CN100441624C - Microporous film of ethylene-acrylic acid copolymer and its prepn process - Google Patents
Microporous film of ethylene-acrylic acid copolymer and its prepn process Download PDFInfo
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- CN100441624C CN100441624C CNB2005100410115A CN200510041011A CN100441624C CN 100441624 C CN100441624 C CN 100441624C CN B2005100410115 A CNB2005100410115 A CN B2005100410115A CN 200510041011 A CN200510041011 A CN 200510041011A CN 100441624 C CN100441624 C CN 100441624C
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Abstract
The present invention discloses an ethene-acrylic acid copolymer (EAA) microporous film and a preparation method thereof. The microporous film has the advantages of better hydrophile performance, high intensity and excellent chemical resistance; meanwhile, the microporous film has the characteristics of uniform pore diameter distribution, easy control over pore diameter and porosity, etc., the pore diameter is generally from 0.5 to 2 mu m, and the porosity is above 70%; therefore, the flux of the microporous film of the present invention is also large, and the separation efficiency is high. The microporous film of the present invention is prepared from 20 to 40% of ethene-acrylic acid copolymer and 60 to 80% of diluent according to weight percentage. The preparation method of the present invention has the advantages of simplicity and convenient operation, and the prepared microporous film can be widely used for the field of solid liquid separation, solution purification, film distillation, etc.
Description
Technical field
The present invention relates to a kind of microporous membrane and preparation method thereof, more specifically also say to relate to a kind of ethylene-acrylic acid copolymer (EAA) microporous membrane and preparation method thereof.
Background technology
Thermally induced phase separation (TIPS) began one's study from the seventies in 20th century.The United States Patent (USP) of delivering in 1977 4247498 is one piece of report that are equipped with microporous membrane about the TIPS legal system the earliest, United States Patent (USP) 453925 and 4867881 has subsequently all been done further report, in the early 1990s, Texas, USA university polymkeric substance research centre is equipped with microporous membrane to the TIPS legal system and has carried out systematic research.Successively reported of the influence of factors such as the mechanism that is separated, thermodynamics interaction, kinetics, thinner, nucleator to microporous membrane structure.Since the nineties, TIPS legal system film has had new development again, and the research focus has been transferred to structure control, unsymmetric structure, hydrophilically modified etc.Thermally induced phase separation is a kind of film-forming method of simple novelty, can be applicable to many because solubility property difference and can not make in the crystalline polymer that embrane method solves micro molding with other.It is that at high temperature (the fusing point Tm that generally is higher than crystalline polymer) is dissolved in polymkeric substance the solvent of high boiling point, low volatility, form uniform solution, cooling cooling then, causing solution to produce solid-liquid is separated or liquid-liquid phase separation, select for use volatile reagent that high boiling solvent is extracted again, thereby obtain the high molecule micropore film of certain structural shape.On thermic was separated the researchdevelopment direction, structure control had become the focus of membrane science research worker research recently.Use polymeric membrane, two perviousness and selectivity that most important index is a film, perviousness to be meant that the mensuration material sees through the absolute magnitude of unit surface separatory membrane in the unit time as separating; Selectivity is meant the ratio of under equal conditions measuring material permeance amount and reference material transit dose.And perviousness and selectivity depend on membrane structure, i.e. the size in hole, pore size distribution and porosity etc.The microporous membrane that adopts thermally induced phase separation to make has higher porosity, and adopts other method (as the fusion drawn method) microporous membrane porosity lower, and about 20～30%.Therefore, how the controlling diaphragm structure becomes one of most important content in the film research.
