DE3529073A1 - Preparations containing phosphoric acid partial esters, their preparation and their use - Google Patents

Abstract

Preparations which are stable on storage and readily dilutable with water, which contain (a) phosphoric acid partial esters of polyalkylene glycol monoethers of higher fatty alcohols, (b1) at least one mono- and/or di-(C2-3-alkylene) glycol mono-(C1-4-alkyl) ether and/or at least one aliphatic alcohol having 4-6 carbon atoms, (b2) mono- and/or diethylene glycol (c) at least one low-aromatic to aromatic-free hydrocarbon oil and (d) a water-miscible alkanolamine, and whose water content (e) is </= 5 % by weight, their preparation and their use, in particular for the fat-liquoring of leather from aqueous medium, if desired with after treatment using polyvalent metal or oxymetal cations.

Description

Preparations containing phosphoric acid partial esters, their manufacture and

their use In DE-OS 30 32 925 are aqueous preparations of certain phosphoric acid partial esters described, which are used to grease leather. The aqueous, concentrated preparations described there can have a relatively high Have a shelf life and also be readily dilutable with water. It was now found that through a certain selection of components almost anhydrous to Anhydrous phosphoric acid partial ester preparations can be produced which have a Have surprisingly improved shelf life and very well with water are dilutable. The invention thus relates to this new almost anhydrous to anhydrous preparations containing phosphoric acid esters, their manufacture and their use, especially for greasing leather.

The invention therefore first relates to hydrocarbon oils and water-soluble and / or water-dispersible phosphoric acid partial esters of Preparations containing polyalkylene glycol monoethers of higher fatty alcohols, which thereby are characterized in that the partial esters (a) in a mixture of: (b1) at least a mono- or di- (C2 ~ 3-alkylene) -glycolmono- (C1 4-alkyl) ether and / or at least an aliphatic alcohol with 4-6 carbon atoms, (b2) mono- and / or dietylene glycol and (c) at least one low to aromatic free hydrocarbon oil is dispersed and / or are dissolved and are present as salts of (d) water-miscible alkanolamines and the water content (e) of the preparations L is 5% by weight.

In the polyalkylene glycol ethers of the higher fatty alcohols are the higher ones Fatty alcohols, alkanols and alkenols with 14 to 20 carbon atoms, preferably n-alkenols and in particular n-alkanols, e.g. tetradecanol, cetyl alcohol, oleyl alcohol and stearyl alcohol, as well as technical mixtures that contain or contain such alcohols consist of such as tallow fatty alcohol; including those aged 16 to 18 Carbon atoms preferred. The polyalkylene glycol residues in these polyalkylene glycol ethers contain an average of 2 to 10 alkyleneoxy units per radical and alkylene is Ethylene-1,2 and optionally propylene-1,2, of which 2 to 6 units are ethyleneoxy units are. The polyalkylene glycol monoethers of the higher alcohols mentioned can be based on customary Wise be prepared, for example by addition of alkylene oxides, in particular Ethylene oxide and propylene oxide. Oxalkylation products are preferred which are exclusively Containing ethyleneoxy units as alkyleneoxy units, of which those are preferred which contain an average of 2 to 6, preferably 3 to 5, ethyleneoxy units.

The corresponding phosphoric acid partial esters (a) can be obtained in the usual way, for example by reacting the polyalkylene glycol monoethers with phosphorus pentoxide, phosphorus oxychloride or polyphosphoric acid in the heat. In the preparations according to the invention, the esters (a) are at least partly in the form of salts, alkanolammonium cations corresponding to the abovementioned component (d) being suitable as salt-forming cations. The phosphoric acid partial esters (component (a) as salts with the amine (d)] can be represented by the following formulas and wherein M is hydrogen or an alkanol ammonium cation corresponding to component (d), X and YM or - + alkylene3-O) n3 R3, R1, R2 and R3 independently of one another, C14-20-alkyl or -alkenyl, alkylene1, alkylene2 and alkylene3 independently 1,2-ethylene or 1,2-propylene and n1, n2 and n3 each mean on average a number from 2 to 10 and the alkyl and alkenyl radicals and alkyleneoxy units which occur can each be identical to or different from one another and an average of 2-6 per chain Oxethylene units occur, and at least some of the symbols M is an alkanolammonium cation which corresponds to component (d).

