EP3704275A1 - A composition useful for pre-treatment in waterless tanning and corresponding tanning process - Google Patents

A composition useful for pre-treatment in waterless tanning and corresponding tanning process

Info

Publication number
EP3704275A1
EP3704275A1 EP18734308.2A EP18734308A EP3704275A1 EP 3704275 A1 EP3704275 A1 EP 3704275A1 EP 18734308 A EP18734308 A EP 18734308A EP 3704275 A1 EP3704275 A1 EP 3704275A1
Authority
EP
European Patent Office
Prior art keywords
composition
tanning
range
water
fatliquor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP18734308.2A
Other languages
German (de)
French (fr)
Other versions
EP3704275B1 (en
Inventor
Palanisamy Thanikaivelan
Rathinam ARAVINDHAN
Balaraman Madhan
Palanivel SARAVANAN
Jonnalagadda Raghava Rao
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.)
Council of Scientific and Industrial Research CSIR
Original Assignee
Council of Scientific and Industrial Research CSIR
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 Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Publication of EP3704275A1 publication Critical patent/EP3704275A1/en
Application granted granted Critical
Publication of EP3704275B1 publication Critical patent/EP3704275B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/10—Vegetable tanning
    • 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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds
    • 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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/28—Multi-step processes
    • 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 present invention relates to a composition useful for pre-treatment in waterless tanning. More particularly, the present invention relates to a composition that finds application in tanning, wherein the said composition uses the inherent water present in the substrate to be tanned, thereby eliminating the need of addition of external water.
  • the developed composition is useful in leather processing industry for making chrome or vegetable tanned leather in an eco-benign way without adding to the environmental pollution.
  • the basification is not necessary in this process (Legesse et al, The Journal of the American Leather Chemists Association, 97, 475-486 2002; Rao et al, The Journal of the American Leather Chemists Association, 99, 82-94, 2004; WO 2012153203A1). Nevertheless, the disclosed process employs aqueous medium in significant quantity and discharge wastewater with fairly low pollution loads in comparison to the conventional pickle based chrome tanning system.
  • a dispersing agent composition was developed for carrying out tanning without water or any other medium (WO 2017009867).
  • the dispersing agent essentially comprises polyalkylene polyhydric compound, an organic acid and a non-ionic surfactant.
  • the major constituent of the said dispersing agent is polyalkylene polyhydric compound, which would increase the cost of the composition and would limit the commercial viability.
  • Our co-pending Indian patent application No. 201611009091 provides a process for waterless chrome tanning that eliminates the use of water, salt, sulfuric acid and basification salts during the chrome tanning process. This process has been receiving more attention in global leather industries and several tanners in India have already adopted the process. However, use of more water and expensive organic acids for pre-treatment are posing problems for implementation in commercial environment. Hence, absorption of these new waterless chrome tanning technologies in worldwide leather industries has been slow thus threatening the sustainability of leather industries.
  • the inventors of the present invention realized that there exists a dire need to provide a composition and process useful for pre treatment during waterless chrome tanning process, which helps to eliminate water from tanning process thereby reducing the wastewater discharge. Elimination of mineral tanning salt and common salt will reduce the pollution load and chemical cost of the tanning process, thereby benefiting the industry.
  • the main objective of the present invention is therefore to provide a composition useful in pre-treatment in waterless tanning process, which obviates the limitations as stated above.
  • Another objective of the present invention is to avoid the use of water both during chrome and vegetable tanning and utilize inherent water present in the substrate.
  • Still another objective of the present invention is to use auxiliary chemicals like acid stable cationic fatliquors during the tanning process.
  • Yet another objective of the present invention is to improve the uptake of chromium and vegetable tannins during the process. Still another objective of the present invention is to reduce the pollution load and toxic chemicals in the effluent.
  • Yet another objective of the present invention is to reduce processing time, water and cost for pre-treatment during waterless tanning in comparison to conventional processing.
  • Still another objective of the present invention is to eliminate the use of salt, sulfuric acid and basification process in comparison to conventional processing.
  • the present invention provides a composition useful in pre-treatment in waterless tanning process, wherein the said composition comprising: i. 90 to 95% (v/v) of organic acid having carbon chain length in the range of Cl to C3; ii. 3 to 8% (v/v) of primary alcohol having carbon chain length in the range of Cl to C3; and
  • the present invention provides a process for the preparation of the pre-treatment composition useful in waterless tanning, which comprises mixing 90 to 95% (v/v) of organic acid having carbon chain length in the range of Cl to C3, 3 to 8% (v/v) of primary alcohol having carbon chain length in the range of Cl to C3 and 2 to 5% (v/v) of a non-ionic surfactant for a period in the range of 5 to 30 min to obtain the composition.
  • the said composition being water soluble, exhibiting a pH in the range of 1.8 to 2.6 as a 10% solution and characterized by transparent appearance.
  • the present invention provides a waterless tanning process using the developed composition, wherein the steps comprising: i. treating the delimed substrate to be tanned with 0.1 to 5% w/w of the developed composition in the presence of 10 to 60% water to adjust the pH in the range of 4.8 to 5.8 followed by draining the float to obtain pre-treated substrate, ii. treating the pre-treated substrate as obtained in step (i) with 0.2 to 2.0% of a conventional fatliquor and 0.2 to 1.0% of an alkali metal salt of organic acid having carbon chain of length not more than two for a period in the range of 20 to 60 min,
  • step (iii) treating the substrate as obtained in step (ii) with 3 to 50% of conventional tanning agent, added in one or more instalments, for a period in the range of 90 to 600 min with simultaneous checking of pH in the range of 3.6 to 4.4 to obtain tanned substrate.
  • the organic acid used may be selected from methanoic acid, ethanoic acid, propionic acid either individually or in different combinations.
  • the primary alcohol used may be selected from methanol, ethanol, propan-2-ol either individually or in different combinations.
  • the non-ionic surfactant used may be selected from 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, polyoxyethylene (20) sorbitan monooleate, [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate either individually or in different combinations.
  • the conventional fatliquor used may be selected from cationic fatliquor, acid stable fatliquor, universal fatliquor, chrome stable fatliquor either individually or in different combinations.
  • the alkali metal salt of organic acid used may be selected from sodium methanoate, sodium ethanoate either individually or in different combinations.
  • the present invention provides a process for the preparation of composition, which comprising mixing 90 to 95% (v/v) of an organic acid having carbon chain length in the range of Cl to C3, 3 to 8% (v/v) of primary alcohol having carbon chain length in the range of Cl to C3 and 2 to 5% (v/v) of a non-ionic surfactant are mixed together for a period of 5 to 30 min to obtain a composition which is useful for pre-treatment in waterless tanning processes.
  • the prepared composition has the following characteristics: pH of 10% solution: 1.8 to 2.6
  • composition is used for waterless tanning process as described below.
  • Delimed substrate is treated with 0.1 to 5% of the composition in the presence of 10-60% water.
  • the pH of the pelt is adjusted in the range of 4.8 to 5.8.
