EP1913164B1 - Agents for the production of leather - Google Patents
Agents for the production of leather Download PDFInfo
- Publication number
- EP1913164B1 EP1913164B1 EP06777879A EP06777879A EP1913164B1 EP 1913164 B1 EP1913164 B1 EP 1913164B1 EP 06777879 A EP06777879 A EP 06777879A EP 06777879 A EP06777879 A EP 06777879A EP 1913164 B1 EP1913164 B1 EP 1913164B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- formaldehyde
- weight
- condensates
- solution according
- 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.)
- Not-in-force
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
- C14C3/28—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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
- C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated
Definitions
- the present invention relates to an aqueous composition for the tanning of pelts or tanning, fatliquoring and dyeing of leather, a process for the tanning of pelts or tanning, fatliquoring and dyeing of leather and the leather treated by the process.
- Chrome-free tanning has become more important in recent years, particularly for the area of automotive leather. However, it is particularly difficult to produce leather with an intense dyeing which was tanned exclusively by an anionic method, with either vegetable or synthetic tanning agents. The anionic character of the tanned leather then evidently does not enable the leather to fix the dye as desired in sufficient concentration. Frequently, the tanner is therefore forced to increase the amount of dyes, tanning agents and fatliquoring agents. This results in substantially poorer liquor exhaustion. Another disadvantage of chrome-free tanning is the substantially higher cost factor.
- DE 28 56 628 describes a process for dyeing grain leather with anionic dyes for both anionically and cationically tanned leather, which is characterized in that the dyeing process is effected in the presence of two neutral surfactants in addition to the anionic dye.
- These surfactants are oxyethylated aliphatic alcohols and oxyethylated primary amines, which are present in a weight ratio of 4:1 to 1:4.
- the dye is first allowed to run for 5 to 90 minutes in the dye liquor separated from the tanning, and the surfactant mixture is then added which leads to a deepening of the colour. The subsequent fatliquoring of the leather can be effected in the presence of the surfactant mixture mentioned.
- the invention firstly relates to an aqueous solution of
- the tanning agents in the form of component B1) are known, cf. for example Ullmanns Enzyklopädie der ischen Chemie [Ullmann's Encyclopaedia of Industrial Chemistry], vol. 16, (4), 138 to 140 (1979 ), and can be prepared by processes as described in the references stated there.
- aromatic compounds naphthalene, biphenyl, terphenyl, phenols, cresols, 4,4'-dihydroxydiphenyl sulphone, ⁇ -naphthol, dihydroxybenzenes, resorcinol, 2,2'-bis(hydroxyphenyl)propane and diaryl ethers, such as diphenyl ether and ditolyl ether, which are sulphonated in a known manner.
- sulphonated aromatic compounds can be subjected, alone or in combination with a further aromatic, optionally likewise sulphonated compound, to a condensation with formaldehyde and/or urea.
- the component B1) is preferably selected from the abovementioned tanning agents b), e), h) and k).
- the oxyethylated aliphatic amines in the form of a component B2) are alkylamine ethoxylates of the following general formula (I). They are obtained by ethoxylation of aliphatic primary amines.
- the data for the chain length n and degree of ethoxylation m in the following general formula (I) for alkylamine ethoxylates are mean values.
- the component B2) is therefore a compound of the general formula (I): in which R denotes a linear or branched hydrocarbon radical having 8-20 C atoms and m denotes 5-80.
- Alkylamine ethoxylates of linear aliphatic primary amines such as, for example, octyl-, nonyl-, tridecyl-, oleyl-, or stearylamine, whose hydrocarbon radical R has 12 to 18 C atoms, the degree of ethoxylation m being 5 to 12, are preferably used.
- the oxyethylated aliphatic alcohols in the form of a component B3) are alkyl alcohol ethoxylates of the following general formula (II). These are prepared by ethoxylation of industrial fatty alcohols from fat hydrogenation or from alkanols of petrochemical (oxo alcohols) origin. Several moles of ethylene oxide are subjected to an addition reaction with one mole of fatty alcohol or oxo alcohol by preferably alkaline catalysis. Adducts having more than 80 ethylene oxide units are possible. This leads to a distribution between polyethylene glycol ethers of different degrees of ethoxylation (EO degree).
- EO degree polyethylene glycol ethers of different degrees of ethoxylation
- Homologues are defined as those AEOs which differ in the length of the alkyl radical and ethoxymers are defined as those AEOs which differ in the number of ethoxy units.
- the data for the chain length n and EO degree m in the following general formula for alkyl alcohol ethoxylates are therefore mean values.
- the component B3) is therefore a compound of the general formula (II): in which R denotes a linear or branched hydrocarbon radical having 8-20 C atoms and m denotes 5-80.
- Alkyl alcohol ethoxylates of linear aliphatic fatty alcohols, whose hydrocarbon radical R has 12 to 18 C atoms and in which the EO degree m is 5 to 12 are preferably used.
- composition according to the invention contains, as a proportion of B), a component B1) in an amount of 5-95% by weight, preferably 20-90% by weight, particularly preferably 40-90% by weight, especially preferably 55-90% by weight.
