Patent Grant
7250456
The invention relates to a composition comprising a) a natural or synthetic oil or wax, b) a liquid polysiloxane substituted in side chains by phosphate, phosphonate, sulphate, sulphonate, —COOH, —OH, —SH, amino or epoxide-groups, preferably in α,ω-positions, c) an anionic emulsifier, preferably from the group c1) consisting of a C8-C30acylamidocarboxylic acid and c2) consisting of a C8-C24alkyl- or C8-C24alkenyl ether carboxylic acid or C8-C24alkaryl ether carboxylic acid, alone or a combination of c1 and c2, d) a molecular mono- or polycarboxylic acid, and e) optionally a hydrophilic or amphiphilic polymer soluble or emulsifiable in water and containing COOH groups, and the use of aqueous emulsions of the composition for imparting water repellency to leather or furskins, textiles and other fibrous materials.
Waterproof and/or washable leathers are of considerable importance in the production of shoes and clothing. Imparting water repellency is therefore an important step in the production of leather. The introduction of liquid siloxanes provided a water repellent with which a good water-repellent effect can be achieved.
EP-B1-0 824 600 discloses that improved water repellency of leathers and furskins can be achieved if leathers or furskins are treated in aqueous float containing special anionic surfactants.
EP-A-0 213 480 describes a process for imparting water repellency to leather and furskins, in which an aqueous emulsion of polysiloxanes is allowed to act on mineral-tanned leather, N-acylamido acids being used as emulsifiers. Polysiloxanes proposed include those having functional groups. After the treatment of the leather, the water absorption and water permeability are reduced. Similar results are obtained according to DE-A-42 14 150 if sulphited reaction products of maleic acid and polysiloxanediols, which contain a paraffinic mineral oil, are used for imparting water repellency.
DE-A-44 15 062 describes a composition for imparting water repellency to leather, which composition contains a silicone oil or a functionalized silicone oil and a carboxymethylated monoetherpolyoxaalkylene as an emulsifier. The compositions may additionally contain a further emulsifier, an oil, wax or a fatliquoring agent/water repellent. The compositions are designated as emulsions which are stable even under application conditions and with which good water repellency can be achieved.
EP-A-1 087 021 describes a leather treatment composition which comprises neutralized polysiloxanes carrying carboxyl or carboxylic anhydride groups, an amphiphilic polymer, an emulsifier and an oil or wax. For use, the water-containing composition is homogenized and a solvent is added. The composition serves for simultaneous imparting of water repellency, softening, filling and retanning of leather. The neutralization of carboxyl groups and the addition of solvent are required in order to provide a storable and stable composition which can be emulsified in the float for the treatment of the leather. A good water repellent effect can be achieved with the composition but the ecological disadvantages of the use of solvents are evident. Furthermore, large total amounts of the individual components are used in order to achieve the desired effects.
Aqueous emulsions are preferably used in leather treatment, and it is not always easy to provide such emulsions which are storable and are also stable during use at the pH of the float (for example 4.5 to 6). If the emulsions break during the treatment, the composition can no longer sufficiently penetrate into the leather. Even the addition of a further component can adversely affect the stability of such emulsions. This results in the formation of undesired precipitates together with deposits on the leather, and the water repellent effect is considerably reduced.
It has now surprisingly been found that compositions having an outstanding water repellent effect are obtained if a mineral oil or wax and a liquid polysiloxane substituted with functional groups preferably in the α,ω-position are mixed with an anionic emulsifier or surfactant, and additionally molecular mono- or polycarboxylic acid is added. Aqueous emulsions of this composition are very stable during storage and use, are distinguished by high float exhaustion and impart to the treated substrates, such as, for example, leather, an excellent water-repellent effect, none of which were achievable using customary compositions with comparable amounts of polysiloxanes.
The invention firstly relates to a substantially solvent-free composition comprising
By substantially solvent-free is understood a composition having at most 3% by weight, preferable at most 1% by weight, more preferable at most 0.5% by weight of an organic solvent, for example a glycol or glycol ether, in each case based on the overall composition. Especially preferred are compositions, which do not contain an organic solvent.
The oils and waxes of component a) are often used in leather production and are known and commercially available. Synthetic oils are, for example, those based on hydrocarbons, such as mineral oils and white oils, and alkyl esters of fatty acids or hydrogenated fatty acids. The natural oils may be vegetable or animal oils, for example fatty acid esters. Examples of synthetic waxes are paraffins, oxidized paraffins and chloroparaffins. The natural waxes may be vegetable or animal waxes. Oils are preferably used, particularly synthetic hydrocarbon-based oils, since these, unlike waxes, need not be first converted into the liquid state at relatively high temperatures.
The polysiloxanes of component b) are likewise known, described in the relevant literature and commercially available. Functionalized liquid polysiloxanes (or silicone oils) for imparting water repellency to leather are described, for example, in EP-B1-0 213 480, DE-A1-42 14 150, DE-A1 44 15 062, EP-A1-1 087 021, WO 98104748, DE-A1-100 12 722, DE-A1-100 03 322, DE-A1-199 59 949, U.S. Pat. No. 4,931,062 and U.S. Pat. No. 5,702,490. C1-C4Alkyl or C1-C4alkoxy groups or phenyl and preferably methyl groups may be bonded to the Si atoms. The functional groups are preferably bonded to Si atoms via C1-C20alkylene groups. The functional groups can be bonded to the terminal Si atoms (α,ω-positions) or to Si atoms in the chain of the polysiloxane (comb-like polysiloxanes). Furthermore, the chains of the comb-like polysiloxanes may comprise structural elements with or without a functional group. The polysiloxanes may also be branched polysiloxanes. Acidic groups may also be present in the form of their anhydrides or in the form neutralized with alkali metal hydroxides or alkaline earth metal hydroxides or ammonia/amines. The polysiloxanes are in general mixtures comprising different chain lengths.
