EP0746630B1 - Utilisation de substances sulfitees pour nourrir le cuir - Google Patents

Utilisation de substances sulfitees pour nourrir le cuir Download PDF

Info

Publication number
EP0746630B1
EP0746630B1 EP95908273A EP95908273A EP0746630B1 EP 0746630 B1 EP0746630 B1 EP 0746630B1 EP 95908273 A EP95908273 A EP 95908273A EP 95908273 A EP95908273 A EP 95908273A EP 0746630 B1 EP0746630 B1 EP 0746630B1
Authority
EP
European Patent Office
Prior art keywords
acid
sulfuric acid
acids
substances
sulfonic acid
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 - Lifetime
Application number
EP95908273A
Other languages
German (de)
English (en)
Other versions
EP0746630A1 (fr
Inventor
Rudolf Zauns-Huber
Hans-Georg Mainx
Gilbert Schenker
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0746630A1 publication Critical patent/EP0746630A1/fr
Application granted granted Critical
Publication of EP0746630B1 publication Critical patent/EP0746630B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

  • the invention relates to the use of special sulfated substances leather greasing. These substances are reaction products of mono- or polybasic carboxylic acids with 12 to 72 carbon atoms or mixtures of such carboxylic acids with a sulfonating reagent from at least an organic sulfonic acid and sulfuric acid.
  • fatty acids are the main aids to to shape the character of leather.
  • the effect of the fatliquor comes due to fiber-insulating lubrication and hydrophobization.
  • the mutual Friction decreases and, consequently, suppleness and elasticity of the tissue improved. This has positive effects on the tensile strength of leather, because straighten in a stretchy material many fibers in tensile stress in the tensile direction and then settle more resistance to tearing than the same fibers within of a brittle material.
  • Vegetable and animal leather greases are generally used Oils, fats and waxes are used, as well as those made from these substances by chemical Conversion obtained hydrolysis, sulfation, oxidation and Hardening products and finally mineral greasing agents; in detail:
  • the saponifiable fats and oils as well as the natural waxes and resins belong to the esters.
  • oils and fats are the leather specialist Glycerin and fatty acid esters are termed solid at room temperature or are liquid.
  • the leather greasing from the group of animal Fats in particular, tears, fish oil, beef tallow and beef claw oil, from the group of vegetable fats castor oil, rape oil and linseed oil.
  • the fatty acids are included instead of with glycerin higher molecular alcohols esterified.
  • waxes are beeswax, Chinese wax, carnauba wax, montan wax and wool fat; to the main resins include rosin, yeast oil and shellac.
  • Mineral greasing agents are also important for leather production. These hydrocarbons are in the natural fats and oils Similar to some properties, but cannot be saponified. It deals fractions of petroleum distillation, the liquid mineral oil, called petroleum jelly in pasty form and paraffin in solid form will.
  • licker oils are self-emulsifying Products containing a neutral oil and an emulsifier in an aqueous medium contain.
  • the emulsifier can either separate the licker oil Be admixed component or by partial sulfonation of the neutral oil have been produced.
  • Examples of means for greasing leather after this classic and still important processes are manufactured sulfated claw oil, sulfated lard oil and rapeseed oil, sulfated fish oil and sulfated beef tallow.
  • sulfation Amounts of concentrated sulfuric acid used are typically in the range from 15 to 60% by weight, based on the oil to be sulfated (cf. Hans Herfeld, ed., "Bibliothek des Leders, Frankfurt 1987, volume 4, pages 77-78).
  • the classic sulfation process however, has the disadvantage that it is complex and requires time-consuming refurbishment measures.
  • the reason is in that the fats and oils to be sulfated are included in practice on these fats and oils - the aforementioned high amounts of concentrated Sulfuric acid, for fish oil e.g. with approx. 20% by weight in contact to be brought. Only part of the sulfuric acid reacts, the rest - usually the majority - is unchanged after the reaction Form before. After neutralization with NaOH usually lies accordingly then a large amount of sodium sulfate. The consequence of which is that the products are not stable in storage. Under lack of storage stability it is understood that a separation into several phases occurs. The aqueous phase contains a large part of the respective inorganic Salts, e.g. As sodium sulfate or ammonium sulfate.
