[go: up one dir, main page]

WO1987003951A1 - Brittle grinding and extraction of animal and plant derived materials - Google Patents

Brittle grinding and extraction of animal and plant derived materials Download PDF

Info

Publication number
WO1987003951A1
WO1987003951A1 PCT/US1986/002741 US8602741W WO8703951A1 WO 1987003951 A1 WO1987003951 A1 WO 1987003951A1 US 8602741 W US8602741 W US 8602741W WO 8703951 A1 WO8703951 A1 WO 8703951A1
Authority
WO
WIPO (PCT)
Prior art keywords
tissue
extraction
material comprises
freezing
organic solvent
Prior art date
Application number
PCT/US1986/002741
Other languages
English (en)
French (fr)
Inventor
Ahmad Reza Kamarei
Robert S. Sinn
Original Assignee
Angio-Medical Corporation
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 Angio-Medical Corporation filed Critical Angio-Medical Corporation
Priority to KR870700751A priority Critical patent/KR880700688A/ko
Publication of WO1987003951A1 publication Critical patent/WO1987003951A1/en
Priority to NO873300A priority patent/NO873300D0/no
Priority to DK432387A priority patent/DK432387D0/da
Priority to FI873598A priority patent/FI873598A0/fi

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C11/00—Other auxiliary devices or accessories specially adapted for grain mills
    • B02C11/08—Cooling, heating, ventilating, conditioning with respect to temperature or water content
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C19/00—Other disintegrating devices or methods
    • B02C19/18—Use of auxiliary physical effects, e.g. ultrasonics, irradiation, for disintegrating
    • B02C19/186—Use of cold or heat for disintegrating
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
    • A61K35/12—Materials from mammals; Compositions comprising non-specified tissues or cells; Compositions comprising non-embryonic stem cells; Genetically modified cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0203—Solvent extraction of solids with a supercritical fluid