The polysiloxanes of component b) preferably correspond to the formula I
X—CmH2m—[Si(R1)2—O]nSi(R1)2—CmH2m—X (I)
in which
In formula I, m is preferably a number from 1 to 18 and particularly from 1 to 12 and particularly preferably from 1 to 6, and n is preferably a number from 10 to 200 and particularly preferably a number from 10 to 100. R1 as alkyl may be, for example, methyl, ethyl, n-propyl, isopropyl or butyl. R1 is particularly preferably methyl. X is preferably a carboxyl, hydroxyl, mercapto, phosphate, phosphonate or epoxide group, and particularly preferably a carboxyl or epoxide group.
Suitable polysiloxanes include those in which —OH, —SH or —NHR groups are carboxyalkylated. The carboxyalkyl group may correspond, for example, to the formula —CaH2a—COOH, in which a is a number from 1 to 6 and preferably from 1 to 4. Such derivatives are obtainable in a simple manner by reacting the functional polysiloxanes with ethylenically unsaturated carboxylic acids, such as, for example, acrylic acid, methacrylic acid or maleic acid. These derivatives can also be prepared by reacting functional polysiloxanes with haloalkanecarboxylic acids.
The polysiloxanes may have a viscosity of, for example, from 30 to 8000 and preferably from 50 to 2000 mPa·s, measured at 25° C. The acid number of polysiloxanes comprising acid groups may be from 2 to 200 mg and preferably from 20 to 100 mg KOH/g. The molecular weight may be, for example, from 200 to 30,000 g/mol and preferably from 500 to 10 000 g/mol.
The anionic surfactants may be organic compounds having an acid group as a hydrophilic radical and, as a hydrophobic radical, a hydrocarbon radical which may be interrupted by hetero atoms from the group consisting of S, NR and preferably O, it being possible for the hydrophobic radicals to comprise from 8 to 50 and preferably from 8 to 30 carbon atoms and optionally hetero atoms. Suitable acids are, for example, phosphonic acids, phosphonous acid, sulphonic acids, sulphinic acids, monosulphates, mono- and diphosphates and preferably carboxylic acids. The acids are generally used in neutralized form, for example as alkali metal, alkaline earth metal or ammonium salts. Examples of salts are the lithium, sodium, potassium, ammonium, methylammonium, ethylammonium, dimethylammonium, diethylammonium, trimethylammonium, triethylammonium and mono-, di- and triethanolammonium salts. Carboxylic acids or sulphonic acids and salts thereof are preferred. The anionic surfactants are preferably chosen so that by themselves they result in a substantial improvement in the hydrophobic properties of treated materials.
Anionic surfactants which have particular utility in leather treatment are C8-C30acylamidocarboxylic acids or -sulphonic acids, C8-C24alkyl or C8-C24alkenyl ether carboxylic acid or mono- or di-C4-C24—, preferably di-C4-C24alkyl- or -alkenylaryl ether carboxylic acid. It has surprisingly been found that particularly good water repellent effects can be achieved in accordance with the invention if mixtures of c1) a C8-C30acylamidocarboxylic acid or -sulphonic acid and c2) a C8-C24alkyl- or -alkenyl ether carboxylic acid or mono- or di-C4-C24alkyl or -alkenylaryl ether carboxylic acid are used.
The acylamidocarboxylic acids of component c1) are likewise known emulsifiers and commercially available. They are preferably C8-C22acylamidocarboxylic acids and particularly preferably C10-C20acylamidocarboxylic acids. The acyl radical is preferably alkyl- or alkenyl-CO. The amidocarboxylic acids preferably comprise from 2 to 6 and particularly preferably from 2 to 4, carbon atoms and an amino group bonded in the β-position and particularly in the α-position. The amino groups can be alkylated, for example with C1-C4alkyl, such as methyl or ethyl. In leather treatment, the use of sarcosides has become established, these also being preferred according to the invention. Known examples are N-oleylsarcosine, N-stearoylsarcosine, N-lauroylsarcosine and N-isononanoylsarcosine. Further examples of known acylamidocarboxylic acids are fatty acid amidoethyl-N-(2-hydroxyethyl)aminopropionic acid, methylcocoyltauric acid, methyloleyltauric acid, N-lauroylethylenediaminetriacetic acid and N-cocoyl-L-glutaric acid. The acylamidocarboxylic acids are generally used in neutralized form, for example as alkali metal or ammonium salts, such as sodium, potassium, ammonium or mono-, di- or triethanolammonium salts.
The ether carboxylic acids of component c2) are likewise known emulsifiers, which are described, for example, in DE-A-44 15 062. The ether carboxylic acids may correspond to the formula II
R2—O[CH(R3)—CH2—O]x—CyH2y—COOH (II),
in which
R2 as alkyl and alkenyl preferably comprises from 12 to 22 and particularly preferably from 12 to 18 carbon atoms. Some examples are dodecyl, tetradecyl, hexadecyl, octadecyl and oleyl. The alkyl group or alkyl groups in the alkaryl radical preferably comprises or comprise from 6 to 12 carbon atoms. Examples are butyl, pentyl, hexyl, octyl, decyl and dodecyl.
R3 is preferably methyl and particularly preferably hydrogen.
In formula II, x is preferably a number from 1 to 12 and particularly preferably from 1.5 to 8.
In formula II, y is preferably the number 1 or 2 and particularly preferably 1.
The molecular, organic compounds of component d) may be mono- or polycarboxylic acids which comprise from 1 to 4 and preferably from 1 to 3 carboxyl groups. They may be aliphatic, cycloaliphatic, heterocycloaliphatic, aromatic and heteroaromatic mono- or polycarboxylic acids whose skeleton preferably comprises altogether from 5 to 25, more preferably from 5 to 16, carbon atoms and optionally hetero atoms from the group consisting of O, S and NR, to which skeleton from 1 to 4 carboxyl groups may be bonded directly or via a bridge group. The skeleton may be substituted by further radicals, in particular by C1-C24alkyl, preferably C1-C20alkyl, or C1-C24alkoxy and preferably C1-C20alkoxy, and particularly preferably C1-C4alkyl or C1C4alkoxy. The molecular, organic compound of component d) may comprise altogether, for example, from 5 to 150, preferably from 5 to 100, more preferably from 5 to 60, and particularly preferably from 5 to 40, carbon atoms and hetero atoms.
