EP0040755A1 - Intensifying agent for the dry-cleaning of textiles - Google Patents
Intensifying agent for the dry-cleaning of textiles Download PDFInfo
- Publication number
- EP0040755A1 EP0040755A1 EP81103665A EP81103665A EP0040755A1 EP 0040755 A1 EP0040755 A1 EP 0040755A1 EP 81103665 A EP81103665 A EP 81103665A EP 81103665 A EP81103665 A EP 81103665A EP 0040755 A1 EP0040755 A1 EP 0040755A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cleaning
- textiles
- weight
- dry
- sulfonates
- 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
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
- D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
Definitions
- the main patent relates to cleaning boosters for the chemical cleaning of textiles based on anionic and cationic surfactants, solvents and water, characterized by the following composition:
- These cleaning boosters have a high dirt-carrying capacity and are particularly suitable for cleaning white or paste.
- ll-colored textiles made of the usual fiber materials, such as wool, cotton, regenerated cellulose, polyamide, polyester, polyacrylonitrile, and also very sensitive textiles made from such fiber materials, whose high graying tendency is known is, can be cleaned easily.
- the cleaning booster of the main patent has a subsequent water-repellent finish armor, especially for sports and weather protection. clothing may impair its effectiveness. This problem is known per se, it is based on the presence of cleaning booster residues in the cleaned textiles (J. Kurz “The Practice of Dry Cleaning", III, p. 222).
- the invention has for its object to develop a cleaning booster for dry cleaning, which is particularly suitable for cleaning textiles, especially sports and weather protection clothing made of graying-sensitive textile materials, without impairing the effectiveness of a subsequent hydrophobization.
- the object is achieved in that the petroleum sulfonate in the cleaning booster mixture of the main patent is replaced by chloroparaffin sulfonates of chain lengths C i2 -C 30 .
- the invention thus relates to cleaning enhancers for the chemical cleaning of textiles based on anionic and cationic surfactants, solvents and water, in accordance with patent 26 44 073, characterized by the following composition:
- the surface-active quaternary ammonium compounds used are the cationic surfactants described in the main patent, which contain a quaternary ammonium group and at least one optionally substituted higher hydrocarbon radical with 7-22 C atoms, which can be an alkyl or alkylaryl radical.
- the quaternary ammonium compounds are present in a mixture with toluenesulfonate or xylenesulfonate and the chloroparaffinsulfonates, it being important for the particular effectiveness of the cleaning enhancer with regard to cleaning power and dirt-carrying capacity that the ratio of cationic surfactant to anionic surfactants as well as the ratio of toluene or xylene sulfonate Chlorinated paraffin sulfonates is observed.
- Both the cationic surfactant and the anionic surfactants are in salt form, and the counterion can be of any type provided that it does not impair the solubility in the organic cleaning liquor.
- the alkali, ammonium and alkanolamine salts are preferred.
- the chloroparaffin sulfonates are preferably derived from straight-chain paraffins of chain lengths C 12 - C 30 , with relatively narrow chain length cuts, e.g. B. C 15 - C 18 , C 20 - C 21 ' C 20 - C 24 are particularly suitable as starting material.
- the chloroparaffin sulfonates are prepared by sulfochlorination of the corresponding paraffin mixtures at elevated temperatures up to 120 ° C and subsequent saponification with the desired base, preferably sodium hydroxide solution, at 90-100 ° C.
- the products are essentially mixtures of paraffin monosulfonates and chloroparaffins ( Ullmanns, Encyclopedia of Industrial Chemistry, 1965, 16th volume, pages 562/563).
- Preferred products contain 3 0 - 5o wt .-% of mono-sulphate and 4 - 25 wt .-% of organically bound chlorine. Corresponding products are commercially available.
- the cleaned textiles were perfectly clean, but showed only a moderate impregnation effect.
- the textiles were perfectly clean, showed no noticeable graying despite the addition of soot and were extremely hydrophobic.