  • the post-processing serves the purpose of adding a large part of the salt remove. This is usually done by neutralizing it First wash the sulfation product with water. Then disconnects the (salt-rich) aqueous phase from the (salt-poor) oil phase. The process however, phase separation is difficult to do in practice and time consuming. In addition, the resulting wash water polluting both with regard to the salt load contained therein, and also with regard to the (small) amounts of sulfated Products. This corresponds to that in the course of classic sulfation processes required postprocessing neither in economic nor in ecological Regarding the requirements of modern and efficient today and at the same time as environmentally friendly production methods as possible be put.
  • DE-A-41 41 532 describes a process for producing hydrophylized Triglycerides known to be saturated, unsaturated and / or blown Triglycerides initially in the presence of glycerin and alkaline catalysts reacted with ethylene oxide, the resulting ethoxylated triglycerides sulfated with gaseous sulfur trioxide and the resulting acidic sulfonation products then neutralized with aqueous bases. After According to the teaching of DE-A-41 41 532, the products thus produced are suitable for Leather greasing.
  • a very important need in practice is greasy substances or to provide equipment that is in the tanned Skin substance can be bound so reliably that one for the practical needs sufficient resistance to washing and cleaning the leather and fur goods are guaranteed.
  • High quality leather goods for example from the clothing industry, both aqueous-surfactant laundry and, if necessary, chemical cleaning be accessible without significant loss of quality.
  • Fogging means that in Over time, volatile substances escape from the leather and settle in precipitate undesirably, e.g. on windshields.
  • Fogging-real substances is understood to mean that these substances, on the one hand are so tightly bound inside the leather that they are practically not are volatile, on the other hand, that these substances have the fogging characteristic improve usual fatliquor or fatlip constituents, i.e. reduce their fogging values.
  • EP-A-498 teaches 634 a treatment of the leather with aqueous dispersions that are free of organic solvents and which contain an amphiphilic copolymer, that of at least one hydrophilic monomer and at least one hydrophobic monomer.
  • the object of the present invention was to provide substances which are suitable for greasing leather.
  • greasing equipment is on the one hand the leather greasing in the narrow To understand literal sense, as well as the hydrophobization of leather.
  • Another task was to treat these substances with the that is, licked leather has good properties Giving scar firmness, fullness, lardiness and that subsequently colored leather is characterized by an unlightened, level shade.
  • Another task was to ensure that these substances good storage stability.
  • the present invention accordingly relates to the use sulfated substances for greasing leather, the sulfated Substances are available through the implementation of mono- or polybasic Carboxylic acids a) with 12 to 72 carbon atoms, with a sulfonating agent b) in addition to subsequent neutralization.
  • the sulfonating reagent b) is used a combination of at least one organic sulfonic acid bl) and sulfuric acid b2), with the proviso that the proportion of sulfuric acid - Based on the sum of organic sulfonic acid and sulfuric acid - 0.5 to 80 wt .-%.
  • the invention is subject to no restrictions at all. As particularly important embodiments may be mentioned the fatty acids, the dicarboxylic acids and the dimer or trimer fatty acids.
  • Fatty acids are - as is generally the case in the specialist world (see, for example, 0.-A.Neumüller, Römpps Chemie-Lexikon, Stuttgart 1973, p.1107ff) - all aliphatic, monobasic carboxylic acids, which are both saturated and unsaturated can.
  • fatty acids which are suitable as fatty acid building blocks of esters a) are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, palmitic acid stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic, melissic, isobutyric, isovaleric acid, acrylic acid, methacrylic acid, crotonic acid, 10-undecenoic, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, petroselinic acid, elaidic acid, ricinoleic acid, sorbic acid, linoleic acid, Linolaidin
  • Dicarboxylic acids are understood to mean dibasic organic carboxylic acids. Preferred are those with 2 to 24 carbon atoms and in particular those which - in the sense of the classic definition of "Römpp" (see, for example, 0.-A.Neumüller, Römpps Chemie-Lexikon, Stuttgart 1973, p.828f ) - Derive from linear paraffins in that both ends are oxidized to carboxyl groups.
  • dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, furthermore maleic acid, fumaric acid, phthalic acid and terephthalic acid.
  • dicarboxylic acids containing OH groups for example malic acid, are preferred.