The bridge group may be a bivalent to tetravalent, preferably divalent to trivalent, aliphatic radical having 1 to 24 and preferably 1 to 20 carbon atoms, which may comprise hetero atoms from the group consisting of O, S and/or NR and is bonded to the skeleton via a carbon atom or a hetero atom from the group consisting of O, S or NR. R is, for example, H or C1-C4alkyl. The alkylene group may be linear or branched and may preferably comprise from 1 to 18 and particularly preferably from 1 to 6 carbon atoms. The bridge group is preferably alkylene-(O)0 or 1-, alkylene-(S)0 or 1- or alkylene-(NR)0 or 1-, alkylene comprising from 1 to 18 carbon atoms and being linear or branched.
The compounds of component e) may correspond, for example, to the formula III
(R5)i—Z—[(Z1)j—(CzH2z—COOH)]k (III)
in which
In the radical NR, R may be, for example, butyl, propyl, ethyl and preferably methyl or H.
Z1 is preferably O or NR.
In formula III, i is preferably from 1 to 3, j is preferably 1, z is preferably a number from 1 to 12 and k is preferably from 1 to 3. The compounds of the formula III preferably comprise from 5 to 25 carbon atoms and optionally additionally hetero atoms from the group consisting of O, S and NR.
The aliphatic radicals may be linear or branched alkyl or alkenyl which particularly preferably comprises from 8 to 18 carbon atoms and to which a carboxyl group or a group —(Z1)—CzH2z—COOH) is bonded. Alkane- and alkenecarboxylic acids are known (for example fatty acids). Alcohols, mercaptans and amines can be derivatized in a known manner with haloalkanecarboxylic acids or ethylenically unsaturated carboxylic acids to give compounds having a group —Z1—CzH2z—COOH.
The aliphatic radicals may be alkylene or alkenylene which preferably has from 5 to 12 carbon atoms and may be interrupted by one or more hetero atoms O, S or NR and to which 2 carboxyl groups, two groups —(Z1)—(CzH2z—COOH) or a carboxyl group or a group —(Z1)—(C2H2z—COOH) and, in the presence of hetero atoms N in the chain, groups —(CzH2z—COOH) are bonded. Alkylenedicarboxylic acids, such as, for example, adipic acid, hexa-, octa- and decamethylenedicarboxylic acids or branched alkylenedicarboxylic acids are familiar to a person skilled in the art. Dicarboxylic acids having two groups —(Z1)—(CzH2z—COOH) are obtainable in a known manner by reacting diols, dimercaptans and diamines with haloalkanecarboxylic acids or ethylenically unsaturated carboxylic acids. Dicarboxylic acids having two groups —(Z1)—(CzH2z—COOH) and one or two groups —(CzH2z—COOH) are obtainable in a known manner by reacting tri- or tetramines, such as, for example, diethylenetriamine and triethylenetetramine, with haloalkanecarboxylic acids or ethylenically unsaturated carboxylic acids. Other dicarboxylic acids are obtainable by reacting ω-carboxylic acids, such as, for example, ω-aminopentanecarboxylic acid or ω-hexanecarboxylic acid with halo-alkanecarboxylic acids or ethylenically unsaturated carboxylic acids.
The cycloaliphatic radicals may comprise cycloalkanes, for example cyclopentane, cyclo-hexane, cycloheptane, cyclooctane, cyclodecane and cyclododecane, to which a carboxyl group or a group —(Z1)—(CzH2z—COOH) is bonded. The cycloalkanes are preferably substituted by one or two C6-C18alkyl or C6-C18alkoxy radicals. Some examples are cyclohexane-carboxylic acid, methylcyclohexanecarboxylic acid, n-butylcyclohexanecarboxylic acid, octylcyclohexanecarboxylic acid, dodecylcyclohexanecarboxylic acid, octadecylcyclo-hexanecarboxylic acid, cyclohexanecarboxymethyl, -ethyl, -propyl or -butyl ether, C6-C18alkylcyclohexanecarboxymethyl, -ethyl, -propyl or -butyl ether, N-carboxymethyl-, N-carboxyethyl-, N-carboxypropyl- or N-carboxybutylcyclohexylamine or N-carboxymethyl-, N-carboxyethyl-, N-carboxypropyl- or N-carboxybutyl-C6-C18alkylcyclohexylamine.
The cycloaliphatic radical may be cycloalkylene, for example cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclodecylene and cyclododecylene, to which two carboxyl groups or two groups —(Z1)—(CzH2z—COOH) or a carboxyl group or a group —(Z1)—(CzH2z—COOH) are bonded. The cycloalkenes may be substituted by a C6-C18alkyl or C6-C18alkoxy radical. Some examples are cyclopentane-, cyclohexane-, cycloheptane- and cyclododecanedi-carboxylic acid, p-carboxymethoxy-, p-carboxyethoxy-, p-carboxylpropoxy-, p-carboxybutoxy- and p-carboxyhexyloxycyclohexanecarboxylic acid, di-p-carboxymethoxy-, di-p-carboxy-ethoxy-, di-p-carboxypropoxy-, di-p-carboxybutoxy- and di-p-carboxyhexyloxycyclohexane, p-carboxymethylamino-, p-carboxyethylamino-, p-carboxypropylamino-, p-carboxybutylamino- and p-carboxyhexylaminocyclohexanecarboxylic acid, di-p-carboxymethylamino-, di-p-carboxyethylamino-, di-p-carboxypropylamino-, di-p-carboxybutylamino- and di-p-carboxyhexyl-aminocyclohexane, and 1-carboxyethylamino-4-carboxyethoxycyclohexane.
The cycloaliphatic radicals may also be a trivalent cycloalkyl radical to which altogether three carboxyl groups or groups —(Z1)—(CzH2z—COOH) are bonded. Some examples are cyclohexanetricarboxylic acid, tricarboxymethoxycyclohexane and tricarboxymethylaminocyclohexane.
