EP0279313B1 - Verfahren zur Herstellung eines für die Papier- und Kartonindustrie geeigneten, die Bedruckbarkeit von Papier und Karton verbessernden Mittels auf Pigmentbasis, das Mittel und seine Verwendung - Google Patents

Verfahren zur Herstellung eines für die Papier- und Kartonindustrie geeigneten, die Bedruckbarkeit von Papier und Karton verbessernden Mittels auf Pigmentbasis, das Mittel und seine Verwendung Download PDF

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Publication number
EP0279313B1
EP0279313B1 EP88101804A EP88101804A EP0279313B1 EP 0279313 B1 EP0279313 B1 EP 0279313B1 EP 88101804 A EP88101804 A EP 88101804A EP 88101804 A EP88101804 A EP 88101804A EP 0279313 B1 EP0279313 B1 EP 0279313B1
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EP
European Patent Office
Prior art keywords
paper
agent
water
pigment
coacervation
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.)
Expired - Lifetime
Application number
EP88101804A
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German (de)
English (en)
French (fr)
Other versions
EP0279313A1 (de
Inventor
Guido Dr. Dessauer
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.)
IKO Erbsloeh Industriemineralien und Kohlenstoffe GmbH and Co
Original Assignee
Institut fuer Papier Zellstoff und Fasertechnik
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 Institut fuer Papier Zellstoff und Fasertechnik filed Critical Institut fuer Papier Zellstoff und Fasertechnik
Priority to AT88101804T priority Critical patent/ATE100849T1/de
Publication of EP0279313A1 publication Critical patent/EP0279313A1/de
Application granted granted Critical
Publication of EP0279313B1 publication Critical patent/EP0279313B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • D21H19/36—Coatings with pigments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated

Definitions

  • the invention relates to a process for producing a pigment-based agent suitable for the paper and board industry, which improves the printability of paper and board, the agent produced by this process and the use thereof.
  • German patent application P 36 34 277.7 dated October 8, 1986 deals with the task of applying a reactive complex which improves the holdout of printing ink from the water phase and without any solvent to paper with the title "Means for improving paper and cardboard ".
  • the object of the present invention is to achieve a simplification and improvement of the method known from DE-OS 35 06 278 and, in particular, an environmentally friendly method which is easy to carry out and avoids the use of organic solvents for the production of a paper and board industry suitable, pigment-based agents that improve the printability of paper and cardboard.
  • the invention is therefore based on the finding that the printing properties of paper, in particular of thin printing papers which are used in gravure printing, can be considerably improved if the paper, but also cardboard, is treated in bulk or on the surface with an agent, which essentially consists of particles obtained by coacervation from at least one pigment, a water-soluble or water-swellable hydrogel containing anionic groups and a quaternary ammonium salt, and in which the solid pigment particles are "microencapsulated" by a kind of shell from the two other components.
  • a pigment or pigment mixture with a water-insoluble envelope e.g. B. a water-insoluble organophilic silicate, in such a finely dispersed form that a coating is applied to practically every pigment grain.
  • the invention achieves organophilic solvents, e.g. B. isopropanol-free, organophilic phyllosilicates both to be introduced into the paper stock and to produce coating compositions.
  • organophilic solvents e.g. B. isopropanol-free, organophilic phyllosilicates both to be introduced into the paper stock and to produce coating compositions.
  • An agent produced according to the method of the invention can be spread onto a paper, cardboard, cardboard or non-woven surface by conventional methods and then smoothed on a calender.
  • the agent can, for example, also be mixed into a paper stock and moved out in a known manner on a paper, cardboard or wet fleece machine, with the finished product being filled with e.g. B. 10 to 35 wt .-% of the reactive properties of the particle shells or capsule walls can be used to improve the holdout and the printing work.
  • pigments in particular kaolins, calcium carbonate, titanium dioxide and talc. From the unpigmented application to a line with approx. 94% pigment and 6% binder content, the most varied variants are possible.
  • an inert white pigment e.g. B. kaolin
  • a reactive, printability-improving complex it follows logically that with the increase in the percentage of the inert pigment, the opacity, the volume or the whiteness of the coating are improved, but at the same time the desired holdout effect decreases, d. H. is watered down.
  • DE-OS 35 06 278 describes a coating slip in Example 3 which consists of 96 parts of kaolin and 4 parts of mechanically finely dispersed reactive organophilic bentonite. As usual, this coating slip is bound with a plastic dispersion. After the hot satin, an improvement is evident, but only with a line application of 7 g / m2 and side. If one starts from the simplified idea that the dispersed reactive organophilbentonite particles are of the same order of magnitude as the kaolin particles, then in this example 26 kaolin particles have a particle made of reactive organophilic complex.
  • organophilic bentonite in the presence of the kaolin presented at the usual concentrations in industry of 200 g / l in the ratio of z. B. 10 parts by weight of bentonite to 1 part by weight of kaolin to the reactive complex, so you get a hydrophobic product with full ion exchange, which is just as difficult to disperse as a pure organophilic silicate.
  • the coacervation takes place by reacting the three components, namely hydrogel, quaternary ammonium salt and in pigment in water, it being possible for the three components to be added in any order. It is preferred first to react the pigment with the quaternary ammonium salt and then to add the hydrogel.
  • hydrogel containing anionic groups e.g. B. Na bentonite
  • quaternary ammonium salt in the presence of the pigment is preferably carried out in a comparatively strong dilution in water.
  • a finely dispersed, comparatively very thin suspension is obtained, in which the pigment and the organophilic silicate are contained, the latter enveloping the pigment particles.
  • the fact that the formation of the organophilic silicate takes place can be seen from the phase separation between the colloid and the pure water which settles on top. The product obtained sediments, if not very quickly. But you can also first prepare a suspension of quaternary salt and pigment particles and add dad hydrogel.
  • quaternary ammonium salt e.g. B. dimethyldioctadecylammonium chloride
  • B. dimethyldioctadecylammonium chloride is first prepared by heating in water to about 70 ° C, based on the active substance, 1 wt .-% solution. This solution is then z. B. added to a 5% kaolin suspension, in an amount necessary to form 10% organophilic silicate is.
