Patent Application
20100144225
The present invention relates to a process for treating a surface, which comprises said surface being treated with
(a) at least one hydrophobicizing agent,
(b) at least one crosslinked organic copolymer in particulate form,
(c) at least one emulsifier,
without use of acrylate or polyurethane binders
and subsequently dried.
The present invention further relates to treated surfaces. The present invention further relates to preferably aqueous formulations and a process for producing preferably aqueous formulations which are in accordance with the present invention.
For some years there has been appreciable interest in treating surfaces such that they are soil repellent or at least difficult to soil. Various methods involve providing the surfaces with texturing, for example with elevations 5 to 100 μm high and 5 to 200 μm spaced apart. A surface has been endowed with texturing that seeks to emulate the lotus plant, see for example WO 96/04123 and U.S. Pat. No. 3,354,022. However, such an approach is not always advisable and unsuitable for treating textile surfaces.
EP 1 283 296 discloses coating textile sheetlike constructions with a coating prepared by coating them with 50% to 80% by weight of at least one finely divided material selected from for example potato starch and oxidic materials such as for example silica gel, quartz flour or kaolin, having diameters in the range from 0.5 to 100 μm (at least 80% by weight of the finely divided material), 20% to 50% by weight of a matrix comprising a binder, a fluorinated polymer and if appropriate auxiliaries.
WO 04/74568 discloses a process for finishing textile materials by treatment with at least one aqueous liquor comprising at least one organic polymer and at least one organic or inorganic solid in particulate form, the organic or inorganic solid or solids being present in the liquor in a fraction of at least 5.5 g/l. Silica gel, in particular fumed silica gel, is preferred as solid in particulate form.
Potato starch, as recommended in EP 1 283 296, however, has a certain solubility in aqueous liquors which varies with the temperature, so that the diameter of the potato starch particles cannot be optimally controlled during a coating operation. Especially in the case of inorganic solids such as silica gel for example, a certain propensity to agglomerate is observed, which is disadvantageous at application and makes policing of the textural parameters more difficult.
It is further observed that there are many cases where such textiles, coated by the aforementioned methods, possess insufficient washability at times. If, for example, sweaty textiles are washed, it is to be observed that the soil-repellent effect is reduced after the first wash and has virtually disappeared after several wash cycles.
WO 2007/031491 discloses a process for treating surfaces, which comprises surfaces being treated with at least one hydrobicizing agent, at least one crosslinked organic copolymer in particulate form, at least one film-forming addition copolymer having epoxy groups, NH—CH2OH groups or acetoacetyl groups and if appropriate with one or more emulsifiers and subsequently dried.
The present invention has for its object to provide a process for treating surfaces which avoids the abovementioned disadvantages, in particular with regard to the treatment of textile surfaces. The present invention further has for its object to provide treated surfaces which avoid the abovementioned disadvantages and exhibit good soil repellency.
We have found that this object is achieved by the process defined at the beginning.
The process of the invention is directed to surfaces. Surfaces for the purposes of the present invention may consist of any desired material and belong to any desired article. Preference is given to surfaces composed of fibrous materials such as for example paper, board, leather, artificial leather, Alcantara, and more particularly surfaces are surfaces of textiles.
Textiles for the purposes of the present invention are textile fibers, textile intermediate and end products and finished articles manufactured therefrom which, as well as textiles for the apparel industry, also comprise for example carpets and other home textiles and also textile constructions for industrial purposes. These include unshaped constructions such as for example staples, linear constructions such as twine, filaments, yarns, lines, strings, laces, braids, cordage and also three-dimensional constructions such as for example felts, wovens, nonwovens and waddings. Textiles for the purposes of the present invention can be of natural origin, examples being cotton, wool or flax, or synthetic, examples being polyamide, polyester, modified polyester, polyester blend fabrics, polyamide blend fabrics, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibers and glass fiber fabrics. Textiles composed of cotton are particularly preferred.
For the purposes of the present invention, textile sheetlike constructions may have one surface (side, face) treated by the process of the present invention and the other not, or both surfaces (sides, faces) may be treated by the process of the present invention. For example, there are some garments such as workwear for example where it may be sensible to treat the outer surface by the process of the present invention and the inside (body-facing) surface not; and it may be sensible on the other hand for both sides (front and back) of some industrial textiles such as awnings for example to be treated by the process of the present invention.
The treating in accordance with the present invention is with
(a) at least one hydrophobicizing agent,
(b) at least one crosslinked organic copolymer in particulate form,
(c) at least one emulsifier,
without the use of acrylate or polyurethane binders.
One embodiment of the present invention comprises selecting hydrophobicizing agents from
(a1) halous organic (co)polymers,
(a2) paraffins,
(a3) compounds having at least one C10-C60-alkyl group per molecule, and
(a4) silicones.
Useful halous organic (co)polymers (a1) include for example chlorinated and especially fluorinated (co)polymers preparable by preferably free-radical (co)polymerization of one or more mono- or poly-halogenated, preferably-chlorinated and more preferably-fluorinated, (co)monomers.
Very particularly preferred halogenated (co)monomers are fluorous olefins such as for example vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, vinyl esters of fluorinated or perfluorinated C3-C11-carboxylic acids as described for example in U.S. Pat. No. 2,592,069 and U.S. Pat. No. 2,732,370, (meth)acrylic esters of fluorinated or perfluorinated alcohols such as for example fluorinated or perfluorinated C3-C14-alkyl alcohols, for example (meth)acrylic esters of HO—CH2—CH2—CF3, HO—CH2—CH2—C2F5, HO—CH2—CH2-n-C3F7, HO—CH2—CH2-iso-C3F7, HO—CH2—CH2-n-C4F9, HO—CH2—CH2-n-C6F13, HO—CH2—CH2-n-C8F17, HO—CH2—CH2—O-n-C6F13, HO—CH2—CH1—O-n-C8F17, HO—CH2—CH2-n-C10F21, HO—CH2—CH2-n-C12F25, described for example in U.S. Pat. No. 2,642,416, U.S. Pat. No. 3,239,557 and U.S. Pat. No. 3,462,296.