  • Dimer fatty acids - as is customary in the art - are understood to mean those carboxylic acids which are accessible by oligomerizing unsaturated carboxylic acids, generally fatty acids such as oleic acid, linoleic acid, erucic acid and the like.
  • the oligomerization is usually carried out at elevated temperature in the presence of a catalyst made of, for example, alumina.
  • the products obtained are mixtures of different substances, with the dimersization products predominating.
  • small amounts of higher oligomers, in particular the trimer fatty acids are also present.
  • Dimer fatty acids are commercially available products and are offered in various compositions and qualities. In the context of the present invention, those dimer fatty acids are preferred which have a dimer content of at least 50%, preferably 75% and in which the number of carbon atoms per dimer molecule is predominantly in the range from 36 to 44.
  • trimer fatty acids are also commercially available products.
  • Preferred trimer fatty acids are those in which the trimer content is at least 50%, preferably 75%.
  • component a) is at least partially ethylenically unsaturated.
  • “At least partially ethylenically unsaturated” is understood to mean that the iodine number of the carboxylic acid a) is at least 5.
  • the iodine number of the carboxylic acid a) is limited in practice by values in the range from approximately 300 to 400.
  • those carboxylic acids or carboxylic acid mixtures a) are generally used whose iodine number is in the range from 40 to 260.
  • the quantitative ratios can of carboxylic acid a) and sulfonating reagent b) within wide limits vary.
  • the quantitative ratios these components are set to range from 1:99 to 99: 1.
  • a range is a): b) from 10: 1 to 1:10 and in particular a range from 4: 1 to 1: 4 is preferred.
  • the sulfonated substances according to the invention are very general due to good greasy or hydrophobic properties as well with good fogging characteristics.
  • the carboxylic acids a) can be used in the form of commercially available products will.
  • leather is also sufficient in qualities such as those found in Distillation residues of the fatty acid production are present.
  • the component to be sulfated is used a) in the form of a mixture of at least one carboxylic acid a) and at least a lower alkyl ester of a fatty acid liquid at 20 ° C with 8 up to 24 carbon atoms.
  • a lower alkyl ester is understood to mean that the alcohol component of the ester has at most 8 carbon atoms, the range from 1 to 4 carbon atoms is preferred.
  • the fatty acid lower alkyl ester can be in saturated or with respect to its alcohol and / or fatty acid building blocks (ethylenically) unsaturated.
  • This embodiment has the advantage that the task of the fatty acid lower alkyl ester is carboxylic acids a) which are completely or partially solid at 20 ° C, liquefy or at least in to bring a homogeneous and flowable state, so that the Allow mixture to stir gently, possibly after slightly warming up.
  • a further embodiment of the present invention consists in reacting those carboxylic acids a) with the sulfonating reagent b) which are alkoxylated and / or epoxidized.
  • carboxylic acids a) with the sulfonating reagent b) which are alkoxylated and / or epoxidized.
  • ethylene oxide, propylene oxide and butylene oxide or mixtures thereof can be used as building blocks for the alkoxylation.
  • the ethoxylated fatty acids which are derived formally from the addition of one or more -CH 2 -CH 2 -O groups.
  • These compounds can be prepared in various ways, for example by reacting the fatty acids with ethylene oxide in the presence of a catalyst (classic ethoxylation) or by reacting the fatty acids with polyethylene oxide in the presence of a catalyst.
  • a combination of at least one organic sulfonic acid b1) and sulfuric acid b2) is used as the sulfonating reagent b) ; the proportion of sulfuric acid - based on the sum of organic sulfonic acid and sulfuric acid - is 0.5 to 80% by weight. However, a sulfuric acid content of 1 to 40 and in particular 5 to 20% by weight is preferred.
  • sulfuric acid there are no restrictions on the nature of sulfuric acid. So can be dilute sulfuric acid, concentrated sulfuric acid or fuming Sulfuric acid (concentrated sulfuric acid, the varying amounts of Contains dissolved sulfur trioxide, the so-called oleum). It is preferred to use sulfuric acid at a concentration in the range of 96 up to 98% by weight or oleum.
  • organic sulfonic acids b1) is in itself not subject to any particular one Restrictions.
  • suitable sulfonic acids are alkane or Haloalkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, Propanesulfonic acid, butanesulfonic acid, long-chain alkanesulfonic acids, chlorosulfonic acid, also naphthalenesulfonic acid, alpha-sulfo fatty acids (available e.g. by reacting saturated fatty acids with gaseous sulfur trioxide), alpha-sulfo fatty acid alkyl esters, e.g. -methyl ester (available e.g. by reacting saturated fatty acid alkyl esters with gaseous Sulfur trioxide).
