Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
  • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C14—SKINS; HIDES; PELTS; LEATHER
  • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
  • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
  • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

• the invention relates to a process for the greasing treatment of leather, in particular for preparing the direct injection of polyurethane reactive compositions while increasing the separating forces between leather and polyurethane within the composites, in particular within leather shaft / polyurethane sole composites.
• the subject of the invention is in particular the use of the leather prepared according to the described method for direct injection of polyurethane reactive compositions into leather / polyurethane composites, in particular the use of the leather pretreated according to the described method in the form of shafts with polyurethane reactive compositions in automatic spraying machines, with the formation of adhesive-free Shank leather-PU soles connected.
• This process can be carried out economically if the leather used is finished with products which have good adhesion under the processing conditions with polyurethanes, as is the case, for example, with with PU-coated split leather.
• This direct injection creates problems, however, when the leather is to be processed naturally, because the products necessary for the usual greasing of the leather usually only appear superficially and thus act as a release agent between leather and PUR material.
• a high level of adhesion, such as is required for sports shoes in particular, cannot be achieved because the polyurethane cannot bond sufficiently to the grease material diffused to the surface of the leather and therefore not to the leather itself under the heat generated during the injection process .
• Polyglycol etheramines behave similarly in accordance with DE-OS 2 539 671).
• novel fat-reducing agents a) to d) according to the invention should be present in the mixture of fat-reducing agents in an amount of 20 to 100%, preferably 40 to 80% by weight.
• Another subject of the invention is particularly Applicable methods dun g of the prepared by the method described for leather NOTEanspritzen of polyurethane reactive compositions to leather / Polyurethane composites.
• the subject matter of the invention is the use of the leather pretreated according to the method in the form of shafts for direct injection with PUR reactive compositions in automatic sprayers with the formation of adhesive-free shaft leather / PU sole compounds.
• the compounds to be used according to the invention if they are not water-soluble by themselves, can also be used as dispersants by using a suitable emulsifier sion or emulsion or by using a water-miscible solvent as a solubilizer in the aqueous phase.
• Oxiranes such as ethylene oxide, 1,2-propylene oxide, 2,3-butylene oxide, 1,2-butylene oxide, epichlorohydrin or styrene oxide, oxetanes such as 1,3-propylene oxide and oxolanes such as tetrahydrofuran are suitable for the production of the hydroxypolyethers. These are generally reacted with di- or polyvalent, hydroxyl- and / or amino-functional starting components to give the polyethers a) by processes which are well known per se.
• the polyethers should contain more than 3 oxyalkylene groups.
• Aminofunctional started hydroxypolyethers result as g E gene often with acid dyes complexes, which are reflected on the leather surface (in the form of dye salts) and result in low wear-resistant dyeings.
• the acidification of the dyed leather is difficult (poor bath consumption) and the fixing of the dyes on the leather surface is sometimes difficult.
• polyether polyols which have started on longer-chain amines (with, for example,> 10 C atoms)
• a lot of foam occurs during the coloring (due to the side effect), which ultimately results in uneven coloring.
• the different oxiranes possibility g e-jointly be polymerized as a mixture or in succession in one or more blocks on the starting component or the already preformed polyol either.
• the hydroxypolyesters to be used according to the invention can be prepared in a manner known per se and are, for example, reaction products of polybasic, preferably dibasic carboxylic acids or their mixtures.
• the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower, monohydric alcohols or mixtures thereof can also be used to produce the polyesters.
• the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic, araliphatic and / or heterocyclic and g e- optionally substituted, for example by halogen atoms such as chlorine or bromine and / or unsaturated.
• carboxylic acids and their derivatives are mentioned: Bernsteinsäsure, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, Indomethylentetrahydrophthal Acidanhydrid, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimerized and trimerized un g e-g Saetti te fatty acid, optionally mixed with monomeric unsaturated fatty acids such as oleic acid, dimethyl terephthalate and terephthalic acid-bis-glykolester.
• monomeric unsaturated fatty acids such as oleic acid, dimethyl terephthalate and terephthalic acid-bis-glykolester.
• polyhydric alcohols optionally in a mixture with one another, for example Ethylene glycol, propanediol 1,2 and 1,3, butanediol 1,4 and 2,3, hexanediol 1,6, octanediol 1,8, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methyl 1,3-propanediol, N, N-bis (2-hydroxypropyl) -N-methylamine, glycerin, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, pentaerythritol, quinite, mannitol, Sorbitol, formitol, methylglycoside, dianhydrohexite, furthermore in particular di-, tri-, tetra-ethylene glycols and higher polyethylene glycols, furthermore di-, tri- and higher polypropylene glycol,
• the low molecular weight polyols can also be set in any mixtures by esterification.
