EP1732996A2 - Utilisation d'amidon de pomme de terre hydroxypropyle et a haute teneur en amylose pour obtenir un indice kit eleve - Google Patents

Utilisation d'amidon de pomme de terre hydroxypropyle et a haute teneur en amylose pour obtenir un indice kit eleve

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Publication number
EP1732996A2
EP1732996A2 EP05716393A EP05716393A EP1732996A2 EP 1732996 A2 EP1732996 A2 EP 1732996A2 EP 05716393 A EP05716393 A EP 05716393A EP 05716393 A EP05716393 A EP 05716393A EP 1732996 A2 EP1732996 A2 EP 1732996A2
Authority
EP
European Patent Office
Prior art keywords
packaging
layer
starch
starch derivative
agents
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.)
Withdrawn
Application number
EP05716393A
Other languages
German (de)
English (en)
Inventor
Uwe Robben
Thomas Luck
Hermann Seyffer
Wolfgang Alois Hormuth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Plant Science GmbH
Original Assignee
BASF Plant Science GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF Plant Science GmbH filed Critical BASF Plant Science GmbH
Publication of EP1732996A2 publication Critical patent/EP1732996A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09D103/04—Starch derivatives
    • C09D103/08—Ethers
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N15/00—Mutation or genetic engineering; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification; Use of hosts therefor
    • C12N15/09—Recombinant DNA-technology
    • C12N15/63—Introduction of foreign genetic material using vectors; Vectors; Use of hosts therefor; Regulation of expression
    • C12N15/79—Vectors or expression systems specially adapted for eukaryotic hosts
    • C12N15/82—Vectors or expression systems specially adapted for eukaryotic hosts for plant cells, e.g. plant artificial chromosomes (PACs)
    • C12N15/8241—Phenotypically and genetically modified plants via recombinant DNA technology
    • C12N15/8242—Phenotypically and genetically modified plants via recombinant DNA technology with non-agronomic quality (output) traits, e.g. for industrial processing; Value added, non-agronomic traits
    • C12N15/8243—Phenotypically and genetically modified plants via recombinant DNA technology with non-agronomic quality (output) traits, e.g. for industrial processing; Value added, non-agronomic traits involving biosynthetic or metabolic pathways, i.e. metabolic engineering, e.g. nicotine, caffeine
    • C12N15/8245—Phenotypically and genetically modified plants via recombinant DNA technology with non-agronomic quality (output) traits, e.g. for industrial processing; Value added, non-agronomic traits involving biosynthetic or metabolic pathways, i.e. metabolic engineering, e.g. nicotine, caffeine involving modified carbohydrate or sugar alcohol metabolism, e.g. starch biosynthesis
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D2565/38—Packaging materials of special type or form
    • B65D2565/381—Details of packaging materials of special type or form
    • B65D2565/385—Details of packaging materials of special type or form especially suited for or with means facilitating recycling
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • 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
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31975—Of cellulosic next to another carbohydrate

