CN105173383A - Polycaprolactone multi-layer composite degradable packaging film - Google Patents
Polycaprolactone multi-layer composite degradable packaging film Download PDFInfo
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- CN105173383A CN105173383A CN201510484442.2A CN201510484442A CN105173383A CN 105173383 A CN105173383 A CN 105173383A CN 201510484442 A CN201510484442 A CN 201510484442A CN 105173383 A CN105173383 A CN 105173383A
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- packaging film
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention relates to the technical fields of degradable materials and packaging and provides a polycaprolactone multi-layer composite degradable packaging film. The packaging film is composed of four or more resin layers and structurally comprises outer layers containing biodegradable composition, and an inner layer covering one outer layer and containing biodegradable composition. Any resin layer of the packaging film is made of polycaprolactone or a blend of polycaprolactone and other resin materials which are mixed in different proportions; furthermore, the content of polycaprolactone in the resin layers of the packaging film becomes larger gradually in a gradient mode from the center to the outer layer, and melting temperature becomes lower gradually in a gradient mode. A novel structure and a novel mode are adopted for the packaging film, and the packaging film has high heat resistance, thermal shrinkage performance, softness and mechanical performance and can be widely applied to the packaging field.
Description
Technical field
The present invention relates to degradation material technical field and packing technique field, particularly relate to a kind of polycaprolactone biodegradable package film be made up of more than four layers or four layers resin beds.
Background technology
Under the large situation that, oil resources serious in environmental problem are short, biodegradable plastic obtains to be paid close attention to widely.Wherein, polycaprolactone is one of hot topic of research and development.The raw material of polycaprolactone industry is the biologicals that can regenerate, and final product of its degraded is also all water and carbon dioxide, can complete biodegradable, is one of Biodegradable material of most competitive power.
The film product of polycaprolactone and copolymerization product has broad application prospects at packaging field.But, polycaprolactone membrane is applied to packaging field, also there is an a lot of technical difficult problem.Such as, the ester bond of polycaprolactone is also unstable, in forming work, easily thermolysis or ester exchange reaction occurs.The goods of polycaprolactone one-component, because of the limitation of its performance, cannot meet the particular/special requirement of the aspects such as the use of goods, processing characteristics and outward appearance.Polycaprolactone and other monomers are formed binary blend by tradition application process, and wherein the content of polycaprolactone is 10 ~ 90%, and polyester forms continuous phase or co-cable transmission, but the tear resistance of the blend produced like this is very poor.The monofilm of polycaprolactone polyol composite is highly brittle usually, lacks elasticity, and erosion-resisting characteristics and heat stability also need to improve.
Seek polycaprolactone and other materials compound, and by its factor such as elasticity, mechanical property of process improving reasonable in design, be the only way that polycaprolactone membrane is exploited market further at packaging field.Japanese Patent Laid-Open 2004-109000 describes a kind of polyester and glass temperature (T
g) be the multilayer film of 0 DEG C or lower group aliphatic resin composition, but these film heat resistances are poor, cause percent thermal shrinkage obviously high.
As can be seen here, also there is above-mentioned multiple technologies problem in current polycaprolactone degradable packaging film.And the invention provides a kind of polycaprolactone MULTILAYER COMPOSITE degradable packaging film, this degradable packaging film is composited by polycaprolactone and other different resins, the melt temperature of every layer presents graded, improve adhesive property between layers, there is excellent flexibility, and stable mechanical property, be highly suitable for the use of packaging field.
Summary of the invention
In view of there is above-mentioned technical matters in prior art, the invention provides a kind of polycaprolactone MULTILAYER COMPOSITE degradable packaging film, this degradable packaging film has good degradable characteristic, can meet again the requirement of packing to resistance to effect of heat, mechanical property, processing characteristics and outward appearance simultaneously.The technical solution used in the present invention is as described below.
