EP0000903B1 - Papier copiant sans carbone et sa fabrication - Google Patents
Papier copiant sans carbone et sa fabrication Download PDFInfo
- Publication number
- EP0000903B1 EP0000903B1 EP78100634A EP78100634A EP0000903B1 EP 0000903 B1 EP0000903 B1 EP 0000903B1 EP 78100634 A EP78100634 A EP 78100634A EP 78100634 A EP78100634 A EP 78100634A EP 0000903 B1 EP0000903 B1 EP 0000903B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- microcapsules
- dye
- capsule
- papers
- 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
Links
- 0 C*N(*N=C=O)*O*N*N=C=O Chemical compound C*N(*N=C=O)*O*N*N=C=O 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
- C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
- C07D273/04—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
-
- 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.]
- Y10T428/2984—Microcapsule with fluid core [includes liposome]
- Y10T428/2985—Solid-walled microcapsule from synthetic polymer
Definitions
- Reaction copy papers are also known from US Pat. No. 3,432,327. This is understood to mean papers in which two layers are in contact with one another, each of which contains a color-forming component which reacts with the other to form a dye. At least one of the color formation components is in the form of microcapsules, which break when a writing tool is pressed and release the encapsulated component for reaction with the second.
- the two color-forming layers can be applied one above the other on a paper surface or separately on two paper surfaces in contact with one another.
- phase interface polymerization a polyreaction at the phase interface of a hydrophilic and a hydrophobic liquid, is used for the production of the microcapsules.
- the reaction to the dye must take place in the hydrophilic medium. Therefore, a color-forming component is first dissolved in a hydrophilic liquid, for example water, and then the first component of the capsule wall material is added to this solution.
- the second component of the capsule wall material is dissolved in a hydrophobic liquid (oil, paraffin, aromatic solvent), and then the hydrophilic solution is dispersed in the hydrophobic.
- the microcapsule then forms from the two capsule wall components at the phase interfaces of the dispersed hydrophilic droplets.
- the second color forming component can also be encapsulated; as a rule, however, it is not encapsulated.
- a large number of pairs of suitable color forming components are given in the US patent; it may a. for inorganic salts (e.g. potassium hexacyanoferrate 11 - ammonium iron (III) sulfate), colored metal complexes (e.g. diacetyl-dioxime-nickel acetate) and organic dyes (e.g. bromocresol purple sodium hydroxide).
- inorganic salts e.g. potassium hexacyanoferrate 11 - ammonium iron (III) sulfate
- colored metal complexes e.g. diacetyl-dioxime-nickel acetate
- organic dyes e.g. bromocresol purple sodium hydroxide
- Capsule wall-forming components are also given in large numbers, for example the combination of certain selected diisocyanates and water, diol or diamine.
- US Patent 3,432,327 is directed to encapsulating a solution of a color former in a hydrophilic solvent, preferably water.
- German Offenlegungsschrift 23 11 712 also discloses the use of reaction products of di- or polyols with a molecular weight of 400-10,000 and di- or polyisocyanates as isocyanate components in microencapsulation.
- Map can thus encapsulate pre-dye solutions for carbonless papers; these capsules are not impermeable to the mostly aromatic and alkylaromatic solvents necessary for the process, although this is absolutely necessary for the effect of the reaction carbonless papers. They also tend to agglomerate very strongly. Capsule agglomerates cause considerable disruption because individual capsules are destroyed during the manufacture of the paper and a stained paper is thus obtained. Under unfavorable conditions, the writing performance of the papers is even significantly reduced. You therefore need individual capsules for carbonless papers that do not tend to agglomerate.
- the invention is based on the knowledge that walls of microcapsules containing color former solutions for carbonless papers are obtained from, on the one hand, diisocyanates of the formula (I) wherein R is an alkylene radical having 2 to 10 carbon atoms and, on the other hand, a diamine.
- the capsule membranes resulting from the reaction product excellently meet the requirements specified above when hydrophobic organic solutions of the color formers are encapsulated.
- the invention relates to a carbonless reaction paper which contains a solution of a color former in microencapsulated form, the color former being encapsulated as a solution in a hydrophobic organic solvent, characterized in that the capsule walls are made from the polyaddition product of a diisocyanate of the formula (I) where R is an alkylene radical having 2 to 10 carbon atoms, and a diamine.
