CN105383133A - Bio-based high-barrier sheet material and preparation method thereof - Google Patents
Bio-based high-barrier sheet material and preparation method thereof Download PDFInfo
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- CN105383133A CN105383133A CN201510947846.0A CN201510947846A CN105383133A CN 105383133 A CN105383133 A CN 105383133A CN 201510947846 A CN201510947846 A CN 201510947846A CN 105383133 A CN105383133 A CN 105383133A
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- bio
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- based high
- barrier sheet
- sheet material
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/156—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is calendered and immediately laminated
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
Abstract
The present invention discloses a bio-based high-barrier sheet material and a preparation method thereof. The bio-based high-barrier sheet material comprises at least one bio-based plastic layer and at least one bio-based barrier layer; the preparation method of the bio-based high-barrier sheet material is as follows: taking layers of raw materials of the bio-based high-barrier sheet material for multi-layer coextrusion to obtain the bio-based high-barrier sheet material. On one hand, the bio-based plastic part replaces a traditional petroleum-based plastic, the bio-based barrier layer replaces a petroleum-based barrier layer, dependence on oil resources and production costs can be significantly reduced; on the other hand, by arrangement of the barrier layer, the bio-based high-barrier sheet material has water and oxygen barrier properties, and protection of an object in a package tray prepared from the sheet material can be improved. The bio-based high-barrier sheet material is prepared by multi-layer composite technology, and has excellent barrier properties, the content of a bio-based plastic material in the sheet material can be adjusted according to the need, the dependence on fossil plastics can be reduced, and the bio-based high-barrier sheet material has important environmentally-friendly significance.
Description
Technical field
The invention belongs to sheet material preparing technical field, particularly relate to a kind of bio-based high barrier sheet and preparation method thereof.
Background technology
Current plastic sheet, is usually used in the plastic products that plastics package manufacturing enterprise produces the various moulding such as cup, dish, dish, and food and pharmaceutical producing enterprise carry out online thermoforming-filling-lidding line.At present, on market for thermoset sheet material mainly polystyrene (PS) sheet material, polyvinyl chloride (PVC) sheet material and polypropylene (PP) sheet material of the company cup packaging of shaping-filling-lidding line.These sheet material advantages are technical maturities, material source is stablized, and the scope of application is extensive.But be all take petroleum-based plastics as primary raw material, barrier is not good, and the shelf life of products of packaging is shorter simultaneously.Due to petroleum resources growing tension, and the greenhouse gases that preparation petroleum-based plastics produces are more serious on global environment impact, reduce the use to petroleum resources and reduction carbon emission, become the target that everyone makes joint efforts.
Summary of the invention
In view of the above problems, the object of the present invention is to provide a kind of bio-based high barrier sheet and preparation method thereof, the manufacture being intended to solve existing packaging tray is overly dependent upon petroleum resources, environmental pollution is serious, and cannot be used in the technical problem in some Special use fields.
Bio-based high barrier sheet provided by the invention comprises at least one deck bio-based plastics layer and at least one deck bio-based barrier layer;
Described bio-based high barrier sheet is prepared by the following method: each layer raw material of described bio-based high barrier sheet is by multi-layer co-extruded obtained bio-based high barrier sheet.
Further, described bio-based plastics layer is starch plastics, the biological polyethylene of Bio-PE(), PHA(polyhydroxyalkanoate), PLA(PLA) in one or more.
Further, described bio-based high-obstruction be biological Geordie dragon, Bio-PET(biobased polyethylene terephthalate), PPC(poly (propylene carbonate)) in one or more.
Further, in described starch plastics, starch quality percentage is 15 ~ 70%, and vitrification point is at 70 ~ 125 DEG C, and fusing point is at 130 ~ 210 DEG C.
Further, described bio-based high-obstruction is adjacent between layer and is also provided with adhesive layer.
Further, described adhesive layer is EVA(vinyl-vinyl acetate copolymer), EEA(EEA), the maleic anhydride modified polyethylene of PE-g-MAH(), EAA(ethylene-acrylic acid copolymer), EMMA(ethylene methyl methacrylate copolymer), PP-g-MAH (maleic anhydride modified polypropylene), EMA(ethylene-methacrylic acid copolymer) in one or more.
Further, described bio-based high barrier sheet gross thickness is 0.3 ~ 2.0mm, and described bio-based plastics layer accounts for 40 ~ 80% of gross thickness.
Further, the thickness of described bio-based barrier layer is 0.06 ~ 0.4mm, and the thickness of described adhesive phase is 0.03 ~ 0.1mm.
