CN1071878A - Single thin film or the multilayer film formed by partial starch - Google Patents
Single thin film or the multilayer film formed by partial starch Download PDFInfo
- Publication number
- CN1071878A CN1071878A CN 91108086 CN91108086A CN1071878A CN 1071878 A CN1071878 A CN 1071878A CN 91108086 CN91108086 CN 91108086 CN 91108086 A CN91108086 A CN 91108086A CN 1071878 A CN1071878 A CN 1071878A
- Authority
- CN
- China
- Prior art keywords
- film
- starch
- processing treatment
- weight
- deck
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The single or multiple lift film that ventilation property is very little basically comprises one deck at least, but it is made up of the thermoplastic starch of processing treatment basically to small part.Because this single or multiple lift film is at least almost insensitive to water, therefore suggestion: this film has at least one deck also to contain at least a hydrophobic polymer (as polyolefine), has at least one deck to mix with starch during manufacturing; And/or starch is partial cross-linked at least on one layer surface at least; And/or one deck is by another layer covering at least at least, and this tectum is at least almost insensitive to water.In order to improve physical strength, also advise to stretch along single shaft or biaxially oriented by the film of manufacturing of the present invention.
Description
The present invention relates to minimum single or multiple lift film of ventilation property and preparation method thereof, improve film quality or mechanical property method, be used to prepare the polymer blend of forming by polyolefine and machinable thermoplastic starch of film, the preparation method of polymer blend, and the preparation method of machinable thermoplastic starch.
Be used to pack to the very sensitive article of oxygen (for example food), important problem is that the ventilation property of wrapping material is very little, with regard to the food that exemplifies, refers to that promptly oxygen-permeable is very little.
Other requirements to this based packaging material then are to insensitive, the enough mechanical propertys of moisture content, and should be transparent by its purposes, but also cheap.
Film especially for wrap food is made by polyvinyl chloride, and what this was well known and now widely used is the film of being made by polyvinylidene chloride (PVDC), for example film of being made by " saran ".The ventilation property of this class material and insensitive fabulous to moisture content, it is worrying to have to but its disadvantage is to contain chlorine, because can produce hydrogenchloride when burning.
In addition, also be well known by starch or the film made by amyloid polymer blend.Or rather, by the many as can be known so-called polymer blends of prior art, comprising being used to prepare the film of being advised and preparing the film that contains starch in any mode.In preparation during packaging film, starch itself without a doubt, because of the ventilation property of this class film is very little, but mechanical property is nowhere near, and suction is a key issue.
In order to enlarge the application of starch in plastics, its problem to be solved has two aspects, the first is not based on petroleum chemistry or film raw material, but according to the needs that enlarge so-called growing raw material, it two is according to plastic prod or can carries out biolytic suitable compacted products without difficulty based on polymkeric substance.
By EP-A-0402826 is known so-called polymkeric substance of this class or polymer blend arranged, its available native starch or derivatives thereof mixes with ethylene copolymer to be produced.In WO 90/14388, advise mixing mutually with polyethylene, and can add ethylene acrylate copolymer or glycerol, produce polymer composites by native starch.When obtaining polyblend thus and being used to prepare injection molding spare, mechanical property is on duty mutually, is unwell to the manufacturing film.The structure of the native starch that obtains in this class polymer blend, during as " engineering plastics ", its mechanical property is also very poor.
Advised many polymer blends at EP-A-0327505, EP-A-0404723, EP-A-0407350, EP-A-0404727 and EP-A-0404728, comprised polymkeric substance far from it or multipolymer based on so-called starch-splitting.Starch-splitting relates to the modification of starch, and it is by containing native starch that 15-20% moisture content promptly has common natural feature moisture content approximately through heating and mechanical workout acquisition.Find that under study for action this so-called starch-splitting can only be applied to what is called " engineering plastics " very limitedly, because natural structure obviously is to exist with this starch form all the time.What prior art that Here it is was advised can not be processed as the reason of high-quality thin-film based on the polymer blend of starch-splitting, because this film of producing can present brown, and mechanical property is on duty mutually, and the water resistance of this film also is on duty mutually in addition.
In addition, EP-A-0400531 and EP-A-0400532 also advise adopting so-called high boiling point plastic material and decomposing material with amylolysis, for example can with glycerol as plastic material and with urea as decomposing material.The ethylene acrylic and/or the polyvinyl alcohol copolymer that mostly are most 15% are added in the starch-splitting.Improve the Decomposition of native starch by plastic material (also available decomposing material), satisfy specification of quality as wrapping material but be not enough to high-mechanical property according to the film that EP-A-0400531 and EP-A-0400532 produce.
Therefore, the object of the present invention is to provide the film that is used for connection with wrapping of piece and other required purposes, the ventilation property of this film (for example oxygen-permeable) is very low, and is extremely insensitive to moisture content, and the transparency and satisfactory mechanical property.
Another task of the present invention is to provide polymeric material, this material at least partly is applicable to and comprises adjacent coil unit, each coil unit of any described coil assembly is twined by one of different described insulated conductor, and the coil unit of each successive coil assembly twines with the direction opposite with the front coil assembly;
Flatten coil assembly, obtain smooth in fact a Double-level Reticulated with one first axle head and one second axle head, a periphery section lap wound that makes each coil unit in the coil assembly of winning on an antipodal periphery section of each coil unit correspondence that also is the successive coil assembly of twining by same insulated conductor, and;
First axle head of described net is linked to each other with its second axle head, make one of each coil unit periphery section lap wound of follow-up coil assembly on an antipodal periphery section of coil unit correspondence that also is first coil assembly of twining by same described insulated conductor.
30. a manufacturing is used for polyphase motor, the method for the wire-wound field copper of generator or alternator comprises step:
Axially twine at least two insulated conductors around a common axis apart with first direction, thus formation with unitary first group of at least two adjacent windings of described first direction winding, each described coil unit has a nominal axial width; With with the distance axis of the specified axial width of relevant coil unit to the relevant described insulated conductor transposition of described first group coil unit;
Center on described axle axially to twine described insulated conductor apart with the opposite second direction of first direction, have unitary second group of two adjacent windings at least thereby form with what second direction was twined, described second group of coil unit is adjacent with first group of coil unit;
Flatten coil assembly and obtain a smooth in fact Double-level Reticulated, so that a periphery section lap wound of first coil unit of the coil unit that twines with first direction is on the corresponding antipodal periphery section of first coil unit of the coil unit that twines with second direction with first shaft end and second axle head; And;
Layer, then preferably at least one deck mainly only constitute by machinable thermoplastic starch, in addition two-layerly mainly makes by polyolefine.But the consumption of the thermoplastic starch of processing treatment in another layer is big more, and the necessity of the middle layer configuration that then is made of segmented copolymer is also low more.