Definitions

  • the invention relates to multilayer, fat-tight packaging materials with a carrier layer, which consist of paper / cardboard or other suitable, polymer-based substances.
  • Another object of the invention is a process for the production of fat-tight packaging material with a KIT number greater than 21 by using hydroxypropylated high-amylose potato starch with an amylose content of greater than 70%.
  • Patent application DE 41 09 983 A1 describes a flexible packaging container with a composite of a paper layer and a thermoplastic layer or film.
  • the thermoplastic layer or film material consists of starch, a synthetic, non-polyolefinic, hydroxyl-containing polymer, e.g. an oxygenated polymer, as well as plasticizers of natural origin, e.g. starch-derived polyalcohols. This material can be melted by applying heat and is therefore extrudable.
  • patent application DE 41 37 802 A1 it is proposed to laminate a cardboard with a coated paper web in order to obtain a rotten, liquid-repellent product.
  • Patent application DE 42 94 110 discloses a coating dispersion which is produced from copolymers of oxidized starch and styrene, butadiene, acrylic acid or similar polymerizable molecules. This dispersion reduces the gas and water permeability of cardboard or paper.
  • Corresponding paper / cardboard packaging commercially available has usually been subjected to a grease-repellent surface and / or bulk treatment.
  • Fluoropolymers in particular are currently used for this bulk treatment or surface treatment, with up to 5% by weight of coating material reaching the material.
  • Already fat densities> 6 to 8 can only be achieved by combinations of Layer and mass treatment can be achieved, fat densities with KIT numbers> 12 cannot be guaranteed with the current systems.
  • the packaging of dry animal feed with a low fat content ( ⁇ 10%) requires a treatment of the back in bulk, with a higher fat content a barrier is created by bulk treatment in combination with a surface coating.
  • Paper, cardboard and cardboard packaging is properly disposed of via the waste paper cycle.
  • the halogen polymers used as a fat barrier thus get either into the new paper or into the process waste water via the paper preparation.
  • Starch ethers are known as auxiliaries and feedstocks in the paper industry. Properties used here are described in detail in the relevant literature. They are used in surface coating and coating as well as in pigmented paper coatings. According to the BGW, papers, boxes and cardboards approved for food contact may also contain starch ethers (e.g. hydroxyethyl and hydroxypropyl ether). Starch ethers are also used as a component of adhesives because of their good film-forming properties and their water-binding capacity. Literature on this can be found, for example, in Ulimann's encyclopedia of industrial chemistry; W. Baumann / B. Herbe, ⁇ g: Paper chemicals - Facts about environmental protection (Springer-Verlag); O.B: Würzburg:
  • WO 02/02412 describes multilayer packaging for greasy goods based on native, modified starch.
  • starch ether derivatives can be processed into foils or films, primarily using a casting technique from an aqueous solution.
  • the aqueous starch suspension is derivatized in alkaline at temperatures up to 50 ° C.
  • the degree of derivatization is usually around 0.2.
  • the preferred derivatization on the C2 atom is characteristic of these processes.
  • Another method which is known primarily from scientific studies (autoclave method), is based on alkaline-activated starch and, at lower dry substance concentrations, leads to more homogeneous derivatizations, although the degree of derivatization is set similarly.
  • a procedure according to this strategy is described in patent application DE 4223471 A1, the starch ethers obtained in this way being used for film production, in particular for use as overhead, copier and printer films or for the surface finishing of specialty paper. as well as packaging material.
  • the ether derivative films mentioned can also be used in combination with other materials.
  • the object of the present invention is to provide fat-tight packaging materials with a very high number of KITs that are permitted under food law.
  • substrates which themselves do not have sufficient fat resistance such as paper, cardboard, cardboard or other materials made from or with cellulose, are fat-tight if they are coated with alkylene oxide-derivatized starch with an amylose content of greater than 70% ,
  • the present invention therefore provides multilayer packaging for greasy goods or parts of such packaging, which have a carrier layer made of a polymeric material as the main component and at least one layer applied to the carrier layer that does not form the outside of the packaging, the layer applied to the carrier layer having one contains alkylene oxide-derived starch with an amylose content of greater than 70% as the main component.
