EP0418343A1 - Procede de fabrication de papier, de carton-pate et de carton en presence de copolymeres contenant des unites de n-vinylformamide. - Google Patents

Procede de fabrication de papier, de carton-pate et de carton en presence de copolymeres contenant des unites de n-vinylformamide.

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Publication number
EP0418343A1
EP0418343A1 EP90904264A EP90904264A EP0418343A1 EP 0418343 A1 EP0418343 A1 EP 0418343A1 EP 90904264 A EP90904264 A EP 90904264A EP 90904264 A EP90904264 A EP 90904264A EP 0418343 A1 EP0418343 A1 EP 0418343A1
Authority
EP
European Patent Office
Prior art keywords
weight
copolymers
cardboard
paper
vinylformamide
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.)
Granted
Application number
EP90904264A
Other languages
German (de)
English (en)
Other versions
EP0418343B1 (fr
Inventor
Dietmar Moench
Heinrich Hartmann
Enrique Freudenberg
Andreas Stange
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 SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to AT90904264T priority Critical patent/ATE89879T1/de
Publication of EP0418343A1 publication Critical patent/EP0418343A1/fr
Application granted granted Critical
Publication of EP0418343B1 publication Critical patent/EP0418343B1/fr
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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised

Definitions

  • the invention relates to a process for the production of paper, cardboard and cardboard by dewatering a paper stock in the presence of
  • JP-A-118 406/86 discloses water-soluble polyvinylamines which are obtained by polymerizing N-vinylformamide or mixtures of N-vinylformamide with other water-soluble monomers, such as acrylamide, N, N-dialkylacrylamides or diallyldialkylammonium salts and subsequent hydrolysis of the polymers with bases , e.g. Ethylamine, diethylamine, ethylenediamine or morpholine can be produced.
  • the polyvinylamines are used as dewatering and retention agents in papermaking and as flocculants for waste water.
  • Polymers are known from US Pat. No. 4,421,602, which are obtainable by partial hydrolysis of poly-N-vinylformamide with acids or bases. Due to the hydrolysis, these polymers contain vinylamine and N-vinylformamide units. They are used, for example, in the manufacture of paper as drainage aids, flocculants and retention aids.
  • EP-A-0 220 603 inter alia, known to subject N-vinylformamide together with basic acrylic esters such as dimethylaminoethyl acrylate or N-vinylimidazole in supercritical carbon dioxide to the copolymerization.
  • the resulting fine-particle copolymers are used in partially hydrolyzed form in which they contain vinylamine units, for example as retention aids and flocculants in the production of paper.
  • a dry strength agent is a mixture of cationic polymers which, as characteristic monomers, can also contain units of vinylamine copolymerized and natively Potato starch is used, the potato starch being converted into a water-soluble form by heating in an aqueous medium in the presence of the cationic polymer to temperatures above the gelatinization temperature of the native potato starch in the absence of oxidizing agents, polymerization initiators and alkali.
  • the object of the invention is to provide aids for paper production which are as effective as possible than those known hitherto and which are more technically accessible.
  • the object is achieved according to the invention with a process for the production of paper, cardboard and cardboard by dewatering a paper stock in the presence of polymers containing N-vinylformamide units, if the polymers containing N-vinylformamide units are non-hydrolyzed copolymers which
  • R 5 , R 6 C 1 to C 10 alkyl
  • N-vinylformamide can be considered as monomer (a) of the copolymers.
  • Suitable monomers of group (b) are the compounds of the formula I, of which the following compounds may be mentioned by way of example:
  • N-ethyldimethylammonium propylacrylamide ethosulfate N-ethyldimethylammonium propylacrylamide ethosulfate.
  • N-Trimethylammonium propyl methacrylamide chloride is preferred.
  • the compounds of formula II are also suitable as monomers of group (b).
  • Compounds of this type are, for example, diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldiethylammonium chloride and diallyldiethylammonium bromide.
  • Diallyldimethylammonium chloride is preferably used.
  • the anion is an acid residue and is preferably chloride, bromide, iodide, sulfate, methosulfate and ethosulfate.
  • the compounds of the formula I or II can be involved in the synthesis of the copolymers either alone or as a mixture with one another. It is also possible to use several compounds of the formula I or II in the copolymerization with the monomer (a).
  • the monomers of group (b) make up 99 to 1, preferably 40 to 5 mol%, of the copolymers.
  • the monomers (a) and (b) are copolymerized in aqueous solution in the presence of polymerization initiators which decompose into free radicals under the polymerization conditions.
  • Suitable polymerization initiators are, for example, hydrogen peroxide, alkali and ammonium salts of peroxidic sulfuric acid, peroxides, hydroperoxides, redox catalysts and particularly non-oxidizing initiators, such as azo compounds which break down into free radicals.
  • azo compounds which break down into free radicals.
  • water-soluble azo compounds such as 2,2'-azo-bis (2-amidinopropane) dihydrochloride, 2,2'-azo-bis (N, N'-methylene-isobutyramidine) dihydrochloride or 2,2'-azo-bis [2-methyl-N- (2-hydroxyethyl) propionamide].
  • the polymerization initiators are used in customary amounts, for example in amounts of 0.01 to 5.0% by weight, based on the monomers to be polymerized.
  • the polymerization can be carried out in a wide temperature range, if appropriate under reduced or also under increased pressure in appropriately designed apparatus.
  • the polymerization is preferably carried out at normal pressure and temperatures up to 100 ° C., in particular in the range from 30 to 80 ° C.
  • the concentration of the monomers in the aqueous solution is preferably selected so that polymer solutions are obtained whose solids content is 10 to 90, preferably 20 to 70,% by weight.
  • the pH of the reaction mixture is adjusted in the range from 4 to 10, preferably 5 to 8.
  • copolymers of different molecular weights are obtained.
  • the K value according to H. Fikentscher is given instead of the molecular weight.
  • the K values (measured in 5% aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.1% by weight) are 5 to 350.
  • Copolymers with low molecular weights and correspondingly low K values are obtained using the customary methods, ie Use of larger amounts of peroxide in the copolymerization or use of polymerization regulators or combinations of the two measures mentioned.
  • Polymers with a high K value and with high molecular weights are obtained, for example, by polymerizing the monomers in the form of the reverse suspension polymerization or by polymerizing the monomers (a) and (b) by the water-in-oil polymerization method.
  • saturated hydrocarbons for example hexane, heptane, cyclohexane, decalin or aromatic hydrocarbons such as benzene, toluene, xylene and cumene, are used as the oil phase.
  • the ratio of oil phase to aqueous phase in the reverse suspension polymerization is, for example, 10: 1 to 1:10, preferably 7: 1 to 1: 1.
  • a protective colloid In order to disperse the aqueous monomer solution in an inert hydrophobic liquid, a protective colloid is required, which has the task of Stabilize suspension of the aqueous monomer solution in the inert hydrophobic liquid.
  • the protective colloids also have an influence on the particle size of the polymer beads formed by polymerization.