  • aromatic sulfonic acids are used as Component b2).
  • Alkylbenzenesulfonic acids and in particular the commercially available linear alkyl benzyl sulfonic acid are particularly preferred.
  • the carboxylic acids a) are finally reacted with a sulfonating reagent b) which consists of a ternary combination of at least one organic sulfonic acid b1), sulfuric acid b2) and at least one hydrogen sulfate b3) (older name: bisulfate).
  • a sulfonating reagent b) which consists of a ternary combination of at least one organic sulfonic acid b1), sulfuric acid b2) and at least one hydrogen sulfate b3) (older name: bisulfate).
  • Suitable hydrogen sulfates are compounds of the structure Alk-HSO 4 , where "Alk" means a monovalent metal or NH 4 .
  • Preferred monovalent metals are the alkali metals, especially sodium and / or potassium.
  • Another object of the present invention is a method for Production of sulfated substances, using mono- or polybasic carboxylic acids a) with 12 to 72 carbon atoms, with a sulfonating reagent b) and the reaction mixture is then neutralized, the reaction being carried out at temperatures in the range of 20 to 130 ° C and as Sulfierreagens b) a combination of at least one organic sulfonic acid b1) and sulfuric acid b2) is used, with the proviso that the proportion sulfuric acid - based on the sum of organic sulfonic acid and Sulfuric acid - 0.5 to 80 wt .-%.
  • the process according to the invention has the advantage that it is usually only moderate reaction temperatures required.
  • the reaction temperature is only in the range from 20 to 80 ° C and especially 20 to 40 ° C.
  • the reaction continues combining components a) and b) spontaneously with the release of Heat, so that in these cases cooling must even be carried out in order to achieve a controlled Ensure the course of the reaction.
  • reaction times are relative in short, usually on the order of 1 to 4 hours. It can but - depending on the nature of the component a) used - reaction times below one hour or above may also be desirable of 4 hours.
  • the process is usually carried out in such a way that the Components a) and b) mixed together at about 20 ° C. Often sets an exothermic reaction - particularly strong in those cases where the sulfating reagent from a mixture of aromatic sulfonic acids and There is sulfuric acid.
  • the reaction mixture is now stirred at a slightly elevated temperature.
  • the method according to the invention is used at lowest possible temperature. This is in cases where 20 ° C liquid carboxylic acids are used as component a) and where the Proportion of sulfuric acid in the sulfonating reagent b) in the preferred range of 1 to 40 wt .-%, preferably in the range of 20 to 40 ° C, wherein often has to cool externally to keep the temperature in this range.
  • carboxylic acids a which are not at 20 ° C or slightly elevated temperature are sufficiently liquid, or where the reaction is to conclude as quickly as possible may be brought, however, the entire mentioned temperature range from 20 to 80 ° C or 20 to 130 ° C to take advantage of.
  • the reaction may even be desirable perform at higher temperatures (up to approx. 250 ° C), e.g. B. if one as component a) uses carboxylic acids with a high melting point, but on wants to dispense with the possible addition of a diluent or if the reaction rate should be increased even further. In the area at these high reaction temperatures, it may be appropriate the reaction in the presence of air in an inert gas atmosphere (e.g. under Nitrogen).
  • an inert gas atmosphere e.g. under Nitrogen
  • neutralization closes on.
  • the reaction mixture is allowed to cool and then doses the desired base.
  • suitable bases are Alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, alkanolamines and alkylamines or mixtures thereof. Are preferred especially sodium hydroxide, potassium hydroxide and ammonium hydroxide. A further processing of the neutralized products is not necessary.
  • carboxylic acid e.g. F-1 to F-8
  • sulfonating agent e.g. S-1 to S-3
  • carboxylic acid e.g. F-1 to F-8
  • S-1 to S-3 sulfonating agent
  • the carboxylic acid used is liquid at room temperature, is stirred for about 2 hours, a temperature in the range of 20 up to 40 ° C. In the case of exothermic reactions, the corresponding chilled.
  • carboxylic acids that are solid, partially solid at 20 ° C or are viscous e.g. carboxylic acid F-6
  • you choose a reaction temperature in which the carboxylic acid is liquid.
  • a Temperature set at a maximum of 80 ° C.
  • the reaction mixture neutralized with a base (e.g. 37% by weight aqueous sodium hydroxide solution), if necessary after cooling the mixture beforehand.
  • a base e.g. 37% by weight aqueous sodium hydroxide solution

