DE10106342A1 - Composition for producing surfactant, used for cleaning and impregnating soiled, oily area, e.g. steel, engine or printing machine roller, contains long-chain, unfluorinated silane and perfluorinated silane forming curable polysiloxane - Google Patents

Abstract

Composition for the production of a surfactant with combined cleaning and impregnating action contains a long-chain, unfluorinated silane (I) and a perfluorinated silane (II), such that the oligomer/polymer (III) formed by hydrolysis and condensation of (I) and (II) has a linear crosslinked polysiloxane network, with free reactive points capable of 3-dimensional crosslinking. Independent claims are also included for the following: (1) A process for cleaning and impregnating soiled and oily areas, especially steel surfaces, by producing (III) from (I) and (II) and applying (III) to the surface; (2) Cleaning fluid containing a highly fluorinated component and a base fluid, which can swell, loosen or remove soil and especially is provided with a long-chain, perfluorinated compound with a functional group that can stick the highly fluorinated components to particulate impurities; (3) A process for cleaning articles by wrapping and/or covering them with sorbent material ensuring slow evaporation of solvents, impregnating this material with cleaning fluid, especially the specified fluid, before or after application, leaving for not less than 3, preferably not less than 30, especially 45 minutes and then removing the material; (4) Articles with a surface enlarged by microstructurization to increase its fluid bearing and/or absorption capacity, in which the microstructures have substructures, which are sealed; (5) An array with article(s) and means of transferring fluid to this, in which the substructure seal has surface energy favoring fluid transfer.

Description

The present invention relates to compositions on the Basis of fluorine-containing inorganic, silicon-containing poly condensates, as well as their production and use.

There are already numerous compositions, mostly to be found application known as coatings, based on organic modes fected inorganic polycondensates, especially those based on Si, Al, Ti and Zr.

For example, DE-A-38 36 815 discloses one method and one Composition for the production of scratch-resistant materials, especially coatings with improved elasticity and Liability. For this purpose, a composition of a by hydrolytic polycondensation of at least one anorga African compound obtained polycondensate and at least a polyfunctional organic compound with activatable  functional groups applied to a substrate, whereupon it is hardened and z. B. by heating the functio nelle groups of the organic compound are activated.

EP-B-0 587 667 describes coating compositions based on polycondensates from one or more hy drolisable connections of elements M of the main groups III to V and subgroups II to IV of the periodic table, where at least some of these compounds in addition to hydrolyses sizable groups A also non-hydrolyzable, carbon contains groups B and the total molar ratio of Groups A to groups B in the underlying monomers Starting compounds is 10: 1 to 1: 2, 0.1 to 100 mol% of groups B are groups B 'which have an average of 5 have up to 30 fluorine atoms attached to one or more alipha tical carbon atoms are bound by at least two atoms are separated from M.

Although these procedures lead to results that ler properties, e.g. B. scratch resistance and transparency very Delivering satisfactory results, these are together settings for a number of applications still need improvement to.

The aim of the present invention is therefore to compose gene and methods for their preparation to provide improved properties over those of the prior art Show technology.

The invention encompasses a polymeric / oligomeric silane which at the same time as a surfactant and impregnating agent for surfaces Chen can serve in special cleaning systems. Built up it is from a polysiloxane network, which preferably  is linearly networked and even more three-dimensional Networking includes competent bodies. The polymer draws is particularly characterized by the fact that the organic sides chains that are bound to the silicon atom have a certain funk have functionality and in a special relationship to each other other occur.

A polymer was made from a fluoroalkyltriethoxysilane and an octyltriethoxysilane manufactured in suitable organic solvents (e.g. cleaning gasoline, Ethylace tat, esters, ketones, etc.) is soluble and completely through distinguishes special cleaning power. In particular, this can then be found when you put this surfactant in Reini mineral spirits dissolves, which is used in the printing industry is set. If necessary, to dissolve the polymer Suitable co-solvents can also be used (e.g. ethyl Lacetat with cleaning gasoline).

Now bring the cleaning gasoline with the surfactant on dirty metal parts and leave it for some time act, it can be observed that the previously insoluble Dirt (e.g. paint residues) and other organic and inorganic after a short time (approx. 2 h) is wandering and can be easily cleaned. This effect becomes very small even with very small additions 1% active ingredient content (e.g. <200 ppm) observed. About that after cleaning the treated area notes that the metal surface is permanently water and has been impregnated to repel dirt.

The mechanism of action of the developed additive is still not fully resolved. It is believed that So-called block amphiphilic polymers form, in which domains  are present in which individual components of the Po enrich lymers. In the case of fluoroalkyltriethoxysilane Octyltriethoxysilane polymer would mean that that separates polymers into fluorine-rich and fluorine-poor areas.