  • Protective colloids which can be used are, for example, those substances which are described in US Pat. No. 2,982,749. Also suitable are the protective colloids known from DE-PS 2 634486, which are obtainable, for example, by reacting oils and / or resins, each of which has allyl-containing hydrogen atoms, with maleic anhydride.
  • 27 10 372 known which are obtainable by thermal or radical solution or bulk polymerization from 60 to 99.9% by weight of dicyclopentadiene, 0 to 30% by weight of styrene and 0.1 to 10% by weight of maleic anhydride.
  • graft polymers which can be obtained by grafting polymers (A) from a) 40 to 100% by weight of monovinylaromatic monomers, b) 0 to 60% by weight of monoethylenically unsaturated carboxylic acids with 3 to
  • the polymers A) have a molecular weight (Number average) from 500 to 20,000 and hydrogenation iodine numbers (according to DIN 53 241) from 1.3 to 51, with monomer mixtures
  • an aliphatic hydrocarbon is used as the inert hydrophobic liquid in the reverse suspension polymerization, a mixture of an inorganic suspending agent based on modified finely divided minerals and a nonionic surfactant has proven to be very advantageous as a protective colloid.
  • the inorganic suspending agents that have a low hydrophilic-lyophilic balance are the agents commonly used in reverse suspension polymerization processes.
  • the mineral component of these substances is formed, for example, by bentonite, montmorillonite or kaolin.
  • the finely divided minerals are treated to C 24 amines or quaternary ammonium salts for modifying with salts of long chain amines, for example C 8 _, wherein a storage of the amine salts or the quaternary ammonium salts between the individual layers of finely divided minerals.
  • the optionally quaternized ammonium salts used for the modification preferably contain 1 to 2 C 10 to C 22 alkyl radicals.
  • the other substituents of the ammonium salts are C 1 to C 4 alkyl or hydrogen.
  • the content of free ammonium salts of the amine-modified minerals is at most 2% by weight. Finely divided minerals modified with ammonium salts are commercially available.
  • the inorganic suspending agents for the reverse suspension polymerization also include silicon dioxide which has been reacted with organosilicon compounds.
  • a suitable organosilicon compound is, for example, trimethylsilyl chloride.
  • the aim of modifying the inorganic fine-particle minerals is to improve the wettability of the minerals with the aliphatic hydrocarbon used as the outer phase of the reverse suspension polymerization.
  • the modification with amines ensures that the modified minerals swell in the aliphatic hydrocarbon and thereby break down into very fine particles.
  • the Particle size is about 1 micron and is generally in the range of 0.5 to 5 microns.
  • the silicas reacted with organosilicon compounds have a particle size in the range from about 10 to 40 nm.
  • the modified, finely divided minerals are wetted both by the aqueous monomer solution and by the solvent and thereby accumulate in the phase interface between the aqueous and organic phases. They prevent coagulation when two aqueous monomer droplets collide in the suspension.
  • part of the water is distilled off azeotropically, so that copolymers having a solids content of 70 to 99, preferably 80 to 95,% by weight are obtained.
  • the copolymers are in the form of fine beads with a diameter of 0.05 to 1 mm.
  • the copolymers described above are used in the non-hydrolyzed form in the manufacture of paper, cardboard and cardboard as an additive to the paper stock.
  • copolymers contain no vinylamine units. They cause an increase in the dewatering speed of the paper stock, so that the production speed in paper production can be increased.
  • the copolymers act as retention agents for fibers and fillers and at the same time as flocculants.
  • the copolymers are added to the paper stock in amounts of from 0.01 to about 0.8% by weight, based on dry paper stock. Higher amounts of copolymers cause dry consolidation.