The invention provides a kind of stuctures and properties to stablize, and have the polycaprolactone MULTILAYER COMPOSITE degradable packaging film of flexibility, described polycaprolactone MULTILAYER COMPOSITE degradable packaging film is made up of more than four layers or four layers resin beds, as shown in Figure 1.Comprising:
(1) skin of biodegradable component is comprised; With
(2) internal layer comprising biodegradable component on one of them skin is covered.
Described " internal layer " means that in a kind of multiple-structure, two first type surface all directly adheres to any layer on another layer of this structure.Described " skin " means in a kind of multiple-structure to be had and any layer only had in a surface adhesion to this structure on another layer.
Any resin bed of described packaging film is the blend of the different proportion of single polycaprolactone material or polycaprolactone and other resin materials; And each resin bed of described packaging film is from the center to skin, its polycaprolactone content is with gradient profile incremental variations, and its melt temperature also to be successively decreased change with gradient profile.
Further, in polycaprolactone MULTILAYER COMPOSITE degradable packaging film of the present invention, the first skin and the second skin, containing 70 ~ 95 % by weight, are preferably the polycaprolactone in 80 ~ 90 % by weight scopes.Described internal layer contains 10 ~ 90 % by weight, is preferably the polycaprolactone in 25 ~ 75 % by weight scopes.
The degradable packaging film that the present invention states, in each resin bed, the component of polycaprolactone changes with gradient profile, the melt temperature of each layer is also changed with gradient profile, reduce the shaping temperature difference between layers, like this when material is extruded, with thermal drop and the transition of stress gradient form, meet the technological requirement of co-extrusion modling processing.
In polycaprolactone MULTILAYER COMPOSITE degradable packaging film of the present invention, the overall weight percentum of each component is as follows:
Described antioxidant can be one kind of multiple in triphenyl phosphite, phosphorous acid ethyl ester, cetyl pentaerythritol diphosphites; Described lubricant is any one in hard acid amides, zinc stearate, ethylenebisstearamide.
Polycaprolactone MULTILAYER COMPOSITE degradable packaging film of the present invention changes the character of each layer and the effect in overall laminated film by means of only the amount or ratio changing difference in functionality additive, such as can reduce the glass temperature of polycaprolactone in the amount of each internal layer interpolation plasticizer tirbutyl citrate, increase the flexibility of overall laminated film.
The thickness of polycaprolactone MULTILAYER COMPOSITE degradable packaging film of the present invention is in the scope of 50 ~ 250 microns.Wherein any two layers of thickness is than at 1:1 to 25:1, is preferably in the scope of 4:1 to 7:1.To comprise a skin of fully biodegradable component for reference, when any one deck is too thick relative to lower a layer thickness, will there will be crystallinity difference and the phenomenon of mechanical property instability, and any one deck too thick relative to last layer thickness time, described film heat adhesive strength will be difficult to reach technological requirement.In actual process, can by hopper Real-Time Monitoring discharge quantity of weighing, controlled reset extruder extrusion capacity, controls each layer thickness ratio.
The present invention has following beneficial effect: in preparation process, 1, decrease the shaping temperature difference produced because melt temperature is different between layers, adopt temperature and stress gradient form to transit to the technological requirement meeting Coextrusion Blow Moulding processing gradually, make composite material have good resistance to effect of heat and thermal contraction performance; 2, a kind of brand-new structure and pattern is provided for preparing polycaprolactone multi-layer compound film; 3 end article toughness are higher, have good flexibility and mechanical property, can be widely used in packaging field.
Accompanying drawing explanation
To be easier to make the present invention below understand, below in the description of embodiment, being described by embodiment with the mode be combined with reference to accompanying drawing, wherein:
Fig. 1 is described polycaprolactone MULTILAYER COMPOSITE degradable packaging film schematic diagram;
Fig. 2 is polycaprolactone four layers of composite degradable packaging film schematic diagram;
Fig. 3 is polycaprolactone five layers of composite degradable packaging film schematic diagram;
Fig. 4 is polycaprolactone six layers of composite degradable packaging film schematic diagram.
Wherein, 1 is the first skin, and 2 is the second skin, and 3 is internal layer a, and 4 is internal layer b, and 5 is internal layer c, and 6 is internal layer d.
