CN1226272A - Biaxially stretched biodegradable and composatable foil - Google Patents
Biaxially stretched biodegradable and composatable foil Download PDFInfo
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- CN1226272A CN1226272A CN97196766A CN97196766A CN1226272A CN 1226272 A CN1226272 A CN 1226272A CN 97196766 A CN97196766 A CN 97196766A CN 97196766 A CN97196766 A CN 97196766A CN 1226272 A CN1226272 A CN 1226272A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
- A01G9/14—Greenhouses
- A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/12—Polyester-amides
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
A foil oriented along two axes substantially consists of one or several polymers which are biologically degradable and compostable, as well as maximum 5 % by weight nucleating agents, maximum 5 % by weight common stabilisers and neutralisers, maximum 5 % by weight common internal lubricants and parting agents and maximum 5 % by weight common antigriping agents.
Description
The present invention relates to a kind of biaxial stretch-formed, biodegradable and the film that can become compost.
But people know some polymeric material biodegrade.Here the material of mentioning mainly is by naturally occurring polymkeric substance directly or those materials that obtain after modification, for example as polyhydroxy-alkanoates, Plasitc fibers element, cellulose ester, plastic starch, chitosan and the water-soluble polysaccharide of multi-hydroxybutyrate and so on.Autotelic change polymkeric substance is formed or structure, as being to be worth from the polymer application viewpoint, but is difficult based on the natural day process of closing, and usually also is very limited.
On the other hand, many synthetic polymkeric substance can not be subjected to the destruction of microorganism, and perhaps it destroys just very slow.Think in main chain, contain heteroatomic most of synthetic polymer can biodegrade.Important class representative is a polyester in these materials.Have biodegradability preferably although only contain the synthesis material of aliphatic monomers, because its material property, they can only obtain using in very limited scope; Can be referring to people such as Witt at ' macromolecular chemistry and physics ' (Macrom.Chem.Phys.) article of 195 (1994) 793-802 pages or leaves.By contrast, have the aromatic polyester of good material property, but show inferior biodegradability significantly.
In recent years, the more and more known road of various Biodegradable polymerics (referring to DE4432161).These polymkeric substance have good thermoplastic workability, and on the other hand, they are biodegradable, and promptly their whole polymer chains are dissociated by enzyme by microorganism (bacterium and mould), and all are degraded into carbonic acid gas, water and biomass.The corresponding test of in physical environment action of microorganisms being carried out is as the microorganism of describing in DIN54900 of particularly often using in compost.Because its thermoplasticity, these biodegradable materials can be processed into the work in-process of picture casting film or blown film and so on.However, these half-finished uses still have been subjected to very big restriction.On the one hand, the bad mechanical property of these films on the other hand, is compared with the film that is made of the typical not biodegradable plastics as polyethylene, polypropylene or polymeric amide and so on, and these films are to the non-constant of the performance of blockading of water vapour and gas.
The objective of the invention is to make a kind of biodegradable and the film that can become compost, this film has improved machinery and optical property and improved sliding capability.By adding the biodegradable of suitable additive and the polymkeric substance that can become compost or, and just can reach described purpose through diaxial orientation by several all biodegradable and the mixture of polymers that can become compost.Term among the present invention " biodegradable and polymkeric substance that can become compost or film " should be understood to according to DIN54900 draft in 1996 to be tested, and verified is the material of " biodegradability ".
Make the contriver surprised be these Biodegradable polymerics, except they can carry out thermoplastic processing, can also carry out diaxial orientation, and on the sliding capability of film, improvement be arranged owing to add some additive.
The purpose of this invention is to provide a kind of film that has diaxial orientation and constitute by one or more polymkeric substance, all these polymkeric substance all are biodegradables and can become compost, in addition, they also contain maximum is 5% (weight) nucleator, maximum is common stablizer and a neutralizing agent of 5% (weight), and maximum is that the common lubricant of 5% (weight) and releasing agent and maximum are the common anti of 5% (weight).
In a particular manner, this film can carry out surface treatment in addition: use corona, and/or flame, and/or plasma body pre-treatment, and/or with the material that plays oxygenizement, and/or with being attached or sedimentary material, and/or the mixture formed of the material of using the material by an oxygenizement maybe can be attached, for example as the gas of the band free radical component of ozone and so on, or by for example hexamethyldisiloxane and nitrogen (N
2) and/or oxygen (O
2) the plasma exciatiaon gaseous mixture formed handles.Described surface preparation is preferably carried out after diaxial orientation.
In the time of in the amorphous thermoplastic plastic is in the temperature range that is higher than glass transition temperature, and when the thermoplastics of partial crystallization is in the temperature range that is lower than the crystal grain temperature of fusion, carry out diaxial orientation.
The objective of the invention is to use some biodegradable to produce this film thus with the polymkeric substance that can become compost or these mixture of polymers.
What be fit to make polymkeric substance is:
By A) or the aliphatic series that B) generates and the polyester of partially aromatic:
A) straight chain difunctional alcohol, ethylene glycol for example, hexylene glycol, or be preferably butyleneglycol, and/or can also be the cyclic aliphatic difunctional alcohol, for example cyclohexanedimethanol can also be to have the more alcohol of high functionality on a small quantity in addition, for example 1,2,3-glycerol or neopentyl glycol, and straight chain difunctional acid, for example Succinic Acid or hexanodioic acid, and/or can also be the cyclic aliphatic difunctional acid, cyclohexane dicarboxylic acid for example, and/or can also be the aromatics difunctional acid, for example terephthalic acid or m-phthalic acid or naphthalic acid, can also be to have the more acid of high functionality on a small quantity in addition, trimellitic acid for example, or
B) acid-functionalized and structural unit carbinol-functionalization, for example hydroxybutyric acid or hydroxypentanoic acid or derivatives thereof, 6-caprolactone for example,
Perhaps generate the polyester of aliphatic series and partially aromatic by A and B mixture or multipolymer,
Wherein in all acid, the ratio of aromatic acid is not more than 50% (weight).