  • the float is drained and the substrate is treated with 0.2 to 2.0% of conventional fatliquor and 0.2 to 1.0% alkali metal salt of organic acid having carbon chain of length not more than two.
  • the substrate is treated with 3 to 50% of conventional tanning agent, added in one or more instalments, for a period in the range of 90 to 600 min.
  • the pH is checked to be in the range of 3.6 to 4.4 to obtain tanned substrate.
  • the inventive step of the present invention lies in preparing the composition by prudent selection and combination of key chemicals such that the resultant composition can be easily used for pre-treatment in waterless tanning, which would help in carrying out the tanning more effectively and easily utilizing the internal moisture content of raw material to reduce the effluent discharge. Further, elimination of common salt and considerable reduction in water requirement, duration of the process and cost are achieved in the new invention.
  • Composition was prepared by mixing of 45 ml of methanoic acid, 4 ml of methanol and 1 ml 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol together for a period of 5 min. pH of 10% solution of the composition was 1.80. The colour of the composition was transparent and it had good solubility in water.
  • One delimed substrate (cow hide) to be tanned weighing 3 kg was treated with the above composition diluted with 500 ml of water and drummed in the presence of 1200 ml water. The pH of the pelt was checked to be 4.8.
  • the float was drained and the hide was treated with 6 g of cationic fatliquor and 6 g of sodium methanoate. After a period of 20 min, 90 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 90 min. The pH was checked to be 3.8 to obtain chrome tanned leather.
  • BCS chrome tanning agent
  • Composition was prepared by mixing of 7 ml of ethanoic acid, 0.2 ml of ethanol and 0.15 ml Polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.41. The color of the composition was transparent and it had good solubility in water.
  • Three delimed substrate (cow hide) to be tanned weighing 7.5 kg were treated with the above composition diluted with 75 ml of water and drummed in the presence of 3000 ml water.
  • the pH of the pelt was checked to be 5.2.
  • the float was drained and the hide was treated with 37.5 g of acid stable fatliquor and 15 g of sodium ethanoate.
  • 375 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 180 min.
  • the pH was checked to be 4.0 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 41 ml of propionic acid, 2.3 ml of propan-2-ol and 2.25 ml [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.58. The color of the composition was transparent and it had good solubility in water.
  • Two delimed substrate (cow hide) to be tanned weighing 5 kg were treated with the above composition diluted with 900 ml of water and drummed in the presence of 2000 ml water.
  • the pH of the pelt was checked to be 5.4.
  • the float was drained and the hide was treated with 15 g of Universal fatliquor and 27.5 g of sodium methanoate.
  • 300 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 180 min.
  • the pH was checked to be 4.10 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 45 ml of methanoic acid, 45 ml of ethanoic acid, 2.5 ml of methanol, 2.5 ml of ethanol, 2 ml of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, 2 ml of Polyoxyethylene (20) sorbitan monooleate and 1 ml of [2-[(2R,3S,4R)-3,4- dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.10. The color of the composition was transparent and it had good solubility in water.
  • Composition was prepared by mixing of 18 ml of methanoic acid, 18 ml of ethanoic acid, 18 ml of propionic acid, 2 ml of methanol, 2 ml of ethanol, 0.8 ml of propan-2-ol, 1 ml of Polyoxyethylene (20) sorbitan monooleate and 0.2 ml of [2-[(2R,3S,4R)-3,4- dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.10. The color of the composition was transparent and it had good solubility in water.
  • Composition was prepared by mixing of 30 ml of methanoic acid, 15 ml of ethanoic acid, 26 ml of propionic acid, 1 ml of methanol, 0.5 ml of propan-2-ol, 0.5 ml of 2-[4-(2,4,4- trimethylpentan-2-yl)phenoxy]ethanol, 0.75 ml of Polyoxyethylene (20) sorbitan monooleate and 1 ml of [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.25. The color of the composition was transparent and it had good solubility in water.
  • delimed substrate to be tanned weighing 10 kg were treated with the above composition diluted with 750 ml of water and drummed in the presence of 4000 ml water.
  • the pH of the pelt was checked to be 5.0.
  • the float was drained and the hide was treated with 10 g of acid stable fatliquor, 10 g of universal fatliquor and 50 g of sodium methanoate.
  • 800 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 420 min.
  • the pH was checked to be 3.9 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 40 ml of methanoic acid, 15 ml of ethanoic acid, 50 ml of propionic acid, 4 ml of methanol, 2 ml of ethanol, 4 ml of propan-2-ol, and 2 ml of polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.6. The color of the composition was transparent and it had good solubility in water.
  • One delimed substrate (cow hide) to be tanned weighing 2 kg was treated with the above composition diluted with 1000 ml of water and drummed in the presence of 800 ml water.
  • the pH of the pelt was checked to be 5.8.
  • the float was drained and the hide was treated with 20 g of cationic fatliquor, 20 g of chrome stable fatliquor and 6 g of sodium ethanoate.
  • 60 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 120 min.
  • the pH was checked to be 4.4 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 10 ml of methanoic acid, 90 ml of ethanoic acid, 5 ml of ethanol and 5 ml of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol together for a period of 5 min. pH of 10% solution of the composition was 2.20. The color of the composition was transparent and it had good solubility in water.
  • delimed substrate to be tanned weighing 10 kg were treated with the above composition diluted with 1000 ml of water and drummed in the presence of 4000 ml water.
  • the pH of the pelt was checked to be 4.8.
  • the float was drained and the hide was treated with 50 g of acid stable fatliquor and 50 g of sodium methanoate.
  • 600 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 300 min.
  • the pH was checked to be 4.1 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 25 ml of methanoic acid, 20 ml of propionic acid, 2.5 ml of ethanol, 2 ml of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol and 0.5 ml of Polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.00. The color of the composition was transparent and it had good solubility in water.
  • Ten delimed substrate (cow hide) to be tanned weighing 20 kg were treated with the above composition diluted with 3000 ml of water and drummed in the presence of 8000 ml water.
  • the pH of the pelt was checked to be 4.8.
  • the float was drained and the hide was treated with 20 g of cationic fatliquor, 100 g of acid stable fatliquor, 25 g of universal fatliquor, 50 g of chrome stable fatliquor, 25 g of sodium methanoate and 25 g of sodium ethanoate.
  • 1600 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 540 min.
  • the pH was checked to be 3.7 to obtain chrome tanned leather.
  • Composition was prepared by mixing of 41 ml of propionic acid, 2.3 ml of propan-2-ol and 2.25 ml [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.58. The color of the composition was transparent and it had good solubility in water.
  • Composition was prepared by mixing of 40 ml of methanoic acid, 15 ml of ethanoic acid, 50 ml of propionic acid, 4 ml of methanol, 2 ml of ethanol, 4 ml of propan-2-ol, and 2 ml of polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.6. The color of the composition was transparent and it had good solubility in water.
  • One delimed substrate (cow hide) to be tanned weighing 2 kg was treated with the above composition diluted with 1000 ml of water and drummed in the presence of 600 ml water.
  • the pH of the pelt was checked to be 5.6.
  • the float was drained and the hide was treated with 20 g of cationic fatliquor, 20 g of Universal fatliquor and 6 g of sodium ethanoate.
  • 1 kg of wattle GS powder was added in 4 feeds with 20 min interval and drummed for a period of 600 min.
  • the pH was checked to be 3.6 to obtain vegetable tanned leather.
  • a versatile composition for facilitating waterless tanning is provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