The water-miscible alkanolamines (d) are generally customary Alkanolamines into consideration, as they are used for salt formation or for the production of amine salts are commonly used, mainly mono-, di- and tri- (C2,3-alkanol) amines and N- (C1,2-alkyl) -N- (CZ, 3-alkanol) amines, in particular mono-, di- and tri-ethanolamine, Mono-, di- and tri-isopropanolamine and methylethanolamine, of which in particular monoethanolamine, Triethanolamine and diisopropanolamine are preferred.

The aliphatic C4-6 alcohols in component (b1) are essentially Alkane mono- or diols with 4 to 6 carbon atoms are suitable. The alkane mono- and diols can be linear or branched. Preferred alkanols are n-butanol, Isoamyl alcohol and isohexanol; preferred alkanediols are tetramethylene glycol, pentamethylene glycol, Hexamethylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 2,5-hexylene glycol and 2-methyl-2,4-pentanediol, of which the latter is particularly preferred. Preferred Alkylene glycol monoalkyl ethers in component (b1) are dietylene glycol and monopropylene glycol mono- (C1 ~ 4 ~ alkyl) ethers, in particular the methyl, ethyl and n-butyl ethers of diethylene glycol. Advantageous (b1) is a C46 alkanol or alkanediol or a diethylene glycol mono C1-4 alkyl ether, in particular as preferred above. (b2) is preferably monoethylene glycol or a mixture of Mono- and diethylene glycol, in which monoethylene glycol predominates. Is advantageous (b2) at least 60% by weight, preferably 65-90% by weight of the mixture of (b1) and (b2).

Low-aromatic to aromatic-free hydrocarbon oils (c) are available generally natural, semi-synthetic and synthetic hydrocarbons into consideration, which are liquid at room temperature (20 "C), mainly non - greasy ones Hydrocarbon oils with an aromatic content (20% by weight. Advantageously, the Hydrocarbon oils (c) have a boiling range which is below 250 ° C.; preferred are hydrocarbons from petroleum processing (mineral oils), in particular those of the following categories: 1. Special gasoline, which is distilled out of the raw gasoline (boiling range within 65-140 ° C) (dearomatized and aromatic-containing Types) 2. White spirits, white spirit and white spirit, (boiling range within 100-250 ° C, preferably within 140-250 "C), in particular: aromatic-free types with a boiling range within 100-2500C (preferably within 140-250 "C) and fractions with one Aromatic content between 12 and 19% with a boiling range within 160-210 "C; 3. Aromatic-free Hydrocarbons with an isoparaffinic structure (boiling range within 110-250 "C) 4. Paraffin oils (= mineral oils) e.g. diesel oils, spindle oils, machine oils, cylinder oils, Lubricating oils and petroleum jelly.

Among the oils mentioned are the aromatic-free ones, primarily gasoline (Boiling range within 80-10 "C) and aromatic-free white spirits (i.e.

Terpenaline) with a boiling range within 150-250 ° C. is preferred, in particular the aromatic-free white spirits, especially those with a boiling range within 200-250 ° C; The preparations according to the invention advantageously contain per 100 parts by weight of Component (a) (non-neutralized form) 30-100 parts by weight the Component (c), preferably 30-65, in particular 30-50 parts by weight of the component (c). The components (b1) + (b2) are advantageously a total of 15-120 parts by weight used per 100 parts by weight of component (a). The component (b1) is advantageously 12-50% by weight, preferably 15-25% by weight of (a) and (b2) is advantageously 50-250% by weight, preferably 80-250% by weight and in particular 100-250% by weight of (c).

The component (d) is advantageously used so much that one aqueous dilution containing 100g of the preparation per liter, a pH of 6-9, preferably 6.5-8.5.

If necessary, the preparations may also contain (f) urea, e.g., up to 20% by weight of (a); the water content of the preparation is advantageous z 4% by weight, the preparation advantageously only containing water if urea is available; urea is preferably present when 1-4% by weight of water is present are, the urea then advantageously makes up 50-200% by weight of the water. Particularly However, the preparations according to the invention are preferably free of water; in one special However, the preparations according to the invention also do not contain any preferred variant Urea.

A preferred composition of the preparations according to the invention is as follows: component (a) - not neutralized -: 100 parts by weight component (b1): 12-50 parts by weight component (b2): 50-250% by weight of (c) component (c): 30-100 parts by weight (preferably 30-65 parts by weight) component (d): up to pH 6-9 (as defined above) component (e): 0-4% by weight of the preparation component (f) : 0-20 parts by weight where (b2) preferably at least 60% by weight of (b1) + (b2) matters.

