Classifications

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

Definitions

• the present invention relates to low-VOC fatliquoring agents, their use in the manufacture and / or treatment of leather and hides, and to processes for producing and / or treating leather and hides with the fatliquoring agents of the invention.
• leather fatliquoring agents soften the leather, increase its fullness and firmness, and protect it against moisture, dirt, and chemical influences from the outside (see H. Herfeld, "Library of the Leather” 1985, Volume 4, p. 13 ff .).
• Commercially available fatliquoring agents generally consist of fatty substances, such as native fats, native oils, waxes, resins and their derivatives and / or petroleum fractions and their derivatives, and waxy products such as "wool fat", in crude, purified and / or prepared (lanolin) Form (see H. Herfeld, "Library of the Leather” 1985, Volume 4, p. 59 ff .).
• the greasing substances can - if desired - be chemically modified, ie present in a modified chemical structure.
• the chemical modification of the fatty substances is usually that the double bonds contained in these substances are at least partially subjected to addition reactions or oxidation reactions. Frequently made modifications exist, for example, in the addition of sulfites, whereby sulfonic acid groups are introduced into the fatty substances, or in the air oxidation, whereby oxygen functions are introduced and sometimes also oligomerizations occur. But it is also possible (partial) hydrolysis of the fats, transesterifications and the like modification reactions.
• DIN 75201 defines “fogging” as the condensation of vaporized components from the vehicle interior trim such as the car upholstery leather on the glass panes, in particular on the windshield. This can lead to a deteriorated view through the windshield, especially during night driving, and thus to a security risk.
• the fogging behavior of leather is characterized by a gravimetric and a reflectometric method.
• the aqueous dispersions used in the leather treatment are substantially free of organic solvents and contain an amphiphilic copolymer.
• This copolymer consists of a predominant proportion of at least one hydrophobic monomer and a small proportion of at least one hydrophilic monomer.
• amphiphilic copolymers are preferably carried out by emulsion polymerization in aqueous solution.
• emulsion polymerization due to the different hydrophilicity of the monomers to be used, naturally problems arise in the copolymerization behavior. In extreme cases, this can lead to the monomers undesirably forming homopolymers each by themselves.
• Another consequence of the unfavorable solution conditions is a complicated work-up for the destruction of unreacted monomers.
• an emulsifier in the cited Examples used was lauryl sulfate
• polymers containing both pendant hydrophobic groups and pendant hydrophilic alkoxylated groups are obtained by carrying out after the actual polymerization process - known in the art - derivatization reactions.
• polymers are preferably prepared from simple monomers such as acrylamide and / or acrylic acid by conventional polymerization and then derivatized with a mixture of primary or hydrophobic amines or primary or secondary alkoxylated amines.
• the described polymers are used as thickeners and soil release agents. Their use in leather treatment is not described.
• Polymeric fatliquoring agents are prepared by polymerization of acrylic acid and / or methacrylic acid and / or their acid chlorides and / or their anhydrides with other copolymerizable water-soluble monomers and with copolymerizable water-insoluble monomers and subsequent reaction of the polymers thus obtained with amines.
• DIN 75201 B gravimetric test
• leathers treated with these polymeric fatliquoring agents have fogging values of 1.2 mg and 1.5 mg, respectively.
• Magnopal ® SOF flaving polymer fatliquoring agent Stockhausen GmbH & Co.
• the reflectometric values according to DIN 75201 A of the polymeric fatliquoring agents are 51% and 55% respectively, those of the comparative products 34% and 40%, respectively.
• hydrophobic monomers which are used are longer-chain alkenes or (meth) acrylic esters of C 4 -C 12 -alkanols or vinyl esters of C 4 -C 12 -carboxylic acids.
• the substances give good fogging values; However, there is no information about the Badauszehrung.
• the preparation of the amphiphilic copolymers is preferably carried out by aqueous emulsion polymerization.
• EP-B 0 753 585 describes a low-fogging surface treatment for furniture leather, in which specially treated native oils, which have less than 3% of fatty acid components with less than 16 carbon atoms, act as the basis for fatliquors.
• Native oils used are soybean, lard, safflower and sunflower oils. The said native oils are first distilled to remove the unwanted low molecular weight components and then reacted with hydrogen sulfite or bisulfate to improve emulsifiability. Then the (partially) functionalized oils are emulsified and applied.
• component A is a C 6 to C 14 alkanol alkoxylated with 4 to 12 AO units, or a mixture of several such alkanols
• component B is a C 12 -C 24 fatty alcohol mixture alkoxylated with 15 to 40 AO units and component C a C 12 to C 24 fatty alcohol mixture alkoxylated with 50 to 100 AO units.
