EP0171039B1 - Die Verwendung eines Kohlenwasserstoffgemisches als Farbstoffvorlauferlösungsmittel für druckempfindliche Kopierpapiere - Google Patents

Die Verwendung eines Kohlenwasserstoffgemisches als Farbstoffvorlauferlösungsmittel für druckempfindliche Kopierpapiere Download PDF

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Publication number
EP0171039B1
EP0171039B1 EP85109696A EP85109696A EP0171039B1 EP 0171039 B1 EP0171039 B1 EP 0171039B1 EP 85109696 A EP85109696 A EP 85109696A EP 85109696 A EP85109696 A EP 85109696A EP 0171039 B1 EP0171039 B1 EP 0171039B1
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EP
European Patent Office
Prior art keywords
dye
solvent
fraction
pressure
sensitive recording
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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
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EP85109696A
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English (en)
French (fr)
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EP0171039A2 (de
EP0171039A3 (de
Inventor
Atsushi Sato
Keiji Endo
Shigenobu Kawakami
Eiichi Matsuzaka
Satoshi Narui
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Eneos Corp
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Nippon Petrochemicals Co Ltd
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Publication of EP0171039A3 publication Critical patent/EP0171039A3/de
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Classifications

    • 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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
    • B41M5/1655—Solvents

Definitions

  • This invention relates to the use as a solvent for the dye of pressure-sensitive recording paper of a certain hydrocarbon mixture that is prepared by disproportionating diarylalkanes or a mixture mainly containing diarylalkanes in the presence of a disproportionation catalyst.
  • a colorless dye that is a dye-precursor
  • a solvent a solvent for solving a colorless dye into microcapsules.
  • One surface of a sheet of paper is coated with microcapsules and the surface of another sheet of paper is coated with clay or a polymeric material such as phenol resin (color developer) which produces a color upon reaction with the dye-precursor.
  • the treated surfaces of the above set of paper sheets are put together face to face and local pressure is applied to the paired sheets by handwriting or any other measure, thereby obtaining desired duplicate impressions.
  • the recording mechanism in the pressure-sensitive recording paper is such that the microcapsules on the surface of a sheet of paper are ruptured by the pressure of handwriting or else to release the dye solution from the microcapsules.
  • the solution containing a dye comes into contact with clay or polymeric material (color developer) on the opposite surface of the other sheet of paper to produce a color.
  • the dyes for pressure-sensitive recording paper are exemplified by Crystal Violet Lactone, Malachite Green, benzoyl Leucomethylene Blue, Rhodamine B and 3-dialkylamino-7-dialkylamino fluoran.
  • diarylalkanes such as diphenylmethane and phenylxylylethane are conventionally used. Some of diarylalkanes, however, have offensive odor due to their chemical structures, and thus are not suitable as the solvents for pressure-sensitive recording paper.
  • aromatic hydrocarbons such as dibenzyltoluene that is heavier than diarylalkanes are also proposed as the solvents for pressure-sensitive recording paper. Due to their higher molecular weight, however, their pour points and viscosities are generally high and their color developing properties are not always satisfactory. Accordingly, heavier aromatic hydrocarbons are scarcely used as solvents for pressure-sensitive recording paper.
  • JP-A-56-161195 discloses the use of an ethylbenzene heavy end fraction, that is of the product obtained from the alkylation of benzene with ethylene, as the solvent for the dye precursor of a pressure-sensitive material.
  • the dye precursor of a pressure-sensitive reproduction system is dissolved in a solvent which consists of dibenzylbenzenes, that is a compound in which the aromatic nuclei are linked via methylene groups.
  • the primary object of the present invention to provide an improved solvent for the dye of pressure-sensitive recording paper which is free from the above-described disadvantages of the conventional art.
  • Another object of the present invention is to provide a solvent for the dye of pressure-sensitive recording paper which solvent has no offensive odor though it is prepared from diarylalkanes, shows excellent color developing property and anti-fading property, and has a sufficiently low pour point and viscosity irrespective of its high boiling point.