Use of water during chrome or vegetable tanning is inevitable as it is important for diffusion and distribution of tanning agent in the matrix. This leads to the generation of wastewater containing pollutants such as chromium that needs to be managed effectively. The present invention relates to a novel composition for carrying out the waterless tanning more effectively and easily. The composition preparation involves judicious combination of key specialty chemicals needed for pre-treatment during waterless tanning. The use of new composition for pre-treatment in waterless tanning enables reduction in water requirement, duration of the process as well as cost. Moreover, the use of salt and the basification process are also avoided. The invention makes an effort to attain sustainability in leather industry.

Description

A COMPOSITION USEFUL FOR PRE-TREATMENT IN WATERLESS TANNING AND CORRESPONDING TANNING PROCESS
FIELD OF THE INVENTION
The present invention relates to a composition useful for pre-treatment in waterless tanning. More particularly, the present invention relates to a composition that finds application in tanning, wherein the said composition uses the inherent water present in the substrate to be tanned, thereby eliminating the need of addition of external water. The developed composition is useful in leather processing industry for making chrome or vegetable tanned leather in an eco-benign way without adding to the environmental pollution.
BACKGROUND OF THE INVENTION
Huge volume of water is being utilized during leather processing, which leads to discharge of enormous quantity of wastewater (Rao et al., Journal of Cleaner Production, 11, 591-599, 2003). Researchers world over are involved in the development of technologies to minimize water utilization in leather processing. Chrome tanning is a widely practiced methodology to make leathers owing to its versatile properties. Vegetable tanning is also in vogue due to its eco-friendly nature compared to chromium, although less than 20% of world leather production follows this tanning procedure. Nevertheless, the use of partial-pickling process and water has been in practice during vegetable tanning. Use of water during chrome tanning is very important for attaining uniform diffusion, distribution and hydrolysis of chromium. The spent chrome liquor contains 1500-3500 ppm of chromium. The discharge of chromium is of major concern and 2 ppm as total chromium is the stipulated norm for the discharge of tannery effluent in inland water bodies (Suresh et al, Journal of Cleaner Production, 9, 483- 491, 2001). Therefore, alternate technologies to reduce the chrome pollution or alternate tanning system are required to combat the present scenario. Owing to the non-availability of best-suited alternate tanning agent, it seems more appropriate to continue with the use of trivalent chromium as the main tanning material and chrome management through reduction of pollution at source or end-of pipe treatment.
Although the use of chrome exhaust aids, high exhaust chrome tanning salts and less chrome technologies have been developed (WO 2014162059 Al), their commercial usage is lacking. The chrome recovery and reuse methodology is a very simple and effective method for combating chrome pollution, which is commercially practised in many countries including India (Rao et al., Journal of Cleaner Production, 11, 591-599, 2003). Pickle-basification free chrome tanning is another commercially feasible development, where the chromium tanning is carried out at elevated pH without the use of common salt. Also, the basification is not necessary in this process (Legesse et al, The Journal of the American Leather Chemists Association, 97, 475-486 2002; Rao et al, The Journal of the American Leather Chemists Association, 99, 82-94, 2004; WO 2012153203A1). Nevertheless, the disclosed process employs aqueous medium in significant quantity and discharge wastewater with fairly low pollution loads in comparison to the conventional pickle based chrome tanning system.
Further, the researchers are also looking at employing alternative medium to water during chrome tanning process. Silambarasan et al (RSC Advances, 5, 66815-66823, 2015) have shown that chrome tanning can be carried out in ethanol and its derivatives instead of water. Similarly, there are reports of using pressurized carbon dioxide as a medium for chrome tanning (Manfred et al., The Journal of Supercritical Fluids, 66, 291-296, 2012). A recent study demonstrates that a minimum of 55-65% internal moisture content within the collagen matrix is required for making chrome tanned leathers with comparable quality (Silambarasan et al., Journal of Cleaner Production, 87, 567-572, 2015).
A dispersing agent composition was developed for carrying out tanning without water or any other medium (WO 2017009867). The dispersing agent essentially comprises polyalkylene polyhydric compound, an organic acid and a non-ionic surfactant. The major constituent of the said dispersing agent is polyalkylene polyhydric compound, which would increase the cost of the composition and would limit the commercial viability. Our co-pending Indian patent application No. 201611009091 provides a process for waterless chrome tanning that eliminates the use of water, salt, sulfuric acid and basification salts during the chrome tanning process. This process has been receiving more attention in global leather industries and several tanners in India have already adopted the process. However, use of more water and expensive organic acids for pre-treatment are posing problems for implementation in commercial environment. Hence, absorption of these new waterless chrome tanning technologies in worldwide leather industries has been slow thus threatening the sustainability of leather industries.