  • the quaternary salt is absorbed on kaolin, especially since it itself has approx. 3 to 5 mVal ion exchange capacity, which must be taken into account when calculating the amounts.
  • a 2% by weight colloidal dispersion in water is prepared from Na bentonite, whereupon it is slowly added to the suspension of the kaolin with the quaternary salt with constant stirring.
  • a hydrogel from the colloidal dispersion of a hydrated, cation-exchangeable, film-forming smectic layered silicate which has an ion exchange capacity of 50 to 120 meq / 100 g.
  • Layered silicates of this type are, for example, montmorillonite, hectorite, saporite, sauconite, beidellite, nontronite and preferably bentonite.
  • customary, known, water-insoluble optical brighteners can also be added, i. H. can be used together with the quaternary ammonium salt. These water-insoluble optical brighteners are then found on the outside of the pigment in the organophilic complex formed.
  • Suitable quaternary organic ammonium salts are those of the following formulas (1) to (8) wherein R is C8-C22-alkyl, C8-C22-alkenyl or a group of the formula - (AO) y -C8-C22-alkyl, R1 C1-C4-alkyl or benzyl, R2 is hydrogen, C1-C22-alkyl, C1- C22-alkenyl or a group of the formula - (AO) y -B or of the formula - (AO) y -C8-C22-alkyl, R3 is hydrogen, C1-C4-alkyl or a group of the formula - (AO) y -B, A C1-C4alkylene, B is hydrogen or a group of the formula -COR, y is a number from 1 to 25 and X is an anion; wherein X, R, R1 and R2 have the meanings given above; wherein z each
  • R C12-C18-alkyl or C12-C18-alkenyl
  • R1 methyl or ethyl
  • R2 methyl, ethyl, C12-C1 oder-alkyl or C12-C18-alkenyl
  • A C2H4 or C3H6
  • n 1 or 2.
  • substituents consist of C8-C22-alkyl or C8-C22-alkenyl groups, groups which are derived from natural fatty acids and their mixtures are particularly suitable here.
  • tallow fatty acid such as tallow fatty acid, coconut fatty acid, oleic acid, palmitic acid, stearic acid.
  • Possible anions are, for example, chloride, bromide, sulfate, methosulfate, dimethophosphate, phosphate or anions of organic acids such as acetic acid, propionic acid, trichloroacetic acid, lactic acid, citric acid, tartaric acid, tartonic acid, oxalic acid, malonic acid.
  • the procedure is such that the weight fraction of the pigment core covering or capsule wall formed by the coacervation, i. H. the proportion of hydrogel, based on the total amount of solid matter of all components, is set to 5 to 40% by weight, preferably 10 to 20% by weight.
  • the proportion by weight of quaternary ammonium salt in the pigment core coating or capsule wall can be different. It depends on the ion exchange ability of the hydrogel, e.g. B. the layered silicate, and the degree of ion exchange. This means that, depending on how much ammonium salt is added, practically a complete ion exchange or an incomplete ion exchange is effected.
  • the agents according to the invention consist of 1 to 50% by weight of quaternary ammonium salt and 50 to 99% by weight of the hydrogel or layered silicate.
  • surface preparations can be applied to paper or cardboard by known methods.
  • the ratio of pigment to formed reactive organophile complex is 10 to 1
  • this order is hot satinized, the z. B. on the kaolin reactive complexes an excellent holdout for gravure ink.
  • the function of the reactivity with the printing ink can be combined in this way with the need for optical coverage of the paper surface without the layer thickness having an influence on the printing behavior.
  • the reactive organophilic complex will have a specific surface of the same order of magnitude in the pigment coating. This means a very substantial increase in the specific surface area of the reactive complexes compared to a simple mixture.
  • the pigments coated by the process of the invention are hydrophobic. This means that they are no longer bound to the usual strengths. Plastic dispersions adjusted to hydrophilic pigments can no longer be used. With plastic dispersions, such as. B. based on methyl methacrylate (Rohagit SD 25) or styrene-acrylate (Dow Latex 695), the coated hydrophobic pigments can be bound perfectly. For example, 6% of the binder, based on the coated pigment, is sufficient to achieve a line binding suitable for gravure printing. As a result of the thermoplastic deformability of the organophilic silicates, adhesion to the outer layer of the pigments occurs during the hot satinization.
  • binding by means of a binder which is compatible with the coated pigment appears expedient.
  • this agent is incorporated into a suitable binder such as polyvinyl alcohol or styrene-acrylate dispersion and applied to the paper in a conventional manner.
  • the proportion of binder here is approximately 5 to 20% by weight, the application amounts of these mixtures to the paper are generally 0.1 to 10 g / m2.
  • the pigments encased by the process of the invention can also be used in the stock of a paper to be treated in bulk. Due to the significantly increased specific surface area, one comes obviously with smaller amounts of the reactive substance.
  • the amount of the agent produced according to the invention is about 12 to 35% by weight, based on the fiber content.