  • a further object of the present invention is to provide a solvent for the dye of pressure-sensitive recording paper, which solvent is inexpensive, has desirable properties and can be prepared from a by-product oil fraction of a hydrocarbon mixture mainly containing diarylalkanes that is obtained from a specific production process.
  • the present invention is directed to the use of a hydrocarbon mixture mainly containing triaryldialkanes as a solvent for the dye of pressure sensitive recording paper, said mixture being obtained by recovering by distillation substantially the whole fraction boiling between 350 and 450°C from the reaction mixture obtained by the process of disproportionating, at temperatures in the range of 20 to 500°C in the presence of a disproportionation catalyst, the by-product oil fraction being obtained in the process of preparing alkylated monocyclic aromatic hydrocarbons by alkylating benzene or toluene with ethylene in the presence of an alkylation catalyst and having boiling points in the range of 260 to 320°C.
  • the above-mentioned by-product oil fraction is a hydrocarbon mixture mainly containing diarylalkanes that is obtained in the process to produce alkylated monocyclic aromatic hydrocarbons by alkylating benzene or toluene with ethylene in the presence of an alkylation catalyst.
  • the above by-product oil fraction is used as a starting material, it is inexpensive and a fraction containing triaryldialkanes can be obtained efficiently.
  • the boiling points of the above diarylalkanes or the hydrocarbon mixture mainly containing the same are in the range of 260 to 320°C and preferably 260 to 310°C. Diarylalkanes or a hydrocarbon mixture having a boiling point higher than the above range is not desirable because the effect of below-described disproportionation cannot be expected.
  • the above diarylalkanes are used singly or in a mixture of two or more kinds.
  • alkylation catalysts mainly used industrially are Lewis acids such as aluminum chloride and boron fluoride, synthetic zeolites that are typically represented by ZSM-5 type zeolite such as ZSM-5 and ZSM-11, and protonic acids such as phosphoric acid.
  • alkylation is widely put into practice as preparation process for lower alkylbenzenes such as ethylbenzene, ethyltoluene and cumene.
  • Ethylbenzene and ethyltoluene which are produced by alkylating benzene and toluene with ethylene, are dehydrogenated into styrene and methylstyrene, respectively, and they are consumed in large quantities for producing polymers.
  • the molar ratio of the feed of benzene to ethylene is, for example, about 10:1 to about 3:1.
  • 0.005 to 0.030 part of catalyst is added to one part of produced ethylbenzene.
  • the reaction is carried out at temperatures of 90 to 150°C, pressures of 0.5 to 15 kg/cm 2 and duration of 20 minutes to 3 hours.
  • the catalyst is removed by a conventional method.
  • the catalyst is separated by sedimentation in a settler, which is followed by neutralization and repeated water rinsing.
  • the by-product oil fraction which is used for the present invention is the fraction obtained from the process to produce ethylbenzene or ethyltoluene by alkylating benzene or toluene with ethylene.
  • This by-product oil fraction substantially comprises diarylalkanes and can be obtained in large quantities at low cost. Furthermore, the effect of disproportionation of the invention can be produced markedly. Accordingly, said by-product oil fraction is desirable as the starting material to be used in the present invention.
  • the above-described starting material is subjected to disproportionation in the presence of a disproportionation catalyst.
  • the disproportionation catalysts are exemplified by Lewis acids such as aluminum chloride and ferric chloride, solid acids such as silica-alumina, and synthetic zeolites represented by ZSM-5 type zeolites such as ZSM-5 and ZSM-11, heteropoly acids such as silicotungstic acid, super strong acids such as trifluoromethane sulfonic acid, and super strongly acidic cation exchange resin such as Nafion (trademark, made by E.I. du Pont de Nemours).
  • Lewis acids such as aluminum chloride and ferric chloride
  • solid acids such as silica-alumina
  • synthetic zeolites represented by ZSM-5 type zeolites such as ZSM-5 and ZSM-11
  • heteropoly acids such as silicotungstic acid
  • super strong acids such as trifluoromethane sulfonic acid
  • super strongly acidic cation exchange resin such as Nafion (trademark, made by E.I. du Pont de Nemours).
  • the temperatures for the disproportionation can be selected in a wide range of 2O to 5OO°C depending on the kind of the catalyst.