Definitions

  • the physical form of feed i.e., the particle size and the attendant ratio of surface area to volume and volume to mass (specific volume) usually has a great impact on the efficiency of the process.
  • This efficiency can be expressed in terms of using less solvent or energy, faster processing rate, higher percent recovery, and in many cases, higher quality of the final products.
  • SCF supercritical fluids
  • the greater the area of the solute exposed to solvent the more efficient the process is.
  • freeze drying the heat flux and the rate of sublimation is directly proportional to the subject area of the material under process.
  • This step is based on freezing the pieces of the desired tissue and lowering its temperature to an emperically critical "Brittleness Temperature" which converts the unbreakable, viscous, and sticky (e.g. fatty tissue) materials into an extremely brittle and fragile substance.
  • Brittleness temperature depends primarily on the species and composition of the tissue (water, lipids, proteins, carbohydrates, minerals) and therefore its thermal properties.
  • the rate of crystallization (i.e., nucleation and crystal growth) of water will affect the size of crystals. Slow rate of crystallization results in formation of large extracellular water crystals which may cause some rupture of cell membranes, but such effects and even repeated freeze-thaw process have negligible effects in comparison to cell rupture by cryogrinding. It is preferred, however, to keep the physical structure of the tissue cells up to the cryogrinding step, intact. This means that, all other factors being equal, the fastest possible freezing rate should be employed.
  • the initial volume increase of the tissue Pure water at 0°C expands approximately 9% when transformed into ice at the same temperature. Most tissues also expand on freezing but to a lesser extent than pure water.
  • Liquid-immersion Freezing 4. Cryogenic Freezing (freezant undergoes a change of state): a) Liquid Nitrogen (LN 2 ), -196°C (77K) b) Subliming Carbon dioxide (dry ice), -79°C (194K) c) CCl 2 F 2 (refrigerant -12), -30°C (243K) Cryogenic freezing with LN 2 , among all above methods, is the most desirable method for the following reasons:
  • Liquid nitrogen is a safe, non-toxic, and non-flammable cryogenic medium which is universally used in food, pharmaceutical, and other industries.
  • tissue powder while extremely fine, is not "uniform" with regard to size. Consequently, if uniformity in a particular size range is desired for the following steps, tissue powder should be sieved at or below its brittleness temperature. For this purpose, one may use stacked stainless steel standard sieves (Table 1; AOAC, 1984).
  • tissue powder is recovered from the top of each individual sieve and can be used individually or in a desired combination of particle sizes. Oversize particles can be recycled for further cryogrinding. Distribution of particle size can be obtained from weighing of material on each sieve.
  • tissue powder To use the uniform cryoground product, one should desirably "thaw" the tissue powder. Since thawing of non-fluid tissues is inherently slower than freezing, when comparable temperature differentials are employed (due to different thermal properties of ice vs. water). Hence, tissue powders may be subject to damage by chemical or physical (and less microbial or enzymatic) means. In light of these considerations, one skilled in the art will recognize that the thawing process must be carefully considered.
  • the process is straight forward, non-complicated, effective, fast, and clean with minimum loss. Since no medium is added for homogenization, there is no need for an extra step (e.g., centrifugation) for removal of any medium.
  • the process is technology adaptable.
  • cryoground and cryosieved tissues are free-flowing powders, their handling (e.g., weighing, transferring, mixing, pouring, etc.) in laboratory and/or plant is very easy.
  • tissue powders due to their extreme homogeniety, may be used as reliable common sources for comparative analytical and preparative research and development studies.
  • cryogrinding was applied to porcine omentum and a pinkish "omentum powder" was obtained. Upon cryosieving, the best uniform fraction of omentum powder appeared to be in the range of 150 to 600 um.
  • pancreas powder was obtained.
  • the best uniform fraction of pancreas powder appeared to be in the range of 150 um to 1.18 mm.
  • liver powder was obtained.
  • the best uniform fraction of liver powder appeared to be in the range of 300 um to 1.18 mm.
  • cryogrinding was applied to porcine blood and a "blood powder" was obtained. Upon cryosieving, the best uniform fraction of blood powder appeared to be in the range of 150 to 300 um.
  • brain spinal chord, spinal fluid, appendages
  • peripheral nervous system tissues and organs cranial nerves, spinal nerves, etc.
  • lymphatic system tissues and organs lymphatic system tissues and organs (lymph nodes, spleen, thymus); respiratory system tissues and organs (upper respiratory tract, lungs); digestive system tissues and organs (including mouth, teeth, tongue, salivary glands, pharynx, esophagus, peritoneum, stomach, small and large intestine, liver, gall bladder, pancreas); skeletal tissue and organs (axial and appendicular skeleton, bone marrow); muscles (smooth and skeletal); endothelial and epithelial tissue; membranes, omentum, and cartiligenous tissues
  • tendons, ligaments, joints tendons, ligaments, joints
  • sensory organs eyes, ear, nose, tongue
  • endocrine or other glandular tissue thyroid gland, parathyroid gland, pituitary gland, adrenal gland
  • urinary tissue and organs kidneys, ureters, urinary bladder, urethra
  • reproductive organs and tissues testes, ovaries, etc.
  • adipose tissues such as is contained in subcutaneous and internal organs, as well as biological exudates, such as feces, urine, sweat, semen, milk, and so forth, are used. In each case such processing conditions are chosen which optimizes the physical and rheological characteristics of the desired powder.
  • Chloroform/Methanol Extraction of Omentum Powder 500 g. uniform porcine omentum powder was warmed up to room temperature and extracted with 10 times chloroform/methanol (2:1, v/v) in a glass blender (22,000 RPM, 30 seconds). The solvent extract was centrifuged (2,000 RPM, 20 minutes) and subjected to rotary evaporation (under vacuum, 37°C) until dryness, i.e., neither any solvent condensation occurs, nor any solvent odor is present. A whitish chloroform/methanol fraction (CMFr) weighing 388 g. (i.e., 77.6%) was obtained. The CMFr could be further subjected to a hexane/ethanol fractionation.
  • CMFr chloroform/methanol fraction
  • cryogrinding causes production of particles with smaller sizes. This may improve the oil recovery, when compared to equally treated, but flaked or R.T. ground soy flour.
  • 250 g. of the resultant cryoground soy flour (from 600 um sieve) was extracted with 15 times hexane at room temperature.
  • the resultant cloudy solution was centrifuged at 2000 RPM for 20 minutes. Upon centrifugation, the clear yellowish supernatant was rotary evaporated at 37°C under vacuum. Total recovery was 24.3 g. (i.e., 9.7%).
  • the materials which can be extracted using the processes described herein include, but are not limited to, complex lipids, such as acylglycerols, phosphoglycerides, sphingolipids, gangliosides and waxes; simple lipids, such as terpenes, pigments, steroids and their alcohols (sterols), prostaglandins, and so forth.
  • complex lipids such as acylglycerols, phosphoglycerides, sphingolipids, gangliosides and waxes
  • simple lipids such as terpenes, pigments, steroids and their alcohols (sterols), prostaglandins, and so forth.
  • Glycolipids, lipoproteins, membrane supramolecular complexes, and their metabolic intermediates be they catabolic or anabolic, and metabolic products of these molecules, as well as molecules which behave in a fashion similar to lipids, may be obtained in a fashion similar to that given in the examples, supra.
  • Proteinaceous substances such as amino acid containing substances (including non-protein amino acids), oligopeptides, peptides, polypeptides, hormones, proteins, enzymes, antibodies, fractions and components of these, as well as metabolic intermediaries and products may be obtained. While the choice of temperatures, solvents, SCFs and reaction parameters will vary, depending upon the substance to be extracted, one skilled in the art will be able to determine which reagents and conditions to use. Saccharides, including mono-, di-, oligo- and polysaccharides, as well as glycoproteins may be extracted in this way as well. Again, metabolic intermediates and products can be obtained as well.
  • nucleotide family of molecules including purines and pyrimidines, and any molecules containing nucleic acid bases, nucleosides (ribonucleosides and deoxyribonucleosides), nucleic acids, supramolecular complexes of nucleic acids and proteins, viruses, and so forth as well as their intermediates and products, metaolic products may also be obtained.
  • materials not grouped into one of the "families” listed supra may be obtained. These include all fat and/or water soluble vitamins, flavors, flavor potentiators, their intermediates, both catabolic and anabolic, and products as well.
  • the desired material may also be treated with one or any combination of more than one of the following methods of treating the samples:
  • the samples need not be treated prior to cryogrinding, but may, e.g., be treated after the preparation of tissue powder.
  • Supercritical fluid extraction may be accomplished with many different gases, including those listed in the following Table II.