- Another object of the invention is the use of a solution of a color former in a hydrophobic, organic solvent as the core material in microcapsules, the walls of which consist of the polyaddition product of a diisocyanate of the formula (I) and a diamine, for the preparation of carbonless reaction papers.
- the diisocyanates of the formula (I) are derivatives of 2,4,6-triketo-1,3,5-oxadiazine with two free isocyanate groups.
- the compounds in which the radicals R are from butane, hexane and octane are particularly suitable descended.
- the n-hexane radical is particularly preferred.
- the products and their manufacture are known from DE-AS 1,670,666.
- Color formers are essentially colorless, basic products that have different chromophoric groups. Examples of these are bis (p-aminoaryl) phthalides, leucoauramines, acylauramines, ⁇ , ⁇ -unsaturated aryl ketones, basic monoazo dyes, rhodamine B-lactams such as the N- (p-nitrophenyl) rhodamine B-lactams, by amino groups substituted polyarylcarbinols and their reaction products, for example their esters or ethers and various heterocyclic spiranes.
- Preferred compounds are 3,3-bis (p-dimethylaminophenyl) -6-dimethylamino-phthalide (crystal violet lactone). Benzoyl leukomethylene blue and derivatives from Michlers Hydrol, especially the p-toluenesulfinate from Michlers Hydrol.
- Solvents for the basic color former component (dye precursor) and for the diisocyanates are generally aromatic hydrocarbons, which can also be substituted by alkyl or halogen.
- Examples are chlorinated diphenyls, dodecylbenzene, mixtures of partially hydrogenated and unhydrogenated terphenyls, isopropyldiphenyl, diisopropylbenzene, ethyl benzoate, mixtures of diphenyl and diphenyl ether, phthalic acid butyl ester, aralkyl or diaryl ethers, the xylenes in aromatics and aromatics.
- the solvent for the diamines is generally water.
- the leaking core material meets the receiver layer, which has a coating on which dyes are formed from the colorless dye precursors, which now make the copy appear.
- Coating materials are natural and synthetic products such as kaolin, attapulgite, montmorillonite, concreteite, acidic bleaching earth or phenolic resins. You can e.g. in the donor layer, i.e. the microcapsule layer, acid-activated dyes and acid-reacting components in the receiver layer.
- microcapsules can be produced in various ways. So you can first dissolve the diisocyanate and the dye precursor in a suitable solvent and emulsify this organic phase in an aqueous diamine solution, which may optionally also contain protective colloids. It is also possible to first emulsify the organic phase with or without surfactants and protective colloids in water to a desired particle size and only then to add the diamine necessary for the capsule wall formation to the aqueous phase.
- emulsifying agents are added to the aqueous phase.
- examples of such products acting as protective colloids are carboxymethyl cellulose, gelatin and polyvinyl alcohol.
- examples of emulsifiers are oxyethylated 3-benzylhydroxybiphenyl, reaction products of nonylphenol with different amounts of ethylene oxide and sorbitan fatty acid ester.
- the course of the capsule wall-forming polyaddition can be followed on the basis of the amine consumption.
- the oxadiazine ring of the isocyanate can be opened by increasing the temperature, a new isocyanate group being formed which can react with the amine already used or with another amine with crosslinking and curing of the polyaddition product.
- the microcapsules can be produced continuously or batchwise. Dispersing devices which generate a shear gradient are generally used. Examples include blade, basket, high-speed stirrers, colloid mills, homogenizers, ultrasonic dispersers, nozzles, jet nozzles, and Supraton machines.
- the strength of the turbulence during mixing is primarily decisive for the diameter of the microcapsules obtained. Capsules from 1 to 2000 ⁇ m in size can be made. Capsules with diameters of 2 to 20 ⁇ m are preferred.
- the capsules do not agglomerate and have a narrow particle size distribution.
- the weight ratio of core material to casing material is 50-90 to 50-10.
- the pressure-sensitive carbonless papers are produced in a known manner (see M. Gutcho, Capsule Technology and Microencapsulation, Noyes Data Corporation, 1972, pages 242-277).