- composition according to the invention thus furthermore contains, as a proportion of B) and summing to 100% by weight, the component B2) in an amount of 95-5% by weight, preferably 80-10% by weight, particularly preferably 60-10% by weight, especially preferably 10-45% by weight.
- the component B2) can be partially replaced by the optional component B3).
- Use of the component B3) is not decisive for the improved dyeing according to the invention and regular distribution of tanning agents and fatliquoring agents and improved liquor exhaustion. However, it was found that an emphatically brilliant dyeing can be achieved with the use of component B3).
- An aqueous solution according to the invention consists of
- a composition according to the invention can be prepared by simply combining the components described above.
- the initially prepared component B1) is initially introduced into a vessel as an aqueous solution which is optionally adjusted with a base to a slightly basic pH of about 7.0 to 8.0, and subsequently aqueous solutions of the component B2) and optionally B3) are stirred in, clear, pale or brown solutions being obtained.
- the solutions are, if required, adjusted to an approximately neutral to moderately basic pH with the aid of bases, such as ammonia or alkali.
- the pH of the solution which is established in this manner should be above 6.0 and should not exceed 9.0.
- Preferred pH values are above 6.5, in particular above 6.8, and should not exceed a value of 8.5.
- the particularly preferred pH range extends from 7.0 to 8.0.
- the tanning agents in the form of the component B1) are therefore always used predominantly, as a rule completely, in the form of their salts, especially lithium, potassium or ammonium salts or in particular their sodium salts.
- Ammonium salts are understood as meaning salts which are derived from ammonia or primary, secondary and tertiary amines.
- a feature essential to the invention is therefore the circumstance that the naturally acidic compounds (free sulphonic acids) in the form of the component B1) are adjusted to an approximately neutral to moderately basic pH, and that furthermore a component B1) neutralized in this manner, together with a fatty amine in the form of the component B2), gives a clear and surprisingly storage-stable solution.
- the addition of an optional component B3) changes nothing about this.
- compositions according to the invention in the form of the solutions described above can advantageously be used in principle with all substrates for leather production.
- the following may be mentioned:
- the following amounts of the solutions according to the invention are suitable for use, for example for a 40-50% strength solution of composition as described above, and based on the shaved weight of the hide or of the leather:
- a wet-white leather pre-tanned in this manner is very suitable for further processing with tanning agents, for example with a solution according to the invention or other tanning agents, for the production of leathers free of heavy metals.
- a solution according to the invention are expedient for the main tanning, dyeing and fatliquoring on already pre-tanned leather in the presence of aldehydes or vegetable tanning agents.
- a substantial effect according to the invention is based on the possibility firstly of carrying out the steps of tanning, dyeing and fatliquoring without changing the liquor, and on the fact that secondly a very good liquor exhaustion is achieved and optimal dyeing can be achieved.
- ком ⁇ онент 4-10% by weight of a composition according to the invention are sufficient for retanning and for deepening the colour in dyeing with dyes.
- the invention therefore furthermore relates to a process for the pretanning of pelts or retanning of wet-white, wet-blue or vegetable-pretanned leather as a substrate, characterized in that a solution according to the invention is added to the aqueous liquor and said liquor is allowed to act on the substrate. Depending on the substrate, the solution according to the invention penetrates completely into the leather within 1 to 3 hours.
- the solution according to the invention is added during the pretanning but after the treatment with aldehyde. If the solution according to the invention is used during the retanning, it should be used firstly before the dyes and secondly together with the fatliquoring agents in order to achieve a deepening of colour and an improvement in the bath exhaustion.
- the present invention furthermore relates to the leathers produced by the process according to the invention or tanned using a composition according to the invention.
- Example 1 Agents consisting of the components B1), B2) and B3)
- Example 2 Agent consisting of the components B1) and B2)
- Example 3 Agent consisting of the components B1), B2) and B3):
- Example 4 Agent consisting of the components B1) and B2):
- Example 5 Agent consisting of the components B1), B2) and B3):
- the stated percentages relate to the salted weight of the leather hides or skins.
- Example B1 Use for the pretanning of pelts
- 100 parts of a pickled calf pelt are first treated with 2.5% of a 25% strength glutardialdehyde solution for 6 hours at 25°C in a rotating drum and then stirred for a further 2 hours with 5% of the composition according to preparation example A1.
- the pH is then adjusted to 4.0 with pulverized sodium bicarbonate or sodium formate.
- the leather thus treated (wet-white leather) is dewatered and is shaved to the desired thickness.
- This pre-tanned leather is outstandingly suitable for further processing with mineral, vegetable or synthetic tanning agents for the production of leather free of heavy metals.
- the dyeing is carried out with 2.2% of commercially available dye, such as C.I. Acid Black 210 and mixtures of this dye with other C.I. Acid Black dyes as secondary components.
- the dyes are allowed to act for 240 minutes.
- the mixture is acidified with 0.8% of formic acid after 60 minutes until complete exhaustion of the liquor.