Landscapes

  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Animal Behavior & Ethology (AREA)
  • Immunology (AREA)
  • Virology (AREA)
  • Zoology (AREA)
  • Cell Biology (AREA)
  • Medicinal Chemistry (AREA)
  • Biotechnology (AREA)
  • Epidemiology (AREA)
  • Developmental Biology & Embryology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Toxicology (AREA)
  • Biomedical Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Cosmetics (AREA)
  • Processing Of Solid Wastes (AREA)
PCT/US1986/002741 1985-12-20 1986-12-17 Brittle grinding and extraction of animal and plant derived materials WO1987003951A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR870700751A KR880700688A (ko) 1985-12-20 1986-12-17 동식물유도물의 바사바삭하게 갈기와 추출
NO873300A NO873300D0 (no) 1985-12-20 1987-08-06 Sproeoppmaling og ekstrahering av stoffer avledet fra planter og dyr.
DK432387A DK432387D0 (da) 1985-12-20 1987-08-19 Skoerformaling og -ekstraktion af materialer afledt af dyr og planter
FI873598A FI873598A0 (fi) 1985-12-20 1987-08-20 Skoermalning och extraktion av material fraon djur och plantor.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US811,507 1977-06-30
US81150785A 1985-12-20 1985-12-20

Publications (1)

Publication Number Publication Date
WO1987003951A1 true WO1987003951A1 (en) 1987-07-02

Family

ID=25206749

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1986/002741 WO1987003951A1 (en) 1985-12-20 1986-12-17 Brittle grinding and extraction of animal and plant derived materials

Country Status (10)

Country Link
EP (1) EP0252124A4 (da)
JP (1) JPS63502090A (da)
KR (1) KR880700688A (da)
AU (1) AU584780B2 (da)
DK (1) DK432387D0 (da)
FI (1) FI873598A0 (da)
IL (1) IL81000A0 (da)
NZ (1) NZ218720A (da)
WO (1) WO1987003951A1 (da)
ZA (1) ZA869569B (da)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2639558A1 (fr) * 1988-11-30 1990-06-01 Strasbourg I Universite Procede de broyage de tissus biologiques d'origine humaine ou animale et dispositif pour la mise en oeuvre de ce procede
EP0584712A1 (fr) * 1992-08-21 1994-03-02 Debio Recherche Pharmaceutique S.A. Broyeur ultra-centrifuge et sa mise en oeuvre pour le broyage cryogénique de matériau thermosensible
US7678931B2 (en) 2004-10-22 2010-03-16 Martek Biosciences Corporation Process for preparing materials for extraction
WO2017040810A1 (en) * 2015-09-04 2017-03-09 Koffeefruit Pte. Ltd. Preparation of coffee fruit extracts and powders
US10800561B2 (en) 2012-01-20 2020-10-13 Koffeefruit Pte. Ltd. Preparation of coffee-based extracts and powders