  • the alkylene oxide used for this can very suitably be a C 2 -C 6 alkylene oxide. C 2 -C 4 alkylene oxides are preferred.
  • HA starch high amylose
  • the coating of a carrier material with the functional layer "high amylose (HA) - starch derivative” realizes a fat-tight composite system.
  • the HA starch component is responsible for the fat tightness and also has the property of biodegradability.
  • Such a starch can also be incorporated well into coating compositions for the stated purpose since, in contrast to native starch, it does not tend to re-aggregate (retrogradation).
  • the packaging of the present invention is not limited to specific configurations.
  • An exemplary, preferred area of application is packaging of food and animal feed with low water contents and at the same time high fat contents, in particular folding boxes. Examples of this are packaging for biscuits, chocolates, other confectionery, dry animal feed, in which a particularly good barrier against the passage of water vapor is not necessary.
  • packaging for fatty non-food e.g. cosmetics, oil-based color pigments or the like
  • fatty non-food can also be designed according to the invention.
  • packagings according to the invention are that their manufacture is compatible with customary paper or cardboard manufacturing processes and that they are biodegradable, and they are particularly advantageous in terms of economic and / or ecological assessments compared to conventional systems, in particular if the factors price of the coating including process costs and the compatibility with the paper recycling process are to be considered.
  • the packaging coated according to the invention ensures good compatibility with the treatment and waste water purification options of waste paper disposal systems.
  • the degradation behavior in the paper cycle is a decisive advantage in terms of avoiding further entry of contaminants.
  • Suitable materials for the backing layer are, in particular, paper, cardboard or cardboard, possibly in a mixture with other suitable substances or substances normally used in food packaging technology such as binders or dyes.
  • other materials or plastics preferably based on natural polymers such as cellulose or the like, can also be used.
  • HA starch derivatives suitable according to the invention are those which have been derivatized with an alkylene oxide such as ethylene oxide or propylene oxide or a longer-chain alkylene oxide.
  • the attached groups increase the distances between the molecular chains and thus increase their mobility. The inner softening effect thus given can only be reversed by destroying the chemical bond.
  • the HA starch derivative should preferably form a closed film on the carrier layer. If this is the case, even very thin layers from about 6 g / m 2 basis weight can be fat-tight, provided the carrier material has a relatively high smoothness.
  • the coating can be provided as a surface layer on the inside of the packaging and / or as an intermediate layer, possibly also with the function of an adhesive layer between paper or cardboard layers or the like.
  • a so-called primer e.g. with conventional paper coating agents such as kaolin or starch, which has the purpose of pre-smoothing the surface.
  • the layer containing the HA starch derivative can optionally be applied to the carrier layer by applying a self-supporting layer made of this material.
  • a solution or suspension of the HA starch derivative with a suitable amount of dry substance is preferably produced and applied to the carrier material, preferably from an aqueous solution or suspension.
  • a very suitable amount of dry substance (TS) of the HA starch derivative is in the range from about 5 to about
  • 50% by weight preferably in the range from about 10 to about 40% by weight, the amount actually to be selected depending on the application method provided. In some cases, an amount down to 4% by weight may be sufficient.
  • the application can be carried out, for example, with a doctor blade, spraying or roller application, as well as by "die casting” a more concentrated solution and by applying a thermoplastic melt ("extrusion") over the surface.
  • the water content of the HA starch derivative should preferably be reduced to ⁇ 25% by weight after application to the carrier material (for example by drying with IR or convective).
  • the layer to be applied to the carrier layer can also contain other additives.
  • the addition of pigments lends itself
  • the KIT number can also be positively influenced in some cases by adding such substances, e.g. by adding glycerin or crosslinker (e.g. Glyoxal).
  • the proportion of high amylose starch derivative should preferably always be so high that the formation of a defect-free film is ensured.
  • Potato starch with an amylose content of greater than 70% is preferably used as the starting material.