On the other hand, the preparation method of described bio-based high barrier sheet comprises:
First get the raw materials ready according to formula metering according to sheet material number of plies candidate material, more each layer material is put into respectively corresponding extruder, extruded material, by Multi-layer coextruding die head, through three-roller calendaring, deburring, rolling, obtains bio-based high barrier sheet.
Further, described extruder is one or more in single screw extrusion machine, conical double screw extruder, parallel double-screw extruder.
The invention has the beneficial effects as follows: the invention provides a kind of nontoxic, high resistant wets, the environment protection biological base sheet of high resistant oxygen, have employed multi-layer co-extruded technique, the material of the different qualities such as bio-based barrier material, bio-based plastics is being combined with each other, recombination process does not use solvent, does not produce three wastes material, simplify production procedure, reduce equipment investment, environmental protection and energy saving.Sheet material provided by the invention can Some substitute tradition petrochemical industry plastics; considerably reduce the dependence to petroleum resources and production cost; and by arranging the oxygen function that blocks water that barrier layer makes high barrier sheet have common sheet material cannot to provide; increase the article protection in packaging; extend the scope of application of sheet material, the packaging field such as food, industrial goods can be used in.
Accompanying drawing explanation
Fig. 1 is the cross section structure figure of the high-barrier bio-based sheet material that first embodiment of the invention provides;
Fig. 2 is the cross section structure figure of the high-barrier bio-based sheet material that second embodiment of the invention provides;
Fig. 3 is the cross section structure figure of the high-barrier bio-based sheet material that third embodiment of the invention provides;
Fig. 4 is the cross section structure figure of the high-barrier bio-based sheet material that fourth embodiment of the invention provides.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The present invention, according to multi-layer co-extruded composite principle, on the basis of the multiple macromolecular material of choose reasonable, prepares not only environmental protection but also has the sheet material of excellent comprehensive performance and using function.Concrete, the high-barrier bio-based sheet material be prepared at least comprises one deck bio-based plastics layer, at least one deck bio-based barrier layer.The plastics that it is raw material that bio-based plastics refers to natural materials such as starch, it has recyclability, therefore very environmental protection.Bio-based plastics as certain one deck in sheet material or which floor, for substituting for conventional petroleum base plastics, greatly can alleviate the consumption to oil and dependence.In addition, by arranging barrier layer, making sheet material have the oxygen resistance that blocks water, the protection to object in sheet material can be improved.Preferably, described barrier layer is adjacent between layer and is also provided with adhesive layer.If barrier layer be adjacent the material polarity of layer similar when, also can without the need to arranging bond layer.Do not bondd by binding agent because polarity is similar, barrier layer is adjacent layer and also can well fits together, and ensures sheet structure stability.
The sheet material produced is generally used for prepares packaging pallet, and surface can be printed, labeling etc., and therefore when specifically arranging each layer position of sheet material, sheet material top layer should have qualified outward appearance, and is convenient to printing, labeling; Middle level or exterior barrier; Internal layer is preferably bio-based plastics layer, utilizes the softness of bio-based plastics and good involution performance, the article in better protection packaging.
Select to explain to the material of above-mentioned sheet material respectively below.
Described bio-based plastics layer has one deck at least, and every layer can be starch plastics, Bio-PE(biological poly ethene), PHA(polyhydroxyalkanoate) or PLA(PLA) etc., include but not limited to this.In wherein said starch plastics, starch quality percentage is 15 ~ 70%, and vitrification point is at 70 ~ 125 DEG C, and fusing point is at 130 ~ 210 DEG C.
Described bio-based barrier layer has one deck at least, and every layer can be biological Geordie dragon, bio-based PET or PPC(poly (propylene carbonate)).Wherein bio-based nylon selects the bio-based nylon 1010 of BASF AG's bio-based NYLON610 or Arkema to be take castor oil as primary raw material; Bio-based PET is that Brazilian Braskem obtains for raw material with sugarcane ethanol, all has the oxygen resistance that well blocks water; PPC is that Meng Xi group company or Henan Tian Guan company produce, and has good oxygen barrier.
When the physical property difference that barrier layer is adjacent layer is larger, in order to make bonding between each layer, firmly, ensure the bulk strength of bio-based high barrier sheet, preferably, described barrier layer is adjacent between layer and is also provided with adhesive layer.If barrier layer be adjacent the material polarity of layer similar when, also can without the need to arranging bond layer.Concrete, described adhesive layer is EVA(vinyl-vinyl acetate copolymer), EEA(EEA), the maleic anhydride modified polyethylene of PE-g-MAH(), EAA(ethylene-acrylic acid copolymer), EMMA(ethylene methyl methacrylate copolymer), PP-g-MAH (maleic anhydride modified polypropylene), EMA(ethylene-methacrylic acid copolymer) in one or more.