- the bath is discharged and the leather is washed for 10 minutes with water at 50°C.
- 3% of product, according to example A5 is added for 20 minutes.
- 200% of water at 50°C and 3% of product according to example A5 are introduced into the drum, and the run time is 20 minutes.
- 12% of the fatliquoring agent are added and, after 60 minutes, the mixture is acidified with 1 % of formic acid for 45 minutes until complete exhaustion of the liquor.
- the leather thus obtained has good fullness and has a deep black brilliant hue.
- the wet-blue leather (cut to 1.0-1.2 mm) is rinsed, washed and neutralized to pH 5.5 in 150% of water containing a sodium bicarbonate/sodium formate mixture, in the usual manner.
- the preparatory fatliquoring (an about 50% strength aqueous solution of a fatliquoring agent based on sulphited natural and synthetic fats) is applied, the fatliquoring agent is discharged and the leather is washed for 10 minutes with 200% of water at 30°C.
- 100% of water at 30°C and 10% of commercially available phenol sulphonic acids as a tanning agent together with 4% of vegetable extract (tara extract) and 3% of fatliquoring agent (an about 50% aqueous solution of a fatliquoring agent based on sulphited natural and synthetic fats) are introduced into the drum, and the run time is 30 minutes.
- Retanning is effected with 6% of product according to example A2 for 20 minutes. Thereafter, 2.5% of C.I. Acid Black 210 is added and dyeing is effected; the process may take up to 60 minutes before the desired dyeing is achieved. After the fatliquoring, discharge is effected in the usual manner and 6% of commercially available phenol sulphonic acids as a tanning agent together with 2% of a vegetable extract are added for 45 minutes.
- the leather thus obtained has a level black dyeing in an optimal hue and fastness.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Description
- The present invention relates to an aqueous composition for the tanning of pelts or tanning, fatliquoring and dyeing of leather, a process for the tanning of pelts or tanning, fatliquoring and dyeing of leather and the leather treated by the process.
- Chrome-free tanning has become more important in recent years, particularly for the area of automotive leather. However, it is particularly difficult to produce leather with an intense dyeing which was tanned exclusively by an anionic method, with either vegetable or synthetic tanning agents. The anionic character of the tanned leather then evidently does not enable the leather to fix the dye as desired in sufficient concentration. Frequently, the tanner is therefore forced to increase the amount of dyes, tanning agents and fatliquoring agents. This results in substantially poorer liquor exhaustion. Another disadvantage of chrome-free tanning is the substantially higher cost factor.
-
DE 28 56 628 describes a process for dyeing grain leather with anionic dyes for both anionically and cationically tanned leather, which is characterized in that the dyeing process is effected in the presence of two neutral surfactants in addition to the anionic dye. These surfactants are oxyethylated aliphatic alcohols and oxyethylated primary amines, which are present in a weight ratio of 4:1 to 1:4. In the case of anionically tanned or retanned leather, the dye is first allowed to run for 5 to 90 minutes in the dye liquor separated from the tanning, and the surfactant mixture is then added which leads to a deepening of the colour. The subsequent fatliquoring of the leather can be effected in the presence of the surfactant mixture mentioned. - Since, as mentioned, chrome-free tanning has become more important in recent years, particularly in the area of automotive leather, there is considerable demand for more economical and more cost-efficient processes for the production of leather.
- It was surprisingly found that complete dyeing and a regular distribution of both tanning agents and fatliquoring agents are possible by the use of stable and approximately neutral solutions of compositions containing specific synthetic tanning agents and surfactants.
- This permits a generally improved liquor exhaustion, and the customary liquor change can be dispensed with. Thus, greater efficiency is achieved with respect to the amounts of tanning agents, dyes and fatliquoring agents used, and the economic advantages achieved thereby have a positive effect particularly in the case of chrome-free tanning, which is more expensive per se. Thus, a means for the treatment and production of leather is present which is suitable in particular for the production of chrome-free wet-white leathers, but can also advantageously be used for the production of wet-blue leathers.
- The invention firstly relates to an aqueous solution of
- A) 20-90% by weight of water and, dissolved therein,
- B) 10-80% by weight of a composition containing
- B1) a tanning aromatic compound having at least one sulpho group or a salt thereof, selected from
- a) Condensates of naphthalenesulphonic acid and formaldehyde;
- b) Formaldehyde condensates of 4,4'-dihydroxydiphenylsulphones with (hydroxy)arylsulphonic acids;
- c) Formaldehyde condensates of aromatic hydroxyl compounds containing sulpho groups with aralkyl halides;
- d) Urea-formaldehyde condensates of phenols and phenol sulphonic acids;
- e) Reaction products of phenol and a sulphonating agent, such as oleum, the molar ratio (phenol):(SO3) being (1):(0.8-2.2);
- f) Condensates of sulphonated diaryl ethers and formaldehyde;
- g) Condensates of sulphonated di- or terphenyls and formaldehyde;
- h) Condensates of 4,4'-dihydroxydiphenyl sulphone and sulphonated 4,4'-dihydroxydiphenyl sulphone with formaldehyde;
- i) Formaldehyde condensates of diaryl ether sulphonic acid and 4,4'-dihydroxydiphenyl sulphone;
- j) Formaldehyde condensates of phenol with aryl sulphonic acids or hydroxyarylsulphonic acids; and
- k) Formaldehyde condensates of dioxydiaryl sulphones with sulphites.