- the microcapsule suspensions obtained primarily contain 10 to 35% by weight of capsules. They need something to cream as long as they do not contain any binding agent. This can be used for concentration.
- the preferred capsule size is around 10 ⁇ m.
- the homogenized capsule suspensions, provided with binders and optionally inert fillers such as talc or kaolin, can be applied manually with a floral wire squeegee or mechanically with an air brush in application quantities of 4-8 91 m 2 on base paper (for example from 40 to 100 g / m 2 ).
- the coating of base papers is described in German Offenlegungsschriften 1,934,457 and 1,955,542.
- the papers coated in this way contain the first color-forming component; they are called encoder components.
- the donor component is generally the back of the top sheet for carbonless sets.
- the front of the next sheet is coated with the second coloring component.
- This layer is called the slave component.
- the slave component In the case of carbonless copies, the slave component is the top of the second sheet of paper.
- the following encoder sheets must have a slave coating on the opposite side.
- the production of such receiver layers is known and is also described in German Offenlegungsschriften 1,934,457 and 1,955,542.
- n-hexane-1,6-diisocyanate 2000 g of n-hexane-1,6-diisocyanate are mixed with 1 g of tri-p-tolylarsine oxide in a 2.7 l autoclave and stirred at 50 ° C. for 8 hours at a CO 2 pressure of 3 atm.
- reaction is interrupted by adding 2 g of phosphorus trichloride and the reaction product is separated from the unreacted starting product in a thin-layer evaporator (two passes, heating temperature 180 ° C. at 1 torr).
- the IR spectrum shows the characteristic carbonyl absorption bands at 5.5 to 5.71 and 5.82 ⁇ m.
- the homogeneous organic phase is then emulsified in 300 g of water, which is 1.5 g. Mowiol 56-98 (polyvinyl alcohol from Hoechst AG) as an emulsifying agent.
- a Kotthoff mixing siren is used for emulsification (8900 rpm, 1 l beaker).
- the mixing siren is replaced by a Lenart-Rapid laboratory stirrer (500 rpm).
- a solution of 0.7 g of 1-aminoethylethylenediamine-1,2- (diethylenetriamine) in 70 g of water is added to the batch.
- the batch is quickly heated to 70 ° C. and kept at this temperature for about 1 hour.
- the heating phase is only used to form a casing that is as stable as possible.
- the diameter of the resulting microcapsules is in the order of 3-25 ⁇ m.
- the organic phase is prepared as described in Example 1 (b) with the change that 25 g of Solvesso 200 (aromatic mixture from Esso AG) are used as the solvent.
- Example 1 (b) The encapsulation and aftertreatment is also carried out as described in Example 1 (b), with the change that 0.7 g of ethylenediamine in 70 g of water are added as the amine component to the outer phase.
- microcapsules are 3-25 ⁇ m in size.
- the resulting organic phase is encapsulated and post-treated as described in Example 1 (b). 0.7 g of diethylenetriamine in 70 g of water are used as the amine component.
- the resulting microcapsules have a diameter of 2-20 ⁇ m.
- 1,4-tetramethylene diisocyanate 280 g are saturated by introducing them with dry CO 2 gas and, with stirring and further introducing carbon dioxide at 60 ° C., with 0.7 g of tri-n-butylphosphine (0.25% ) offset. After 2 hours, the NCO value has dropped to 53.8%.
- the reaction mixture is separated in a thin-film evaporator (heating temperature 180 ° C. at 1 torr), 219 g of 1,4-tetramethylene diisocyanate being recovered and 54 g of a viscous oil being obtained.
- microcapsules are obtained with a diameter of 1-35 ⁇ m.
- a microcapsule dispersion with about 30% capsule content can be produced with the aid of an ultrasound homogenizer (type Minisonic from Ultrasonics) with a solution of 4.5 parts of crystal violet lactone and 17 parts of the oxadiazinone described in Example 1 (b) Perform 75 parts of Santosol 340 (partially hydrogenated terphenyl from Monsanto and 25 parts of Solvesso 100 (Esso AG) as the organic phase.