Copolymers of for example (meth)acrylic acid and/or C1-C20-alkyl esters of (meth)acrylic acid or glycidyl (meth)acrylate with esters of the formula I
where
R1 is hydrogen, CH3, C2H5,
R2 is CH3, C2H5,
x is an integer in the range from 4 to 12, preferably 6 to 8,
y is an integer in the range from 1 to 11, preferably 1 to 6,
or glycidyl (meth)acrylate with vinyl esters of fluorinated carboxylic acids are also useful as halous organic (co)polymers (a1).
Useful halous organic (co)polymers (a1) further include copolymers of (meth)acrylic esters of fluorinated, especially perfluorinated, C3-C12-alkyl alcohols such as for example HO—CH2—CH2—CF3, HO—CH2—CH2—C2F5, HO—CH2—CH2-n-C3F7, HO—CH2—CH2-iso-C3F7, HO—CH2—CH2-n-C4F9, HO—CH2—CH2-n-C6F13, HO—CH2—CH2-n-C8F17, HO—CH2—CH2—O-n-C6F13, HO—CH2—CH2-O-n-C8F17, HO—CH2—CH2-n-C10F21, HO—CH2—CH2-n-C12F25, with (meth)acrylic esters of nonhalogenated C1-C20-alcohols, for example methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, n-eicosyl (meth)acrylate.
An overview of fluorinated polymers and copolymers useful as halous organic (co)polymers (a1) is to be found for example in M. Lewin et al, Chemical Processing of Fibers and Fabrics, Part B, volume 2, Marcel Dekker, New York (1984), pages 172 ff. and pages 178-182.
Further fluorinated (co)polymers useful as halous organic (co)polymers (a1) are described for example in DE 199 120 810.
The process of the present invention may be carried out using one halous (co)polymer (a1) or a plurality of different halous (co)polymers (a1).
Halous (co)polymer (a1) is preferably used in uncrosslinked form to carry out the process of the present invention, but it may crosslink during drying.
Halous organic (co)polymer (a1) may preferably be in dispersed form, more preferably with a number average particle diameter in the range from 50 to 100 nm and even more preferably in the range from 60 to 70 nm.
Other suitable hydrophobicizing agents (a) are paraffins (a2). Paraffins (a2) may be for example liquid or solid at room temperature and of natural or preferably synthetic origin. Preferred paraffins (a2) are synthetic paraffins such as for example Fischer-Tropsch waxes, high density polyethylene waxes, prepared using Ziegler-Natta catalysts or metallocene catalysts for example, also partially oxidized high density polyethylene waxes having an acid number in the range from 1 to 150 mg KOH/g of paraffin, determined according to DIN 53402, with high density polyethylene waxes comprising not just homopolymer waxes of ethylene, but also copolymers of polyethylene with in total up to 20% by weight of comonomer such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-dodecene, especially so-called paraffin waxes and isoparaffin waxes, for example crude paraffins (crude paraffin waxes), slack wax raffinates, deoiled crude paraffins (deoiled crude paraffin waxes), semi- or fully refined paraffins (semi- or fully refined paraffin waxes) and bleached paraffins (bleached paraffin waxes). By paraffin waxes are herein meant in particular room temperature solid paraffins melting in the range from 40 to 80° C., and preferably in the range from 50 to 75° C., i.e. saturated hydrocarbons, branched or unbranched, cyclic or preferably acyclic, individually or preferably as a mixture of a plurality of saturated hydrocarbons. Paraffin waxes in the context of the present invention are preferably composed of saturated hydrocarbons having 18 to 45 carbon atoms. Isoparaffins in the context of the present invention are preferably composed of saturated hydrocarbons having 20 to 60 carbon atoms per molecule.
Useful hydrophobicizing agents (a) further include linear or heterocyclic, preferably heteroaromatic compounds having at least one C10-C60-alkyl group, preferably having a C12-C40-alkyl group per molecule (a3), hereinafter also abbreviated to compound (a3), the C10-C60-alkyl groups being different or preferably the same and branched or preferably unbranched. Preference is given to such compounds (a3) as are able to detach at least one fatty amine or at least one fatty alcohol on heating to temperatures in the range from 120 to 200° C., i.e. to an amine or an alcohol having a C10-C60-alkyl group.
Very particular preference is given to compounds of the general formula II
where
Further particularly preferred examples of compounds (a3) are compounds of the general formula III
where the variables are each as defined above.
Further examples of hydrophobicizing agents are silicones (a4). Examples of silicones (a4) are compounds of the general formula IV
where
R10 is selected from Si(CH3)3 and hydrogen,
X1 is selected from C1-C4-alkyl, particularly methyl, and
hydrogen,
epoxy groups, particularly
NH2, aminoalkylene, preferably w-aminoalkylene, particularly (CH2)w—NH2, where w is from 1 to 20 and preferably from 2 to 10 and one or more preferably nonadjacent CH2 groups may be replaced by oxygen or NH. Examples of X are CH2—NH2, CH2CH2—NH2, (CH2)3—NH2, (CH2)4—NH2, (CH2)6—NH2, (CH2)3—NH—(CH2)2—NH2, (CH2)2—NH—(CH2)3—NH2,
The [Si(CH3)2—O] and [SiX(CH3)—O] units may be disposed for example blockwise or randomly.
x and y are each integers. The sum of x and y can be from 30 to 2000 and preferably from 50 to 1500.
Preferably, x is greater than y. More preferably, x is from 1 to 10, particularly when X is not CH3, and m is chosen accordingly.