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Coloring (AREA)

Claims (11)

  1. Utilisation de substances sulfitées pour nourrir le cuir, dans laquelle on peut obtenir les substances sulfitées par réaction d'acides carboxyliques mono- ou polybasiques a) avec de 12 à 72 atomes de carbone, avec un réactif de sulfonation b) outre une neutralisation ultérieure,
    caractérisée en ce qu'
    on utilise comme réactif de sulfonation b) une combinaison d'au moins un acide sulfonique organique b1) et d'acide sulfurique b2), sous réserve que la proportion d'acide sulfurique - par rapport à la somme de l'acide sulfonique organique et de l'acide sulfurique - s'élève à 0,5 à 80% en poids.
  2. Utilisation selon la revendication 1,
    dans laquelle
    on règle les rapports quantitatifs de l'acide carboxylique a) et du réactif de sulfonation b) de manière qu'ils se situent dans une plage de 1:99 à 99:1.
  3. Utilisation selon la revendication 1 ou 2,
    dans laquelle
    le composant a) est au moins en partie éthyléniquement insaturé.
  4. Utilisation selon l'une des revendications 1 à 3,
    dans laquelle
    il s'agit, pour l'acide sulfonique organique, d'un acide sulfonique aromatique, de préférence d'un acide alkylbenzènesulfonique.
  5. Utilisation selon la revendication 4,
    dans laquelle
    la proportion de l'acide sulfurique - par rapport à la somme de l'acide sulfonique organique et de l'acide sulfurique - s'élève à 1 à 40% en poids.
  6. Utilisation selon l'une des revendications 1 à 5,
    dans laquelle
    on utilise comme composant a) des mélanges d'acides carboxyliques.
  7. Utilisation selon l'une des revendications 1 à 5,
    dans laquelle
    on utilise comme composant a) un acide carboxylique qui est choisi dans le groupe des acides gras, des acides dicarboxyliques, des acides gras dimères et des acides gras trimères.
  8. Utilisation selon l'une des revendications 1 à 7,
    dans laquelle
    on utilise comme composant à sulfoner a) un mélange composé de :
    i) au moins un acide carboxylique mono- ou polybasique comportant de 12 à 72 atomes de carbone et
    ii) au moins un ester d'alkyle inférieur d'acides gras comportant de 8 à 24 atomes de carbone.
  9. Utilisation selon l'une des revendications 1 à 8,
    dans laquelle
    on utilise des acides carboxyliques a) qui sont alcoxylés et/ou époxydés.
  10. Procédé de fabrication de substances sulfonées, dans lequel on fait réagir des acides carboxyliques mono- ou polybasiques a) à ayant de 12 à 72 atomes de carbone avec un réactif de sulfonation b) puis on neutralise le mélange réactionnel,
    caractérisé en ce qu'
    on effectue la réaction à des températures comprises entre 20 et 130°C,
    on utilise comme réactif de sulfonation b) une combinaison d'au moins un acide sulfonique organique b1) et d'acide sulfurique b2), sous réserve que la proportion d'acide sulfurique - par rapport à la somme de l'acide sulfonique organique et de l'acide sulfurique - s'élève à 0,5 à 80% en poids.
  11. Procédé selon la revendication 10,
    dans lequel
    on règle les proportions quantitatives de l'acide carboxylique a) et du réactif de sulfonation b) de manière qu'elles se situent dans une plage de 1:99 à 99:1 et dans lequel on utilise comme composant b) un acide sulfonique aromatique, de préférence un acide alkylbenzènesulfonique.
EP95908273A 1994-02-21 1995-02-13 Utilisation de substances sulfitees pour nourrir le cuir Expired - Lifetime EP0746630B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4405416A DE4405416A1 (de) 1994-02-21 1994-02-21 Verwendung sulfierter Substanzen zur Fettung von Leder
DE4405416 1994-02-21
PCT/EP1995/000511 WO1995022632A1 (fr) 1994-02-21 1995-02-13 Utilisation de substances sulfitees pour nourrir le cuir

Publications (2)

Publication Number Publication Date
EP0746630A1 EP0746630A1 (fr) 1996-12-11
EP0746630B1 true EP0746630B1 (fr) 1998-09-23