Abstract
Description
Gegenstand des Hauptpatentes sind Reinigungsverstärker zum Chemischreinigen von Textilien auf der Basis von anionaktiven und kationaktiven Tensiden, Lösungsmitteln und Wasser, gekennzeichnet durch folgende Zusammensetzung:
Diese Reinigungsverstärker besitzen ein hohes Schmutztragevermögen und eignen sich besonders zur Reinigung von weißen oder paste.llfarbigen Textilien aus den üblichen Fasermaterialien, wie Wolle, Baumwolle, Regeneratcellulose, Polyamid, Polyester, Polyacrylnitril, wobei auch sehr empfindliche Textilien aus solchen Fasermaterialien, deren hohe Vergrauungstendenz bekannt ist, problemlos gereinigt werden können.These cleaning boosters have a high dirt-carrying capacity and are particularly suitable for cleaning white or paste.ll-colored textiles made of the usual fiber materials, such as wool, cotton, regenerated cellulose, polyamide, polyester, polyacrylonitrile, and also very sensitive textiles made from such fiber materials, whose high graying tendency is known is, can be cleaned easily.
Es hat sich jedoch gezeigt, daß die Reinigungsverstärker des Hauptpatentes eine nachfolgende wasserabweisende Ausrüstung, wie sie besonders für Sport- und Wetterschutz-. bekleidung infrage kommt, in ihrer Wirksamkeit beeinträchtigen können. Dieses Problem ist an sich bekannt, es beruht auf der Anwesenheit von Reinigungsverstärker-Resten in den gereinigten Textilien (J. Kurz "Die Praxis der Chemischreinigung", III, S. 222).However, it has been shown that the cleaning booster of the main patent has a subsequent water-repellent finish armor, especially for sports and weather protection. clothing may impair its effectiveness. This problem is known per se, it is based on the presence of cleaning booster residues in the cleaned textiles (J. Kurz "The Practice of Dry Cleaning", III, p. 222).
Der Erfindung liegt die Aufgabe zugrunde, einen Reinigungsverstärker für die Chemischreinigung zu entwickeln, welcher für die Reinigung von Textilien, insbesondere Sport- und Wetterschutzbekleidung, aus vergrauungsempfindlichen Textilmaterialien besonders geeignet ist, ohne eine nachfolgende Hydrophobierung in ihrer Wirksamkeit zu beeinträchtigen. Die Aufgabe wird dadurch gelöst, daß man in der Reinigungsverstärker-Mischung des Hauptpatentes das Petrolsulfonat durch Chlorparaffinsulfonate der Kettenlängen Ci2 - C30 ersetzt.The invention has for its object to develop a cleaning booster for dry cleaning, which is particularly suitable for cleaning textiles, especially sports and weather protection clothing made of graying-sensitive textile materials, without impairing the effectiveness of a subsequent hydrophobization. The object is achieved in that the petroleum sulfonate in the cleaning booster mixture of the main patent is replaced by chloroparaffin sulfonates of chain lengths C i2 -C 30 .
Gegenstand der Erfindung sind somit Reinigungsverstärker zum Chemischreinigen von Textilien auf der.Basis von anionaktiven und kationaktiven Tensiden, Lösungsmitteln und Wasser, gemäß Patent 26 44 073, gekennzeichnet durch folgende Zusammensetzung:
Die quaternären Ammoniumverbindungen liegen im Gemisch mit Toluolsulfonat oder Xylolsulfonat und den Chlorparaffinsulfonaten vor, wobei es für die besondere Wirksamkeit des Reinigungsverstärkers hinsichtlich Reinigungskraft und Schmutztragevermögen von Bedeutung ist, daß das angegebene Verhältnis von Kationtensid zu Aniontensiden, sowie das Verhältnis von Toluol- bzw. Xylolsulfonat zu Chlorparaffinsulfonaten eingehalten wird.The quaternary ammonium compounds are present in a mixture with toluenesulfonate or xylenesulfonate and the chloroparaffinsulfonates, it being important for the particular effectiveness of the cleaning enhancer with regard to cleaning power and dirt-carrying capacity that the ratio of cationic surfactant to anionic surfactants as well as the ratio of toluene or xylene sulfonate Chlorinated paraffin sulfonates is observed.