  • a potato starch with an amylose content of over 70% can, for example, be isolated from genetically modified potato plants in which the enzymatic activity of the starch branching enzymes SBE I and II is reduced compared to the non-genetically modified starting plant.
  • a method for producing plants of this type is described by way of example in Example 1.
  • Starches with an amylose content of greater than 70% from other crops such as, for example, maize, wheat, peas or tapioca can also be used as starting materials. Plants with an amylose content of greater than 70% can be produced by genetic modification using molecular biological methods and / or by breeding and selection.
  • HA starch means a starch with an amylose content of at least 70%.
  • the amylose content is preferably at least 80%, particularly preferably at least 90%.
  • the chemical modification of the potato starch with an amylose content of greater than 70% takes place, for example, with a C 2 or C 3 alkylene oxide. Propylene oxide is preferred.
  • the HA starch is suitably modified in the presence of base, but the mass intended for the coating should react favorably in about 3 neutral, so that normally neutralization with acid must take place, the modified HA starch is in the Usually heavily contaminated with salts. It is an advantage if this salinity is not too high. It is therefore recommended that the coating composition in the concentration provided for the application has a conductivity of no more than 4,000 - 5,000 pS / cm, preferably of ⁇ 2,000 pS / cm.
  • acids and alkalis should be carried out from the point of view that the salt formed is harmless to food law.
  • Suitable acids are phosphoric acids, a suitable base is sodium hydroxide solution. Desalination can be done, for example, by dialysis.
  • Coatings with higher derivatized HA starch show more favorable KIT numbers than those with lower degrees of derivatization. However, it is not necessary to achieve high levels of substitution, since even low levels can lead to positive effects. However, these also depend on the origin of the HA starch used. While a degree of derivatization of 0.05 to 1.5 may be suitable in general, ranges between 0.1 to 1.0, very particularly preferably between 0.1 and 0.3, are preferred.
  • a HA starch ether solution suitable as a coating composition or casting solution for the present invention can be prepared, for example, as follows: the starch with an amylose content of greater than 70% (for example wheat, corn, tapioca, Potato or HA pea starch) is stirred in approximately twice its weight in water for a few hours and then roughly freed from the water, for example by suction filtering. It absorbs about its own weight of water, so that it has about 40 to 60% dry matter. Then it is resuspended in about 1.5 times its wet weight and disintegrated by adding the same amount of about 10% base or lye.
  • the starch with an amylose content of greater than 70% for example wheat, corn, tapioca, Potato or HA pea starch
  • alkylene oxide preferably propylene oxide
  • HA starch a few minutes to about 1 hour, with mild temperatures being maintained. Room temperature is well suited.
  • the mixture is allowed to stir for several hours and then left to rest for about 20 hours; then it is neutralized with acid. If desalination is to take place, this is done, for example, by dialysis against water. The desalted solution is gently concentrated if necessary.
  • the degree of derivatization of the HA starch is about 0.2 when using about 50% by weight of propylene oxide, in other cases correspondingly above or below.
  • Desalination or separation of disruptive inhomogeneities can also be carried out, for example, by means of ultrafiltration. If the product is too concentrated, it can be diluted with deionized water.
  • a mechanical separation can be carried out using a filter or centrifuge if necessary, and at the same time degassing of the solution to be processed can be achieved.
  • additives e.g. preservatives, fillers, antistatic agents, agents to improve elasticity, crosslinking agents
  • a coating solution which is particularly suitable for the purposes of the invention has the following rheological properties:
  • the method also offers the advantage that the HA starch is reacted and processed particularly gently and in particular continuously at relatively low temperatures ( ⁇ 60 ° C.) or completely at room temperature, which has positive effects for the coating of the carrier material. Due to the cold water solubility after neutralization, separation, salt separation and concentration, the starch with an amylose content of 70% can be processed gently so that no or only insignificant degradation reactions occur.
  • the aqueous casting solution can preferably be applied to the material web (paper) to be coated using a suitable application system (for example a doctor blade) at room temperature or slightly elevated temperatures.