Family

ID=6510719

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95908273A Expired - Lifetime EP0746630B1 (fr) 1994-02-21 1995-02-13 Utilisation de substances sulfitees pour nourrir le cuir

Country Status (5)

Country Link
EP (1) EP0746630B1 (fr)
AT (1) ATE171481T1 (fr)
DE (2) DE4405416A1 (fr)
TR (1) TR28870A (fr)
WO (1) WO1995022632A1 (fr)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1768548A1 (de) * 1968-05-25 1971-11-18 Henkel & Cie Gmbh Verfahren zur Herstellung von Sulfonierungsprodukten
DE3617657C2 (de) * 1986-05-26 1994-08-18 Stockhausen Chem Fab Gmbh Bei Raumtemperatur flüssige Derivate von natürlichen Fetten oder Ölen, Verfahren zu deren Herstellung, und ihre Verwendung
HRP930646A2 (en) * 1992-04-10 1994-10-31 Hoechst Ag Leather greasing material

Also Published As

Publication number Publication date
DE59503704D1 (de) 1998-10-29
ATE171481T1 (de) 1998-10-15
WO1995022632A1 (fr) 1995-08-24
EP0746630A1 (fr) 1996-12-11
TR28870A (tr) 1997-07-17
DE4405416A1 (de) 1995-10-05

Similar Documents

Publication Publication Date Title
DE3617657C2 (de) Bei Raumtemperatur flüssige Derivate von natürlichen Fetten oder Ölen, Verfahren zu deren Herstellung, und ihre Verwendung
EP0178557B1 (fr) Procédé pour la fabrication d'agents de graissage pour cuir et fourrures
DE2245077C3 (de) Fettungsmittel für Leder oder Pelze und ihre Verwendung
DE3826179C2 (de) Bei Raumtemperatur flüssige Derivate von natürlichen Fetten oder Ölen, Verfahren zu ihrer Herstellung und deren Verwendung
EP0746630B1 (fr) Utilisation de substances sulfitees pour nourrir le cuir
EP0746628B1 (fr) Utilisation de substances sulfitees pour nourrir le cuir
EP0763138B1 (fr) Utilisation de substances sulfurees pour nourrir le cuir
EP0746631B1 (fr) Utilisation de substances sulfurees pour nourrir le cuir
EP0746629B1 (fr) Utilisation de substances sulfonees pour nourrir le cuir
EP0763139B1 (fr) Agents utilises pour nourrir des cuirs et des fourrures
DE2311344A1 (de) Verfahren zur herstellung kaeltebestaendiger, fluessiger fettsaeureester
DE744878C (de) Verfahren zur Herstellung von Sulfonierungserzeugnissen
WO1994012471A1 (fr) Graisses sulfitees a teneur reduite en sulfite d'hydrogene libre
DE2819937A1 (de) Praeparat zum einfetten von leder
DE625637C (de) Verfahren zur Herstellung von hochbestaendigen Sulfonsaeuren oder deren Salzen
DE731392C (de) Herstellung von Sulfonsaeuren
DE2355503C3 (de) Verfahren zur Herstellung eines fettenden Chromgerbmittels und dessen Verwendung zum Gerben und Nachgerben
DE19804828A1 (de) Sulfitierte Maleinsäurederivate
DE19510527A1 (de) Derivate natürlicher Fette und/oder Öle
DE19715833A1 (de) Verfahren zur Herstellung von sulfatierten Fettsäureestern
CH171359A (de) Verfahren zur Herstellung eines Reinigungs-, Wasch-, Emulgier-, Dispergier- und Weichmachungsmittels.
CH200666A (de) Verfahren zur Herstellung einer neuen beständigen, wasserlöslichen, neutralen, ungiftigen chemischen Substanz, welche zur Herabsetzung der Berührungsflächenspannung von Wasser-Öl-Gemischen geeignet ist.
DE1230518B (de) Leder- und Pelzfettungsmittel

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

17P Request for examination filed

Effective date: 19960812

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI NL PT SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19971021

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980923

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19980923

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980923

Ref country code: GB

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980923

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980923

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19980923

REF Corresponds to:

Ref document number: 171481

Country of ref document: AT

Date of ref document: 19981015

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59503704

Country of ref document: DE

Date of ref document: 19981029

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981223

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981223

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981223

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990213

EN Fr: translation not filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990228

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990228

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990228

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 19980923

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990504

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19990228

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991201