It is to scribble one deck aluminum oxide and/or silicon oxide at least on its one side that the present invention also has a kind of film, preferably one deck silicon monoxide coating.This class film can be foregoing individual layer, bilayer or multiwalled film.
The coating amount of aluminium or silicon oxide is 100-400A.When farthest obtaining the transparency of film if desired, then film coating is selected silicon oxide for use, preferentially selects silicon monoxide for use.When film aluminising or silicon oxide, preferably in high vacuum, carry out.
Another kind of film of the present invention is to be coated with siloxanes at least on its one side, and this coating is crosslinked and/or crosslinked with starch to small part and itself.This class film also can be foregoing single or multiple lift film.Siloxanes is filmed and can be coated with siloxanyl monomers on the one side of film at least, and for example alkylsiloxane is handled siloxanes with the electronics ray gun then, thereby makes siloxanes and itself and part crosslinked with the starch on the film surface.In addition photosensitizers is added on siloxanyl monomers or the starch, then can increases crosslinked action.
When filming, preferentially adopt so-called Dipping method, be about to film and be immersed in the bathing pool that siloxanyl monomers is housed, make it produce siloxane film with scraper then with siloxanyl monomers.By the different energy sources of selecting UV-light or electron rays for use, immersion depth is about 7-10 μ when crosslinked.
Siloxanes is filmed can the single face coating, also can two finishing coats.
The alkylsiloxane of particularly suitable is diethoxy dimethylsilane or tetraethoxy-silicane.Siloxanyl monomers coating preferred thickness is 1 μ.
Another kind of film of the present invention is coating not, but handles on film surface with UV-light or electron rays rifle, makes the starch on the film surface at least partly crosslinked, this crosslinked water tolerance that improves starch.Starch added use photosensitizers, can improve crosslinking degree.
But another kind of film of the present invention is with the thermoplastic starch of processing treatment and borax, Mg
NianAnd/or potassium
NianOr other polyvalent cations mix mutually.But this is by when making the thermoplastic starch of processing treatment, it is mixed obtaining with borax, sal epsom or salt of wormwood.The advantage of these additives is to reduce the susceptibility of starch to water.
After above-mentioned single or multiple lift film of the present invention is made, stretch, can improve mechanical property along single shaft or biaxially oriented.
This known stretching technique of simple plastics film is all used in the known technology of the film of being produced by starch so far, because starch or obviously be considered to unfavorable with starch-mixed polymkeric substance.Used polymer blend in prior art produces phase decomposition between starch and other polymer phases during stretching, and therefore, this type of film almost can not use.A kind of possible method is the higher polymer blend of use water content that prior art is advised, but causes stretching to have no effect when making film.
But, but serve as basis when making film of the present invention with the thermoplastic starch of processing treatment, by stretching physical strength is significantly improved, this may be because film can extend along single shaft or biaxially oriented.
In addition, the present invention advises that also the scope of stretch ratio is chosen as 1: 4-1: 10.
According to the component and the structure of film, select 1 for use: the stretch ratio of 6-1.85 is favourable, and especially to select about 1 for use: the stretch ratio scope of 7-1.75 is good.
The film of making can at room temperature stretch, and equally also can stretch down at about 130 ℃.But proving, is favourable in about 90 ℃ to 130 ℃ temperature range in-draw.
In addition, the present invention also advises, before the polymer melt or its molten mass when making film, be dried to water content hardly at least.
But be dried at least and be lower than 1% or remove gas then be favourable if will be used to make the water content of thermoplastic starch of the processing treatment that contains polymkeric substance or polymer melt of film.When water content was higher, its danger was that film may or cause the mechanical property of film not good with look (as with brown).
Above-mentioned single or multiple lift film can be made by the method for known general manufacturing film, but preferably adopts right to want one of 10 to 14 described method preparations.
But but one deck at least of film is to adopt wide nozzle to extrude thermoplastic starch and at least a polyolefinic polymer blend bonding or that blow the thermoplastic starch of the bonding processing treatment of spray or contain processing treatment to make.Film is extrusion bonded or blow that the coextrusion trilaminar at least method of spray makes with wide nozzle, the two sides of one deck is respectively topped by another layer at least in these three layers, but described another layer formed polyolefine preferably polyethylene or polypropylene by the thermoplastic starch and the polyolefinic polymer blend of polyolefine and/or processing treatment.Each surface of film is gone up and is handled with UV-light or electron rays rifle, makes starch at least partly crosslinked.At least the one side of film use siloxanyl monomers, as the alkylsiloxane coating, handles with the electronics ray gun then, thereby makes siloxanes itself or its part crosslinked on film surface with starch.At least the one side of film adopts high vacuum to be coated with aluminum oxide or silicon oxide.
Extruding condition or winding-up condition depend on the scope of the melt temperature of the polymkeric substance selected for use or polymer blend, but for the thermoplastic starch of processing treatment, extrusion temperature surpass 210 ℃ too many, otherwise starch can decompose.
The present invention also advises, the polymer blend of being made up of polyolefine and starch is particularly suitable for making the film of the invention described above.Producing of this polymer blend can be lower than 3.5(weight with water content with polyolefine (as polyethylene or polypropylene)) %[is especially to be lower than 1(weight) % is good] but the thermoplastic starch of processing treatment mix mutually, starch content should not surpass 70% of total mixture weight.But the content of the thermoplastic starch of processing treatment is preferably 30-70%(weight) %(is in the polymer blend gross weight).
Additional tackifier preferably add to 30(weight) %, used tackifier are segmented copolymers, for example can be used as the middle layer when making multilayer film, but also can use when making polymer blend by polarity and non-polar polymer.Tackifier also can use polyvinyl-maleic anhydride-acrylate of being produced by ethene, acrylate and maleic anhydride.When making polymer blend, a kind of comonomer and starch form covalent chemical bond.
The polymer blend of the invention described above also can preferentially use 30-70(weight) but the thermoplastic starch of % processing treatment is produced fine film and molding, and its mechanical property or physicals and the difference of being produced by polyolefine are little.But the usage quantity of the thermoplastic starch of processing treatment is decided by the insensitive degree of needed polymer blend to moisture content, still can obtain enough to the moisture content insensitivity when using 70% starch.This polymer blend is exposed under 100% atmospheric moisture, and its surface just is sticky shape, and when 70% atmospheric moisture and room temperature, storage then is out of question.
For the film or polymer blend of the invention described above, but the thermoplastic starch of processing treatment is adopted in suggestion.
