CN106393919A - High-toughness high-water-steam-baffled completely-biodegraded composite multilayer film and preparation method thereof - Google Patents
High-toughness high-water-steam-baffled completely-biodegraded composite multilayer film and preparation method thereof Download PDFInfo
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
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Abstract
The invention relates to the technical field of polymer materials, and specifically relates to a high-toughness high-water-steam-baffled completely-biodegraded composite multilayer film and a manufacturing method thereof. The film comprises a structure from the second layer to the seventh layer and is composed of a PBAT based high-toughness high-barrier biodegradable material (A), a high-weatherability high-barrier biodegradable material (B), and a high-toughness functional biodegradable material layer (C). A multi-layer co-extrusion film blowing technology is adopted. Multiple material layers are compounded to prepare the film. The film is highly tough, the tensile strength can reach 18 MPa, the horizontal/vertical breaking elongation rate can reach more than 500%, no prominent difference exists in the vertical direction and the horizontal direction, the water steam baffling performance is strong, the water steam penetration rate of the film with a thickness of 10 [mu]m is 240 g/m2.24h; the processing performance is good, the minimal thickness of the film can reach 5 [mu]m; the processing equipment does not need frequent adjustment, and the film is used as a package film, an agricultural cover film, and the like.
Description
Technical field
The present invention relates to a kind of high tenacity high water vapor intercepts complete biodegradable complex multi layer films and preparation method, belong to
Technical field of polymer materials.
Background technology
While plastics bring civilization, also bring environmental hazard, the whole world annual plastic refuse total amount is high
Reach 50,000,000 t, account for the plastic refuse of plastic total amount about 10% because of its application extensively, using dispersion, and waste material
Amount is light, small volume, so recycling is unrealistic and uneconomic, and these products are the masters of white pollution in urban environment
Want source, biodegradable plastic is used then advantageously for this based article.Therefore, fully bio-degradable under exploitation natural environment
Green plastic receive the extensive concern of countries in the world government, scientific research institution and industrial circle.
In fact, complete biodegradable membrane-based article is in shopping bag, refuse bag, and the application of plastic film for agricultural use class is quite wide
General, so that agricultural mulching covers as a example, national mulch film usage amount will reach 1,400,000 tons, and area coverage, up to more than 400,000,000 mu, is China
Grain, cotton and oil increases production stable yields key technology, and current whole life cycle design is all right for suitable for crop Applied D emonstration, and following two
400,000 tons of actual amount will be formed, each provinces and cities also makes different acts in terms of propulsion complete biodegradable film class packaging bag in year
Arrange, such as the province with Jilin as representative has begun to implement " taboo is moulded and made " for normal packet pack, completely forbids commonly not
The use of degradable package product, Jiangsu Province also will release corresponding policy in 2017, comprehensive biological support degradable package bag
Use.Application for full-biodegradable film leaves wide space.
The production material of domestic film article at present, article technology also imperfection, in some key performances, such as draftability
Can, tear resistance, vapor water barriers performance etc., compared with ordinary plastic articles, also fails to be fully achieved replacement requirement, domestic
The research in this respect of a part of enterprise and research institution is also at the starting stage.Through to domestic existing technical literature patent
Retrieval finds, Chinese patent CN 201410770466.X is disclosed a kind of biodegradable high-performance PPC and intercepted with PBS multilamellar
Film it is characterised in that：Its group is divided into：Modified and light Calcium Carbonate with the mass ratio of PPC is:1～20：100；Chain extender is with PPC's
Mass ratio is 0.1～3:100；PBS and PPC, chain extender, the total mass ratio of modified nano calcium carbonate are 10～100:100.Its system
The multiplayer barrier films and methods of making obtaining, is primarily adapted for use in the obstruct to oxygen, and base material used by it is PBS and PPC, and its stability is resistance to
Time property cannot be guaranteed, and Chinese patent CN201410325225.4 discloses a kind of biodegradable high-barrier thermoplasticity polymerization
Thing, preparation method and its polymer application.Its polymer monomer includes the composite multi-component of a) Merlon segment and polyether segment
Alcohol, b) one or more micromolecular compounds with two or more hydroxyls, amido, c) one or more diisocyanate
Class compound, d) one or more cross-linking agent, its preparation method be a), b), c) hybrid reaction, then in mixed reactant again plus
Enter monomer d), carry out graft crosslinking.Although although the method improves the barrier of vapor, there is production stage loaded down with trivial details
(including head product to synthesize, modified processing), it is related to isocyanates residual in monomer and is allowed to limited in food and medicine packaging use
System.
