Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
  • B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F6/00—Post-polymerisation treatments
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F6/00—Post-polymerisation treatments
  • C08F6/001—Removal of residual monomers by physical means
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F6/00—Post-polymerisation treatments
  • C08F6/008—Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00654—Controlling the process by measures relating to the particulate material
  • B01J2208/00672—Particle size selection
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00027—Process aspects
  • B01J2219/00033—Continuous processes

Definitions

• Emulsifier composition and low-fogging, high-exhaustion fatliquoring agents, their production and use.
• the present invention relates to an emulsifier composition which is particularly suitable for the production of low-fogging, high-exhaustion fatliquoring agents, the fatliquoring agents thus obtained and the use of the
• Emulsifier composition and the fatliquor in the production of leather as well as the manufactured, low-fogging leather.
• Greasing agents are used in leather production to soften the leather, to increase its fullness and strength and to protect it from moisture, dirt and chemical influences from outside (see H. Herfeld, "Library of Leather", Vol. 4, (1985), P. 13 ff.).
• greasing agents generally consist of greasing substances, such as chemically modified native fats, fatty oils, waxes, resins and their derivatives and / or petroleum fractions and their derivatives, and wax-like products such as "wool fat", in raw, purified and / or prepared (Lanolin) form, (see H. Herfeld, "Bibliothek des Leders", vol. 4, (1985), pp. 59 ff.)
• the fatty substances can, if desired, be chemically modified, ie they can be in a modified chemical structure.
• the chemical modification of the fatty substances generally consists in that the double bonds contained in these substances are at least partially subjected to addition reactions and / or oxidation reactions. Frequently carried out modifications consist, for example, in the addition of sulfites, sulfonic acid groups being introduced into the fatty substance, or in air oxidation, with oxygen functions be introduced and some oligomerizations also occur. However, (partial) saponification of the fatty substances, transesterification and the like modification reactions are also possible.
• the aim of these chemical modifications is to optimally adapt the application-related properties of the greasing substances, such as, for example, hydrophilicity, hydrophobicity, solubility, dispersibility, penetration and anchoring properties, special uses or the requirements of the users.
• modification by partial sulfite addition (introduction of sulfonic acid groups) and partial oxidation are of particular importance.
• the combination of at least these modification measures can influence a number of valuable application properties, in particular the hydrophilicity, the penetration capacity and the anchoring properties.
• the present invention relates to new leather treatment compositions for the production of leathers with low volatile constituents, in particular for high-quality car upholstery leather, a process for the production of these compositions and their use in the production of low-fogging leather.
• Car upholstery leather has to meet certain criteria.
• the softness is essential, on the other hand the fastness to light and heat and finally the so-called fogging behavior.
• DIN 75201 defines fogging as the condensation of evaporated volatile components from the vehicle interior on the glass panes, especially on the windshield.
• the same standard also describes a gravimetric and a reflectometric method for characterizing the fogging behavior of leather.
• EP 498634 A2 recommends special polymers for the production of so-called low fogging leathers, the aqueous dispersions being essentially free of organic solvents and containing an amphiphilic copolymer which consists of a predominant proportion of at least one hydrophobic monomer and a small proportion of at least one hydrophilic monomer. Treatment of the leather with these dispersions leads to good results in a gravimetric test according to DIN 75201. Reflectometric studies have not been disclosed.
• amphiphilic copolymers are preferably prepared in an aqueous emulsion polymerization.
• this naturally results in problems with the copolymerization behavior, which in extreme cases can lead to the monomers in undesirably form homopolymers for themselves.
• Another consequence of the inherently unfavorable solution ratios is that an expensive post-processing is necessary to destroy residual monomers.
• an emulsifier (lauryl sulfate was used in the examples given), which can lead to wastewater problems in leather processing.
• EP 466 392 B1 describes a process for the preparation of polymers which contain both pendant hydrophobic groups and pendant alkoxylated groups which are obtained by derivatizing polymers after the actual polymerization process using customary processes.