But when making the thermoplastic starch of processing treatment, suggestion is preferably lower than 1(weight with water content) starch of % and/or starch derivative and 20(weight at least) %[is preferably 25-45(weight) %] additive with the deformation energy form gadgetize of 0.25-0.5KWH/kg starch/additive agent mixture can condition under mix, be heated at least and can make the each component uniform mixing, additive contains a kind of material in the above-mentioned additive at least.The additive of particularly suitable has glycerol, sorbyl alcohol, amino alcohol, dimethyl sulfoxide (DMSO) or urea.Other can consult WO 90/05161.
Promptly to add the method that big water gaging decomposes different with the method for traditional so far decomposition native starch, but the thermoplastic starch of the processing treatment that the method for advising by the present invention obtains can carry out processing treatment without difficulty by known extrusion process and jet molding, can produce mechanical well behaved molding and extrudate whereby.Different with starch with water decomposition, but the thermoplastic starch of processing treatment especially has fabulous stress-strain ratio, does not also cause it to degenerate when aging.
In addition, the application's dependent claims 24-26 is a preferred method of the present invention.
But the thermoplastic starch of above-mentioned processing treatment and polymer blend are suitable for making the single or multiple lift film of the invention described above especially.Certain this raw material also is suitable for making extrudate or injection model spare.
Starch and 25-40(weight) %, preferred 32-38(weight) % amino alcohol, as monoethanolamine, aminopropanol, and/or trihydroxy-ethylamino methane mixes mutually, and respectively press additive and additive capacity, in 60 ℃ of-120 ℃ of temperature ranges, in extrusion machine or kneading machine, supply with the deformation energy of 0.3-0.36KWh/kg starch-monoethanolamine mixture, be processed into homogeneous material, the natural moisture content of starch can with remove by drying before amino alcohol mixes, or when mixing, remove by abundant exhaust by currently known methods with amino alcohol.
Starch and/or starch derivative and 12-40(weight) %, preferred 20-35(weight) the % polyalcohols, mix mutually as sorbyl alcohol or glycerol, and respectively press additive capacity, in 120 ℃ of-180 ℃ of temperature ranges, in extrusion machine or kneading machine, supply with the deformation energy of 0.3-0.36KWh/kg starch-glycerol mixture, be processed into uniform material, the natural moisture content of starch or starch derivative is fully removed by currently known methods when mixing.
The amount of the additive that is replaced by borax, sal epsom or salt of wormwood may be up to 20(weight) %, the about 10(weight of preferred amounts) %.
Now describe the present invention in detail according to the following drawings and embodiment.
Fig. 1-5 and embodiment illustrate the various possible films of the present invention.
Fig. 1 represents only to have the single thin film of one deck.But this layer film is to be made of the polymer blend of the present invention that the thermoplastic starch of polyolefine and processing treatment is produced.But the content of the thermoplastic starch of processing treatment is 30-70(weight) %(is in the polymer blend gross weight).But the consumption of the thermoplastic starch of processing treatment is determined the requirement of water sensitivity according to film.In this class film, but oxygen-permeable is not to determine that by the amount of the thermoplastic starch of processing treatment watertightness then can be regulated by the amount of polyolefine (as polyethylene).
Fig. 2 is that the two sides is all by the topped single thin film of coating 3.Shown in example in, but thin film layer 1 form by the thermoplastic starch of processing treatment, coating 3 can be aluminum coating, silica coating or silicon coating.Under aluminising or silicon oxide situation, the thickness of coating is 100-400A; Be coated with under the situation of siloxanes, the thickness of coating is 1 μ.In being coated with the film of aluminium lamination, oxygen-permeable is not fabulous, and water tolerance is also splendid.The advantage that is coated with silicon oxide (as silicon monoxide) is that film still keeps transparent, but water-fast and antioxygen is not as the film of aluminising.The advantage that is coated with siloxanes is that the water tolerance of film is splendid.
The three-layer thin-film that Fig. 3 is made up of one deck central core 1 and two-layer perisphere 5.But central core 1 is made up of the thermoplastic starch of processing treatment, and two-layer perisphere 5 is made by polyolefine (for example polyethylene).Can be coated with the middle layer of one deck segmented copolymer between layer 1 and layer 5, coating can adopt the used method of common manufacturing multilayer film.
In the example shown, middle layer 1 pair of prevention oxygen sees through and works, and the two layers of polyethylene layer guarantees not permeate water of film.Each layer thickness can be selected on demand, and for example two-layer 5 can respectively select 1 μ for use, and the middle layer can be selected 7 μ for use.But the thickness that also can select two skins 5 fully is 30 μ, and 60 μ are selected in middle layer 1.
The example of Fig. 4 almost film with Fig. 3 is identical, but the polymer blend that to be two-layer perisphere 5 produced by the thermoplastic starch of polyolefine and processing treatment is formed.The water tolerance of two-layer perisphere 5 is decided according to polyolefinic content in the polymer blend.If the requirement to watertightness is not too high, then can select this film.The advantage of this class film is cheap, because starch is more cheap than polyethylene, and starch is easy to by biological decomposition, and polyethylene can be burnt.
Fig. 5 is similar to the three-layer thin-film of Fig. 4 again, and the two sides of coating 3 all was coated with.Coating 3 can be selected the coating 3 among similar Fig. 2 for use, and promptly this coating is formed by aluminium, silicon oxide or by siloxanes.
Certainly, thin-film examples of the present invention can be changed by any-mode shown in Fig. 1-5.Therefore, can make two-layer, four layers, five layers or multilayer film in the nature of things, also can make the film of single face coating.
But now press the manufacturing that embodiment and accompanying drawing 6-13 describe thermoplastic starch, polymer blend and the film of the present invention of processing treatment in detail.
But the A. manufacturing of the thermoplastic starch of processing treatment
1. embodiment: glycerol starch
Water content being lower than 0.3% potato and 36(weight) % glycerol (by the gross weight of glycerol/starch) places double-shafted extruder.This mixture feeds the deformation energy of 0.3-0.5KWh/kg starch/glycerol mixture in about 160 ℃-190 ℃ extrusion machine, the violent mixing.By the mixing of two kinds of components, produce uniform molten mass, take out the back and granulate.But the about 0.3(weight of the water content of the even thermoplastic starch of the processing treatment that obtains thus) %.
But the thermoplastic starch of the processing treatment that makes thus is uniform amorphous state, small amount of crystalline during storage.But the feature the during thermoplastic starch of formation processing treatment is a following structures to be changed:
-on 0 glycosidic link, lose natural starch conformation, the dihedral angle on the glucosides Sauerstoffatom (expansion of spirane structure) by less than |-20 ° | increase to greater than |-20 ° |;
-lost the double refraction of starch;
But-on the starch of detection of reflected, lost more than 2 ° scattering angle in the wide-angle x-ray diffraction.