Therefore, innovate on the basis of existing, a kind of good processability is obtained, production method is easy, low cost, serviceability
Good, there is the thin film being greatly improved to vapor water barriers, widen the range of biodegradation material, be that the present invention is urgently to be resolved hurrily
Problem.
Content of the invention
The purpose of the present invention is for technical limitations domestic at present, provides a kind of high tenacity high water vapor to intercept entirely biological
Degraded complex multi layer films and manufacture method.With weatherability high barrier material layer and high tenacity high barrier material layer and high tenacity
Functional material layer is arranged in pairs or groups, to reach effect that is toughness reinforcing and improving water vapor barrier property.
The present invention is achieved by the following technical solutions：
In a first aspect, the invention provides a kind of high tenacity high water vapor intercepts complete biodegradable complex multi layer films, its
Including interspersed stacked a floor height toughness high barrier material layer, the weather-proof high barrier material of b floor height and c floor height toughness functional living being
Degradable material layer, wherein, a is the integer more than or equal to 1, and b is the integer more than or equal to 1, and c is the integer more than or equal to 0,
Described high durable high barrier material layer includes the following component of meter by weight：
Preferably, described high tenacity high barrier material layer includes the following component of meter by weight：
Wherein main material is such as：Organically-modified material, inorganic modified material component changes less than this scope moisture-vapor transmission
Kind DeGrain, may cause solution intensity too low higher than this scope, lead to processing problems, also result in film article draftability
(such as tensile strength, elongation at break) can reduce, lead to composite membrane entirety serviceability to reduce.
Described PBAT is thermoplastic biodegradable's polyester, is being total to of ethanedioic acid butanediol ester and mutual-phenenyl two acid bromide two alcohol ester
Polymers, two segment ratios of PBAT (i.e. ethanedioic acid butanediol ester and p-phthalic acid butanediol ratio) ensure for commercial production can
Any ratio under degradability.
Preferably, described high tenacity functional living being degradable material layer include meter by weight as the following group
Point：
1～100 part of full-biodegradable material；
0.1～5 part of compatilizer.
Preferably, described full-biodegradable material is equal polyester or copolyesters.
Preferably, described compatilizer is selected from oxide-based compound, isocyanate ester compound, polyfunctional group ring
One or more of oxygen compound, phosphate compounds.Preferably, described peroxide compounds are diphenyl peroxides
One or more of formyl, cumyl peroxide, di-t-butyl peroxide, azodiisobutyronitrile；Described isocyanates
Compound is methyl diphenylene diisocyanate, in toluene di-isocyanate(TDI), hexamethylene diisocyanate, O-phthalic base two different
Cyanate, naphthalene diisocyanate one or more；The Joncryl that described multi-group epoxy compound such as BASF AG produces
ADR series of products；JoncrylADR series as a kind of chain extender, based on it in system specific response, also serve as compatilizer
Use；Described phosphate compounds are triphenyl phosphates, in trisnonylphenyl phosphite one or more of.