Can also use the acid that is derivative form, for example chloride of acid or ester.
By C) or the aliphatic polyester urethane that D) generates:
C) ester moiety that generates by following compound: straight chain difunctional alcohol, for example ethylene glycol, butyleneglycol, hexylene glycol, butyleneglycol preferably, and/or can also be the cyclic aliphatic difunctional alcohol, cyclohexanedimethanol for example, can also be to have the more alcohol of high functionality on a small quantity in addition, for example 1,2,3-glycerol or neopentyl glycol, also have the straight chain difunctional acid, for example Succinic Acid or hexanodioic acid, and/or can also be cyclic aliphatic and/or aromatics difunctional acid, for example cyclohexane dicarboxylic acid and terephthalic acid, can also be to have the more acid of high functionality on a small quantity in addition, trimellitic acid for example, or
D) ester moiety that generates by acid-functionalized and carbinol-functional structural unit, for example hydroxybutyric acid and hydroxypentanoic acid or derivatives thereof, 6-caprolactone for example,
Perhaps by C) and D) and following E) mixture or the aliphatic polyester urethane that generates of multipolymer,
E) C) and/or D) and the reaction product of following compound: aliphatic series and/or cyclic aliphatic bifunctional isocyanate, can also be to have the more isocyanic ester of high functionality in addition, tetramethylene diisocyanate, 1 for example, the reaction product of hexamethylene-diisocyanate, isophorone diisocyanate, straight chain and/or cyclic aliphatic difunctional alcohol can also be arranged in addition and/or have the more alcohol of high functionality, for example ethylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol, cyclohexanedimethanol
Wherein with C), D) and E) summation meter, C) and/or D) amount of ester moiety is at least 75% (weight).
By F) or the aliphatic-aromatic polyesters carbonic ether that G) generates:
F) ester moiety that generates by following compound: straight chain difunctional alcohol, for example ethylene glycol, butyleneglycol, hexylene glycol, butyleneglycol preferably, and/or cyclic aliphatic difunctional alcohol, cyclohexanedimethanol for example, can also be to have the more alcohol of high functionality on a small quantity in addition, for example 1,2,3-glycerol or neopentyl glycol, and the straight chain difunctional acid, for example Succinic Acid or hexanodioic acid, and/or can also be the cyclic aliphatic difunctional acid, cyclohexane dicarboxylic acid for example, can also be to have the more acid of high functionality on a small quantity in addition, trimellitic acid for example, or
G) ester moiety that forms by acid-functionalized and carbinol-functional structural unit, for example hydroxybutyric acid or hydroxypentanoic acid or derivatives thereof, 6-caprolactone for example,
Perhaps by F) and G) and following H) mixture or the aliphatic-aromatic polyesters carbonic ether that generates of multipolymer,
H) by aromatics difunctionality phenol, the carbonate moiety that generates to body of the carbonic ether of dihydroxyphenyl propane and picture carbonyl chloride and so on preferably,
Wherein with F), G) and summation meter H), ester moiety F) and/or amount G) be at least 70% (weight).
By I) or the aliphatic polyester acid amides that K) generates:
I) ester moiety that generates by following compound: straight chain and/or cyclic aliphatic difunctional alcohol, for example ethylene glycol, hexylene glycol or butyleneglycol, preferably butyleneglycol or cyclohexanedimethanol, can also be to have the more alcohol of high functionality on a small quantity in addition, for example 1,2,3-glycerol or neopentyl glycol, and straight chain and/or cyclic aliphatic difunctional acid, for example Succinic Acid, hexanodioic acid, cyclohexane dicarboxylic acid, preferably hexanodioic acid can also be to have the more acid of high functionality on a small quantity in addition, trimellitic acid for example, or
K) ester moiety that generates by acid-functionalized and carbinol-functional structural unit, for example hydroxybutyric acid or hydroxypentanoic acid or derivatives thereof, 6-caprolactone for example,
Perhaps by I) and K) and L) or the aliphatic polyester acid amides that generates of mixture M) or multipolymer,
L) amide moieties that generates by following compound, straight chain and/or cyclic aliphatic bifunctional amine, can also be to have the more amine of high functionality on a small quantity in addition, for example tetramethylene-diamine, hexamethylene-diamine, isophorone diamine, and straight chain and/or cyclic aliphatic difunctional acid, can also be to have the more acid of high functionality on a small quantity in addition, for example Succinic Acid or hexanodioic acid, or
M) amide moieties that generates by acid-functionalized and amine-functionalized structural unit, omega-lauric lactam preferably, ε-Ji Neixianan particularly preferably,
Perhaps by L) and the aliphatic polyester acid amides that generates as amide moieties of mixture M)
Wherein with I), K), L) and summation meter M), ester moiety I) and/or amount K) be at least 30% (weight).
Biodegradable of the present invention and the nucleator that is generally used for polyester that can become composting material to contain mostly to be 5% (weight) most are (for example, 1,5-sulfonic acid naphthalene disodium or layered silicate, talcum for example, or granularity is in the millimicro scope, it is average particulate diameter＜1 micron, by for example titanium nitride, aluminium hydroxide, the nucleator that barium sulfate or zirconium compounds are formed), maximum is common stablizer and a neutralizing agent of 5% (weight), maximum is common lubricant and a releasing agent of 5% (weight), with maximum be the common anti of 5% (weight), can also be from the teeth outwards with corona or flame or plasma body pre-treatment, or with the material or the substance mixture that play oxygenizement, for example as the gas of the band free radical component of ozone and so on, or by for example hexamethyldisiloxane and nitrogen (N
2) and/or oxygen (O
2) the plasma exciatiaon gaseous mixture formed handles.