The industrialized at present hydrophobic materials such as polypropylene, polyethylene, tetrafluoroethylene, polysulfones that mostly are.Thereby poor because of these material water-absorbents, easy static electrification causes solute absorption and fenestra to stop up, and makes that separating effect descends in the process of membrane sepn; And because its non-wettability, when carrying out lock out operation, must have pressure gradient in the presence of just can make fluid infiltrate fenestra.So, these materials are made the microporous membrane use separately also be very restricted, in order to improve its work-ing life and to be applied, must carry out hydrophilic modifying to these materials in the high-performance field.In traditional hydrophilic modifying, graft copolymerization is a kind ofly can give some superiority of hydrophobic material and do not influence the method for body fundamental property.By treatment technologies such as radiation grafting, plasma graftings hydrophilic radical is attached to matrix surface, makes material obtain hydrophilic effect preferably.But because its unstable is difficult to realize industrialization, application still is very limited.Though can consider to use hydrophilic material, such as cellulose acetate, polyvinyl alcohol, polyacrylonitrile, they often do not possess the thermostability and the chemical resistance of hydrophobic high polymer.A kind of ideal method prepares stable hydrophilic macromolecule microporous membrane with regard to being to use the copolymer material that contains hydrophobic component and hydrophilic component simultaneously.Hydrophobic group has improved the stability of film because of its crystalline texture, and hydrophilic radical then can improve the wetting ability of film.Ethylene-acrylic acid copolymer (EAA) is owing to be to have introduced a spot of vinylformic acid on the main chain of ethene, thereby has certain wetting ability, though a spot of vinylformic acid has destroyed the regularity of main chain simultaneously, but EAA still is a half hitch crystal formation superpolymer, makes EAA have intensity, the anti-solvent of oil resistant and resistance to acids and bases preferably.
Summary of the invention
Purpose of the present invention solves the above-mentioned problems in the prior art and deficiency, and a kind of microporous film of ethylene-acrylic acid copolymer is provided, and this membrane pore size is evenly distributed, and the aperture of system is all lower, the porosity height.
Another purpose of the present invention simultaneously also provides the preparation method of above-mentioned microporous film of ethylene-acrylic acid copolymer, and method is simple and easy to operate.
Technical scheme of the present invention is as follows:
Microporous film of ethylene-acrylic acid copolymer of the present invention, mainly be to make by following raw materials by weight percent: ethylene-acrylic acid copolymer 20%～40%, thinner 60%～80%, acrylic acid content is 5%～10% (weight percent) in the wherein said ethylene-acrylic acid copolymer; Described thinner is the mixture of vegetables oil, di (2-ethylhexyl) phthalate or vegetables oil and di (2-ethylhexyl) phthalate; Proportioning raw materials is preferably: ethylene-acrylic acid copolymer 20%～30%, thinner 70%～80%.Described vegetables oil is a kind of or its combination in soybean oil, peanut oil, Semen Maydis oil or the sesame oil.
A kind of preparation method of above-mentioned microporous film of ethylene-acrylic acid copolymer may further comprise the steps:
A) take by weighing each raw material in proportion, standby;
B) described materials of weight proportions is added in the reactor, begin to stir after being heated to the ethylene-acrylic acid copolymer fusion, stirring velocity is 40～100 rev/mins, stirs after 4 hours to stop, and naturally cooling curing obtains compound sample;
C) compound sample that obtains is downcut a thin slice and put into lidded container, in temperature is 180 ℃ electric drying oven with forced convection, heat, treat to take out after the complete fusion of sample;
D) take out rapidly in 0 ℃～60 ℃ following quenchings 0～20 minute, treat that it cools off the back fully with the extraction agent extraction, changes the single extraction agent, and extracts 4～12 times in per 6 hours;
E) to put into temperature after finishing be 30～60 ℃ in extraction, and vacuum tightness is in the vacuum drying oven of 0.05～0.15MPa dry 24～48 hours approximately, will remain extraction agent and evaporate and promptly get microporous membrane of the present invention after removing.Wherein said extraction agent is methyl alcohol, ethanol, acetone, butanone or trichloromethane.
The preparation method of a kind of microporous film of ethylene-acrylic acid copolymer of the present invention may further comprise the steps:
A) ethylene-acrylic acid copolymerization by weight percentage 25%, di (2-ethylhexyl) phthalate 55%, sesame oil 20% take by weighing raw material, therein ethylene-acrylic acid copolymer 25g, di (2-ethylhexyl) phthalate 55g, sesame oil 20g, acrylic acid content in the ethylene-acrylic acid copolymer: 9.7% (weight percent);
B) described materials of weight proportions is added in the reactor, reactor is begun to stir after being heated to the ethylene-acrylic acid copolymer fusion in 180 ℃ the oil bath, stirring velocity is 80 rev/mins, stirs after 4 hours to stop, and naturally cooling solidifies, and obtains compound sample;
C) compound sample that obtains being downcut a thin slice and put into lidded container, is heating 10 minutes in 180 ℃ the electric drying oven with forced convection in temperature, treats to take out after the complete fusion of sample;
D) take out rapidly in 30 ℃ of following quenchings 4 minutes, treat that it cools off the back fully and uses the extraction agent methanol extraction, changes the single extraction agent, and extracts 12 times in per 6 hours;
E) to put into temperature after finishing be 50 ℃ in extraction, and vacuum tightness is in the vacuum drying oven of 0.1MPa dry 48 hours, will remain extraction agent and evaporate and promptly get microporous membrane of the present invention after removing.
