ES2258506T3 - CATION COMPOSITIONS FOR CLEANING HARD SURFACES. - Google Patents

Abstract

Cationic compositions for cleaning hard surfaces, characterized in that they contain esterquats by way of cationic surfactants, the remainder or whose acyl moieties are derived from unsaturated fatty acids with 8 to 22 carbon atoms and the iodine number is in the range from 100 to 150

Description

Cationic compositions for cleaning hard surfaces.

Field of the Invention

The invention is in the field of cleaning agents and refers to new preparations, especially for cleaning (by spraying) sheet metal, parts for bodies and motor vehicles, with a content in special esterquats as well as the use of these surfactants cationic for cleaning hard surfaces.

State of the art

An important stage in the manufacture of motor vehicles consists of cleaning the plates or of greased bodies towards the end of the process of manufacturing. To do this, the pieces are passed through immersion baths, however cleaning is carried out frequently under high pressure with surfactant compositions specially developed for this purpose. Independently that the preparations have a cleaning power enough and, first and foremost, they have to shed the fat from a fast and deep way, it is presented precisely in the case of the spray cleaning the need for a complete absence of foam. Since the procedure is carried out under pressure, static load of the sheet of the parts of the body through the spray nozzles, which should be avoided in any case. Also this requirement has to be taken into account in industrial cleaning agents. Without However, similar problems also arise in the field of Individual car cleaning, both in chains automatic washing as well as a series of chains cleaning, which offer the user the cleaning of your car by itself with a high pressure water jet and using similar surfactant compositions in this case such as those that find application for degreasing of bodies.

In this case, cationic surfactants have a special meaning, since they not only have a high cleaning force - especially in combination with non-ionic surfactants - but also hydrophobic the bodies of motor vehicles and, therefore, protect them. At the same time they act as antistatic, that is to say that even in the case of high pressure spray cleaning, a static load of the metal parts is performed. In practice, tetraalkylammonium salts of the dimethyldiestearylammonium chloride type (DMDSAC) have been revealed as especially active, while cationic surfactants of the conventional type of esterquats, which have otherwise replaced, in many applications, the DMDSAC, were ineffective until now for this application. However, it is a disadvantage that the tetraalkylammonium salts that are commercially available do not have sufficient biodegradability, which makes it difficult to use them in many European countries in accordance with the law on detergents. It is also an inconvenience that, for example, DMDSACs are presented in the form of cut-resistant pastes with an active substance content of 80% by weight and, therefore, can only be made at a cost
industrial.

Therefore, the task of the present invention it consisted of making available new preparations for the hard surface cleaning, especially for cleaning by sheet metal spraying and high pressure cleaning of motor vehicles, which certainly contained surfactants cationic but that, however, were characterized by a improved biodegradability and at the same time reach at least level of state of the art as regards hydrophobicity and to the antistatic finish.

Description of the invention

The object of the invention is constituted by new cationic preparations for surface cleaning hard, characterized in that they contain esterquats by way of cationic surfactants, whose residue or whose acyl moieties are derived from unsaturated fatty acids with 8 to 22 and, preferably, with 16 to 22 carbon atoms and with an index of iodine in the range from 100 to 150. Another advantage of the new esterquats is that they are transparent and liquid still at very high concentrations and therefore are easily manipulable

Surprisingly, it has been found that, by the exact choice of fatty acids can be obtained esterquats specials that not only have biodegradability clearly improved against tetraalkylammonium salts of state of the art, but also treated surfaces remain hydrophobic for a longer period of time and cause a smaller static load. This discovery is so much more unexpected as the conventional esterquats, based on tallow fatty acids or coconut fatty acids are absolutely inadequate in the application.