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990333A (en) * 1985-12-20 1991-02-05 Angio Medical Corporation Method for healing bone damage
NL1009437C2 (nl) * 1998-06-18 1999-12-21 Xenobiosis Extractiewerkwijze.
JP5287524B2 (ja) * 2009-06-05 2013-09-11 東京電力株式会社 植物系バイオマスの多元的有効利用システム

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US637465A (en) * 1899-06-07 1899-11-21 Robert H Hutchinson Process of extracting oils.
US1979124A (en) * 1931-02-25 1934-10-30 Tival Henri Louis Paul Process for the preparation in dry powdered form of animal, fish and vegetable matter
US2575341A (en) * 1946-01-24 1951-11-20 Koppers Co Inc Process for the recovery of butadiene from cyclohexane pyrolate
US3172546A (en) * 1961-05-19 1965-03-09 Union Carbide Corp Size reduction of biological substances
US3470942A (en) * 1966-12-10 1969-10-07 Sanyo Electric Co Microwave heating apparatus and method
US3609987A (en) * 1970-04-01 1971-10-05 Du Pont Method and apparatus for extracting heat from articles with an ebullient liquid freezant
US3771729A (en) * 1971-06-17 1973-11-13 Air Prod & Chem Cryogenic comminution system
US4023734A (en) * 1974-10-18 1977-05-17 Herve Rene A Method and apparatus for communiting marine algae and the resulting product
US4162617A (en) * 1976-03-18 1979-07-31 Paul Schmidt Pulsed crystallizer with strips of reduced heat exchange
US4273294A (en) * 1979-03-15 1981-06-16 Air Products And Chemicals, Inc. Method and apparatus for cryogenic grinding
US4406700A (en) * 1979-11-14 1983-09-27 Allied Corporation Powder produced by embrittling of metallic glassy alloy by hydrogen charging
US4471629A (en) * 1983-05-31 1984-09-18 Mount Carmel Research And Education Corporation Method of freezing and transplant of kidneys and apparatus
US4483488A (en) * 1981-06-30 1984-11-20 Air Products And Chemicals, Inc. Method and apparatus for recovering thermoplastic from coated fabric scrap
US4509695A (en) * 1983-07-18 1985-04-09 Spectrum Medical Industries, Inc. Tissue pulverizer
US4559298A (en) * 1982-11-23 1985-12-17 American National Red Cross Cryopreservation of biological materials in a non-frozen or vitreous state

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR742623A (da) * 1933-03-10
GB1534274A (en) * 1975-01-21 1978-11-29 Boc International Ltd Size reduction
DK140584B (da) * 1975-07-18 1979-10-08 Leo Sa Lab Fremgangsmåde til findeling af frosne blokke af animalske organer eller animalsk væv.

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US637465A (en) * 1899-06-07 1899-11-21 Robert H Hutchinson Process of extracting oils.
US1979124A (en) * 1931-02-25 1934-10-30 Tival Henri Louis Paul Process for the preparation in dry powdered form of animal, fish and vegetable matter
US2575341A (en) * 1946-01-24 1951-11-20 Koppers Co Inc Process for the recovery of butadiene from cyclohexane pyrolate
US3172546A (en) * 1961-05-19 1965-03-09 Union Carbide Corp Size reduction of biological substances
US3470942A (en) * 1966-12-10 1969-10-07 Sanyo Electric Co Microwave heating apparatus and method
US3609987A (en) * 1970-04-01 1971-10-05 Du Pont Method and apparatus for extracting heat from articles with an ebullient liquid freezant
US3771729A (en) * 1971-06-17 1973-11-13 Air Prod & Chem Cryogenic comminution system
US4023734A (en) * 1974-10-18 1977-05-17 Herve Rene A Method and apparatus for communiting marine algae and the resulting product
US4162617A (en) * 1976-03-18 1979-07-31 Paul Schmidt Pulsed crystallizer with strips of reduced heat exchange
US4273294A (en) * 1979-03-15 1981-06-16 Air Products And Chemicals, Inc. Method and apparatus for cryogenic grinding
US4406700A (en) * 1979-11-14 1983-09-27 Allied Corporation Powder produced by embrittling of metallic glassy alloy by hydrogen charging
US4483488A (en) * 1981-06-30 1984-11-20 Air Products And Chemicals, Inc. Method and apparatus for recovering thermoplastic from coated fabric scrap
US4559298A (en) * 1982-11-23 1985-12-17 American National Red Cross Cryopreservation of biological materials in a non-frozen or vitreous state
US4471629A (en) * 1983-05-31 1984-09-18 Mount Carmel Research And Education Corporation Method of freezing and transplant of kidneys and apparatus
US4509695A (en) * 1983-07-18 1985-04-09 Spectrum Medical Industries, Inc. Tissue pulverizer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0252124A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2639558A1 (fr) * 1988-11-30 1990-06-01 Strasbourg I Universite Procede de broyage de tissus biologiques d'origine humaine ou animale et dispositif pour la mise en oeuvre de ce procede
EP0584712A1 (fr) * 1992-08-21 1994-03-02 Debio Recherche Pharmaceutique S.A. Broyeur ultra-centrifuge et sa mise en oeuvre pour le broyage cryogénique de matériau thermosensible
US5431348A (en) * 1992-08-21 1995-07-11 Debio Recherche Pharmaceutique Sa Ultracentrifugal disintegrator and its use for the cryocomminution of heat sensitive material
US7678931B2 (en) 2004-10-22 2010-03-16 Martek Biosciences Corporation Process for preparing materials for extraction
US10800561B2 (en) 2012-01-20 2020-10-13 Koffeefruit Pte. Ltd. Preparation of coffee-based extracts and powders
WO2017040810A1 (en) * 2015-09-04 2017-03-09 Koffeefruit Pte. Ltd. Preparation of coffee fruit extracts and powders
US10709149B2 (en) 2015-09-04 2020-07-14 Koffeefruit Pte. Ltd. Preparation of coffee fruit extracts and powders