In one embodiment of the present invention, the dynamic viscosity of silicones (a4) is in the range from 100 mPa·s to 50 000 mPa·s measured at 23° C., particularly when X═CH3 and R10═Si(CH3)3.
One embodiment of the present invention utilizes a hydrophobicizing agent (a) comprising a combination of at least one paraffin (a2) and at least one compound (a3).
Useful crosslinked organic copolymers in particulate form (b) are halous and preferably halogen-free copolymers obtainable by free-radical copolymerization of at least one monoethylenically unsaturated comonomer and at least one at least diethylenically unsaturated comonomer (crosslinker) and which are in particulate form.
Examples of monoethylenically unsaturated comonomers useful for preparing crosslinked organic copolymers in particulate form (b) are monovinylaromatics, for example α-methylstyrene and especially styrene, and C1-C10-alkyl esters of ethylenically unsaturated carboxylic acids such as for example acrylic acid or methacrylic acid, more particularly methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, ethylhexyl acrylate, n-butyl methacrylate, t-butyl methacrylate and methyl methacrylate. Acrylonitrile may also be used.
Useful crosslinkers include for example di- and trivinylaromatics, for example ortho-divinylbenzene, meta-divinylbenzene and para-divinylbenzene, also ethylenically unsaturated carboxylic acids esterified with ethylenically unsaturated alcohol, examples being allyl (meth)acrylate, and also (meth)acrylates of di- or trihydric alcohols, examples being ethylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,1,1-trimethylolpropane di(meth)acrylate, 1,1,1-trimethylolpropane tri(meth)acrylate.
Crosslinked organic copolymers in particulate form (b) may be prepared by using for example up to 20 mol %, preferably from 1 to 10 mol % and more preferably at least 3 mol % of crosslinker with at least 80 mol %, preferably at least 90 mol % and more preferably up to 97 mol % of one or more aforementioned monoethylenically unsaturated comonomers.
Crosslinked organic copolymer in particulate form (b) is obtainable by comminuting the copolymer by suitable methods of particle formation, for example by grinding, after the actual synthesis. The synthesis may also be carried out such that copolymer of monoethylenically unsaturated comonomer or monounsaturated comonomers and crosslinker is generated in particulate form, for example by conducting the synthesis in the form of an emulsion polymerization or else as a polymerization in miniemulsion, or as a suspension polymerization.
Particulate form in the context of the present invention is to be understood as meaning that crosslinked copolymer (b) is present in the form of particles which are not dissolved in water or aqueous medium. The particles in question may have an irregular shape or may preferably have a regular shape, for example an ellipsoidal or spherical shape, this is to be understood as encompassing such particles where at least 75% by weight and preferably at least 90% by weight are present in spherical form and further particles may be present in granular form.
One embodiment of the present invention comprises crosslinked organic copolymer in particulate form (b) being present neither in the form of aggregates nor in the form of agglomerates.
One embodiment of the present invention comprises crosslinked organic copolymer in particulate form (b) having a weight average diameter in the range from 10 to 450 nm, preferably in the range from 20 to 250 nm and more preferably in the range from 50 to 100 nm. Particle diameter may be measured using common methods such as transmission electron microscopy for example.
One embodiment of the present invention comprises crosslinked organic copolymer in particulate form (b) having a homogeneous distribution of particle sizes, i.e., at least 80% by weight of the particles have a diameter in the range from ±20% of the average diameter.
Another embodiment of the present invention comprises crosslinked organic copolymer in particulate form (b) having a bimodal or multimodal distribution of particle sizes.
One embodiment of the present invention comprises crosslinked organic copolymer in particulate form (b) having a certain thermal dimensional stability in that crosslinked organic copolymer in particulate form (b) stored at 30 to 200° C., preferably from 120 to 180° C. and more preferably 150 to 170° C. does not change its dimensions to any measurable extent for a period in the range from 1 second to 30 minutes and preferably up to 3 minutes.
Crosslinked organic copolymer in particulate form (b) is preferably present as a unitarily constructed particle; that is, the chemical composition at the surface is essentially exactly the same as in the interior of the respective particles. The particles in question are accordingly not core-shell particles.
The treatment is further carried out with at least one emulsifier (c). Emulsifiers (c) may be anionic, nonionic or preferably cationic.
Suitable anionic emulsifiers (c) are for example alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C8 to C12), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation in the range from 4 to 30, alkyl radical: C12 to C18) and of ethoxylated alkylphenols (degree of ethoxylation in the range from 3 to 50, alkyl radical: C4 to C12), of alkylsulfonic acids (alkyl radical: C2-C18) and of alkylarylsulfonic acids (alkyl radical: C9 to C18).
Suitable nonionic emulsifiers (c) are for example ethoxylated mono-, di- and trialkylphenols (degree of ethoxylation in the range from 3 to 50, alkyl radical: C4 to C12) and also ethoxylated fatty alcohols (degree of ethoxylation in the range from 3 to 80; alkyl radical: C8 to C36). Examples are the Lutensol® brands of BASF Aktiengesellschaft.
Useful cationic emulsifiers (c) include cationic surface-active compounds.
Suitable cationic surface-active compounds are generally C6-C18-alkyl-, C6-C18-aralkyl- or heterocyclyl-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and also salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples which may be mentioned are dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2-(N,N,N-trimethylammonium)ethylparaffinic acid esters, N-cetylpyridinium chloride, N-laurylpyridinium sulfate, N-cetyl-N,N,N-trimethylammonium bromide, N-dodecyl-N,N,N-trimethylammonium bromide, N,N-distearyl-N,N-dimethylammonium chloride and also the Gemini surfactant N,N-(lauryldimethyl)ethylenediamine dibromide.
Numerous further examples may be found in H. Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.
Of very particular suitability are compounds of the general formula V
where
The process of the present invention is carried out without use of acrylate or polyurethane binders; that is, neither acrylate binders nor polyurethane binders are used to carry out the process of the present invention.