The heterocycloaliphatic radical may be heterocycloalkyl which preferably has from 5 to 8 ring atoms and from 1 to 3, preferably 1 or 2, hetero atoms from the group consisting of O, S and NR and in which a carboxyl group, a group —(Z1)—(CzH2z—COOH) or a group —(Cz—H2z—COOH) is bonded to a ring N atom. Examples of heterocycles are pyrrolidine, tetrahydrofuran, pyrazolidine, oxazolidine, thiazolidine, piperidine, piperazine and morpholine. Some examples are proline, N-nonylproline, tetrahydrofurancarboxylic acid, N-nonylpiperidinecarboxylic acid, piperidinecarboxylic acid, N-octyl-N′-carboxyethylpiperazine and N-carboxyethylmorpholine.
The heterocycloaliphatic radicals may be heterocycloalkylene which preferably has 5 to 8 ring atoms and from 1 to 3, preferably 1 or 2, hetero atoms from the group consisting of O, S and NR and in which altogether two carboxyl groups, groups —(Z1)—(CzH2z—COOH) or a group —(CzH2z—COOH) is bonded to a ring N atom. Some examples are tetrahydrofurandicarboxylic acid, N-carboxymethylproline, N,N′-carboxymethylpyrazolidine, N,N′-carboxyethylpiperazine, N,N′-carboxyhexylpiperazine and N-carboxymethylpiperidinecarboxylic acid.
The cycloaliphatic radical may also be a trivalent heterocycloalkyl radical in which altogether three carboxyl groups, groups -(Z1)-(CzH2z—COOH) or groups —(CzH2z—COOH) are bonded to a ring N atom. Examples of heterocycles have been mentioned above. Some examples are N-carboxymethyl-4-carboxymethoxyproline, N-carboxymethyl-4-carboxymethylaminoproline, N-carboxyethyl-4-carboxyethoxyproline, N-carboxybutyl-4-carboxybutoxyproline, N-carboxy-hexyl-4-carboxyhexyloxyproline, carboxyethyl-4-carboxyethylaminoproline, carboxybutyl-4-carboxybutylaminoproline and carboxyhexyl-4-carboxyhexylaminoproline.
The aromatic radicals may be naphthalene or benzene to which a carboxyl group, a carboxy-C1-C24alkyl group, a carboxy-C2-C24alkenyl group or a group —(Z1)—(CzH2z—COOH) is bonded and which may be substituted by one or two C1-C24alkyl and/or C1-C24alkoxy and preferably C1-C12alkyl and/or C1-C12alkoxy radicals. Some examples are benzoic acid, methylbenzoic acid, naphthalenecarboxylic acid, phenylacetic acid, methyl-, butyl-, octyl- or nonylphenyl-acetic acid, phenylpropionic acid, phenylbutyric acid, cinnamic acid; carboxymethoxy-benzene; carboxyethoxybenzene, carboxypropoxybenzene, carboxybutoxybenzene, carboxypentyloxybenzene, carboxyhexyloxybenzene; carboxymethoxy-, carboxyethyoxy-, carboxypropoxy-, carboxybutoxy-, carboxypentyloxy- or carboxyhexyloxy-C1-C12alkylbenzene, such as, for example, carboxymethoxynonylbenzene or carboxyhexyloxymethylbenzene; carboxymethylamino-, carboxyethylamino-, carboxypropylamino-, carboxybutylamino-, carboxypentylamino- or carboxyhexylaminobenzene, carboxymethylamino-C1-C12alkyl-, carboxyethylamino-C1-C12alkyl-, carboxypropylamino-C1-C12alkyl-, carboxybutylamino-C1-C12alkyl-, carboxypentylamino-C1-C12alkyl- and carboxyhexylamino-C1C12alkylbenzene, such as, for example, 1-carboxymethylamino-4-nonylbenzene.
The aromatic radical may be divalent naphthalene or preferably divalent benzene, to each of which two of the groups carboxyl, carboxy-C1-C24alkyl, carboxy-C2-C24-alkenyl or —(Z1)—(CzH2z—COOH) are bonded and each of which may be substituted by one or two C1-C24alkyl and/or C1-C24alkoxy and preferably C1-C12alkyl and/or C1-C12alkoxy radicals. Some examples are phthalic, isophthalic and terephthalic acid, naphthalenedicarboxylic acid, carboxyphenylacetic acid, carboxyphenylpropionic acid, carboxyphenylbutyric acid, carboxyphenylhexanecarboxylic acid, carboxymethoxybenzoic acid, carboxyethoxybenzoic acid, carboxypropoxybenzoic acid, carboxybutoxybenzoic acid, carboxypentyloxybenzoic acid, carboxyhexyloxybenzoic acid, carboxymethylaminobenzoic acid, carboxyethylaminobenzoic acid, carboxypropylaminobenzoic acid, carboxybutylaminobenzoic acid, carboxypentylaminobenzoic acid, carboxyhexylaminobenzoic acid, dicarboxymethoxybenzene, dicarboxyethoxybenzene, dicarboxypropoxybenzene, dicarboxybutoxybenzene, dicarboxypentyloxybenzene, dicarboxyhexyloxybenzene, dicarboxymethylaminobenzene, dicarboxyethylaminobenzene, dicarboxypropylaminobenzene, dicarboxybutylaminobenzene, di(carbaminopentyloxy)benzene, dicarboxyhexylaminobenzene, carboxymethylaminocarboxymethoxybenzene, carboxyethylaminocarboxyethoxybenzene, carboxypropylaminocarboxypropoxybenzene, carboxybutylaminocarboxybutoxybenzene, carboxypentylaminocarboxypentyloxybenzene, carboxyhexylaminocarboxyhexyloxybenzene and carboxymethylaminocarboxyhexyloxybenzene. Alkyl and alkenyl preferably comprise from 1 to 6 and from 2 to 6 carbon atoms, respectively.