Preferably, described organically-modified material is biodegradable equal polyester or copolyesters；Described inorganic change
Property material be one or more of silicates, silica-based, oxide-based, surface modification fiber-like additive, its
In, the fiber-like additive of described surface modification is surface hydroxylation or carboxylated modified fiber-like additive.Inorganic modified
The further preferred organic modification montmonrillonite of material, Kaolin, Calcium Carbonate, calcium sulfate, Pulvis Talci, asbestos, Muscovitum, silicon dioxide,
One or more of attapulgite, clay, white carbon black and potter's clay.Organically-modified material is more preferably polylactic acid, poly- methyl second
One or more of support carbonic ester, polyhydroxyalkanoate, poly butylene succinate.
Preferably, in described initiator, there is anhydride functional group, can be with PBAT and table under high temperature process environment
One class compound of the face reaction of the inorganic material with carboxyl.Preferably, described initiator is maleic anhydride, succinic anhydride, phthalic
Dicarboxylic acid anhydride etc. therein one or more.
Preferably, described catalyst is carboxylate metal salt, and described metal includes aluminum, stannum, zinc or terres rares.Excellent
Choosing, described catalyst is stannous octoate, dibutyl tin laurate, dibutyl oxalic acid antimony, the one of which such as antimony acetate or
Several mixing.
Preferably, described waterproofing agent includes one or more of solid long-chain esters, liquid branched ester class, its
In preferably, be octyl stearate, butyl stearate, glyceryl monolaurate, frost flower wax, palm wax is therein a kind of or many
Kind.
Preferably, described ultraviolet-resistant aid is light stabilizer or UV absorbent.Preferably, described light is stable
Agent is 2 for the steady agent of described light, 2 '-thiobiss (4- t-octyl phenol epoxide) nickel, three (1,2,2,6,6- pempidine base) phosphorous acid
Ester, 4- benzoyloxy -2, one or more of 2,6,6- tetramethyl piperidines, HMPA.Described anti ultraviolet agent
It is oxybenzoic acid phenyl ester, 2,4-DihydroxyBenzophenone, ESCALOL 567, the just pungent oxygen of 2- hydroxyl -4-
Base benzophenone, 2- (the 2- hydroxyl -3- tert-butyl group -5- aminomethyl phenyl) -5- chlorinated benzotriazole, or 2- (2- hydroxyl -3,5- bis-
Tert-butyl-phenyl) -5- chlorinated benzotriazole, single benzoic acid resorcinol, 2,4,6- tri- (2 ' n-butoxyphenyl) -1,3,5-
One or more of triazine, ortho-nitraniline, p-cresol.
Preferably, described high tenacity high water vapor intercepts complete biodegradable complex multi layer films to include a floor height tough
Property high barrier material layer and a floor height weather-proof high barrier material layer.
Preferably, described high tenacity high water vapor intercepts complete biodegradable complex multi layer films to include a floor height tough
Property high barrier material layer and two-layer high durable high barrier material layer, described high tenacity high barrier material layer is located in two-layer high durable
Between high barrier material layer.
Second aspect, the invention provides a kind of high tenacity high water vapor as the aforementioned intercepts complete biodegradable composite multi-layer
The preparation method of thin film, it comprises the steps：
Prepare high tenacity high barrier material (abbreviation materials A) and high durable high barrier material (abbreviation material B) respectively；
Described high tenacity high barrier material and high-weatherability high barrier material are squeezed respectively using Multi-layer blown film equipment
Go out, composite membrane-forming, make described high tenacity high water vapor and intercept complete biodegradable complex multi layer films.
Preferably, described Multi-layer blown film equipment screw slenderness ratio be 25～65, screw speed be 100～
300rpm, the film mouth number of plies is 2～7 layers.
Preferably, described high tenacity high water vapor intercepts complete biodegradable complex multi layer films to include two floor heights resistance to
Wait high barrier material layer, two-layer high tenacity high barrier material layer and a floor height toughness functional living being degradable material layer, two-layer institute
State the upper and lower surface that high tenacity high barrier material layer is respectively arranged at high tenacity functional living being degradable material layer, two-layer
Described high durable high barrier material layer is respectively arranged at the surface of high tenacity high barrier material layer.