During concrete preparation bio-based high barrier sheet, first get the raw materials ready according to formula metering according to sheet material number of plies candidate material, more each layer material is put into respectively corresponding extruder, extruded material passes through Multi-layer coextruding die head, through three-roller calendaring, deburring, rolling, obtain bio-based high barrier sheet.
As instantiation, final obtained bio-based high barrier sheet gross thickness is 0.3 ~ 2.0mm, and described bio-based plastics layer accounts for 40 ~ 80% of gross thickness.The thickness of described barrier layer is 0.06 ~ 0.4mm, and the thickness of described adhesive phase is 0.03 ~ 0.1mm.During actual use, sheet material can be made into required pallet, such as electronic packaging pallet, fresh packaging pallet, prepared food packaging pallet etc.
Due to each layer position of bio-based high barrier sheet, the thickness effect parameters such as the hot strength of product, elongation at break, gas barrier property, oxygen transit dose, be described below by several specific embodiment.
embodiment one:
Fig. 1 shows the cross section structure of the bio-based high barrier sheet that first embodiment of the invention provides, and as shown in Figure 1, sheet material has three layers, is respectively layer 11,12,13.Its middle level 11 is biological Geordie dragon barrier layer PA610, accounts for 10% ~ 20%(percentage thickness, lower same), layer 12 is bond layer EVA, accounts for 5% ~ 10%; Layer 13 starch bio-based plastics (Wuhan Huali Environmental Protection Science and Technology Co., Ltd produces, and commodity are called PSM), account for 65% ~ 80%.Sheet material gross thickness is 0.3 ~ 1.5mm.
Empirical tests, the present embodiment product hot strength is: 22MPa; The present embodiment product gas barrier is: steam penetrating capacity≤0.8mg/24HL; Oxygen transit dose≤1.6cm
3/ m
224H0.1Mpa.
embodiment two:
Fig. 2 shows the cross section structure of the bio-based high barrier sheet that second embodiment of the invention provides, and as shown in Figure 2, sheet material has 4 layers, is respectively layer 21,22,23,24,25.Its middle level 21 is PLA (production of Natureworks company of the U.S.), accounts for 20 ~ 30%(percentage thickness, lower same); Layer 22 is bond layer EAA, accounts for 3% ~ 8%; Layer 23 bio-based nylon barrier PA1010, account for 8% ~ 25%; Layer 24 is bond layer EVA, accounts for 5% ~ 10%; Layer 25 is bio-based vinyon layer (Brazilian Braskem company produces, and product are called GreenPE), accounts for 35% ~ 50%.Sheet material gross thickness is 0.5 ~ 1.8mm.
Empirical tests, the present embodiment product hot strength is: horizontal 25MPa; The present embodiment product gas barrier is: steam penetrating capacity≤0.7mg/24HL; Oxygen transit dose≤1.5cm
3/ m
224H0.1Mpa.
embodiment three:
Fig. 3 shows the cross section structure of the bio-based high barrier sheet that third embodiment of the invention provides, and as shown in Figure 3, sheet material has five layers, is respectively layer 31,32,33,34,35.Its middle level 31 is bio-based PET barrier layer (Brazilian Braskem company produces), accounts for 10% ~ 15%(percentage thickness, lower same), layer 32 is bond layer EAA, accounts for 4% ~ 10%; Layer 33 is that bio-based barrier layer PPC(Henan Tian Guan company produces), account for 15% ~ 20%; Layer 34, for being bond layer EEA, accounts for 5% ~ 12%; Layer 35 is bio-based vinyon layer (Brazilian Braskem company produces, and product are called GreenPE), accounts for 40% ~ 70%.Sheet material gross thickness is 0.5 ~ 2.0mm.
Empirical tests, the present embodiment product hot strength is: 23MPa; The present embodiment product gas barrier is: steam penetrating capacity≤0.6mg/24HL, oxygen transit dose≤1.3cm
3/ m
224H0.1Mpa.
embodiment four:
Fig. 4 shows the cross section structure of the bio-based high barrier sheet that fourth embodiment of the invention provides, and as shown in Figure 4, sheet material has 7 layers, is respectively layer 41,42,43,44,45,46,47.Layer 41 is PLA (production of Natureworks company of the U.S.), accounts for 20 ~ 30%(percentage thickness, lower same); Layer 42 is bonding agent EAA, accounts for 2% ~ 5%; Layer 43 bio-based nylon barrier PA1010, account for 10% ~ 20%; Layer 44 is bonding agent EEA, accounts for 3% ~ 8%; Layer 45 is that barrier layer PPC(Henan Tian Guan company produces), account for 10% ~ 15%; Layer 46 is bonding agent EEA, accounts for 5% ~ 10%; Layer 47 is bio-based plastic layer PHA, accounts for 20% ~ 25%.Sheet material gross thickness is 1.6 ~ 2.0mm.