The aromatic radical may be trivalent naphthalene or preferably trivalent benzene, to each of which two of the groups carboxyl, carboxy-C1-C24alkyl, carboxy-C2-C24alkenyl or —(Z1)—(CzH2z—COOH) are bonded and each of which may be substituted by one or two C1-C24alkyl and/or C1-C18alkoxy and preferably C1-C12alkyl and/or C1-C12alkoxy radicals. Some examples are trimellitic acid, naphthalenetricarboxylic acid, tricarboxymethylbenzene, tricarboxymethoxybenzoic acid, tricarboxyethoxybenzoic acid, tricarboxypropoxybenzoic acid, tricarboxybutoxybenzoic acid, tricarboxypentyloxybenzoic acid, tricarboxyhexyloxybenzoic acid, tricarboxymethylaminobenzoic acid, tricarboxyethylaminobenzoic acid, tricarboxypropylaminobenzoic acid, tricarboxybutylaminobenzoic acid, tricarboxypentylaminobenzoic acid, tricarboxyhexylaminobenzoic acid and analogous tricarboxylic acids having one or two carboxyalkoxy radicals and two or one carboxyalkylamino radicals.
Examples of such tetracarboxylic acids are pyromellitic acid, prehenitic acid, mellophanic acid and naphthalenetetracarboxylic acids.
The heteroaromatic radicals may comprise five- or six-membered rings or fused ring systems which have from 1 to 3 hetero atoms from the group consisting of O, S and NR and to which a carboxyl group, a carboxy-C1-C6alkyl group, a carboxy-C2-C6alkenyl group or a group -(Z1)-(CzH2z—COOH) is bonded and which may be substituted by one or two C1-C24alkyl and/or C1-C24alkoxy and preferably C1-C12alkyl and/or C1-C12alkoxy radicals. Some examples of heterocycles are pyrrole, furan, thiophene, pyrazole, imidazole, pyran, pyridine, pyrimidine, pyrazine, indole, isoindole, coumarone, thionaphthene, carbazole, quinoline, isoquinoline, acridine, chromene, phenothiazine and 1,3,5-triazine. Some examples of carboxylic acids are pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, indolecarboxylic acid, N-carboxymethylpyrrole, N-carboxyethylpyrrole, N-carboxybutylpyrrole, N-carboxyhexylpyrrole, N-carboxymethylpyrazole, N-carboxyethylpyrazole, N-carboxypropylpyrazole, N-carboxybutylpyrazole, N-carboxyhexylpyrazole, N-carboxymethylimidazole, carboxyethylimidazole, carboxybutylimidazole, carboxyhexylimidazole, carboxymethoxypyrrole, carboxyethoxypyrrole, carboxypropoxypyrrole, carboxybutoxypyrrole, carboxymethylaminopyrrole, carboxy-ethylaminopyrrole, carboxypropylaminopyrrole, carboxybutylaminopyrrole, carboxymethoxypyridine, carboxyethoxypyridine, carboxypropoxypyridine, carboxybutoxypyridine, carboxymethylaminopyridine, carboxyethylaminopyridine, carboxypropylaminopyridine and carboxybutylaminopyridine.
The heteroaromatic radicals may comprise bivalent, five- or six-membered rings or fused ring systems which have from 1 to 3 hetero atoms from the group consisting of O, S and NR and to which altogether two of the groups carboxyl, carboxy-C1-C24alkyl, carboxy-C2-C24alkenyl or —(Z1)—(CzH2z—COOH) are bonded and which may be substituted by one or two C1-C24alkyl and/or C1-C18alkoxy and preferably C1-C12alkyl and/or C1-C12alkoxy radicals. Heterocycles have been mentioned above. Some examples are pyrroledicarboxylic acid, pyridinedicarboxylic acid, furandicarboxylic acid, N-carboxymethylpyrrolecarboxylic acid, N-carboxyethylpyrrolecarboxylic acid, N-carboxybutylpyrrolecarboxylic acid, N-carboxyhexylpyrrolecarboxylic acid, carboxymethoxypyrrolecarboxylic acid, carboxyethoxypyrrolecarboxylic acid, carboxypropoxypyrrolecarboxylic acid, carboxybutoxypyrrolecarboxylic acid, carboxymethylaminopyrrolecarboxylic acid, carboxyethylaminopyrrolecarboxylic acid, carboxypropylaminopyridinecarboxylic acid, carboxybutylaminopyridinecarboxylic acid, carboxymethoxypyridinecarboxylic acid, carboxyethoxypyridinecarboxylic acid, carboxypropylaminopyridinecarboxylic acid, carboxybutoxypyridinecarboxylic acid, dicarboxymethoxypyrrole, dicarboxyethoxypyrrole, dicarboxypropoxypyrrole, dicarboxybutoxypyrrole, dicarboxymethylaminopyrrole, dicarboxyethylaminopyrrole, dicarboxypropoxypyridine, dicarboxybutoxypyridine, dicarboxymethoxypyridine, dicarboxyethoxypyridine, dicarboxypropylaminopyridine, dicarboxybutylaminopyridine, N-carboxymethylcarboxymethoxypyrrole, N-carboxymethylcarboxymethylaminopyrrole, carboxymethoxycarboxymethylaminopyrrole, carboxybutoxycarboxybutylaminopyrrole, carboxymethoxycarboxymethylaminopyridine, carboxybutoxycarboxybutylaminopyridine, dicarboxymethoxypyrimidine and dicarboxybutylaminopyrimidine.
The heteroatomatic radical may comprise trivalent, five- or six-membered rings or fused ring systems which have from 1 to 3 hetero atoms from the group consisting of O, S and NR and to which altogether three groups carboxyl, carboxy-C1-C24alkyl, carboxy-C2-C24alkenyl or —(Z1)—(CzH2z—COOH) are bonded and which may be substituted by one or two C1-C24alkyl and/or C1-C24alkoxy and preferably C1-C12alkyl and/or C1-C12alkoxy radicals. Heterocycles have been mentioned above. Some examples are N-carboxymethyldicarboxymethoxypyrrole, carboxymethyldicarboxymethylaminopyrrole and tricarboxymethylaminopridine.
Compounds of component d) which are particularly preferred according to the invention are those in which carboxy-C1-C6alkyl groups or groups —(Z1)—(CzH2z—COOH), in which Z is O or NR and z is a number from 1 to 18 and preferably from 1 to 6, are bonded to the skeleton.
Very particularly preferred compounds of component e) are carboxyalkylated melamine derivatives of the formula IV
in which A is a group —(CzH2z—) and z is a number from 1 to 24, preferably from 1 to 18, more preferably from 1 to 12 and particularly preferably from 1 to 6.