A particularly preferred composition of the preparations according to the invention is as follows: Component (a) - not neutralized -: 100 parts by weight Component (b1): 15-25 parts by weight Component (b2): 80-250% by weight (preferably 100-250% by weight) of (c) component (c): 30-50 parts by weight component (d): up to pH 6.5-8.5 (as defined above) component (e): <1% by weight of the preparation, preferably 0% component (f): 0-20 parts by weight, preferably 0 parts by weight where (b2) preferably 65 to 90% by weight of (b1) + (b2).

The phosphoric acid partial esters can, analogously to DE-OS 32 30 925 described.

The preparations according to the invention are generally produced in a manner known per se by mixing the corresponding components together.

An advantageous manufacturing process is that one of the submitted phosphoric acid partial ester melt (component (a)] the oil (c) and then adding the remaining components; Component (b2) is advantageous as the last admitted.

Another advantageous manufacturing variant is that add the melted component (a) to the mixture of all the remaining components admits.

For mixing component (a) with the other components, in particular with the oil (c), the temperature is advantageously in the range from 40-100 ° C., preferably 50-90 "C; the heat of neutralization of component (a) with the component (d) can be used here.

The preparations according to the invention have a long shelf life and crystallize not off even after a long period of storage; they are relatively thick and particular also frost-resistant; They are advantageous for the addition of stock preparations prediluted with water, advantageous im Weight ratio preparation: water from 1: 1 to 1: 5, preferably 1: 1.5 to 1: 3. Leave the preparations according to the invention can be diluted very well with water and excellent for applications from water Insert medium.

The preparations according to the invention are particularly suitable as leather fatliquors for greasing tanned leather from an aqueous medium, especially with an aftertreatment with polyvalent metal or oxymetal cations.

The leather is greased from an aqueous medium and can be For common fatliquors common treatment methods take place, namely according to the exhaust process or the impregnation process (e.g. by padding on, spraying on or foaming); the exhaust process is preferred. The concentration of the phosphoric acid partial esters, based on the wet weight of the leather is advantageously 0.2 to 15%, preferably 2 to 8%; the aqueous liquors advantageously have a slightly alkaline to clearly acidic pH (in particular pH 2 to 9), the treatment liquor is preferred neutral to slightly acidic (pH 4 to 7). The treatment (fatliquoring) of the leather with these aqueous liquors of the phosphoric acid partial esters are advantageously carried out at temperatures between 20 and 70 "C, preferably between 40 and 60" C. The pH adjustment takes place advantageously with the usual acids, bases and / or buffers, preferably with formic acid or ammonium or alkali metal carbonate.

The leather treated in this way can be dried and finished in the usual way or if desired (especially if it has not been colored beforehand war) to be colored.

Any customary leather dyes are suitable as dyes, i.e. those that are generally suitable for dyeing leather, especially anionic, metal-free or metal-containing azo dyes.

As polyvalent cations that are used for the post-treatment of the treated Leather are particularly suitable, the magnesium, calcium, barium, aluminum, Chromium-III and zirconyl cations are mentioned; of which are especially the aluminum, Chromium-III and zirconyl cations preferred. The follow-up treatment with the ones mentioned Cations are expediently made by using appropriate Links, in particular oxides, hydroxides and / or salts; preferably are water-soluble Salts of the cations mentioned are used, in particular aluminum sulfate, potassium alum, Chromium III sulfate, potassium chromium alum, chromium hydroxysulfate, zirconyl chloride, zirconyl sulfate and zirconyl acetate.

The concentration of the mentioned aftertreatment compounds, based on the dry weight of the partial esters used, is advantageously 1 to 100%, preferably 5 to 20%. Post-treatment can be carried out using an impregnation process (by Padding, spraying or foaming) or preferably by exhaustion process take place, preferably from an aqueous medium, advantageously at 20 to 70 ° C., preferably at 40 to 60 "C, advantageous for slightly alkaline to clearly acidic pH values (especially pH 2-9), preferably at neutral to slightly acidic pH values (especially pH 4-7). The pH is advantageously adjusted with customary acids, bases and / or Buffers, e.g. as mentioned above for the fatliquoring process. Successful greasing and follow-up treatment, as preferred, in the same aqueous medium, then a correction of the pH is necessary Usually no longer necessary for follow-up treatment. After the follow-up treatment with the The leather can be finished with polyvalent cations in the usual way.