  • hydroxypropyl ether starches produced by the autoclave process in particular from potato starch with an amylose content of greater than 70%, which have been found to be solutions with dry matter contents of 12 to 20% by weight and preferably with derivatization (DS) ) Degrees of 0.1 to 1.0, more preferably to 0.4, are used.
  • DS derivatization
  • these show significantly better grease-tightness, especially in areas with kinks, which are particularly critical in folding box applications.
  • the basis weights used for coating with these starches can be reduced.
  • Potato plants with an amylose content greater than 70% can be produced using antisense or RNAi technology with the aim of. To reduce or eliminate the enzymatic activity of the starch branching enzymes SBE I and SBE II.
  • the HA starch producing transgenic potato line Solanum tuberosum AM99-2003 was produced in which the activity of the starch branching enzymes is inhibited.
  • the genetic transformation of the starting variety Dinamo was carried out using a gene construct which contains gene fragments under the control of a GBSS promoter of SBE I and SBE II in an antisense orientation.
  • PBIuescript contains a 1620 base pair fragment of the 3 'end of the SBE I gene between EcoRV and Spei is cut with Spei and Xbal and ligated with a 1243 base pair Sstl-Xbal fragment of the 3' end of SBE II.
  • SBE I and SBE 2 Complex is cut out with the help of EcoRV and Xbal and ligated into the binary vector pHo3.1 opened with Smal and Xbal.
  • the resulting vector is designated pHabe12A, see Figure 1 and nucleic acid sequence SEQ-ID No. 1.
  • PHo3.1 is based on pGPTVKan (Becker, D. et al., Plant Molecular Biology 20 (1992), 1195-1197) and additionally contains the 987 base pairs GBSS promoter (see EP 0 563 189) of the Hindill site of pGPTVKan cloned and its uidA gene was removed with the help of Smal and Sstl.
  • the parent line Dinamo is transformed with the construct pHAbe12A using the method described in US Pat. No. 6,169,226, and the transgenic lines on kanamycin-containing ones Media selected.
  • the analysis of the amylose content of the transgenic plants was carried out according to the method described in (Morrison, WR and Laignelet, B., J. Cereal. Sci. 1 (1983), 9-20).
  • transgenic potato plants with an amylose content of at least 70% were selected and grown.
  • the high amylose starch was isolated by conventional methods.
  • Potato starch containing high amylose obtained from genetically modified potato plants - see Example 1 - was hydroxypropylated on a laboratory scale.
  • the potato starch with an amylose content of 70% was modified in accordance with an autoclave or homogeneous process.
  • the solution was prepared for the subsequent coating of cardboard by desalting and concentration.
  • the end product should have a degree of derivatization of approx. 0.2, a dry content (w / w) of approx. 18% 20 and a conductivity of approx. 600 // S / cm.
  • the HA starch was heated to 40 ° C.
  • the HA starch solution was applied (once or twice) to the coated and uncoated side of the box.
  • Example 4 Starting from 713 g HA starch from potato plants with an amylose content of 70% - produced according to the method described in Example 1 - became 1770 g hydroxyproply HA starch with a dry weight of 27 (w / w)% and a conductivity made from 880 // S / cm. The conductivity could not be reduced further by diafiltration.
  • Example 4 Starting from 713 g HA starch from potato plants with an amylose content of 70% - produced according to the method described in Example 1 - became 1770 g hydroxyproply HA starch with a dry weight of 27 (w / w)% and a conductivity made from 880 // S / cm. The conductivity could not be reduced further by diafiltration.
  • Example 4 Example 4
  • the coating is tested for tightness against mixtures with 2 I test solutions of different concentrations of castor oil, toluene and n-heptane.
  • the coating with a KIT number> 21 turned out to be fat-tight according to the KIT test according to 3M.
  • the HA starch ether obtained has a degree of derivatization of about 0.2.
  • the conductivity of the coating material is around 1100 pS / cm.
  • the coating compositions below are produced analogously to this example and applied with a 20 // m doctor blade onto chromo duplex cardboard (GD2), 310 g / m 2 , thickness approx. 420 // m, coated on one side. After drying the first a second layer is applied slowly (dry to the touch, approx. 2 h duration) and dried at room temperature and about 50% room humidity for about 1 week, possibly even longer.
  • GD2 chromo duplex cardboard
  • the KIT number for non-polar substances is determined according to the 3M KIT test. Solvent mixtures of castor oil, toluene and heptane are used as test liquids. The KIT solution with the highest number, which is on the sample for 15 seconds without causing a breakdown or discoloration, is the characteristic KIT number.