Other variations can be consulted aforesaid WO90/05161.It is emphasized that in this respect changing native starch uses other additives without glycerol, for example thanomin or Propanolamine, sorbyl alcohol or urea.
But the thermoplastic starch and the difference between the starch-splitting of processing treatment are the water vapor sorption isotherms.
But Fig. 6 represents the thermoplastic starch and the diastatic water vapor sorption isotherms of processing treatment.
But the suction situation of the thermoplastic starch of the processing treatment that water vapor sorption isotherms 11 expression is produced by embodiment 1.This thermoisopleth does not have point of inversion substantially.It is also to be noted that desorption isotherm is identical with absorption isotherm.Curve 12 is illustrated in moisture 25% diastatic water vapor sorption isotherms of 125 ℃ of decomposition.Different with thermoisopleth 11, curve 12 has 2 point of inversion.
Thermoisopleth among Fig. 6 is normally measured in the time of 20 ℃.
But be along with aging by the thermoplastic starch of the present invention's processing treatment and another difference between the starch-splitting, but the water vapor sorption isotherms of the thermoplastic starch of processing treatment is still basic identical, and diastatic water vapor sorption isotherms then changes along with wearing out.
But the thermoplastic starch of processing treatment also is different glass transition point with the difference that starch is separated in hydrolysis.But the glass transition point of the thermoplastic starch of processing treatment or second-order transition temperature are below room temperature, and water content is lower than 18(weight) the diastatic second-order transition temperature of % is always more than 40 ℃, thus material is become fragile.Water content is higher than 18(weight) during %, starch is sticky shape, thus make material always have to a certain degree pliability.When but the thermoplastic starch of processing treatment was aging, this feature still kept, and starch-splitting is along with aging, and glass transition point also improves thereupon, and through after the regular hour, material just becomes fragile.
It is extremely low that but another of the thermoplastic starch of processing treatment is characterised in that water content, is usually less than 3.5(weight) %, be lower than 1(weight) % is then better.
Embodiment 2: but contain the thermoplastic starch of the processing treatment of amino alcohol
2.1 thanomin
Native starch was placed 100 ℃ of loft drier inner dryings 2 days, preparation contains two mixtures of thanomin then, one of them contains 30(weight) thanomin (by the gross weight of starch/ethanolamine mixtures) of %, another mixture contains 34(weight) thanomin of %.
2 mixtures are placed 100 ℃ of kneading machines and even, and wherein to select the moment of torsion of kneading machine for use be the deformation energy of supplying with 0.3KWh/kg starch/alcohol mixture to first mixture, and second mixture is supplied with 0.34KWh/kg starch/alcohol mixture by adjusting moment of torsion.In 15 minutes and under 100 ℃ of temperature, be squeezed into 2 uniform material plates.With no longer including any undecomposed starch granules on 2 plates of microscopic examination.The sample of 2 blocks of plates is carried out pliability test, and first sample contains 30(weight) the % thanomin, because the fracture at once that is highly brittle; Second sample contains 34(weight) the % thanomin, owing to the pliability that has to a certain degree, so can be crooked.
In addition, prove that also the water absorption of first sample is significantly higher than the water absorption of second flexible sample.
2.2 3-amino-1-propyl alcohol
Native starch was placed 100 ℃ of loft drier dry 2 days, prepare two mixtures again, one of them contains 32(weight) 3-amino-1-propyl alcohol of %, another contains 36(weight) 3-amino-1-propyl alcohol (all by the mixture total weight amount) of %.
Two mixtures are placed 100 kneading machines and even.The selection of kneading machine moment of torsion: first mixture is supplied with the deformation energy of 0.29KWh/kg mixture, and second mixture supplied with the deformation energy of 0.32KWh/kg mixture.Evenly the back extruding is in blocks, following 15 minutes at 100 ℃ again.
Pliability test proves: the sheet of first mixture is quite crisp, just breaks when minimum bend.Second sample has higher pliability, just breaks when bends.Compare with first sample, first sample has higher water sorbency.
Certainly only as an example in mixture described in above-mentioned first and second embodiment and processing treatment condition.But native starch is containing other additives and also have the thermoplasticity of processing treatment under other processing temperature condition.In addition, prove that also addition is a 36-38(weight when using glycerol) %(is by total mixture weight) then be to conform with ideal.
Under the condition of adding monoethanolamine or thanomin, addition is a 35(weight) be to conform with ideal during %; Adding under the condition of aminopropanol, addition is a 34-36(weight) be to conform with ideal during %; Under the condition of adding trihydroxy-ethylamino methane, addition is a 34-36(weight) be to conform with ideal during %.When supplying with deformation energy, ideal value is 0.32KWh/kg starch/additive agent mixture, departs from this value and also can obtain same purpose.
B. the preparation of polymer blend
3. embodiment: but prepare polymer blend by the thermoplastic starch of polyethylene and processing treatment
With 50(weight) % new LDPE (film grade) (LDPE), 40(weight) % glycerol starch and 10(weight) after % segmented copolymer (Orevac 18211 der Firma Ato Chemie) mixes, place kneading machine together, at 160 ℃ with supply with and to mix the back under the condition of 0.2KWh/kg mixture and granulate.
The polymer blend that makes thus contains 40(weight) but the thermoplastic starch of % processing treatment, and injection mould is made master die system body then, measures its water-absorbent and stress-strain ratio.
Molding was placed boiling water 10 hours, and can measure maximum water regain then is 2%.
Stress-strain ratio adopts simple strain-gauge test to measure down at 20 ℃.The response curve that obtains is shown in Figure 10, represents with figure number 21.To discuss below about stress-strain(ed) curve.
Another mixture contains 70(weight) but thermoplastic starch, 20% polyethylene and 10% segmented copolymer of % processing treatment are made corresponding polymer blend in kneading machine.The chemical combination condition is as above selected.Make water-proof molding again by prepared polymer blend.This molding was placed 70% atmospheric moisture and room temperature following 10 hours, can determine that deformation does not take place on its surface.
Can also prove: under 100% atmospheric moisture, promptly contact with liquid water, the molding surface is sticky state.
The result who is obtained by two polymer blends being produced proves: according to water-proof requirement, must select the starch addition by the polymer blend gross weight, but should not surpass 70(weight) %.Obviously in polymer blend, also there are many polyethylene, so that in polymer blend, form poly dependency structure.Excellent water tolerance if desired, but so in polymer blend the content of the thermoplastic starch of processing treatment should not surpass 50(weight) %.