• polymers are preferably produced 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 polymers described are used as thickeners and soil release agents.
• WO 98/10103 describes a further process for the preparation of polymeric fatliquoring agents by polymerizing acrylic acid and / or methacrylic acid and / or their acid chlorides and / or their anhydrides with further copolymerizable water-soluble monomers and with copolymerizable water-insoluble monomers and subsequent reaction of the polymers with amines.
• DIN 75201 B gravitationmetry
• fogging values of 1.2 mg and 1.5 mg are found for leather that has been treated with the listed sample products; those with the comparative products (Magnopal ® SOF, low-fogging
• the reflectometric values according to DIN 75201 A of the sample products are 51% and 55%, respectively, of the comparison products 34% and 40%.
• US Pat. No. 5,348,807 also describes a process in which selected amphiphilic copolymers, consisting of a predominant proportion of hydrophobic and a smaller proportion of hydrophilic assemblies, as low-solvent, low-fogging Fatliquor can be used.
• the hydrophilic monomers used are acid-substituted or basic-substituted esters of unsaturated carboxylic acids, such as, for example, sulfatoethyl (meth) acrylate or dimethylaminoethyl (meth) acrylate: longer-chain alkenes or (meth) acrylic acid ( C -C 12 ) alkyl esters or vinyl esters of C 4 to C 12 carboxylic acids.
• the substances give good fogging values; however, there is no information about bath consumption.
• amphiphilic copolymers are preferably prepared by aqueous emulsion polymerization.
• this again leads to the production problems already mentioned in the discussion of EP-A-498634.
• EP 0 753 585 B1 describes a process for producing low-fogging 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 fatliquoring agents.
• Native oils used are soybean, lard, safflower and sunflower oil. The said native oils are first distilled to remove the undesirable low molecular weight constituents and then reacted with hydrogen sulfite or hydrogen sulfate in order to improve the emulsifiability. Then the (partially) functionalized oils are emulsified and applied.
• An object of the present invention was to find a process for greasing leather or to develop a greasing agent which no longer has these disadvantages of the prior art. Surprisingly, it has been found that the disadvantages of the prior art can be overcome by using a new emulsifier composition or a fatliquor mixture of the composition given below.
• the present invention relates to an emulsifier composition
• an emulsifier composition comprising three components A, B and C, component A being a C 6 to C 1 alkanol alkoxylated with 4 to 12 AO units, or a mixture of several such alkanols, component B being a 15 up to 40 AO units alkoxylated C 12 -C 24 fatty alcohol mixture and component C is a C 12 to C 24 fatty alcohol mixture alkoxylated with 50 to 100 AO units.
• the AO units are expediently alkylene oxide units with 2 to 4, preferably with 2 to 3, carbon atoms.
• the building blocks of the polyether chains can all be the same or different and - if they are different - they can be arranged randomly or in blocks.
• the proportions by weight of the components in the emulsifier composition are for component A: 20 to 60, preferably 25 to 50, in particular 28 to 40% by weight, for component B 20 to 70, preferably 25 to 60, in particular 30 to 45% by weight and for component C 10 up to 50, preferably 15 to 40, in particular 22 to 32% by weight of the total weight of the composition.
• the alkoxylated alkanol or the alkoxylated alkanol mixture of component A preferably has an average of 8 to 12 carbon atoms, in particular 10 carbon atoms, and the alkoxylated alkanol mixture of components B and C has an average of 14 to 20 carbon atoms, in particular 16 to 18 carbon atoms -Atoms, on.
• emulsifier compositions in which component A has 5 to 10 AO units, component B has 20 to 30 AO units and component C has 50 to 100 AO units.