• the polyesters to be used can also have a proportion of carboxyl groups as end groups.
• Lactone polyesters e.g. Caprolactone or hydroxycarboxylic acids, e.g. ⁇ -hydroxycaproic acid, these compounds being used either alone or as a mixture with polyhydroxyl compounds to prepare the polyesters.
• Preferred polyesters are hydrophilic polyesters or else hydrophilic polycarbonates which have been produced using di-, tri-, tetra- or polyethylene glycols.
• polycarbonates can be prepared in a manner known per se and are for example reaction products of polyhydric, preferably two and g e-optionally three or tetrahydric alcohols, with certain carbonic acid derivatives such as phosgene, phenyl chloroformate, ethyl chloroformate, but in particular, diphenyl carbonate, diethyl carbonate, ethylene carbonate, propylene or dimethyl pyrocarbonate.
• polyhydric preferably two and g e-optionally three or tetrahydric alcohols
• carbonic acid derivatives such as phosgene, phenyl chloroformate, ethyl chloroformate, but in particular, diphenyl carbonate, diethyl carbonate, ethylene carbonate, propylene or dimethyl pyrocarbonate.
• polyesters, polylactones and / or polycarbonates can also be used. Unless they are inherently soluble, emulsifiable or dispersible in water, the polyethers, polyesters or polycarbonates according to the invention can be transferred into the aqueous phase by adding conventional emulsifiers.
• the emulsifiability of polyesters, polylactones, polycarbonates or polyethers is also simplified by incorporating small amounts of ionizable groups (cationic or anionic type or of tertiary amines which can form salts).
• Possible external emulsifiers are: long-chain alkyl sulfates or alkyl sulfonates, ethoxylation products of alkylphenols, e.g. para-nonylphenol or of aromatically substituted phenols such as phenylphenol or of alkylation or benzylation products of phenylphenol; long chain alkyl carboxylic acids or quaternized long chain alkyl ammonium salts.
• the products according to the invention are used together with or instead of the normal leather greasing agents.
• the amount of normal leather greasing agents known per se is generally restricted to amounts of less than 80% by weight.
• leather greasing is used to impart the final softness to the leather before and especially after dyeing.
• the fatliquors so superficially that later operations such as dressing or, in particular, the direct injection of polyurethane soles are severely hampered by the fatliquors which act as release agents in this case.
• the fiction, g e-Maessen products do not have these disadvantages. Their use thus represents a significant improvement in the further processing of the leather treated with them.
• the leather treated according to the invention can be dyed excellently with deep shades with high levelness. After the oiling treatment, the leathers are subjected to the customary aftertreatment, for example dried, placed and, if necessary, finished by known methods.
• hydroxyl-polycarbonate greasing agents in particular hydroxy-polyalkylene oxide polycarbonates as greasing agents.
• the fat-reducing agents a) to d) according to the invention are generally used in the field of leather production which is characterized by "wet finishing", i.e. in the area of retanning / greasing. Exemplary applications can be found in the description in the examples.
• results which can be achieved by the process according to the invention or the use according to the invention depend on the type of leather and on the type of tanning, as well as the type of fatliquor and the polyurethane reactive injection mixture.
• Chrome-tanned leathers are e.g. washed, then neutralized (to pH 4.5 to 6.0) treated with 2 to 20% by weight of vegetable, mineral or organic synthetic retanning agents and, if appropriate, colored. Then 0.1 to 20 wt.
• the leather is processed in machines that are common in the shoe industry.
• the uppers are made from the leather, a base (mostly made of textile) is sewn in, the uppers are pulled over a (metal) last and then the polyurethane materials (soles) are molded on in suitable machines.
• the polyurethane reactive mixtures contain the usual starting components, for example higher molecular weight compounds with at least 2, preferably 2 to 4, end groups reactive towards NCO, such as OH, NH 2 , NHR, COOH or -CONHNH 2 end groups, with a molecular weight of about 400 to 10,000, the usual aliphatic, cycloaliphatic, aromatic or heterocyclic polyisocyanates, as are known in the art, and optionally low molecular weight chain extenders with the above End groups and molecular weights of 18, 32 to 399, for example water, di-polyols or di- / polyamines or other known compounds.
• the polyhydroxyl compounds can also be more complex natural substances such as castor oil or modified linseed oil.
• the reactive mixtures can furthermore have the usual PU catalysts and other customary auxiliaries and additives, for example pigments, fillers, fibers, glass tube balls, blowing agents, stabilizers, dyes and the like.
• PU catalysts for example pigments, fillers, fibers, glass tube balls, blowing agents, stabilizers, dyes and the like.