Preferably, described high tenacity high water vapor intercepts complete biodegradable complex multi layer films to include two floor heights resistance to
Wait high barrier material layer, three floor height toughness high barrier material layers and two-layer high tenacity functional living being degradable material layer, three layers of institute
State the setting of high tenacity high barrier material layer and described in two-layer between high-weatherability high barrier material layer, high-ductility sexual function described in two-layer
Packing layer is arranged between three floor height toughness high barrier material layers interspersedly.
The third aspect, present invention also offers a kind of high tenacity high water vapor obstruct complete biodegradable as the aforementioned is compound many
The preparation method of layer film, it comprises the steps：
Preparation high tenacity functional living being degradable material (abbreviation material C)；
Described high tenacity high barrier material, high-weatherability high barrier material and high-ductility function packing material are adopted multilamellar altogether
Crowded blow moulding equipment is extruded respectively, composite membrane-forming, makes described high tenacity high water vapor and intercepts complete biodegradable complex multi layer films.
More specifically, the preparation method of described high tenacity high-obstruction material is：
A) by PBAT, organically-modified material, inorganic modified material, initiator, compatilizer, catalyst is dried；
B) weigh quantitative dried PBAT, organically-modified material, inorganic modified material, initiator, compatilizer,
Catalyst；
C) each for step B raw material is put into blender to be sufficiently mixed；
D) step C gained mixture is melt extruded and water-cooled pelletizing through double screw extruder；
E) it is dried in drying baker after pelletizing, get product；
Preferably, in step a), the condition of described drying is 30～80 DEG C, 2～10h；Further, described dry employing
Vacuum drying oven or air drier；
Preferably, in step c), described mixing refers specifically to stirring at normal temperature；Further, the time of described stirring be 2～
3min, rotating speed are 300～500r/min；
Preferably, in step d), the temperature of described melt blending is 120～200 DEG C；Described extruding pelletization adopts twin screw
The die temperature of extruder is 120～200 DEG C, screw slenderness ratio is 25～65：1st, rotating speed 100～300r/min；
Preferably, in step e), the condition of described drying is 30～80 DEG C, 4～12h；Described drying specifically adopts vacuum
Drying baker or air drier；
The preparation method of described high-weatherability high barrier material B is：
A) by full-biodegradable material, inorganic modified material, waterproofing agent, compatilizer, ultraviolet-resistant aid is dried；
B) quantitative dried biodegradation material, inorganic modified material, compatilizer, waterproofing agent, anti-purple are weighed
Outer auxiliary agent；
C) each for step b) raw material is put into blender to be sufficiently mixed；
D) step c) gained mixture is melt extruded and water-cooled pelletizing through double screw extruder；
E) it is dried in drying baker after pelletizing, get product；
Preferably, in step a), the condition of described drying is 30～80 DEG C, 2～10h；Further, described dry employing
Vacuum drying oven or air drier；
Preferably, in step c), described mixing refers specifically to stirring at normal temperature；Further, the time of described stirring be 2～
3min, rotating speed are 300～500r/min；
Preferably, in step d), the temperature of described melt blending is 120～200 DEG C；Described extruding pelletization adopts twin screw
The die temperature of extruder is 120～200 DEG C, screw slenderness ratio is 25～65：1st, rotating speed 100～300r/min；
Preferably, in step e), the condition of described drying is 30～80 DEG C, 4～12h；Described drying specifically adopts vacuum
Drying baker or air drier；
Described high tenacity packing material preparation method is：
A) by full-biodegradable material, compatilizer is dried；
B) weigh quantitative dried full-biodegradable material, compatilizer, and be sufficiently stirred in blender；
C) step c) gained mixture is melt extruded and water-cooled pelletizing through double screw extruder；
D) it is dried in drying baker after pelletizing, get product；
Preferably, in step a), the condition of described drying is 30～80 DEG C, 2～10h；Further, described dry employing
Vacuum drying oven or air drier；
Preferably, in step c), described mixing refers specifically to stirring at normal temperature；Further, the time of described stirring be 2～
3min, rotating speed are 300～500r/min；
Preferably, in step d), the temperature of described melt blending is 120～200 DEG C；Described extruding pelletization adopts twin screw
The die temperature of extruder is 120～200 DEG C, screw slenderness ratio is 25～65：1st, rotating speed 100～300r/min；
Preferably, in step e), the condition of described drying is 30～80 DEG C, 4～12h；Described drying specifically adopts vacuum
Drying baker or air drier.