As can be seen in the prior art, the current knowledge on the cleaner chrome tanning processes as well as other chrome management options is well known. Not many cleaner technologies are developed for vegetable tanning. The prior art focused on technologies such as waterless chrome tanning process, dispersing agent for waterless tanning, etc. In short, it may be concluded that during the tanning process water is used in order to facilitate distribution and penetration of the tanning salts in the matrix and as per the literature available till date, the following drawbacks are associated with the prior art:
• Use of water and generation of chrome containing wastewater during chrome tanning;
• Reduced uptake of chrome tanning agent by the matrix;
• Release of huge amounts of neutral salts owing to the pickling and basification process;
• Partial pickling and use of water during vegetable tanning;
Thus, keeping in view the drawbacks of the hitherto reported prior art and problems associated with the available prior art technologies, the inventors of the present invention realized that there exists a dire need to provide a composition and process useful for pre treatment during waterless chrome tanning process, which helps to eliminate water from tanning process thereby reducing the wastewater discharge. Elimination of mineral tanning salt and common salt will reduce the pollution load and chemical cost of the tanning process, thereby benefiting the industry.
OBJECTS OF THE INVENTION
The main objective of the present invention is therefore to provide a composition useful in pre-treatment in waterless tanning process, which obviates the limitations as stated above.
Another objective of the present invention is to avoid the use of water both during chrome and vegetable tanning and utilize inherent water present in the substrate.
Still another objective of the present invention is to use auxiliary chemicals like acid stable cationic fatliquors during the tanning process.
Yet another objective of the present invention is to improve the uptake of chromium and vegetable tannins during the process. Still another objective of the present invention is to reduce the pollution load and toxic chemicals in the effluent.
Yet another objective of the present invention is to reduce processing time, water and cost for pre-treatment during waterless tanning in comparison to conventional processing.
Still another objective of the present invention is to eliminate the use of salt, sulfuric acid and basification process in comparison to conventional processing.
SUMMARY OF THE INVENTION
The present invention provides a composition useful in pre-treatment in waterless tanning process, wherein the said composition comprising: i. 90 to 95% (v/v) of organic acid having carbon chain length in the range of Cl to C3; ii. 3 to 8% (v/v) of primary alcohol having carbon chain length in the range of Cl to C3; and
iii. 2 to 5% (v/v) of a non-ionic surfactant.
The present invention provides a process for the preparation of the pre-treatment composition useful in waterless tanning, which comprises mixing 90 to 95% (v/v) of organic acid having carbon chain length in the range of Cl to C3, 3 to 8% (v/v) of primary alcohol having carbon chain length in the range of Cl to C3 and 2 to 5% (v/v) of a non-ionic surfactant for a period in the range of 5 to 30 min to obtain the composition. The said composition being water soluble, exhibiting a pH in the range of 1.8 to 2.6 as a 10% solution and characterized by transparent appearance.
In an embodiment, the present invention provides a waterless tanning process using the developed composition, wherein the steps comprising: i. treating the delimed substrate to be tanned with 0.1 to 5% w/w of the developed composition in the presence of 10 to 60% water to adjust the pH in the range of 4.8 to 5.8 followed by draining the float to obtain pre-treated substrate, ii. treating the pre-treated substrate as obtained in step (i) with 0.2 to 2.0% of a conventional fatliquor and 0.2 to 1.0% of an alkali metal salt of organic acid having carbon chain of length not more than two for a period in the range of 20 to 60 min,
iii. treating the substrate as obtained in step (ii) with 3 to 50% of conventional tanning agent, added in one or more instalments, for a period in the range of 90 to 600 min with simultaneous checking of pH in the range of 3.6 to 4.4 to obtain tanned substrate.
In an embodiment of the present invention, the organic acid used may be selected from methanoic acid, ethanoic acid, propionic acid either individually or in different combinations.
In another embodiment of the present invention, the primary alcohol used may be selected from methanol, ethanol, propan-2-ol either individually or in different combinations.
In still another embodiment of the present invention, the non-ionic surfactant used may be selected from 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, polyoxyethylene (20) sorbitan monooleate, [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate either individually or in different combinations.
In another embodiment of the present invention, the conventional fatliquor used may be selected from cationic fatliquor, acid stable fatliquor, universal fatliquor, chrome stable fatliquor either individually or in different combinations.
In still another embodiment of the present invention, the alkali metal salt of organic acid used may be selected from sodium methanoate, sodium ethanoate either individually or in different combinations.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a process for the preparation of composition, which comprising mixing 90 to 95% (v/v) of an organic acid having carbon chain length in the range of Cl to C3, 3 to 8% (v/v) of primary alcohol having carbon chain length in the range of Cl to C3 and 2 to 5% (v/v) of a non-ionic surfactant are mixed together for a period of 5 to 30 min to obtain a composition which is useful for pre-treatment in waterless tanning processes. The prepared composition has the following characteristics: pH of 10% solution: 1.8 to 2.6