• the AO units are expediently alkylene oxide units having 2 to 4, preferably 2 to 3, carbon atoms.
• the building blocks of the polyether chains can all be identical or different and, if they are different, can be arranged randomly or in blocks.
• the proportions by weight of the components in the emulsifier composition for component A are from 20 to 60, preferably from 25 to 50, in particular from 28 to 40,% by weight, for component B from 20 to 70, preferably from 25 to 60, in particular from 30 to 45,%. -% and for the component C 10 to 50, preferably 15 to 40, especially 22 to 32 wt .-% of the total weight of the composition.
• the object of the present invention is to provide a fatliquoring agent which largely avoids the disadvantages of the prior art.
• the with these fatliquors treated leather should be low in VOC and optionally have sufficient fastness to light and heat.
• (hetero) cycloaliphatic C 4 - to C 30 -hydrocarbon radicals is understood as meaning saturated, mono- or polyunsaturated C 4 - to C 30 -hydrocarbon rings in which, if appropriate, methylene groups -CH 2 - denoted by -O-, - N (H) - and / or -S- are replaced, and optionally one or more linear C 1 - to C 10 alkyl radicals, linear C 1 - to C 10 alkylene bridges, branched C 3 - to C 10 -alkyl radicals and / or branched C 3 - to C 10 -alkylene bridges carry, which are optionally mono- or polyunsaturated.
• cycloaliphatic C 4 - to C 30 -hydrocarbon radicals are in the scope of the invention, optionally with one or more - saturated, monounsaturated or polyunsaturated - linear C 1 - to C 10 -alkyl radicals and / or branched C 3 - to C 10 alkyl radicals substituted, lactones and lactams and urea derivatives understood.
• the term includes both mono- and polycyclic ring systems, in particular bicyclic and tricyclic ring systems.
• the term includes both mono- and polycyclic ring systems, in particular bicyclic and tricyclic ring systems.
• Explicit examples which are not intended to be limiting, however, are phenyl, toluyl, cumyl, naphthyl, phenanthryl, pyridyl, indyl, optionally with one or more linear C 1 - to C 10 -alkyl radicals, linear C 1 - to C 10 -alkylene bridges , branched C 3 - to C 10 -alkyl radicals and / or branched C 3 - to C 10 -alkylene bridges are substituted.
• the fatliquoring agents according to the invention are particularly suitable for the fatliquoring of leathers and skins, since the leathers and skins treated in this way show low fogging.
• the fatliquoring agents of the invention are used in Cr-free tanned leathers and skins.
• Cr-free tanning is understood to mean all the tanning processes of leathers and skins in which no Cr (III) is used for tanning. In particular, it means processes known to the person skilled in the art, such as vegetable tanning, syntan tanning and wet-white tanning.
• component A modified by oxidation and / or sulfitation native oils.
• modified native oils which have a relatively high degree of oxidation and a relatively low degree of sulfitation.
• Fats of vegetable or animal origin, in particular glycerides of natural fatty acids, with a sufficient proportion of unsaturated acids are expediently used as native oils.
• Highly suitable native oils are those having an iodine value of about 10 to about 200. In the lower portion of this range, e.g. Stearic and tung oil, in the upper section in particular the fish oils and chaulmoogra oil.
• Preferred are native oils with iodine numbers of about 30 to about 120, especially from 40 to 85.
• Examples of particularly preferred native oils are fish oil, foot oil, lard oil, soybean oil, rapeseed oil, nut oil, olive oil and castor oil.
• the sulfite products or oxidation products of the monounsaturated or polyunsaturated fats are formed by the reaction of the olefinic double bonds present in the fats with the sulfiting and / or oxidation reagents. All double bonds present in the fats or only a part of them can react.
• oxidation reagent air at temperatures of 60 to 80 ° C is used as the oxidation reagent.
• the oxidation can also be carried out by other methods known in the art.
• a relatively high degree of oxidation in the sense of this invention is when ⁇ d, the difference in the specific gravity of the oil or fat before and after the oxidation, in the range of 0.01 to 0.1 g / ml, preferably from 0.03 to 0 , 05 g / ml.
• the sulfitation is generally carried out by reaction in aqueous bisulfite. However, it can also be done by other species known in the art.
• a relatively low degree of sulfitation in the context of this invention is present when the native oil with 2 to 8 wt .-%, preferably with 3 to 5 wt .-%, of its weight with a sulfite, calculated as sodium bisulfite (Na 2 S 2 O 5 ) has been implemented.