Acrylate binders herein are (meth)acrylic acid copolymers of (meth)acrylic acid and one or more comonomers selected from monovinylaromatics such as for example α-methylstyrene, para-methylstyrene, 2,4-dimethylstyrene and styrene, halogen-free C1-C10-alkyl esters of monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated carboxamides and comonomeres having epoxy groups, NH—CH2OH groups or acetoacetyl groups, and also compounds of the general formula VI:
where
R13, R14 and R15 are the same or different and selected from C1-C10-alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, more preferably unbranched C1-C4-alkyl such as methyl, ethyl, n-propyl and n-butyl.
Examples of comonomers having NH—CH2OH groups are for example N-methylolacrylamide and N-methylolmethacrylamide.
Polyurethane binders are film-forming polyurethanes, preferably anionic film-forming polyurethanes, for example anionic film-forming polyurethanes incorporating at least one compound having at least one sulfonic acid group or at least one carboxylic acid group such as for example dimethylolpropionic acid.
One embodiment of the present invention comprises treating additionally with at least one crosslinker (d), which may also be referred to as hardener (d).
Examples of crosslinkers (d) are:
(d1) condensation products of urea, aldehydes such as in particular formaldehyde and if appropriate one or more dialdehydes such as for example glyoxal and if appropriate one or more alcohol,
(d2) isocyanurates, which may be in a hydrophilicized state.
Preference is given for example to compound of formula VI
and also compound of formula VII etherified with preferably linear C1-C4-alkanol, in particular doubly, triply or quadruply methanol- or ethanol-etherified compound of formula VII.
Examples of isocyanurates (d2) are isocyanurates of aliphatic diisocyanates and in particular hydrophilicized isocyanurates and also mixed hydrophilicized diisocyanates/isocyanurates, for example the reaction product of C1-C4-alkyl polyethylene glycol with the isocyanurate of hexamethylene diisocyanate (HDI). Examples of suitable crosslinkers of this type are known from EP-A 0 486 881 for example.
Further classes of compound useful as crosslinkers (d) are:
(d3) melamine derivatives, which can if appropriate be in an alkoxylated, alkoxyalkylated or hemiaminalized state,
(d4) polyglycidyl ethers having 2 to 5 glycidyl groups per molecule,
(d5) carbodiimides,
(d6) urea or urea derivatives which may if appropriate have been converted to aminals or hemiaminals.
Examples of melamine derivatives (d3) are optionally alkoxylated or alkoxyalkylated compounds or hemiaminalized melamines.
Examples of polyglycidyl ethers (d4) having 2 to 5 glycidyl groups per molecule, preferably 2 to 4 glycidyl groups per molecule, are pentaerythritol triglycidyl ether and glycerol 1,3-diglycidyl ether and mixtures thereof.
Examples of carbodiimides (d5) are dicyclohexylcarbodiimide and also the systems described in the patent applications EP-A 1 002 001, DE-A 199 54 500 and DE-A 100 00 656.
Carbodiimides (d5) are preferably polymeric carbodiimides. Polymeric carbodiimides for the purposes of the present invention are such compounds as bear from 2 to 50, and preferably up to 20 —N═C═N— groups per mole.
Polymeric carbodiimides are known per se and are obtainable by methods known per se, for example by condensation or polycondensation of diisocyanate in the presence of a catalyst, for example trialkyl phosphine oxide, acyclic or preferably cyclic, phospholene oxide, triaryl phosphine oxide, alkali metal alkoxide, for example sodium ethoxide, alkali metal carbonate, for example sodium carbonate or potassium carbonate, or tertiary amine, for example triethylamine. Particularly suitable catalysts are phospholane oxides and phospholene oxides, examples being 1-phenyl-2-methyl 2-phospholene oxide, 1-phenyl-2-methyl 3-phospholene oxide, 1-methyl 2-phospholene oxide and 1-methyl 3-phospholene oxide, see for example U.S. Pat. No. 2,853,473. Carbon dioxide is eliminated in the course of the condensation or polycondensation to form polymeric carbodiimide.
Examples of preferred polymeric carbodiimides are obtainable by condensation or polycondensation of at least one aromatic diisocyanate, for example 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate or 1,7-naphthylene diisocyanate or at least one aliphatic or cycloaliphatic carbodiimide such as for example isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane 1,4-diisocyanate, 2,4-hexahydrotolylene diisocyanate, 2,6-hexahydrotolylene diisocyanate and 4,4′-dicyclohexylmethane diisocyanate.
Preferred polymeric carbodiimides are copolycarbodiimides obtainable by condensation or polycondensation of at least one aromatic diisocyanate, for example 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate or 1,7-naphthylene diisocyanate, with at least one aliphatic or cycloaliphatic carbodiimide such as for example isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane 1,4-diisocyanate, 2,4-hexahydrotolylene diisocyanate, 2,6-hexahydrotolylene diisocyanate and 4,4′-dicyclohexylmethane diisocyanate.
It is very particularly preferred for carbodiimide (d5) to comprise a polymeric carbodiimide obtainable by polycondensation of m-TMXDI or p-TMXDI
or mixtures of m-TMXDI and p-TMXDI having 2 to 20, preferably up to 15 and more preferably up to 10 —N═C═N— groups per mole.
Examples of urea or urea derivatives (d6), which may if appropriate be converted to aminals or hemiaminals, are:
unmodified or multiply, especially singly, doubly, triply or quadruply, alkylolated, especially methylolated and also alkoxyalkylolated, and especially methoxymethylolated urea compounds and their di-, tri- and tetramers or oligomeric or polymeric, linear, branched or cyclic precondensates. Also alkoxylated urea compounds as di-/tri-tetrameric or oligomeric or polymeric, linear or branched or cyclic addition/condensation products of urea and multiply functional alkylaldehydes, in particular glyoxal and their alkoxylated and especially methoxylated compounds.