• NCO prepolymers or semiprepolymers can also be used.
• the NCO-ratios can be varied in a conventional width, such as from 60 to measure indicators 125, preferably ratios from 90 to 115.
• the injection process can by automatic metering and mixing of the reaction components, preferably rhythmically, successes g s.
• the density of the pole from the y urethanregentmassen forming Polvurethanelastomeren 800 may kq / m 3 (zelliae elastomers) to the homogeneous density of the polyurethane elastomer composition, respectively.
• Oxyethylenend phenomenon of 3.6 kg containing polyether of Example 1.1 and 0.4 k g of a commercial, linear Polyoxypropylenetherdiols molecular weight of 2000 are mixed together.
• 500 g of a hydroxy polycarbonate based on hexanediol polycarbonate with a molecular weight of 1800 are dispersed in 600 g water using 10 g of an emulsifier based on 3-benzyl-4-hydroxy-biphenyl polyglycol ether. An emulsion is formed.
• 500 g of a bifunctional polydiethylene glycol adipate, molecular weight 2000, are in 100 g of diacetone alcohol dissolved and converted into an emulsion with 10 g of an emulsifier based on stearamine + 8 moles of ethylene oxide and 500 g of water.
• 500 g of a linear polyether based on oxyethylene / oxypropylene mixed ether with a molecular weight of 4000 and 18% by weight of terminal oxyethylene groups are dispersed in 500 g of water using 10 g of the above-described emulsifier and 100 g of ethyl glycol.
• Example 1.5 200 g of a polyester of adipic acid, hexanediol and neopentyl glycol of Example 1.5 are with the aid of 200 g of a polyether as described in Example 1.1 (e g molecular-weight 4000) was dispersed in 592 g of water.
• 200 g of the polyester as in Example 1.5 and 200 g of the polyether as in Example 1.1 are emulsified with 8 g of 3-benzyl-4-hydroxy-diphenyl-polyglycol ether as an emulsifier in water to form an emulsion containing 25% solids.
• a bifunctional triethylene glycol polycarbonate with a molecular weight of 2000 is stirred with a 50% emulsion with the addition of 2% emulator, as in Example 1.8.
• a chrome-tanned leather is mixed with 200% water (45 ° C) and 0.2% 10% acetic acid and 2.5% of a highly lightfast exchange tanning agent (Tanigan-3LN®,
• Comparable halves were treated on the one hand with a lubricant mixture known to be well effective according to the state of the art (Coripol-DX-902, Stockhausen, sperm oil replacement product Chromopol-UFB / W + chloroparaffin Coripol-ICA, Stockhausen, Krefeld - 8% refatting fat) , or (according to the invention) with 4% of the fat mixture from Example 1.1.
• a lubricant mixture known to be well effective according to the state of the art (Coripol-DX-902, Stockhausen, sperm oil replacement product Chromopol-UFB / W + chloroparaffin Coripol-ICA, Stockhausen, Krefeld - 8% refatting fat) , or (according to the invention) with 4% of the fat mixture from Example 1.1.
• the leather was molded directly without roughening.
• the separating force of the PU sole mixture on the leather was determined on a tearing machine in accordance with DIN 53 328.
• the leather can be dyed with leather dyes.
• a very full or full coloration of the leather is achieved with the leathers greased according to the invention (greasing 2 or 3), with good to very good levelness of the coloring.
• the color depth that can be achieved on the comparison leather with bold 1 is only slight (light) with only a moderate level.
• the leather with grease 1, 2 and 3 was sprayed with reactive PU mixtures on a conventional automatic spray gun.
• the results of the gating tests were: According to the invention, the separating forces between the molded-on sole and g e-greased leather show significantly higher values, in particular if products made from ether or ester base are used both for leather greasing and for the reactive PU composition.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dispersion Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Treatment And Processing Of Natural Fur Or Leather (AREA)
• Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
• Adhesives Or Adhesive Processes (AREA)

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• 1985
  • 1985-05-17 DE DE19853517803 patent/DE3517803A1/de not_active Withdrawn
• 1986
  • 1986-05-01 US US06/858,160 patent/US4810251A/en not_active Expired - Fee Related
  • 1986-05-05 DE DE8686106114T patent/DE3669532D1/de not_active Expired - Lifetime
  • 1986-05-05 EP EP86106114A patent/EP0204162B1/fr not_active Expired - Lifetime
  • 1986-05-05 AT AT86106114T patent/ATE51031T1/de not_active IP Right Cessation
  • 1986-05-13 CA CA000509061A patent/CA1257453A/fr not_active Expired
  • 1986-05-15 JP JP61109746A patent/JPH0631440B2/ja not_active Expired - Lifetime

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