Color: Transparent
Solubility in water: High
The composition is used for waterless tanning process as described below.
Delimed substrate is treated with 0.1 to 5% of the composition in the presence of 10-60% water. The pH of the pelt is adjusted in the range of 4.8 to 5.8. After attaining the pH, the float is drained and the substrate is treated with 0.2 to 2.0% of conventional fatliquor and 0.2 to 1.0% alkali metal salt of organic acid having carbon chain of length not more than two. After a period of 20 to 60 min, the substrate is treated with 3 to 50% of conventional tanning agent, added in one or more instalments, for a period in the range of 90 to 600 min. The pH is checked to be in the range of 3.6 to 4.4 to obtain tanned substrate.
The inventive step of the present invention lies in preparing the composition by prudent selection and combination of key chemicals such that the resultant composition can be easily used for pre-treatment in waterless tanning, which would help in carrying out the tanning more effectively and easily utilizing the internal moisture content of raw material to reduce the effluent discharge. Further, elimination of common salt and considerable reduction in water requirement, duration of the process and cost are achieved in the new invention.
EXAMPLES
The following examples are given by way of illustration only and therefore, should not be construed to limit the scope of the present invention in any manner.
Example 1
Composition was prepared by mixing of 45 ml of methanoic acid, 4 ml of methanol and 1 ml 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol together for a period of 5 min. pH of 10% solution of the composition was 1.80. The colour of the composition was transparent and it had good solubility in water. One delimed substrate (cow hide) to be tanned weighing 3 kg was treated with the above composition diluted with 500 ml of water and drummed in the presence of 1200 ml water. The pH of the pelt was checked to be 4.8. After attaining the pH, the float was drained and the hide was treated with 6 g of cationic fatliquor and 6 g of sodium methanoate. After a period of 20 min, 90 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 90 min. The pH was checked to be 3.8 to obtain chrome tanned leather.
Example 2
Composition was prepared by mixing of 7 ml of ethanoic acid, 0.2 ml of ethanol and 0.15 ml Polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.41. The color of the composition was transparent and it had good solubility in water.
Three delimed substrate (cow hide) to be tanned weighing 7.5 kg were treated with the above composition diluted with 75 ml of water and drummed in the presence of 3000 ml water. The pH of the pelt was checked to be 5.2. After attaining the pH, the float was drained and the hide was treated with 37.5 g of acid stable fatliquor and 15 g of sodium ethanoate. After a period of 30 min, 375 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 180 min. The pH was checked to be 4.0 to obtain chrome tanned leather.
Example 3
Composition was prepared by mixing of 41 ml of propionic acid, 2.3 ml of propan-2-ol and 2.25 ml [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.58. The color of the composition was transparent and it had good solubility in water.
Two delimed substrate (cow hide) to be tanned weighing 5 kg were treated with the above composition diluted with 900 ml of water and drummed in the presence of 2000 ml water. The pH of the pelt was checked to be 5.4. After attaining the pH, the float was drained and the hide was treated with 15 g of Universal fatliquor and 27.5 g of sodium methanoate. After a period of 40 min, 300 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 180 min. The pH was checked to be 4.10 to obtain chrome tanned leather.
Example 4
Composition was prepared by mixing of 45 ml of methanoic acid, 45 ml of ethanoic acid, 2.5 ml of methanol, 2.5 ml of ethanol, 2 ml of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, 2 ml of Polyoxyethylene (20) sorbitan monooleate and 1 ml of [2-[(2R,3S,4R)-3,4- dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.10. The color of the composition was transparent and it had good solubility in water.
Five delimed substrate (cow hide) to be tanned weighing 10 kg were treated with the above composition diluted with 1000 ml of water and drummed in the presence of 4000 ml water. The pH of the pelt was checked to be 4.8. After attaining the pH, the float was drained and the hide was treated with 20 g of chrome stable fatliquor and 80 g of sodium methanoate. After a period of 20 min, 800 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 420 min. The pH was checked to be 3.6 to obtain chrome tanned leather.
Example 5
Composition was prepared by mixing of 18 ml of methanoic acid, 18 ml of ethanoic acid, 18 ml of propionic acid, 2 ml of methanol, 2 ml of ethanol, 0.8 ml of propan-2-ol, 1 ml of Polyoxyethylene (20) sorbitan monooleate and 0.2 ml of [2-[(2R,3S,4R)-3,4- dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.10. The color of the composition was transparent and it had good solubility in water.
Four delimed substrate (cow hide) to be tanned weighing 8 kg were treated with the above composition diluted with 3000 ml of water and drummed in the presence of 3200 ml water. The pH of the pelt was checked to be 4.8. After attaining the pH, the float was drained and the hide was treated with 8 g of acid stable fatliquor, 8 g of chrome stable fatliquor, 40 g of sodium methanoate and 40 g of sodium methanoate. After a period of 60 min, 240 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 360 min. The pH was checked to be 3.8 to obtain chrome tanned leather.
Example 6