Compared with prior art, the present invention has following beneficial effect：
1st, high tenacity high barrier material layer, bridges nano modified inorganic material using organic material, makes partly inorganic material
Material oriented alignment in system, improves the water vapor barrier property of material layer；
2nd, high durable high barrier material layer, is base material using weatherability biology degradation material, system small molecular esters
Material is uniformly distributed in material surface, increases surface hydrophobic, improves material water vapor barrier property；
3rd, in whole membrane structure, by A, B bi-material interlayer every compound, the different vapor water barriers mechanism association of bi-material
Same, improve water vapor barrier property, 10m moisture-vapor transmission minimum can reach 242g/m2·24h.Wherein high tenacity high-barrier
The presence of property material, has slowed down small molecular ester material migration velocity in the material, has allowed it to have in whole film surface longer
Time be uniformly distributed the time, increased the weatherability of thin film；
4th, the addition of high-toughness material, improves the processing characteristics of thin-film material, and prepared film thickness minimum can reach 5
μm.Improve the mechanical performance of finished film, the tensile strength of film reaches 20Mpa, and elongation at break can reach 500% simultaneously；
5th, adopt compound structure, greatly improve the difference of thin film vertically and horizontally tensile property；
6th, composite adopts full-biodegradable material to add blending, maintains the biodegradability of material；
7th, composite low cost, good processability, preparation process is simple, workable it is easy to large-scale application is general
And.
Brief description
The detailed description with reference to the following drawings, non-limiting example made by reading, the further feature of the present invention,
Objects and advantages will become more apparent upon：
Fig. 1 is that the high tenacity high water vapor in this present invention intercepts the structural representation that complete biodegradable is combined double-layer filmses
Figure；
Fig. 2 is the structural representation of the high tenacity high water vapor obstruct complete biodegradable composite three-layer thin film in the present invention；
Fig. 3 is that the high tenacity high water vapor in the present invention intercepts the structural representation that complete biodegradable is combined five layer films；
Fig. 4 is that the high tenacity high water vapor in the present invention intercepts the structural representation that complete biodegradable is combined seven layer films；
In figure：1st, high-weatherability high barrier material layer；2nd, high tenacity high barrier material layer；3rd, high tenacity functional living being fall
Solution material layer.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, some deformation can also be made and improve.These broadly fall into the present invention
Protection domain.
As shown in figures 1-4, the invention provides the high tenacity high water vapor of 4 kinds of different numbers of plies intercepts complete biodegradable again
Close thin film, wherein, high tenacity high water vapor intercepts the compound double-layer filmses of complete biodegradable and includes the weather-proof high barrier material of a floor height
Layer 1 and a floor height toughness high barrier material layer 2；High tenacity high water vapor intercepts complete biodegradable composite three-layer thin film and includes two-layer
High durable high barrier material layer 1 and a floor height toughness high barrier material layer 2, high tenacity high barrier material layer 2 is located in two floor heights
Between weather-proof high barrier material layer 1；High tenacity high water vapor intercepts compound five layer films of complete biodegradable and includes two-layer high durable
High barrier material layer 1, two-layer high tenacity high barrier material layer 2 and a floor height toughness functional living being degradable material layer 3, two floor heights
Toughness high barrier material layer 2 is respectively arranged at the upper and lower surface of high tenacity functional living being degradable material layer 3, two floor heights
Weather-proof high barrier material layer 1 is respectively arranged at the surface of high tenacity high barrier material layer 2；High tenacity high water vapor intercepts entirely biological
Compound seven layer films of degraded are including two-layer high durable high barrier material layer 1, three floor height toughness high barrier material layers 2 and two-layer
High tenacity functional living being degradable material layer 3, three floor height toughness high barrier material layers 2 are arranged at high-weatherability high resistant described in two-layer
Between barrier material layer 1, two-layer high tenacity functional stuffing layer 3 is arranged between three floor height toughness high barrier material layers 2 interspersedly.
