CN108456351A - A kind of water vapor rejection film and preparation method thereof - Google Patents
A kind of water vapor rejection film and preparation method thereof Download PDFInfo
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- CN108456351A CN108456351A CN201810091623.2A CN201810091623A CN108456351A CN 108456351 A CN108456351 A CN 108456351A CN 201810091623 A CN201810091623 A CN 201810091623A CN 108456351 A CN108456351 A CN 108456351A
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Abstract
The present invention provides a kind of water vapor rejection films and preparation method thereof.The water vapor rejection film of the present invention, by weight percentage, by following material composition：60~85% polyolefin, 10~30% polyester, 0~5% elastomer, 1~10% compatilizer.The present invention uses polyolefin, polyester, elastomer, compatilizer for raw material, make water vapor rejection film obtained under the ability for having water vapor rejection, also there is good thermal stability and mechanical performance, longitudinal tensile strength is in 28Mpa or more, transverse tensile strength is in 20Mpa or more, longitudinal fracture extensibility is up to 250%, and transverse breakage extensibility is up to 110%, and minimum water vapor transmittance is 0.1g/m2Day, longitudinal percent thermal shrinkage minimum 0.02%, lateral percent thermal shrinkage minimum 0.01%.The preparation method of the water vapor rejection film of the present invention, it is simple for process, it is suitble to the mass production of water vapor rejection film.
Description
Technical field
The invention belongs to thin film technique field, it is related to a kind of water vapor rejection film and preparation method thereof.
Background technology
Film has a wide range of applications as a kind of usual products in Polymer Processing in packaging, protection field.With
Social progress, scientific and technological development just proposes increasingly higher demands for high molecular film material.Water vapor rejection type is thin
Using and developing for film just has been to be concerned by more and more people.
In packaging field, the protection problem of packaging content is frequently involved, to ensure that the content the latter that never degenerates is to prevent
Product corruption, water suction, oxidation etc., need packaging structure that can play extraordinary iris action.In food packaging either medicine
Packaging industry needs the application for the Obstruct membrane used with regard to more.
In field of solar energy, solar energy backboard is located at the outermost layer of module backside, plays protection to cell piece and support is made
With.Backboard should have reliable electric insulating quality, water vapor barrier property and good resistance to ag(e)ing in general.In order to make solar energy
Battery keeps best working condition and maintains 25 years service life, and excellent water vapor barrier property becomes that weigh backboard performance good
One of bad important indicator.If solar energy backboard water vapor barrier property is bad, steam is penetrated by backboard inside encapsulation system
The cementability that can influence packaging adhesive film causes backboard and packaging adhesive film delamination, makes cell piece by oxidation to seriously reduce battery
The service life of piece generating efficiency and component.In the manufacture use of backboard, should have good anti-hydrolytic performance, mainly
Index is can be 2000 hours by double 85 (85 DEG C and 85% humidity)；And backboard at this stage is mostly using PET base material,
Can preparation method be biaxial tension, be replaced using other methods, the cost for reducing manufacture is also important research side
To.
CN204773918U discloses a kind of novel co-extrusion packaging film, including packs surface layer, packaging internal layer, is set in turn in
The packaging surface layer to five layers of sandwich layer between the packaging internal layer, the material on the packaging surface layer is polyamide, gathers
The material of alkene or polyester, the internal layer is polyethylene, and the material that first layer sandwich layer, second layer sandwich layer use is polyamide,
The material that third layer sandwich layer uses is ethylene-vinyl alcohol copolymer, and the material that the 4th layer of sandwich layer, layer 5 sandwich layer use is poly- second
Alkene.The novel co-extrusion packaging film of the utility model has excellent barrier oxygen for being packed to products such as food, drugs
The entrance such as gas and water vapour, while the volatilization of food flavor can be also prevented, ensure food original flavor, there is good heat sealability, meets
The requirement of sterilization avoids microorganism from existing and destroys food, is protected with higher barrier property food, drug etc..The practicality is new
The novel co-extrusion packaging film of type can the entrance such as blocking oxygen, steam well, but its thermal stability and mechanical performance need into
One step improves.
Therefore it provides a kind of having good water vapor barrier property, while there is good thermal stability and the water of mechanical performance
Vapour locking diaphragm is necessary.
Invention content
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of water vapor rejection films, have very high
Water vapor barrier property and good thermal stability and mechanical performance.