- B2) an aliphatic amine having a degree of oxyethylation of 5 to 80 and 8 to 20 carbon atoms and optionally
- B3) an aliphatic alcohol having a degree of oxyethylation of 5 to 80 and 8 to 20 carbon atoms, the solution having a pH of more than 6.0.
- B1) a tanning aromatic compound having at least one sulpho group or a salt thereof, selected from
- The tanning agents in the form of component B1) are known, cf. for example Ullmanns Enzyklopädie der technischen Chemie [Ullmann's Encyclopaedia of Industrial Chemistry], vol. 16, (4), 138 to 140 (1979), and can be prepared by processes as described in the references stated there.
- For example, the following may be mentioned as possible aromatic compounds: naphthalene, biphenyl, terphenyl, phenols, cresols, 4,4'-dihydroxydiphenyl sulphone, β-naphthol, dihydroxybenzenes, resorcinol, 2,2'-bis(hydroxyphenyl)propane and diaryl ethers, such as diphenyl ether and ditolyl ether, which are sulphonated in a known manner.
- These sulphonated aromatic compounds can be subjected, alone or in combination with a further aromatic, optionally likewise sulphonated compound, to a condensation with formaldehyde and/or urea.
- The component B1) is preferably selected from the abovementioned tanning agents b), e), h) and k).
- The oxyethylated aliphatic amines in the form of a component B2) are alkylamine ethoxylates of the following general formula (I). They are obtained by ethoxylation of aliphatic primary amines. The data for the chain length n and degree of ethoxylation m in the following general formula (I) for alkylamine ethoxylates are mean values. The component B2) is therefore a compound of the general formula (I):
- Alkylamine ethoxylates of linear aliphatic primary amines, such as, for example, octyl-, nonyl-, tridecyl-, oleyl-, or stearylamine, whose hydrocarbon radical R has 12 to 18 C atoms, the degree of ethoxylation m being 5 to 12, are preferably used.
- The oxyethylated aliphatic alcohols in the form of a component B3) are alkyl alcohol ethoxylates of the following general formula (II). These are prepared by ethoxylation of industrial fatty alcohols from fat hydrogenation or from alkanols of petrochemical (oxo alcohols) origin. Several moles of ethylene oxide are subjected to an addition reaction with one mole of fatty alcohol or oxo alcohol by preferably alkaline catalysis. Adducts having more than 80 ethylene oxide units are possible. This leads to a distribution between polyethylene glycol ethers of different degrees of ethoxylation (EO degree). Homologues are defined as those AEOs which differ in the length of the alkyl radical and ethoxymers are defined as those AEOs which differ in the number of ethoxy units. The data for the chain length n and EO degree m in the following general formula for alkyl alcohol ethoxylates are therefore mean values.
-
- Alkyl alcohol ethoxylates of linear aliphatic fatty alcohols, whose hydrocarbon radical R has 12 to 18 C atoms and in which the EO degree m is 5 to 12 are preferably used.
- The composition according to the invention contains, as a proportion of B), a component B1) in an amount of 5-95% by weight, preferably 20-90% by weight, particularly preferably 40-90% by weight, especially preferably 55-90% by weight.
- The composition according to the invention thus furthermore contains, as a proportion of B) and summing to 100% by weight, the component B2) in an amount of 95-5% by weight, preferably 80-10% by weight, particularly preferably 60-10% by weight, especially preferably 10-45% by weight.
- In the composition according to the invention, the component B2) can be partially replaced by the optional component B3). Use of the component B3) is not decisive for the improved dyeing according to the invention and regular distribution of tanning agents and fatliquoring agents and improved liquor exhaustion. However, it was found that an emphatically brilliant dyeing can be achieved with the use of component B3).
- If this special colour effect is desired, it is sufficient in practice if 1-30, preferably 5-20, particularly preferably 5-15, % by weight of the component B2) is replaced by a component B3).
- It is also possible to use mixtures of in each case 2 or more than 2 of the respective components as component B1), B2) and B3).
- An aqueous solution according to the invention consists of
- A) 20-90, preferably 35-65, particularly preferably 45-60, % by weight of water and, dissolved therein,
- B) 10-80, preferably 35-65, particularly preferably 40-55, % by weight of a composition described above.
- About 40-50% strength solutions of the compositions according to the invention are regarded as being suitable in practice.
- A composition according to the invention can be prepared by simply combining the components described above. For this purpose, the initially prepared component B1) is initially introduced into a vessel as an aqueous solution which is optionally adjusted with a base to a slightly basic pH of about 7.0 to 8.0, and subsequently aqueous solutions of the component B2) and optionally B3) are stirred in, clear, pale or brown solutions being obtained.