Sowohl das Kationtensid wie auch die Aniontenside liegen in Salzform vor, wobei das Gegenion beliebig sein kann, sofern es die Löslichkeit in der organischen Reinigungsflotte nicht beeinträchtigt. Bevorzugt werden die Alkali-, Ammonium- und Alkanolaminsalze.Both the cationic surfactant and the anionic surfactants are in salt form, and the counterion can be of any type provided that it does not impair the solubility in the organic cleaning liquor. The alkali, ammonium and alkanolamine salts are preferred.
Die Chlorparaffinsulfonate leiten sich bevorzugt von geradkettigen Paraffinen der Kettenlängen C12 - C30 ab, wobei relativ enge Kettenlängenschnitte, z. B. C15 - C18, C20 - C 21' C20 - C24 als Ausgangsmaterial besonders geeignet sind. Die Herstellung der Chlorparaffinsulfonate erfolgt durch Sulfochlorierung der entsprechenden Paraffingemische bei erhöhten Temperaturen bis zu 120° C und anschließende Verseifung mit der gewünschten Base, vorzugsweise Natronlauge, bei 90 - 100° C. Die Produkte stellen im wesentlichen Gemische aus Paraffin-Monosulfonaten und Chlorparaffinen dar (Ullmanns, Enzyklopädie der technischen Chemie, 1965, 16. Band, Seiten 562/563). Bevorzugte Produkte enthalten 30 - 5o Gew.-% an Monosulfat und 4 - 25 Gew.-% an organisch gebundenem Chlor. Entsprechende Produkte sind im Handel erhältlich.The chloroparaffin sulfonates are preferably derived from straight-chain paraffins of chain lengths C 12 - C 30 , with relatively narrow chain length cuts, e.g. B. C 15 - C 18 , C 20 - C 21 ' C 20 - C 24 are particularly suitable as starting material. The chloroparaffin sulfonates are prepared by sulfochlorination of the corresponding paraffin mixtures at elevated temperatures up to 120 ° C and subsequent saponification with the desired base, preferably sodium hydroxide solution, at 90-100 ° C. The products are essentially mixtures of paraffin monosulfonates and chloroparaffins ( Ullmanns, Encyclopedia of Industrial Chemistry, 1965, 16th volume, pages 562/563). Preferred products contain 3 0 - 5o wt .-% of mono-sulphate and 4 - 25 wt .-% of organically bound chlorine. Corresponding products are commercially available.
Der Ersatz der Petrolsulfonate durch Chlorparaffinsulfonate in den Reinigungsverstärkern des Hauptpatentes hat einen entscheidenden Einfluß auf die Wirksamkeit einer wasserabstoßenden Imprägnierung, wie sie z. B. für Sport-und Wetterschutzbekleidung regelmäßig im Anschluß an die Reinigung durchgeführt wird. Überraschenderweise wird hierdurch eine wesentliche Verbesserung des Hydrophobiereffektes, wie er beispielsweise durch eine übliche Trockenhydrophobierung erzielt wird, erreicht. Hinsichtlich der Reinigungswirkung besteht kein wesentlicher Unterschiede zwischen den Petrolsulfonaten und den Chlorparaffinsulfonaten, so daß mit den erfindungsgemäß zusammengesetzten Reinigungsverstärkern ebenfalls ausgezeichnete Reinigungsresultate auch bei pastellfarbigen oder weißen Textilien erreicht werden.The replacement of the petroleum sulfonates by chloroparaffinsulfonates in the cleaning enhancers of the main patent has a decisive influence on the effectiveness of a water-repellent impregnation, such as that used for. B. for sports and weather protection clothing is carried out regularly after cleaning. Surprisingly, this results in a significant improvement in the hydrophobizing effect, as is achieved, for example, by conventional dry hydrophobization. With regard to the cleaning effect, there are no significant differences between the petroleum sulfonates and the chloroparaffinsulfonates, so that excellent cleaning results can also be achieved with pastel-colored or white textiles with the cleaning boosters composed according to the invention.