For this purpose, the present invention uses following technical scheme：
A kind of water vapor rejection film, by weight percentage, by following material composition：
In the present invention, main material of the polyolefin as water vapor rejection film is selected, because of the design feature of polyolefin itself
And crystallinity in process, film barrier moisture capacity prepared therefrom are strong.But the film that only prepared by polyolefin
The mechanical performance of itself is bad, and especially break-draw rate is insufficient, and the film of pure polyolefin is easy to send out under the high temperature conditions
Heat is shunk, and the present invention by polyolefin, polyester and elastomer by way of carrying out tertiary blending, the water vapor rejection that is prepared
Film also has heat resistanceheat resistant shrinkage and good mechanical strength under the ability for having water vapor rejection.
In the present invention, a kind of water vapor rejection film, by weight percentage, by following material composition：
Polyolefin 60~85%, for example, polyolefin weight percent be 60%, 61%, 62%, 63%, 64%, 65%,
66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%,
81%, 82%, 83%, 84%, 85%.
Polyester 10~30%, for example, polyolefin weight percent be 10%, 11%, 12%, 13%, 14%, 15%,
16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%.
Elastomer 0~5%, such as the weight percent of polyolefin is 0,1%, 2%, 3%, 4%, 5%.
Compatilizer 1~10%, for example, polyolefin weight percent be 1%, 2%, 3%, 4%, 5%, 6%, 7%,
8%, 9%, 10%.
Wherein, polyolefin of the present invention is one kind in polyethylene, polypropylene, ethylene-propylene copolymer and cycloolefin
Or at least two mixture, the mixture it is typical but unrestricted be combined as polyethylene, polyacrylic mixture, poly- second
The mixture of alkene, ethylene-propylene copolymer, polyethylene, cycloolefin mixture, the mixing of polypropylene, ethylene-propylene copolymer
Object, polypropylene, cycloolefin mixture, the mixture of ethylene-propylene copolymer and cycloolefin, polyethylene, polypropylene, ethylene-
The mixture of propylene copolymer, polyethylene, polypropylene, cycloolefin mixture, polypropylene, ethylene-propylene copolymer and cyclenes
The mixture of hydrocarbon, polyethylene, polypropylene, ethylene-propylene copolymer and cycloolefin mixture.
Wherein, polyester of the present invention is polyethylene terephthalate, Isosorbide-5-Nitrae cyclohexanedimethanol polyester, gathers to benzene
Dioctyl phthalate butanediol ester, poly- 2,6- (ethylene naphthalate)s and one kind in polypropylene terephthalate or at least two
Mixture.The mixture it is typical but unrestricted to be combined as polyethylene terephthalate, 1,4 cyclohexanedimethanols poly-
The mixture of ester, polyethylene terephthalate, polybutylene terephthalate (PBT) mixture, poly terephthalic acid second two
The mixture of alcohol ester, poly- 2,6-naphthalenedicarboxylic acid glycol ester, polyethylene terephthalate, polypropylene terephthalate
Mixture, the mixing of polyethylene terephthalate, Isosorbide-5-Nitrae cyclohexanedimethanol polyester, polybutylene terephthalate (PBT)
Object, polyethylene terephthalate, Isosorbide-5-Nitrae cyclohexanedimethanol polyester, poly- 2,6-naphthalenedicarboxylic acid glycol ester mixture, gather
The mixture of ethylene glycol terephthalate, Isosorbide-5-Nitrae cyclohexanedimethanol polyester, polypropylene terephthalate gathers to benzene two
The mixture of formic acid glycol ester, polybutylene terephthalate (PBT), poly- 2,6-naphthalenedicarboxylic acid glycol ester, poly terephthalic acid
The mixture of glycol ester, polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene terephthalate
The mixture of ester, poly- 2,6-naphthalenedicarboxylic acid glycol ester and polypropylene terephthalate, polyethylene terephthalate,
The mixture of Isosorbide-5-Nitrae cyclohexanedimethanol polyester, polybutylene terephthalate (PBT), poly- 2,6-naphthalenedicarboxylic acid glycol ester, poly- pair
Ethylene terephthalate, 1,4 cyclohexanedimethanol polyester, polybutylene terephthalate (PBT), poly terephthalic acid propylene glycol
The mixture of ester, Isosorbide-5-Nitrae cyclohexanedimethanol polyester, polybutylene terephthalate (PBT), poly- 2,6-naphthalenedicarboxylic acid glycol ester and
The mixture of polypropylene terephthalate, polyethylene terephthalate, gather to benzene Isosorbide-5-Nitrae cyclohexanedimethanol polyester
The mixture of dioctyl phthalate butanediol ester, poly- 2,6- (ethylene naphthalate)s and polypropylene terephthalate.