The process of the present invention may be carried out by the surface to be treated being treated in one or more steps with
(a) at least one hydrophobicizing agent,
(b) at least one crosslinked organic copolymer in particulate form,
(c) at least one emulsifier, and
(d) if appropriate at least one crosslinker
without use of acrylate or polyurethane binders.
The process of the present invention may be carried out for example by the surface to be treated being treated with at least one preferbly aqueous formulation comprising
(a) at least one hydrophobicizing agent,
(b) at least one crosslinked organic copolymer in particulate form,
(c) at least one emulsifier, and
(d) if appropriate at least one crosslinker
and neither acrylate nor polyurethane binder.
It is also possible to perform a plurality of treating steps using identical or different preferably aqueous formulations.
Aqueous formulations may be any desired aqueous suspensions and preferably are aqueous liquors.
Aqueous formulations and especially aqueous liquors may have a solids content in the range from 10% to 70% by weight and preferably in the range from 30% to 50% by weight.
One embodiment of the present invention comprises conducting the process of the present invention by treating the surface to be treated by initially treating it with a preferably aqueous formulation comprising at least one hydrophobicizing agent (a) and at least one emulsifier (c) and further one crosslinked organic copolymer in particulate form (b) and subsequently with a new liquor comprising at least one crosslinker (d) but no crosslinked organic copolymer in particulate form (b).
One embodiment of the present invention comprises conducting the process of the present invention by treating the surface to be treated by initially treating it with a preferably aqueous formulation comprising at least one hydrophobicizing agent (a) and at least one emulsifier (c) and further at least one crosslinked organic copolymer in particulate form (b) and subsequently with a new preferably aqueous formulation comprising a different hydrophobicizing agent (a) and if appropriate at least one crosslinker (d) but no crosslinked organic copolymer in particulate form (b).
Another embodiment of the present invention comprises conducting the process of the present invention by treating the surface to be treated by initially treating it with a preferably aqueous formulation comprising at least one crosslinked organic copolymer in particulate form (b) and subsequently with a new preferably aqueous formulation comprising a hydrophobicizing agent (a), at least one emulsifier (c) and if appropriate at least one crosslinker (d).
Another embodiment of the present invention comprises conducting the process of the present invention by treating the surface to be treated by initially treating it with a preferably aqueous liquor comprising at least one hydrophobicizing agent (a), at least one crosslinked organic copolymer in particulate form (b) and one emulsifier (c) and subsequently with a new liquor comprising neither hydrophobicizing agent (a) nor emulsifier (c), but the crosslinked organic copolymer in particulate form (b) already used in the first step.
The temperature for practicing the treatment of the present invention is in itself not critical. The temperature may be in the range from 10 to 60° C. and preferably in the range from 15 to 30° C.
Preferably aqueous formulation and especially preferably aqueous liquor may have a pH in the range from 2 to 9 and preferably up to 4.
To practice the process of the present invention by treating the surface to be treated with an aqueous liquor, the wet pickup may be chosen such that the process of the present invention results in a wet pickup in the range from 25% by weight to 95% by weight and preferably in the range from 60% to 90% by weight.
The process of the present invention is in one embodiment of the present invention carried out in common machines used for the finishing of textiles, for example padmangles. Preference is given to vertical textile feed pad-mangles, where the essential element is two rollers in pressed contact with each other, through which the textile is led. Preferably aqueous formulation is filled in above the rollers and wets the textile.
The pressure causes the textile to be squeezed off and ensures a constant add-on. In other preferred pad-mangles, textile is first led through a dip bath and then upwardly through two rollers in pressed contact with each other. In the latter case, the padmangles are also said to have a vertically upward textile feed. Preference is further given to pad-mangles having a trough in which the textile is drenched with aqueous liquor and to which a horizontal pair of rollers is attached, through which the textile is led. The textile is squeezed off by the pressure to ensure a constant add-on. Padmangles are described for example in Hans-Karl Rouette, “Handbuch der Textilveredlung”, Deutscher Fachverlag 2003, pages 618 to 620.
Contacting in accordance with the present invention may be accomplished for example by single or multiple spraying, drizzling, overpouring or printing.
Aqueous formulations for the purposes of the present invention may comprise one or more organic solvents, for example alcohols such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, acetic acid, n-butanol, isobutanol, n-hexanol and isomers, n-octanol and isomers, n-dodecanol and isomers. Organic solvents may comprise from 1% to 40% by weight and preferably from 2% to 25% by weight of the continuous phase of aqueous formulation used in accordance with the present invention. Aqueous formulations is to be understood as referring to such formulations where the continuous phase consists predominantly or, at the extreme, exclusively of water.
The treated surface is dried after the treatment of the present invention. Drying may be accomplished for example at temperatures in the range from 20 to 120° C.
Drying may be carried out at atmospheric pressure for example. It may also be carried out at reduced pressure, for example at a pressure in the range from 1 to 850 mbar.
Drying may utilize a heated or unheated stream of gas, in particular a heated or unheated stream of an inert gas such as nitrogen for example. To utilize a heated stream of gas, suitable temperatures range for example from 30 to 200° C., preferably from 120 to 180° C. and more preferably from 150 to 170° C.
The treatment of the present invention and the drying operation may be followed by a thermal treatment, also referred to as tempering in the context of the present invention, as a continuous operation or as a batch operation. The duration of the tempering treatment can be chosen within wide limits. The tempering treatment can typically be carried out for a duration in the range from about 1 second to 30 minutes and especially up to 3 minutes. A tempering treatment is carried out by heating to temperatures of up to 180° C., preferably in the range from 150 to 170° C. It is of course necessary to adapt the temperature of the tempering treatment to the sensitivity of the material of which the surface is made that has been treated according to the present invention.
Hot air drying is an example of a specific suitable method of tempering.