- As mentioned, the solutions are, if required, adjusted to an approximately neutral to moderately basic pH with the aid of bases, such as ammonia or alkali. The pH of the solution which is established in this manner should be above 6.0 and should not exceed 9.0. Preferred pH values are above 6.5, in particular above 6.8, and should not exceed a value of 8.5. The particularly preferred pH range extends from 7.0 to 8.0.
- The tanning agents in the form of the component B1) are therefore always used predominantly, as a rule completely, in the form of their salts, especially lithium, potassium or ammonium salts or in particular their sodium salts. Ammonium salts are understood as meaning salts which are derived from ammonia or primary, secondary and tertiary amines.
- A feature essential to the invention is therefore the circumstance that the naturally acidic compounds (free sulphonic acids) in the form of the component B1) are adjusted to an approximately neutral to moderately basic pH, and that furthermore a component B1) neutralized in this manner, together with a fatty amine in the form of the component B2), gives a clear and surprisingly storage-stable solution. The addition of an optional component B3) changes nothing about this.
- The compositions according to the invention in the form of the solutions described above can advantageously be used in principle with all substrates for leather production. The following may be mentioned:
- pickled hide;
- pre-tanned wet-white leather, treated for example, with aldehyde derivatives, such as, for example, glutardialdehyde or formaldehyde, or hydroxyalkylphosphine compounds, such as, for example, tetrakis(hydroxymethyl)phosphonium sulphate;
- leather treated with vegetable tanning agents; or
- chrome-tanned leather (wet-blue).
- Depending on substrate and intended use, the following amounts of the solutions according to the invention are suitable for use, for example for a 40-50% strength solution of composition as described above, and based on the shaved weight of the hide or of the leather:
- For pickled hide, the use of 2-10% by weight of a solution according to the invention for pretanning after the preliminary treatment with aldehydes or vegetable tanning agents is expedient. A wet-white leather pre-tanned in this manner is very suitable for further processing with tanning agents, for example with a solution according to the invention or other tanning agents, for the production of leathers free of heavy metals.
- For the production of leathers free of heavy metals, in particular chrome-free wet-white leathers, 30-40% by weight altogether of a solution according to the invention are expedient for the main tanning, dyeing and fatliquoring on already pre-tanned leather in the presence of aldehydes or vegetable tanning agents. A substantial effect according to the invention is based on the possibility firstly of carrying out the steps of tanning, dyeing and fatliquoring without changing the liquor, and on the fact that secondly a very good liquor exhaustion is achieved and optimal dyeing can be achieved.
- For chrome-tanned wet-blue leather, 4-10% by weight of a composition according to the invention are sufficient for retanning and for deepening the colour in dyeing with dyes.
- The invention therefore furthermore relates to a process for the pretanning of pelts or retanning of wet-white, wet-blue or vegetable-pretanned leather as a substrate,
characterized in that a solution according to the invention is added to the aqueous liquor and said liquor is allowed to act on the substrate. Depending on the substrate, the solution according to the invention penetrates completely into the leather within 1 to 3 hours. - Depending on the aim, it is advisable to add the solution according to the invention during the pretanning but after the treatment with aldehyde. If the solution according to the invention is used during the retanning, it should be used firstly before the dyes and secondly together with the fatliquoring agents in order to achieve a deepening of colour and an improvement in the bath exhaustion.
- The present invention furthermore relates to the leathers produced by the process according to the invention or tanned using a composition according to the invention.
- 1200 parts of a molten reaction product of phenol and oleum (20%), the molar ratio (phenol):(SO3) being 1:1.0 to 1.1, are dissolved in 288 parts of water and adjusted to a pH of 7.3 to 7.5 with 557 parts of 50% strength sodium hydroxide solution, and then 194 parts of 37% strength formaldehyde solution are added and condensation is then effected at 105°C until (about 6 hours) a sample which - diluted with a little water - remains clear on acidification with dilute sulphuric acid to a pH of 3.5. A solution of 1100 parts of water, 175 parts of tallow fatty amine ethoxylate with 8 mol of ethylene oxide and 20 parts of isodecyl alcohol with 7 mol of ethylene oxide is then added to the reaction mass. A clear, pale solution which has a pH of 7.0 to 8.0 is obtained. The solids content is about 48% by weight and is outstandingly suitable for the tanning of leather.
- 1200 parts of a molten reaction product of phenol and oleum (20%), the molar ratio (phenol):(SO3) being 1:0.8 to 0.9, are melted at 90°C with 42 parts of water, and 14.4 parts of urea are added. After cooling to 55°C, 38.5 parts of a 37% strength formaldehyde solution are added dropwise in the course of 2 hours and stirring is effected for about a further 4 hours until the condensate has dissolved in water to give a clear solution. The reaction product obtained is adjusted to a pH of 7.3 to 7.5 with 38 parts of 50% strength sodium hydroxide solution.
- A solution of 415 parts of water and 265 parts of tallow fatty amine ethoxylate with 8 mol of ethylene oxide is then added to the reaction mass. A clear, pale solution which has a pH of 7.0 to 8.0 is obtained. The solids content is about 45% by weight and is outstandingly suitable for the retanning of dark dyeings.