Wherein, elastomer of the present invention is polyolefin elastomer (POE), bibasic ethylene propylene rubber (EPM), ethylene-propylene-diene monomer
Glue (EPDM), ethylene-ethyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-acrylate
Copolymer (EAA), butadiene-styrene rubber (SBR), Polystyrene-Polyethylene-polybutene-polystyrene (SEBS) and polystyrene-poly
One kind in butylene-polystyrene (SBS) or at least two mixture.The mixture it is typical but unrestricted be combined as two
The mixture of kind of elastomer, the mixture of three kinds of elastomers, the mixture of four kinds of elastomers, the mixture of five kinds of elastomers, six
The mixture of the mixture of kind of elastomer, the mixture of seven kinds of elastomers, the mixture of eight kinds of elastomers, nine kinds of elastomers,
This is not listed one by one.
Wherein, compatilizer of the present invention is polyethylene-g- maleic anhydrides, polypropylene-g- maleic anhydrides, ethylene-propylene
Copolymer-g- maleic anhydrides, polyethylene-g- glycidyl methacrylate, polypropylene-g- methyl propenoic acid glycidyls
Ester, ethylene-propylene copolymer-g- glycidyl methacrylate, polyolefin elastomer-g- maleic anhydrides, the third rubber of binary second
Glue-g- maleic anhydrides, ethylene propylene diene rubber-g- maleic anhydrides, ethylene-ethyl acetate copolymer-g- maleic anhydrides, ethylene-first
Base acrylate copolymer-g- maleic anhydrides, vinyl-acrylate copolymer-g- maleic anhydrides, butadiene-styrene rubber-g- maleic acids
Acid anhydride, Polystyrene-Polyethylene-polybutene-polystyrene-g- maleic anhydrides, polystyrene-poly butylene-Malaysias polystyrene-g-
Acid anhydrides, polyolefin elastomer-g- glycidyl methacrylate, bibasic ethylene propylene rubber-g- glycidyl methacrylate,
Ethylene propylene diene rubber-g- glycidyl methacrylate, ethylene-ethyl acetate copolymer-g- methyl propenoic acid glycidyls
Ester, ethylene-methyl acrylate copolymer-g- glycidyl methacrylate, vinyl-acrylate copolymer-g- methyl
Glycidyl acrylate, butadiene-styrene rubber-g- glycidyl methacrylate, Polystyrene-Polyethylene-polybutene-polyphenyl
Ethylene-g- glycidyl methacrylate and polystyrene-poly butylene-polystyrene-g- glycidyl methacrylate
In one kind or at least two mixture.
The long-term heat resistance humidity index (TI) of water vapor rejection film of the present invention is more than 105 DEG C.
Surface free energy of the water vapor rejection film of the present invention after sided corona treatment is not less than 40dyne.
The second object of the present invention is to provide a kind of preparation method of water vapor rejection film, and the preparation method includes as follows
Step：By weight percentage, weigh 60~85% polyolefin, 10~30% polyester, 0~5% elastomer, 1~
10% compatilizer is blended, squeezes out, film forming, and the water vapor rejection film is prepared.
The mode of the film forming is one kind in biaxial tension film forming, simple tension film forming and casting film-forming.
As the preferred embodiment of the present invention, the preparation method includes the following steps：By weight percentage, 60 are weighed~
85% polyolefin, 10~30% polyester, 0~5% elastomer, 1~10% compatilizer are blended, squeeze out, are cast into
The water vapor rejection film is prepared in film.
As the preferred embodiment of the present invention, the preparation method includes the following steps：By weight percentage, 60 are weighed~
85% polyolefin, 10~30% polyester, 0~5% elastomer, 1~10% compatilizer are blended, squeeze out, two-way drawing
It is stretched into film, the water vapor rejection film is prepared.
As the preferred embodiment of the present invention, the preparation method includes the following steps：By weight percentage, 60 are weighed~
85% polyolefin, 10~30% polyester, 0~5% elastomer, 1~10% compatilizer are blended, squeeze out, unidirectional drawing
It is stretched into film, the water vapor rejection film is prepared.
Compared with prior art, beneficial effects of the present invention are：
(1) water vapor rejection film of the invention, uses polyolefin, polyester, elastomer, compatilizer for raw material, by by polyene
Hydrocarbon, polyester and elastomer carry out tertiary blending, are mixed under compatilizer effect, and the consumption proportion by adjusting raw material, make system
The water vapor rejection film obtained also has good thermal stability and mechanical performance under the ability for having water vapor rejection, wherein vertical
To (MD) tensile strength in 28Mpa or more, laterally in 20Mpa or more, longitudinal fracture extensibility is up to (TD) tensile strength
250%, transverse breakage extensibility is up to 110%, and minimum water vapor transmittance is 0.1g/m2Day, longitudinal percent thermal shrinkage are minimum
It is 0.02%, the long-term heat resistance humidity index (TI) of lateral percent thermal shrinkage minimum 0.01%, water vapor rejection film is more than 105
DEG C, and surface free energy of the water vapor rejection film after sided corona treatment is not less than 40dyne.