- ultrasound homogenizer type Minisonic from Ultrasonics
- aqueous phase 150 parts of the organic phase to 250 parts of aqueous phase are used for emulsification.
- the aqueous phase contains 0.5% Mowiol 26-88 and 0.1% Tween 80 (emulsifier from Atlas Chemie) as an emulsifying aid.
- the two phases or the emulsion produced therefrom are passed 5 times through the ultrasonic homogenizer. Immediately afterwards, the resulting emulsion is transferred to a beaker and swiftly stirred with a laboratory stirrer (type Lenart-Rapid, 500 rpm) the amount of ethylenediamine corresponding to the NCO value of the oxadiazinone used stoichiometrically added (as an aqueous 4% solution).
- a laboratory stirrer type Lenart-Rapid, 500 rpm
- microcapsule dispersion is stirred at room temperature for about 1 hour.
- the microcapsules obtained are in the range of 1-30 ⁇ m in diameter.
- the resulting organic phase is with the aid of a Kotthoff mixing siren at 8900 rpm.
- a solution of 0.7 g of diethylenetriamine in 70 g of water is added to the mixture.
- the mixing siren is replaced by a laboratory stirrer (Lenart-Rapid type, 500 rpm) and the microcapsule dispersion is kept at 70 ° C. for about 1 hour with stirring.
- the microcapsules have a diameter of 3-25 ⁇ m.
Claims (2)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2738509 | 1977-08-26 | ||
DE19772738509 DE2738509A1 (de) | 1977-08-26 | 1977-08-26 | Reaktionsdurchschreibepapiere |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0000903A2 EP0000903A2 (fr) | 1979-03-07 |
EP0000903A3 EP0000903A3 (en) | 1979-03-21 |
EP0000903B1 true EP0000903B1 (fr) | 1982-01-20 |
Family
ID=6017367
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100634A Expired EP0000903B1 (fr) | 1977-08-26 | 1978-08-09 | Papier copiant sans carbone et sa fabrication |
Country Status (9)
Country | Link |
---|---|
US (1) | US4253682A (fr) |
EP (1) | EP0000903B1 (fr) |
JP (1) | JPS5444919A (fr) |
BR (1) | BR7805520A (fr) |
CA (1) | CA1121159A (fr) |
DE (2) | DE2738509A1 (fr) |
DK (1) | DK145888C (fr) |
IL (1) | IL55416A (fr) |
IT (1) | IT1105782B (fr) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2909950A1 (de) * | 1979-03-14 | 1980-10-02 | Bayer Ag | Mikrokapseln |
DE2930408A1 (de) * | 1979-07-26 | 1981-02-12 | Bayer Ag | Reaktionsdurchschreibepapier |
DE3020148A1 (de) | 1980-05-28 | 1981-12-03 | Bayer Ag, 5090 Leverkusen | Konzentrierte mikrokapselsuspensionen fuer reaktionsdurchschreibepapiere |
JPS5777589A (en) * | 1980-11-04 | 1982-05-14 | Mitsubishi Paper Mills Ltd | Capsule sheet for non-carbon copying |
JPS6312582U (fr) * | 1986-07-11 | 1988-01-27 | ||
DE3623413A1 (de) * | 1986-07-11 | 1988-01-14 | Basf Ag | Verbundschichtstoff |
US5225118A (en) * | 1990-08-15 | 1993-07-06 | Boise Cascade Corporation | Process for manufacturing polyurea microcapsules and product therefrom |
JP2729538B2 (ja) * | 1991-02-13 | 1998-03-18 | 富士写真フイルム株式会社 | マイクロカプセルの製造方法 |
US5164126A (en) * | 1991-03-05 | 1992-11-17 | Appleton Papers Inc. | Process for microencapsulation |
EP0505648B1 (fr) * | 1991-03-28 | 1994-06-15 | Dainippon Ink And Chemicals, Inc. | Microcapsules, méthode d'encapsulation et méthode d'utilisation des dites capsules |
EP0573210B2 (fr) * | 1992-06-04 | 2005-11-23 | Arjo Wiggins Limited | Matériau d'enregistrement sensible à la pression |