Esterquats

In general, the term "esterquats" means quaternized salts of fatty acid triethanolamines. In this case they are known products, which can be obtained according to the methods of the preparative organic chemistry industry. In this context, reference will be made to international patent application WO 91/01295 (Henkel), according to which triethanolamine is partially esterified in the presence of hypophosphorous acid with fatty acids, air is passed therethrough and then quaternized with dimethyl sulfate or with ethylene oxide. It is also known from the German patent application DE 4308794 C1 (Henkel) a process for obtaining solid esterquats, in which quaternization of the triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Compilations on this topic have been published for example by R. Puchta et al . in Tens.Surf.Det , 30 , 186 (1993) , by M.Brock in Tens.Surf.Det 30 , 394 (1993) , by R.Lagerman et al . in J.Am. Oil.Chem.Soc ., 71 , 97 (1994) as well as by I. Shapiro in Cosm.Toil . 109 , 77 (1994) .

The quaternized salts of the triethanolamines of the fatty acids follow the formula (I),

\melm{\delm{\para}{CH _{2} CH _{2} O(CH _{2} CH _{2} O) _{p} R ^{3} }}{N}{\uelm{\para}{R ^{4} }}

^{+} --- CH_{2}CH_{2}O --- (CH_{2}CH_{2}O)_{n}R^{2}]X^{-}(I) [R 1 CO --- (OCH 2 CH 2) m OCH 2 CH 2 ---

 \ melm {\ delm {\ para} {CH 2 CH 2 O (CH 2 CH 2 O) p p R 3} {N} {\ uelm {\ para} {R 4}} 

<+> --- CH 2 CH 2 O --- (CH 2 CH 2 O) n R 2] X -

where R 1 CO means a unsaturated acyl moiety with 8 to 22, preferably with 16 to 22 carbon atoms and with an iodine index from 50 to 200, R 2 and R 3 mean, independently of each other, hydrogen or R 1 CO, R 4 means an alkyl moiety with 1 to 4 carbon atoms or a group (CH 2 CH 2 O) q H, m, n and p mean, in sum, 0 or numbers from 1 to 12, which means numbers from 1 to 12 and X means halide, sulfate alkyl or alkyl phosphate. Typical examples of esterquats, which they can find application in the sense of the invention, they are products based on unsaturated fatty acids with 16 to 22 carbon atoms and with iodine indices in the range from 100 up to 150 such as palmoleic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid as well as their industrial mixtures, such as those produced for example in the pressure dissociation of fats and natural oils. Preferably sunflower fatty acids or, especially, industrial rapeseed fatty acids with 16/18 atoms carbon, which essentially have a chain length from 16 to 22 carbon atoms and having chain counterparts shorter in quantities less than 20, preferably smaller than 15% by weight. For obtaining quaternized esters fatty acids and triethanolamine can be used in the molar ratio from 1.1: 1 to 3: 1. As regards the industrial application properties of the esterquats has a proportion of employment since 1.2: 1 to 2.2: 1, preferably from 1.5: 1 to 1.9: 1. The Preferred esters represent industrial mixtures of monoesters, diesters and tri esters with an esterification degree average 1.5 to 1.9. From the point of view of the application industrial salts have been revealed as especially advantageous quaternized fatty acid triethanolamine of the formula (I), wherein R 1 CO means the unsaturated acyl moiety of the rapeseed fatty acids, R2 means R1CO, R3 means hydrogen, R 4 means a methyl group, m, n and p mean 0 and X means sulfate of methyl.

In addition to the quaternized salts of the triethanolamine of fatty acids, come into consideration, as esterquats, also quaternized salts of fatty acid esters with diethanolalkylamines of the formula (II),

\melm{\delm{\para}{R ^{5} }}{N ^{+} }{\uelm{\para}{R ^{4} }}

--- CH_{2}CH_{2}O --- (CH_{2}CH_{2}O)_{n}R^{2}]X^{-}(II) [R 1 CO --- (OCH 2 CH 2) m OCH 2 CH 2 ---

 \ melm {\ delm {\ para} {R 5}} {N ^ {}} {\ uelm {\ para} {R 4}}} 

--- CH 2 CH 2 O --- (CH 2 CH 2 O) n R 2] X -

where R 1 CO means a unsaturated acyl moiety with 8 to 22, preferably with 16 to 22 carbon atoms and with an iodine index from 100 to 150, R 2 means hydrogen or R 1 CO, R 4 and R 5 mean, independently of each other, alkyl moieties with 1 to 4 carbon atoms or a group (CH 2 CH 2 O) q H, m, n and p mean, in sum, 0 or numbers from 1 to 12, q means numbers from 1 to 12 and X means halide, alkyl sulfate or phosphate I rent.