  • the temperature range of 2O to 150°C is suitable for aluminum chloride; 150 to 230°C, for Nafion; and 250 to 500°C, for synthetic zeolite.
  • the disproportionation does not occur at temperatures lower than the above range, while side reactions such as decomposition occur at temperatures higher than the above range, neither of which is, accordingly, desirable.
  • any of batchwise and continuous types can be employed.
  • Preferable reaction times are 20 minutes to 10 hours in batchwise reaction and 0.5 to 10 in LHSV in continuous reaction.
  • the pressures of disproportionation are not especially limited, however, they are generally in the range of atmospheric pressure to 10 bar (kg/cm 2 ).
  • monocyclic aromatic hydrocarbons i.e. benzene and alkylbenzene,such as toluene that are lighter than the starting hydrocarbons and triaryldialkanes that are heavier than the starting hydrocarbons and are represented by the following general formula (I)
  • R 1 , R 2 and R 3 is a hydrogen atom or a straight chain or branched chain alkyl group
  • each of R 4 and R 5 is an ethylidene group
  • each of p, q and r is an integer from 0 to 3.
  • the present invention is characterized in that the fraction mainly containing the foregoing triaryldialkanes is used as the solvent for the dye of pressure-sensitive recording paper. Accordingly, after the disproportionation, the catalyst is removed by settling or filtration and the above fraction mainly containing triaryldialkanes is obtained by distillation.
  • the boiling temperature of the fraction that is suitable as the solvent for the dye of pressure-sensitive recording paper is above 350°C but not higher than 450°C, preferably below 420°C as converted to atmospheric pressure basis. In the fraction containing triaryldialkanes having boiling points above 450°C, the viscosity and pour point are too high which are not desirable.
  • the fraction mainly containing triaryldialkanes is preferable because it has no offensive odor.
  • the viscosity and pour point are relatively low.
  • the dissolving property (dissolving power) and color developing property relative to the conventional dyes are also excellent. Accordingly, the above fraction is most suitable for use as the solvent for the dye of pressure-sensitive recording paper. Still further, when the by-product oil fraction in alkylation process is used as a starting material, it is desirable because the solvent can be produced at lower cost.
  • the solvents according to the present invention can be used singly or in a mixture with one or more kinds of known solvents, for example, kerosene, alkylbenzenes such as dodecylbenzene, diarylalkanes such as 1-phenyl-1-xylylethane and 1-phenyl-2-isopropylphenylethane, alkylbiphenyls such as isopropylbiphenyl, and alkylnaphthalenes such as diisopropylnaphthalene.
  • alkylbenzenes such as dodecylbenzene
  • diarylalkanes such as 1-phenyl-1-xylylethane and 1-phenyl-2-isopropylphenylethane
  • alkylbiphenyls such as isopropylbiphenyl
  • alkylnaphthalenes such as diisopropylnaphthalene.
  • dyes there are typically triarylmethane type compounds, diphenylmethane type compounds, xanthene type compounds, thiazine type compounds, and spiropyran type compounds.
  • the dye-precursors of triarylmethane type compounds are exemplified by: 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (Crystal Violet Lactone); 3,3-bis(p-dimethylaminophenyl)phthalide; 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)-phthalide; 3-(p-dimethylaminophenyl)-3-(2-methylindole-3-yl)phthalide; 3-(p-dimethylaminophenyl)-3-(2-phenylindole-3-yl)phthalide; 3,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophthalide; 3,3-bis(1,2-dimethylindole-3-yl)-6-dimethylaminophthalide; 3,3-bis(9-ethylcarbazole-3-y
  • the dye-precursors of diphenylmethane type compounds are exemplified by: 4,4-bis-dimethylaminobenzhydrine benzyl ether; N-halophenyl leuco Auramine; and N-2,4,5-trichlorophenyl leuco Auramine.
  • the xanthene type dye-precursors are exemplified by: Rhodamine B-anilinolactam; Rhodamine B-(p-nitroanilino)lactam; Rhodamine B-(p-chloroanilino)lactam; 3-dimethylamino-6-methoxyfluoran; 3-diethylamino-7-methoxyfluoran; 3-diethylamino-7-chloro-6-methylfluoran; 3-diethylamino-7-(acetylmethylamino)fluoran; 3-diethylamino-7-(dibenzylamino)fluoran; 3-diethylamino-7-(methylbenzylamino)fluoran; 3-diethylamino-7-(chloroethylmethylamino)fluoran; 3-diethylamino-7-(diethylamino)fluoran; and 3-diethylamino-6-methyl-7-anil
  • the thiazine type dye-precursors are exemplified by: benzoyl leuco methylene blue and p-nitrobenzoyl leuco methylene blue.
  • the spiro type dye-precursors are exemplified by: 3-methyl-spiro-dinaphthopyran; 3-ethyl-spiro-dinaphthopyran; 3,3'-dichloro-spiro-dinaphthopyran; 3-benzyl-spiro-dinaphthopyran; 3-methylnaptho-(3-methoxybenzo)spiropyran; and 3-propyl-spiro-dibenzodipyran.