• Alkoxylated longer-chain and long-chain alcohols are known. They are obtained by reacting the corresponding alkanols or alkanol mixtures, as are present in the fatty alcohols, with the desired molar amounts of the alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide. Depending on how the alkylene oxides are metered into the batches, statistical or block-like polyether chains can be produced in a targeted manner. The reaction can be catalyzed by small amounts of water and / or alkali.
• the emulsifier compositions according to the invention are prepared by mixing the components with stirring and optionally with gentle heating. If desired, they can be converted into solutions by adding water, which, depending on the wishes of the users, expediently have a solids content of about 40 to 80% by weight. Of course, other concentrations of the emulsifier compositions according to the invention can also be provided for special purposes.
• the invention further relates to oiling agents for oiling leather comprising one or more, optionally modified, native oiling components and / or optionally a synthetic lipid component, in particular a polymeric lipid component, emulsifiers and optionally diluents, especially water, which are characterized in that they contain one of the emulsifier compositions described above.
• the fatliquoring agents according to the invention contain 2 to 20, preferably 5 to 15% by weight of the emulsifier composition according to the invention.
• Well-suited fatty substances are vegetable and animal fats and oils with an iodine number of approx. 10 to approx. 200.
• the selection of fatty substances depends, among other things, on the special purpose for which the mixture according to the invention is to be used. For example, prohibit the use of fish oils in the manufacture of fine leather goods because of the smell of these fats.
• Fatty substances with iodine numbers of approximately 30 to approximately 120, in particular 40 to 85, are preferred.
• particularly preferred fatty substances are sebum types of different origins, bone oil, nitro oil, claw oil, lard oil, triolein, rapeseed oil, olive oil, nut oil and castor oil.
• the sulfitation or oxidation products of the mono- or polyunsaturated fatty substances are formed by the reaction of the olefinic double bonds present in the fatty substances with the sulfitation and / or oxidation reagents. All double bonds present in the fatty substances or only some of them can react.
• Fish and rapeseed oil are particularly favorable for use in accordance with the invention.
• a relatively high degree of oxidation in the sense of this invention is present when ⁇ d, the difference in the specific weights of the oil or fat before and after the oxidation, is in the range from 0.01 to 0.1, preferably from 0.03 to 0.05 ,
• a relatively low degree of sulfitation within the meaning of this invention is when the neutral oil has been reacted with 2 to 8%, preferably 3 to 5%, of its weight as a sulfite, calculated as sodium bisulfite (Na 2 S 2 O 5 ).
• particularly preferred fatliquoring agents include one or more, optionally modified, native fatliquoring components and / or optionally a synthetic, for example a polymeric, fatliquoring component, emulsifiers and optionally diluents, in particular water, which are characterized in that they are one of the emulsifier compositions described above contain and the fatty components comprise a relatively highly oxidized, relatively low sulfited neutral oil.
• the particularly preferred fatliquoring agents according to the invention contain 80 to 98% by weight, preferably 85 to 95% by weight of fatliquoring components, 20 to 80% by weight, in particular 25 to 75% by weight of the fatliquoring components to be used relatively according to the invention are highly oxidized, relatively low sulfited neutral oils.
• the fatliquoring agents according to the invention can also be provided undiluted or, depending on the wishes of the users, in the form of aqueous emulsions, advantageously with solids contents of 40 to 80% by weight.
• the components of the preferred fatliquoring agents according to the invention namely the emulsifier mixtures according to the invention and the relatively highly oxidized, relatively low sulfitated neutral oils, can of course also be added separately to the fatliquoring liquors in any order.
• the invention thus also relates to a process for oiling leather and hides by treatment with aqueous liquors which contain oiling agents and emulsifiers, which is characterized in that 10 to 90% by weight, preferably 25-75% by weight, of the oiling agents relative highly oxidized, relatively low are sulfited neutral oils and the liquor contains 1 to 10% by weight, preferably 2.5 to 7.5% by weight, of an emulsifier composition according to the invention.