As another group of suitable esterquats should finally, the quaternized salts of esters of the fatty acids with 1,2-dihydroxypropylialkylamines of the formula (III),

\melm{\delm{\para}{R ^{7} }}{N ^{+} }{\uelm{\para}{R ^{6} }}

--- CH_{2}

\uelm{C}{\uelm{\para}{O ---
(CH _{2} CH _{2} O) _{m} OCR ^{1} }}

HCH_{2}O --- (CH_{2}CH_{2}O)_{n}R^{2}]X^{-}(III) [R 4 ---

 \ melm {\ delm {\ para} {R 7}} {N ^ {}} {\ uelm {\ para} {R 6}}} 

--- CH_ {2}

 \ uelm {C} {\ uelm {\ para} {O ---
(CH 2 CH 2 O) m OCR 1 

HCH 2 O --- (CH 2 CH 2 O) n R 2] X -

where R 1 CO means a unsaturated acyl moiety with 8 to 22, preferably with 16 to 22 carbon atoms and with an iodine index from 100 to 150, R 2 means hydrogen or R 1 CO, R 4, R 6 and R 7 mean, independently of each other, alkyl moieties with 1 to 4 carbon atoms or a group (CH 2 CH 2 O) q H, m, n and p mean, in sum, 0 or numbers from 1 to 12, q means numbers from 1 to 12 and X means halide, alkyl sulfate or phosphate I rent.

In addition, they come into consideration as esterquats also products in which the ester link is replaced by an amide bond and that are preferably based on diethylenetriamine, following the formula (IV),

\melm{\delm{\para}{R ^{7} }}{N ^{+} }{\uelm{\para}{R ^{6} }}

--- CH_{2}CH_{2} --- NH --- R^{2}]X^{-}(IV) [R 1 CO --- NH --- CH 2 CH 2 ---

 \ melm {\ delm {\ para} {R 7}} {N ^ {}} {\ uelm {\ para} {R 6}}} 

--- CH 2 CH 2 --- NH --- R 2] X -

where R 1 CO means a unsaturated acyl moiety with 8 to 22, preferably with 16 to 22 carbon atoms and with an iodine index from 100 to 150, R 2 means hydrogen or R 1 CO, R 6 and R 7 mean, independently of each other, alkyl moieties with 1 to 4 carbon atoms or a group (CH 2 CH 2 O) q H, q means numbers from 1 to 12 and X means halide, sulfate of alkyl or phosphate of I rent.

Regarding the choice of acids Preferred fatty acids and to the optimum degree of esterification are valid the examples cited for (I) also for the esterquats of the formulas (II) to (IV).

To obtain the esterquats of formulas (I) through (IV), both fatty acids and corresponding triglycerides can be used. Such a procedure, which will be cited as representative of the corresponding state of the art, has been proposed in the specification of European patent EP 0750606 B1 (Cognis). In the same way it is possible to carry out the condensation of the alkanolamines with the fatty acids in the presence of defined amounts of dicarboxylic acids, such as for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or dodecanedioic acid. In this way a partially oligomerized ester structure is produced, which can have an advantageous effect on the clear solubility of the product especially when used together with adipic acid. The esterquats are usually marketed in the form of alcoholic solutions of 80 to 90% by weight, which can be diluted with water without problem, in case
necessary.