Beneficial effect of the present invention is as follows:
Ethylene-acrylic acid copolymer membrane micropore film contact angle of the present invention is less, has hydrophilicity preferably, can be widely used in the separation of water-soluble substances, thereby prevents that micropore from stopping up; EAA is a half hitch crystal formation superpolymer in addition, makes microporous membrane of the present invention have higher intensity and excellent chemical proofing (being insoluble to the number of chemical solvent under the room temperature), can also oil resistant, anti-solvent and acid and alkali-resistance; Microporous membrane also has even aperture distribution simultaneously, aperture and porosity are easy to characteristics such as control, and generally at 0.5～2 μ m, porosity is up to more than 70% in the aperture of microporous film of ethylene-acrylic acid copolymer, thereby make the flux of microporous membrane of the present invention also big, separation efficiency is also high.Microporous membrane of the present invention can be widely used in fields such as solid-liquid separation, solution refining and membrane distillation.
It is simple, easy to operate that the present invention adopts thermally induced phase separation to prepare the method for microporous film of ethylene-acrylic acid copolymer; Feed diluent (vegetables oil, softening agent) is easy to get, cheap, nontoxic, pollution-free.Can adopt simultaneously the method that changes acrylic acid content in the ethylene-acrylic acid copolymer to control the hydrophilicity of microporous membrane.
Embodiment
Further specify the present invention below by embodiment and Comparative Examples, in embodiment and Comparative Examples, the measuring method in the aperture of microporous membrane is as follows: with sample be placed on quench in the liquid nitrogen disconnected, plate one deck gold film with ion sputtering instrument at sample surfaces, observe with scanning electronic microscope then and take pictures, with Xi Gemasi 50～100 holes of (Sigmascan) software random measurement of showing mercy, averaging promptly obtains micropore size with stereoscan photograph.Use A
kThe expression porosity, the performance of the high more explanation microporous membrane of this numerical value is good more, the flux of microporous membrane is big more, separation efficiency is high more, measuring method and formula are as follows: the microporous membrane of the present invention of certainweight was soaked in isopropylcarbinol 24 hours, take out the back and inhale the isopropylcarbinol of surface attachment gently, weigh rapidly with filter paper.Calculate porosity A according to following formula
k:
In the formula, W
1And W
2Be respectively the weight of EAA microporous membrane before and after soaking; ρ
1Density for the EAA body material; ρ
2Density for isopropylcarbinol.
The wetting ability of representing the EAA microporous membrane with contact angle, this numerical value is more little, show that wetting ability is good more, just more help the separation of water-soluble substances, prevent that micropore from stopping up, measuring method is as follows: use ethylene-acrylic acid copolymer (EAA) microporous membrane that makes at 120 ℃, 5～10MPa condition presses down laminates, and at the deionized water that drips 2 μ L on the thin slice, measures contact angle by the contact angle instrument under room temperature, each sample testing 3 times is got its mean value.
Embodiment 1
A) ethylene-acrylic acid copolymer 20%, di (2-ethylhexyl) phthalate (DOP) 80% take by weighing raw material by weight percentage, therein ethylene-acrylic acid copolymer 20g, di (2-ethylhexyl) phthalate 80g, ethylene-acrylic acid copolymer: Dow Chemical company produces, model Primacor3003, acrylic acid content: 6.5% (weight percent);
B) described materials of weight proportions is added in the reactor, reactor is begun to stir after being heated to the ethylene-acrylic acid copolymer fusion in 180 ℃ the oil bath, stirring velocity is 80 rev/mins, stirs after 4 hours to stop, and naturally cooling solidifies, and obtains compound sample;
C) compound sample that obtains being downcut a thin slice and put into lidded container, is heating 10 minutes in 180 ℃ the electric drying oven with forced convection in temperature, treats to take out after the complete fusion of sample;
D) take out rapidly in 0 ℃ of following quenching 10 minutes, treat that its cooling back uses the extraction agent methanol extraction, changed the single extraction agent, and extracted 12 times in per 6 hours;
E) putting into temperature after extraction is finished is 50 ℃, vacuum tightness is in the vacuum drying oven of 0.1MPa dry 24 hours, will remain extraction agent and evaporate and promptly get microporous membrane of the present invention after removing, and recording as a result, micropore size is 1.02 μ m, porosity is 71.8%, and contact angle is 79.6 °.