• the invention further relates to the use of the described emulsifier composition according to the invention, preferably in combination with relatively highly oxidized, relatively low sulfited neutral oils, in leather production, and the use of the emulsifier composition according to the invention preferably in combination with relatively highly oxidized, relatively low sulfited neutral oils for the production of fat liquors.
• the use of the fatliquoring agents according to the invention serves to soften the leather, to increase its fullness and strength and to protect it against moisture, dirt and chemical influences from outside.
• the presence of the emulsifier compositions according to the invention in the leather treatment liquors leads to very good bath consumption and thus to particularly low COD values with at the same time good anchoring of the fatliquor inside the leather and thus to low fogging values.
• Example 1 Production of an Emulsifier Preparation According to the Invention.
• the preparation obtained is soluble in water. It can be used either directly or in the form of an aqueous dilution (40-80% by weight is expedient) in leather production.
• Example 2 leather production without greasing.
• 100 parts by weight of chrome cowhide with a fold 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 adding sodium formate and sodium hydrogen carbonate.
• the leather is drummed at 40 ° C for 60 minutes in a barrel and then washed with 200 parts by weight of water.
• the liquor is then adjusted to a pH of 3.5 to 3.8 using formic acid, the leather briefly rinsed cold and processed further, as is customary. Then a 20 ml sample is taken from the liquor to determine the COD value.
• the leather obtained is well colored, of little fullness and hard.
• the COD value is determined in the sample taken from the liquor (in accordance with DIN 38409-H43-1) and the fogging value in the leather obtained in accordance with DIN 75201B. The results obtained in these tests are summarized in Table 2.
• Example 3 leather production with greasing, conventional.
• 100 parts by weight of chrome cowhide with a fold 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 adding sodium formate and sodium hydrogen carbonate.
• the leather is drummed at 40 ° C for 60 minutes in a barrel and then washed with 200 parts by weight of water.
• the liquor is then adjusted to a pH of 3.5 to 3.8 using formic acid, the leather briefly rinsed cold and processed further, as is customary. Then a 20 ml sample is taken from the liquor to determine the COD value.
• a leather is obtained with a very good color, good firm grain, with good fullness and medium softness. The leather surface has a slim handle.
• the COD value is determined in the sample taken from the liquor after the end of the greasing period in accordance with DIN 38409-H43-1 and the fog value in the leather obtained in accordance with DIN 75201B. The results obtained in these tests are summarized in Table 2.
• Example 4 leather production with greasing, according to the invention.
• Example 3 is repeated under the same conditions and using the same tanning agents and the Licker mixtures A and B used there. It will however, 5.2 parts by weight of the emulsifier preparation prepared according to Example 1 were added to the liquor mixtures in the liquor. The greasing and further treatment of the leather is continued exactly as described in Example 3. •
• the leather produced has the same quality as that obtained in Example 3.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• General Chemical & Material Sciences (AREA)
• Treatment And Processing Of Natural Fur Or Leather (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Colloid Chemistry (AREA)

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• 2001
  • 2001-09-07 DE DE10143949A patent/DE10143949A1/de not_active Withdrawn
• 2002
  • 2002-09-03 AR ARP020103322A patent/AR036417A1/es not_active Application Discontinuation
  • 2002-09-06 EP EP02777026A patent/EP1427861A1/de not_active Withdrawn
  • 2002-09-06 CN CNB028173163A patent/CN1238527C/zh not_active Expired - Fee Related
  • 2002-09-06 BR BR0212245-6A patent/BR0212245A/pt not_active Application Discontinuation
  • 2002-09-06 JP JP2003527131A patent/JP2005502458A/ja not_active Withdrawn
  • 2002-09-06 US US10/487,536 patent/US20040216241A1/en not_active Abandoned
  • 2002-09-06 WO PCT/EP2002/010017 patent/WO2003023069A1/de not_active Application Discontinuation
  • 2002-09-06 KR KR20047003360A patent/KR20040044859A/ko not_active Application Discontinuation

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