Surfactant preparations

Usually, finished preparations contain to the esterquats -referred to the agents- in quantities from 1 up to 10 and, preferably, from 2 to 8% by weight. In addition these may also contain other auxiliary products and usual additives, especially however may contain co-surfactants, the latter being composed of compounds non-ionic due to its special compatibility with surfactants cationic

Typical examples of nonionic surfactants are polyglycol ethers of fatty alcohols, polyglycol ethers of alkylphenol, polyglycol esters of fatty acids, polyglycol ethers of fatty acid amides, polyglycol ethers of fatty amines, alkoxylated triglycerides, mixed ethers or well the mixed formal, the alkyl (en) iloligoglycosides, the N-alkylglucamides of fatty acids, protein hydrolysates (especially plant based products wheat), polyol esters of fatty acids, esters saccharics, sorbitan esters, polysorbates and oxides of amina. As long as the non-ionic surfactants contain polyglycol ether chains, these may have a distribution of conventional counterparts, but nevertheless preferably a narrow distribution of homologues. Preferably they will use polyglycol ethers of fatty alcohols, alkyl esters lower fatty acid, alkoxylated or alkyl oligoglycosides.

Polyglycol ethers of fatty alcohols Preferred follow the formula (V),

(V) R 8 O (CH 2 CHR 9 O) n H

in which R 8 means a linear or branched alkyl and / or alkenyl moiety with 6 to 22, preferably with 12 to 18 carbon atoms, R 9 means hydrogen or methyl and n1 means numbers from 1 to 20. Typical examples are the addition products of, on average, 1 up to 20 and preferably 5 to 10 moles of ethylene oxide and / or propylene oxide on capronic alcohol, on alcohol caprylic, on 2-ethylhexyl alcohol, on goat alcohol, on lauryl alcohol, on alcohol isotridecyl, on myristyl alcohol, on cetyl alcohol, about palmoleil alcohol, about stearyl alcohol, about isostearyl alcohol, on oleyl alcohol, on alcohol elaidyl, on petroselinyl alcohol, on alcohol Linolyl, on linolenyl alcohol, on alcohol elaeoestearilic, on arachidic alcohol, on alcohol gadoleil, on behenyl alcohol, on erucyl alcohol and about brasidyl alcohol as well as its industrial mixtures. Especially preferred are the addition products of 3, 5 or 7 moles of ethylene oxide over coconut fatty alcohols Industrial

As lower alkyl esters of acids fatty, alkoxylated, the surfactants of the formula (VI),

(VI) R 10 CO- (OCH 2 CHR 11) n 2 OR 12

wherein R 10 CO means a linear or branched acyl moiety, saturated and / or unsaturated with 6 to 22 carbon atoms, R 11 means hydrogen or methyl, R 12 means a linear or branched alkyl moiety with 1 to 4 carbon atoms and n2 means numbers from 1 to 20. Typical examples are the formal insertion products of average, 1 to 20 and, preferably, 5 to 10 moles of oxide of ethylene and / or of propylene oxide in the methyl ester, of ethyl, propyl, isobutyl, butyl or tert-butyl ester capronic acid, caprylic acid, acid 2-ethylhexanoic acid, caprinic acid, acid lauric, isotridecanoic acid, myristic acid, acid palmitic, palmoleic acid, stearic acid, acid isostearic, oleic acid, elaidinic acid, acid petroselinic, linoleic acid, linolenic acid, acid elaeoestearic acid, arachidic acid, gadoleic acid, acid Behenic and erucic acid as well as its industrial mixtures. Usually the products are obtained by insertion of alkylene oxides in the carbonyl ester bond in presence of special catalysts, such as for example calcined hydrotalcite. Products are especially preferred reaction of, on average, 5 to 10 moles of ethylene oxide in the ester bond of the fatty acid methyl esters of coconut Industrial

The alkyl- and alkenyl oligoglycosides, which they also represent preferred nonionic surfactants, usually follow the formula (VII)