By oiling the leather with the preparations according to the invention respectively.

Fatliquoring agents and preferably after treatment with the ones mentioned polyvalent metal cations (preferably from the same aqueous medium in which the Greasing with the partial esters has taken place) are optimally greased and good Hydrophobized leather is obtained, which is characterized by good tensile strength and suppleness as well as characterized by a good grip and also the general ones desired for leather Have fastnesses, of which the dry cleaning fastness should be emphasized in particular is.

In the following examples the temperatures are in degrees Celsius indicated, the percentages are percentages by weight. The phosphoric acid partial ester used is made as follows: 2609 tallow fatty alcohol, 1679 ethylene oxide and 719 phosphorus pentoxide are heated to 60 °; the resulting melt is that in the examples is used.

Example 1 2009 Partial Phosphorate and 709 Odorless Petroleum (aromatic-free white spirit with boiling range 201-243 °) are placed in a 750ml four-necked flask presented and heated to 60-70 °. A clear brown solution results. In addition 309 monoethanolamine are added dropwise within 30 minutes; the temperature rises to 85-90 °. Then 409 diethyl glycol monomethyl ether are added one after the other, 109 diethylene glycol and 1509 monoethylene glycol. The temperature is during the Maintained the dilution process at 60-80 °. Finally, it is cooled to 50 ° and unloaded.

As in Example 1, those listed in Table 1 below are listed Prepared preparations.

Table 1 Example 2 example. 3 Example 4 Example 5 Phosphoric acid ester as in example 1 40% 40% 40% 40% white spirit as in example 1 14% 14% 14% 14% Monoethanol ani n - 6% 6% Triethanolamine 14% 14% - 1-butanol 8% - - 2-methylbutanol-2 - 8% - 8% Diethylene glycol monomethyl ether - 8% Monoethylene glycol 24% 24% 32% 32% Example 6 30 g of monoethanolamine, 309 hexylene glycol, 70 g of white spirit, as in Example 1, 1209 ethylene glycol, 209 demineralized water and 309 urea are placed in a beaker and heated to 60 [deg.]. A clear solution is created. To this end, the phosphoric acid partial ester, heated to 60-70 °, is added dropwise in 2009; the temperature rises to 80-90 °.

The mixture is stirred until the mixture is homogeneous and then it is discharged.

The preparations described in are listed in Table 2 below.

Table 2 Ex. Ex. Ex. Ex. Ex. Ex. Ex. 7 8 9 10 11 12 13 14 Phosphoric acid ester as in example 3 40% 40% 40% 40% 40% 40% 40% 40% White spirit as in example 6 24% 20% 16% 18% 20% 26% 18% 16% Monoethanolamine 6% 6% 6% 6% 6% 6% 6% 6% Hexylene glycol 6% 6% 6% 8% 8% 6% 6% 6% Ethylene glycol 14% 18% 26% 18% 20% 16% - - Diethylene glycol - - - - - - 24% 26% Urea 6% 6% 6% 6% 6% 6% 6% 6% water (demineralized) 4% 4% - 4% - - - - In the following examples, the percentages on the left-hand margin of the text relate to the folded weight, unless otherwise stated. The chromium hydroxysulphate used is titrated as Cr203, the titrated Cr203 content is 25%.

Application example A (cattle box) Wet blue leather is in 200% water Waxed up for 5 minutes at 40 °. Then 30 minutes with 2% chromium hydroxysulfate and 4% dimethyloxethylene urea. This is followed by 6% mimosa extract and 1% Color Index Acid Brown 359 dye, drummed for 60 minutes.

Then 250% water at 40 ° and 0.3% 85% formic acid admitted. The bath is drained.

Then it is made with 200% water at 50 ° and with 12.5% of the paste according to example 1 * (= 5% active substance, i.e.

Pure fat, based on damp leather) 45 minutes. Thereafter 2% chromium hydroxysulphate and 0.3% 85% formic acid are drummed in for 30 minutes. The bath is drained and the leather is rinsed with 200% 20 ° warm water. The water is drained, the leather is hung on the box overnight and in the usual way further processed.