• L n R are used with a total of at least 20 C-atoms, in particular with a total of at least 28 C-atoms.
• L represents one of the following radicals: and / or n is an integer from 1 to 4.
• Preferred monovalent radicals R are linear or branched saturated alkyl radicals and alkoxycarbonyl-substituted linear or branched alkyl radicals - (C m H 2m ) -C (O) OX 1 , where m is an integer from 0 to 28, and X 1 is a linear Alkyl radical having 1 to 28 carbon atoms or a branched alkyl radical having 3 to 28 carbon atoms.
• Further preferred monovalent radicals R are connected via linear C 1 - to C 4 -alkylene bridges or branched C 3 - to C 4 -alkylene bridges connected with L, optionally with (un) saturated linear C 1 - to C 10 -alkanols or (un) saturated branched C 4 - to C 10 -alkanols etherified or esterified with (un) saturated linear C 1 - to C 10 -carboxylic acids or (un) saturated branched C 4 - to C 10 -carboxylic acids, phenol derivatives which am Phenyl ring with one or more linear C 1 - to C 10 - and / or branched C 3 - to C 10 -alkyl radicals and / or C 6 - to C 12 -cycloalkyl radicals may be substituted.
• the etherified or esterified phenol derivatives are preferably those radicals L- mentioned above which are substituted by linear C 1 - to C 4 -alkylene bridges or branched C 3 - to C 4 -alkylene bridges, where the hydroxy group is substituted by (un ) saturated linear C 1 - to C 10 -alkanols or (un) saturated branched C 4 - to C 10 -alkanols or etherified with (un) saturated linear C 1 - to C 10 -carboxylic acids, or (un) saturated branched C 4 - is esterified to C 10 carboxylic acids.
• Preferred divalent radicals R are saturated, mono- or polyunsaturated, linear C 1 - to C 18 -alkylene groups and branched C 3 - to C 18 -alkylene groups, which are optionally substituted in the hydrocarbon chain of the alkylene groups ester groups -C (O) O- and / or amide groups -C (O) N (H) and / or hydrazide groups -C (O) -N (H) -N (H) -C (O) - and / or where appropriate in the hydrocarbon chain of the alkylene groups one or more methylene groups -CH 2 - by -S-, -O- or -N (H) -park.
• Further preferred divalent radicals R are -S-, -O- and -N (H) -.
• Preferred trivalent radicals R are trivalent linear C 3 to C 10 or branched, (a) cyclic, (un) saturated C 4 to C 10 or aromatic C 6 to C 10 hydrocarbon radicals in which three protons are in each case represented by the Rest L are replaced.
• preferred Hydrocarbon radicals are existing methylene groups -CH 2 - optionally substituted by - N (H) - replaced.
• the attachment of the radical L can also take place via linear C 1 - to C 10 -alkylene bridges or branched C 3 - to C 10 -alkylene bridges to such a nitrogen atom.
• methylene groups -CH 2 - may be replaced by -O-, -N (H) - or -S-.
• Particularly preferred trivalent radicals R are selected from the following group:
• Preferred R are tetravalent, substituted with alkylcarbonyloxy groups and / or O and / or N (H) units, saturated linear C 3 - to C 20 - or branched aliphatic C 4 - to C 20 hydrocarbon radicals, in which four Protons are replaced by the radicals L.
• R C (CH 2 -OC (O) -CH 2 -CH 2 -) 4 .
• the fatliquoring agents according to the invention preferably contain at least 40% by weight, more preferably at least 50% by weight, very preferably at least 70% by weight, of a component A or of a mixture of components A and at most 1% by weight, more preferably at most 0.5 wt .-%, most preferably at most 0.2 wt .-%, of a component B or a mixture of components B, based on the total weight of the fatliquoring agent.
• the fatliquoring agents according to the invention can be used undiluted or, depending on the wishes of the users, in the form of aqueous dispersions (aqueous liquors), preferably with solids contents of 40 to 80% by weight, preferably with solids contents of 50 to 80% by weight, particularly preferably with solids contents of 60 to 75 wt .-% are provided.
• aqueous dispersions aqueous liquors
• the components of the preferred fatliquoring agents according to the invention namely the moficated native oils according to the invention and the stabilizers according to the invention, can be added to the fatliquoring liquors together or separately in any order.
• the invention thus also relates to a process for the fatliquoring of leather and hides by treatment with the abovementioned aqueous liquors.
• the invention further relates to the use of the described fatliquoring agent according to the invention in leather production.