Embodiment 2
A) ethylene-acrylic acid copolymer 30%, sesame oil 70% take by weighing raw material by weight percentage, therein ethylene-acrylic acid copolymer 30g, sesame oil 70g, ethylene-acrylic acid copolymer: Dow Chemical company produces, model Primacor3003, acrylic acid content: 6.5% (weight percent);
B) described materials of weight proportions is added in the reactor, reactor is begun to stir after being heated to the ethylene-acrylic acid copolymer fusion in 180 ℃ the oil bath, stirring velocity is 100 rev/mins, stirs after 4 hours to stop, and naturally cooling solidifies, and obtains compound sample;
C) compound sample that obtains being downcut a thin slice and put into lidded container, is heating 10 minutes in 180 ℃ the electric drying oven with forced convection in temperature, treats to take out after the complete fusion of sample;
D) take out rapidly in 30 ℃ of following quenchings 5 minutes, treat that it cools off the back fully and uses the extraction agent acetone extract, changes the single extraction agent, and extracts 8 times in per 6 hours;
E) putting into temperature after extraction is finished is 30 ℃, vacuum tightness is in the vacuum drying oven of 0.15MPa dry 24 hours, will remain extraction agent and evaporate and promptly get microporous membrane of the present invention after removing, and recording as a result, micropore size is 0.77 μ m, porosity is 67.5%, and contact angle is 79.4 °.
Embodiment 3
A) ethylene-acrylic acid copolymer 35%, di (2-ethylhexyl) phthalate (DOP) 65% take by weighing raw material by weight percentage, therein ethylene-acrylic copolymer 35g, di (2-ethylhexyl) phthalate 65g, ethylene-acrylic acid copolymer: Dow Chemical company produces, model Primacor3003, acrylic acid content: 6.5% (weight percent);
B) described materials of weight proportions is added in the reactor, reactor is begun to stir after being heated to the ethylene-acrylic acid copolymer fusion in 180 ℃ the oil bath, stirring velocity is 60 rev/mins, stirs after 4 hours to stop, and naturally cooling solidifies, and obtains compound sample;
C) compound sample that obtains being downcut a thin slice and put into lidded container, is heating 10 minutes in 180 ℃ the electric drying oven with forced convection in temperature, treats to take out after the complete fusion of sample;
D) take out rapidly in 60 ℃ of following quenchings 10 minutes, treat that it cools off the back fully with extraction agent methyl alcohol and alternately extraction of trichloromethane, changes the single extraction agent, and extracts 10 times in per 6 hours;
E) putting into temperature after extraction is finished is 60 ℃, vacuum tightness is in the vacuum drying oven of 0.05MPa dry 24 hours, will remain extraction agent and evaporate and promptly get microporous membrane of the present invention after removing, and recording as a result, micropore size is 0.97 μ m, porosity is 61.2%, and contact angle is 79.5 °.
Embodiment 4
A) ethylene-acrylic acid copolymer 30%, soybean oil 70% take by weighing raw material by weight percentage, therein ethylene-acrylic acid copolymer 30g, soybean oil 70g, ethylene-acrylic acid copolymer: Dow Chemical company produces, model Primacor1410, acrylic acid content: 9.7% (weight percent);
B) described materials of weight proportions is added in the reactor, reactor is begun to stir after being heated to the ethylene-acrylic acid copolymer fusion in 180 ℃ the oil bath, stirring velocity is 80 rev/mins, stirs after 4 hours to stop, and naturally cooling solidifies, and obtains compound sample;
C) compound sample that obtains being downcut a thin slice and put into lidded container, is heating 10 minutes in 180 ℃ the electric drying oven with forced convection in temperature, treats to take out after the complete fusion of sample;
D) take out rapidly in 0 ℃ of following quenching 10 minutes, treat that it cools off the back fully and uses the extraction agent alcohol extraction, changes the single extraction agent, and extracts 4 times in per 6 hours;
E) putting into temperature after extraction is finished is 50 ℃, vacuum tightness is in the vacuum drying oven of 0.1MPa dry 48 hours, will remain extraction agent and evaporate and promptly get microporous membrane of the present invention after removing, and recording as a result, micropore size is 0.86 μ m, porosity is 66.9%, and contact angle is 72.1 °.
