-9
Defined in any one；
(b) first material is subjected to melting extrusion and is cast slab, obtain polyvinyl alcohol slab；
(c) polyvinyl alcohol slab is subjected to biaxial tension to form a film, obtains polyvinyl alcohol film；
(2) polylactic acid film is provided, the preparation of the polylactic acid film includes:
(A) second material containing polylactic acid is provided；
(B) second material is subjected to melting extrusion and is cast slab, obtain polylactic acid slab；
(C) polylactic acid slab is subjected to biaxial tension to form a film, obtains polylactic acid film；
(3) polyvinyl alcohol film and polylactic acid film progress is compound, obtain polyving alcohol/polylactic acid laminated film.
11. according to the method described in claim 10, wherein, the second material is polylactic acid group defined in claim 8
Close the mixture of object ingredient.
12. according to the method described in claim 10, wherein, step (a) includes: first to mix polyvinyl alcohol and plasticizer
It closes, is then re-introduced into lubricant and optional auxiliary agent；
Wherein, by the condition that polyvinyl alcohol and plasticizer mix include: temperature be 50-90 DEG C, time 0.5-4h.
13. method described in 0 or 12 according to claim 1, wherein in step (b), the temperature of the melting extrusion is 100-
200℃；The curtain coating chilling roll temperature of the curtain coating slab is 15-50 DEG C；
In step (B), the temperature of the melting extrusion is 150-220 DEG C；The curtain coating chilling roll temperature of the curtain coating slab is 30-
70℃。
14. method described in any one of 0-13 according to claim 1, wherein the biaxial tension includes that Synchronos method stretches
Or the method for fractional steps stretches；
In step (c), it includes first preheating polyvinyl alcohol slab that the Synchronos method, which stretches, then carries out MD and TD simultaneously and draws
It stretches；The condition that the Synchronos method stretches includes: that draft temperature is 120-170 DEG C, and MD stretching ratio is 3 times or more, and TD is stretched again
Rate is 3 times or more, and MD rate of extension is 300%/s or more, and TD rate of extension is 300%/s or more；
In step (c), the method for fractional steps stretching includes: first to preheat polyvinyl alcohol slab, then first carries out MD stretching, then
Preheating then carries out TD stretching；The condition that the method for fractional steps stretches includes: that MD draft temperature is 80-100 DEG C, and TD draft temperature is
120-200 DEG C, MD stretching ratio is 3 times or more, and TD stretching ratio is 3 times or more, and MD rate of extension is 100%/s or more, TD
Rate of extension is 100%/s or more；
In step (C), it includes first preheating polylactic acid slab that the Synchronos method, which stretches, then carries out MD and TD simultaneously and draws
It stretches；The condition that the Synchronos method stretches includes: that draft temperature is 70-90 DEG C, and MD stretching ratio is 3 times or more, TD stretching ratio
It is 3 times or more, MD rate of extension is 300%/s or more, and TD rate of extension is 300%/s or more；
In step (C), the method for fractional steps stretching includes: first to preheat polylactic acid slab, then first carries out MD stretching, then in advance
Heat then carries out TD stretching；The condition that the method for fractional steps stretches includes: that MD draft temperature is 50-80 DEG C, and TD draft temperature is 70-
90 DEG C, MD stretching ratio is 3 times or more, and TD stretching ratio is 3 times or more, and MD rate of extension is 100%/s or more, and TD stretches speed
Rate is 100%/s or more.
15. method described in 0 or 14 according to claim 1, wherein this method further includes after step (c) and/or step (C)
Annealing setting processing is carried out to resulting film,
In step (c), the temperature of annealing setting processing is 180-200 DEG C；
In step (C), the temperature of annealing setting processing is 100-140 DEG C.
16. polyving alcohol/polylactic acid laminated film made from the method as described in any one of claim 10-15.
17. polyving alcohol/polylactic acid laminated film according to claim 16, wherein the polyving alcohol/polylactic acid is multiple
The MD tensile strength for closing film is 80MPa or more, preferably 90MPa or more, more preferably 100MPa or more；TD tensile strength is
100MPa or more, preferably 120MPa or more, more preferably 140MPa or more；Oxygen transmission rate is 2.6ccmil/m2It hereinafter,
Preferably 2.5ccmil/m2It is following.
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