EP0591784B1 - Utilisation de polyorganosiloxane greffé pour le finissage du cuir - Google Patents

Utilisation de polyorganosiloxane greffé pour le finissage du cuir Download PDF

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Publication number
EP0591784B1
EP0591784B1 EP93115450A EP93115450A EP0591784B1 EP 0591784 B1 EP0591784 B1 EP 0591784B1 EP 93115450 A EP93115450 A EP 93115450A EP 93115450 A EP93115450 A EP 93115450A EP 0591784 B1 EP0591784 B1 EP 0591784B1
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weight
stirring
leather
polyorganosiloxane
latex
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EP0591784A3 (en
EP0591784A2 (fr
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Harro Dr. Träubel
Andreas Dr. Endesfelder
Martin Dr. Matner
Fritz Novotny
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Bayer AG
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Bayer AG
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    • 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
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds

Definitions

  • the invention relates to the use of graft products which can be obtained by grafting ethylenically unsaturated monomers onto polyorganosiloxanes containing vinyl and / or mercapto groups as dressing binders for leather.
  • Crosslinkable and non-crosslinkable binder systems can be used as leather finishing binders.
  • the most common leather finishing binders are butadiene and acrylate polymers and polyurethanes.
  • the coatings produced from the graft products to be used according to the invention have excellent adhesion, high flexural strength and excellent elastic properties, which can be improved even further by heating or aging by prolonged storage, in general even then when the graft products of the invention are greatly diluted by other components of the dressing agent.
  • the polyorganosiloxane latices can be prepared by known processes by equilibration of the mixtures of linear or cyclic polyorganosiloxanes, such as, for example, octaalkyl-cyclotetrasiloxane, with corresponding mercaptoalkyl-alkylcyclotetrasiloxanes, mercaptoalkyl-alkyl-dialkoxysilanes, vinylalkyl-alkylcyclotetrasiloxanes or with dialkoxysiloxanes Acid or alkaline equilibration catalysts are present.
  • linear or cyclic polyorganosiloxanes such as, for example, octaalkyl-cyclotetrasiloxane, with corresponding mercaptoalkyl-alkylcyclotetrasiloxanes, mercaptoalkyl-alkyl-dialkoxysilanes, vinylalkyl-alkylcyclotetrasilox
  • quaternary ammonium hydroxides or sulfonic acids such as dodecyl-trimethylammonium hydroxide, dioctadecyldimethyl-ammonium hydroxide or dodecylbenzene sulfonic acid, which are known from US Pat. No. 2,891,920 and US Pat to call.
  • These equilibration catalysts also act as emulsifiers. However, since the emulsifier requirement is generally higher than that of catalyst, mixtures of the free acids or bases with their corresponding water-soluble salts can also be used.
  • the majority of the polyorganosiloxane graft base is formed by dialkylsiloxane, preferably dimethylsiloxane units I.
  • Preferred organosiloxane units II containing mercapto groups are those in which R 3 is divalent linear or branched C 1 -C 8 -alkyl groups and R 4 C 1 -C 24 -alkyl radicals, C 6 -C 18 -aryl radicals, C 1 -C 6 -alkoxy radicals or a hydroxyl group.
  • Such siloxane units II are, for example, 2-mercaptoethyl-methyl-siloxane, 3-mercaptopropyl-methyl-siloxane, 3-mercaptohexyl-methyl-siloxane, 3-mercaptopropyl-phenyl-siloxane, 3-mercaptopropyl-ethoxy-siloxane, 3-mercaptopropyl -hydroxy-siloxane.
  • Organosiloxane units II in which R 3 and R 4 form a 5- or 6-membered ring together with the silicon atom are, for example, the following structures:
  • the polyorganosiloxanes can also contain siloxane units with HSR 3 SiR 4 O 3/2 or HSR 3 SiR 4 O 1/2 contain. Higher proportions of the former result in overly cross-linked latex particles, the latter, on the other hand, have a too strong regulating effect. It mixtures of the above-mentioned mercaptoalkyl-alkyl-siloxane units II can of course also be introduced.
  • Preferred organosiloxane units III containing vinyl groups are those in which R 5 is linear or branched C 1 -C 8 -alkylene groups or a single bond and R 6 is C 1 -C 24 -alkyl, C 1 -C 6 -alkoxy or hydroxyl.
  • Such preferred organosiloxane units III include, for example, vinyl-methyl-siloxane, allyl-methyl-siloxane, 5-hexenyl- (1) -methyl-siloxane, (1-methyl-propenyl-2) -methyl-siloxane, vinyl-phenyl- siloxane, allyl-phenyl-siloxane, 5-hexenyl- (1) -phenyl-siloxane.