Embodiment 5
A) ethylene-acrylic acid copolymer 40%, di (2-ethylhexyl) phthalate (DOP) 60% take by weighing raw material by weight percentage, therein ethylene-acrylic acid copolymer 40g, di (2-ethylhexyl) phthalate 60g, ethylene-acrylic acid copolymer: Dow Chemical company produces, model Primacor3002, acrylic acid content: 8.0% (weight percent);
B) described materials of weight proportions is added in the reactor, reactor is begun to stir after being heated to the ethylene-acrylic acid copolymer fusion in 180 ℃ the oil bath, stirring velocity is 80 rev/mins, stirs after 4 hours to stop, and naturally cooling solidifies, and obtains compound sample;
C) compound sample that obtains being downcut a thin slice and put into lidded container, is heating 10 minutes in 180 ℃ the electric drying oven with forced convection in temperature, treats to take out after the complete fusion of sample;
D) take out rapidly in 0 ℃ of following quenching 4 minutes, treat that it cools off the back fully with the extraction of extraction agent butanone, changes the single extraction agent, and extracts 12 times in per 6 hours;
E) putting into temperature after extraction is finished is 50 ℃, vacuum tightness is in the vacuum drying oven of 0.1MPa dry 36 hours, will remain extraction agent and evaporate and promptly get microporous membrane of the present invention after removing, and recording as a result, micropore size is 0.67 μ m, porosity is 54.3%, and contact angle is 77.9 °.
Embodiment 6
A) ethylene-acrylic acid copolymer 25%, di (2-ethylhexyl) phthalate (DOP) 55%, sesame oil 20% take by weighing raw material by weight percentage, therein ethylene-acrylic acid copolymer 25g, di (2-ethylhexyl) phthalate 55g, sesame oil 20g, ethylene-acrylic acid copolymer: Dow Chemical company produces, model Primacor1410, acrylic acid content: 9.7% (weight percent);
B) described materials of weight proportions is added in the reactor, reactor is begun to stir after being heated to the ethylene-acrylic acid copolymer fusion in 180 ℃ the oil bath, stirring velocity is 80 rev/mins, stirs after 4 hours to stop, and naturally cooling solidifies, and obtains compound sample;
C) compound sample that obtains being downcut a thin slice and put into lidded container, is heating 10 minutes in 180 ℃ the electric drying oven with forced convection in temperature, treats to take out after the complete fusion of sample;
D) take out rapidly in 30 ℃ of following quenchings 4 minutes, treat that it cools off the back fully and uses the extraction agent methanol extraction, changes the single extraction agent, and extracts 12 times in per 6 hours;
E) putting into temperature after extraction is finished is 50 ℃, vacuum tightness is in the vacuum drying oven of 0.1MPa dry 48 hours, will remain extraction agent and evaporate and promptly get microporous membrane of the present invention after removing, and recording as a result, micropore size is 0.71 μ m, porosity is 70.1%, and contact angle is 72.0 °.
Comparative Examples
A) by weight percentage polyethylene (HDPE, 5000S) 30%, peanut oil 70% takes by weighing raw material, wherein polyethylene 30g, peanut oil 70g;
B) described materials of weight proportions is added in the reactor, reactor is begun to stir after being heated to the polyethylene fusion in 180 ℃ the oil bath, stirring velocity is 80 rev/mins, stirs after 4 hours to stop, and naturally cooling solidifies, and obtains compound sample;
C) compound sample that obtains being downcut a thin slice and put into lidded container, is heating 10 minutes in 180 ℃ the electric drying oven with forced convection in temperature, treats to take out after the complete fusion of sample;
D) take out rapidly in 0 ℃ of following quenching 10 minutes, treat that its cooling back uses the extraction agent methanol extraction, changed the single extraction agent, and extracted 12 times in per 6 hours;
E) putting into temperature after extraction is finished is 50 ℃, vacuum tightness is in the vacuum drying oven of 0.1MPa dry 24 hours, will remain extraction agent and evaporate and promptly get microporous membrane of the present invention after removing, and recording as a result, micropore size is 2.03 μ m, porosity is 60.8%, and contact angle is 91 °.