  • the polymers are used in amounts of approximately 0.5 to 3.5% by weight, based on dry paper stock. It is particularly preferred to use the copolymers mentioned together with native potato starch as a dry strength agent.
  • Mixtures have good retention compared to paper fibers in the paper stock.
  • the COD value in the white water is significantly reduced with these mixtures compared to native starch.
  • the interfering substances contained in the water circuits of paper machines affect the effectiveness of the mixtures of the copolymers to be used according to the invention and native starch only slightly.
  • the pH of the pulp suspension can be in the range from 4 to 9, preferably 6 to 8.5.
  • These mixtures of native starch and cationic polymer, which are added to the paper stock for dry strengthening are preferably prepared by mixing native potato starch in the presence of the non-hydrolyzed copolymers in aqueous solution to temperatures above the gelatinization temperature of the native potato starch in the absence of oxidizing agents, polymerization initiators and Alkali heated.
  • the native potato starch is modified in this way.
  • the gelatinization temperature of the starch is the temperature at which the birefringence of the starch grains is lost, cf. Ullmann's Encyclopedia of Technical Chemistry, Urban and Schwarzenberg, Kunststoff-Berlin, 1965, 16th volume, page 322.
  • the modification of the native potato starch can be done in different ways.
  • a previously excluded native potato starch which is in the form of an aqueous solution, can be reacted with the cationic polymers in question to temperatures in the range from 15 to 70 ° C. Longer contact times are required at even lower temperatures. If the reaction is carried out at even higher temperatures, e.g. up to 110 ° C, shorter contact times are required, e.g. 0.1 to 15 min.
  • the simplest way of modifying the native potato starch is to heat an aqueous slurry of the starch in the presence of the cationic copolymers in question to a temperature above the gelatinization temperature of the native potato starch.
  • the starch is modified to temperatures in the range of Heated from 70 to 110 ° C, the reaction being carried out in pressure-tight apparatus at temperatures above 110 ° C.
  • the starch is solubilized in the absence of oxidizing agents, initiators and alkali in about 3 minutes to 5 hours, preferably 5 to 30 minutes. Higher temperatures here require a shorter dwell time.
  • aqueous phase of the reaction mixture increases.
  • a 3.5% by weight aqueous solution of the dry strength agent has viscosities in the range from 50 to 10,000 mPas (measured according to Brookfield at 20 rpm and 20 ° C.).
  • the copolymers to be used according to the invention can be used in the production of all known paper, cardboard and cardboard qualities, for example for the production of writing, printing and packaging papers.
  • the papers can be made from a variety of different types of fiber materials, such as sulfite or Sulphate filler in bleached or unbleached condition. Wood pulp, waste paper, thermomechanical material (TMP) and chemothermomechanical material (CTMP).
  • TMP thermomechanical material
  • CTMP chemothermomechanical material
  • the basis weight of the papers can be between 30 and 200, preferably 35 and 150 g / m2, while for cardboard it can be up to 600 g / m 2 .
  • the papers which are produced using the copolymers to be used according to the invention in a mixture with native potato starch have a markedly improved strength compared to papers which are obtainable in the presence of the same amount of native potato starch.
  • the parts given in the examples are parts by weight, the percentages relate to the weight.
  • the viscosities were determined in aqueous solution at a solids concentration of 3.5% by weight and at a temperature of 20 ° C. in a Brookfield viscometer at 20 rpm.