Also Published As

Publication number Publication date
AU584780B2 (en) 1989-06-01
KR880700688A (ko) 1988-04-11
NZ218720A (en) 1989-01-27
FI873598L (fi) 1987-08-20
EP0252124A1 (en) 1988-01-13
AU6839287A (en) 1987-07-15
FI873598A0 (fi) 1987-08-20
ZA869569B (en) 1987-08-26
DK432387A (da) 1987-08-19
JPS63502090A (ja) 1988-08-18
DK432387D0 (da) 1987-08-19
IL81000A0 (en) 1987-03-31
EP0252124A4 (en) 1989-11-07

Similar Documents

Publication Publication Date Title
US4776173A (en) Method for extracting a substance from animal derived material
US4749522A (en) Supercritical fluid extraction of animal derived materials
US3172546A (en) Size reduction of biological substances
Crowe et al. Stabilization of dry phospholipid bilayers and proteins by sugars
Young et al. Microencapsulating properties of whey proteins. 1. Microencapsulation of anhydrous milk fat
Entenman [55] General procedures for separating lipid components of tissue
US6884866B2 (en) Bulk drying and the effects of inducing bubble nucleation
AU584780B2 (en) Brittle grinding and extraction of animal and plant derived materials
US1979124A (en) Process for the preparation in dry powdered form of animal, fish and vegetable matter
EP1955749A1 (en) Microwave hydrodiffusion for isolation of natural products
CN109010385B (zh) 一种灵芝粉的制备方法
US2358869A (en) Process of fractionating and refining organ extracts
López-Olmos et al. Comprehensive comparison of industrial cannabinoid extraction techniques: Evaluation of the most relevant patents and studies at pilot scale
US3579360A (en) Lyophilising a carbon dioxide solution
Chemat et al. Combined extraction techniques
KR890003995B1 (ko) 꽃가루의 처리방법
WO2004066743A1 (en) Improved vegetable granulation
MASSALDI et al. RETENTION OF D‐LIMONENE DURING FREEZE DRYING OF ORANGE JUICE
US2731731A (en) Method of drying heat sensitive biologically active substances
CN111076504A (zh) 热敏物质的冷冻干燥方法
Yatsu et al. Extraction of lipids from cottonseed tissue: VI. Ultrastructural morphology of isolated pigment glands
RU2291702C2 (ru) Ультрадисперсный порошок из пантов, способ его получения, эликсир "эксирус" для бальнеотерапии на его основе и раствор на основе эликсира "эксирус" для бальнеотерапии
JPH04244203A (ja) 抽出改良法
US2358870A (en) Process of fractionating and refining liver extracts
Kuk et al. The potential of soapstock-derived film: cottonseed and safflower

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU DK FI HU JP KR NO

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1987900565

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 873598

Country of ref document: FI

WWP Wipo information: published in national office

Ref document number: 1987900565

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1987900565

Country of ref document: EP