Composition was prepared by mixing of 30 ml of methanoic acid, 15 ml of ethanoic acid, 26 ml of propionic acid, 1 ml of methanol, 0.5 ml of propan-2-ol, 0.5 ml of 2-[4-(2,4,4- trimethylpentan-2-yl)phenoxy]ethanol, 0.75 ml of Polyoxyethylene (20) sorbitan monooleate and 1 ml of [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.25. The color of the composition was transparent and it had good solubility in water.
Five delimed substrate (cow hide) to be tanned weighing 10 kg were treated with the above composition diluted with 750 ml of water and drummed in the presence of 4000 ml water. The pH of the pelt was checked to be 5.0. After attaining the pH, the float was drained and the hide was treated with 10 g of acid stable fatliquor, 10 g of universal fatliquor and 50 g of sodium methanoate. After a period of 40 min, 800 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 420 min. The pH was checked to be 3.9 to obtain chrome tanned leather.
Example 7
Composition was prepared by mixing of 40 ml of methanoic acid, 15 ml of ethanoic acid, 50 ml of propionic acid, 4 ml of methanol, 2 ml of ethanol, 4 ml of propan-2-ol, and 2 ml of polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.6. The color of the composition was transparent and it had good solubility in water.
One delimed substrate (cow hide) to be tanned weighing 2 kg was treated with the above composition diluted with 1000 ml of water and drummed in the presence of 800 ml water. The pH of the pelt was checked to be 5.8. After attaining the pH, the float was drained and the hide was treated with 20 g of cationic fatliquor, 20 g of chrome stable fatliquor and 6 g of sodium ethanoate. After a period of 60 min, 60 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 120 min. The pH was checked to be 4.4 to obtain chrome tanned leather. Example 8
Composition was prepared by mixing of 10 ml of methanoic acid, 90 ml of ethanoic acid, 5 ml of ethanol and 5 ml of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol together for a period of 5 min. pH of 10% solution of the composition was 2.20. The color of the composition was transparent and it had good solubility in water.
Five delimed substrate (cow hide) to be tanned weighing 10 kg were treated with the above composition diluted with 1000 ml of water and drummed in the presence of 4000 ml water. The pH of the pelt was checked to be 4.8. After attaining the pH, the float was drained and the hide was treated with 50 g of acid stable fatliquor and 50 g of sodium methanoate. After a period of 20 min, 600 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 300 min. The pH was checked to be 4.1 to obtain chrome tanned leather.
Example 9
Composition was prepared by mixing of 25 ml of methanoic acid, 20 ml of propionic acid, 2.5 ml of ethanol, 2 ml of 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol and 0.5 ml of Polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.00. The color of the composition was transparent and it had good solubility in water.
Ten delimed substrate (cow hide) to be tanned weighing 20 kg were treated with the above composition diluted with 3000 ml of water and drummed in the presence of 8000 ml water. The pH of the pelt was checked to be 4.8. After attaining the pH, the float was drained and the hide was treated with 20 g of cationic fatliquor, 100 g of acid stable fatliquor, 25 g of universal fatliquor, 50 g of chrome stable fatliquor, 25 g of sodium methanoate and 25 g of sodium ethanoate. After a period of 20 min, 1600 g of conventional chrome tanning agent (BCS) was added in 2 feeds with 30 min interval and drummed for a period of 540 min. The pH was checked to be 3.7 to obtain chrome tanned leather.
Example 10
Composition was prepared by mixing of 41 ml of propionic acid, 2.3 ml of propan-2-ol and 2.25 ml [2-[(2R,3S,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate together for a period of 5 min. pH of 10% solution of the composition was 2.58. The color of the composition was transparent and it had good solubility in water.
Five delimed substrate (goat skins) to be tanned weighing 5 kg were treated with the above composition diluted with 900 ml of water and drummed in the presence of 2000 ml water. The pH of the pelt was checked to be 5.3. After attaining the pH, the float was drained and the skins were treated with 15 g of Universal fatliquor and 27.5 g of sodium methanoate. After a period of 30 min, 1 kg of wattle GS powder was added in 2 feeds with 45 min interval and drummed for a period of 240 min. The pH was checked to be 3.80 to obtain vegetable tanned leather.
Example 11
Composition was prepared by mixing of 40 ml of methanoic acid, 15 ml of ethanoic acid, 50 ml of propionic acid, 4 ml of methanol, 2 ml of ethanol, 4 ml of propan-2-ol, and 2 ml of polyoxyethylene (20) sorbitan monooleate together for a period of 5 min. pH of 10% solution of the composition was 2.6. The color of the composition was transparent and it had good solubility in water.
One delimed substrate (cow hide) to be tanned weighing 2 kg was treated with the above composition diluted with 1000 ml of water and drummed in the presence of 600 ml water. The pH of the pelt was checked to be 5.6. After attaining the pH, the float was drained and the hide was treated with 20 g of cationic fatliquor, 20 g of Universal fatliquor and 6 g of sodium ethanoate. After a period of 30 min, 1 kg of wattle GS powder was added in 4 feeds with 20 min interval and drummed for a period of 600 min. The pH was checked to be 3.6 to obtain vegetable tanned leather.
ADVANTAGES OF THE PRESENT INVENTION
A versatile composition for facilitating waterless tanning.
Utilization of inherent moisture present in the delimed pet for tanning.
Reduces the use of water during pre-treatment step.
Eliminates the use of process water during tanning process.
Use of salt and the basification process are avoided.
Reduction of pollution load to the environment. Reduction of process time.
A suitable process for all kinds of raw materials.
Production of soft and flexible leather.
Strength characteristics of the crust leathers meet the standard norms.