- 100 parts of naphthalenesulphonic acid are heated with 55.8 parts of a molten reaction product of phenol and oleum (20%), the molar ratio (phenol):(SO3) being 1:1.40 to 1.45, and 100 parts of water and 30 parts of formaldehyde to 105°C to 110°C for about 3 hours until the condensate dissolves in water to give a clear solution. Thereafter, the solution is adjusted to a pH of 7.0 to 8.0 with 80 parts of a 25% strength ammonia solution, and a solution of 100 parts of water, 30 parts of tallow amine with 6 mol of ethylene oxide and 5 parts of isodecyl alcohol with 7 mol of ethylene oxide is added. A clear, brown solution which has a pH of 7.0 to 8.0 is obtained. The solids content is about 43%. The solution is outstandingly suitable for the retanning of chrome-free leather.
- 135 parts of dihydroxydiphenyl sulphone (59% strength) are heated with 43.5 parts of formaldehyde (37% strength) and 26 parts of sodium sulphite in a closed reactor for about 3 hours to 130°C until the condensate dissolves in water to give a clear solution. 75 parts of water and 20 parts of tallow fatty amine ethoxylate with 8 mol of ethylene oxide are then added. A clear, brown solution which has a pH of 7.0 to 8.0 is obtained. The solids content is about 45%. The solution is outstandingly suitable for the tanning and retanning of chrome-free leather.
- Sodium hydroxide solution (30% strength) and 88 parts of formaldehyde solution (37% strength) are carefully added to 400 parts of a molten reaction product of phenol and oleum (20%), the molar ratio (phenol):(SO3) being 1:0.80 to 0.90, and condensation is then effected at 100°C to 105°C until (about 6 hours) a sample, diluted with a little water, remains clear on acidification with dilute sulphuric acid to a pH of 3.5. A solution of 240 parts of water, 35 parts of tallow fatty amine ethoxylate with 8 mol of ethylene oxide and 9 parts of isodecyl alcohol with 7 mol of ethylene oxide is then added to the reaction mass. A clear, pale solution which has a pH of 7.0 to 8.0 is obtained. The solids content is about 48% by weight and is outstandingly suitable for the pretanning, tanning and retanning of leather:
- The stated percentages relate to the salted weight of the leather hides or skins.
- 100 parts of a pickled calf pelt are first treated with 2.5% of a 25% strength glutardialdehyde solution for 6 hours at 25°C in a rotating drum and then stirred for a further 2 hours with 5% of the composition according to preparation example A1. The pH is then adjusted to 4.0 with pulverized sodium bicarbonate or sodium formate.
- The leather thus treated (wet-white leather) is dewatered and is shaved to the desired thickness. This pre-tanned leather is outstandingly suitable for further processing with mineral, vegetable or synthetic tanning agents for the production of leather free of heavy metals.
- 200% of water at 30°C and 0.5 % of formic acid are acidified together with the hide pretanned with 1% of glutardialdehyde (cut to 0.9-1.0 mm) for the duration of 15 minutes. 6% of the product from example A5 are then added and said product is allowed to act for 20 minutes.
- 4% of the prepared fatliquoring agent (an about 50% strength aqueous solution of a fatliquoring agent based on sulphited natural and synthetic fats) are then added and, after 20 minutes, 25% of the product from example A5 are added.
- The dyeing is carried out with 2.2% of commercially available dye, such as C.I. Acid Black 210 and mixtures of this dye with other C.I. Acid Black dyes as secondary components. The dyes are allowed to act for 240 minutes. The mixture is acidified with 0.8% of formic acid after 60 minutes until complete exhaustion of the liquor. The bath is discharged and the leather is washed for 10 minutes with water at 50°C.
- 3% of product, according to example A5, is added for 20 minutes. For the fatliquoring, 200% of water at 50°C and 3% of product according to example A5 are introduced into the drum, and the run time is 20 minutes. 12% of the fatliquoring agent are added and, after 60 minutes, the mixture is acidified with 1 % of formic acid for 45 minutes until complete exhaustion of the liquor.
- The leather thus obtained has good fullness and has a deep black brilliant hue.
- The wet-blue leather (cut to 1.0-1.2 mm) is rinsed, washed and neutralized to pH 5.5 in 150% of water containing a sodium bicarbonate/sodium formate mixture, in the usual manner.
- The preparatory fatliquoring (an about 50% strength aqueous solution of a fatliquoring agent based on sulphited natural and synthetic fats) is applied, the fatliquoring agent is discharged and the leather is washed for 10 minutes with 200% of water at 30°C. For the retanning, 100% of water at 30°C and 10% of commercially available phenol sulphonic acids as a tanning agent together with 4% of vegetable extract (tara extract) and 3% of fatliquoring agent (an about 50% aqueous solution of a fatliquoring agent based on sulphited natural and synthetic fats) are introduced into the drum, and the run time is 30 minutes. Retanning is effected with 6% of product according to example A2 for 20 minutes. Thereafter, 2.5% of C.I. Acid Black 210 is added and dyeing is effected; the process may take up to 60 minutes before the desired dyeing is achieved. After the fatliquoring, discharge is effected in the usual manner and 6% of commercially available phenol sulphonic acids as a tanning agent together with 2% of a vegetable extract are added for 45 minutes.