* The 12.5% of the paste according to Example 1 are mixed with 25% water from 50 ° prediluted and then added to the remaining 175% water at 50 °.

Application example A-bis Proceed as described in example A, but uses, instead of the 12.5% of the paste according to Example 1, 12.5% of the paste according to example 5.

Application example A-ter Proceed as described in example A, but uses, instead of the 12.5% of the paste according to Example 1, 12.5% of the paste according to example 13.

Application example B (Hunting) Calfskins are wet-blue with 150% water at 30 ° and 5% chromium hydroxysulphate for 3 hours retanned. The bath is drained and the leather for 10 minutes with 200% Rinsed with 40 ° warm water. The bath will drain and the leathers will be during Set to pH 6.5 to 7 with 200% water at 35 ° and ammonium bicarbonate for 2 hours.

The liquor is then allowed to run off and rinsed with 200% water at 35 ° for 10 minutes, lets the rinse water run off and colors by adding 1% 25% ammonia solution and 3% dye Color Index Acid Brown 126 for 45 minutes.

Then with 200% water and 20% preparation according to Example 4 * (= 8% active substance, i.e. pure fat, based on damp leather) for one hour 45 "greased. By adding 2% chromium hydroxysulphate and 2% formic acid (85%) is fixed for 30 minutes. The remaining liquor is drained off and the leather is left on overnight hung the buck and processed in the usual way.

* The 20% of the preparation according to Example 4 are prediluted with 40% water and then added to the remaining 160% water.

Application example B-bis Proceed as described in example B, but uses, instead of the 20% of the preparation according to Example 4, 20% of the preparation according to example 6.

Application example B-ter Proceed as described in example B, but uses, instead of the 20% of the preparation according to Example 4, 20% of the preparation according to example 14.

Application example C (sheep clothing) Sheepskin in wet blue condition are drummed up with 800% water at 50 ° and 2% 25% ammonia for 60 minutes. then is retanned with 3% zirconyl sulfate for 60 minutes and the bath is then drained.

Then 600% water at 50 ° and 1% 25% ammonia are added and let it continue for 10 minutes.

Then, with 4% dye, Color Index Acid Brown 303 60 Stained in minutes and then diluted with 12.5% preparation according to Example 1 - 1: 2 with 25% water - (= 5% active substance, i.e. pure fat, based on damp leather), 60 minutes greased. Then, by adding 2% chromium hydroxysulphate and 2% formic acid fixed for 40 minutes, the bath allowed to drain, the leather on overnight put the buck and processed in the usual way.

Application example C-bis Proceed as described in example C, but used, instead of the 12.5% of the preparation according to Example 1, 12.5% of the paste according to example 8.

Application example C-ter Proceed as described in example C, but used instead of the 12.5% of the preparation according to Example 1, 12.5% of the preparation according to example 9.

In the same way as described in the application examples above, the preparations described in the remaining examples 1-14 can be used will.

The leathers obtained correspond to the dyes used well colored and the grease produced is easy to dry clean.

Claims (8)

Preparations containing phosphoric acid partial esters, their manufacture and their use Patent claims 1. Hydrocarbon oil and water-soluble and / or water-dispersible phosphoric acid partial esters of polyalkylene glycol monoathers Preparations containing higher fatty alcohols, characterized in that the partial esters (a) in a mixture of: (bl) at least one mono- and / or di- (C23-alkylene) -glycolmono- (C1,4-alkyl) ether and / or at least one aliphatic alcohol with 4-6 carbon atoms, (b2) Mono- and / or dietylene glycol and (c) at least one low-aromatic to aromatic-free Hydrocarbon oil are dispersed and / or dissolved and as salts of (d) with water miscible alkanolamines are present and the water content (s) of the preparations -d 5 percent by weight is. 2. Preparations according to claim 1, characterized in that they additionally Contain urea. 3. Preparations according to claims 1-2, characterized in that (bl) a C4-6 alkanol or alkanediol and / or a diethylene glycol mono-C1,4-alkyl ether is. 4. Preparations according to claims 1-3, characterized in that (b2) Is monoethylene glycol or a mixture of mono and diethylene glycol. 5. Use of the preparations according to claims 1-4 for greasing leather. 6. Use according to claim 5 from an aqueous medium. 7. Use according to claims 5-6, characterized in that one aftertreated with polyvalent metal or oxymetal cations. 8. The leather treated according to claims 5-7.