This creates a surfactant-like structure, which the Reini effect would explain. In addition, that can be described bene polymer also act as an impregnating agent because of the long chain remains a full three-dimensional Networking is sterically hindered. So are in the polymer free SiOH or SiOR groups still present, which with the Metal surface or other surfaces can interact NEN. After cleaning the dirt, the surfactant has Access to surface metal hydroxide groups and partial form very strong (covalent) bonds. Through this Mechanism of action will significantly he a later cleaning facilitated. The polymer needs to have its creep ability receives, have a low, oily viscosity. The solution means, e.g. B. petrol, supports the infiltration and loosening of dirt and is ideally composed so that it promotes the creep properties of the surfactant.

In addition to the described and extensively investigated co-polymer from fluoroalkyl and octylsian it is also conceivable that other co-polymers, which consist of hydrophilic, hydrophobic (alkyl, Cycloalkyl) and oleophobic (fluorine-containing) residues together a comparable surfactant effect sit, e.g. B. hydrophobic-oleophobic, hydrophilic-oleophilic, hydro phil-oleophobic. It is also conceivable that a hydrophobic oleophobic-oleophilic mixed low molecular weight polymer has a special effect.

In general, alkyl, cycloalkyl,  and arylsilanes are used, preferably with further functional groups (halogen, amine, alcohol, Ep oxy, mercapto, sulfonyl, quaternary ammonium, phosphonium, and Like.) Can be substituted. Also glycidoxypropyl (too ring opened to dialcohol) as well as aminopropyl and polyether modified silanes can be used.

As hydrophobic-oleophilic silanes there are also alkyl, cy cloalkyl, and aryl silanes in question. These silanes can also if necessary with further functional group, such as. B. halogen, Amine, alcohol, epoxy, mercapto, sulfonyl, quaternary ammonium, Phosphonium, and the like. Oc are preferred tyl, methyl, dimethyl, propyl, and trimethyl silanes.

As hydrophobic-oleophobic silanes, i.e. i.e., fluorinated silanes general (partially) fluorinated alkyls, cycloalkyl, aryl, optionally with heteroatoms in the chain (N, O, S...) or in one Side chain, usable. Between the fluoroalkyl and the Si atom should have a distance of at least two carbon atoms hen. Preferred groups here are trifluoropropyl, tride cafluorooctyl, trifluoropropylmethyl and tridecafluorooctyl methyl.

Halogen, alkoxy, (preferably ethoxy, methoxy), acyloxy, -OH and oximes in Be costume.

An equal molar ratio (50:50) is preferred two silanes. In general, every relationship in the opposite ben solvent to a desired creep and surfactant effect against the dirt to be removed, applicable.

A mixture of different surfactants can also be used  with different hydrophilic-lipophilic balance- Values (HLB).

Such surfactants can be used in conjunction with suitable ones Solvents and co-solvents e.g. B. as a cold cleaner for engine cleaning or especially the cleaning of Printing machine parts, as electronic cleaner or in general find as a cleaner for dirt and oil contaminated areas. The solvent can either be volatile, so that a quick cleaning is guaranteed, or be particularly volatile so that the active ingredient has a long time, Infiltrate dirt.

The polymers / oligomers described are produced usually after the sol-gel process. The alk oxides of the corresponding silanes by means of hydrolysis and Process polycondensation to suitable polymers / oligomers beitet. The resulting alcohol can either be as Solvents or co-solvents serve or will if he is disadvantageous, removed. The polymers can then be used in a suitable solvent or solvent mixture be taken. To this end, it can be advantageous to use suitable or ganic or inorganic auxiliaries or stabilizers add to the solubility / dispersibility of the To effect or improve polymers / oligomers.

Such stabilizers can be, for example, quaternary ammonium compounds such as tetramethylammonium hydroxide (TMAH), phosphonium compounds, inorganic salts / hydroxides (NaOH, AlCl ₃ , etc.) and betaines.

Also surfactants (anionic, cationic, nonionic), color and Fragrances, acids, such as glycolic acid, citric acid or  Acetic acid), bases (ammonia, amines, ethanolamines), and com plexer to remove the dirt or metal ions in solution hold (e.g. ethylenediaminetetraacetic acid, EDTA) can be added be set.

Another, particularly preferred variant of the production of the polymers / oligomers described is the so-called what water-free sol-gel process, in which one anhydrous carbonic acid ren to the silanes and an ester as solvent stands. In the case of the co-polymer already mentioned several times from fluoroalkylsilane and octylsilane z. B. anhydrous Acetic acid used for the reaction. The resulting acetic acid reethylester is an excellent solvent for that resulting polymer / oligomer and mediates the solubility speed of the polymer / oligomer in suitable cleaning agents, such as B. gasoline fractions. Another way of making also includes the polymer / oligomer production from the chlorine lanes in a suitable inert solvent, e.g. B. directly in petrol, whereby defined amounts of water (e.g. by Passage of water-containing air) are added to un ter splitting off hydrochloric acid to allow polymerization chen. However, this method has the disadvantage that the split hydrochloric acid has a corrosive effect and in some applications conditions can therefore not be used, or a distance tion / neutralization is necessary.