Usually the compound that petchem is played stabilization can be used as stablizer and neutralizing agent.Its add-on is 5% (weight) to the maximum.
Suitable especially is phenol stabilizers, basic metal/alkaline earth metal stearate and/or basic metal/alkaline earth metal carbonate with used as stabilizers.The amount of phenol stabilizers is 0-3% (weight), and preferably 0.15-0.3% (weight), molar mass are to be preferred more than the 500 gram/moles.Pentaerythrityl base-four-3 (3,5-two-tert-butyl-hydroxy phenyl) propionic ester or 1,3,5-trimethylammonium-2,4,6-three (3,5-two-tertiary butyl-4-hydroxy benzyl) benzene is particularly advantageous.
Neutralizing agent is dihydro talcite, calcium stearate, lime carbonate and/or montanic acid calcium preferably, and 0.7 micron at the most of its mean particle size, absolute granularity be less than 10 microns, specific surface at least 40 meters squared per gram.
In particularly preferred film embodiment, the nucleator ratio of this film is 0.0001-2% (weight), and the ratio of stablizer and neutralizing agent is 0.0001-2% (weight).
Lubricant and releasing agent are more high-grade aliphatic series acid amides, tertiary amine, aliphatic acid acylamide, more high-grade aliphatic acid ester, low molecular polarity sex change wax, montanin wax, ring-type wax, phthalic ester, metallic soap and silicone oil.It is specially suitable adding more higher aliphatic acid acid amides and silicone oil.
In aliphatic acid amides, commercially available be specially suitable from the ethylidene acid amides to the stearylamide form.Aliphatic acid amides is that 8-24 carbon atom arranged, preferably the acid amides of the water-fast monocarboxylic acid of 10-18 carbon atom (so-called lipid acid).In these acid amides, erucicamide, stearylamide and oleylamide are preferred.
In addition, what be fit to make releasing agent or lubricant is both to have contained ester group, contains the compound of amide group again, for example as stearylamide-Stearic ethyl stearate or 2-tristearin-amido-Stearic ethyl stearate.
Title " montanin wax " comprises a large amount of different compounds.Can be for this referring to people's such as Neum ü ller R mpps chemistry encyclopedia (Chemie-Lexikon), Franckh ' scheVerlagshandlung, Stuttgart, 1974.
What be fit to make ring-type wax for example is picture ring-type tetramethylene adipate or 1,6-Er Evil-2, the component of 7-dioxo cyclododecane and so on, or homology hexamethylene derivative.Such material is known with trade(brand)name Glycolube VL.
Suitable silicone oil is a polydialkysiloxane, preferably polydimethylsiloxane, PSI, with the siloxanes of alkene modification, use polyether-modified siloxanes, for example as polyoxyethylene glycol and polypropylene glycol and with epoxy amino modified and with the siloxanes of pure modification.Suitable silicone oil viscosity is 5,000-1,000,000 square millimeter/second.Having viscosity is 10, and 000-100,000 square millimeter/second polydimethylsiloxane are preferred.
The add-on of lubricant is maximum 5% (weight).In particularly preferred film embodiment, the lubricant ratio in the film is 0.005-4% (weight).In more particularly preferred film embodiment, the lubricant ratio in the film is 0.05-1% (weight).
Suitable anti not only can be inorganic but also can be organic additive that they were protuberantia form projection in biaxial stretch-formed back from film surface, thereby have produced effect at interval.
With optimal way, following material is used as inorganic anti:
Aluminium hydroxide
Pure aluminium silicate, for example kaolin or kaolin clay
Aluminum oxide, for example Θ-aluminum oxide
Tai-Ace S 150
The pottery that constitutes by the oxidation sial
Barium sulfate
Natural or synthetic silicic acid
Layered silicate, for example asbestos
Silicon-dioxide
Calcite type calcium carbonate
Calcium phosphate
Magnesium Silicate q-agent
Magnesiumcarbonate
Magnesium oxide
Titanium dioxide
Zinc oxide
Micro-granulated glass sphere
Following material is used as organic anti:
With the inconsistent organic polymer of biodegradable polymer, as
Starch
Polystyrene
Polymeric amide
Polycarbonate
Crosslinked or noncrosslinking polymethylmethacrylate
Crosslinked polysiloxane (for example Tospearl)
Polarity-modified polyethylene (for example using the polyethylene of maleic anhydride graft)
The polypropylene of polarity-modification (for example using the polypropylene of maleic anhydride graft)
Statistics (statistische) multipolymer based on ethene and propylene and vinyl alcohol or vinyl acetate or vinylformic acid or propylene ester or methacrylic acid or methacrylic ester or methacrylic acid metal salt or methacrylic ester metal-salt
The benzoguanamine yuban
Have aliphatic series and partially aromatic polyester with the film raw material different melting points
Has aliphatic polyester acid amides with the film raw material different melting points
Has aliphatic polyester type polyurethane with the film raw material different melting points
Has aliphatic-aromatic polyesters carbonic ether with the film raw material different melting points
The significant quantity of anti is up to being 5% (weight) to the maximum.In particularly preferred embodiments, film contains 0.005-4% (weight) anti.In particularly preferred embodiment more, film contains 0.05-1% (weight) anti.Mean particle size is the 1-6 micron, and preferably the 2-5 micron is specially suitable as the globular particle of describing among EP-A0236945 and the DE-A-3801535 that is wherein.The combination of different interval system also is specially suitable.