  • the sheet formation was carried out in a Rapid Köthen laboratory sheet former.
  • the dry tear length was determined according to DIN 53 112, sheet 1, the dry burst pressure according to Müllen, DIN 53 141, the CMT value according to DIN 53 143 and tear propagation resistance according to Brecht-Inset according to DIN 53 115.
  • the leaves were tested after 24-hour air conditioning at a temperature of 23 ° C and a relative humidity of 50%.
  • copolymer 1 The following feedstocks were used: copolymer 1
  • Copolymer of 90 mol% N-vinylformamide (VFA) and 10 mol% 3-methacrylamidopropyltrimethylammonium chloride (MAPTAC) copolymer 1 was prepared by 800 g in a 2 1 flask equipped with a stirrer, thermometer, gas inlet tube and reflux condenser Cyclohexane and 3 g of the protective colloid, which is described in Example 1 of EP-A-0 290 753. The initial charge was heated to a temperature of 50 ° C. under a nitrogen atmosphere and with stirring at a speed of the stirrer of 300 revolutions per minute.
  • Copolymer 6 Homopolymer of N-vinylformamide with a
  • Copolymer 7 Partially hydrolyzed polymer 6, which by
  • a degree of hydrolysis of 90% means that 90% of the formamide groups originally present in the polymer have been converted into amino groups or the corresponding ammonium salt groups.
  • Examples A newsprint stock containing wood and kaolin was first produced with a consistency of 2 g / l and a pH of 6 with an alum content of 0.5% by weight. This paper stock was used as a model substance for all examples and comparative examples. First the Schopper-Riegler device was used to determine the degree of grinding (° SR), the drainage time (ie the time in which 600 ml of white water ran out of the device) and the degree of transmittance (optical transmission of the white water in%) for the above Paper stock model. Then 1 1 samples each of the paper stock described above were tested with the amounts of copolymers 1 to 8 given in Table 2. The measurement results obtained in this way are given in Table 2.
  • the strengthening agents 1 to 5 specified below were tested, which were each prepared by heating native potato starch with the copolymers given in Table 3.
  • the consolidators 1 to 5 described above were each tested on the paper stock specified above.
  • the amount added was 3.0% by weight, based on dry paper stock.
  • the test results are shown in Table 4.
  • Further strengthening agents were prepared by heating native potato starch in an aqueous slurry to a temperature of 90 to 110 ° C. for 15 minutes in the presence of the copolymers given in Table 5.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Selon un procédé de fabrication de papier, de carton-pâte et de carton, on déshydrate la pâte de papier en présence de copolymères non hydrolysés qui contiennent: (a) entre 99 et 1 moles % de N-vinylformamide et (b) entre 1 et 99 moles % d'au moins un monomère basique soluble dans l'eau ayant les formules (I) ou (II), dans lesquelles R1 = H, CH3, C2H5; R2, R3 et R4 = H, CH3, C2H5, (-CH2-CH2-O-)nH; R5, R6 = C1-C10-alkyle; A = C1-C6-alkylène; n = 1 à 6 et Y = un anion, le tout étant polymérisé. La quantité de ces deux éléments est comprise entre 0,01 et 3,5 % en poids de la pâte déshydratée de papier.
EP90904264A 1989-03-18 1990-03-14 Procede de fabrication de papier, de carton-pate et de carton en presence de copolymeres contenant des unites de n-vinylformamide Expired - Lifetime EP0418343B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90904264T ATE89879T1 (de) 1989-03-18 1990-03-14 Verfahren zur herstellung von papier, pappe und karton in gegenwart von n-vinylformamid-einheiten enthaltenden copolymerisaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3909004A DE3909004A1 (de) 1989-03-18 1989-03-18 Verwendung von nicht hydrolysierten n-vinylformamid-einheiten enthaltenden copolymerisaten bei der papierherstellung
DE3909004 1989-03-18