Empirical tests, the present embodiment product hot strength is: 30MPa; The present embodiment product gas barrier is: steam penetrating capacity≤0.3mg/24HL, oxygen transit dose≤1.1cm
3/ m
224H0.1Mpa.
To sum up, each layer material of choose reasonable sheet material of the present invention, according to multi-layer co-extruded composite principle, gives full play to the advantage of layers of material, prepares not only environmental protection but also has the sheet material of excellent comprehensive performance and using function.Sheet material has high obstructing performance, uses bio-based plastics Some substitute conventional petroleum base plastics, improves the mechanical property of product.
It should be noted last that, above detailed description of the invention is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (10)
1. a bio-based high barrier sheet, is characterized in that, described bio-based high barrier sheet comprises at least one deck bio-based plastics layer and at least one deck bio-based barrier layer;
Described bio-based high barrier sheet is prepared by the following method: get each layer raw material of described bio-based high barrier sheet by multi-layer co-extruded obtained bio-based high barrier sheet.
2. bio-based high barrier sheet according to claim 1, is characterized in that, described bio-based plastics layer is one or more in starch plastics, biological poly ethene, polyhydroxyalkanoate, PLA.
3. bio-based high barrier sheet according to claim 1, is characterized in that, described bio-based barrier layer is one or more any combination in biological Geordie dragon, biobased polyethylene terephthalate, poly (propylene carbonate).
4. bio-based high barrier sheet according to claim 2, is characterized in that, in described starch plastics, starch quality percentage is 15 ~ 70%, and vitrification point is at 70 ~ 125 DEG C, and fusing point is at 130 ~ 210 DEG C.
5. bio-based high barrier sheet according to claim 1, is characterized in that, described barrier layer is adjacent between layer and is also provided with adhesive layer.
6. bio-based high barrier sheet according to claim 5, it is characterized in that, described adhesive layer is one or more any combination in vinyl-vinyl acetate copolymer, EEA, maleic anhydride modified polyethylene, ethylene-acrylic acid copolymer, ethylene methyl methacrylate copolymer, maleic anhydride modified polypropylene or ethylene-methacrylic acid copolymer.
7. bio-based high barrier sheet according to claim 5, is characterized in that, described bio-based barrier layer thickness is 0.06 ~ 0.4mm, and the thickness of described adhesive phase is 0.03 ~ 0.1mm.
8. bio-based high barrier sheet according to claim 1, it is characterized in that, described sheet material gross thickness is 0.3 ~ 2.0mm, and described bio-based plastics layer accounts for 40 ~ 80% of gross thickness.
9. the preparation method of the bio-based high barrier sheet described in any one of claim 1 ~ 8, is characterized in that, described method comprises:
First get the raw materials ready according to formula metering according to sheet material number of plies candidate material, more each layer material is put into respectively corresponding extruder, extruded material, by Multi-layer coextruding die head, through three-roller calendaring, deburring, rolling, obtains bio-based high barrier sheet.
10. the preparation method of bio-based high barrier sheet according to claim 9, is characterized in that, described extruder is one or more in single screw extrusion machine, conical double screw extruder, parallel double-screw extruder.
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| CN201510947846.0A CN105383133A (en) | 2015-12-17 | 2015-12-17 | Bio-based high-barrier sheet material and preparation method thereof |
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| CN201510947846.0A CN105383133A (en) | 2015-12-17 | 2015-12-17 | Bio-based high-barrier sheet material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108909114A (en) * | 2018-06-14 | 2018-11-30 | 深圳市通产丽星股份有限公司 | A kind of carbon dioxide-base composite material and preparation method |
| CN109159501A (en) * | 2018-08-16 | 2019-01-08 | 金国轴 | A kind of high biomass content high barrier biology base packing container and preparation method thereof |
| CN110126416A (en) * | 2019-05-13 | 2019-08-16 | 无锡风鹏新材料科技有限公司 | A kind of furyl high barrier biological poly ester film and preparation method thereof |
| CN113942746A (en) * | 2021-09-06 | 2022-01-18 | 大连天汇荣环保科技有限公司 | Multilayer double-color environment-friendly bio-based plastic packaging container |
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