  • either the emulsifier can be added to the organosiloxane mixture with stirring and then the water can be added with stirring or, conversely, the emulsifier can be dissolved in water and the organosiloxane mixture can be added slowly with vigorous stirring. In both cases, vigorous stirring and expediently an emulsification carried out under very high shear forces using a homogenizer is advantageous.
  • the ratio of the aqueous to organic phase is not critical, but it should expediently be in the range of the weight ratio of the two components from 4: 1 to 1: 2, preferably from 2: 1 to 1: 1.
  • the equilibration is generally carried out without pressure, but in particular in the presence of volatile constituents it is advantageous to equilibrate in closed reactors under the autogenous pressure of the mixture or under increased pressure.
  • the temperature during equilibration is kept at 60 to 100, preferably at 70 to 80 ° C. Higher temperatures up to 200 ° C are also possible, but less advantageous, since the average molecular weight of the polyorganosiloxane is very strongly dependent on the equilibration temperature. The highest molecular weights can be achieved at temperatures of 20 to 50 ° C. However, it should be borne in mind that under such conditions the reaction rate is very slow and very long reaction times are therefore required to achieve extensive conversion. At temperatures around 70 to 80 ° C, about 5 to 12 hours are usually sufficient.
  • the latex is adjusted to the pH value of 7 as precisely as possible by adding alkali lye or ammonia in the case of acidic catalysis or hydrochloric acid or acetic acid in the case of an alkali-catalyzed equilibration.
  • the graft products to be used according to the invention can be linear (with structures III but without structures II) or crosslinked (with structures II and optionally III).
  • the number average molecular weight the polysiloxane B is generally at least 20,000. If crosslinked polysiloxanes B are used, the gel content, determined by extraction with tetrahydrofuran, can be up to 100% by weight.
  • the gel content can be determined, for example, by mixing the aqueous polysiloxane dispersion with tetrahydrofuran (20 ml of THF per dispersion containing 250 mg of solids), shaking the mixture for 24 hours at room temperature, centrifuging for 12 hours, then decanting and the gel (residue) dries.
  • the grafting of vinyl monomers can be carried out immediately after neutralizing the polyorganosiloxane latex in the same reactor. However, if the generally only a few% by weight of the cyclic polysiloxanes used are to be removed before grafting, steam distillation is carried out in this phase under somewhat reduced pressure.
  • the amount of emulsifier contained in the polyorganosiloxane is usually also sufficient for the grafting reaction. In some cases, however, the addition of small amounts of emulsifier may be necessary, depending on the type and amount of the vinyl monomers to be grafted on. In some cases it may be advantageous to supplement the anionic or cationic emulsifiers present in terms of equilibration with nonionic emulsifiers.
  • Preferred ethylenically unsaturated graft monomers include, for example, styrene, ⁇ -methylstyrene, acrylic and methacrylic acid, acrylic and methacrylic acid-C 1 -C 18 alkyl esters, acrylic and methacrylic acid hydroxy-C 1 -C 18 alkyl esters, Acrylic and methacrylic acid amide (where the amide nitrogen atom can carry one or two C 1 -C 18 alkyl groups), acrylic and methacrylic acid C 1 -C 6 alkoxy-C 1 -C 18 alkyl esters, such as methyl methacrylate, ethyl acrylate , n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl me
  • the particular composition of the monomers to be grafted on depends on the requirements. If, in addition to the good rubber properties, good heat stability is in the foreground, styrene is to be used as the grafting monomer, possibly with the addition of a small proportion of acrylates or methacrylates. In order to introduce further crosslinkable groups, some other vinyl monomers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and others can also be copolymerized in small amounts. Methyl methacrylate is preferably used in combination with styrene and / or other alkyl acrylates.
  • graft products with a higher content of grafted-on acrylonitrile should be sought.
  • the acrylonitrile gives the graft products - similar to styrene and, to a lesser extent, methyl methacrylate - a very high tensile strength.
  • the vinyl monomer mixture should preferably contain at least 20, preferably more than 30% by weight of styrene and / or acrylic and / or methacrylic ester.