Publications (2)

Publication Number Publication Date
EP0418343A1 true EP0418343A1 (fr) 1991-03-27
EP0418343B1 EP0418343B1 (fr) 1993-05-26

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Application Number Title Priority Date Filing Date
EP90904264A Expired - Lifetime EP0418343B1 (fr) 1989-03-18 1990-03-14 Procede de fabrication de papier, de carton-pate et de carton en presence de copolymeres contenant des unites de n-vinylformamide

Country Status (9)

Country Link
US (1) US5262008A (fr)
EP (1) EP0418343B1 (fr)
JP (1) JPH03505239A (fr)
CA (1) CA2030540A1 (fr)
DE (2) DE3909004A1 (fr)
ES (1) ES2043361T3 (fr)
FI (1) FI95943C (fr)
PT (1) PT93472B (fr)
WO (1) WO1990011404A1 (fr)

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US5280077A (en) * 1992-07-14 1994-01-18 Air Products And Chemicals, Inc. Process for the synthesis of oligomeric vinylamines
US5473033A (en) * 1993-11-12 1995-12-05 W. R. Grace & Co.-Conn. Water-soluble cationic copolymers and their use as drainage retention aids in papermaking processes
US5720888A (en) * 1993-11-12 1998-02-24 Betzdearborn Inc. Water-soluble cationic copolymers and their use as flocculants
US5700893A (en) * 1993-11-12 1997-12-23 Betzdearborn Inc. Water-soluble cationic copolymers and their use as flocculants and drainage aids
US5516852A (en) * 1993-11-12 1996-05-14 W. R. Grace & Co.-Conn. Method of producing water-soluble cationic copolymers
AU672159B2 (en) * 1994-06-14 1996-09-19 National Starch And Chemical Investment Holding Corporation High performance PVOH stabilised EVA adhesives
US5609857A (en) * 1995-04-05 1997-03-11 National Starch And Chemical Investment Holding Corporation Methods of conditioning hair which utilize polymeric N-vinyl formamide
JP3628702B2 (ja) * 1994-08-05 2005-03-16 ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション 高分子量ｎ−ビニルホルムアミドを含むヘアケア用組成物及び頭髪を処理する方法
DE4438708A1 (de) * 1994-10-29 1996-05-02 Basf Ag Verfahren zur kationischen Modifizierung von Stärke und Verwendung der kationisch modifizierten Stärke
US5853542A (en) * 1995-09-11 1998-12-29 Hercules Incorporated Method of sizing paper using a sizing agent and a polymeric enhancer and paper produced thereof
DE19701524A1 (de) * 1997-01-17 1998-07-23 Basf Ag Polymermodifizierte Stärke, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19701523A1 (de) * 1997-01-17 1998-07-23 Basf Ag Polymermodifizierte anionische Stärke, Verfahren zu ihrer Herstellung und ihre Verwendung
US6599999B1 (en) 1997-02-04 2003-07-29 National Starch And Chemical Investment Holding Corporation Hair care compositions containing polymeric N-vinyl acetamide and methods of treating hair
DE19713755A1 (de) * 1997-04-04 1998-10-08 Basf Ag Verfahren zur Herstellung von Papier, Pappe und Karton mit hoher Trockenfestigkeit
JP4666558B2 (ja) * 2001-05-31 2011-04-06 ハイモ株式会社 濾水性向上方法
US7873576B2 (en) * 2002-09-25 2011-01-18 Cummins-Allison Corp. Financial document processing system
US7135598B2 (en) * 2002-09-06 2006-11-14 University Of Pittsburgh N-vinylformamide derivatives, polymers formed therefrom and synthesis thereof
US7494566B2 (en) * 2002-09-13 2009-02-24 University Of Pittsburgh - Of The Commonwealth System Of Higher Education Composition for increasing cellulosic product strength and method of increasing cellulosic product strength
US7090745B2 (en) * 2002-09-13 2006-08-15 University Of Pittsburgh Method for increasing the strength of a cellulosic product
BRPI0508227A (pt) * 2004-02-27 2007-07-17 Univ Pittsburgh géis poliméricos interligados e uso de tais géis poliméricos na recuperação de hidrocarboneto
US7919639B2 (en) 2009-06-23 2011-04-05 Chevron Phillips Chemical Company Lp Nano-linked heteronuclear metallocene catalyst compositions and their polymer products
KR20230116829A (ko) 2020-12-04 2023-08-04 에이지씨 케미컬스 아메리카스 인코포레이티드 처리된 물품, 처리된 물품을 제조하는 방법, 및 처리된 물품을 제조하는 데 이용하기 위한 분산액

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Also Published As

Publication number Publication date
WO1990011404A1 (fr) 1990-10-04
FI95943B (fi) 1995-12-29
DE3909004A1 (de) 1990-09-27
DE59001550D1 (de) 1993-07-01
ES2043361T3 (es) 1993-12-16
FI905661A0 (fi) 1990-11-15
US5262008A (en) 1993-11-16
CA2030540A1 (fr) 1990-09-19
PT93472A (pt) 1990-11-07
JPH03505239A (ja) 1991-11-14
PT93472B (pt) 1996-03-29
EP0418343B1 (fr) 1993-05-26
FI95943C (fi) 1996-04-10

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