  • the dye-precursors can be dissolved in the solvent of the invention in the same manner as when using conventional solvents.
  • the color developer there are clay, polymers, and aromatic carboxylic acids or their metal salts.
  • the polymers are exemplified by phenol-aldehyde polymer, phenol-acetylene polymer, maleic acid-rosin polymer, partially or completely hydrolyzed styrene-maleic anhydride copolymer, partially or completely hydrolyzed ethylene-maleic anhydride copolymer, carboxy polyethylene, and partially or completely hydrolyzed vinyl methyl ether-maleic anhydride copolymer.
  • aromatic carboxylic acids and their derivatives are exemplified by: 3,5-di( ⁇ -methylbenzyl)salicylic acid; 3-( ⁇ -methylbenzyl)-5-( ⁇ , ⁇ -dimethylbenzyl)salicylic acid; 3-(4'- ⁇ ', ⁇ '-dimethylbenzyl)phenyl-5-( ⁇ , ⁇ -dimethylbenzyl)salicylic acid; 3,5-di-tert-butyl salicylic acid; 3,5-di-tert-octyl salicylic acid; 3-cyclohexyl-5-( ⁇ , ⁇ -dimethylbenzyl)salicylic acid; 3-phenyl-5-( ⁇ , ⁇ -dimethylbenzyl)salicylic acid; and 3,5-di( ⁇ , ⁇ -dimethylbenzyl)salicylic acid.
  • their salts of polyvalent metals such as zinc, aluminum, barium, tin, iron, calcium and lead can also be used.
  • the method to prepare the microcapsules of the dye-precursor solution which is obtained by dissolving a dye-precursor in the solvent, there is a coacervation method in which the fine particles of the dye-precursor solution that are dispersed in water are coated by a protective colloidal material such as gelatin or gum arabic, thereby obtaining the microcapsules which contain the dye-precursor solution.
  • Another method is the interfacial polymerization method or a in situ polymerization method in which a monomer or a partially condensed polymerizable product is employed and a polymerization initiator, an accelerator or a catalyst is added to cause polymerization on the surfaces of fine particles of the dye-precursor solution, thereby preparing the microcapsules containing the dye-precursor solution.
  • the specific solvent of the present invention can be used in any one of the above methods.
  • an auxiliary solvent has been used in dissolving a dye-precursor in order to control the viscosity and volatility of the dye-precursor solution, the particle size of the fine dispersion in microcapsule formation, the dissolving property to the polymeric material that is coated onto the surface to be recorded, and the rate of color development.
  • the specific solvent of the present invention can satisfactorily be used without employing such an auxiliary solvent. Nevertheless, any solvent which does not degrade the characteristics of the solvent of the present invention may be used as an auxiliary solvent. It should be noted also that the specific solvent of the present invention can be used together with conventional solvents.
  • alkylation was carried out by reacting batchwise benzene with ethylene in a molar ratio (benzene:ethylene) of 5:1 at 130°C and 4.9 kg/cm 2 for 1 hour.
  • the above by-product oil fraction had strong offensive odor and could not be used as a solvent.
  • a paste (CMC aqueous solution) and a blocking agent were added to the above obtained microcapsule slurry and they were mixed well.
  • the above mixture was applied uniformly to sheets of quality paper using a wire bar and they were dried.
  • the coated paper sheets were used as test papers where the the quantity of coated microcapsules was determined by weighing the test paper that was maintained at 25 ⁇ 1°C and 60% humidity.
  • This test paper was combined with another sheet of paper that was coated with acid clay to obtain a set of pressure-sensitive recording paper.
  • This pressure-sensitive recording paper was applied with a load of 675 kg/cm 2 for 1 minute and color densities at 1 minute and 60 minutes after removing the load were obtained by determining the absorbances at 610 nm. The results are shown in the following Table 1.
  • Boiling Point 260 - 300°C Composition % by weight C 14 - C 15 diarylmethane 59.1 C 16 diarylethane 25.9 Others 15.0 Total 100.0 (Triaryldialkane was scarcely contained)
  • the above by-product oil fraction (2000 ml) was disproportionated at 200°C for 3 hours under atmospheric pressure by using 50 g of strongly acidic cation exchange resin (trademark: Nafion made by du Pont de Nemours). During the disproportionation, the produced lighter fractions of benzene and C 7 - C 9 alkylbenzenes such as toluene were removed continuously from the reaction system.
  • Fraction 3 mainly contained triaryldialkanes by GC-mass spectrum analysis. This fraction had almost no odor and the properties of the fraction were low as follows: Pour point -35°C Viscosity 16.8 cSt (at 40°C)