  • Na bentonite is used as the hydrogel containing anionic groups to carry out the process according to the invention, it is not necessary to start from a purified Na bentonite. Rather, it is e.g. B. also possible, commercial, about 75% active ingredient containing simple Na bentonite, as z. B. is used in wastewater treatment as a coacervable colloid. Strangely enough, the strong intrinsic color of this material does not play the expected negative role in the case of coating a pigment which is whiter per se.
  • the pigment-based compositions which can be prepared by the process of the invention can also advantageously be used for the production of paints based on plastic dispersions, for the production of water-based paints, for the production of wallpaper primers and wallpaper paints, i.e. H.
  • paints based on plastic dispersions for the production of water-based paints
  • wallpaper primers and wallpaper paints i.e. H.
  • a commercially available fine paper kaolin (Dorfner FP 75) are finely dispersed in one liter of water using a high-shear mixer (Ultraturrax, manufacturer: Jahnke and Kunkel) for 15 minutes.
  • a dispersing agent is not added since practically all commercially available paper kaolins already contain such, mostly anionic ones.
  • the fully hydrated, film-forming water-Na-bentonite mixture obtained has an active substance content of reactive and ion-exchangeable bentonite of 3.23 g.
  • About 5 g of an organophilic layered silicate which is insoluble in water are deposited on the kaolin.
  • the total amount of the aqueous dispersion of almost 1,500 ml obtained separates into a water phase and a sedimenting dispersion phase. This separation is accelerated at 70 ° C.
  • the reaction mixture obtained can be concentrated in a separating funnel overnight to about 700 ml, which then contain 55 g of solid substance. This corresponds to a solids content of approx. 7.86% by weight.
  • styrene-acrylate latex based on the solids content, 6% by weight of a styrene-acrylate latex (3.3 g solid or 6.6 g of a commercially available plastic dispersion with a solids content of 50%).
  • a line of 3.5 g / m2 and page is applied in the customary manner to a conventional wood-containing coating base paper of 38 g / m2.
  • the satin is calendered to an optimal gloss at a temperature of 90 ° C in a conventional calender.
  • This line now contains approximately 8.63% by weight of a reactive organophilic silicate, corresponding to approximately 0.3 g / m2 per side.
  • An intaglio print from a toluene solution attached to it shows an outstanding holdout for the color and an excellent print gloss.
  • the fiber mixture consists of 25% long fiber sulfate pulp, ground on 23 ° Schopper-Riegler and 75% of a softwood cut with 74 ° S.R.
  • a sheet of 45 g / m 2 with a filler content of 32% by weight is produced from this mixture on a Rapid Koethen sheet former. After calendering on a calender with roller temperatures of 110 ° C, the paper is printed in a test printer. This shows a significantly improved acceptance of the gravure printing ink, an improved gloss, a greater depth of color and a reduced tendency to missing dots.
  • 35 g of a commercially available calcium carbonate (Durcal) are added to one liter of water without the addition of an auxiliary dispersed using an intensive stirrer.
  • a 2% dispersion of a purified Na bentonite in water is produced with vigorous stirring. 162 ml of this calcium carbonate dispersion are mixed into the calcium carbonate dispersion with intensive stirring.
  • Starting from commercially available dimethyldistearylammonium chloride a 2% by weight solution is prepared using hot water. This solution is added while stirring to the mixture of carbonate and Na bentonite until approximately 120 to 125 ml have been added. This corresponds to an equimolar amount, based on bentonite, of approx. 130 to 135 meq. This means that in addition to the amount that can be converted via the ion exchange, a small excess of the strongly cationic quaternary ammonium salt was used. This improves the repulsion of the enveloped particles formed with one another.
  • Waste paper obtained from this coated paper or cardboard has an increased resistance to the Calcium carbonate in paper mixtures containing aluminum sulfate.
  • the deinkability of this line is also improved according to the invention, since less printing ink is required to achieve the same depth of color.
  • a high quality spreadable kaolin (type SPS, manufacturer: English China Clay Corp.) are finely dispersed in 1000 ml of water. 0.7% of an optical brightener for oils and fats, dissolved in isopropanol in a ratio of 1 to 2, is mixed into a stock paste of dimethyldistearylammonium chloride, based on the active ingredient content, and stirred vigorously. It is recommended to heat the paste in a water bath to approx. 60 to 70 ° C. The quaternary ammonium salt is then diluted down in hot water to a concentration of 1% by weight. 245 ml of this solution are mixed into the kaolin suspension with stirring. Then 215 ml of a 2% commercial Na bentonite slurry are added (Opazil, manufacturer: Südchemie AG).
  • pigments coated with the organophilic silicate are obtained which are already highly white, the pigment coating containing the water-insoluble optical brightener.
  • a compatible plastic binder as described in Example 3, a bright white, optically brightened line is obtained which shows a particularly good holdout for gravure and web offset printing inks.
  • a good hot satin finish is to be carried out after the stroke and drying of the paper web.
  • the packing density of the coated kaolin particles is also of great importance here