The following examples illustrate the present invention:

example 1

25.5 g of fluoroalkyltriethoxysilane (from Degussa-Hüls) are added 13.6 g of octyltriethoxysilane mixed. In parallel, in  883 g glacial acetic acid and 0.026 g concentrate in a separate vessel te hydrochloric acid mixed.

Both mixtures are combined with stirring and 20 days aged at room temperature.

50 g of the batch are in 950 g of gasoline (boiling point fraction 50-80 ° C) solved.

A greasy steel surface is first cleaned with pure Gasoline roughly pre-cleaned and then with the modifier gasoline and a lint-free rag stained with dirt freed. After cleaning, the surface with wiped with a dry, lint-free cloth. It's right results in a water and dirt repellent surface.

Example 2

25.5 g fluoroalkyltriethoxysilane (from Sivento) with 13.8 g Octyltriethoxysilane mixed. In this mix successively 15 g isopropanol, 2.5 g water and 0.03 g con centered hydrochloric acid. After stirring for 6 h and 12 h another 2.5 g of water were metered in. After stirring for 24 h The addition of 50 g of water causes phase separation. The Si Lan phase is separated off in 50 g of ethyl acetate taken and with 190 g of gasoline (boiling point fraction 50-80 ° C) mixed.

A greasy steel surface is first cleaned with pure Gasoline roughly pre-cleaned and then with the modifier gasoline and a lint-free rag stained with dirt freed. After cleaning, the surface with  wiped with a dry, lint-free cloth. It's right results in a water and dirt repellent surface.

Example 3

The mixture is prepared as in Example 1 and with 2% Aerosil R972 offset. Due to the grinding effect of the Powder is the cleaning effect of this mixture better than that in example 1.

Alternatively, 2% hydrophobic silane can also be used as an abrasive ized Neuburg Siliceous Earth can be dispersed.

Claims (21)

1. Composition for the preparation of a surfactant with com binary cleaning and impregnation effect, ent holding a long chain non-fluorinated silane and a perfluorinated silane, the two Si Lan compounds by hydrolysis and condensation forming oligomer / polymer is a linear cross-linked poly siloxane network forms, the free, to the three-dimensional len networking reaction sites. 2. Composition according to claim 1, characterized net that the non-fluorinated silane is a hydrophilic or hydrophobic silane.   3. Composition according to claim 1, characterized in net that the fluorinated silane is a oleophobic silane. 4. Composition according to. Claim 2, characterized net that the non-fluorinated silane octyltriethoxysi lan is. 5. Composition according to claim 3, characterized in net that the fluorinated silane is a fluoroalkyl is triethoxysilane. 6. Composition according to claim 1, characterized in net that bil from the two silane compounds ending oligomer / polymer in an organic solution is medium soluble. 7. Composition according to claim 6, characterized in net that the solvent is selected from the Group consisting of esters, ketones, alkanes, aroma ten, cycloalkanes, ethers, alcohols and mixtures it. 8. Composition according to one of the preceding claims, characterized in that the silane compounds in have the same molar ratio. 9. Process for cleaning and impregnating dirt and oil contaminated areas, in particular Stahloberflä Chen, characterized by the steps

• a) preparing an oligomer / polymer from a long chain silane and a perfluorinated silane; and
• b) applying the oligomer / polymer to the surface to be treated.

10. The method according to claim 9, characterized in that the oligomer / polymer prior to application to the surface to be treated in a suitable solution medium is solved. 11. The method according to any one of claims 9 or 10, characterized characterized in that the oligomer / polymer by means of egg Sol-gel process by processing the alkoxides the corresponding silanes by means of hydrolysis and poly condensation is established. 12. The method according to any one of claims 9 or 10, characterized characterized in that the oligomer / polymer by means of egg an anhydrous sol-gel process is produced, with the anhydrous carboxylic acids to the initial sila NEN is given. 13. The method according to claim 12, characterized in that that used anhydrous acetic acid as the carboxylic acid becomes. 14. The method according to claim 10, characterized in that the solution is suitable organic or inorganic Auxiliaries and / or stabilizers are added. 15. The method according to claim 14, characterized in that the excipients are selected from the group consisting of quaternary ammonium compounds, phospho nium compounds, inorganic salts, hydroxides and  Betaines. 16. The method according to claim 15, characterized in that it is tetramethylammonium hydroxide (TMAH) is. 17. The method according to claim 14, characterized in that the auxiliaries are anionic, ka ionic or nonionic surfactants or surfactant mixtures acts. 18. The method according to any one of claims 10 to 12, characterized characterized that the solution other substances like For example. Dyes and fragrances, acids, bases or com plexing agents are added. 19. The method according to claim 10, characterized in that the amount of oligomer / polymer in the solvent is less than 1% by volume. 20. Use of the composition according to one of the claims che 1 to 8 for cleaning and impregnation of Areas contaminated with dirt and oil, in particular Steel surfaces. 21. Use of the composition according to one of the claims che 1 to 8 for cold cleaning of engines and for cleaning cleaning of press and electronic parts.