As for tackifier or segmented copolymer, adding 2-5(weight) % just can make two kinds of abundant mixings of multipolymer.Certainly tackifier also can consider to use other materials, the Lotader of CDF-chemical company for example, the Novatec of Mitsubishi Chemical Ind, the Lonply of the Surlyn of E.I.Du Pont Company and Mitsui Toatsu company etc.About the product of segmented copolymer, when chemical combination, can use the two-phase polymer blend usually.
The stress of the amount that tackifier are added in Fig. 7-9 explanation during, the relative strain during to yield-point and the influence of modulus of elasticity to yield-point.In polymer blend, contain 50-60(weight) the % polypropylene, 40(weight) but the thermoplastic starch and the 10-0(weight of the processing treatment of % embodiment 1) % tackifier Lotader 3318.
Fig. 7-9 gives the influence of the different additions of tackifier.Stress when Fig. 7 provides yield-point is in order to bear about 5(weight) steady state value of %, about 3(weight) addition of % tackifier can obtain best effect.
Therefore, in Fig. 8, under the condition of the relative strain in the time of can determining yield-point, add 5(weight) % left and right sides tackifier, can keep constant equally.
Relative therewith, the addition and the modulus of elasticity of tackifier are linear.
4. embodiment: but prepare polymer blend by the thermoplastic starch and the polypropylene of processing treatment
Fig. 7 provides corresponding stress-strain(ed) curve, and figure number is represented with 22.
Discussion about Figure 10:
Figure 10 provides the different tests molding and carry out the stress-strain diagram that strain-gauge test obtains under 20 ℃ of condition.
But this stress-strain diagram is to compare by containing polyethylene and polyacrylic polymer blend standard molding of making and the standard molding of only being made by the thermoplastic starch of processing treatment aforesaid.Curve 21 expression contains polyethylene and 40(weight) but the stress-strain relation of the polymer blend of the thermoplastic starch of % processing treatment.
In order to contrast, two stress-strain(ed) curves are all represented with starch sample in Figure 10, by figure number 23 and 24 marks.
But curve 24 expressions promptly contain 36(weight by the thermoplastic starch of the processing treatment that embodiment 1 produces) the % glycerol.
When 4 curves are compared, can see that significantly the intensity of sample 23 is minimum.
Contrast therewith, the intensity of sample 24 is higher, but crackle just occurs when quite short about 12% strain.
Can reach a conclusion thus, produce polymer blend, particularly contain poly polymer blend, but its tensile strength roughly can be comparable with the thermoplastic starch of simple processing treatment.Especially since curve 24 than the tensile strength height of curve 21, so can imagine, but owing in polyethylene, added the thermoplastic starch of processing treatment, compare with simple polyethylene, mechanical property does not reduce.But its prerequisite is to make the starch plastification according to processing conditions of the presently claimed invention.
Also can replenish a bit,, when its strain is significantly higher than simple starch sample, crack on the sample by the sample that two polymer blends are formed.
C. the manufacturing of film
5. embodiment: the manufacturing of individual layer starch film
By containing 35.6(weight) % glycerol and 0.5(weight) the % water gross weight of starch mixture (all by) but the thermoplastic starch of processing treatment make the individual layer starch film.
With starch place L/D than be 30 and temperature range be 180 ℃-200 ℃ single shaft extrusion machine fusion, the revolution of extrusion machine is 110 rev/mins, pressure 90-120 crust.Measuring temperature of charge is 212 ℃.Obtain clean clear films in 170 ℃ clearance type nozzle, the speed of drawing can reach 12 meters/minute, and pulling roll is cooled to 15 ℃.In the single shaft forcing machine, use the sieve plate that different filter sieve are housed, with the homogeneity that improves molten mass with prevent that nozzle from polluting.
When making film, the residence time of starch in extrusion machine is 3 minutes, can not surpass.When the residence time surpassed 3 minutes in extrusion machine, starch will decompose, and the film of pulling out will become brown.Also have a bit very important, starch granules can not be in air before extruding overstand (more than 5 hours), otherwise can absorb moisture content, thereby in film, produce bubble.Change and draw speed, can produce the starch film that the film degree is 9-270 μ.
6. embodiment: the manufacturing of another kind of individual layer starch film
Produce for the native starch of＜0.3g/100g dry starch by water content.In 200kg gross weight (total prescription), produce by glycerol, 50kg high density polyethylene(HDPE) (measuring melt flow index at 190 ℃ with 5.16kg is 0.1/10 minute) and the 50kg ethylene-propylene acetoacetic ester-copolymer-maleic anhydride (maleic anhydride of ethyl propenoate/2mol% of ethene/8mol% of 90mol%) of above-mentioned starch of 75kg and 25kg99%.
Polymer blend is granulated by the condition preparation back of similar embodiment 5.But also can directly continue to be processed into following film.
Select following condition to prepare film:
Screw diameter 25mm
Screw rod total length 25D
160 ℃ of charging zone 9D
165 ℃ of crush zone 8D
170 ℃ of baffle area 4D
Spiral degree of depth 3.5mm
Spiral degree of depth 1.75mm in the baffle area
Film can prepare with blow moulding or wide injection lamination Method for bonding.When using particle, should notice that its water content is lower than 1(weight) %.
Thickness be the blown film of 20-80 μ m through measuring down column data:
Tensile stress (DIN 53455) 22mpa
Yield strain (DIN 53455) 5%
Tensile stress during fracture (DIN 53455) 25mpa
Unit elongation during fracture (DIN53455) 350-400%
Elasticity energy storage 10MJ/m during fracture
2
Seepage force (DIN 53142) 3.5J
Burstpressures (DIN 53113) 40kpa
Physical-chemical data:
Density (23 ℃) is 1.2-1.3g/cm (DIN53479)
3
The permeability coefficient of oxygen in the time of 23 ℃ (DIN 53380) 1.5 * 10
-15Cm
2/ spa
Water-absorbent in damp atmosphere
-thin slice, under 70% relative humidity 4 days 3.5%
-film, under 70% relative humidity 4 days 6.8%
Rheology:
Melt flow index (DIN 53735)
-190/21.6 8.7g/10 minute
-190/10 2.0g/10 minute
-190/5 0.3g/10 minute
Figure 11 and 12 be illustrated in the water and room temperature under, the extension tension force of the fracture of blown film and the relation of extension at break and storage.Table 12 and the explanation of 13 method Chu: although hydrophilic contents of starch is quite high, 1000 minutes later water tolerance of seasoning are still fine, and therefore the film of seasoning in water still keeps well extending tension force and extension at break value.