Table 1 shows the sample that the test result of average steam penetrating capacity (WVTR), each embodiment and comparative example use, and carries
For standard deviation.Test is as follows, and 10 μm of thin film (alleged thin film is this thickness below) made on blow moulding equipment by extrusion pellet,
Make standard sample test by GB/T 30412-2013.
The performance of each film product in table 1 contrast groups
1st, embodiment group 1
The concrete material of table 2-1 embodiment group 1 and interlayer proportioning
Table 2-2 embodiment group 1 moisture-vapor transmission test result
Table 2-3 embodiment group 1 film stretchability energy test result
Table 2-1 gives the different ratio of high tenacity high barrier material A, remaining high-weatherability high barrier material proportioning and
What trilamellar membrane different material layer thickness ratio was constant is embodied as situation.
Table 2-2 moisture-vapor transmission test result shows, all proportionings all have good vapor water barriers effect, averagely exist
Through rate score 300, wherein 1-1,260, the 1-2 that can reach of 1-4,1-5 provides the inorganic modified material of the limit (lacking), and organic changes
Property material addition situation, it also can reach the function of necessarily improving moisture-vapor transmission, but inconspicuous.The Film laminated number of plies
After change includes adding high tenacity functional living being degradable material (abbreviation material C), overall vapor water barriers performance is had necessarily
Impact, but non-dominant effect.
Table 2-3 film stretchability energy test result shows, embodiment group 1 proportioning thin film has excellent tensile property, no
The interpolation of the material modified and organically-modified material of machine, improves the tensile property of thin film, and its tensile strength energy average energy reaches
18Mpa, elongation at break average energy reaches 450%, and the elongation at break of wherein 1-2,1-5 film sample can reach 500%.Say
Understand inorganic modified material, the rational proportion of organically-modified material can at utmost lift the tensile property of thin film.In addition, passing through
The test data of different composite number of plies thin film can be seen that in the case that bi-material stratum proportion is certain, the compound number of plies plus
Enter high tenacity functional living being degradable material and can improve performance on a small quantity, but do not play a leading role.
2nd, embodiment group 2
The concrete material of table 3-1 embodiment group 2 and interlayer proportioning
Table 3-2 case study on implementation group 2 moisture-vapor transmission test result
Table 3-3 case study on implementation group 2 film stretchability energy test result
Embodiment group 2 is mainly in combination with the enforcement feelings of the different ratio situation explanation present invention of high-weatherability high barrier material B
Condition.
Table 3-1 gives specific proportioning situation, and the object form below with reference to five layers of laminated film further illustrates
The service condition of true case group 2.
Table 3-2 moisture-vapor transmission test result shows, all film samples of embodiment group 2 have to vapor water barriers rate
Certain positive raising effect, average moisture-vapor transmission as little as 400, wherein embodiment 2-4, water can be steamed by 2-5 mix proportion scheme
Vapor permeability numerical value is reduced to 260 about, illustrate the coordinated of nano inorganic filling material and waterproofing agent using can reach into
One step improves the effect of thin film water vapor barrier property.
Table 3-3 is film stretchability energy test result it can be seen that thin film involved by embodiment group 2 all has excellent stretching
Performance, tensile strength average energy reaches 19MPa, and elongation at break is not less than 350%, inorganic modified nano material adding proportion
Increase can improve thin film tensile strength, but the reduction along with elongation at break.Thin film involved by embodiment 2-1,2-3,2-6
Elongation at break can reach 500% it can be seen that the appropriate interpolation of waterproofing agent can produce toughening effect, increases by a small margin
The elongation at break of thin film.