  • the grafting reaction can be carried out by various processes customary in emulsion polymerization, for example by the so-called batch process or by the various feed processes.
  • the polyorganosiloxane latex is initially introduced and the monomer mixture, if appropriate at a temperature at which no polymerization takes place, ie at temperatures from 0 to 50 ° C., preferably from 10 to 30 ° C. added together with the polymerization initiators soluble therein with good stirring over the course of about 1 hour.
  • the mixture can then be stirred at this temperature for a maximum of 18 hours.
  • the grafting reaction is started and brought to an end by gradually increasing the temperature.
  • this method of operation is not always practical in view of the sometimes very violent, exothermic course of the reaction.
  • the process can be modified in such a way that the relatively concentrated latex pretreated in the cold as described above at a temperature adapted to the decomposition temperature of the polymerization initiator used is added to a small amount of the emulsifier solution initially introduced at such a rate that the heat of reaction which arises can be removed in the process.
  • Another alternative method in this case is the slow metering in of a water-soluble polymerization initiator, such as e.g. of potassium peroxydisulfate or a redox initiator to the latex presented at a temperature adapted to the decomposition point of the initiator.
  • a water-soluble polymerization initiator such as e.g. of potassium peroxydisulfate or a redox initiator
  • the unpolymerized monomer parts can, if necessary, be removed by steam distillation under reduced pressure.
  • the radical grafting reaction of the vinyl monomers can be started in a known manner with the addition of radical formers, UV rays, ⁇ , ⁇ or ⁇ rays or thermally without further additives.
  • radical formers UV rays, ⁇ , ⁇ or ⁇ rays or thermally without further additives.
  • these can be used in amounts between 0.001 to 10, preferably 0.1 to 1.5% by weight, based on the total mixture of polyorganosiloxane and vinyl monomers.
  • Suitable radical formers are, for example, azo initiators such as azo-bis-isobutyronitrile (AIBN), azo esters, azo amino esters or azo-N-alkyl amides; Peroxides such as dibenzoyl peroxide, dilauroyl peroxide, di-tert-butyl peroxide, 2,4-dichlorobenzoyl peroxide; Peroxyesters such as butyl perpivalate, tert-butyl peroctoate, tert. Butyl perbenzoate, tert.
  • azo initiators such as azo-bis-isobutyronitrile (AIBN), azo esters, azo amino esters or azo-N-alkyl amides
  • Peroxides such as dibenzoyl peroxide, dilauroyl peroxide, di-tert-butyl peroxide, 2,4-dichlorobenzoyl peroxide
  • Peroxyesters
  • Butyl perneodecanoate Percarbonates such as cyclohexyl percarbonate, bis-isopropyl percarbonate or hydroperoxides such as tert-butyl peroxide or cumyl hydroperoxide.
  • the grafting reaction can also be carried out in the presence of thermally labile, highly substituted ethane derivatives, e.g. Benzpinakol or its derivatives.
  • redox initiator systems which can be used at much lower temperatures than the purely thermally decomposing radical formers.
  • examples are the combinations of peroxides and amines, e.g. Benzoyl peroxide and triethylamine, trialkylboron compounds and oxygen, hydroperoxides and sulfinic acids, formaldehyde or aldoses or combinations with low-value transition metal salts and sulfur dioxide / peroxide redox systems.
  • the grafting reaction can be carried out continuously or batchwise, without pressure or at pressures of up to 200 bar, at a reaction temperature of 0 to 200 ° C., preferably 20 to 150 ° C.
  • the grafting reaction can be carried out in the presence of molecular weight regulators; however, their use is given the regulatory effect the mercapto groups that may be present in the polyorganosiloxane are not required in most cases.
  • Suitable controllers are listed, for example, in EP-PS 084 321 on pages 10 to 12.
  • graft polymers are also understood to mean those products which, in addition to the actual graft polymers, also contain polymers of the graft monomers used.
  • the graft products to be used according to the invention are largely known; see. e.g. DE-OS 39 22 521, EP-A 421 588, US-PS 4 071 577 and 4 123 472.
  • leather finishes are multiple orders from fleets containing binder.
  • the graft products to be used according to the invention can be used for all, i.e. can also be used for the lower Zurich layers; However, it is particularly preferred to use it as a binder for finishing - that is to say the last layer.
  • the graft products to be used according to the invention can be used as the only binder component of the individual Zurich layers. Preferably they will however, as a binder mixed component together with other binders, preferably polyacrylates, butadiene polymers or - in particular - polyurethanes, the amount of the graft products to be used according to the invention being 10 to 100, preferably 15 to 65% by weight, based on the sum of all binders (in each case based on solids content).
  • binders preferably polyacrylates, butadiene polymers or - in particular - polyurethanes
  • Binders suitable for such blends are described, for example, in JSLTC 74 , pages 7 to 9, in JALCA volume 83 (1988), pages 317 to 327, in the magazine Das Leder, volume 38 (1987), pages 177 to 183, and in methods of Organic Chemistry (Houben-Weyl), Volume E20, Georg Thieme Verlag, Stuttgart 1987, pages 1659 to 1692, including the literature cited there.
  • the graft products to be used according to the invention are preferably used in the form of aqueous dispersions.
  • the solids content of these aqueous dispersions is generally 10 to 65, preferably 20 to 40,% by weight.
  • the liquors containing graft products to be used according to the invention can contain conventional additives and auxiliaries, such as e.g. Contain pigments, leveling, handle, thixotropic agents, defoamers, crosslinkers and / or organic solvents.
  • auxiliaries such as e.g. Contain pigments, leveling, handle, thixotropic agents, defoamers, crosslinkers and / or organic solvents.
  • the graft products to be used according to the invention still contain free mercapto groups, they are self-crosslinkable at temperatures above 100.degree.
  • crosslinkers such as polyisocyanates, polyepoxides or polycarbodiimides, polyaziridines, formaldehyde releasers.
  • the dressings produced with the aid of the graft products to be used according to the invention are highly abrasion-resistant and have a pleasant handle.
  • the leathers do not turn gray (i.e. they do not lose their black depth when stretched). This appears very surprising because these properties are usually only obtained when using binders with a high modulus of elasticity and high hardness - prerequisites which do not apply to the graft products to be used according to the invention.
  • 1550 g of octamethylcyclotetrasiloxane are placed in a 6 liter dispersion vessel with an intensely acting stirrer equipped with two 10 mm dissolver disks and stirred at 1000 rpm.
  • 180 g of mercaptopropyl-methyl-dimethoxysilane and 30 g of dodecylbenzenesulfonic acid are first added. After stirring for 5 minutes, a homogeneous mixture is formed. 2300 g of deionized water are then run in over the course of 20 minutes and the mixture is stirred at room temperature for 1 hour. The resulting emulsion is then homogenized for 12 minutes at 200 bar using a Gaulin machine.
  • the homogeneous emulsion is poured into a 4 l sulfation beaker equipped with a butterfly stirrer and heated to 85 ° C. with stirring at 170 rpm for 24 h.
  • the latex is then cooled to room temperature in 6 h and adjusted to a pH of 7 to 7.5 by adding 105.4 ml of potassium hydroxide solution.
  • a milky white emulsion containing 38.1% by weight of non-volatile constituents is obtained.
  • the average particle size determined by the laser scattered light method is 200 nm.
  • the gel content determination gives approximately 65% by weight.
  • the latex contains 2.0% by weight of potassium dodecylbenzenesulfonate as an emulsifier.
  • Example 2 Analogously to Example 1, 1650 g of octamethylcyclotetrasiloxane, 46.3 g of mercaptopropyl-methyl-dimethoxysilane and 30 g of dodecylbenzenesulfonic acid are reacted.
  • the latex contains 2.0% by weight of potassium dodecylbenzenesulfonate as an emulsifier.
  • Example 2 Analogously to Example 1, 1650 g of octamethylcyclotetrasiloxane, 46.3 mercaptopropyl-methyl-dimethoxysilane and 30 g of dodecylbenzenesulfonic acid are reacted.
  • the latex contains 2.0% by weight of potassium dodecylbenzenesulfonate as an emulsifier.
  • the homogeneous emulsion is poured into a 4 l sulfation beaker equipped with a butterfly stirrer and heated to 85 ° C. with stirring at 170 rpm for 24 h.
  • the latex is then cooled to room temperature in 6 h and adjusted to a pH of 8.1 by adding 106.5 ml of potassium hydroxide solution.
  • a milky white emulsion containing 36.9% by weight of non-volatile constituents is obtained.
  • the average particle size determined by the laser scattered light method was 192 nm.
  • the gel content determination gives 0.40% by weight.
  • the latex contains 2.0% by weight of potassium dodecylbenzenesulfonate as an emulsifier.
  • the latex contains 2.0% by weight of potassium dodecylbenzenesulfonate as an emulsifier.
  • 1580.0 g of the polyorganosiloxane latex produced according to Example 1 are placed in a 4 l stirring vessel equipped with a paddle stirrer, diluted with 653.0 g of deionized water at 200 rpm while stirring and the air is passed out of the reactor by introducing Nitrogen displaced.
  • a solution of 381.0 g of styrene and 19.0 g of methacrylic acid is first added dropwise with stirring over the course of 1 h, then 2.7 g of t-butyl perpivalate (75% strength) are added and the mixture is at room temperature and 5 h for 2 h stirred at 65 ° C. Finally, the latex is heated to 90 ° C. with stirring for 1 h and then cooled to room temperature.
  • a milky-white, medium-viscosity latex with a pH of 4.5 and a content of 38.1% by weight of non-volatile components is obtained.
  • 1580.0 g of the polyorganosiloxane latex prepared according to Example 2 are placed in a 4 l stirring vessel equipped with a paddle stirrer, diluted with 653.0 g deionized water at 200 rpm while stirring, and the air is passed out of the reactor by introducing Nitrogen displaced.
  • a solution of 381.0 g of styrene and 19.0 g of methacrylic acid is first added dropwise with stirring over the course of 1 h, then 2.7 g of t-butyl perpivalate (75% strength) are added and the mixture is at room temperature and 5 h for 2 h stirred at 65 ° C. Finally, the latex is heated to 90 ° C. with stirring for 1 h and then cooled to room temperature.
  • a milky-white, medium-viscosity latex with a pH of 4.2 and a content of 37.0% by weight of non-volatile components is obtained.
  • 1580.0 g of the polyorganosiloxane latex prepared according to Example 1 are placed in a 4 liter stirring vessel equipped with a paddle stirrer, diluted with 653.0 g deionized water at 200 rpm while stirring, and the air is passed out of the reactor by introducing Nitrogen displaced. It is stirring first a solution of 381.0 g of styrene and 19.0 g of methacrylic acid was added dropwise in the course of 1 h, then 2.7 g of t-butyl perpivalate (75% strength) were added and the mixture was stirred at room temperature for 2 h and at 65 ° C. for 5 h . Finally, the latex is heated to 90 ° C. with stirring for 1 h and then cooled to room temperature.
  • a milky-white, medium-viscosity latex with a pH of 4.3 and a content of 39.0% by weight of non-volatile components is obtained.
  • 1440.0 g of the polyorganosiloxane latex produced according to Example 1 are placed in a 4 l stirring vessel equipped with a paddle stirrer, diluted with 967.0 g of deionized water at 200 rpm while stirring and the air is passed out of the reactor by introducing Nitrogen displaced.
  • a solution of 330.6 g of styrene and 34.2 g of methacrylic acid, 228.0 g of ethyl acrylate and 5.9 g of azo-bis-isobutyronitrile is first added dropwise with stirring over the course of 1 h, and then the mixture is added at room temperature for 2 h Stirred at 70 ° C for 5 h. Finally, the latex is heated to 90 ° C. with stirring for 1 h and then cooled to room temperature.
  • a milky-white, medium-viscosity latex with a pH of 4.6 and a content of 38.6% by weight of non-volatile components is obtained.
  • 1580.0 g of the polyorganosiloxane latex prepared according to Example 1 are placed in a 4 l stirring vessel equipped with a paddle stirrer, diluted with 967.0 g of deionized water at 200 rpm while stirring and the air is passed out of the reactor by introducing Nitrogen displaced.
  • a solution of 330.6 g of styrene, 34.2 g of methacrylic acid, 114.0 g of ethyl acrylate, 114.0 g of butyl acrylate and 5.9 g of azo-bis-isobutyronitrile is first added dropwise with stirring, then the Mixture was stirred for 2 h at room temperature and 5 h at 70 ° C. Finally, the latex is heated to 90 ° C. with stirring for 1 h and then cooled to room temperature.
  • a milky-white, medium-viscosity latex with a pH of 4.4 and a content of 38.3% by weight of non-volatile components is obtained.
  • 960.0 g of the polyorganosiloxane latex prepared according to Example 1 are placed in a 4 liter stirring vessel equipped with a paddle stirrer, diluted with 641.0 g deionized water at 200 rpm while stirring and the air is passed out of the reactor by introducing Nitrogen displaced.
  • a solution of 231.5 g of styrene, 11.5 g of methacrylic acid, 156.0 g of butyl acrylate and 4.0 g of azo-bis-isobutyronitrile is first added dropwise with stirring, and then the mixture Stirred for 2 h at room temperature and 5 h at 70 ° C. Finally, the latex is heated to 90 ° C. with stirring for 1 h and then cooled to room temperature.
  • a milky-white, medium-viscosity latex with a pH of 4.4 and a content of 38.8% by weight of non-volatile components is obtained.
  • 960.0 g of the polyorganosiloxane latex prepared according to Example 1 are placed in a 4 liter stirring vessel equipped with a paddle stirrer, diluted with 641.0 g deionized water at 200 rpm while stirring and the air is passed out of the reactor by introducing Nitrogen displaced.
  • a solution of 231.5 g of styrene, 11.5 g of methacrylic acid, 156.0 g of ethyl acrylate and 4.0 g of azo-bis-isobutyronitrile is first added dropwise with stirring over the course of 1 h, and the mixture is then added at room temperature for 2 h Stirred at 70 ° C for 5 h. Finally, the latex is heated to 90 ° C. for 1 hour with stirring and then cooled to room temperature.
  • a milky-white, medium-viscosity latex with a pH of 4.3 and a content of 38.3% by weight of non-volatile components is obtained.
  • 960.0 g of the polyorganosiloxane latex prepared according to Example 1 are placed in a 4 liter stirring vessel equipped with a paddle stirrer, diluted with 641.0 g deionized water at 200 rpm while stirring and the air is passed out of the reactor by introducing Nitrogen displaced.
  • a solution of 231.5 g of styrene, 11.5 g of methacrylic acid, 78.0 g of butyl acrylate, 78.0 g of ethyl acrylate and 4.0 g of azo-bis-isobutyronitrile is first added dropwise with stirring, then the Mixture was stirred for 2 h at room temperature and 5 h at 70 ° C. Finally, the latex is heated to 90 ° C. with stirring for 1 h and then cooled to room temperature.
  • a milky-white, medium-viscosity latex with a pH of 4.4 and a content of 38.7% by weight of non-volatile components is obtained.
  • a milky-white, medium-viscosity latex with a pH of 5.6 and a content of 40.4% by weight of non-volatile components is obtained.
  • 1520.0 g of the polyorganosiloxane latex prepared according to Example 5 are placed in a 4-liter stirring vessel equipped with a paddle stirrer, while stirring at 200 rpm with a solution of 2.7 g of potassium persulfate and 1.1 g of sodium hydrogen carbonate in 625 , 0 g of deionized water and the air is displaced from the reactor by introducing nitrogen.
  • a solution of 216.0 g of styrene, 13.5 g of methacrylic acid and 324.0 g of butyl acrylate is first added dropwise with stirring over the course of 1 h, and the mixture is then stirred at room temperature for 2 h and at 80 ° C. for 5 h. Finally, the latex is heated to 90 ° C. with stirring for 1 h and then cooled to room temperature.
  • a milky-white, medium-viscosity latex with a pH of 5.4 and a content of 39.5% by weight of non-volatile components is obtained.
  • This leather which had been primed in this way, was then treated in a double spray application with 200 g of ®Bayderm-finish 80 UD, 450 g of water, 200 g of the graft product from Example 6, 150 g of ®Bayderm matting PC and 20 g of ®Bayderm additive VA. After drying and ironing, a very well finished automotive leather was obtained which, in the Taber Abrasion Test with an A18 stone, could withstand 300 revolutions under the load of 1 k without any damage.
  • 3 g of a bentonite are dispersed in 97 g of water by applying shear forces. 198 g of water are added to 100 g of this 3% bentonite dispersion. 25 g of caprolactam and 4 g of a defoamer were added. Then 225 g of ®Bayderm-finish 60 UD, 23 g of talc, 47 g of a hydrolyzed silica which is used as a matting agent, 150 g of ®Impranil Dispersion DLV and 225 g of the graft product from Example 6 are added with vigorous stirring. After intensive stirring for one hour, a paste is created that is suitable as a matt finish for synthetic leather or primed leather.
  • a leather primed analogously to application example 1 was finished with the following mixture (twice spray application): 200 parts DESMODERM Finish M, 200 parts diacetone alcohol, 600 parts BAYDERM Thinner NU, 20 parts DESMODERM Additive Z, 30 parts BAYDERM Fix DN and 50 parts XERODERM LF.
  • the finished trimmed leather had a slightly straw-like, dry feel.
  • Example of use 14 dressing with polyurethane dispersion - aqueous
  • the leather handle was too dry.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Graft Or Block Polymers (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Claims (3)

  1. Utilisation de produits de greffage obtenus par réaction de greffage de
    A) 30 à 95 % en poids, par rapport à la somme A + B, de polymères de greffage insaturés éthyléniquement sur
    B) 5 à 70 % en poids, par rapport à la somme A + B, d'un polyorganosiloxane qui, outre des groupes hydroxyles terminaux, est constitué de motifs répétés de formules
    Figure imgb0006
     où
    la structure I est en une quantité de 80 à 99,5 % molaires*,
    les structures II et/ou III sont en une quantité de 0,5 à 20 % molaires*,
    (* = par rapport à la somme I + II + III),
    sont incorporées dans le polyorganosiloxane et
    R1 et R2 représentent indépendamment l'un de l'autre un alkyle C1-C24 ou un aryle C6-C10,
    R3 est un alkylène C1-C8 linéaire ou ramifié,
    R4 représente un alkyle C1-C24, un alcoxy C1-C6, un aryle C6-C18, un hydroxy ou une liaison simple ou
    R3 et R4 représentent ensemble un hydrocarbure C4-C8 saturé à trois valences, de sorte qu'ils forment ensemble un cycle de 5 ou 6 maillons avec l'atome Si, R5 représente un alkylène C1-C8, et
    R6 représente un alkyle C1-C24, un alcoxy C1-C6, un aryle C6-C18 ou un hydroxy,
    comme liants de finissage du cuir.
  2. Utilisation selon la revendication 1, où les produits de greffage peuvent être obtenus par réaction de greffage de 35 à 80 % en poids de A sur 20 à 65 % en poids de B.
  3. Utilisation selon la revendication 1, où la structure I est incorporée en une quantité de 80 à 99,5 % molaires, la structure II est incorporée en une quantité de 0 à 10 % molaires et la structure III est incorporée en une quantité de 0 à 10 % molaires dans le polyorganosiloxane B à la condition que la somme des structures II et III représente au moins 0,5 % molaire (par rapport à la somme I + II + III).
EP93115450A 1992-09-30 1993-09-24 Utilisation de polyorganosiloxane greffé pour le finissage du cuir Expired - Lifetime EP0591784B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4232896A DE4232896A1 (de) 1992-09-30 1992-09-30 Verwendung von Polyorganosiloxan-Pfropfprodukten zur Lederzurichtung
DE4232896 1992-09-30

Publications (3)

Publication Number Publication Date
EP0591784A2 EP0591784A2 (fr) 1994-04-13
EP0591784A3 EP0591784A3 (en) 1994-06-15
EP0591784B1 true EP0591784B1 (fr) 1997-08-13

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ID=6469301

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EP93115450A Expired - Lifetime EP0591784B1 (fr) 1992-09-30 1993-09-24 Utilisation de polyorganosiloxane greffé pour le finissage du cuir

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EP (1) EP0591784B1 (fr)
JP (1) JPH06200300A (fr)
DE (2) DE4232896A1 (fr)
ES (1) ES2105029T3 (fr)

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* Cited by examiner, † Cited by third party
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JP6512083B2 (ja) * 2014-12-22 2019-05-15 日信化学工業株式会社 皮革用コーティング剤及び該コーティング剤を形成した皮革
WO2019082882A1 (fr) * 2017-10-24 2019-05-02 日信化学工業株式会社 Agent de revêtement pour cuir, et cuir revêtu par cet agent de revêtement
CN116396713B (zh) * 2023-03-21 2025-06-17 浙江红蜻蜓鞋业股份有限公司 一种制鞋用耐水解的水性胶黏剂及其加工工艺

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3542585A (en) * 1968-02-23 1970-11-24 Dow Corning Method for adhering acrylate finishes to silicone impregnated leather and resulting article
US3624015A (en) * 1969-04-09 1971-11-30 Dow Corning Finish/polish for white leather
DE3201194A1 (de) * 1982-01-16 1983-07-28 Bayer Ag, 5090 Leverkusen Vernetzbare pfropfpolymerisat-dispersionen aus hydrogensiloxan-gruppen und si-vinyl-gruppen enthaltenden organopolysiloxanen

Also Published As

Publication number Publication date
EP0591784A3 (en) 1994-06-15
ES2105029T3 (es) 1997-10-16
DE59307112D1 (de) 1997-09-18
EP0591784A2 (fr) 1994-04-13
JPH06200300A (ja) 1994-07-19
DE4232896A1 (de) 1994-03-31

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