Figure 13 is relevant with Fig. 6, provides good biological decomposition figure system and measures according to OECD regulation (improved MITI tests), provides biological decomposition figure by the unit time oxygen absorbed thus.As seen from Figure 14, the three-layer thin-film of simple starch, the edge is topped by layer of polyethylene, decomposes fully after 10 days in theory.But the film by the polymer blend of embodiment 6 is made should just decompose after more than 30 days in theory.
7. embodiment: three-layer thin-film
The three-layer thin-film that manufacturing is made up of new LDPE (film grade)/starch/new LDPE (film grade).Used starch is but that water content is a 0.3(weight by the thermoplasticity glycerol starch of the processing treatment of embodiment 1 preparation) %.
Additional single shaft extrusion machine on the used single shaft extrusion machine in embodiment 5, the extrusion ratio of selecting for use is 1: 3, the L/D ratio is 28.The temperature of additional extrusion machine is transferred to 180-190 ℃, operating pressure 180 crust, about 40 rev/mins of revolution, poly temperature of charge transfers to 230 ℃, and throughput is 10kg/h.
With blowing head three-layer thin-film is sprayed, use the middle layer of making in the present embodiment by segmented copolymer.Certainly, obtain optimum adhesion, preferably use the segmented copolymer middle layer in order to make between three layers.All be suitable for as embodiment 2 and 3 described whole segmented copolymers, also can use other improved adhesive bonding methods, corona treatment for example, ozonation treatment etc.
D. starch film films
8. embodiment: aluminising film
The thick starch film of 50 μ that embodiment 5 is made carries out the high vacuum aluminising.The pressure that aluminising is selected for use is 6 * 10
-4Torr, all film in the two sides to starch film in 20 minutes.The coating that forms in this time respectively is that 400nm or total thickness are 800nm or 0.8 μ.
Another starch film is under similarity condition, and the two sides aluminising was filmed 24 minutes, and every layer thickness is 500nm, and total thickness is 1000nm.
The starch film of two sides aluminising film is carried out ventilation property and water-permeable test, and the gained aggregation of data is listed in table 11.
9. embodiment: silicon oxide is filmed
Similar the foregoing description method, the thick starch film of 50 μ that adopts embodiment 5 to make.High vacuum is carried out with silicon oxide in the two sides of this film film, promptly 4 * 10
-4Evaporate silicon with Jupiter in the oxygen of torr, for the time 100 minutes, form on the film two sides and to film, every layer thickness is 400nm.
Under the same condition of filming, to film 150 minutes time, the thickness of every layer of silicon oxide is 600nm.
The starch film that scribbles silicon oxide film is carried out ventilation property and water-permeable test, and its gained data summary is listed in table 2.
The discussion of table 2:
Table 2 is oxygen-permeable and a permeable steam of measuring the various films of the invention described above.
Compare with film of the present invention, also comprise the test of various other films of making by rhodia, hydrocellulose, polyvinylidene chloride (PVDC) and polyvinyl chloride.
Measurement about permeable steam, usually it should be noted: this measurement is carried out under 23 ℃, aluminising under 100% relative air humidity is coated with silicon oxide under 75% relative air humidity, is coated with rhodia, hydrocellulose and polyethylene under 90% atmospheric moisture.
About ventilation property, then be to measure oxygen-permeable.
The discussion of ventilation property:
As the reference data, known this class film is widely used owing to oxygen-permeable is low with the ventilation property data of polyvinylidene chloride (PVDC) film and polyvinyl chloride (PVC) film.Can see that in contrast the oxygen-permeable of polyethylene film is very high, compare that the three-layer thin-film that contains the starch middle layer then has oxygen-permeable with the PVDC film.
The ventilation property of aluminising starch film is hanged down 10 times than PVDC film or above-mentioned three-layer thin-film.In contrast to this, the oxygen-permeable that scribbles the starch film of silicon oxide slightly is worse than three-layer thin-film, may be owing to be coated with undesirablely on the starch film.The data that obtain are roughly consistent with the data of the three-layer thin-film with starch middle layer.
The discussion of water-permeable:
With the data of polyethylene film as a reference, because known polyethylene is very waterproof.In addition, also explanation has only the three-layer thin-film with starch middle layer of embodiment 7 just to have the optimum data same as simple polyethylene.
In contrast to this, the permeable steam of the starch film of aluminising or silicon oxide is significantly relatively poor, but compares with rhodia obviously better with hydrocellulose.
The data of table 11 obviously represent, can select needed membrane structure when adding what additive.It is further noted that; Compare with containing poly three-layer thin-film, the advantage of the starch film of aluminising or silicon oxide is can be fully promptly by biological decomposition, because aluminium becomes aluminum oxide, silicon oxide becomes sand.
The advantage that is coated with the starch film of silicon oxide is to have the good transparency.
Describe the degree of drawing of film as suggested in the present invention at last in detail according to embodiment 10 and 11.
10. embodiment: the single thin film of making by stretched polymer blend
The polymer blend that embodiment 6 is made is dried to water content and is lower than 1(weight) %, then by blowing out the thick film of 50-120 μ in the polyblend.Processing conditions is equivalent to embodiment 6.
The film of being produced by the starch blending polymkeric substance is in room temperature or high to 140 ℃ of temperature, with 1: 6-1: 7.5 stretch ratio stretches, thereby obtains having the film of following mechanical property:
Stress 40-200MPa during fracture
Strain 10-270% during fracture
Energy expenditure～4MJ/mm when rupturing
2
Different stretching conditions and the corresponding various mechanical propertys of measurement are listed in the table below 1.Below given definition help to understand.
Stress during-σ B=fracture, the power (by initial cross-section) (technology stress) that records when being defined as fracture;
Relative strain (%)=((L)/(L of-DB%=sample initial length
0)) * 100%, the length in the formula under the L=state of strain, L
0=initial length);
-E=is calculated by the initial slope of stress-strain(ed) curve in simple extension test;
The energy expenditure of-WB=when rupturing;
-λ R=stretch ratio ((L)/(L0));
-
Draw speed=ln ((L)/(L during=stretching
0))/S;
Terminal speed when-VK=stretches;
Temperature when-TR=stretches.
Tension test is undertaken by dual mode:
-general uniaxial strain;
-wait biaxial strain.
Table 1
Can be clear that by table 1, stretched film, the data of its rupture stress and modulus of elasticity significantly are better than unstretched film as a comparison.
Equally meaningfully, compare with simple polyethylene film, can think: starch is added in the polymer blend, and the data of mechanical property only have unconspicuous negatively influencing.In other words, make by polyethylene with the film of making by embodiment 2 polymer blends, after stretching with 1: 7 ratio approximately, its mechanical property is basic identical.
