DE2029598A1 - - Google Patents

Description

Patent attorney Or. Ing. A. van der Worth Dr. F.!. «Of those

"■■ si Hamburg 00 June 15, 1970

Wilstorfer Strasse 32

Gas 56ο 65ο06

LA CITRIQUE BELGE, SoA,
Tirlemont, Pastori «jstraat, Belgium

Aqueous cleaning agents

Priority: British patent application Kr ₀ 30640/69 dated June 17, 1969ο

The invention relates to aqueous detergents which, although they contain higher amounts of sodium tripolyphosphate than the saturation concentration of this salt in water, take the form of essentially homogeneous solutions «These agents are for cleaning objects with a non-porous surface and can be used for washing textiles «,

Sodium tripolyphosphate (abbreviated TPP) is currently that most widely used alkali phosphate in solid detergents for household and industrial use because of its multiple benefits * it sequesters the heavy cations of water and is therefore an effective water softener dar} it enhances the cleaning effect of surface-active substances anionic and / or nonionic agents, as they are commonly used in detergents; it greatly helps to remove dirt from the objects to be cleaned and facilitates the cleaning

009 8 52/21 10

the dirt remains in suspension in the washing liquor j it is less corrosive to the metals and / or metallic alloys which are used for the construction of washing machines, washing vessels and the like. In addition to the many advantages of TPP, there is also its cost price, which explains why it has practically replaced all other alkali polyphosphates, such as sodium pyrophosphate and sodium hexametaphosphate ₀

The TPP has a relatively low solubility in water, its saturation concentration in water at ordinary temperature is about 164 g / l, that is, about 14 wt . By contrast, it represents a virtually insurmountable obstacle for the production of homogeneous liquid detergent because these usually about 18 percent by 40. _o # should contain it, as is usually the Pail for commercial solid detergent. In fact, the amount of TPP that can be incorporated into liquid detergents can only be significantly less than the 14 wt. # Of theory (which represents the saturation concentration of TPP) due in particular to the presence of the surfactants. It is well known that the surfactants and the TPP mutually influence each other in terms of their solubility. The higher the concentration of the surfactants, the less the TPP can dissolve in the liquid agents and vice versa. Another problem as critical as the solubility of the TPP is that of its resistance to hydrolysis. It is known that in the presence of water the TPP hydrolyzes according to the equation

gjpp ™ _ _ra ™ «™ _ _m _- sodium pyrophosphate Ί- latriumortia © -

This hydrolysis destroys an important part of the beneficial properties of the TPP.

Now, however, there is an increasing slope, the solid detergent by liquid aqueous detergent to @ r ~

0ÖÖ852 / 2110

29598

put »i) The superiority of the latter is obvious iagej

(a) They are homogeneous while the solid detergents are are rare because of the different grain sizes and specific weights of their components;

(b) The liquid detergents are much easier to measure in To use quantities as the solid means in automatic washing machines (no clogging, no sticking, no dusting);

(c) They are more suitable for topical application the items to be cleaned

The previous liquid cleaning agents contain practically only potassium phosphates (pyrophosphate, tripolyphosphate) as phosphates, because these are much more soluble than the corresponding sodium phosphates (see 0 Pfrengle and C. pWtruck, Fette, Seifen, Anstrichmittel, 64, 1962, Sc 321-326) «, Man can bring concentrations of phosphates in this way, which are practically of the same order of magnitude as.in'-den usual solid "detergents. But the potassium pyrophosphate and tripolyphosphate are much more expensive than the corresponding sodium salts. So it would be interesting be to create liquid detergents in which the the predominant phosphate would be sodium tripolyphosphate. The invention relates to the solution to this problem.

It has surprisingly been found that it is possible to produce aqueous cleaning agents which contain considerably higher amounts of sodium tripolyphosphate than the limit concentration of the solubility of this salt in water under normal conditions, i.e. a concentration of sodium tripolyphosphate of over 14% by weight, which is even 35% can reach wt _o # © the inventive method is characterized in that in addition to the Natriumtripoly- 'phosphate, an appropriate amount of inorganic or organic salts of potassium and / or ammonium, if appropriate in suitably selected surfactants, further optionally

009852/2110

Hydrotropes, organic sequestrants, per compounds and other common additives to solid and / or liquid cleaning agents imports, with the remainder being water "

The object of the invention is therefore liquid homogeneous Detergents which contain by weight?

(a) 14 - 35 wt% sodium tripolyphosphate,

(b) 0.1-50 wt% of at least one salt of potassium and / or Ammonium with an inorganic or organic acid,

(c) 0-35 wt. # of at least one ester salt of a sulfopolycarboxylic acid,

(d) 0-20 Gewe # of at least one anionic surfactant,

(e) 0-15 wt. # of at least one nonionic surfactant,

(f) 0-20 Gewo # at least one hydrotrope,

(g) 0-20% by weight of at least organic sequestrants, (h) 0-20 Gewo # at least one per connection,

(i) 0-5 Gewo # in total of dye, perfume, thickener, optical brightener, corrosion inhibitor, anti-tarnish substance,