A specific embodiment of the present invention comprises treating surfaces with a preferably aqueous formulation comprising
One embodiment of the present invention comprises practicing the process of the present invention by utilizing an aqueous formulation further comprising one or more auxiliaries (e), for example up to 50% by weight, based on the entire preferably aqueous formulation. Especially when one or more textile surfaces are to be treated, it may be advantageous to include one or more auxiliaries (e) in preferably aqueous formulation utilized for the purposes of the present invention, in which case auxiliaries (e) are selected from biocides, thickeners, foam inhibitors, wetting agents, plasticizers, hand modifiers (hand-modifying agents), fillers, and film-forming assistants.
An example of a biocide useful as an auxiliary (e) is 1,2-benzisothiazolin-3-one (BIT) (commercially available as Proxel® brands from Avecia Lim.) and its alkali metal salts; other suitable biocides are 2-methyl-2H-isothiazol-3-one (MIT) and 5-chloro-2-methyl-2H-isothiazol-3-one (CIT). In general, from 10 to 150 ppm of biocide will be sufficient, based on preferably aqueous formulation.
Useful auxiliaries (e) further include one or more thickeners, which may be of natural or synthetic origin. Suitable synthetic thickeners are poly(meth)acrylic compounds, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes, especially copolymers comprising 85% to 95% by weight of acrylic acid, 4% to 15% by weight of acrylamide and about 0.01% to 1% by weight of the (meth)acrylamide derivative of the formula VIII
having molecular weights Mw in the range from 100 000 to 200 000 g/mol, in each of which R16 is methyl or preferably hydrogen. Examples of thickeners of natural origin are agar-agar, carrageen, modified starch and modified cellulose.
The amount of thickener included may be for example in the range from 0% to 10% by weight, preferably in the range from 0.05% to 5% by weight and more preferably in the range from 0.1% to 3% by weight, based on aqueous formulation used in the process of the present invention.
Examples of foam inhibitors useful as auxiliaries (e) are room temperature liquid silicones, nonethoxylated or singly or multiply ethoxylated.
Examples of wetting agents useful as auxiliaries (e) are alkyl polyglycosides, alkyl phosphonates, alkylphenyl phosphonates, alkyl phosphates and alkylphenyl phosphates.
Examples of plasticizers useful as auxiliaries (e) are ester compounds selected from the groups of the aliphatic or aromatic di- or polycarboxylic acids fully esterified with alkanols and of the at least singly alkanol-esterified phosphoric acid.
Alkanols are C1-C10-alkanols in one embodiment of the present invention.
Preferred examples of aromatic di- or polycarboxylic acids fully esterified with alkanol are fully alkanol-esterified phthalic acid, isophthalic acid and mellitic acid; specific examples are di-n-octyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate, di-n-octyl isophthalate, di-n-nonyl isophthalate, di-n-decyl isophthalate.
Preferred examples of aliphatic di- or polycarboxylic acids fully esterified with alkanol are for example dimethyl adipate, diethyl adipate, di-n-butyl adipate, diisobutyl adipate, dimethyl glutarate, diethyl glutarate, di-n-butyl glutarate, diisobutyl glutarate, dimethyl succinate, diethyl succinate, di-n-butyl succinate, diisobutyl succinate and also mixtures thereof.
Preferred examples of phosphoric acid at least monoesterfied with an alkanol are C1-C10-alkyl di-C6-C14-aryl phosphates such as isodecyl diphenyl phosphate.
Further suitable examples of plasticizers are aliphatic or aromatic di- or polyols at least monoesterified with C1-C10-alkylcarboxylic acid.
Preferred examples of aliphatic or aromatic di- or polyols at least monoesterified with C1-C10-alkylcarboxylic acid is 2,2,4-trimethylpentane-1,3-diol monoisobutyrate.
Further suitable plasticizers are polyesters obtainable by polycondensation of aliphatic dicarboxylic acid and aliphatic diol, for example adipic acid or succinic acid and 1,2-propanediol, preferably having an Mw of 200 g/mol, and polypropylene glycol alkylphenyl ether, preferably having an Mw of 450 g/mol.
Further suitable plasticizers are polypropylene glycols etherified with two different alcohols and having a molecular weight Mw in the range from 400 to 800 g/mol, wherein preferably one of the alcohols may be an alkanol, especially a C1-C10-alkanol, and the other alcohol may preferably be an aromatic alcohol, for example o-cresol, m-cresol, p-cresol and especially phenol.
Examples of fillers useful as an auxiliary (e) are melamine and pigments in particulate form.
Examples of hand improvers useful as an auxiliary (e) are silicone emulsions, i.e., aqueous emulsions of silicones which may preferably bear hydrophilic groups such as for example OH groups or alkoxylate groups.
Diethylene glycol is an example of a film-former (film-forming assistant) useful as an auxiliary (e).
In a further embodiment of the present invention, surface to be coated is provided with at least one primer (f) before the treatment with (a) to (c), if appropriate crosslinker (d) and if appropriate auxiliary or auxiliaries(e). Primer (f) preferably endows the surface which is to be treated in accordance with the present invention with a charge which is opposite to the charge of crosslinked organic copolymer in particulate form (b). When, for example, a cationic crosslinked organic copolymer in particulate form (b) is to be used, it is advantageous to use an anionic primer (f). When, however, an anionic crosslinked organic copolymer in particulate form (b) is to be used, it is advantageous to use a cationic primer (f).
Suitable primers (f) may be for example polymeric or nonpolymeric in nature. Suitable polymeric primers may for example have a number average molecular weight in the range from 5000 to 500 000 g/mol.