(2) preparation method of water vapor rejection film of the invention, simple for process, water vapor rejection film obtained has very high water
Vapour barrier property and good thermal stability and mechanical performance are suitble to the mass production of water vapor rejection film.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
Unless specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this field
It obtains.
The water vapor rejection film of the present invention, by weight percentage, by following material composition：
The preparation method of the water vapor rejection film of the present invention, the preparation method include the following steps：By weight percentage,
It is blended, crowded to weigh 60~85% polyolefin, 10~30% polyester, 0~5% elastomer, 1~10% compatilizer
Go out, form a film, the water vapor rejection film is prepared.
There is high water vapor rejection come the water vapor rejection film for verifying preparation of the embodiment of the present invention below by embodiment, well
Mechanical performance and thermal stability.
The ability of thin-film barrier steam determines that test steam penetrating capacity is used by steam penetrating capacity experiment
Instrument be U.S. MOCON moisture-inhibiting instrument.Wherein, steam penetrating capacity is lower, illustrates that water vapor rejection ability is stronger；Vapor is saturating
It is excessive higher, illustrate that water vapor rejection ability is weaker.
The mechanical performance of film is weighed by the directions MD and TD tensile strength and break-draw rate, test mechanical
Instrument used in energy is electronic universal tester AGS-X Shimadzus.Wherein, tensile strength and break-draw rate are bigger, explanation
The mechanical performance of film is better.
The thermal stability of film is weighed by testing the percent thermal shrinkage in the directions MD and TD, and test is heat-shrinked and is used
Instrument be Nikon Quadratic Finite Element.Wherein, shrinking percentage is smaller, illustrates that thermal stability is better.
Embodiment 1
By polyethylene 600g, polyethylene terephthalate 300g, ethylene-ethyl acetate copolymer-g- maleic anhydrides
100g is mixed, then is formed a film using biaxial tension, and water vapor rejection film is prepared.
Embodiment 2
By polypropylene 550g, polybutylene terephthalate (PBT) 300g, polyolefin elastomer 50g, polypropylene-g- maleic acids
Acid anhydride 100g is mixed, then uses casting film-forming, and water vapor rejection film is prepared.
Embodiment 3
By ethylene-propylene copolymer 850g, poly- 2,6-naphthalenedicarboxylic acid glycol ester 100g, ethylene propylene diene rubber 40g, second
Alkene-methacrylate copolymer-g- glycidyl methacrylate 10g is mixed, then is formed a film using simple tension, system
It is standby to obtain water vapor rejection film.
Embodiment 4
By cycloolefin 800g, Isosorbide-5-Nitrae cyclohexanedimethanol polyester 150g, Polystyrene-Polyethylene-polybutene-polystyrene
20g, vinyl-acrylate copolymer-g- maleic anhydrides 30g are mixed, then are formed a film using biaxial tension, and steam is prepared
Obstruct membrane.
Embodiment 5
By polypropylene 700g, poly- 2,6-naphthalenedicarboxylic acid glycol ester 200g, vinyl-acrylate copolymer 30g, polyphenyl second
Alkene-polybutene-polystyrene-g- glycidyl methacrylate 70g is mixed, then uses casting film-forming, is prepared
Water vapor rejection film.
Comparative example 1
It weighs polyethylene 1000g to form a film using the tape casting, water vapor rejection film is prepared.
Comparative example 2
It weighs polyethylene terephthalate 1000g to form a film using biaxial tension, water vapor rejection film is prepared.
Water vapor rejection film made from embodiment 1-5 and comparative example 1-2 is tested for the property, experimental result is as shown in table 1.
Table 1
Compared with polyethylene terephthalate film made from polyethylene film made from comparative example 1 and comparative example 2, this hair
Bright water vapor rejection film obtained also has good thermal stability and mechanical performance under the ability for having water vapor rejection,
In, longitudinal (MD) tensile strength is in 28Mpa or more, and laterally (TD) tensile strength is in 20Mpa or more, longitudinal fracture extensibility highest
Up to 250%, transverse breakage extensibility is up to 110%, and minimum water vapor transmittance is 0.1g/m2Day, longitudinal percent thermal shrinkage is most
Low is 0.02%, lateral percent thermal shrinkage minimum 0.01%, and the long-term heat resistance humidity index (TI) of water vapor rejection film is more than 105
DEG C, and surface free energy of the water vapor rejection film after sided corona treatment is not less than 40dyne.