11. embodiment: multilayer film
The present embodiment introduction be three-layer thin-film with ABA stratotype, its outside two-layer overcoat produce every bed thickness 10 μ by embodiment 6 described polymer blends; But middle layer B is produced by the thermoplastic starch of the processing treatment of embodiment 1, and thickness is 120 μ.
Known coextrusion techniques is adopted in the manufacturing of this three-layer thin-film, and promptly three-layer thin-film can adopt blow moiding method or plane laminating method.The conditional likelihood that extruding condition provides with embodiment 3 basically, promptly the temperature range in the extrusion machine is selected about 160 ℃-170 ℃ for use.
But owing to there is the thermoplastic starch of processing treatment in A layer or the B layer, each ply adhesion gets fabulous, does not need additional tackifier or middle layer.
Described three-layer thin-film is same, and to adopt 1: 7 ratio, 128 ℃ of temperature and draw speed be that 0.2 condition stretches, stretched film, and its mechanical property is measured as follows:
σB：35MPa
DB：10%
E：700MPa
WB：3MJ/mm
2。
Though but described three-layer thin-film is formed (total amount of polyethylene and multipolymer is lower than 10%) by the thermoplastic starch of processing treatment to a great extent, but except being made by polymer blend, mechanical propertys such as stress during about fracture and modulus of elasticity significantly are better than unstretched film among as a comparison the embodiment 3.
The all respects of the present invention that provide among Fig. 1-13 and the embodiment 1-11 under any circumstance all can be according to embodiment, change or modification by any way.But its used starch all is to carry out thermoplasticity processing completely basically, and does not relate to the crystallization field.
Claims (24)
1, the single or multiple lift film that ventilation property is very little basically is characterized in that this film comprises one deck at least, but this layer film to small part is made up of the thermoplastic starch of processing treatment basically.
2, by the film of claim 1, but it is characterized in that this film at least one deck form by thermoplastic starch that comprises processing treatment and polyolefinic polymer blend.
3, by the film of claim 1 or one of 2, it is characterized in that this film at least one deck form by polymer blend, but this polymer blend comprises thermoplastic starch, polyethylene and/or the polypropylene of processing treatment and the tackifier between at least two kinds of polymkeric substance.
4, press the very little basically film of ventilation property of one of claim 1 to 3, this film is at least almost water insensitive, it is characterized in that this film comprises one deck at least, this layer at least partly comprises that water content is lower than 3.5(weight) but the thermoplastic starch of the processing treatment basically of %, this film at least also comprises a kind of hydrophobic polymer, make when comprising the film of one deck at least, this hydrophobic polymer is mixed with starch; And/or starch has partly covalent cross-linking at least at least on one layer surface; And/or one deck at least of this film is by at least almost water insensitive another layer is topped, thereby makes this film insensitive to water.
5, by the film of one of claim 1 to 4, it is characterized in that this film comprises one deck at least, at least respectively there is another layer on the two sides of this layer, but described another layer formed by polyolefine and/or by the thermoplastic starch and the polyolefinic polymer blend of processing treatment.
6,, it is characterized in that at least between another layer of one deck and each, in addition as one deck middle layer of forming by segmented copolymer of tackifier between each layer by the film of claim 5.
7, by the film of one of claim 1 to 6, it is characterized in that this film has one to be coated with aluminium lamination or to be coated with silicon oxide layer at least on one side, preferred silicon monoxide coating or silicon coating, this coating is to small part and self and/or crosslinked with starch.
8, press the film of one of claim 1 to 7, but it is characterized in that the thermoplastic starch of described processing treatment comprises borax, Mg
NianAnd/or K
NianAnd/or other polyvalent cations.
9,, it is characterized in that this film is stretched along single shaft or biaxially oriented by the film of one of claim 1 to 8.
10, make the method for the single or multiple lift film of one of claim 1 to 9, but but the one deck at least that it is characterized in that this film is to adopt wide nozzle to extrude thermoplastic starch and at least a polyolefinic polymer blend bonding or that blow the thermoplastic starch of the bonding processing treatment of spray or contain processing treatment to make.
11, press the method for claim 10, it is characterized in that this film is extrusion bonded or blow that the coextrusion trilaminar at least method of spray makes with wide nozzle, the two sides of one deck is respectively topped by another layer at least in these three layers, but described another layer formed polyolefine preferably polyethylene or polypropylene by the thermoplastic starch and the polyolefinic polymer blend of polyolefine and/or processing treatment.
12, by the method for one of claim 10 or 11, it is characterized in that on each surface of this film, handling, make starch at least partly crosslinked with UV-light or electron rays rifle.
13, by the method for claim 10 or one of 11, it is characterized in that the one side at least of film use siloxanyl monomers, as the alkylsiloxane coating, handle with the electronics ray gun then, thereby make siloxanes itself or its part crosslinked on film surface with starch.
14,, it is characterized in that the one side at least of this film adopts high vacuum to be coated with aluminum oxide or silicon oxide by the method for one of claim 10 or 11.
15, improve and to contain at least the quality of the single or multiple lift film of one deck or the method for mechanical property, but described one deck at least partly forms by the thermoplastic starch of processing treatment, it is characterized in that this film after manufacturing again through along single shaft or biaxially oriented stretching.
16,, it is characterized in that this film stretches by 1: 4 to 1: 0 ratio by the method for claim 15.
17, by the method for claim 15 or one of 16, it is characterized in that this film by 1: 6 to 1: 8.5 ratio, preferential about 1: 7 ratio stretches.
18, by the method for one of claim 15 to 17, it is characterized in that this film is to carry out tensile in room temperature to about 140 ℃ temperature range, preferential temperature range is 90 ℃ to 130 ℃.
19, by the method for one of claim 15 to 18, when it is characterized in that making film, with described polymkeric substance before fusion or its molten mass dry to being less than to water content hardly.
20, by the method for one of claim 15 to 19, but the water content of thermoplastic starch that it is characterized in that being used to making the processing treatment that contains polymkeric substance or polymer melt of film is lower than 1% at least.
But the polymer blend that the thermoplastic starch by polyolefine and processing treatment that 21, is used for one of claim 2 to 9 film is formed, it contains high to 70(weight) but the thermoplastic starch of % processing treatment, preferred amounts is a 30-70(weight) %, high to 30(weight) % segmented copolymer tackifier, surplus is polyolefine, preferably polyethylene and/or polypropylene.