Useful cationic primers (f) include for example polyethyleneimine and especially aminosiloxanes such as for example siloxanes at least one (CH2)wNH—R17 group in each of which w is an integer in the range from 1 to 10 and especially from 2 to 7 and R17 is selected from hydrogen, preferably linear C1-C4-alkyl and (CH2)wNH—R17, where R17 is selected from hydrogen and preferably linear C1-C4-alkyl, also polyvinylimidazole. Further suitable cationic primers (f) are polymers of diallyl di-C1-C4-alkylammonium halide, in each of which C1-C4-alkyl is preferably linear.
Further suitable cationic primers (f) are reaction products of equimolar amounts of preferably cyclic diamines with epichlorohydrin and an alkylating agent such as for example dimethyl sulfate, C1-C10-alkyl halide, especially methyl iodide, or benzyl halide, especially benzyl chloride. Such reaction products may have molecular weights Mw in the range from 1000 to 1 000 000 g/mol and are constructed as follows, illustrated with reference to the example of the reaction products of equimolar amounts of piperazine with epichlorohydrin and benzyl chloride:
Suitable anionic primers (f) are for example homo- or copolymers of anionic monomers, especially of ethylenically unsaturated sulfonic acids, ethylenically unsaturated amine oxides or (meth)acrylic acid, if appropriate with one or more C1-C10-alkyl esters of (meth)acrylic acid. Further suitable anionic primers are for example anionic polyurethanes, i.e., herein such polyurethanes as comprise at least one sulfonic acid group or carboxylic acid group per molecule, preparable using 1,1-dimethylolpropionic acid for example.
To use one or more primers (f), it is preferable for it to be used in an aqueous formulation and to be applied prior to the treatment with crosslinked organic copolymer in particulate form (b). Suitable operating techniques include for example spraying, drizzling and especially padding.
The application of primer (f) and the treatment with crosslinked organic copolymer in particulate form (b) may be respectively followed and preceded by thermal treatment, the conditions of thermal treatment corresponding to the conditions described above.
One embodiment of the present invention comprises applying a cationic primer (f) to cotton surface, treating thermally if appropriate and subsequently treating with crosslinked organic copolymer in particulate form (b), emulsifier (c) and hydrophobicizing agent (a). This is followed by thermal treatment.
Another embodiment of the present invention comprises applying an anionic primer (f) to polyester surface, treating thermally if appropriate and with crosslinked organic copolymer in particulate form (b), emulsifier (c) and hydrophobicizing agent (a). This is followed by thermal treatment.
The present invention further provides surfaces coated with
(f) if appropriate at least one primer,
(a) at least one hydrophobicizing agent,
(b) at least one crosslinked organic copolymer in particulate form, and which are free of acrylate binder and of polyurethane binder, especially free of filmed acrylate binder and of polyurethane binder.
Surfaces in accordance with the present invention can advantageously be produced by the above-described process of the present invention. Surfaces in accordance with the present invention are textured and repel water and have little tendency to soil.
One embodiment of the present invention comprises any emulsifier (c) or emulsifiers (c) used being applied only in traces, if at all, to surfaces of the present invention, and thus are essentially absent from the coated surfaces of the present invention.
One embodiment of the present invention comprises any auxiliary (e) or auxiliaries (e) used being applied only in traces, if at all, to surfaces of the present invention, and thus are essentially absent from the coated surfaces of the present invention.
In one embodiment of the present invention, surfaces of the present invention are characterized in that the treatment results in a coating which may be nonuniform or preferably uniform. Uniform is to be understood as meaning that the texturing is regular, while nonuniform means that the texturing is irregular, i.e., there are textured areas and nontextured areas on the surface.
In one embodiment of the present invention, surfaces of the present invention have a coating having an average add-on in the range from 1 to 10 g/m2, preferably in the range from 1.5 to 5 g/m2.
In one embodiment of the present invention, surfaces of the present invention are surfaces of textiles.
The present invention further provides aqueous formulations comprising
In one embodiment of the present invention, preferably aqueous formulations of the present invention comprise
In one embodiment of the present invention, preferably aqueous formulations in accordance with the present invention have a pH in the range from 2 to 9 and preferably in the range from 3.5 to 7.5.
In one embodiment of the present invention, preferably aqueous formulations in accordance with the present invention have a solids content in the range from 10% to 70% by weight, preferably in the range from 30% to 50% by weight.
In one embodiment of the present invention, preferably aqueous formulations in accordance with the present invention have a dynamic viscosity in the range from 50 to 5000 mPa·s, preferably in the range from 100 to 4000 mP·s and more preferably in the range from 200 to 2000 mPa·s, measured with a Brookfield viscometer to DIN 51562-1 to 4 for example.
In one embodiment of the present invention, preferably aqueous formulations in accordance with the present invention comprise crosslinked organic (co)polymer (b) having a weight average diameter in the range from 10 to 450 nm.
Aqueous formulations in accordance with the present invention make the above-described process of the present invention particularly effective, and are readily processible, for example by dilution with water, into liquors which likewise make the process of the present invention effective.
The present invention further provides a process for producing aqueous formulations that are in accordance with the present invention, hereinafter also referred to as inventive production process. The inventive production process is preferably carried out by mixing, for example stirring up
(a) at least one hydrophobicizing agent,
(b) at least one crosslinked organic copolymer in particulate form,
(c) at least one emulsifier,
(d) if appropriate a crosslinker,
(e) if appropriate one or more auxiliaries
with water.
The inventive production process can be carried out using any desired vessels, preferably stirred vessels.
The order of adding the components water and
(a) at least one hydrophobicizing agent,
(b) at least one crosslinked organic copolymer in particulate form,
(c) at least one emulsifier,
(d) if appropriate a crosslinker and
(e) if appropriate one or more auxiliaries
is generally not critical in the practice of the process according to the present invention. It is preferable if, first, water is introduced as an initial charge and then the components (a) to (c) and if appropriate (d) and (e) are mixed in.
The invention is illustrated by working examples.
The particle diameter distribution of dispersed or emulsified addition copolymers was determined using a Coulter Counter from Malvern in accordance with ISO 13321.