1.1. In einer 9 kg-Chemischreinigungsanlage wurden 6 kg pastellfarbige und weiße Skibekleidung aus Polyester/Baumwolle bei einem Flottenverhältnis von 1 : 8 in Perchlorethylen 6 min ohne Filtration chemisch gereinigt, 1 min abgeschleudert und mit. sauberem Lösungsmittel 4 min bei gleichzeitiger Filtration nachgespült, 1 1/2 min zentrifugiert und dann mit 5o ml einer flüssigen Trockenhydrophobierung pro kg Ware während 5 min im Sprühverfahren imprägniert. Anschließend wurde die so behandelte Ware wie üblich getrocknet.1.1. In a 9 kg dry cleaning system, 6 kg of pastel-colored and white ski clothing made of polyester / cotton with a liquor ratio of 1: 8 in perchlorethylene were chemically cleaned for 6 minutes without filtration, spun off for 1 minute and with. rinsed clean solvent for 4 min with simultaneous filtration, centrifuged for 1 1/2 min and then impregnated with 50 ml of liquid dry water repellent per kg of goods for 5 min using the spray process. The goods treated in this way were then dried in the customary manner.
Zu Beginn des ersten Bades wurden 5 g eines erfindungsgemäßen Reinigungsverstärkers pro Liter Flotte zugesetzt. Dieses Produkt hatte folgende Zusammensetzung:
Für die nachfolgende Hydrophobierung wurde ein Imprägniermittel mit folgender Zusammensetzung verwendet:
Die so gereinigten Textilien waren einwandfrei sauber, wiesen keine Vergrauung auf und der Imprägniereffekt war ausgezeichnet.The textiles cleaned in this way were perfectly clean, showed no graying and the impregnation effect was excellent.
1.2 Zum Vergleich wurden in der unter 1.1. beschriebenen Reinigungsanlage ebenfalls 6 kg verschmutzte hellfarbige Sportbekleidung unter Verwendung eines Reinigungsverstärkers gemäß Hauptpatent der folgenden Zusammensetzung gereinigt und imprägniert:
Die gereinigten Textilien waren zwar einwandfrei sauber, zeigten aber nur einen mäßigen Imprägniereffekt.The cleaned textiles were perfectly clean, but showed only a moderate impregnation effect.
Zur Bestimmung der Reinigungswirkung wurde bei den Versuchen künstlich angeschmutztes Testgewebe aus Polyester/Baumwolle mitgereinigt und die Aufhellung sowie die Vergrauung an dem nicht angeschmutzten Teil des Gewebes mit einem Reflektometer bestimmt.To determine the cleaning effect, artificially soiled test fabric made of polyester / cotton was also cleaned in the tests, and the lightening and graying of the non-soiled part of the fabric were determined using a reflectometer.
Die Prüfung des Imprägniereffektes erfolgte an mitbehandelten Polyester/Baumwoll-Abschnitten gemäß AATCC 22-164.
2.1 In einer 1o kg-Reinigungsanlage wurden 6kg weiße und pastellfarbige Wettermäntel und Anoraks aus Polyester/Baumwolle bei einem Flottenverhältnis von 1 : 8 vier min lang in Monofluortrichlormethan ohne Filtration gereinigt, 1/2 min abgeschleudert und anschließend mit sauberem Lösungsmittel bei gleichzeitiger Filtration der Flotte 6 min gespült, 1 min zentrifugiert, wie unter 1.1 beschrieben im Sprühverfahren imprägniert und wie üblich getrocknet.2.1 In a 100 kg cleaning system, 6 kg of white and pastel-colored weather coats and anoraks made of polyester / cotton with a liquor ratio of 1: 8 were cleaned for four minutes in monofluorotrichloromethane without filtration, spun off for 1/2 min and then with clean solvent while simultaneously filtering the liquor Rinsed for 6 min, centrifuged for 1 min, impregnated by spraying as described under 1.1 and dried as usual.