- 200% of water at 50°C are added and, after 30 minutes, 2% of formic acid are introduced for 40 minutes.
- The leather thus obtained has a level black dyeing in an optimal hue and fastness.
Claims (10)
- Aqueous solution ofA) 20-90% by weight of water and, dissolved therein,B) 10-80% by weight of a composition containingB1) a tanning aromatic compound having at least one sulpho group or a salt thereof, selected from:a) Condensates of naphthalenesulphonic acid and formaldehyde;b) Formaldehyde condensates of 4,4'-dihydroxydiphenylsulphones with (hydroxy)arylsulphonic acids;c) Formaldehyde condensates of aromatic hydroxyl compounds containing sulpho groups with aralkyl halides;d) Urea-formaldehyde condensates of phenols and phenol sulphonic acids;e) Reaction products of phenol and a sulphonating agent, such as oleum, the molar ratio (phenol):(SO3) being (1):(0.8=2.2);f) Condensates of sulphonated diaryl ethers and formaldehyde;g) Condensates of sulphonated di- or terphenyls and formaldehyde;h) Condensates of 4,4'-dihydroxydiphenyl sulphone and sulphonated 4,4'-dihydroxydiphenyl sulphone with formaldehyde;i) Formaldehyde condensates of diaryl ether sulphonic acid and 4,4'-dihydroxydiphenyl sulphone;j) Formaldehyde condensates of phenol with aryl sulphonic acids or hydroxyarylsulphonic acids; andk) Formaldehyde condensates of dioxydiaryl sulphones with sulphites,B2) a compound of the general formula (I):
and optionally - Solution according to Claim 1, characterized in that the component B1) is selected from b), e), h) and k).
- Solution according to Claim 1, characterized in that the component B2) is present as a lithium, potassium or ammonium salt or in particular as a sodium salt.
- Solution according to Claim 1, characterized in that alkylamine ethoxylates of linear aliphatic primary amines, whose hydrocarbon radical R has 12 to 18 C atoms, the degree of ethoxylation m being 5 to 12, are used as component B2).
- Solution according to Claim 1, characterized in that alkyl alcohol ethoxylates of linear aliphatic primary alcohols, whose hydrocarbon radical R has 12 to 18 C atoms, the degree of ethoxylation m being 5 to 12, are used as component B3).
- Solution according to Claim 1, characterized in that the composition contains
a component B1) in an amount of 5-95, preferably 20-90, % by weight and
a component B2) in an amount of 95-5, preferably 10-80, % by weight. - Solution according to Claim 6, characterized in that, in the composition, 1-30, preferably 5-20, particularly preferably 5-15, % by weight of the component B2) is replaced by a component B3).
- Solution according to Claim 1, characterized in that the pH of the solution is above 6.5 and does not exceed 9.0, preferably is above 6.8 and does not exceed 8.5, in particular ranges from 7.0 to 8.0.
- Solution according to Claim 1, which consists ofA) 35-65, preferably 45-60, % by weight of water and, dissolved therein,B) 35-65, preferably 40-55, % by weight of the composition.
- Process for the pretanning of pelts or retanning of wet-white, wet-blue or vegetable-pre-tanned leather as a substrate, characterized in that a solution according to any of Claims 1 to 9 is added to the aqueous liquor and said liquor is allowed to act on the substrate.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH12352005 | 2005-07-25 | ||
PCT/EP2006/064487 WO2007012606A1 (en) | 2005-07-25 | 2006-07-21 | Agents for the production of leather |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1913164A1 EP1913164A1 (en) | 2008-04-23 |
EP1913164B1 true EP1913164B1 (en) | 2008-11-19 |
Family
ID=35478893
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06777879A Not-in-force EP1913164B1 (en) | 2005-07-25 | 2006-07-21 | Agents for the production of leather |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1913164B1 (en) |
AR (1) | AR057081A1 (en) |
AT (1) | ATE414796T1 (en) |
DE (1) | DE602006003772D1 (en) |
WO (1) | WO2007012606A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104450993A (en) * | 2014-12-24 | 2015-03-25 | 上海金狮化工有限公司 | Retanning agent and preparation method thereof |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011131542A1 (en) * | 2010-04-21 | 2011-10-27 | Basf Se | Products, method for producing same, and use thereof |
US9924816B2 (en) | 2010-06-08 | 2018-03-27 | Gpcp Ip Holdings Llc | System and method for holding cutlery together |
US8839522B2 (en) | 2010-08-12 | 2014-09-23 | Dixie Consumer Products Llc | Interlocking cutlery and related methods |
CA2805734C (en) | 2010-08-24 | 2018-09-18 | Dixie Consumer Products Llc | Removable strip for packaging cutlery and related methods |
MX342721B (en) | 2010-12-10 | 2016-10-11 | Dixie Consumer Products Llc | Dispensing mechanism for utensil dispenser and related methods. |
MX2013005936A (en) | 2010-12-10 | 2013-09-26 | Dixie Consumer Products Llc | Screw drive for dispensing cutlery and related methods. |
CA2819646C (en) | 2010-12-14 | 2019-10-01 | Dixie Consumer Products Llc | Belt drive for dispensing cutlery and related methods |
US9439518B2 (en) | 2011-08-19 | 2016-09-13 | Dixie Consumer Products Llc | Cutlery dispenser |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2856628C2 (en) * | 1978-12-29 | 1980-04-24 | Basf Ag, 6700 Ludwigshafen | Process for dyeing grain leather |
CH671052A5 (en) * | 1985-01-30 | 1989-07-31 | Sandoz Ag | |
US5300121A (en) * | 1987-04-28 | 1994-04-05 | Commonwealth Scientific And Industrial Research Organisation | Process for the treatment of wool skins |
-
2006
- 2006-07-21 AT AT06777879T patent/ATE414796T1/en not_active IP Right Cessation
- 2006-07-21 DE DE602006003772T patent/DE602006003772D1/en active Active
- 2006-07-21 EP EP06777879A patent/EP1913164B1/en not_active Not-in-force