From the result of embodiment and Comparative Examples as can be seen, the contact angle of high density polyethylene(HDPE) microporous membrane is 91 °, shows that hydrophilicity is relatively poor; Generally at 70.0 °～80.0 °, its wetting ability obviously is better than the polyethylene kind microporous membrane to the contact angle of microporous film of ethylene-acrylic acid copolymer of the present invention.
Claims (6)
1, a kind of microporous film of ethylene-acrylic acid copolymer is characterized in that it is to be made by following raw materials by weight percent:
Ethylene-acrylic acid copolymer 20%～40%
Thinner 60%～80%
The Acrylic Acid Monomer unit content of weight percent is 5%～10% in the described ethylene-acrylic acid copolymer; Described thinner is the mixture of vegetables oil and di (2-ethylhexyl) phthalate.
2, microporous film of ethylene-acrylic acid copolymer according to claim 1 is characterized in that it is to be made by following raw materials by weight percent:
Ethylene-acrylic acid copolymer 20%～30%
Thinner 70%～80%.
3, microporous film of ethylene-acrylic acid copolymer according to claim 1 is characterized in that described vegetables oil is a kind of or its combination in soybean oil, peanut oil, Semen Maydis oil or the sesame oil.
4, the preparation method of a kind of microporous film of ethylene-acrylic acid copolymer as claimed in claim 1 may further comprise the steps:
A) take by weighing each raw material in proportion, standby;
B) described materials of weight proportions is added in the reactor, begin to stir after being heated to the ethylene-acrylic acid copolymer fusion, stirring velocity is 40～100 rev/mins, stirs after 4 hours to stop, and naturally cooling curing obtains compound sample;
C) compound sample that obtains is downcut a thin slice and put into lidded container, in temperature is 180 ℃ electric drying oven with forced convection, heat, treat to take out after the complete fusion of sample;
D) take out rapidly in 0 ℃～60 ℃ following quenchings 0～20 minute, treat that it cools off the back fully with the extraction agent extraction, changes the single extraction agent, and extracts 4～12 times in per 6 hours;
E) to put into temperature after finishing be 30～60 ℃ in extraction, and vacuum tightness is in the vacuum drying oven of 0.05～0.15MPa dry 24～48 hours, will remain extraction agent and evaporate and promptly get microporous film of ethylene-acrylic acid copolymer after removing.
5, the preparation method of microporous film of ethylene-acrylic acid copolymer according to claim 4 is characterized in that described extraction agent is methyl alcohol, ethanol, acetone, butanone or trichloromethane.
6, the preparation method of a kind of microporous film of ethylene-acrylic acid copolymer according to claim 4 may further comprise the steps:
A) ethylene-acrylic acid copolymer 25%, di (2-ethylhexyl) phthalate 55%, sesame oil 209% take by weighing raw material by weight percentage, therein ethylene-acrylic copolymer 25g, di (2-ethylhexyl) phthalate 55g, sesame oil 20g, the Acrylic Acid Monomer unit content of weight percent in the ethylene-acrylic acid copolymer: 9.7%;
B) described materials of weight proportions is added in the reactor, reactor is begun to stir after being heated to the ethylene-acrylic acid copolymer fusion in 180 ℃ the oil bath, stirring velocity is 80 rev/mins, stirs after 4 hours to stop, and naturally cooling solidifies, and obtains compound sample;
C) compound sample that obtains being downcut a thin slice and put into lidded container, is heating 10 minutes in 180 ℃ the electric drying oven with forced convection in temperature, treats to take out after the complete fusion of sample;
D) take out rapidly in 30 ℃ of following quenchings 4 minutes, treat that it cools off the back fully and uses the extraction agent methanol extraction, changes the single extraction agent, and extracts 12 times in per 6 hours;
E) to put into temperature after finishing be 50 ℃ in extraction, and vacuum tightness is in the vacuum drying oven of 0.1MPa dry 48 hours, will remain extraction agent and evaporate and promptly get microporous film of ethylene-acrylic acid copolymer after removing.
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