Zu Beginn des ersten Bades wurden der Flotte 5 g/1 eines erfindungsgemäßen Reinigungsverstärkers mit folgender Zusammensetzung zugesetzt:
Zur Demonstration des Schmutztragevermögens wurden dem ersten Bad 2 g/l gepulverte Aktivkohle zugesetzt. Die Textilien waren einwandfrei sauber, zeigten keine merkliche Vergrauung und waren einwandfrei hydrophob.To demonstrate the dirt-carrying capacity, 2 g / l powdered activated carbon were added to the first bath. The textiles were perfectly clean, showed no noticeable graying and were perfectly hydrophobic.
2.2 In der unter 2.1 beschriebenen Reinigungsanlage w den in gleicher Weise nochmals 6 kg weiße und pastellfarbige Wettermäntel sowie Anoraks aus Polyester/Baumwolle gereinigt und imprägniert. Als Reinigungsverstärker wurden 5 g/l eines Produktes gemäß Hauptpatent mit folgender Zusammensetzung dosiert:
Auch hier wurden dem ersten Bad 2 g/l Aktivkohle zur Demonstration des Schmutztragevermögens zugesetzt. Die Textilien waren auch bei diesem Verfahren einwandfrei sauber, erwiesen sich aber als unzureichend wasserabweisend.Here too, 2 g / l activated carbon was added to the first bath to demonstrate the dirt-carrying capacity. The textiles were also perfectly clean in this process, but proved to be insufficiently water-repellent.
Um eine exakte Bestimmung des Reinigungs- und Hydrophobiereffektes bei den nach 2.1 und 22 gereinigten Textilien zu ermöglichen, wurden künstlich angeschmutzte Testgewebe sowie unangeschmutztes Testmaterial bei den verschiedenen Verfahren mitgereinigt und wie unter 1.1 beschrieben, ausgewertet.
3.1 In einer lo kg-Reinigungsanlage wurden 6 kg weiße Polyamid-Skianzüge bzw. Anoraks bei einem Flottenverhältnis von 1 : 8 während 4 min in 1.1.1-Trichlorethan gereinigt, 1/2 min abgeschleudert und anschließend 6 min in reinem Lösungsmittel bei gleichzeitiger Filtration gespült. Anschließend wurde 1 min zentrifugiert, 5 min im Sprühverfahren wie unter 1.1 beschrieben, imprägniert und wie üblich getrocknet.3.1 In a 10 kg cleaning system, 6 kg of white polyamide ski suits or anoraks were cleaned at a liquor ratio of 1: 8 for 4 min in 1.1.1-trichloroethane, centrifuged for 1/2 min and then in pure solvent for 6 min with simultaneous filtration rinsed. The mixture was then centrifuged for 1 min, sprayed for 5 min as described under 1.1, impregnated and dried in the customary manner.
Dem ersten Bad wurden zu Beginn 3 g/l eines erfindungsgemäßen Reinigungsverstärkers mit folgender Zusammensetzung zugegeben:
Außerdem wurden zur Demonstration des Schmutztragevermögens der ersten Flotte o,5 g/l Ruß zugesetzt.In addition, 0.5 g / l of carbon black were added to demonstrate the dirt-carrying capacity of the first fleet.
Die Textilien waren einwandfrei sauber, zeigten trotz Rußzugabe keine merkliche Vergrauung und waren ausgeprägt hydrophob.The textiles were perfectly clean, showed no noticeable graying despite the addition of soot and were extremely hydrophobic.