The acids of component d) are generally used in neutralized form, for example as alkali metal or ammonium salts, such as sodium, potassium, ammonium, trimethylammonium, triethylammonium, tributylammonium or mono-, di- or triethanolammonium salts.
The ratios of the components in the composition according to the invention may be, for example, based on the total amount,
If mixtures of c1) a C8-C30acylamidocarboxylic acid or -sulphonic acid and c2) a C8-C24alkyl or C8C24alkenyl ether carboxylic acid or mono- or di-C4-C14alkyl or -alkenylaryl ether carboxylic acid is used, the amounts are, for example,
The composition according to the invention may additionally comprise e) a hydrophilic or amphiphilic polymer emulsifiable or soluble in water and comprising COOH groups for improving the stability and the performance characteristics. The amount may be, for example, from 1 to 20 and preferably from 7.5 to 18% by weight, based on the composition according to the invention. Amphiphilic polymers are known and are already used in the treatment of leather. They are, for example, polymers of ethylenically unsaturated hydrophobic monomers and ethylenically unsaturated hydrophilic monomers. Examples of hydrophobic monomers are optionally substituted alkenes having preferably from 6 to 24 carbon atoms, optionally substituted styrene, vinyl ether, vinyl ester, allyl ether, allyl ester and esters of acrylic acid, methacrylic acid or maleic acid and alkanols having preferably from 6 to 24 carbon atoms and with polyoxyalkylene monoethers, or amides of said acids. The hydrophilic monomers may be, for example, ethylenically unsaturated mono- or dicarboxylic acids, for example acrylic acid, methacrylic acid and maleic acid or maleic monoesters. Such polymers are described, for example, in EP-A-0 658 172, EP-A-0 372 746, EP-A-0 670 909, EP-A-0 412 389 and DE-A-1 196 25 984.
Hydrophilic polymers are likewise known and are composed of hydrophilic monomers which optionally comprise small amounts of hydrophobic monomers. The hydrophilic monomers may be, for example, ethylenically unsaturated mono- or dicarboxylic acids, for example acrylic acid, methacrylic acid and maleic acid, or maleic monoesters, and hydroxyalkyl (for example C2-C6hydroxyalkyl) or polyoxaalkylene esters (polyoxyethylene or polyoxypropylene esters), or vinyl, allyl or methallyl hydroxyalkyl (for example C2-C6hydroxyalkyl) or -polyoxa-alkylene ethers (polyoxyethylene or polyoxypropylene ethers), it being possible for the polymers to comprise identical or different monomers of these types. Hydrophilic polymers are described, for example, in EP-A-0 658 172 and DE-A-196 25 984.
Such polymers are commercially available and are generally offered as aqueous formulations. The composition according to the invention and comprising polymers can in this case additionally comprise small amounts of water, for example up to 16% by weight. Some or all of the carboxyl groups may have been neutralized, for example with NaOH. With the polymers comprising COOH groups, a further improvement in the hydrophobic properties of the treated leather can also be achieved.
The preparation of the composition according to the invention can be carried out in a simple manner by mixing components, the order of the addition being unimportant. The mixing can be effected by stirring, extrusion or kneading. Depending on the choice and ratios of the components, compositions having an oily to pasty consistency are obtained. In order to improve the consistency, water may be added to the composition as early as during the preparation. The compounds of component e) may also be used in the form of concentrated aqueous solutions, the composition according to the invention then additionally comprising small amounts of water, for example up to 16% by weight. These compositions can be used directly in tanning, but the metering and formation of an emulsion in the float may not be very simple. Expediently, an aqueous emulsion is therefore prepared beforehand and added to the float, or the composition is offered in the form of aqueous and easily meterable emulsion concentrates.
It is therefore more advantageous to use an aqueous emulsion and in particular emulsion concentrates of the composition according to the invention. The invention furthermore relates to an emulsion concentrate comprising
The pH of the emulsion concentrates is preferably from 5 to 10 and particularly preferably from 7 to 9. The pH can be established by adding organic bases, ammonia or amines. Suitable organic bases are in particular sodium hydroxide or potassium hydroxide. Suitable amines are in particular mono-, di- or trialkylamines, such as methylamine, ethylamine, N-propylamine, N-butylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, trimethylamine, triethylamine, tri-n-propylamine and tri-n-butylamine, and alkanolamines, such as ethanolamine, propanolamine, butanolamine, diethanolamine and triethanolamine. The composition may comprise, for example, from 0.01 to 8 and preferably from 0.1 to 5% by weight of inorganic base, ammonia or amine.
The emulsion concentrates according to the invention have a relatively long shelf life. They do not form any deposits in containers, can be readily reemulsified on phase separation and can be removed without problems from containers. The emulsion concentrates according to the invention have surprisingly also proved very stable in an aqueous acidic medium, for example at a pH of about 4 to 5. At this pH of an aqueous float, wet blue leather, tanned skins or textiles are treated in order to permit penetration of the water repellent. With the composition according to the invention and its high stability in the acidic range of the float, high exhaustion of the float in combination with a surprisingly high water repellency of the treated material is achieved. The properties of leather which are achieved in preceding treatment stages, for example the optical aspect (uniformity), the outstanding feel, physical and mechanical properties and the uniform dyeing of the leather are not adversely affected.
The preparation of the emulsion concentrates according to the invention can be carried out in a simple manner by emulsifying the compositions in water. Furthermore, it is possible and preferable to prepare the emulsion directly with stirring by adding the components a) to d) and optionally e) to water.
The invention furthermore relates to a process for treating and imparting water repellency to fibrous materials, leather, skins and textiles, wherein
The invention furthermore relates to the use of the composition according to the invention for imparting water repellency to fibrous materials, leather, furskins and textiles.
In one variant of the process according to the invention, a hydrophilic or amphiphilic polymer soluble or emulsifiable in water and comprising COOH groups can be added to the float before, with or after addition of the composition used in process stage 1.
The composition according to the invention can be used in an amount of from 1 to 20% by weight and preferably from 5 to 15% by weight, based on the shaved weight of a wet blue leather or the dry weight of a tanned skin, textile or fibrous material.