Dynamic viscosities were always determined using a Brookfield viscometer to DIN 51562-1 to 4.
I. Preparation of Components for Inventive Formulations
I.1 Preparation of Crosslinked Organic Copolymers in Particulate Form (b)
I.1.1. Preparation of Crosslinked Organic Copolymer in Particulate Form (b.1)
The following mixtures were prepared:
Mixture I.1.1.1:
209 g of ion-free water
344.8 g of styrene, 3,2 g of acrylic acid,
40 g of allyl methacrylate (see below)
8 g of compound V.1 (see below) where R11.1 is cis-(CH2)8—CH═CH—(CH2)7CH3 in 12 ml of water
12 g of N,N-dimethylaminopropylmethacrylamide
R11.1—[N(CH2CH2O)6H]2 V.1
adjusted to pH 4.0 with formic acid.
Mixture 1.1.1.2:4 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 80 ml of completely ion-free water
A 5 l tank equipped with anchor stirrer, nitrogen connection and three metering devices was charged with an emulsion comprising 250 ml of completely ion-free water, 40 g of compound V.1 (dissolved in 60 ml of water), 62.9 g of mixture 1.1.1.1 and 8.2 g of mixture I.1.1.2. A pH of 4.0 was set with formic acid. Then, nitrogen was passed through the resulting emulsion over a period of a quarter of an hour. The emulsion was subsequently heated to 75° C.
The simultaneous addition was then commenced of the rest of mixture I.1.1.1 and mixture I.1.1.2. The rest of mixture I.1.1.1 was added within 3 hours, the rest of mixture I.1.1.2 within 3 hours 15 minutes. During the addition, stirring was carried out at a temperature of 75° C.
Completion of the addition was followed by 30 minutes of stirring at 75° C. and subsequently, for deodorization, by the simultaneous metered addition of a solution of 2.9 g of tert-butyl hydroperoxide (70% by weight in water), diluted with 30 ml of distilled water, and of a solution of 15.4 g of acetone disulfite (13% by weight in water), diluted with 30 ml of distilled water, over a period of 60 minutes. Completion of the addition was followed by a further 30 minutes of stirring at 75° C.
This was followed by cooling at room temperature. Subsequently, the dispersion thus obtainable was filtered through a 125 μm net. The filtration took 4 minutes. It removed about 1 g of coagulum.
This gave an aqueous dispersion WD.1 having a pH of 4.1 and comprising crosslinked organic copolymer in particulate form (b.1). The solids content was 36.8% by weight, the dynamic viscosity was 35 mPa·s. Particle diameter distribution: maximum at 52 nm.
I.2 Production of Aqueous Liquors
The following ingredients were used:
Random copolymer of Mn 30 000 g/mol (GPC) from 10% by weight of methacrylic acid and 90% by weight of CH2═CHCOO—CH2—CH2—O-n-C6F13 in aqueous dispersion (28% by weight solids content) (a1.1), paraffin wax (unbranched, melting range 65-70° C., average number of carbon atoms per molecule: 40) (a2.1)
(c.1): reaction product of oleylamine with 6 equivalents of ethylene oxide, from the preparation of (b.1) or WD.1.
(d2.1): compound from Example 4 of EP 0 486 881.
The components of Table 1 were mixed in a stirred vessel and made up with water to 1 liter if appropriate to obtain the aqueous liquors F.1 to F.3.
The particles of (b) in the inventive aqueous liquor F.3 did not tend to agglomerate.
(b.1) in the form of WD.1. For each the amounts of solids are reported in the table.
II. Inventive Treatment of Textile Surfaces
The following textiles were used:
Cotton: 1 m·30 cm, 100% woven cotton, bleached, nonmercerized, twill construction, basis weight 196 g/m2 (Co)
The following equipment was used in all cases:
Pad-mangle: manufactured by Mathis, model HVF12085, contact pressure 1-3 bar.
The contact pressure setting in all cases was such that the wet pickup (based on weight of goods) was 60% in the case of polyester and 90% in the case of cotton, unless otherwise stated. The liquor was at room temperature, unless otherwise stated.
Dryer: continuous dryer from Mathis THN 12589
Test methods:
Spray test: AATCC 22-2001, Oil rating: AATCC 118-2002,
Hydrophobicization: AATCC 193-2004, Smoothness: AATCC 124-2001
Wash conditions: delicates cycle at 30° C., 15 g/l of a mild laundry detergent,
Washing machine: Miele Novotronic T440C, Setting: tumbler dry, hand iron moist.
II.1 Treatment of Textile Surfaces—Production of V-Co.1 (Comparative Example)
Textile (Co) was padded with aqueous liquor F.1. This was followed by drying on a tenter at 110° C. to a residual moisture content of 7% for 2 minutes. Thereafter, the textile thus treated was treated in a dryer at 160° C. for a period of 2 minutes. This gave comparative textiles V-Co.1 of Table 2.
II.2 Inventive Treatment of Textile Surfaces—Production of Co.2
Textile (Co) was padded with aqueous liquor F.2. This was followed by drying on a tenter at 110° C. to a residual moisture content of 6% for 2 minutes. Thereafter, the textile thus treated was treated in a dryer at 160° C. for a period of 2 minutes. This gave inventive textiles Co.2 of Table 2.
II.3 Inventive Treatment of Textile Surfaces in Two or more Stages—Production of Co.3
Textile (Co) was padded with an aqueous liquor F.3 (step 1). This was followed by drying on a tenter at 110° C. for 2 minutes and subsequent padding with aqueous liquor F.1. Thereafter, the textile thus treated was treated in a dryer at 160° C. for a period of 2 minutes. This gave inventive textile Co.3 of Table 2.
| Number | Date | Country | Kind |
|---|---|---|---|
| 07108597.1 | May 2007 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2008/056197 | 5/20/2008 | WO | 00 | 11/19/2009 |