GB9522233D0 (en) * | 1995-10-31 | 1996-01-03 | Wiggins Teape Group The Limite | Pressure-sensitive copying paper |
DE19840583A1 (de) | 1998-09-05 | 2000-03-09 | Bayer Ag | Mikrokapsel-Formulierungen |
US6653256B1 (en) | 1999-08-24 | 2003-11-25 | Bayer Aktiengesellschaft | Microcapsule formulations |
KR100514904B1 (ko) * | 2002-11-18 | 2005-09-14 | 한국전자통신연구원 | Ofdma/fdd 통신 시스템에서의 mcs 관련 제어정보 감소 방법 |
LT1840145T (lt) * | 2006-03-30 | 2018-02-26 | Fmc Corporation | Acetileno karbamido dariniai - polikarbamido polimerai ir mikrokapsulės ir kompozicijos jų kontroliuojamam atpalaidavimui |
WO2008122051A1 (fr) * | 2007-04-02 | 2008-10-09 | Acoustic Cytometry Systems, Inc. | Procédés et dispositifs pour l'analyse amplifiée de cellules et particules focalisées sur champ |
CN104829976A (zh) * | 2015-05-27 | 2015-08-12 | 陕西科技大学 | 聚偏氟乙烯-端羧基多壁碳纳米管复合介电材料的制备方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH453305A (fr) * | 1963-10-21 | 1968-06-14 | Pilot Pen Co Ltd | Procédé pour encapsuler de fines gouttelettes de liquides dispersées |
US3432327A (en) * | 1964-03-13 | 1969-03-11 | Pilot Pen Co Ltd | Pressure sensitive copying sheet and the production thereof |
US3748329A (en) * | 1970-07-08 | 1973-07-24 | Bayer Ag | Compounds containing the 2,4,6-triketo-1,3,5-oxadiazine ring |
US3886085A (en) * | 1971-08-31 | 1975-05-27 | Fuji Photo Film Co Ltd | Process for producing fine oil-containing microcapsules having strong protective shells and microcapsules produced thereby |
BE790373A (fr) * | 1971-10-21 | 1973-02-15 | Fuji Photo Film Co Ltd | Feuille d'enregistrement sensible a la pression comportant des micro-capsules ayant des parois en polyuree |
DE2221756C3 (de) * | 1972-05-04 | 1980-06-26 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von lösungsmittelbeständigen, lichtechten, knick- und reibfesten Polyurethanüberzügen auf textlien Substraten, Leder oder Kunstleder oder von Folien |
-
1977
- 1977-08-26 DE DE19772738509 patent/DE2738509A1/de not_active Withdrawn
-
1978
- 1978-08-09 DE DE7878100634T patent/DE2861546D1/de not_active Expired
- 1978-08-09 EP EP78100634A patent/EP0000903B1/fr not_active Expired
- 1978-08-23 IL IL55416A patent/IL55416A/xx unknown
- 1978-08-24 JP JP10238278A patent/JPS5444919A/ja active Granted
- 1978-08-24 CA CA000309949A patent/CA1121159A/fr not_active Expired
- 1978-08-24 IT IT50838/78A patent/IT1105782B/it active
- 1978-08-25 DK DK377578A patent/DK145888C/da active
- 1978-08-25 BR BR7805520A patent/BR7805520A/pt unknown
-
1979
- 1979-03-13 US US06/020,074 patent/US4253682A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
IT7850838A0 (it) | 1978-08-24 |
IT1105782B (it) | 1985-11-04 |
JPS5444919A (en) | 1979-04-09 |
DK377578A (da) | 1979-02-27 |
IL55416A (en) | 1982-01-31 |
DE2861546D1 (en) | 1982-03-04 |
DE2738509A1 (de) | 1979-03-08 |
EP0000903A2 (fr) | 1979-03-07 |
CA1121159A (fr) | 1982-04-06 |
BR7805520A (pt) | 1979-04-17 |
JPS5647874B2 (fr) | 1981-11-12 |
US4253682A (en) | 1981-03-03 |
DK145888B (da) | 1983-04-05 |
EP0000903A3 (en) | 1979-03-21 |
IL55416A0 (en) | 1978-10-31 |
DK145888C (da) | 1983-09-19 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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