The float length (percent by weight of water, based on shaved weight or dry weight) may be, for example, from 50 to 200%.
The temperature of the float during the water repellent treatment is, for example, from 30 to 70° C. and preferably from 40 to 60° C.
The pH of the float is advantageously adjusted to 4 to 9.
The treatment time may be, for example, 0.5 to 2 hours, excellent results already being obtained in times of about 0.5 to 1.5 hours.
An acid is added to the float after the treatment according to the invention for fixing, so that the pH is from about 3 to 4.5. In the treatment of leather, the use of formic acid has proved particularly suitable for this purpose.
In the second process stage, the water repellent is fixed with metal salts on and in the fibres of leather, furskins, textiles and fibrous materials. Metal salts which are used in leather production also for tanning are particularly suitable, for example metal salts having metal cations of chromium, aluminium, zirconium and titanium. Examples are basic chromium(III) sulphate and basic alum.
The amount of metal salts may be, for example, from 0.1 to 6 and preferably from 0.5 to 4 percent by weight, based on the shaved weight or dry weight.
The treatment time may be, for example, from 0.5 to 2 hours, times of only about 0.5 to 1.5 hours often being sufficient for achieving excellent results.
The temperature of the liquor during the fixing is, for example, from 30 to 70° C. and preferably from 30 to 60° C.
After fixing, the material which has been rendered water repellent is finished in a manner known per se by removing it from the wash, hanging it overnight, sammying it and then setting it out, drying it (optionally in vacuo), conditioning it, staking it and plating it.
The following examples explain the invention in more detail. The Maeser test is carried out according to ASTM D 2099-70.
Abbreviations
Mineral oil: paraffinic mineral oil, specific gravity 0.86 g/cm3 at 15° C.
Carboxypolysiloxane: polydimethylsiloxane having terminal carboxyl groups, an acid number of about 40 mg KOH/g and a viscosity of 550 mPa·s at 25° C.
Polycarboxylic acid a: 6,6′,6″-(1,3,5-triazine-2,4,6-triyltriimino)trihexanoic acid
Polycarboxylic acid b: stearic acid
Polycarboxylic acid c: sebacic acid (disodium salt)
Polycarboxylic acid d: phthalic acid
Polycarboxylic acid e: trimellitic acid
Polycarboxylic acid f: pyromellitic acid
Polycarboxylic acid g: citric acid
Polycarboxylic acid h: p-isononylphenoxyacetic acid
Polycarboxylic acid i: (2-benzothiazolylthio)succinic acid (60% strength)
Polycarboxylic acid j: N-lauroylethylenediaminetriacetic acid
Polycarboxylic acid k: N-cocoyl-L-glutamic acid (monosodium salt, 23% strength)
Carboxyl polymer A: 40% strength copolymer emulsion based on acrylic acid (Brookfield viscosity <2000 mPa·s at 25° C.).
Carboxyl polymer B: 20% strength copolymer emulsion based on styrene (Brookfield viscosity <500 mPa·s at 30° C.).
Carboxyl polymer C: 33% strength copolymer emulsion based on acrylic acid (Brookfield viscosity about 2000 mPa·s at 25° C., analogous to DE-B1-19625984).
Carboxyl polymer D: 35% strength copolymer emulsion based on acrylic acid (Brookfield viscosity 100-500 mPa·s at 25° C.).
Oleyl ether carboxylic acid: oleyl-O—(CH2CH2—O)2—CH2—COOH
A) Preparation of Compositions
The following components (amounts stated in percent by weight)
are stirred at 60° C. until a homogeneous mixture has formed, and then cooled. A light brown, milky emulsion is obtained.
B) Preparation of Emulsions
2.3 g of polycarboxylic acid a and 2.5 g of 50% strength NaOH are dissolved in 42.7 g of water and heated to 85° C. Thereafter, at constant temperature, 31.3 g of mineral oil, 10 g of carboxypolysiloxane, 4.5 g of N-oleoylsarcosine and 6.7 g of oleyl ether carboxylic acid are added and then stirring is continued until a homogeneous emulsion has formed. Cooling to room temperature is then effected with stirring. A whitish, milky emulsion having a pH of 8.5 and a water content of about 45% is obtained.
Comparative Composition 1
2.5 g of 50% strength NaOH are dissolved in 43.8 g of water and heated to 85° C. At constant temperature, 32.4 g of mineral oil, 10 g of carboxypolysiloxane and 11.3 g of N-oleoylsarcosine are then slowly added. Stirring is then continued until a homogeneous emulsion is formed. The homogeneous emulsion is cooled with stirring.
A whitish milky emulsion having a pH of 8.0 and a water content of about 45% is obtained.
Comparative Composition 2
1.8 g of 50% strength NaOH are dissolved in 44.2 g of water and heated to 85° C. At constant temperature, 32.7 g of mineral oil, 10 g of carboxypolysiloxane and 11.3 g of N-oleyl ether carboxylic acid are then slowly added. Stirring is then continued until a homogeneous emulsion is formed. The homogeneous emulsion is cooled with stirring.
A whitish, milky emulsion having a pH of 8.5 and a water content of about 45% is obtained.
Comparative Composition 3
2 g of 50% strength NaOH are dissolved in 44 g of water and heated to 85° C. At constant temperature, 32.7 g of mineral oil, 10 g of carboxypolysiloxane, 4.5 g of N-oleoylsarcosine and 6.8 g of N-oleyl ether carboxylic acid are then slowly added. Stirring is then continued until a homogeneous emulsion has formed. The homogeneous emulsion is cooled with stirring.
A whitish, milky emulsion having a pH of 8.4 and a water content of about 45% is obtained.
2.3 g of polycarboxylic acid a and 2.9 g of 50% strength NaOH are dissolved in 42.5 g of water and heated to 85° C. At constant temperature, 31 g of mineral oil, 10 g of carboxypolysiloxane and 11.3 g of N-oleoylsarcosine are then slowly added. Stirring is then continued until a homogeneous emulsion has formed. The homogeneous emulsion is cooled with stirring.