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Claims (9)

  1. Verwendung eines hauptsächlich Triaryldialkane enthaltenden Kohlenwasserstoffgemisches als Lösungsmittel für den Farbstoff eines druckempfindlichen Aufzeichnungspapiers, wobei dieses Gemisch erhalten wird, indem im wesentlichen die gesamte zwischen 350 und 450°C siedende Fraktion aus dem Reaktionsgemisch gewonnen wird, welches durch das Verfahren, bei dem bei Temperaturen im Bereich von 20 bis 500°C in Gegenwart eines Disproportionierungskatalysators die Nebenproduktölfraktion disproportioniert wird, die bei dem Verfahren zur Herstellung von alkylierten monocyclischen aromatischen Kohlenwasserstoffen durch Alkylieren von Benzol oder Toluol mit Ethylen in Gegenwart eines Alkylierungskatalysators erhalten wird und Siedepunkte im Bereich von 260 bis 320°C hat, erhalten wird.
  2. Verwendung nach Anspruch 1, wobei das Gemisch erhalten wird, indem durch Destillation im wesentlichen die gesamte zwischen 351 und 400°C siedende Fraktion aus dem mit Hilfe des Disproportionierungsverfahrens erhaltenen Reaktiongemisch gewonnen wird.
  3. Verwendung nach Anspruch 1 oder Anspruch 2, wobei der Disproportionierungskatalysator eine Lewis-Säure ist.
  4. Verwendung nach Anspruch 3, wobei die Lewis-Säure Aluminumchlorid ist.
  5. Verwendung nach Anspruch 1 oder Anspruch 2, wobei der Disproportionierungskatalysator eine feste Säure ist.
  6. Verwendung nach Anspruch 5, wobei die feste Säure ein synthetischer Zeolith ist.
  7. Verwendung nach einem der Ansprüche 1 bis 6, wobei der Alkylierungskatalysator eine Lewis-Säure oder eine feste Säure ist.
  8. Verwendung nach Anspruch 7, wobei die Lewis-Säure Aluminiumchlorid ist.
  9. Verwendung nach Anspruch 7, wobei die feste Säure ein synthetischer Zeolith ist.
EP85109696A 1984-08-06 1985-08-02 Die Verwendung eines Kohlenwasserstoffgemisches als Farbstoffvorlauferlösungsmittel für druckempfindliche Kopierpapiere Expired - Lifetime EP0171039B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP16453384A JPS6141593A (ja) 1984-08-06 1984-08-06 感圧紙染料用溶剤
JP164533/84 1984-08-06