Detailed description of the invention:
Can further illustrate the present invention by the following example, embodiment is unrestricted of the present invention in order to illustrate.Any those of ordinary skill of this area can both be understood these embodiments and not limit the present invention in any way, and can make suitable amendment and data transformation and without prejudice to essence of the present invention with depart from scope of the present invention to it.Table one is each embodiment product mechanics performance comparison situation.
Embodiment 1
Polycaprolactone MULTILAYER COMPOSITE degradable packaging film described in the present embodiment, as shown in Figure 2, be made up of four layers of resin bed, its structure comprises the first outer 1 and second skin 2 containing biodegradable component, and the internal layer a3 comprising biodegradable component covered on one of them skin and internal layer b4.Described internal layer is that in a kind of multiple-structure, two first type surface all directly adheres to any layer on another layer of this structure, and described skin is any layer having in a kind of multiple-structure and only have in a surface adhesion to this structure on another layer.
Any resin bed of described packaging film is the blend of the different proportion of single polycaprolactone material or polycaprolactone and other resin materials; And each resin bed of described packaging film is from the center to skin, its polycaprolactone content is with gradient profile incremental variations, and its melt temperature also to be successively decreased change with gradient profile.Concrete preparation method is as described below.
By the first outer 1 masterbatch component namely containing the polycaprolactone of 70 % by weight, poly-valerolactone, the ATBC of 14 % by weight, the tris phosphite input double screw extrusion machine of 12 % by weight of 4 % by weight.By the second outer 2 masterbatch components namely containing the polycaprolactone of 70 % by weight, poly-valerolactone, the ATBC of 14 % by weight, the tris phosphite input double screw extrusion machine of 12 % by weight of 4 % by weight.Namely internal layer a3 masterbatch component is contained the polycaprolactone of 10 % by weight, the poly-valerolactone of 35 % by weight, ATBC, the PTMC of 20 % by weight, the tris phosphite input double screw extrusion machine of 20 % by weight of 15 % by weight.Namely internal layer b4 masterbatch component is contained the polycaprolactone of 10 % by weight, the poly-valerolactone of 35 % by weight, ATBC, the PTMC of 20 % by weight, the tris phosphite input double screw extrusion machine of 20 % by weight of 15 % by weight.Each master batch makes masterbatch converge in the cylindrical shell of the concetrated pipe by extrusion die, and together by die head under the condition of streamline flow, wherein die head size can need to regulate according to film thickness.The film that thickness is 50 microns is obtained by up-coiler.Obtain product properties in table 1, show that described polycaprolactone MULTILAYER COMPOSITE degradable package film properties meets general packing requirement.
The expression formula of described composite package film is: the first skin/internal layer a/ internal layer b/ second is outer.
Embodiment 2
Polycaprolactone MULTILAYER COMPOSITE degradable packaging film prepared by the present embodiment, as shown in Figure 3, be made up of five layers of resin bed, its structure comprises the first outer 1 and second skin 2 containing biodegradable component, with three internal layers comprising biodegradable component covered on one of them skin, i.e. internal layer a3, internal layer b4 and internal layer c5.
Any resin bed of described packaging film is the blend of the different proportion of single polycaprolactone material or polycaprolactone and other resin materials; And each resin bed of described packaging film is from the center to skin, its polycaprolactone content is with gradient profile incremental variations, and its melt temperature also to be successively decreased change with gradient profile.