Claims

CLAIMS:
1. A composition useful for pre-treatment in waterless tanning, wherein the said composition comprising: a) 90 to 95% (v/v) of an organic acid having carbon chain length in the range of Cl to C3 with transparent appearance;
b) 3 to 8% (v/v) of a primary alcohol having carbon chain length in the range of Cl to C3; and
c) 2 to 5% (v/v) of a non-ionic surfactant.
2. The composition as claimed in claim 1, wherein the organic acid used is selected from methanoic acid, ethanoic acid, propionic acid either individually or in different combinations.
3. The composition as claimed in claim 1, wherein the primary alcohol used is selected from methanol, ethanol, propan-2-ol, either individually or in different combinations.
4. The composition as claimed in claim 1, wherein the non-ionic surfactant used is selected from 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol, polyoxyethylene (20) sorbitan monooleate, [2- [(2R,3 S ,4R)-3 ,4-dihydroxyoxolan-2-yl] -2-hydroxyethyl] octadecanoate either individually or in different combinations.
5. A process for the preparation of the composition as claimed in claim 1, wherein the steps comprising mixing 90 to 95% (v/v) of organic acid having carbon chain length in the range of Cl to C3, 3 to 8% (v/v) of primary alcohol having carbon chain length in the range of Cl to C3 and 2 to 5% (v/v) of a non-ionic surfactant for a period in the range of 5 to 30 min to obtain the desired composition, wherein the said composition being water soluble, exhibiting a pH in the range of 1.8 to 2.6 as a 10% solution and characterized by transparent appearance.
6. An improved tanning process using the composition as claimed in claim 1, wherein the steps comprising: a) treating delimed substrate to be tanned with 0.1 to 5% w/w of the composition as claimed in claim 1 in the presence of 10 to 60% water to adjust the pH in the range of 4.8 to 5.8 followed by draining the float to obtain pre-treated substrate; b) treating the pre-treated substrate as obtained in step [a] with 0.2 to 2.0% of a conventional fatliquor and 0.2 to 1.0% of an alkali metal salt of organic acid having carbon chain of length not more than two for a period in the range of 20 to 60 min; c) treating the substrate as obtained in step [b] with 3 to 50% of conventional tanning agent added in one or more instalments for a period in the range of 90 to 600 min with simultaneous checking of pH in the range of 3.6 to 4.4 to obtain tanned leather.
7. The process as claimed in claim 6, wherein the conventional fatliquor used is selected from cationic fatliquor, acid stable fatliquor, universal fatliquor, chrome stable fatliquor, either individually or in different combinations.
8. The process as claimed in claim 6, wherein the alkali metal salt of organic acid used is selected from sodium methanoate, sodium ethanoate, either individually or in different combinations.
EP18734308.2A 2017-11-24 2018-05-30 A composition useful for pre-treatment in waterless tanning and corresponding tanning process Active EP3704275B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN201711042200 2017-11-24
PCT/IN2018/050347 WO2019102487A1 (en) 2017-11-24 2018-05-30 A composition useful for pre-treatment in waterless tanning and corresponding tanning process

Publications (2)

Publication Number Publication Date
EP3704275A1 true EP3704275A1 (en) 2020-09-09
EP3704275B1 EP3704275B1 (en) 2022-12-07

Family

ID=62749134

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18734308.2A Active EP3704275B1 (en) 2017-11-24 2018-05-30 A composition useful for pre-treatment in waterless tanning and corresponding tanning process