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Cartons (AREA)
EP88101804A 1987-02-10 1988-02-08 Verfahren zur Herstellung eines für die Papier- und Kartonindustrie geeigneten, die Bedruckbarkeit von Papier und Karton verbessernden Mittels auf Pigmentbasis, das Mittel und seine Verwendung Expired - Lifetime EP0279313B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88101804T ATE100849T1 (de) 1987-02-10 1988-02-08 Verfahren zur herstellung eines fuer die papierund kartonindustrie geeigneten, die bedruckbarkeit von papier und karton verbessernden mittels auf pigmentbasis, das mittel und seine verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3703957 1987-02-10
DE19873703957 DE3703957A1 (de) 1987-02-10 1987-02-10 Verfahren zur herstellung eines fuer die papier- und kartonindustrie geeigneten, die bedruckbarkeit von papier und karton verbessernden mittels auf pigmentbasis, das mittel und seine verwendung

Publications (2)

Publication Number Publication Date
EP0279313A1 EP0279313A1 (de) 1988-08-24
EP0279313B1 true EP0279313B1 (de) 1994-01-26

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EP88101804A Expired - Lifetime EP0279313B1 (de) 1987-02-10 1988-02-08 Verfahren zur Herstellung eines für die Papier- und Kartonindustrie geeigneten, die Bedruckbarkeit von Papier und Karton verbessernden Mittels auf Pigmentbasis, das Mittel und seine Verwendung

Country Status (11)

Country Link
US (1) US4963192A (no)
EP (1) EP0279313B1 (no)
JP (1) JPS6485394A (no)
AT (1) ATE100849T1 (no)
AU (1) AU606918B2 (no)
BR (1) BR8800529A (no)
CA (1) CA1335947C (no)
DE (2) DE3703957A1 (no)
DK (1) DK169554B1 (no)
FI (1) FI92616C (no)
NO (1) NO176882C (no)

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JP2770409B2 (ja) * 1989-04-28 1998-07-02 ソニー株式会社 表示組成物、着色顔料および記録材
DE4015252A1 (de) * 1990-05-12 1991-11-21 Hoechst Ag Verfahren zur einbindung eines binders in ein in der masse gefuelltes papier
US5298064A (en) * 1990-12-06 1994-03-29 Hoechst Aktiengesellschaft Water-containing organophilic phylloisilicates
DE4038886C2 (de) * 1990-12-06 2000-08-03 Brabon Gmbh & Co Kg Verwendung wasserhaltiger organophiler Schichtsilikate
DE4137062A1 (de) * 1991-11-11 1993-05-13 Roehm Gmbh Verfahren zur behandlung einer waessrigen pigmentsuspension mit einem waessrigen bindemittel
DE4137091C2 (de) * 1991-11-12 1995-06-01 Hoechst Ag Wäßrige Feindispersion eines organophilen Schichtsilikates
US5281286A (en) * 1992-04-09 1994-01-25 The United States Of America As Represented By The Secretary Of The Army Microcoacervation of propellant ingredients
DE4419201A1 (de) * 1994-06-01 1996-01-11 Hoechst Ag Verfahren zur Herstellung einer wäßrigen Feindispersion eines organophilen Schichtsilikates
US5700319A (en) * 1995-09-28 1997-12-23 Southern Clay Products, Inc. Method for extending pigments
EP1134258A1 (en) * 2000-03-13 2001-09-19 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Biodegradable thermoplastic material
US6440537B1 (en) * 2000-03-27 2002-08-27 Eastman Kodak Company Ink jet recording element
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AU2002361095A1 (en) * 2001-12-26 2003-07-15 Nippon Paper Industries, Co., Ltd. Dullish coated paper for printing
EP2053163A1 (en) * 2007-10-26 2009-04-29 SAPPI Netherlands Services B.V. Coating formulation for offset paper and paper coated therewith
DE102008025697A1 (de) 2008-05-29 2009-12-03 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Stärkebasierte thermoplastische Formmasse, Verfahren zu deren Herstellung sowie deren Verwendung
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Also Published As

Publication number Publication date
BR8800529A (pt) 1988-09-27
NO176882C (no) 1995-06-14
DK65888A (da) 1988-08-11
NO880554L (no) 1988-08-11
FI880553A (fi) 1988-08-11
US4963192A (en) 1990-10-16
DE3887358D1 (de) 1994-03-10
FI880553A0 (fi) 1988-02-08
DK65888D0 (da) 1988-02-09
ATE100849T1 (de) 1994-02-15
NO176882B (no) 1995-03-06
NO880554D0 (no) 1988-02-09
AU1144988A (en) 1988-08-11
JPS6485394A (en) 1989-03-30
EP0279313A1 (de) 1988-08-24
AU606918B2 (en) 1991-02-21
FI92616C (fi) 1994-12-12
DE3703957A1 (de) 1988-08-18
DK169554B1 (da) 1994-11-28
CA1335947C (en) 1995-06-20
FI92616B (fi) 1994-08-31

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