By the first outer 1 masterbatch component namely containing the polycaprolactone of 80 % by weight, poly-valerolactone, the ATBC of 7 % by weight, the tris phosphite input double screw extrusion machine of 1 % by weight of 12 % by weight.By the second outer 2 masterbatch components namely containing the polycaprolactone of 80 % by weight, poly-valerolactone, the ATBC of 7 % by weight, the tris phosphite input double screw extrusion machine of 1 % by weight of 12 % by weight.Namely internal layer a3 masterbatch component is contained the polycaprolactone of 50 % by weight, the poly-valerolactone of 12 % by weight, ATBC, the PTMC of 22 % by weight, the tris phosphite input double screw extrusion machine of 1 % by weight of 15 % by weight.Namely internal layer b4 masterbatch component is contained the polycaprolactone of 25 % by weight, the oligomerization caprolactone of 17 % by weight, ATBC, the caprolactone-ethanol copolymer of 37 % by weight, the tris phosphite input double screw extrusion machine of 1 % by weight of 20 % by weight.Namely internal layer c5 masterbatch component is contained the polycaprolactone of 65 % by weight, the poly-valerolactone of 17 % by weight, ATBC, the PTMC of 2 % by weight, the tris phosphite input double screw extrusion machine of 1 % by weight of 15 % by weight.Each master batch makes masterbatch converge in the cylindrical shell of the concetrated pipe by extrusion die, and together by die head under the condition of streamline flow, wherein die head size can need to regulate according to film thickness.The film that thickness is 150 microns is obtained by up-coiler.Obtain product properties in table 1, show that described polycaprolactone MULTILAYER COMPOSITE degradable package film properties meets general packing requirement.
The expression formula of described composite package film is: the first skin/internal layer a/ internal layer b/ internal layer c/ second is outer.
Embodiment 3
Polycaprolactone MULTILAYER COMPOSITE degradable packaging film prepared by the present embodiment, as shown in Figure 4, be made up of six layers of resin bed, its structure comprises the first outer 1 and second skin 2 containing biodegradable component, with four internal layers comprising biodegradable component covered on one of them skin, i.e. internal layer a3, internal layer b4, internal layer c5 and internal layer d6.
Any resin bed of described packaging film is the blend of the different proportion of single polycaprolactone material or polycaprolactone and other resin materials; And each resin bed of described packaging film is from the center to skin, its polycaprolactone content is with gradient profile incremental variations, and its melt temperature also to be successively decreased change with gradient profile.
By the first outer 1 masterbatch component namely containing the polycaprolactone of 95 % by weight, poly-valerolactone, the ATBC of 2 % by weight, the tris phosphite input double screw extrusion machine of 2 % by weight of 1 % by weight.By the second outer 2 masterbatch components namely containing the polycaprolactone of 95 % by weight, poly-valerolactone, the ATBC of 2 % by weight, the tris phosphite input double screw extrusion machine of 2 % by weight of 1 % by weight.Namely internal layer a3 masterbatch component is contained the polycaprolactone of 90 % by weight, the poly-valerolactone of 1 % by weight, ATBC, the PTMC of 2 % by weight, the tris phosphite input double screw extrusion machine of 6 % by weight of 1 % by weight.Namely internal layer b4 masterbatch component is contained the polycaprolactone of 88 % by weight, the poly-valerolactone of 1 % by weight, ATBC, the PTMC of 2 % by weight, the tris phosphite input double screw extrusion machine of 6 % by weight of 3 % by weight.Namely internal layer c5 masterbatch component is contained the polycaprolactone of 86 % by weight, the poly-valerolactone of 1 % by weight, ATBC, the PTMC of 2 % by weight, the tris phosphite input double screw extrusion machine of 6 % by weight of 5 % by weight.Namely internal layer d6 masterbatch component is contained the polycaprolactone of 86 % by weight, the poly-valerolactone of 1 % by weight, ATBC, the PTMC of 2 % by weight, the tris phosphite input double screw extrusion machine of 6 % by weight of 5 % by weight.Each master batch makes masterbatch converge in the cylindrical shell of the concetrated pipe by extrusion die, and together by die head under the condition of streamline flow, wherein die head size can need to regulate according to film thickness.The film that thickness is 250 microns is obtained by up-coiler.Obtain product properties in table 1, show that described polycaprolactone MULTILAYER COMPOSITE degradable package film properties meets general packing requirement.
The expression formula of described composite package film is: the first skin/internal layer a/ internal layer b/ internal layer c/ internal layer d/ second is outer.