The present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, but the present invention is not
It is confined to above-mentioned detailed process equipment and technological process, that is, does not mean that the present invention has to rely on above-mentioned detailed process equipment and work
Skill flow could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to product of the present invention
The equivalence replacement of each raw material and the addition of auxiliary element, the selection of concrete mode etc., all fall within protection scope of the present invention and public affairs
Within the scope of opening.
Claims (10)
1. a kind of water vapor rejection film, which is characterized in that by weight percentage, by following material composition：
2. water vapor rejection film according to claim 1, which is characterized in that the polyolefin is polyethylene, polypropylene, second
One kind in alkene-propylene copolymer and cycloolefin or at least two mixture.
3. water vapor rejection film according to claim 1 or 2, which is characterized in that the polyester is poly terephthalic acid second two
Alcohol ester, 1,4 cyclohexanedimethanol polyester, polybutylene terephthalate (PBT), poly- 2,6- (ethylene naphthalate)s and poly- to benzene
One kind in naphthalate or at least two mixture.
4. the water vapor rejection film according to one of claim 1-3, which is characterized in that the elastomer is polyolefin elastic
Body, bibasic ethylene propylene rubber, ethylene propylene diene rubber, ethylene-ethyl acetate copolymer, ethylene-methyl acrylate copolymer, second
Alkene-acrylate copolymer, butadiene-styrene rubber, Polystyrene-Polyethylene-polybutene-polystyrene and polystyrene-poly butylene-
One kind in polystyrene or at least two mixture.
5. the water vapor rejection film according to one of claim 1-4, which is characterized in that the compatilizer is polyethylene-g- horses
It is sweet to come acid anhydrides, polypropylene-g- maleic anhydrides, ethylene-propylene copolymer-g- maleic anhydrides, polyethylene-g- Glycidyl methacrylates
Grease, ethylene-propylene copolymer-g- glycidyl methacrylate, gathers at polypropylene-g- glycidyl methacrylate
Olefin elastomer-g- maleic anhydrides, bibasic ethylene propylene rubber-g- maleic anhydrides, ethylene propylene diene rubber-g- maleic anhydrides, ethylene-vinegar
Acetoacetic ester copolymer-g- maleic anhydrides, ethylene-methyl acrylate copolymer-g- maleic anhydrides, ethylene-acrylate copolymers
Object-g- maleic anhydrides, butadiene-styrene rubber-g- maleic anhydrides, Polystyrene-Polyethylene-polybutene-polystyrene-g- maleic anhydrides,
Polystyrene-poly butylene-polystyrene-g- maleic anhydrides, polyolefin elastomer-g- glycidyl methacrylate, binary
EP rubbers-g- glycidyl methacrylate, ethylene propylene diene rubber-g- glycidyl methacrylate, ethyl vinyl acetate
Methacrylate copolymers-g- glycidyl methacrylate, ethylene-methyl acrylate copolymer-g- Glycidyl methacrylates are sweet
Grease, vinyl-acrylate copolymer-g- glycidyl methacrylate, butadiene-styrene rubber-g- methyl propenoic acid glycidyls
Ester, Polystyrene-Polyethylene-polybutene-polystyrene-g- glycidyl methacrylate and polystyrene-poly butylene-are poly-
One kind in styrene-g- glycidyl methacrylate or at least two mixture.
6. the water vapor rejection film according to one of claim 1-5, which is characterized in that the water vapor rejection film it is long-term heat-resisting
Property humidity index (TI) be more than 105 DEG C.
7. the water vapor rejection film according to one of claim 1-6, which is characterized in that the water vapor rejection film is through sided corona treatment
Surface free energy afterwards is not less than 40dyne.
8. a kind of preparation method of water vapor rejection film as described in claim 1, which is characterized in that the preparation method includes such as
Lower step：By weight percentage, weigh 60~85% polyolefin, 10~30% polyester, 0~5% elastomer, 1~
10% compatilizer is blended, squeezes out, film forming, and the water vapor rejection film is prepared.
9. preparation method according to claim 8, which is characterized in that the mode of the film forming is biaxial tension film forming, list
To the one kind stretched in film forming and casting film-forming.
10. preparation method according to claim 8 or claim 9, which is characterized in that the preparation method includes the following steps：It presses
Weight percent meter, weigh 60~85% polyolefin, 10~30% polyester, 0~5% elastomer, 1~10% it is compatible
Agent is blended, squeezes out, casting film-forming, and the water vapor rejection film is prepared.
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