A whitish, milky emulsion having a pH of 8.0 and a water content of about 45% is obtained.
2.3 g of polycarboxylic acid a and 2.4 g of 50% strength NaOH are dissolved in 42.9 g of water and heated to 85° C. At constant temperature, 31.1 g of mineral oil, 10 g of carboxypolysiloxane and 11.3 g of N-oleyl ether carboxylic acid are then slowly added. Stirring is then continued until a homogeneous emulsion is formed. The homogeneous emulsion is cooled with stirring.
A whitish, milky emulsion having a pH of 8.0 and a water content of 45% is obtained.
x g of polycarboxylic acid b-k (table 1) and 2.5 g of 50% strength NaOH are dissolved in 43 g of water and heated to 85° C. Thereafter, at constant temperature, 31.3 g of mineral oil, 10 g of carboxypolysiloxane, 4.5 g of N-oleoylsarcosine and 6.7 g of oleyl ether carboxylic acid are added and stirring is then continued until a homogeneous emulsion is formed. Cooling to room temperature is then effected with stirring. A whitish, milky emulsion having a pH of from 7 to 8.5 and a water content of about 45% is obtained.
2.3 g of polycarboxylic acid a and 1.8 g of 50% strength NaOH are dissolved in 35 g of water and heated to 85° C. At constant temperature, 30 g of mineral oil, 10 g of polysiloxane, 4.5 g of N-oleoylsarcosine and 6.8 g of oleyl ether carboxylic acid are then added. y g of carboxyl polymer (A, A/B, C) are then added (table 2), after which stirring is continued until a homogeneous emulsion has formed. The homogeneous emulsion is cooled with stirring.
Properties
A whitish, milky emulsion having a pH of 7.5-8.5 and a water content of about 43% is obtained.
2.3 g of polycarboxylic acid a and 2.9 g of 50% strength NaOH are dissolved in 35.6 g of water and heated to 85° C. At constant temperature, 27 g of mineral oil, 10 g of polysiloxane, 4.5 g of N-oleoylsarcosine and 6.7 g of oleyl ether carboxylic acid are then added. 11 g of carboxyl polymer D are then added, after which stirring is continued until a homogeneous emulsion is formed. The homogeneous emulsion is cooled with stirring.
Properties
A whitish, milky emulsion having a pH of 8.5 and a water content of about 45% is obtained.
C) Use Examples
The stated percentages are based on the shaved weight of the wet blue leather. A retanned and dyed wet blue (chrome-tanned leather) having a shaved thickness of 1.8 mm is added to 100% by weight of water heated to 50° C. Thereafter, 10% by weight of an emulsion concentrate according to example B1, diluted in the ratio of 1:4 with water, are added and the float is allowed to act on the leather for 90 minutes (pH about 5). Thereafter, 1% by weight of 85 percent strength formic acid diluted in the ratio 1:5 with water is added and treatment is carried out for 10 minutes. Thereafter, a further 1% by weight of 85 per cent strength formic acid diluted in the ratio 1:5 with water is added and treatment is carried out for a further 30 minutes. The pH is then 3.6.
The float is discharged and the leather is washed with 300% by weight of water heated to 40° C. After the wash water has been discharged, 100% by weight of water heated to 40° C. and 3% by weight of chromium salt (Chromosale BD) are added and treatment is carried out for 60 minutes. Thereafter, washing is effected with 300% by weight each of water at 30° C. and at 20° C. for 10 minutes in each case and the leather is removed and dried.
The properties are shown in table 3.
With the comparative composition 1, the procedure is as in example C1. The properties are shown in table 3.
With the comparative composition 2, the procedure is as in example C1. The properties are shown in table 3.
With the comparative composition 3, the procedure is as in example C1. The properties are shown in table 3.
1)Mean value of 3 measurements
2)The emulsion stability is determined as follows: the concentrate is diluted with water at 60° C., cooled and allowed to stand. The time when a phase separation is visible is then determined.
With the composition according to example B2, the procedure is as in example C1. The properties are shown in Table 4.
With the composition according to example B3, the procedure is as in example C1. The properties are shown in table 4.
With the composition according to example B4 (with polycarboxylic acid b), the procedure is as in example C1. The properties are shown in table 5.
With the composition according to example B5 (with polycarboxylic acid c), the procedure is as in example C1. The properties are shown in table 5.
With the composition according to example B6 (with polycarboxylic acid d), the procedure is as in example C1. The properties are shown in table 5.
With the composition according to example B7 (with polycarboxylic acid e), the procedure is as in example C1. The properties are shown in table 6.
With the composition according to example B8 (with polycarboxylic acid f), the procedure is as in example C1. The properties are shown in table 6.
With the composition according to example B9 (with polycarboxylic acid g), the procedure is as in example C1. The properties are shown in table 6.
With the composition according to example B10 (with polycarboxylic acid h), the procedure is as in example C1. The properties are shown in table 6.
With the composition according to example B11 (with polycarboxylic acid i), the procedure is as in example C1. The properties are shown in table 6.
With the composition according to example B12 (with polycarboxylic acid j), the procedure is as in example C1. The properties are shown in table 6.
With the composition according to example B13 (with polycarboxylic acid k), the procedure is as in example C1. The properties are shown in table 6.
With the composition according to example B14 (with carboxyl polymer A), the procedure is as in example C1. The properties are shown in table 7.
With the composition according to example B15 (with carboxyl polymer A/B), the procedure is as in example C1. The properties are shown in table 7.
With the composition according to example B16 (with carboxyl polymer C), the procedure is as in example C1. The properties are shown in table 7.
With the composition according to example B17, the procedure is as in example C1. The properties are shown in table 7.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0167/02 | Jan 2002 | CH | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP03/00595 | 1/22/2003 | WO | 00 | 7/28/2004 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO03/064707 | 8/7/2003 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4076672 | Huber et al. | Feb 1978 | A |
| Number | Date | Country |
|---|---|---|
| 196 29 986 | Jan 1998 | DE |
| 1087021 | Mar 2001 | EP |
| Number | Date | Country | |
|---|---|---|---|
| 20050148702 A1 | Jul 2005 | US |