- 2006-07-21 WO PCT/EP2006/064487 patent/WO2007012606A1/en not_active Application Discontinuation
- 2006-07-25 AR ARP060103196A patent/AR057081A1/en unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104450993A (en) * | 2014-12-24 | 2015-03-25 | 上海金狮化工有限公司 | Retanning agent and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
DE602006003772D1 (en) | 2009-01-02 |
EP1913164A1 (en) | 2008-04-23 |
AR057081A1 (en) | 2007-11-14 |
WO2007012606A1 (en) | 2007-02-01 |
ATE414796T1 (en) | 2008-12-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1913164B1 (en) | Agents for the production of leather | |
AU689984B2 (en) | Aqueous composition for the pretanning of hide pelts or retanning of leather | |
US20060185094A1 (en) | Condensates containing acid groups | |
US8163398B2 (en) | Leather production method and products suited thereof | |
EP1831405B1 (en) | Composition for the treatment of leather | |
US5264000A (en) | Aqueous solutions of synthetic tanning agents | |
US5256317A (en) | Compositions for the treatment of leather and furs | |
US4245996A (en) | Condensation products of terphenylsulphonic acids, naphthalenesulphonic acids, bis-(4-hydroxyphenyl) sulphone and formaldehyde | |
GB2314342A (en) | Aqueous composition for pre-tanning pelts or re-tanning leather | |
US20040148707A1 (en) | Condensates for the retanning of Fe-tanned leather | |
US6881356B2 (en) | Method for producing tanning agents containing sulphone | |
US2315951A (en) | Condensation products of diaryl ether sulphonic acids with formaldehyde | |
US2716098A (en) | Water soluble condensation products with a tanning action | |
US4390340A (en) | Tanning agent, its preparation and its use for retanning | |
TW201326401A (en) | Process for dyeing collagen fibre substrates | |
US2129553A (en) | Tanning material | |
EP1656460B1 (en) | A process for the preparation of a synthetic tanning agent | |
US1919756A (en) | Process of tanning | |
US3029212A (en) | Synthetic tanning agent and process for preparing same | |
US1945461A (en) | Method of retanning of chrome leather | |
GB2194537A (en) | Mixtures of phosphoric acid partial esters | |
US4834896A (en) | Phosphoric acid partial ester compositions and method of fatting leather therewith | |
EP0362134B1 (en) | Leather treating agent | |
GB2070632A (en) | Tanning | |
US3482925A (en) | Process for the rapid tanning of leather |
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: 20080124 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK 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 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 602006003772 Country of ref document: DE Date of ref document: 20090102 Kind code of ref document: P |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20081119 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20090301 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: 20081119 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: 20081119 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20090319 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: 20081119 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: 20081119 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: 20081119 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: 20081119 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: 20081119 |
|
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: 20081119 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: 20081119 Ref country code: BG 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: 20090219 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: 20081119 Ref country code: BE 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: 20081119 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20090420 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: 20090219 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: 20081119 |
|
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: 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: 20081119 |
|
26N | No opposition filed |
Effective date: 20090820 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20090731 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20100331 |
|
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: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090731 |
|
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: 20090721 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20090220 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20100721 |
|
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: 20081119 |
|
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: 20100731 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100731 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090721 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU 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: 20090520 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100721 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR 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: 20081119 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY 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: 20081119 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20160722 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602006003772 Country of ref document: DE Representative=s name: MAUCHER JENKINS, DE Ref country code: DE Ref legal event code: R082 Ref document number: 602006003772 Country of ref document: DE Representative=s name: MAUCHER JENKINS PATENTANWAELTE & RECHTSANWAELT, DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602006003772 Country of ref document: DE |
|
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: 20180201 |