EP0962585A2 - Poromere Kunstleder - Google Patents
Poromere Kunstleder Download PDFInfo
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- EP0962585A2 EP0962585A2 EP99110686A EP99110686A EP0962585A2 EP 0962585 A2 EP0962585 A2 EP 0962585A2 EP 99110686 A EP99110686 A EP 99110686A EP 99110686 A EP99110686 A EP 99110686A EP 0962585 A2 EP0962585 A2 EP 0962585A2
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- European Patent Office
- Prior art keywords
- monomers
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- polyurethane
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Classifications
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
Definitions
- the invention further relates to these poromeric synthetic leather self.
- poromeric synthetic leather should that of high quality natural types of leather, in particular Suede, come as close as possible. This mainly affects properties like a good water vapor permeability, a high one Tear resistance and pleasant haptic properties.
- poromeric synthetic leather is generally known (cf. plastic handbook, Carl Hanser Verlag, Kunststoff, Vienna, vol. 7: Polyurethane, 3rd edition 1993, chapter 10.2.1.4).
- the previously known Procedure is common that the synthetic leather from solutions or dispersions of polyurethanes that are contain organic solvents.
- the so-called Coagulation process a textile fabric with a organic solution of a polyurethane, if necessary. mixed with a polyurethane dispersion and if necessary. a polyelectrolyte impregnated and the fabric thus pretreated one after the other through several baths with mixtures of dimethylformamide and Water with decreasing dimethylformamide concentration led.
- JP 09/18 89 75 A variant of this process, which leads to textile articles leads particularly pleasant, leather-like handle, is in JP 09/18 89 75.
- a disadvantage of this process is that large amounts of exhaust air or Wastewater that contain organic solvents and cumbersome have to be processed.
- the object was therefore to provide poromeric synthetic leather, which differ as far as possible with regard to their usage properties differ little from natural types of leather and with less technical effort as known poromeric synthetic leather are producible.
- poromeric synthetic leather described above as well as the processes for their production.
- textile fabrics are used, which are woven or non-woven textiles with a weight per unit area of 100 to 1000 g / m2, particularly preferably 250 to 500 g / m 2 .
- the usual fibers are particularly suitable extendable polymers, for example polyamides, polyurethanes, Polypropylene, polyethylene, polyacrylonitrile and especially preferably polyester.
- Natural fibers such as Wool, cotton, Viscose or silk can be used.
- the polyesters are preferably poly (ethylene terephthalate), Poly (tetramethylene terephthalate) or poly (-1,4-dimethylenecyclohexane terephthalate).
- Polyester nonwovens that are needled are very particularly preferred could be.
- the monomers (a1) which are usually used in polyurethane chemistry diisocyanates used into consideration.
- diisocyanates X (NCO) 2 where X represents an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
- diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecanethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane, trimethylhexane diisocyanate , 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanato-diphenylmethane, 2,4'-diisocyanato-diphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), the isomers of the bis - (4-isocyan
- Mixtures of these are, in particular, mixtures of these isocyanates respective structural isomers of diisocyanatotoluene and diisocyanato-diphenylmethane important, especially the mixture from 80 mol% 2,4 diisocyanatotoluene and 20 mol% 2,6-diisocyanatotoluene suitable.
- the mixtures of aromatic isocyanates such as 2,4 diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic Isocyanates such as hexamethylene diisocyanate or IPDI in particular advantageous, the preferred mixing ratio of the aliphatic to aromatic isocyanates is 4: 1 to 1: 4.
- diols (a2) primarily higher molecular weight diols (a2.1), which have a molecular weight from about 500 to 5000, preferably from about 1000 to Have 3000 g / mol.
- the diols (a2.1) are, in particular, polyester polyols which are known, for example, from Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 19, pages 62 to 65. Polyester polyols are preferably used, which are obtained by reacting dihydric alcohols with dihydric carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures can also be used to prepare the polyester polyols.
- the polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally substituted, for example by halogen atoms, and / or unsaturated. Examples of these are suberic acid, azelaic acid, phthalic acid anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic endomethylenetetrahydrophthalic, glutaric anhydride, alkenylsuccinic acid, maleic anhydride, fumaric acid, dimer fatty acids.
- Dicarboxylic acids of the general formula HOOC- (CH 2 ) y -COOH are preferred, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, dodecanedicarboxylic acid and sebacic acid.
- polyhydric alcohols include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1 , 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methyl-propane-1,3-diol, methylpentanediols, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol , Polypropylene glycol, dibutylene glycol and polybutylene glycols.
- Alcohols of the general formula HO- (CH 2 ) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
- Examples include ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Neopentyl glycol and 1,5-pentanediol are further preferred.
- polycarbonate diols such as those e.g. by Implementation of phosgene with an excess of the structural components for the low molecular weight polyester polyols Alcohols can be obtained.
- Lactone-based polyester diols are also suitable, these being homopolymers or copolymers of lactones, preferably addition products of lactones with terminal hydroxyl groups onto suitable difunctional starter molecules.
- Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit also by a C 1 - bis C 4 alkyl radical may be substituted. Examples are epsilon-caprolactone, ⁇ -propiolactone, gamma-butyrolactone and / or methyl-epsilon-caprolactone and mixtures thereof.
- the monomers (a2.1) are polyether diols. They are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 or by addition of these compounds, if appropriate in a mixture or in succession, to starting components with reactive hydrogen atoms, such as alcohols or amines, for example Water, ethylene glycol, propane-1,2-diol, propane-1,3-diol, 1,2-bis (4-hydroxydiphenyl) propane or aniline are available. Polytetrahydrofuran with a molecular weight of 240 to 5000, and especially 500 to 4500, is particularly preferred.
- the polyols can also be used as mixtures in a ratio of 0.1: 1 to 1: 9 can be used.
- the hardness and elastic modulus of the polyurethanes can be increase if as diols (a2) in addition to the diols (a2.1) are still low molecular weight Diols (a2.2) with a molecular weight of about 62 up to 500, preferably from 62 to 200 g / mol, are used.
- the structural components of the. are used as monomers (a2.2) for the production of polyester polyols called short-chain Alkanediols used, the unbranched diols having 2 to 12 C atoms and an even number of C atoms as well Pentane-1,5-diol are preferred.
- the proportion of the diols is preferably (a2.1), based on the Total amount of diols (a2) 10 to 100 mol% and the proportion of Monomers (a2.2), based on the total amount of diols (a2) 0 to 90 mol%.
- the ratio is particularly preferably Diols (a2.1) to the monomers (a2.2) 0.1: 1 to 5: 1, especially preferably 0.2: 1 to 2: 1.
- the polyurethanes in addition to components (a1), (a2) and (a4) from monomers different from components (a1), (a2) and (a4) (a3), the at least one isocyanate group or at least a group reactive toward isocyanate groups and beyond at least one hydrophilic group or a group that is can be converted into a hydrophilic group, wear, built.
- hydrophilic groups or potentially hydrophilic groups “with” (potentially) hydrophilic groups " abbreviated.
- the (potentially) hydrophilic groups react with Isocyanates much slower than the functional groups of the monomers that are used to build the main polymer chain.
- the proportion of components with (potentially) hydrophilic groups on the total amount of components (a1), (a2), (a3) and (a4) generally such that the molar amount of (potentially) hydrophilic groups, based on the amount by weight of all monomers (a1) to (a4), 30 to 1000, preferably 50 to 500 and particularly is preferably 80 to 300 mmol / kg.
- the (potentially) hydrophilic groups can be non-ionic or preferably around (potentially) ionic hydrophilic Trade groups.
- the nonionic hydrophilic groups are polyalkylene oxide residues, in particular polyethylene glycol ether from preferably 5 to 100, preferably 10 to 80 repeating ethylene oxide units, in Consideration.
- the content of polyethylene oxide units is general 0 to 10, preferably 0 to 6 wt .-%, based on the Weight amount of all monomers (a1) to (a4).
- Preferred monomers with nonionic hydrophilic groups are Polyethylene oxide diols, polyethylene oxide monools and the reaction products from a polyethylene glycol and a diisocyanate, the carry a terminally etherified polyethylene glycol residue.
- diisocyanates and processes for their preparation are in the patents US 3 905 929 and US 3 920 598.
- Ionic hydrophilic groups are mainly anionic groups such as the sulfonate, carboxylate and phosphate groups in the form of their Alkali metal or ammonium salts as well as cationic groups such as ammonium groups, especially protonated tertiary amino groups or quaternary ammonium groups.
- Potentially ionic hydrophilic groups are primarily those that through simple neutralization, hydrolysis or quaternization reactions into the above ionic hydrophilic Have groups transferred, e.g. Carboxylic acid groups, Anhydride groups or tertiary amino groups.
- cationic monomers (a3) Monomers with tertiary amino groups of particularly practical Meaning, for example: tris (hydroxyalkyl) amines, N, N'-bis (hydroxyalkyl) alkylamines, N-hydroxyalkyl dialkylamines, Tris (aminoalkyl) amines, N, N'-bis (aminoalkyl) alkylamines, N-aminoalkyl dialkylamines, where the alkyl radicals and alkanediyl units these tertiary amines independently of one another from 1 to 6 Carbon atoms exist.
- tertiary amines are converted into the ammonium salts either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic acids, or by reaction with suitable quaternizing agents such as C 1 -C 6 -alkyl halides or benzyl halides, for example bromides or chlorides.
- acids preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic acids
- suitable quaternizing agents such as C 1 -C 6 -alkyl halides or benzyl halides, for example bromides or chlorides.
- Suitable monomers with (potentially) anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which carry at least one alcoholic hydroxyl group or at least one primary or secondary amino group.
- Dihydroxyalkylcarboxylic acids are preferred, especially those with 3 to 10 carbon atoms, as are also described in US Pat. No. 3,412,054.
- compounds of the general formula in which R 1 and R 2 are a C 1 to C 4 alkanediyl unit and R 3 is a C 1 to C 4 alkyl unit and especially dimethylolpropionic acid (DMPA) is preferred.
- DMPA dimethylolpropionic acid
- Dihydroxysulfonic acids and Dihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid.
- dihydroxyl compounds with a molecular weight are suitable over 500 to 10,000 g / mol with at least 2 carboxylate groups, which are known from DE-A 3 911 827.
- aminocarboxylic acids such as lysine, ⁇ -alanine, which in the DE-A-2034479 adducts of aliphatic diprimaries Diamines on ⁇ , ⁇ -unsaturated carboxylic or sulfonic acids in Consideration.
- Particularly preferred compounds of the formula (a3.1) are N- (2-aminoethyl) -2-aminoethane carboxylic acid and the as well as the N- (2-aminoethyl) -2-aminoethanesulfonic acid or the corresponding Alkali salts, Na being particularly preferred as the counter ion.
- the adducts of the abovementioned are also particularly preferred aliphatic diprimary diamines on 2-acrylamido-2-methylpropanesulfonic acid, such as in which D 1 954 090 are described.
- monomers with potentially ionic groups can be converted into the ionic form before, during, but preferably after the isocyanate polyaddition, because the ionic monomers in the reaction mixture often only difficult to solve.
- the monomers (a4) which are from the monomers (a1) to (a3) are generally used for networking or Chain extension. They are generally more than two-valued non-phenolic alcohols, amines with 2 or more primary and / or secondary amino groups and compounds which in addition to a or more alcoholic hydroxyl groups one or more wear primary and / or secondary amino groups.
- Polyamines with 2 or more primary and / or secondary amino groups are mainly used when the chain extension or crosslinking should take place in the presence of water, since Amines are generally faster than using alcohols or water Isocyanates react. This is often necessary when aqueous dispersions of cross-linked polyurethanes or polyurethanes with a high molecular weight. In such cases the procedure is such that prepolymers with isocyanate groups manufactures, quickly dispersed in water and then by adding compounds with more than isocyanates reactive amino groups chain-extended or cross-linked.
- Suitable amines are generally polyfunctional amines of the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which at least amino groups, selected from the group of primary and secondary amino groups.
- Examples include diamines such as diaminoethane, diaminopropanes, Diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, Amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, Aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as Diethylenetriamine or 1,8-diamino-4-aminomethyloctane.
- diamines such as diaminoethane, di
- the amines can also be in blocked form, e.g. in the form of corresponding ketimines (see e.g. CA-1 129 128), ketazines (cf. e.g. US-A 4 269 748) or amine salts (see US-A 4 292 226) be used.
- Mixtures of di- and triamines are preferably used, especially preferably mixtures of isophoronediamine and diethylenetriamine.
- the polyurethanes preferably contain no polyamine or 1 to 20, particularly preferably 4 to 15 mol%, based on the total amount of components (a2) and (a4) of a polyamine with at least 2 amino groups reactive towards isocyanates as monomers (a4).
- Alcohols with a higher valence than 2, for adjustment serve a certain degree of branching or networking can be e.g. Trimethylolpropane, glycerin or sugar.
- monomers (a4) can also be higher than divalent isocyanates are used.
- Commercial Compounds are, for example, isocyanurate or biuret of hexamethylene diisocyanate.
- Monomers (a5) which may also be used are monoisocyanates, Monoalcohols and mono-primary and secondary amines. in the in general, their proportion is at most 10 mol%, based on the total molar amount of monomers.
- These monofunctional Compounds usually carry further functional groups such as olefinic groups or carbonyl groups and are used for introduction of functional groups in the polyurethane that the Dispersion or crosslinking or other polymer-analog Enable implementation of the polyurethane.
- TMI isopropenyl-a
- TMI a-dimethylbenzyl isocyanate
- esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
- the ratio A: B is very particularly preferably as close as possible to 1: 1.
- monomers with only one reactive group are generally used in amounts of up to 15 mol%, preferably up to 8 mol%, based on the total amount of components ( a1), (a2), (a3) and (a4) are used.
- the monomers (a1) to (a4) used bear on average usually 1.5 to 2.5, preferably 1.9 to 2.1, particularly preferably 2.0 isocyanate groups or functional groups with Isocyanates can react in an addition reaction.
- the polyaddition of components (a1) to (a4) is generally carried out according to the known methods, preferably the so-called “Acetone process” or the prepolymer blend process ", the are described for example in DE-A-4418157 becomes.
- the general procedure is to start with one inert organic solvents, a prepolymer or the polyurethane (a) and then the prepolymer or Polyurethane (a) dispersed in water.
- the prepolymer the conversion to polyurethane (a) takes place by reaction with the Water or by adding an amine (component a4).
- the solvent is used after dispersion All or part of the distillation removed.
- the dispersions generally have a solids content of 10 to 75, preferably 20 to 65% by weight and a viscosity of 10 to 500 m Pas (measured at a temperature of 20 ° C. and a shear rate of 250 s -1 ).
- Hydrophobic aids that can be difficult to homogenize to be distributed in the finished dispersion, for example Phenol condensation resins made from aldehydes and phenol or phenol derivatives or epoxy resins and others e.g. in DE-A-3903538, 43 09 079 and 40 24 567 polymers mentioned in the polyurethane dispersions serve, for example, as a liability improver, can be described in the three fonts mentioned above Methods already before the polyurethane or the prepolymer be added to the dispersion.
- the polyurethane dispersions can, based on their solids content up to 40, preferably up to 20% by weight of other polymers (B) contained in dispersed form. Such polyurethane dispersions are generally mixed with Dispersions containing the polymers (B) are produced. Prefers however, the polyurethane dispersions are free of effective amounts other polymers.
- (Meth) acrylic is a shortening for methacrylic or acrylic.
- Examples of monomers (b1) include (meth) acrylic acid alkyl esters with a C 1 -C 10 alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate, and acrylic or methacrylic acid.
- mixtures of the (meth) acrylic acid alkyl esters suitable.
- Vinyl esters of carboxylic acids with 1 to 20 C atoms are e.g. Vinyl laurate, stearate, vinyl propionate and vinyl acetate.
- vinyl aromatic compounds come vinyl toluene, alpha and p-methylstyrene, alpha-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
- nitriles are acrylonitrile and methacrylonitrile.
- the vinyl halides are substituted with chlorine, fluorine or bromine ethylenically unsaturated compounds, preferably vinyl chloride and Vinylidene chloride.
- non-aromatic hydrocarbons with 2 to 8 carbon atoms and one or two olefinic double bonds are butadiene and isoprene and chloroprene, as well as ethylene, propylene and isobutylene called.
- the main monomers are also preferably mixed used.
- Vinylaromatic compounds such as styrene are frequently used, for example, in a mixture with C 1 -C 20 -alkyl (meth) acrylates, in particular with C 1 -C 8 -alkyl (meth) acrylates, or non-aromatic hydrocarbons such as isoprene or preferably butadiene.
- Possible monomers (b3) are: esters of acrylic and methacrylic acid of alcohols with 1 to 20 carbon atoms, which in addition to Oxygen atom in the alcohol group at least one more Contain heteroatom and / or an aliphatic or aromatic Contain ring, such as 2-ethoxyethyl acrylate, 2-butoxyethyl (meth) acrylate, Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (Meth) acrylic acid aryl, alkaryl or Cycloalkyl esters, such as cyclohexyl (meth) acrylate, phenylethyl (meth) acrylate, Phenylpropyl (meth) acrylate or acrylic acid ester of heterocyclic alcohols such as furfuryl (meth) acrylate called.
- esters of acrylic and methacrylic acid of alcohols with 1 to 20 carbon atoms which in addition to
- hydroxy-functional monomers for example (meth) acrylic acid-C 1 -C 15 -alkyl esters, which are substituted by one or two hydroxyl groups.
- hydroxy-functional comonomers are (meth) acrylic acid-C 2 -C 8 -hydroxyalkyl esters, such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl (meth) acrylate.
- monomers with carboxylic acid or carboxylic anhydride groups e.g. Acrylic acid, methacrylic acid, Itaconic acid, maleic anhydride; these monomers are preferably in amounts of 0 to 10, particularly preferred from 0.1 to 3% by weight, based on the copolymer, used.
- the copolymer is produced by free radicals Polymerization. Suitable polymerization methods, such as substance, Solution, suspension or emulsion polymerization are that Known specialist.
- the copolymer is preferably obtained by solution polymerization with subsequent dispersion in water or particularly preferred made by emulsion polymerization.
- the comonomers can be used as usual in emulsion polymerization in the presence of a water-soluble initiator and one Emulsifier can be polymerized at preferably 30 to 95 ° C.
- Suitable initiators are e.g. Sodium, potassium and ammonium persulfate, Peroxides such as tert-butyl hydroperoxide, water soluble Azo compounds or redox initiators.
- E.g. serve as emulsifiers Alkali salts of longer-chain fatty acids, Alkyl sulfates, alkyl sulfonates, alkylated aryl sulfonates or alkylated biphenyl ether sulfonates. Furthermore come as Emulsifiers Reaction products of alkylene oxides, in particular Ethylene or propylene oxide with fatty alcohols or acids or Phenol or alkylphenols into consideration.
- aqueous secondary dispersions the copolymer first by solution polymerization in an organic Solvent and then with the addition of salt formers, e.g. from ammonia to carboxylic acid groups Copolymers in water without the use of an emulsifier or Dispersing aid dispersed.
- the organic solvent can be distilled off.
- aqueous secondary dispersions is known to the person skilled in the art and e.g. in DE-A-37 20 860.
- Suitable are e.g. -SH groups containing compounds such as mercaptoethanol, mercaptopropanol, Thiophenol, thioglycerol, thioglycolic acid ethyl ester, thioglycolic acid methyl ester and tert-dodecyl mercaptan. You can e.g. in Quantities from 0 to 0.5% by weight, based on the copolymer, be used.
- the type and amount of the comonomers is preferably chosen so that that the copolymer obtained has a glass transition temperature between -60 to + 140 ° C, preferably -60 to + 100 ° C.
- the Glass transition temperature of the copolymer is determined by Differential thermal analysis or differential scanning calorimetry determined according to ASTM 3418/82.
- the number average molecular weight M n is preferably 10 3 to 5 ⁇ 10 6 , particularly preferably 10 5 to 2 ⁇ 10 6 g / mol (determined by gel permeation chromatography with polystyrene as standard).
- the polyurethane dispersions can be commercially available auxiliaries and Additives such as blowing agents, defoamers, emulsifiers, Thickeners and thixotropic agents, colorants such as Dyes and pigments included.
- the polyurethane dispersions contain less than 10, preferably less than 0.5% by weight of organic solvents.
- the impregnates from the textile fabrics and the polyurethane dispersions is generally made by using the Applies polyurethane dispersions by conventional methods.
- Application methods are particularly suitable for spraying, dipping, knife coating, Brushing, padding.
- drying is carried out, preferably at temperatures of 20 to 150 ° C.
- Suitable Bronsted bases preferably have a pK B value of at most 5.
- Bronsted bases are alkali metal hydroxides, -Carbonates and -hydrogen carbonates, ammonia, amines, which if necessary. can also be used in a mixture. Is particularly preferred Caustic soda.
- the aqueous solutions generally contain 1 to 40, preferably 2 to 10% by weight of the Bronsted bases.
- the temperature of the aqueous solutions that are impregnated can act, is usually 0 to 120 ° C, preferred 20 to 100 ° C.
- the exposure time is generally 1 to 300 mm, preferably 1 to 120 min.
- aqueous solutions are expediently left on the impregnates act by spraying them completely wetted or immersed the impregnate in the aqueous solutions.
- poromeric Synthetic leather With increasing exposure time, temperature and concentration of Brönsted base in the aqueous solution becomes the poromeric Synthetic leather has a softer grip and a rougher surface.
- the impregnates have practically no water vapor permeability, measured according to DIN 53333, whereas the poromeric synthetic leather has a water vapor permeability of more than 1, usually from 1 to 10 mg / hcm 2 .
- the Bronsted base for example by making the poromeric synthetic leather washed out with water. After that, the poromeric synthetic leather usually dried.
- poromeric synthetic leather then treated or post-treated analogously to natural leather e.g. by brushing, milling, milling or ironing.
- the poromeric leathers are basically suitable for all applications in which natural leather is used, in particular, they can be used instead of suede.
- Emuldur® DS 2299 (BASF AG) was used as the PU dispersion.
- Emuldur DS 2299 is an aliphatic polyester urethane dispersion with 40% fixed salary.
- the dried nonwovens were subsequently in 5% sodium hydroxide solution treated at 90 ° C with constant, gentle stirring.
- the nonwovens were removed after 15, 30, 45 and 60 min Sodium hydroxide solution removed, washed out and dried.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
- a1)
- Diisocyanaten mit 4 bis 30 C-Atomen,
- a2)
- Diolen, von denen
- a2.1)
- 10 bis 100 mol-%, bezogen auf die Gesamtmenge der Diole
- (a2),
- ein Molekulargewicht von 500 bis 5000 aufweisen, und
- a2.2)
- 0 bis 90 mol-%, bezogen auf die Gesamtmenge der Diole
- (a2),
- ein Molekulargewicht von 60 bis 500 g/mol aufweisen,
- a3)
- von den Monomeren (a1) und (a2) verschiedene Monomere mit wenigstens einer Isocyanatgruppe oder wenigstens einer gegenüber Isocyanatgruppen reaktiven Gruppe, die darüberhinaus wenigstens eine hydrophile Gruppe oder eine potentiell hydrophile Gruppe tragen, wodurch die Wasserdispergierbarkeit der Polyurethane bewirkt wird,
- a4)
- gegebenenfalls weiteren von den Monomeren (a1) bis (a3) verschiedenen mehrwertigen Verbindungen mit reaktiven Gruppen, bei denen es sich um alkoholische Hydroxylgruppen, primäre oder sekundäre Aminogruppen oder Isocyanatgruppen und
- a5)
- gegebenenfalls von den Monomeren (a1) bis (a4) verschiedenen einwertigen Verbindungen mit einer reaktiven Gruppe, bei der es sich um eine alkoholische Hydroxylgruppe, eine primäre oder sekundäre Aminogruppe oder eine Isocyanatgruppe handelt.
- R4 und R5 unabhängig voneinander für eine C1- bis C6-Alkandiyl-Einheit,
bevorzugt Ethylen
und X für COOH oder SO3H stehen.
Neben den Komponenten (a1), (a2), (a3) und (a4) werden Monomere mit nur einer reaktiven Gruppe im allgemeinen in Mengen bis zu 15mol-%, bevorzugt bis zu 8 mol-%, bezogen auf die Gesamtmenge der Komponenten (a1), (a2), (a3) und (a4) eingesetzt.
- Vlies A:
- ca. 300 g/m2 (leichter vernadelte Ware)
- Vlies B:
- ca. 450 g/m2 (dichter vernadelte Ware)
Beispiel | Vlies | Festauftrag |
1 | A | 30% |
2 | A | 40% |
3 | B | 30% |
4 | B | 40% |
Claims (11)
- Verfahren zur Herstellung von poromerem Kunstleder, wobei manI. ein im wesentlichen porenfreies Imprägnat herstellt, indem man ein textiles Flächengebilde mit einer wässerigen Polyurethandispersion imprägniert, trocknet undII. aus dem Imprägnat ein poromeres Kunstleder herstellt, indem man auf das Imprägnat eine wässerige Lösung einer Brönsted-Base einwirken läßt.
- Verfahren nach Anspruch 1, wobei man als textile Flächengebilde Polyestervliesstoffe mit einem Flächengewicht von 100 bis 1000 g/m2 einsetzt.
- Verfahren nach Anspruch 1 oder 2, wobei man eine wässerige Polyurethandispersion, enthaltend ein Polyurethan, welches ionische und/oder nicht-ionische hydrophile Gruppen trägt, einsetzt.
- Verfahren nach den Ansprüchen 1 bis 3, wobei das Polyurethan aufgebaut ist aus
- a1)
- Diisocyanaten mit 4 bis 30 C-Atomen,
- a2)
- Diolen, von denen
- a2.1)
- 10 bis 100 mol-%, bezogen auf die Gesamtmenge der Diole
- (a2),
- ein Molekulargewicht von 500 bis 5000 aufweisen, und
- a2.2)
- 0 bis 90 mol-%, bezogen auf die Gesamtmenge der Diole
- (a2),
- ein Molekulargewicht von 60 bis 500 g/mol aufweisen,
a3) von den Monomeren (a1) und (a2) verschiedene Monomere mit wenigstens einer Isocyanatgruppe oder wenigstens einer gegenüber Isocyanatgruppen reaktiven Gruppe, die darüberhinaus wenigstens eine hydrophile Gruppe oder eine potentiell hydrophile Gruppe tragen, wodurch die Wasserdispergierbarkeit der Polyurethane bewirkt wird,a4) gegebenenfalls weiteren von den Monomeren (a1) bis (a3) verschiedenen mehrwertigen Verbindungen mit reaktiven Gruppen, bei denen es sich um alkoholische Hydroxylgruppen, primäre oder sekundäre Aminogruppen oder Isocyanatgruppen unda5) gegebenenfalls von den Monomeren (a1) bis (a4) verschiedenen einwertigen Verbindungen mit einer reaktiven Gruppe, bei der es sich um eine alkoholische Hydroxylgruppe, eine primäre oder sekundäre Aminogruppe oder eine Isocyanatgruppe handelt. - Verfahren nach den Ansprüchen 1 bis 4, wobei die wässerige Dispersion, bezogen auf den Feststoffgehalt des Polyurethans, bis zu 40 Gew.-% ein durch radikalisch initiierte Polymerisation hergestelltes Polymer (Polymer B) enthält, welches aufgebaut ist ausb1) 30 bis 100 Gew.-Teilen wenigstens eines Monomeren aus der Gruppe umfassend C1- bis C20-Alkyl(meth)acrylate, Vinylester, von 3 bis zu 20 C-Atome aufweisende ungesättigte Carbonsäuren, ethylenisch ungesättigte Nitrile, Vinylaromaten mit bis zu 20 C-Atomen, Vinylhalogenide und aliphatische Kohlenwasserstoffe mit 2 bis 8 C-Atomen und 1 oder 2 Doppelbindungen (Monomere b1) undb2) 0 bis 70 Gew.-Teilen sonstigen, wenigstens eine ethylenisch ungesättigte Gruppe aufweisenden Verbindungen I (Monomere b2)
- Verfahren nach den Ansprüchen 1 bis 5, wobei bei der Herstellung des Imprägnats 20 bis 100 Gew.-%, bezogen auf das Gewicht des textilen Flächengebildes, der Polyurethandispersion, bezogen auf deren Feststoffgehalt, eingesetzt werden.
- Verfahren nach den Ansprüchen 1 bis 6, wobei man eine Brönsted-Base mit einem pKB-Wert von maximal 5 einsetzt.
- Verfahren nach den Ansprüchen 1 bis 7, wobei man als Brönsted-Base Alkalihydroxide, -Carbonate und -Hydrogencarbonate, Ammoniak, Amine, gegebenenfalls auch im Gemisch einsetzt.
- Verfahren nach den Ansprüchen 1 bis 8, wobei man eine wässerige Lösung, die 2 bis 10 Gew.-% der Brönsted-Base enthält, bei einer Temperatur von 20 bis 100°C über einen Zeitraum von 1 bis 300 min einwirken läßt.
- Verfahren nach den Ansprüchen 1 bis 9, wobei man im Anschluß an die Einwirkung der wässerigen Lösung der Brönsted-Base das entstandene poromere Kunstleder mit Wasser auswäscht und trocknet.
- Poromere Kunstleder erhältlich nach den Verfahren gemäß den Ansprüchen 1 bis 10.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19825453 | 1998-06-06 | ||
DE19825453A DE19825453A1 (de) | 1998-06-06 | 1998-06-06 | Poromere Kunstleder |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0962585A2 true EP0962585A2 (de) | 1999-12-08 |
EP0962585A3 EP0962585A3 (de) | 2002-04-10 |
Family
ID=7870219
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99110686A Withdrawn EP0962585A3 (de) | 1998-06-06 | 1999-06-02 | Poromere Kunstleder |
Country Status (4)
Country | Link |
---|---|
US (1) | US6231926B1 (de) |
EP (1) | EP0962585A3 (de) |
CA (1) | CA2273630A1 (de) |
DE (1) | DE19825453A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004061198A1 (en) * | 2002-12-20 | 2004-07-22 | Dow Global Technologies Inc. | Process to make synthetic leather and synthetic leather made therefrom |
DE102009014699A1 (de) | 2009-03-27 | 2010-10-07 | Carl Freudenberg Kg | Verfahren zur Herstellung einer reaktiven Polyurethan-Emulsion |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100349041B1 (ko) * | 1999-03-30 | 2002-08-21 | 가부시키가이샤 구라레 | 피혁형 시트의 제조방법 |
DE10221704A1 (de) | 2001-06-05 | 2003-01-23 | Compo Gmbh & Co Kg | Düngemittel mit verzögerter Freisetzung und Verfahren zu dessen Herstellung |
AU2003214115A1 (en) * | 2002-03-15 | 2003-09-29 | Basf Aktiengesellschaft | Use of polyelectrolytes in the production of leather |
DE10322266A1 (de) | 2003-05-16 | 2004-12-02 | Basf Ag | Selbstemulgierende wäßrige Polyurethandispersion |
US20050182187A1 (en) * | 2004-02-12 | 2005-08-18 | Koonce William A. | Polyurethane dispersions and coatings made therefrom |
DE102004010456A1 (de) * | 2004-03-01 | 2005-09-22 | Carl Freudenberg Kg | Verfahren zur Herstellung eines lichtechten Syntheseleders und danach hergestellte Produkte |
US20060111506A1 (en) * | 2004-11-22 | 2006-05-25 | Bedri Erdem | Filled polyurethane dispersions |
US20060116454A1 (en) * | 2004-12-01 | 2006-06-01 | Bedri Erdem | Stable thermally coaguable polyurethane dispersions |
ES2344176T3 (es) * | 2007-01-17 | 2010-08-19 | Basf Se | Laminado que contiene pelicula y vellon a base de poliuretano termoplastico. |
CN101959914B (zh) * | 2007-12-26 | 2014-02-12 | 陶氏环球技术有限责任公司 | 聚氨酯分散体和从该分散体制得的涂层 |
US9732026B2 (en) | 2012-12-14 | 2017-08-15 | Resinate Technologies, Inc. | Reaction products containing hydroxyalkylterephthalates and methods of making and using same |
US9963822B2 (en) | 2013-01-11 | 2018-05-08 | Dow Global Technologies Llc | Polyurethane dispersion based synthetic leathers |
MX2021001999A (es) | 2018-08-21 | 2021-04-28 | Dow Global Technologies Llc | Proceso para formar un cuero sintetico. |
BR112021002988A2 (pt) | 2018-08-21 | 2021-05-11 | Dow Global Technologies Llc | processo, e, couro sintético |
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US4171391A (en) * | 1978-09-07 | 1979-10-16 | Wilmington Chemical Corporation | Method of preparing composite sheet material |
US4496624A (en) * | 1982-07-14 | 1985-01-29 | Norwood Industries, Inc. | Fibrous web impregnated with coagulated polyurethane and polyolefin admixture |
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JPS4824431B1 (de) * | 1970-08-04 | 1973-07-20 | ||
JPS5328773A (en) * | 1976-08-25 | 1978-03-17 | Kuraray Co | Animallfurrlike knitted woven goods and method of producing same |
JPS5362804A (en) * | 1976-11-12 | 1978-06-05 | Unitika Ltd | Production of suede like fabric |
JPS54101403A (en) * | 1978-01-27 | 1979-08-10 | Toyo Purodakutsu Kk | Preparation of artificial leather |
-
1998
- 1998-06-06 DE DE19825453A patent/DE19825453A1/de not_active Withdrawn
-
1999
- 1999-06-02 EP EP99110686A patent/EP0962585A3/de not_active Withdrawn
- 1999-06-04 CA CA002273630A patent/CA2273630A1/en not_active Abandoned
- 1999-06-04 US US09/325,798 patent/US6231926B1/en not_active Expired - Fee Related
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Publication number | Priority date | Publication date | Assignee | Title |
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US4171391A (en) * | 1978-09-07 | 1979-10-16 | Wilmington Chemical Corporation | Method of preparing composite sheet material |
US4496624A (en) * | 1982-07-14 | 1985-01-29 | Norwood Industries, Inc. | Fibrous web impregnated with coagulated polyurethane and polyolefin admixture |
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Title |
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DATABASE WPI Section Ch, Derwent Publications Ltd., London, GB; Class A00, AN 1968-01303Q XP002190207 & JP 43 004671 B (TOYM) * |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004061198A1 (en) * | 2002-12-20 | 2004-07-22 | Dow Global Technologies Inc. | Process to make synthetic leather and synthetic leather made therefrom |
DE102009014699A1 (de) | 2009-03-27 | 2010-10-07 | Carl Freudenberg Kg | Verfahren zur Herstellung einer reaktiven Polyurethan-Emulsion |
Also Published As
Publication number | Publication date |
---|---|
DE19825453A1 (de) | 1999-12-09 |
US6231926B1 (en) | 2001-05-15 |
EP0962585A3 (de) | 2002-04-10 |
CA2273630A1 (en) | 1999-12-06 |
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