• Their use serves to soften the Leather, to increase its fullness and strength and to protect against moisture, dirt, and chemical influences from the outside.
• the presence of the stabilizers according to the invention leads to low fogging values.
• the composition of the conventional fatliquoring agents A1 to A5 and B1 to B5 used and the fatliquoring agents C1 to C5 and D1 to D5 used according to the invention are shown in Tables 1 and 3.
• the proportion of the individual components is given in% by weight, based on the total fatliquoring agent, and can be found in Tables 2 and 4.
• the non-ionic surfactant Lutensol® AT 25 from BASF AG in Ludwigshafen is a G 16 to C 18 fatty alcohol mixture which has been ethoxylated with 25 mol of ethylene oxide.
• Acetylated lecithin is available from Compte & Rivera SA in Spain.
• the triolein is native oleic acid triglyceride from Smit & Zoon.
• Ebotec MO (4-octylisothiazolinone) is a biocide of Bode Chemie in Hamburg.
• Example 1 Treatment of Cr-tanned leather with conventional fatliquoring agents (A1 to A5, B1 to B5) and fatliquoring agents (C1 to C5, D1 to D5) according to the invention
• 100 parts by weight of chrome cattle leather with a thickness of 2.0 to 2.2 mm are placed in 100 parts by weight of water at 40 ° C. and adjusted to a pH of 4.5 by addition of sodium formate and sodium bicarbonate.
• the leather is tumbled at 40 ° C for 60 minutes in the barrel and then washed with 200 parts by weight of water.
• the liquor is adjusted with formic acid to a pH of 3.5 to 3.8, the leather briefly rinsed cold and further processed as usual.
• a tanning agent such as Relugan® GTP from BASF AG in Ludwigshafen were drummed for 60 minutes.
• an auxiliary tanning agent such as Tamol® NA BASF AG in Ludwigshafen and 30 minutes Walken 4 parts by weight of a conventional fatliquoring agent (A1 to A5, B1 to B5) or 4 parts by weight of a fatliquoring agent of the invention (C1 to C5, D1 to D5 ) was added and drummed for a further 60 minutes.
• the fastnesses to thermal yellowing as a function of the temperature are determined on the wet blue-tanned leathers obtained after completion of the fatliquoring with the fatliquoring agents A4, B3, C4 or D3 according to Example 1.
• the leathers were tested here 144 h after storage at 100 ° C or alternatively 4 h after storage at 120 ° C. The measurement results are shown in Table 5.
• Db are the values for heat yellowing
• DE is a measure of the gray values. The lower the numerical value, the better the light resistance.
• the leathers treated with the fatliquoring agents (C4, D3) according to the invention have lower fogging values than the leathers treated with conventional fatliquoring agents (A4, B3).
• Table 7 According to PB VWL 709 (Daimler Chrysler) certain VOC and fogging values ⁇ / u> fatliquors absolute fogging values in ppm relative fogging values in% absolute VOC values in ppm relative VOC values in% A4 - - 228 100 C4 - - 185 81.1 Blend A4 / B3 (3/1 by weight) 1389 100 - - Blend C4 / D3 (3/1 by weight) 797 57.4 - -
• the results of the measurements show that the leathers treated with the fatliquoring agents (C4, C4 + D3) according to the invention show less fogging and also lower volatile organic compounds (VOC) values than the leathers treated with conventional fatliquoring agents (A4, A4 + B3).
• VOC volatile organic compounds

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

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• 2002
  • 2002-02-21 DE DE10207277A patent/DE10207277A1/de not_active Withdrawn
• 2003
  • 2003-02-17 AR ARP030100513A patent/AR038550A1/es not_active Application Discontinuation
  • 2003-02-20 WO PCT/EP2003/001740 patent/WO2003070988A1/de not_active Application Discontinuation
  • 2003-02-20 AU AU2003206938A patent/AU2003206938A1/en not_active Abandoned
  • 2003-02-20 ES ES03704668T patent/ES2375108T3/es not_active Expired - Lifetime
  • 2003-02-20 US US10/503,306 patent/US7192534B2/en not_active Expired - Lifetime
  • 2003-02-20 EP EP03704668A patent/EP1478785B1/de not_active Expired - Lifetime
  • 2003-02-20 CN CNB038042843A patent/CN1264992C/zh not_active Expired - Lifetime
  • 2003-02-20 BR BR0307592-3A patent/BR0307592A/pt not_active IP Right Cessation
  • 2003-02-20 KR KR10-2004-7013071A patent/KR20040096602A/ko not_active Application Discontinuation
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