3rd, embodiment group 3
The concrete material of table 4-1 embodiment group 3 and interlayer proportioning
Table 4-2 embodiment group 2 moisture-vapor transmission test result
Table 4-3 embodiment group 2 film stretchability energy test result
By different composite thickness degree facilities, case study on implementation group 3 illustrates that the present invention's is embodied as situation.Table 4-1
Give Ju Ti Pei Fang and three-layer thin-film and the concrete facilities of five layer films.
Table 4-2 moisture-vapor transmission test result shows that each thickness degree sets in the case that bi-material AB formula determines
The difference put can affect the vapor water barriers performance of thin film, various kinds film water vapor transmission rates digital average involved by embodiment group 3
It is maintained at 300, wherein corresponding to embodiment 3-2, thin film moisture-vapor transmission numerical value is further decreased to 240, each thickness degree is described
Suitable setting can largest optimization thin film moisture-vapor transmission.The impact to moisture-vapor transmission for the change of the compound number of plies is overall relatively
Little.
Table 4-3 film stretchability energy test result shows, the raising of high tenacity high barrier material A layer thickness proportion contributes to
Improve thin film entirety elongation at break, 550% can be reached, but simultaneously with the reduction of tensile strength.Comparative example 3-2
Can find with 3-5, the thickness proportion increase of high-weatherability high-obstruction can lead to vertically and horizontally extension at break difference problem.Composite bed
The increase of number has the small size effect improving film stretchability energy.
The present invention uses Multi-layer blown film technology, optimizes material modified A, B formula, makes complex multi layer films, and it leads to
Cross the high dispersive bridging technology of nano modified inorganic material, being uniformly distributed and the mechanism such as fixing, greatly of small molecule material water-proof material
The vapor water barriers performance and the tensile property that improve this product, and taken into account the weather resistance of thin film, its stretching is strong simultaneously
Degree reaches as high as 22MPa, and film elongation at break rate ranges up to 550%, and essentially eliminates vertically and horizontally elongation at break difference,
Moisture-vapor transmission reduces by 30%.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various modifications or modification within the scope of the claims, this not shadow
Ring the flesh and blood of the present invention.
Claims (17)
1. a kind of high tenacity high water vapor intercepts complete biodegradable complex multi layer films it is characterised in that including interspersed stacked a
Floor height toughness high barrier material layer, the weather-proof high barrier material of b floor height and c floor height toughness functional living being degradable material layer, wherein,
A is the integer more than or equal to 1, and b is the integer more than or equal to 1, and c is the integer more than or equal to 0,
Described high durable high barrier material layer includes the following component of meter by weight：
2. high tenacity high water vapor as claimed in claim 1 intercepts complete biodegradable complex multi layer films it is characterised in that institute
State the following component that high tenacity high barrier material layer includes meter by weight：
3. high tenacity high water vapor as claimed in claim 1 intercepts complete biodegradable complex multi layer films it is characterised in that institute
State the following component that high tenacity functional living being degradable material layer includes meter by weight：
1～100 part of full-biodegradable material；
0.1～5 part of compatilizer.
4. the high tenacity high water vapor as described in any one in claims 1 to 3 intercepts complete biodegradable complex multi layer films,
It is characterized in that, described full-biodegradable material is equal polyester or copolyesters.
5. the high tenacity high water vapor as described in any one in claims 1 to 3 intercepts complete biodegradable complex multi layer films,
It is characterized in that, described compatilizer be selected from oxide-based compound, isocyanate ester compound, multi-group epoxy compound,
One or more of phosphate compounds.