According to the method for using so far, the film polymer of being furnished with additive has added the organic or inorganic filler of aequum (by weight) in the feedstock production process.This is to take place in the granulating process of raw material, for example carries out in that additive is added in the twin screw extruder that goes in the raw material.Except this adding method, also might with a part must additive or all must additive join and do not have filler or have in the raw material of part filler with master batch form.To be interpreted as be masterbatch to term " masterbatch " within the scope of the present invention, granulated, the non-dusting plastic raw material enriched material that particularly contains the heavy addition agent, this enriched material is used as intermediates and (is added to as material and does not contain additive in batch processing, only the part or contain by halves in the particulate material of additive), so that produce the film that contains a certain amount of additive by it.Before the polymer particles pellet of packing into to forcing machine, masterbatch with such amount with do not contain additive or only part or the raw material that not exclusively contains additive mixes, consequently reach the required weight percent of filler in film.
Except additive, the preferred substance of producing masterbatch is and the compatible material of biodegradable raw material of the present invention.In particularly preferred mode, except additive, the material of producing masterbatch also is biodegradable material.
In the corona treatment process, practical method is to allow film pass through between two conductor elements that play the electrode effect, applies the high pressure that high-voltage corona or corona discharge can take place between two electrodes, normally voltage of alternating current (about 5-20 kilovolt, 5-30 kilohertz).Because high-voltage corona or corona discharge, the air of film surface top is ionized, and reacts with the molecule of film surface, so that additional polarity has taken place in polymeric matrix mixes.
For carry out flame treating (referring to US-A-4622237) with polarization flame, between burner (negative pole) and cold roll, apply volts DS.Applying voltage levvl is 400-3,000 volt, and 500-2 preferably, 000 volt.Because the voltage that is applied, ionized atom is constantly quickened, and with bigger kinetic energy bump polymer surfaces.Chemical bond ratio in the polymer molecule is easier to be interrupted, and the generation of free radical also takes place rapider.To this, the thermal load of polymkeric substance is far smaller than the thermal load under the standard flame source disposition, and the film that obtains is better than the sealing property of untreated one side in its sealing property of the one side of handling.
Under the pretreated situation of plasma body, gas, for example oxygen or nitrogen or carbonic acid gas or methane or halohydrocarbon or silane compound or more macromolecular compound, or the mixture of these compounds, in low-pressure chamber, be subjected to the effect of high energy field, for example the effect of microwave radiation.High-energy electron occurs, their bump molecules also shift its energy.Therefore, local radical structure occurs, its excited state is corresponding to several ten thousand degrees centigrade approximately of temperature, although the temperature of plasma body itself almost is a room temperature.Therefore, the reaction that chemical bond rupture and generation only can at high temperature just be carried out usually.Monomer free radical and ion have been generated.Can generate short chain oligomer-part by the monomer free radical that has occurred in plasma body, to generate-its cohesion and polymerization on surface to be coated then.Therefore, the layer of even thin film deposition is on material surface to be coated.
But, before on the matrix, also may in so-called after glow district, add other substance flow again to the molecule of being excited at monomer free radical or ion deposition.By this method, can produce the mixture of a kind of material or material, when its bump polymeric film surface, under the situation of matrix polymer, oxidative attack take place.Formed the layer crosslinked with the common height of the allo vitreous state of film surface.If it is suitable that this material is formed, can increase the surface tension on the film by this method.
Thus, the biodegradable that the objective of the invention is to use some class and the polymkeric substance that can become compost are to produce this film, and wherein such material is a polyesteramide.In this respect, film of the present invention can be made by the mixture of polyesteramide or various polyesteramides.
Thus, the method that the purpose of this invention is to provide production film of the present invention.The method is characterized in that at first one or more biodegradables are carried out fragmentation with the material that can become compost by heating and shearing, this melt is packed in the mould, cooling is up to curing, then under the situation of partial crystallization material, just it is adjusted to the temperature that is lower than crystal melting, under the amorphous material situation, just it is adjusted to and be higher than glass transition temp, carry out once biaxial stretch-formed or several times then.Once or after each time stretching step, all can carry out the fixing of film.After the stretching process and the fixing step that may often adopt, the film of Sheng Chaning can be through online surface preparation thus.The mixture of available corona, flame, plasma body or a kind of oxidizing substance or oxidizing substance is for example as the gas that the free radical component is arranged of ozone and so on, or by for example hexamethyldisiloxane and nitrogen (N
2) and/or oxygen (O
2) plasma body-the be excited gaseous mixture formed carries out pre-treatment with a kind of like this method, increase to cause the surface tension on this film.
Thus, the method that the purpose of this invention is to provide oriented film.Biaxial stretch-formed can carrying out with the while stretching method, or with two the step continuous processings carry out, adopt this two-step approach, both can first longitudinal stretching, cross directional stretch then also can first cross directional stretch, longitudinal stretching perhaps carries out with three step continuous processings again, adopts this method, both can first longitudinal stretching, cross directional stretch then, last longitudinal stretching, also can first cross directional stretch, longitudinal stretching then, last cross directional stretch, perhaps carry out with four step continuous processings, adopt this method, both can first longitudinal stretching, cross directional stretch then, longitudinal stretching again, last cross directional stretch also can first cross directional stretch, longitudinal stretching then, cross directional stretch again, last longitudinal stretching.Fixed film and then after each time stretching step.Each time stretching all can be finished by a step or by several steps with longitudinal stretching and two kinds of stretchings of cross directional stretch.
In the optimal way of film of the present invention, biaxial stretch-formedly be characterised in that it is a continuation method that begins with longitudinal stretching.