Country Status (4)

Country Link
EP (1) EP3704275B1 (en)
CN (1) CN111556901B (en)
BR (1) BR112020010308A2 (en)
WO (1) WO2019102487A1 (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19507572A1 (en) * 1995-03-03 1996-09-12 Helmut Geihsler Process for dressing animal hides or skins
ZA200900840B (en) * 2006-08-21 2010-05-26 Unilever Plc Detergent composition
ES2514522T3 (en) * 2009-12-17 2014-10-28 The Procter & Gamble Company Liquid acid hard surface cleaning composition
WO2012153203A1 (en) 2011-05-10 2012-11-15 Council Of Scientific & Industrial Research Chrome tanning process for leather making reusing exhaust chrome liquor
AR095971A1 (en) 2013-04-02 2015-11-25 Taminco Finland Oy A METHOD OF RESPECTFUL CURTIDE OF THE ENVIRONMENT
IN2014DE00085A (en) * 2014-01-13 2015-07-17 Council Scient Ind Res
US10280474B2 (en) * 2015-07-13 2019-05-07 Council Of Scientific & Industrial Research Dispersing agent composition for tanning of hides/skins and process for the preparation thereof

Also Published As

Publication number Publication date
CN111556901A (en) 2020-08-18
WO2019102487A1 (en) 2019-05-31
BR112020010308A2 (en) 2020-11-17
EP3704275B1 (en) 2022-12-07
CN111556901B (en) 2022-07-08

Similar Documents

Publication Publication Date Title
EP2179065B1 (en) Method of preserving hides and skins
KR101415399B1 (en) Agent and method for tanning skins and pelts
EP1565584A1 (en) An ecofriendly bio-process for leather processing
US20240002961A1 (en) Methods of preserving hides
KR20180030052A (en) Improved tanning methods of animal skins
EP3704275B1 (en) A composition useful for pre-treatment in waterless tanning and corresponding tanning process
EP3469104B1 (en) A process for producing leather
US6957554B2 (en) Dehairing and fiber opening process for complete elimination of lime and sodium sulfide
CN105238888A (en) Production technology for preparing wet white leather on basis of Zr-Al-Ti complex
EP3094754B1 (en) A composition for water free, pickle free chrome tanning of hides/skins
EP3322826B1 (en) A dispersing agent composition for tanning of hides/skins and a process for the preparation thereof
EP3430174B1 (en) Chrome tanning process
Yanan et al. Progress of key clean technologies in leather industry
US7651531B2 (en) Bio-tanning process for leather making
WO2018104968A1 (en) Tanning agent composition, its use and process for preparation thereof
CN110914460A (en) Dispersant composition for tanning and preparation process thereof
Castiello et al. Reutilization of skin fleshing-derived collagen hydrolizate in the re-tanning dyeing/fatliquoring phases
Slabbert Leather manufacture with wattle tannins
AU2003280066A1 (en) A lime-sulphide free dehairing and fibre opening process
Radnaeva et al. NEW TECHNOLOGIES FOR PROCESSING RAW MATERIALS IN CONDITIONS OF THE SIBERIA
Krishnamoorthy et al. USE OF GREENER CHEMICALS FOR ENVIRONMENTAL FRIENDLY TANNING PROCESSES.

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200602

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 1/72 20060101ALI20220609BHEP

Ipc: C14C 3/10 20060101ALI20220609BHEP

Ipc: C14C 3/28 20060101ALI20220609BHEP

Ipc: C14C 9/02 20060101ALI20220609BHEP

Ipc: C11D 3/20 20060101ALI20220609BHEP

Ipc: C14C 3/06 20060101AFI20220609BHEP

INTG Intention to grant announced

Effective date: 20220713

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1536332

Country of ref document: AT

Kind code of ref document: T

Effective date: 20221215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018043966

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20221207

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: 20221207

Ref country code: NO

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: 20230307

Ref country code: LT

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: 20221207

Ref country code: FI

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: 20221207

Ref country code: ES

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: 20221207

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1536332

Country of ref document: AT

Kind code of ref document: T

Effective date: 20221207

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

Ref country code: RS

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: 20221207

Ref country code: PL

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: 20221207

Ref country code: LV

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: 20221207

Ref country code: HR

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: 20221207

Ref country code: GR

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: 20230308

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: 20221207

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

Ref country code: SM

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: 20221207

Ref country code: RO

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: 20221207

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: 20230410

Ref country code: EE

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: 20221207

Ref country code: CZ

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: 20221207

Ref country code: AT

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: 20221207

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

Ref country code: SK

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: 20221207

Ref country code: IS

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: 20230407

Ref country code: AL

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: 20221207

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018043966

Country of ref document: DE

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

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

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: 20221207

26N No opposition filed

Effective date: 20230908

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

Ref country code: SI

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: 20221207

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602018043966

Country of ref document: DE

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: MC

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: 20221207

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230530

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20230531

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

Ref country code: MC

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: 20221207

Ref country code: LU

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

Effective date: 20230530

Ref country code: LI

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

Effective date: 20230531

Ref country code: CH

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

Effective date: 20230531

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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: 20230530

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: 20230530

Ref country code: DE

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

Effective date: 20231201

Ref country code: GB

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

Effective date: 20230530

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

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 PRESCRIBED TIME-LIMIT

Effective date: 20221207

Ref country code: FR

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

Effective date: 20230531

Ref country code: BE

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

Effective date: 20230531