(VII) R 13 O- [G] p

in which R 13 means a alkyl and / or alkenyl moiety with 4 to 22 carbon atoms, G means a saccharic moiety with 5 or 6 carbon atoms and p means numbers from 1 to 10. These can be obtained according to the procedures of the preparative organic chemistry branch. In This case will be referred to as representatives of the people number of publications, to publications EP 0301298 A1 and WO 90/03977. The alkyl- and / or alkenyl oligoglycosides can derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucoses. The alkyl- and / or alkenyl oligoglycosides Preferred are, therefore, the alkyl- and / or alkenyl oligoglycosides. The p index in the general formula (VII) indicates the degree of oligomerization (DP), that is the distribution of monoglycosides and oligoglycosides and represents a number between 1 and 10. While p in a compound given must always be an integer and in this case it can take first of all the values p = 1 to 6, the value p for a determined alkyl oligoglycoside is a numerical magnitude, analytically determined, which represents, most of the time, a fractional number Preferably alkyl- and / or alkenyl oligoglycosides with an average degree of oligomerization p from 1.1 to 3.0. From the point of view of the application industrial are preferred those alkyl- and / or alkenyl oligoglycosides, whose degree of oligomerization is lower that 1.7 and that is included, especially between 1.2 and 1.4. The alkyl or alkenyl radical R 13 may be derived from primary alcohols with 4 to 11, preferably with 8 to 10 carbon atoms Typical examples are butanol, alcohol capronic, caprylic alcohol, caprinic alcohol and alcohol undecyl as well as its industrial mixtures, such as those they obtain, for example, in the hydrogenation of methyl esters of fatty acids, industrial, or in the course of hydrogenation of aldehydes from Roelen oxosynthesis. Are preferred alkyl oligoglycosides with chain lengths from 8 to 10 carbon atoms (DP = 1 to 3), which are presented as a product head during distillation separation of alcohols industrial coconut fats with 8 to 18 carbon atoms and that they may be impurified with a proportion less than 6% in weight of alcohol with 12 carbon atoms, as well as alkyl oxoglycosides based on industrial oxoalcohols with 9/11 carbon atoms (DP = 1 to 3). The rest I rent or alkenyl R 13 can also be derived from alcohols primary with 12 to 22, preferably with 12 to 14 atoms of carbon. Typical examples are lauryl alcohol, alcohol myristyl, cetyl alcohol, palmolethyl alcohol, stearyl alcohol, isostearyl alcohol, alcohol oleyl, elaidyl alcohol, petroselinic alcohol, arachidic alcohol, gadoleyl alcohol, behenyl alcohol, belching alcohol, brasidyl alcohol as well as mixtures industrial, which can be obtained as described above. Coconut alcohol-based alkyloligoglycosides are preferred, hardened, with 12/14 carbon atoms with a DP from 1 to 3.

As a general rule agents present a surfactant content from 30 to 50, preferably from 35 to 45 and a water content from 50 to a 70, preferably from 55 to 65% by weight.

Industrial application

The new esterquats are also liquid highly concentrated and transparent. These have a power excellent cleaner, high hydrophobic capacity and excellent antistatic properties. If you take as 100% the biodegradability of a dicolzaoylmethylethoximonium metosulfate according to the invention, according to the Sturm test, then reaches the DSDMAC, under equal conditions, a value of 62%. Other The object of the invention therefore refers to the use of esterquats whose remainder or whose acyl remains are derived from unsaturated fatty acids with 8 to 22, preferably with 16 up to 22 carbon atoms and with iodine levels in the range from 100 to 150, for manufacturing preparations for cleaning hard surfaces, on which they can be contained in quantities from 1 to 30, preferably from 5 to 25 and, especially, from 10 to 15% in weight -referred to the agent-.

Examples

Table 1 gives examples of formulation:

TABLE 1 Formulation examples for final cleaning of body parts

Composition Example 1 Example 2 Esterquat 1) 7.5 11.0 Coconut Imidazoline - 2.0 2-ethylhexyl ester of coconut fatty acids 7 12.0 Octanol + 4EO - 3.0 Butyl glycol 10 20.0 Water until 100 1) Metosulfate dicolzaoylmethylethoximonium

Claims (10)

1. Cationic compositions for cleaning hard surfaces, characterized in that they contain esterquats by way of cationic surfactants, whose remainder or whose acyl moieties are derived from unsaturated fatty acids with 8 to 22 carbon atoms and the iodine index is found in the range from 100 to 150. 2. Preparations according to claim 1, characterized in that they contain esters of the formula (I), (I) [R 1 CO --- (OCH 2 CH 2) m OCH 2 CH 2 ---