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EP0171039A2 EP0171039A2 (de) 1986-02-12
EP0171039A3 EP0171039A3 (de) 1987-05-13
EP0171039B1 true EP0171039B1 (de) 1996-12-11

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EP85109696A Expired - Lifetime EP0171039B1 (de) 1984-08-06 1985-08-02 Die Verwendung eines Kohlenwasserstoffgemisches als Farbstoffvorlauferlösungsmittel für druckempfindliche Kopierpapiere

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EP (1) EP0171039B1 (de)
JP (1) JPS6141593A (de)
CA (1) CA1238187A (de)
DE (1) DE3588130T2 (de)
ES (1) ES8801152A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH074986B2 (ja) * 1986-05-26 1995-01-25 富士写真フイルム株式会社 感熱記録材料
EP0273752B1 (de) * 1986-12-25 1992-08-19 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung eines wärmeempfindlichen Aufzeichnungsmaterials
JPH02106387A (ja) * 1988-10-14 1990-04-18 Kanzaki Paper Mfg Co Ltd 感圧複写シート
JPH0761387B2 (ja) * 1989-04-05 1995-07-05 ペガサスミシン製造株式会社 空環縫い込み装置つきマツリ縫い用オーバーロックミシン

Citations (1)

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Publication number Priority date Publication date Assignee Title
EP0170282A1 (de) * 1984-08-03 1986-02-05 Nippon Petrochemicals Company, Limited Verarbeitungsöl für Polymere

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JPS5016967B1 (de) * 1971-08-04 1975-06-17
GB1361638A (en) * 1971-09-23 1974-07-30 Wiggins Teape Res Dev Pressure-sensitive copying systems
BE790321A (fr) * 1971-10-20 1973-04-19 Monsanto Co Solvants pour colorants de materiaux d'enregistrement sensiblesa la pression
JPS4886612A (de) * 1972-02-17 1973-11-15
JPS4886614A (de) * 1972-02-17 1973-11-15
JPS498289A (de) * 1972-05-10 1974-01-24
JPS5321328B2 (de) * 1973-10-31 1978-07-01
US4130299A (en) * 1977-09-12 1978-12-19 Monsanto Company Low-odor dye solvents for pressure-sensitive copying systems
JPS5571589A (en) * 1978-11-24 1980-05-29 Mitsubishi Petrochem Co Ltd Solvent for pressure-sensitive duplicating paper dye
JPS56161195A (en) * 1980-05-18 1981-12-11 Mitsubishi Petrochem Co Ltd Solvent for dyeing pressure-sensitive paper
JPS5738878A (en) * 1980-08-21 1982-03-03 Nippon Mining Co Ltd Preparation of electrical insulating oil, solvent for pressure-sensitive paper and heat medium oil
IT1136651B (it) * 1981-06-04 1986-09-03 Caffaro Spa Ind Chim Solvente per coloranti in carte autocopianti
US4365103A (en) * 1981-12-04 1982-12-21 The Dow Chemical Company Process for the preparation of bis(1-phenylethenyl) compounds
JPS615982A (ja) * 1984-06-21 1986-01-11 Nippon Petrochem Co Ltd 感圧複写材料
JPS6112389A (ja) * 1984-06-29 1986-01-20 Nippon Petrochem Co Ltd 感圧紙染料用溶剤

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
EP0170282A1 (de) * 1984-08-03 1986-02-05 Nippon Petrochemicals Company, Limited Verarbeitungsöl für Polymere

Also Published As

Publication number Publication date
DE3588130T2 (de) 1997-07-03
EP0171039A2 (de) 1986-02-12
JPS6141593A (ja) 1986-02-27
JPH0441664B2 (de) 1992-07-09
EP0171039A3 (de) 1987-05-13
CA1238187A (en) 1988-06-21
DE3588130D1 (de) 1997-01-23
ES8801152A1 (es) 1988-01-01
ES553588A0 (es) 1988-01-01

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