The performance of table one polycaprolactone MULTILAYER COMPOSITE degradable packaging film
Claims (8)
1. a polycaprolactone MULTILAYER COMPOSITE degradable packaging film, it is characterized in that, described packaging film is made up of more than four layers or four layers resin beds, and its structure comprises the skin containing biodegradable component, and covers the internal layer comprising biodegradable component on one of them skin; Described internal layer is that in a kind of multiple-structure, two first type surface all directly adheres to any layer on another layer of this structure, and described skin is any layer having in a kind of multiple-structure and only have in a surface adhesion to this structure on another layer; Any resin bed of described packaging film is the blend of the different proportion of single polycaprolactone material or polycaprolactone and other resin materials; And each resin bed of described packaging film is from the center to skin, its polycaprolactone content is with gradient profile incremental variations, and its melt temperature also to be successively decreased change with gradient profile.
2. degradable packaging film according to claim 1, is characterized in that, described skin contains the polycaprolactone in 70 ~ 95 % by weight scopes, and described internal layer contains the polycaprolactone in 10 ~ 90 % by weight scopes.
3. degradable packaging film according to claim 2, is characterized in that, described skin contains the polycaprolactone in 80 ~ 90 % by weight scopes, and described internal layer contains the polycaprolactone in 25 ~ 75 % by weight scopes.
4. degradable packaging film according to claim 1, it is characterized in that, the component of each resin bed of described packaging film comprises polycaprolactone, caprolactone-ethanol copolymer, Caprolactone oligomers, poly-valerolactone, tris phosphite, poly-tetramethyl adipyl terephthalate, polytetramethylene glycol-adipic acid-terephthalic acid, PTMC, ATBC, polynite, antioxidant and lubricant altogether.
5. degradable packaging film according to claim 4, is characterized in that, described antioxidant is one or more in triphenyl phosphite, phosphorous acid ethyl ester, cetyl pentaerythritol diphosphites; Described lubricant is any one in hard acid amides, zinc stearate, ethylenebisstearamide.
6. degradable packaging film according to claim 1, is characterized in that, the thickness of described packaging film is 50 ~ 250 microns.
7. degradable packaging film according to claim 6, is characterized in that, any two layers of thickness of described packaging film is than being 1:1 ~ 25:1.
8. degradable packaging film according to claim 7, is characterized in that, any two layers of thickness of described packaging film is than being 4:1 ~ 7:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108017888A (en) * | 2017-12-02 | 2018-05-11 | 无锡福尔顺科技有限公司 | One kind sealing polycaprolactone pack case and its application |
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| EP2144221A1 (en) * | 2008-07-08 | 2010-01-13 | LG Chem, Ltd. | Biodegradable film for advertisement |
| CN102407644A (en) * | 2011-07-22 | 2012-04-11 | 蚌埠蓝天塑料包装有限公司 | Biodegradable multilayer composite polyethylene film and preparation method thereof |
| CN102858649A (en) * | 2010-03-12 | 2013-01-02 | 斯塔诺阿埃索澳吉有限公司 | Heat-sealable biodegradable packaging material, a method for its manufacture, and a product package made from the material |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN201026690Y (en) * | 2007-01-17 | 2008-02-27 | 广东德冠包装材料有限公司 | Paper or plastic complex photodegradation biaxial tension polypropylene film without glue |
| EP2144221A1 (en) * | 2008-07-08 | 2010-01-13 | LG Chem, Ltd. | Biodegradable film for advertisement |
| CN102858649A (en) * | 2010-03-12 | 2013-01-02 | 斯塔诺阿埃索澳吉有限公司 | Heat-sealable biodegradable packaging material, a method for its manufacture, and a product package made from the material |
| CN102407644A (en) * | 2011-07-22 | 2012-04-11 | 蚌埠蓝天塑料包装有限公司 | Biodegradable multilayer composite polyethylene film and preparation method thereof |
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| CN108017888A (en) * | 2017-12-02 | 2018-05-11 | 无锡福尔顺科技有限公司 | One kind sealing polycaprolactone pack case and its application |
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