In the preferred mode of film of the present invention, biaxial stretch-formedly be characterised in that the total drawing ratio of longitudinal stretching is 1: 1.5 to 1: 10, the total drawing ratio of cross directional stretch is 1: 2 to 1: 20.
In the preferred mode of film of the present invention, the biaxial stretch-formed longitudinal stretching total drawing ratio that is characterised in that is 1: 2.8 to 1: 8, and the total drawing ratio of cross directional stretch is 1: 3.8 to 1: 15.
In the preferred mode of film of the present invention, the thickness of film is less than 500 microns.
In the preferred mode of film of the present invention, the thickness of film is less than 80 microns.
Thus, the objective of the invention is the application of film of the present invention.This film uses in following field: in field of food or non-food product field with pre-treatment or not pre-treatment form and with printing or not the simple film of printed form be used for packing; or the simple film with pre-treatment or not pre-treatment form is used for greenhouse coverture or coating film in gardening or agriculture field; perhaps through being processed into bag; be used for storage or transportation as biological waste and so on material; or be used for protection relevant and buffer action (for example being used for diaper or sanitary towel) with makeup or sanitary product with the simple film of pre-treatment or not pre-treatment form; or at pressboard coating; simple film with pre-treatment or not pre-treatment form in paper coating and the window envelope coatings art is used for surface protection or finishing; or, use as label or adhesive tape with pre-treatment or not pre-treatment form and with printing or printed form and have the finished film of tackiness agent not.For improving pressure binding or bond properties, can be during film production and/or subsequently at mixture with corona, flame, plasma body or another kind of oxidizing substance or oxidizing substance, for example as the gas that has the free radical component of ozone and so on, or use by for example hexamethyldisiloxane and nitrogen (N
2) and/or oxygen (O
2) plasma body formed is excited gaseous mixture film surface is carried out a kind of like this pre-treatment of method, increase to cause film surface tension force.
The objective of the invention is to be used for coating film or laminated film with film of the present invention.In this respect, to other films in the laminated film, it can be the non-degradable film, or biodegradable and the film that can become compost.In addition, used coated material or tackiness agent may belong to common non-degradable system, also can belong to biodegradable and the raw material that can become compost.
In the particularly preferred application mode of film of the present invention, in order to produce coating film or laminated film, only use biodegradable and the material that can become compost, so that whole mixture equally also is a biodegradable and can become compost.
In addition, the objective of the invention is with the raw material of film of the present invention as the production bag, after decomposing by biological degradation, this bag discharges its content.Can produce this bag by gummed, also can be by this bag of sealing-in film production, this bag can seal, and also the opening that seals or connect with corresponding can be arranged.
In addition, the objective of the invention is to have the raw material of the infiltrative packaging film of high water vapor or isolated film or surface protective film with film of the present invention or mixture as production, wherein said film is through cold or thermoregulated porcupine roller perforation.The purposes of this film is that packing is emitted the goods of moisture, for example bread or various vegetables, or in health field, be used as isolated film or protective film.
Embodiment 1
Melt viscosity is the biodegradable polyesteramide of 250Pas (measuring according to DIN 54 811-B), fusing point 125 ℃ (measuring according to ISO3146/C2) when having 190 ℃, it contains lubricant is that 1% (weight), anti-even stick are 0.1% (weight), and this polyesteramide carries out biaxial stretch-formed with following processing parameter.The highest extrusion temperature reaches 205 ℃.Correspondingly, it is 182 ℃ that the constant temperature section of forcing machine is adjusted to top temperature, and it is 205 ℃ that this mould is adjusted to top temperature.Melt is 20 ℃ with the plain film shape in roll temperature, is cooled on the cold breakdown press.Formed the solid thick film, this film is that 65 ℃ constant temperature roller is heated to draft temperature by temperature in next treatment step.In fact the roller that stretches is 70 ℃ of operations with temperature.In this processing, at first flat film is stretched in a longitudinal direction in two steps, the one-off drawing ratio is 1: 1.5, another time stretch ratio is 1: 2.5.Thereby total drawing ratio is 1: 3.75 longitudinally.The concurrent heating roll temperature that film moves thereon is 85 ℃.The preheating zone of cross directional stretch stove is adjusted to 100 ℃ of temperature.The temperature of actual cross directional stretch part reaches 95 ℃.Here, this film is 1: 5 cross directional stretch with stretch ratio.Thereby the area-stretch ratio of calculating is 1: 18.75.Behind the cross directional stretch, it is 105 ℃ that this film is fixed on temperature.Production rate in the cross directional stretch outlet reaches 32.0 meters/minute.Can produce the film of 46 microns of thickness.
Embodiment 2
Under the processing conditions of the embodiment 1 that has described, produce the biodegradable polyesteramide identical, to make the film of diaxial orientation with embodiment 1.Owing to reduced extruded velocity, produce thickness in this case and be 24 microns film.
The comparative example 1
Under embodiment 1 described processing conditions, produce the biodegradable polyesteramide identical, but this polyesteramide does not contain any lubricant, to make biaxially oriented film with embodiment 1.Can produce thickness and be 24 microns film.
The following physicals of institute's production sample is with can to become compost mensuration as follows:
Mechanical property:
According to the DIN53455 working sample vertically with the horizontal tensile strength and the mechanical value of degree of drawing.Be determined at the modulus of elasticity of vertical and horizontal according to DIN53457.Measure each sample thickness according to DIN53370.Penetrate the piercing force of analysis of experiments sample and penetrate distance by twin shaft according to DIN53373.
The slip ability:
According to DIN 53 370, measured at room temperature and film and film between film slip ability.
Optical property:
For optical property, the film surface gloss when having measured the test angle and be 20 ° according to DIN67530 has been measured the mist degree of film according to ASTM D1003.Measure the gloss on two faces of film.Calculate the mean number of measured value then, this mean number is as a result of listed.
Can become compost:
Measured according to the testing regulation of DIN draft standard DIN54900 the 3rd part in 1996 and can become compost.Based on result of study,, film sample is decided to be corresponding grade according to the DIN standard.
Embodiment 1 and 2 and the result of study of comparative example 1 sample be listed in the table 1.
Table 1
| Mechanical property | Embodiment 1 | Embodiment 2 | The comparative example 1 |
| Thickness [micron] | 46 | 24 | 50 |
| Young's modulus is [MPa] vertically | 226 | 252 | 230 |
| Young's modulus is [MPa] laterally | 292 | 306 | 295 |
| Tensile strength is [MPa] vertically | 90 | 91 | 89 |
| Tensile strength is [MPa] laterally | 109 | 111 | 108 |
| Degree of drawing is [%] vertically | 224 | 186 | 231 |
| Degree of drawing is [%] laterally | 111 | 75 | 109 |
| Piercing force [newton] | 227 | 151 | 238 |
| Penetrate distance [millimeter] | 18 | 16 | 19 |
| Sliding capability sliding friction [-] | 0.38 | 0.38 | 0.78 |
| Optical property gloss [GE] | 110 | 120 | 125 |
| Mist degree [%] | 14 | 3.3 | 12 |
| Can become the compost biodegradability | Be | Be | Be |
Claims (18)
1, a kind of film, it is characterized in that it has diaxial orientation, and mainly constitute by one or more polymkeric substance, all these polymkeric substance all are biodegradables and can become compost, also containing maximum in addition is that 5% (weight) nucleator and maximum are common stablizer and neutralizing agent of 5% (weight), and maximum is that the common lubricant of 5% (weight) and releasing agent and maximum are the common anti of 5% (weight).
2, film according to claim 1, it is characterized in that with corona and/or flame and/or plasma body pre-treatment, and/or use oxidizing substance, and/or with can adhering to or sedimentary material, and/or use the mixture process surface of forming by the material of oxygenizement and/or the material that can adhere to.
According to claim 1 and 2 described films, it is characterized in that under the situation of one or more Biodegradable polymerics that 3, it is the aliphatic series made by following compound and the polyester of partially aromatic:
By following A) or the aliphatic series that B) generates and the polyester of partially aromatic:
A) straight chain difunctional alcohol and/or can also be the cyclic aliphatic difunctional alcohol, can also be to have the more alcohol of high functionality on a small quantity in addition, and form by the straight chain difunctional acid, and/or can also be the cyclic aliphatic difunctional acid, and/or can also be the aromatics difunctional acid, can also be to have the more acid of high functionality on a small quantity in addition, or
B) structural unit or derivatives thereof acid-functionalized and carbinol-functionalization
Perhaps A) and the aliphatic series that generates of mixture B) or multipolymer and the polyester of partially aromatic,
Wherein all acid meters, the ratio of aromatic acid are not more than 50% (weight), perhaps
By C) or the aliphatic polyester urethane that D) generates:
C) ester moiety that generates by following compound: straight chain difunctional alcohol, and/or can also be the cyclic aliphatic difunctional alcohol, can also be to have the more alcohol of high functionality on a small quantity in addition, and straight chain difunctional acid, and/or can also be cyclic aliphatic and/or aromatics difunctional acid, can also be to have the more acid of high functionality on a small quantity in addition, or
D) ester moiety that generates by structural unit or derivatives thereof acid-functionalized and carbinol-functionalization,
Perhaps by C) and D) and following E) mixture or the aliphatic polyester urethane that generates of multipolymer,
E) by C) and/or D) and aliphatic series and/or cyclic aliphatic bifunctional isocyanate, can also be to have the more reaction product of the isocyanic ester of high functionality in addition, can also be C) and/or D) and straight chain and/or cyclic aliphatic difunctional alcohol and/or the reaction product of the alcohol of high functionality more
Wherein with C), D) and summation meter E), C) and/or D) ester moiety is at least 75% (weight).
By F) or the aliphatic-aromatic polyesters carbonic ether that G) generates:
F) ester moiety that is generated by following compound: straight chain difunctional alcohol and/or cyclic aliphatic difunctional alcohol can also be to have the more alcohol of high functionality on a small quantity in addition; And straight chain difunctional acid and/or can also be the cyclic aliphatic difunctional acid, can also be to have the more acid of high functionality on a small quantity, or
G) ester moiety that generates by structural unit or derivatives thereof acid-functionalized and carbinol-functionalization,
Perhaps by F) and G) and following H) mixture or the aliphatic-aromatic polyesters carbonic ether made of multipolymer,
H) carbonate moiety that generates to body by aromatics difunctionality phenol and carbonic ether,
Wherein with F), G) and summation meter H), ester moiety F) and/or G) be at least 70% (weight), perhaps
By I) or the aliphatic polyester acid amides that K) generates:
I) ester moiety that is generated by following compound: straight chain and/or cyclic aliphatic difunctional alcohol can also be to have the more alcohol of high functionality on a small quantity in addition; And straight chain and/or cyclic aliphatic difunctional acid, can also be to have the more acid of high functionality on a small quantity in addition, or
K) ester moiety that generates by structural unit or derivatives thereof acid-functionalized and carbinol-functionalization,
Perhaps by I) and K) and following L) or the aliphatic polyester acid amides that generates of mixture M) or multipolymer,
L) amide moieties that generates by following compound: straight chain and/or cyclic aliphatic bifunctional amine, can also be to have the more amine formation of high functionality on a small quantity in addition, can also be by straight chain and/or cyclic aliphatic difunctional acid, can also be that the acid that has high functionality more on a small quantity forms in addition, or
M) by the acid-functionalized amide moieties that generates with the functional structural unit of amine,
Perhaps by L as amide moieties) and the aliphatic polyester acid amides that generates of mixture M),
Wherein with I), K), L) and summation meter M), ester moiety I) and/or K) be at least 30% (weight).
4,, it is characterized in that be polyesteramide at one or more biodegradables with the polymkeric substance that can become compost according to the described film of claim 1-3.
5, according to the described film of claim 1-4, the content that it is characterized in that lubricant is 0.005-4% (weight), and anti particulate content is 0.005-4% (weight).
6, according to the described film of claim 1-5, the content that it is characterized in that lubricant is 0.05-1% (weight), and anti particulate content is 0.05-1% (weight).
7, according to the described film of claim 1-6, it is characterized in that one or more biodegradables and the material that can become compost are at first by heating with shear and pulverize, this melt is packed in the mould, cooling is up to curing, then under the situation of partial crystallization material, its temperature adjusted to be lower than the crystal grain temperature of fusion, under the situation of amorphous material, its temperature adjusted to be higher than glass transition temp, then carry out once or biaxial stretch-formed several times, after one-off drawing or each time stretch, all can carry out film and fix, in these stretchings with fixedly after the operation, can be through surface treatment.
8, according to the described film of claim 1-7, it is characterized in that the biaxial stretch-formed while stretching method that adopts carries out, or carry out with two step continuous processings, adopt two-step approach, both can first longitudinal stretching, cross directional stretch then, again can first cross directional stretch, longitudinal stretching perhaps adopts three step continuous processings to stretch again, adopt this method, both can first longitudinal stretching, cross directional stretch then, last longitudinal stretching, again can first cross directional stretch, longitudinal stretching then, last cross directional stretch perhaps stretches with four step continuous processings, adopt this method, both can first longitudinal stretching, cross directional stretch, longitudinal stretching more then, last cross directional stretch, again can first cross directional stretch, longitudinal stretching, cross directional stretch more then, last longitudinal stretching, fixed film and then after each stretching step.
9,, it is characterized in that biaxial stretch-formed is to carry out with the continuous processing that longitudinal stretching begins according to the described film of claim 1-8.
10, according to the described film of claim 1-9, it is characterized in that total drawing ratio is 1: 1.5 to 1: 10 longitudinally, horizontal total drawing ratio is 1: 2 to 1: 20.
11, according to the described film of claim 1-10, it is characterized in that total drawing ratio is 1: 2.8 to 1: 8 longitudinally, horizontal total drawing ratio is 1: 3.8 to 1: 15.
12. according to the described film of claim 1-11, the thickness that it is characterized in that film is less than 500 microns.
13. according to the described film of claim 1-12, the thickness that it is characterized in that film is less than 80 microns.
14. application according to the described film of claim 1-13; food product pack or non-food product packaging field with pre-treatment or be untreated form and with printing or not the simple film of printed form be used for packing; or the simple film with pre-treatment or not pre-treatment form is used for greenhouse coverture or coating film in gardening or agriculture field; perhaps through processing to make bag; be used for the storage or the transportation of goods; with pre-treatment or not pre-treatment form and with printing or not the simple film of printed form be used for makeup or sanitary product plays relevant protection and buffer action; or at pressboard coating; simple film with pre-treatment or not pre-treatment form in paper coating and the window envelope coatings art is used for surface protection or finishing; in order to pre-treatment or not pre-treatment form and printing or printed form and have the finished film of tackiness agent not, use as label or adhesive tape.
15, according to the application of the described film of claim 1-13, described film is used to laminated film or the laminate film producing coating film or be made of identical or different biodegradables and the film that can become compost, perhaps use with other non-biodegradation type films, use therein coated material or tackiness agent may not be biodegradable and can synthesize compost.
16, the application of film according to claim 15, all films that it is characterized in that in laminated film or laminate film or in coating film, use and coated material and tackiness agent be biodegradable with can become compost, thereby laminated film or laminate film itself also be biodegradable with can become compost.
17, according to the application of claim 1-13 and 15 and 16 described films, it is characterized in that bag made by this film or laminated film or laminate film, this film discharges its content through biological degradation after decomposing.
18, according to the application of claim 1-13 and 15 and 16 described films, it is characterized in that having the raw material of the infiltrative packaging film of high water vapor very or isolated film or protection film with film of the present invention or laminated film as production, wherein said film is through cold or thermoregulated needle-like roller perforation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19630233.1 | 1996-07-26 | ||
| DE19630233A DE19630233A1 (en) | 1996-07-26 | 1996-07-26 | Biaxially stretched, biodegradable and compostable film with improved sliding properties |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1226272A true CN1226272A (en) | 1999-08-18 |
Family
ID=7800954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97196766A Pending CN1226272A (en) | 1996-07-26 | 1997-07-14 | Biaxially stretched biodegradable and composatable foil |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0914379A2 (en) |
| JP (1) | JP2001501648A (en) |
| KR (1) | KR20000029556A (en) |
| CN (1) | CN1226272A (en) |
| AU (1) | AU732420B2 (en) |
| BR (1) | BR9710572A (en) |
| CA (1) | CA2261975A1 (en) |
| DE (1) | DE19630233A1 (en) |
| IL (1) | IL128214A0 (en) |
| WO (1) | WO1998004627A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721984A (en) * | 2017-10-31 | 2019-05-07 | 丹阳博亚新材料技术服务有限公司 | A kind of heat-insulated antifog greenhouse film |
| US20200113143A1 (en) * | 2011-11-21 | 2020-04-16 | Innovation Hammer Llc | Methods And Systems For Growing Plants Using Silicate-Based Substrates, Cultivation Of Enhanced Photosynthetic Productivity And Photosafening By Utilization Of Exogenous Glycopyranosides For Endogenous Glycopyranosyl-Protein Derivatives, And Formulations, Processes And Systems For The Same |
| US11968978B2 (en) | 2016-04-29 | 2024-04-30 | Innovation Hammer Llc | Formulations and methods for treating photosynthetic organisms and enhancing qualities and quantities of yields with glycan composite formulations |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19811773A1 (en) * | 1998-03-18 | 1999-09-23 | Wolff Walsrode Ag | Opaque, biodegradable and compostable film for packaging fruit and vegetables and for covering plants or greenhouses |
| DE19811225A1 (en) * | 1998-03-18 | 1999-09-30 | Wolff Walsrode Ag | Improving the hydrolysis stability of films made from biodegradable polymers and processes for producing such films |
| DE19912996A1 (en) * | 1999-03-23 | 2000-09-28 | Wolff Walsrode Ag | Biodegradable agricultural films |
| DE102005052441C5 (en) * | 2005-11-03 | 2013-05-16 | Treofan Germany Gmbh & Co. Kg | A method for increasing the surface tension of a biaxially oriented film of thermoplastic polymers, as well as processes for the production of printed, metallized, laminated, laminated or coated films, prepared by this method for increasing the surface tension |
| ITPG20110034A1 (en) * | 2011-11-08 | 2013-05-09 | Polycart S R L | SUPPORT SYSTEM FOR BIODEGRADABLE ADHESIVE LABELS AND ITS APPLICATION METHOD |
| NL2021594B1 (en) * | 2018-09-10 | 2019-10-07 | Compostable Coffee Cups Ip B V | Improved cartridge for the preparation of a beverage |
| NL2021596B1 (en) * | 2018-09-10 | 2019-10-07 | Compostable Coffee Cups Ip B V | Biodegradable beverage cartridge |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2124847C (en) * | 1992-10-02 | 2005-05-10 | Patrick R. Gruber | Melt-stable lactide polymer films and processes for manufacture thereof |
| JP3307748B2 (en) * | 1993-03-31 | 2002-07-24 | 大日本インキ化学工業株式会社 | Method for producing lactic acid-based copolyester |
| DE4437792A1 (en) * | 1994-10-21 | 1996-04-25 | Inventa Ag | Molding compounds based on aliphatic polyesters |
| EP0747416B1 (en) * | 1994-12-21 | 2004-11-10 | Showa Denko Kabushiki Kaisha | Aliphatic polyester resin and process for producing the same |
| EP0736563A1 (en) * | 1995-04-07 | 1996-10-09 | SAFTA S.p.A. | Process for the manufacture of totally bio-decomposable films with high mechanical characteristics and relevant products and applications |
| US5786408A (en) * | 1995-06-22 | 1998-07-28 | Daicel Chemical Industries, Ltd. | Biodegradable polyester resin composition, and a biodegradable molded article |
| GB9600006D0 (en) * | 1996-01-02 | 1996-03-06 | Courtaulds Fibres Holdings Ltd | Polymeric films |
-
1996
- 1996-07-26 DE DE19630233A patent/DE19630233A1/en not_active Withdrawn
-
1997
- 1997-07-14 JP JP50843598A patent/JP2001501648A/en active Pending
- 1997-07-14 CN CN97196766A patent/CN1226272A/en active Pending
- 1997-07-14 KR KR1019997000614A patent/KR20000029556A/en not_active Application Discontinuation
- 1997-07-14 AU AU38484/97A patent/AU732420B2/en not_active Ceased
- 1997-07-14 CA CA 2261975 patent/CA2261975A1/en not_active Abandoned
- 1997-07-14 IL IL12821497A patent/IL128214A0/en unknown
- 1997-07-14 BR BR9710572A patent/BR9710572A/en not_active Application Discontinuation
- 1997-07-14 EP EP97935520A patent/EP0914379A2/en not_active Withdrawn
- 1997-07-14 WO PCT/EP1997/003748 patent/WO1998004627A2/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200113143A1 (en) * | 2011-11-21 | 2020-04-16 | Innovation Hammer Llc | Methods And Systems For Growing Plants Using Silicate-Based Substrates, Cultivation Of Enhanced Photosynthetic Productivity And Photosafening By Utilization Of Exogenous Glycopyranosides For Endogenous Glycopyranosyl-Protein Derivatives, And Formulations, Processes And Systems For The Same |
| US11968978B2 (en) | 2016-04-29 | 2024-04-30 | Innovation Hammer Llc | Formulations and methods for treating photosynthetic organisms and enhancing qualities and quantities of yields with glycan composite formulations |
| CN109721984A (en) * | 2017-10-31 | 2019-05-07 | 丹阳博亚新材料技术服务有限公司 | A kind of heat-insulated antifog greenhouse film |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9710572A (en) | 1999-08-17 |
| WO1998004627A2 (en) | 1998-02-05 |
| EP0914379A2 (en) | 1999-05-12 |
| AU3848497A (en) | 1998-02-20 |
| AU732420B2 (en) | 2001-04-26 |
| JP2001501648A (en) | 2001-02-06 |
| DE19630233A1 (en) | 1998-01-29 |
| KR20000029556A (en) | 2000-05-25 |
| CA2261975A1 (en) | 1998-02-05 |
| WO1998004627A3 (en) | 1998-03-05 |
| IL128214A0 (en) | 1999-11-30 |
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