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Abstract

Procédé de fabrication de matières étanches aux graisses ayant un indice KIT supérieur à 21 par utilisation d'amidon de pomme de terre hydroxypropylé à haute teneur en amylose.
EP05716393A 2004-03-31 2005-03-26 Utilisation d'amidon de pomme de terre hydroxypropyle et a haute teneur en amylose pour obtenir un indice kit eleve Withdrawn EP1732996A2 (fr)

Applications Claiming Priority (2)

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DE102004016653 2004-03-31
PCT/EP2005/003220 WO2005095117A2 (fr) 2004-03-31 2005-03-26 Utilisation d'amidon de pomme de terre hydroxypropyle et a haute teneur en amylose pour obtenir un indice kit eleve

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EP1732996A2 true EP1732996A2 (fr) 2006-12-20

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US (1) US20080171213A1 (fr)
EP (1) EP1732996A2 (fr)
JP (1) JP2007532339A (fr)
KR (1) KR20070009657A (fr)
CN (1) CN1938389A (fr)
BR (1) BRPI0509311A (fr)
NO (1) NO20064885L (fr)
WO (1) WO2005095117A2 (fr)

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CN101768224B (zh) * 2010-01-22 2012-01-11 鲁郑全 一种羟丙基淀粉的制备方法
CN102746408A (zh) * 2012-06-18 2012-10-24 新疆光大山河化工科技有限公司 一种制备羟丙基淀粉醚的方法
AU2015246657B2 (en) * 2014-04-16 2017-12-14 Plantic Technologies Ltd Starch compositions and use thereof
CN105421144A (zh) * 2015-11-03 2016-03-23 广东志造生物科技有限公司 一种纸张的防油处理方法
CN111072791A (zh) * 2019-12-27 2020-04-28 河南新孚望新材料科技有限公司 一种包膜剂用高直链淀粉的制备方法
CN111100215A (zh) * 2019-12-30 2020-05-05 河南新孚望新材料科技有限公司 一种水性漆用羟丙基高直链淀粉的制备方法
US11549216B2 (en) 2020-11-11 2023-01-10 Sappi North America, Inc. Oil/grease resistant paper products

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US5374304A (en) * 1989-04-29 1994-12-20 Battelle-Institut E.V. Special amyloses and their use for producing biodegradable plastics
AU628975B2 (en) * 1989-04-29 1992-09-24 Ems-Inventa Ag Special amyloses and their use in the production of biologically degradable plastics
US5856467A (en) * 1990-12-21 1999-01-05 Amylogene Hb Genetically engineered modification of potato to form amylose-type starch
DE4104782B4 (de) * 1991-02-13 2006-05-11 Bayer Cropscience Gmbh Neue Plasmide, enthaltend DNA-Sequenzen, die Veränderungen der Karbohydratkonzentration und Karbohydratzusammensetzung in Pflanzen hervorrufen, sowie Pflanzen und Pflanzenzellen enthaltend dieses Plasmide
DE4223471C2 (de) * 1992-07-16 1996-03-14 Inventa Ag Stärkezwischenprodukt, Verfahren zu dessen Herstellung sowie Verfahren zu dessen Weiterverarbeitung
WO1995026407A1 (fr) * 1994-03-25 1995-10-05 National Starch And Chemical Investment Holding Corporation Procede pour produire une fecule modifiee a partir de plants de pommes de terre
SE513209C2 (sv) * 1995-11-29 2000-07-31 Lars Rask Förfarande för produktion av transgena potatisar med ökad eller minskad grad av förgrening av amylopektinstärkelse
WO1997033934A1 (fr) * 1996-03-15 1997-09-18 Orville Spence Feuille biodegradable et son procede de fabrication
US7326743B2 (en) * 1998-12-14 2008-02-05 Plantic Technologies Ltd. Biodegradable polymer
CZ302008B6 (cs) * 1998-12-14 2010-09-01 Plantic Technologies Limited Biodegradovatelná polymerní smes, její použití a zpusob její výroby
EP1296790B1 (fr) * 2000-07-03 2004-02-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Emballage a plusieurs couches pour denrees alimentaires grasses

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WO2005095117A2 (fr) 2005-10-13
JP2007532339A (ja) 2007-11-15
WO2005095117A3 (fr) 2006-06-22
BRPI0509311A (pt) 2007-09-04
KR20070009657A (ko) 2007-01-18
NO20064885L (no) 2006-10-26
CN1938389A (zh) 2007-03-28
US20080171213A1 (en) 2008-07-17

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