3.2 In der unter 3.1 beschriebenen Reinigungsanlage wurden ebenfalls 6 kg weiße Polyamid-Skianzüge und Anoraks in der gleichen Weise gereinigt und imprägniert. Der verwendete Reinigungsverstärker enthielt jeodch anstelle des Chlorparaffinsulfats die gleiche Menge Petrolsulfonat.3.2 In the cleaning system described under 3.1, 6 kg of white polyamide ski suits and anoraks were also cleaned and impregnated in the same way. However, the cleaning booster used contained the same amount of petroleum sulfonate instead of chloroparaffin sulfate.
Das Reinigungsresultat war fast gleich gut wie bei dem Versuch 3.1; der Hydrophobiereffekt jedoch war nur mäßig.The cleaning result was almost as good as in test 3.1; however, the water repellency effect was only moderate.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT81103665T ATE4825T1 (en) | 1980-05-21 | 1981-05-13 | DETERGENTS FOR DRY CLEANING OF TEXTILES. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3019319 | 1980-05-21 | ||
DE19803019319 DE3019319A1 (en) | 1980-05-21 | 1980-05-21 | CLEANING AMPLIFIER FOR CHEMICAL CLEANING TEXTILES |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0040755A1 true EP0040755A1 (en) | 1981-12-02 |
EP0040755B1 EP0040755B1 (en) | 1983-09-28 |
Family
ID=6102916
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81103665A Expired EP0040755B1 (en) | 1980-05-21 | 1981-05-13 | Intensifying agent for the dry-cleaning of textiles |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0040755B1 (en) |
JP (1) | JPS5716096A (en) |
AT (1) | ATE4825T1 (en) |
DE (2) | DE3019319A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2502171A1 (en) * | 1981-03-21 | 1982-09-24 | Kreussler Chem Fab | CLEANING REINFORCEMENT DEVICE FOR USE IN CHEMICAL CLEANING MACHINES WITH ADSORPTION FILTERS |
WO1989001290A1 (en) * | 1987-08-11 | 1989-02-23 | H. Maurer + Söhne Rauch- Und Wärmetechnik Gmbh & C | Attachment for a sausage filler |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4494149B2 (en) * | 2004-09-24 | 2010-06-30 | 花王株式会社 | Cleaning composition for clothing |
JP5651817B2 (en) * | 2009-02-26 | 2015-01-14 | 真鍋 征一 | Cleaning method and cleaning device for work clothes with severe oil contamination |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2644073A1 (en) * | 1976-09-30 | 1978-04-06 | Henkel Kgaa | CLEANING AMPLIFIER FOR CHEMICAL CLEANING OF TEXTILES |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4943925A (en) * | 1972-08-31 | 1974-04-25 |
-
1980
- 1980-05-21 DE DE19803019319 patent/DE3019319A1/en not_active Withdrawn
-
1981
- 1981-05-13 AT AT81103665T patent/ATE4825T1/en not_active IP Right Cessation
- 1981-05-13 EP EP81103665A patent/EP0040755B1/en not_active Expired
- 1981-05-13 DE DE8181103665T patent/DE3161015D1/en not_active Expired
- 1981-05-20 JP JP7510781A patent/JPS5716096A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2644073A1 (en) * | 1976-09-30 | 1978-04-06 | Henkel Kgaa | CLEANING AMPLIFIER FOR CHEMICAL CLEANING OF TEXTILES |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2502171A1 (en) * | 1981-03-21 | 1982-09-24 | Kreussler Chem Fab | CLEANING REINFORCEMENT DEVICE FOR USE IN CHEMICAL CLEANING MACHINES WITH ADSORPTION FILTERS |
WO1989001290A1 (en) * | 1987-08-11 | 1989-02-23 | H. Maurer + Söhne Rauch- Und Wärmetechnik Gmbh & C | Attachment for a sausage filler |
Also Published As
Publication number | Publication date |
---|---|
EP0040755B1 (en) | 1983-09-28 |
JPH0129840B2 (en) | 1989-06-14 |
JPS5716096A (en) | 1982-01-27 |
DE3161015D1 (en) | 1983-11-03 |
ATE4825T1 (en) | 1983-10-15 |
DE3019319A1 (en) | 1981-11-26 |
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