22, make the method for the polymer blend of claim 21, it is characterized in that (by the polymer blend total amount), polyolefine is with containing 30-70(weight) water content of % is lower than 3.5(weight) %, preferably be lower than 1(weight) but the thermoplastic starch of the processing treatment of %, and respectively by the polyolefinic fusion range of selecting for use in 150 ℃ of-200 ℃ of temperature ranges kneading machine or extrusion machine in carry out processing treatment, in mixture, add the segmented copolymer tackifier, as polyvinyl-maleic anhydride-acrylate, comonomer and starch form covalent chemical bond.
But the method for the thermoplastic starch of 23, manufacturing processing treatment, it is characterized in that water content is lower than 1(weight) starch of % and/or starch derivative and 20(weight at least) the % additive mixes under the mechanical energy condition of supplying with 0.25-0.5KWh/kg starch-additive agent mixture, this mixture is heated at least and makes each component be mixed into uniform material, and wherein at least a additive comprises following at least a kind of material: glycerol, sorbyl alcohol, amino alcohol, methyl-sulphoxide, N-methylacetamide and urea.
24, press the method for claim 23, it is characterized in that this starch and 25-40(weight) %, preferred 32-38(weight) % amino alcohol, as monoethanolamine, aminopropanol, and/or trihydroxy-ethylamino methane mixes mutually, and respectively presses additive and additive capacity, in 60 ℃ of-120 ℃ of temperature ranges, in extrusion machine or kneading machine, supply with the deformation of 0.3-0.36KWh/kg starch-monoethanolamine mixture
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108086 CN1071878A (en) | 1991-10-25 | 1991-10-25 | Single thin film or the multilayer film formed by partial starch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108086 CN1071878A (en) | 1991-10-25 | 1991-10-25 | Single thin film or the multilayer film formed by partial starch |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1071878A true CN1071878A (en) | 1993-05-12 |
Family
ID=4909017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91108086 Pending CN1071878A (en) | 1991-10-25 | 1991-10-25 | Single thin film or the multilayer film formed by partial starch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1071878A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574374A (en) * | 2009-07-23 | 2012-07-11 | 特里斯塔诺私人有限公司 | Multilayer film |
| WO2012122898A1 (en) * | 2011-03-11 | 2012-09-20 | Colgate-Palmolive Company | Packaging and materials for making same |
| CN101835836B (en) * | 2007-10-22 | 2013-11-13 | 生物天然包装材料研究与开发有限及两合公司 | Polymer material and method for the production thereof |
| CN103739881A (en) * | 2013-12-18 | 2014-04-23 | 戴骏超 | Environment-friendly degradable plastic hanger product material formula |
| CN104470986A (en) * | 2012-05-31 | 2015-03-25 | 沙特基础工业公司 | Bi-axially stretched article |
| CN105531115A (en) * | 2013-05-29 | 2016-04-27 | 特里斯塔诺私人有限公司 | Polymer film with renewable content |
| CN110511437A (en) * | 2019-07-25 | 2019-11-29 | 安徽新翔包装材料有限公司 | A kind of Biodegradable environment protection type packaging material for food |
-
1991
- 1991-10-25 CN CN 91108086 patent/CN1071878A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101835836B (en) * | 2007-10-22 | 2013-11-13 | 生物天然包装材料研究与开发有限及两合公司 | Polymer material and method for the production thereof |
| CN102574374A (en) * | 2009-07-23 | 2012-07-11 | 特里斯塔诺私人有限公司 | Multilayer film |
| CN102574374B (en) * | 2009-07-23 | 2015-07-01 | 特里斯塔诺私人有限公司 | Multilayer film |
| US9539793B2 (en) | 2009-07-23 | 2017-01-10 | Tristano Pty Ltd. | Multilayer film |
| WO2012122898A1 (en) * | 2011-03-11 | 2012-09-20 | Colgate-Palmolive Company | Packaging and materials for making same |
| CN103502000A (en) * | 2011-03-11 | 2014-01-08 | 高露洁-棕榄公司 | Packaging and materials for making same |
| US9138968B2 (en) | 2011-03-11 | 2015-09-22 | Colgate-Palmolive Company | Packaging and materials for making same |
| CN103502000B (en) * | 2011-03-11 | 2016-06-29 | 高露洁-棕榄公司 | Pack and prepare material |
| CN104470986A (en) * | 2012-05-31 | 2015-03-25 | 沙特基础工业公司 | Bi-axially stretched article |
| CN105531115A (en) * | 2013-05-29 | 2016-04-27 | 特里斯塔诺私人有限公司 | Polymer film with renewable content |
| CN103739881A (en) * | 2013-12-18 | 2014-04-23 | 戴骏超 | Environment-friendly degradable plastic hanger product material formula |
| CN110511437A (en) * | 2019-07-25 | 2019-11-29 | 安徽新翔包装材料有限公司 | A kind of Biodegradable environment protection type packaging material for food |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1067017C (en) | Moisture-proof film | |
| CN1048024C (en) | Infraed absorbing film improved in transparency | |
| CN1024514C (en) | Laminar articles made from mixtures of polyolefin and ethylene/vinyl alcohol copolymers | |
| CN1066749C (en) | Liquid crystal polyester resin composition film | |
| CN1093463C (en) | Barrier composite film and process for the production thereof | |
| CN1090561C (en) | Multi-layer films | |
| CN1860025A (en) | Multilayer oriented high modulus film | |
| CN1089629A (en) | Heat-shrinkable coextruded profiled film and manufacture method thereof | |
| CN1275145A (en) | Polypropylene composition useful for making solid state oriented film | |
| CN1212714A (en) | Rheology-modified polyolefins | |
| CN1065478C (en) | Squeezable tubular container and process for the production thereof | |
| CN1334756A (en) | Extrusion coating process for making high transparency protective and decorative films | |
| CN1260361A (en) | Film or thin-sheet material comprising crystalline propene polymer composition | |
| CN1724254A (en) | High resistively nine-layer co-extrusion-blown moulding film and its preparation process | |
| CN87104852A (en) | Ventilated membrane and manufacture method thereof | |
| CN1118603A (en) | Thermoplastic elastomer copolymer films | |
| JP5852234B2 (en) | Method for producing solar cell encapsulant sheet | |
| CN1150442A (en) | Medium modulus film and fabrication method | |
| CN1461768A (en) | Polyropylene resin composite and thermal contraction film made by it | |
| CN115071236A (en) | Ultralow-temperature heat-sealing plastic film and preparation method thereof | |
| CN1071878A (en) | Single thin film or the multilayer film formed by partial starch | |
| CN1933970A (en) | Polypropylene type laminated film and package using it | |
| CN1046541A (en) | Gastight material | |
| CN1289579C (en) | Method for producing resin film material and resin film material | |
| CN1543396A (en) | Heat-shrinkable polystyrene based resin film roll and method for production thereof, and heat-shrinkable label |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |