Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica

Definitions

• the invention relates to silica sol-modified aqueous polyurethane-polyurea dispersions and their use as coating compositions with improved chemical resistance and water vapor permeability as well as improved mechanical properties, in particular for the textile and leather sector.
• Aqueous systems are increasingly used in the coating of textiles and leather.
• the requirements for such coating systems are above all high resistance to chemicals and water, high mechanical strength as well as high tensile and tear strength and adhesion. These requirements are largely met by polyurethane dispersions.
• the various options for producing such dispersions have been described in e.g. B. summarized by D. Dieterich in an overview article [D. Dieterich, Prog. Org. Coatings 9, 281 (1981)].
• the chemical and mechanical resistance of coatings made from polyurethane-polyurea dispersions can be determined from US Pat. Nos. 5,041,494, 5,354,808 and 5,554,686, and EP-A 0 924231 and EP-A 0 924230 , hereinafter referred to as PU dispersions, can be improved if the PUR dispersions are modified with alkoxysilane groups.
• the present invention was therefore based on the object of providing alternative PU dispersions for the field of textile and leather coating, which on the one hand have the advantages of the silane-modified products, namely the improved chemical resistance compared to conventional PUR dispersions with the same good swelling behavior
• the advantages of the silane-modified products namely the improved chemical resistance compared to conventional PUR dispersions with the same good swelling behavior
• PUR dispersions which do not have alkoxysilane groups, in combination with silica sols correspond to the property profile described above.
• these dispersions among other things, have a significantly improved water vapor permeability and their gloss levels do not change.
• the dispersions according to the invention are more easily accessible than those known from the prior art (DE 4 236 569A1) according to known water vapor-permeable PUR coating compositions and have better water vapor permeability with the same good swelling behavior in water.
• the invention therefore relates to binder compositions, characterized in that they consist of a combination of
• the invention further relates to the use of the coating compositions described as binders for textiles and leather.
• PUR dispersions (A) are generally composed of:
• polymeric polyols with average molecular weights from 400 to 6000
• one or more of the compounds (A3) and / or (A4) contains an ionic group or is capable of forming an ionic group.
• This ionic group can be cationic or preferably anionic.
• Neutralization can be converted into ionic groups, d. H. they are able to form an ionic group and
• Suitable diisocyanates (Al) are in principle those of the molecular weight range 140 to 400 with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups, such as, for. B.
• HDI 1,4-diisocyanatobutane
• HDI 1,6-diisocyanate hexane
• 2-methyl-l 5-diisocyanatopentane
• l 5-diisocyanato-2,2-dimethylpentane
• 2,2,4- or 2,4,4-trimethyl-l 6-diisocyanatohexane
• 1,10-diisocyanatodecane 1,10-diisocyanatodecane
• 1,3- and 1,4-diisocyanatocyclohexane 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane, l-isocyanato-l-methyl-4 (3) isocyanatomethylcyclohexane, bis (isocyanatomethyl) norboman, 1,3- and l, 4-bis- (2-isocyanato- prop-2-yl) benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane, 1,5-diisocyanatonaphthalene or any mixture of such diisocyan
• AI is polyisocyanates or polyisocyanate mixtures based on HDI, IPDI and / or 4,4'-diisocyanatodicyclohexylmethane.
• AI polyisocyanates
• any polyisocyanates made from at least two diisocyanates and modified by modifying simple aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates with uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure, as described, for example, in J. Prakt. Chem. 336 (1994) 185-200, DE-A-1 670 666, DE-A-1 954 093,
• DE-A-2 414 413, DE-A-2 452 532, DE-A-2 641 380, DE-A-3 700 209, DE-A-3 900 053 and DE-A-3 928 503 or EP- A-0 336 205, EP-A-0 339 396 and EP-A-0 798 299 are described by way of example.
• the polymeric polyols (A2) in the molecular weight range from 400 to 6000 are the usual ones that have long been used for polyurethanes, with a OH functionality of at least 1.8 to about 4 such as polyacrylates, polyesters, polylactones, polyethers, polycarbonates, polyester carbonates, polyacetals, polyolefins and polysiloxanes.
• Polyols in a molecular weight range from 600 to 2500 with an OH functionality of 2 to 3 are preferably used.
• Suitable monoalcohols (A3) are preferably aliphatic monoalcohols with 1-18 C atoms, such as, for example, ethanol, n-butanol, ethylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, or 1-hexadecanol.
• Polyols, aminopolyols or polyamines with a molecular weight below 400 (A4), which can be used as chain extenders in polyurethanes or polyurethane dispersions, are also described in large numbers in the corresponding literature. Examples include: ethanediol, 1,4-butanediol, cyclohexanedimethanol, trimethylolpropane, glycerol and hydrazine, ethylenediamine, 1,4-diaminobutane, isophoronediamine, diethylenetriamine and 4,4-diaminodicyclohexylmethane.
• polyurethane dispersions according to the invention can contain hydrophilic polyoxyalkylene ethers (A5) with at least one hydroxyl or amino group.
• These polyethers contain a high proportion (approx. 30% by weight to 100% by weight) of building blocks which are derived from ethylene oxide.
• Linear polyethers with a functionality between 1 and 3 come into question, but also
• R and R each independently represent a divalent aliphatic, cycloaliphatic or aromatic radical having 1 to 18 carbon atoms, which can be interrupted by oxygen and / or nitrogen atoms, and R 3 is a non-hydroxy-terminated polyester or preferably polyether. R 3 particularly preferably represents an alkoxy-terminated polyethylene oxide radical.
• the hydroxy components (A2), (A3) and (A4) may contain double bonds, which, for. B. from long-chain aliphatic carboxylic acids or fatty alcohols. Functionalization with olefinic double bonds is e.g. B. possible by the incorporation of allylic groups or of acrylic acid or methacrylic acid and their respective esters.
• Components (A3) or (A4) which contain an ionic group or are capable of forming an ionic group are, for. B. dimethylolpropionic acid, hydroxypivalic acid, the sodium salt of 2- (2-amino-ethylamino) -ethanesulfonic acid, polyether sulfonate, the propoxylated adduct of 2-butenediol and NaHSO 3 and building blocks which can be converted into cationic groups such as N-methyl-diethanolamine.
• Components (A3) or (A4) which have carboxy or carboxylate and / or sulfonate groups are preferably used.
• aqueous polyurethane dispersions (A) are prepared in the known, conventional manner: the polyisocyanate component is allowed to react with a polymeric polyol and low molecular weight chain extenders to give a polyurethane, a solvent being used optionally and advantageously, which can later be removed if necessary ,
• the conventional solvents known per se are suitable as solvents
• Paint solvents such as. B. ethyl acetate, butyl acetate, 1-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene, white spirit, mixtures, the above contain all higher substituted aromatics, such as those under the names Solvent Naphtha, Solvesso ® (Exxon), Cypar ® (Shell), Cyclo Sol ® (Shell), Tolu Sol ® (Shell),
• Shellsol ® (Shell) are commercially available, carbonic acid esters, such as dimethyl carbonate, Diethyl carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate, lactones such as ß-propiolactone, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -methyl caprolactone, propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl and n-butyl ether -Methylpyrrolidone and N-methylcaprolactam, or any mixture of such solvents.
• carbonic acid esters such as dimethyl carbonate, Diethyl carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate
• lactones such as ß-propiolactone
• ⁇ -butyrolactone ⁇ -caprolactone
• ⁇ -methyl caprolactone ⁇ -methyl caprolactone
• propylene glycol diacetate
• groups capable of neutralization are then converted into the salt form and the dispersion is produced with water.
• the dispersion can be adjusted very finely so that it practically has the appearance of a solution, but very coarse settings are also possible, which are also sufficiently stable.
• low average particle sizes of ⁇ 300 nm or high proportions of hydrophilic groups are advantageous, since this improves the emulsification of the polyisocyanate and thus the quality of the paint film.
• the solids content can also be within wide limits of e.g. B. 20 - 60% can be varied.
• the silica sol-modified PU dispersions according to the invention preferably contain a solids content of 20-60% and particularly preferably 30-50% in the polyurethane part (A).
• the silica sol-modified PU dispersions according to the invention are preferably composed of PUR dispersions (A) which have been prepared by the acetone process known from the literature.
• Excess isocyanate groups are then reacted with polyfunctional isocyanate-reactive compounds (chain extension).
• water or the polyamines already mentioned under (A4) particularly preferably di- and triamines, hydrazine and the sodium salt of 2- (2-aminoethylamino) ethanesulfonic acid are preferably used.
• Termination with a monoamine such as e.g. B. diethylamine, dibutylamine, ethanolamine, N-methylethanolamine or N, N-diethanolamine is possible.
• a monoamine such as e.g. B. diethylamine, dibutylamine, ethanolamine, N-methylethanolamine or N, N-diethanolamine is possible.
• an emulsion polymerization of olefinically unsaturated monomers for. B. esters of (meth)
• the monomers contain one or more olefinic double bonds.
• the monomers can contain functional groups such as hydroxyl, epoxy, methylol or acetoacetoxy groups.
• the emulsion polymerization can take place before or after the modification with silica sols.
• polyurethane dispersions according to the invention are used either alone or in combination with other aqueous binders.
• aqueous binders can e.g. B. from polyester, polyacrylate, polyepoxide or
• Silica sols according to the invention are colloidal solutions of amorphous silicon dioxide in water. They are obtained by neutralizing water glass, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry (Vol. 21, 4th edition, Verlag Chemie, Weinheim, 1982, Chapter 5, p. 456 ff). Silica sols are, for example, under the brand names Levasil ® (Bayer AG), Ludox ® (DuPont),
• SiO 2 particles have diameters between 1-150 nm.
• Silica sols whose SiO 2 particles have a diameter between 5 and 100 nm are preferably used in the dispersions according to the invention. Silica sols with an average SiO 2 particle diameter of 7 to 50 nm are particularly preferred
• Silica sols can be both basic (pH> 7) and acidic (pH ⁇ 7) be set.
• the solids content of silica sols is usually between 1-60%, preferably 20-40% and particularly preferably 25-35%.
• the use of basic silica sol types is preferred.
• Coating compositions according to the invention can be prepared by mixing a PUR dispersion (A) and a silica sol (B) using all known mixing techniques.
• silica-modified PU dispersions according to the invention contain one
• the dispersions according to the invention particularly preferably contain a proportion of 60-85% of a PU dispersion (A) and a proportion of 15-40% of a silica sol dispersion (B), it being true that the percentages relate to the weight of nonvolatile components and 100 Add% by weight.
• a particularly preferred production process for the dispersions according to the invention is the possibility of introducing the silica sols during the production of the PU dispersion.
• the prepolymer synthesized according to one of the known production methods is dispersed in silica sol or a silica sol / water mixture instead of pure water. This makes it possible to reduce the process costs by the subsequent mixing step and the system costs by the proportion of a mixing device. It is also possible to add crosslinkers before application. Hydrophilic or hydrophilized polyisocyanate crosslinkers are preferably suitable for this.
• silica sol-modified PU dispersions according to the invention are called
• Coatings based on the PUR dispersions according to the invention can e.g. on metal, plastic, paper, leather, textiles, felt, wood, glass, glass fibers, mineral substrates.
• a particularly preferred application is the coating of textiles and leather.
• the silica sol-modified PU dispersions can be used as such or in combination with the auxiliaries and additives known from coating technology, such as. B. nonionic and / or anionic thickeners, fillers, pigments, waxes, handle agents, dyes, solvents, flow control agents for the production of
• the coating materials can be applied in known ways, e.g. B. by brushing, pouring, knife coating, spraying, rolling or dipping.
• the drying of the paint film can take place at room temperature or elevated temperature, but also by
• the dispersions according to the invention are particularly suitable for coating or for covering and for impregnating woven and non-woven textiles.
• the dispersions according to the invention are used for the production of water vapor permeable coated flexible substrates, especially leather and textile.
• the dispersions to be used according to the invention can be stored and shipped and can be processed at any later point in time. Depending on the chemical composition of the polyurethane chosen and the silica sol content, coatings with different properties are obtained. In this way, soft, sticky layers, thermoplastic and rubber-elastic products of various degrees of hardness up to glass-hard thermosets can be obtained.
• the dispersions to be used according to the invention are generally applied to the substrate without further additives. This can be done by brushing directly onto the substrate using doctor blades, rollers or wire doctor blades.
• a plurality of lines are applied in succession, but preferably two, so that the total thickness of the coating comprising the base and top coat (s) is 10 to 100 ⁇ m, preferably 20 to 60 ⁇ m.
• a paste which dries to a microporous layer can also be used as the base coat, as described in DE-A
• the subsequent top coat protects the entire composite against mechanical stress and abrasion.
• Impranil ® DLN (Bayer AG): 40% anionic aliphatic polyester-polyurethane dispersion with the following properties (DIN 53504): 100% modulus: 2 MPa; Tensile strength: 20 MPa; Elongation at break: 700%.
• Impranil ® DLN-SD (Bayer AG): 40% anionic aliphatic polyester-polyurethane dispersion with the following properties (DIN 53504): 100% modulus: 2 MPa; Tensile strength: 20 MPa; Elongation at break: 700%.
• Impranil ® DLP 50% strength anionic aliphatic polyester-polyurethane dispersion having the following properties (DIN 53504): 100% modulus: 1.3 MPa; Tensile strength: 15 MPa; Elongation at break: 650%.
• Impranil ® DLV 40% anionic aliphatic polyester-polyethane-urethane dispersion with the following properties (DIN 53504):
• F. Levasil ® 200/30 (Bayer AG): 30% strength anionic silica sol dispersion having the following properties: specific surface area: 200 m 2 / g; middle
• H. Levasil® ® VP AC 4038 (Bayer AG): 30% strength anionic silica sol dispersion having the following characteristics: Specific surface: 200 m 2 / g; middle
• K. Euderm ® Filier VF01 (Bayer AG): leveling agents, containing 2.5% of a layered silicate, 1.5% of a non-functional silicone, and 1.5%
• Bayderm ® Soft Q (Bayer AG): anti-adhesive emulsion, containing 5% wool fat, 20% associative polyurethane thickener, and 1% high-boiling aromatic blend.
• Bayderm ® Grund 50 DU (Bayer AG): Medium-hard 40% aliphatic - aromatic polyester - polyurethane dispersion with the following properties:
• O. Euderm ® Matt AnlagenSN (Bayer AG): commercially available drying matting agent; containing 19% of a precipitated silica with an average particle size of 4.3 ⁇ m.
• P. Vemetzer 50% solution consisting of Desmodur N 3100 in
• hexamethylene diisocyanate (HDI) and 1.25 g of phosphoric acid dibutyl ester are placed in a 21-liter flask.
• 615 g of trimethylolpropane-started ethylene oxide (EOV-propylene oxide (PO) - copolyether 62.5% by weight of PO; 17.5% by weight of EO, the ethylene oxide portion being present as a terminal block; characteristic data: Mn: 4800 ; OHZ: 35; F: 3
• the resulting product has an NCO content of 4.2%; a viscosity of 2400 mPa s (22 ° C) and an equivalent weight of 1000 g per Val NCO.
• Hardener formulation of isophoronediamine in butanone, containing 2.17% water; 600 g hardener correspond to 1 Val NH 2 .
• PUR dispersions for textile coating are determined on free films, which are produced as follows:
• a release paper is placed in front of the rear roller in a film puller consisting of two polished rollers that can be set to an exact distance.
• the distance between the paper and the front roller is set with a feeler gauge. This distance corresponds to the film thickness (wet) of the resulting coating and can be adjusted to the desired level of each stroke.
• Coating can also be carried out consecutively in several strokes.
• the products aqueous formulations are made beforehand by adding ammonia / polyacrylic acid to a viscosity of 4500 mPa s
• the release paper is pulled vertically downwards, on the paper the corresponding film is created. If several strokes are to be applied, each individual stroke is dried and the paper is reinserted.
• the modulus of elasticity was determined in accordance with DIN 53504 on films> 100 ⁇ m in thickness.
• the mean particle sizes (the number average is given) of the PU dispersions were determined by means of laser correlation spectroscopy (device: Malvem
• the swelling of the ethyl acetate was calculated after 2 hours' storage in ethyl acetate by measuring the difference in length and width.
• the water vapor permeability (WDD) is measured in accordance with the requirements as deposited in the publication DS 2109 TM1, the British Textile Technology Group, Manchester, England.
• the leather was first made with a formulation of 330 parts of primer I with 100T1. Pre-primed isopropanol and 600 parts water (spray in cross).
• This mixture is sprayed twice (one cross each) onto the pre-primed leather. It is dried for 5 min at 70 ° C.
• the leather is ironed hydraulically (80 ° C, 200 bar, 6 sec) and then another spray application of the above mixture (a cross) is applied. After drying, iron again (80 ° C, 50 bar, kiss plate).
• Top coats are applied to the leather so primed to produce the test specimens.
• the top coat formulations were 12% in (silica sol-modified) PUR (dry substance) and contained 2.2% crosslinker P.
• the formulations were set to an outlet viscosity (DIN cup, 4 mm) of 19 seconds using a commercially available thickener.
• the formulation bars were sprayed at 5 g per 1 A square feet onto the primed leathers.
• the leathers were then dried at 80 ° C. for 5 minutes and ironed hydraulically (80 ° C., 200 bar, 3 sec).
• test specimens were tested for rub fastness and kink fastness.
• Aqueous formulations are produced, containing: X% silica sol-modified PUR; 5% color J; 5% matting agent O; 5% flow aid K.
• the amount X% of the modified PUR is measured so that the
• Formulations are 12% dry in terms of this PUR.
• a reference with non-modified PUR is used as a reference.
• formulations are set to an outlet viscosity (DIN cup; 4 mm nozzle) of 16 seconds using a commercially available associative thickener.
• the formulations are sprayed once onto undressed beef furniture appa (10 ml on Vi square feet) and dried for 5 minutes at 80 ° C. It is ironed (Rotopress, 90 ° C, 6 m / min), and the same formulations are sprayed on twice (with intermediate drying).
• the leather primed in this way is tested for resistance to cold kinks.
• a release paper is placed in front of the rear roller in a film puller consisting of two polished rollers that can be set to an exact distance. The distance between the paper and the front roller is set with a feeler gauge. This distance corresponds to the film thickness
• Formulations are previously made by adding ammonia / polyacrylic acid to a viscosity of 4500 mPas) poured onto the gap between the paper and the front roller, the release paper is pulled vertically downwards, the corresponding film being formed on the paper. If several strokes are to be applied, each individual stroke is dried and the paper is reinserted.
• Val ratio binder / hardener 1.08 / 1; Film thickness (wet): 0.2 mm. These parameters correspond almost to the usual under production-technical conditions.
• top coats were made.
• the gap width was chosen so that a solid coating of 25 g per square meter resulted (0.07 mm at 40% dryness).
• the top coats were dried.
• the following top coats were used: bl) 8 to 2 - mixture of PU dispersion Q and D (usual top coat); b2) pure PUR dispersion D as comparison to b3, because of extremely blocky
• the grip obtained with the dash b3 is smooth and corresponds to that of the commonly used dash b 1.
• the WDD numbers are in mg / cm 2 h.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Paints Or Removers (AREA)
• Silicon Compounds (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Treatment And Processing Of Natural Fur Or Leather (AREA)
• Paper (AREA)
• Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Adhesives Or Adhesive Processes (AREA)

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• 2000
  • 2000-05-22 DE DE10025304A patent/DE10025304A1/de not_active Withdrawn
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