 \ melm {\ delm {\ para} {CH 2 CH 2 O (CH 2 CH 2 O) p p R 3} {N} {\ uelm {\ para} {R 4}} 

<+> --- CH 2 CH 2 O --- (CH 2 CH 2 O) n R 2] X - where R 1 CO means a unsaturated acyl radical with 8 to 22 carbon atoms and an index of iodine from 100 to 150, R 2 and R 3 mean, independently of each other, hydrogen or R 1 CO, R 4 means an alkyl moiety with 1 to 4 carbon atoms or a group (CH 2 CH 2 O) q H, m, n and p mean, in sum, 0 or numbers from 1 to 12, which means numbers from 1 to 12 and X means halide, alkyl sulfate or phosphate of I rent. 3. Preparations according to claim 1, characterized in that they contain esters of the formula (II), (II) [R 1 CO --- (OCH 2 CH 2) m OCH 2 CH 2 ---

 \ melm {\ delm {\ para} {R 5}} {N ^ {}} {\ uelm {\ para} {R 4}}} 

--- CH 2 CH 2 O --- (CH 2 CH 2 O) n R 2] X - where R 1 CO means a unsaturated acyl moiety with 8 to 22 carbon atoms and with a iodine number from 100 to 150, R2 means hydrogen or R 1 CO, R 4 and R 5 mean, independently between yes, alkyl radicals with 1 to 4 carbon atoms or a group (CH 2 CH 2 O) q H, m, n and p mean, in sum, 0 or numbers from 1 to 12, which means numbers from 1 to 12 and X means halide, alkyl sulfate or phosphate of I rent. 4. Preparations according to claim 1, characterized in that they contain esterquats of the formula (III), (III) [R 4 ---

 \ melm {\ delm {\ para} {R 7}} {N ^ {}} {\ uelm {\ para} {R 6}}} 

--- CH_ {2}

 \ uelm {C} {\ uelm {\ para} {O ---
(CH 2 CH 2 O) m OCR 1 

HCH 2 O --- (CH 2 CH 2 O) n R 2] X - where R 1 CO means a unsaturated acyl moiety with 8 to 22 carbon atoms and with a iodine number from 100 to 150, R2 means hydrogen or R 1 CO, R 4, R 6 and R 7 mean, independently of each other, alkyl moieties with 1 to 4 atoms of carbon or a group (CH 2 CH 2 O) q H, m, n and p they mean, in sum, 0 or numbers from 1 to 12, which means numbers from 1 to 12 and X means halide, sulfate alkyl or phosphate of I rent. 5. Preparations according to claim 1, characterized in that they contain esters of the formula (IV), (IV) [R 1 CO --- NH --- CH 2 CH 2 ---

 \ melm {\ delm {\ para} {R 7}} {N ^ {}} {\ uelm {\ para} {R 6}}} 

--- CH 2 CH 2 --- NH --- R 2] X - where R 1 CO means a unsaturated acyl moiety with 8 to 22 carbon atoms and with a iodine number from 100 to 150, R2 means hydrogen or R 1 CO, R 6 and R 7 mean, independently between yes, alkyl radicals with 1 to 4 carbon atoms or a group (CH 2 CH 2 O) q H, which means numbers from 1 up to 12 and X means halide, alkyl sulfate or phosphate of I rent. 6. Preparations according to at least one of claims 1 to 5, characterized in that they contain the esterquats in amounts from 1 to 10% by weight -referred to the agents-. 7. Preparations according to at least one of claims 1 to 6, characterized in that the agents also contain co-surfactants. 8. Preparations according to claim 7, characterized in that the agents contain non-ionic surfactants. 9. Preparations according to at least one of claims 1 to 8, characterized in that the agents have a surfactant content from 30 to 50 and a water content from 50 to 70% by weight. 10. Use of esterquats, whose rest or whose acyl moieties are derived from unsaturated fatty acids with 8 to 22 carbon atoms and with iodine indices in the range from 100 up to 150, for the manufacture of preparations for cleaning hard surfaces.