6. the high tenacity high water vapor as described in any one in claims 1 to 3 intercepts complete biodegradable complex multi layer films,
It is characterized in that, described organically-modified material is biodegradable equal polyester or copolyesters；Described inorganic modified material is silicon
One or more of Barbiturates, silica-based, oxide-based, surface modification fiber-like additive, wherein, described surface
Modified fiber-like additive is surface hydroxylation or carboxylated modified fiber-like additive.
7. the high tenacity high water vapor as described in any one in claims 1 to 3 intercepts complete biodegradable complex multi layer films,
It is characterized in that, in described initiator, there is anhydride functional group.
8. the high tenacity high water vapor as described in any one in claims 1 to 3 intercepts complete biodegradable complex multi layer films,
It is characterized in that, described catalyst is carboxylate metal salt, and described metal includes aluminum, stannum, zinc or terres rares.
9. the high tenacity high water vapor as described in any one in claims 1 to 3 intercepts complete biodegradable complex multi layer films,
It is characterized in that, described waterproofing agent includes one or more of solid long-chain esters, liquid branched ester class.
10. the high tenacity high water vapor obstruct complete biodegradable composite multi-layer as described in any one in claims 1 to 3 is thin
Film is it is characterised in that described ultraviolet-resistant aid is light stabilizer or UV absorbent.
11. high tenacity high water vapors as claimed in claim 1 intercept complete biodegradable complex multi layer films it is characterised in that
Including a floor height toughness high barrier material layer and a floor height weather-proof high barrier material layer.
12. high tenacity high water vapors as claimed in claim 1 intercept complete biodegradable complex multi layer films it is characterised in that
Including a floor height toughness high barrier material layer and two-layer high durable high barrier material layer, described high tenacity high barrier material layer sandwiched
Between two-layer high durable high barrier material layer.
A kind of 13. high tenacity high water vapors as described in claim 11 or 12 intercept the system of complete biodegradable complex multi layer films
Preparation Method is it is characterised in that comprise the steps：
Prepare high tenacity high barrier material and high durable high barrier material respectively；
Described high tenacity high barrier material and high-weatherability high barrier material are extruded respectively using Multi-layer blown film equipment, answers
Synthesis film, makes described high tenacity high water vapor and intercepts complete biodegradable complex multi layer films.
14. high tenacity high water vapors as claimed in claim 13 intercept the preparation method of complete biodegradable complex multi layer films,
It is characterized in that, described Multi-layer blown film equipment screw slenderness ratio is 25～65, and screw speed is 100～300rpm, film mouth
The number of plies is 2～7 layers.
15. high tenacity high water vapors as claimed in claim 1 intercept complete biodegradable complex multi layer films it is characterised in that
Including two-layer high durable high barrier material layer, two-layer high tenacity high barrier material layer and floor height toughness functional living being degraded material
The bed of material, high tenacity high barrier material layer described in two-layer be respectively arranged at high tenacity functional living being degradable material layer upper surface and
Lower surface, described in two-layer, high durable high barrier material layer is respectively arranged at the surface of high tenacity high barrier material layer.
16. high tenacity high water vapors as claimed in claim 1 intercept complete biodegradable complex multi layer films it is characterised in that
Including two-layer high durable high barrier material layer, three floor height toughness high barrier material layers and two-layer high tenacity functional living being degraded material
The bed of material, three layers of described high tenacity high barrier material layer are arranged and described in two-layer between high-weatherability high barrier material layer, two-layer institute
State high tenacity functional stuffing layer to be arranged between three floor height toughness high barrier material layers interspersedly.
A kind of 17. high tenacity high water vapors as described in claim 15 or 16 intercept the system of complete biodegradable complex multi layer films
Preparation Method is it is characterised in that comprise the steps：
Preparation high tenacity functional living being degradable material；
Described high tenacity high barrier material, high-weatherability high barrier material and high-ductility function packing material are blown using multi-layer co-extruded
Equipment of moulding is extruded respectively, composite membrane-forming, makes described high tenacity high water vapor and intercepts complete biodegradable complex multi layer films.
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Application publication date: 20170215 |