(j) water to make up to 100 #

(a) The sodium tripolyphosphate used in the aqueous agents according to the invention, Na ₅ P ₅ O ₁₀ , can be in any crystallographic form and in any hydration level from the anhydrous compound Na ₅ P ₅ O ₁₀ to the hexahydrate _{compound Na 5} P ₅ O ₁₀ ^ H ₂ O, are * is in the inventive compositions in a concentration of 14-35 wt "#, preferably from 18 - about 28 wt * #, used depending on the use for which the agents are determined, and also taking into account the Concentrations of the other ingredients of the respective agent *

(b) The potassium and / or ammonium salt which is used to increase the solubility of the TPP in the aqueous according to the invention To enlarge detergents, the salt of any inorganic or organic acid can be, for example a sulfate, chloride, nitrate, carbonate, bicarbonate, borate, orthophosphate, methaphosphate, pyrophosphate,

009852/2110

Maleate, adipate, aconitate, citrate, tartrate, ethylenediamine tetraacetate, Nitrile triacetate, diethylenetriamine pentaacetate j Succinate, etc. While the organic and inorganic sodium salts decrease the solubility of TPP in water, increase the organic and inorganic salts of potassium and / or ammonium, which are used according to the invention, this solubility, as will be shown below o However, the nature of the organic or inorganic anion of the potassium and / or ammonium salt added to the agents considerably affect the solubility of the TPP « For example, potassium sulfate is more effective than potassium chloride © Potassium carbonate is more effective than potassium bicarbonate, etc. Where appropriate The content of potassium and / or ammonium salt can be only 0.1 wt% of the total liquid cleaning agent and can reach 50 wt. # · However, one has to reveal out for economic reasons there is no interest in exaggerating the potassium salt content, and therefore the preferred potassium salt content is 1 - 10% by weight of the total agent

Potassium pyrophosphate has a preferred position among the potassium salts. Bs is not only a sequestrant which improves the solubility of the TPP in water, but it has also been found to be effective in stabilizing the tripolyphosphate against hydrolysis in aqueous solution to sodium pyrophosphate and sodium orthophosphate, as will also be shown. It is therefore particularly interesting to use the potassium pyrophosphate in the liquid cleaning agents according to the invention / its content, however, cannot be so great as to form double exchanges with the TPP sodium pyrophosphate, which, as is known, has very low solubility in water and could therefore be deposited in the form of a precipitate _β It has also been shown that the optimal amount of potassium pyrophosphate which is to be used in the liquid agents according to the invention should be about 5 - 25 $ of the amount of TPP present in the agents.

(c) Eateraalsä-type surfactants of a sulfopolycarboxylic acid

ΟΟΟβδ-2/2110

the use of which is contemplated according to the invention have properties superior to the anionic and nonionic surfactants with regard to the production of liquid aqueous cleaning solutions because 1. they are just as effective are like these, but at much lower concentrations, 2o they have better solubility in water, 3. they have a much greater resistance to salting out by the electrolytes and 4. they have hydrotropic properties have, which is shown in the following examples ©

Examples of ester salts of sulfopolycarboxylic acids are the potassium salts of sulfonated derivatives of one or more Alpha-di- or tricarboxylic acids, beta-unsaturated esterified with the hydroxyl group of one or more nonionic surfactants, as described in the German patent application P 1 803. 881 “8 of the applicant, or the potassium salts of Sulfopolycarboxylic acids, partially esterified by the hydroxyl group of one or more nonionic surfactants, as described in German patent application P 1 768 842 «> 5 der Applicant, or the potassium salts of sulfopolycarboxylic acids, esterified with the hydroxyl group of a nonionic Surfactants, as described in the applicant's German patent application P 1 962 5IO06. Instead of potassium salts you can if necessary, sodium or organic amine salts, for example of triethanolamine, can also be used »

Specific examples of these compounds are

for compounds No. 1 - Ir. 6 inclusive, the starting acid is obtained from the unsaturated polycarboxylic acids by pyrolysis of calcium citrate according to the process of German patent specification 1 768842 <> 5 of the Registrar Ein®

Compound No. ₈ 1 (abbreviated ASP 1) is obtained by reacting the pyrolysis product of calcium citrate in order to fix an SO, H group on the double bond, and so after acidification a sulfopolycarboxylic acid is obtained COOH groups of this acid with a nonionic surfactant obtained by ithoxying a linear 0 -C alcohol with 6 MoI ii.ii.layi «m ~

it 14

009852/2110 ORIGINAL BATHROOM

oxide (AoOo). The remaining 3/4 of the COOH groups and the SO, H groups are then neutralized with potassium hydroxide (see German patent applications P 1 962 510.6 and P 1 768 842o5) or similar

The connection Mr. 2 (ASP 2) is the same as ASP I ₁ except that the nonionic agent is a 0-j2 ~ ^ 14 alcohol ethoxylated with 3 moles _o 0 _o

The compound ITr ₀ 3 (ASP 3) is the same as ASP 1, except that the nonionic agent is a nonylphenol "ethoxylated" _{with 6 moles of Ä o 0}

., Compound No. 4 (ASP 4) is the same as ASP 1, except that the nonionic agent is an ethoxylated with 7 moles ÄoOo sTmndärer C ^ -C .., - is alcohol _e lie Compound No. ₀ 5 (ASP 5) is the same as ASP 4, but it has been neutralized with sodium hydroxide ©

The connection Ur. 6 (ASP 6) is the same as ASP 1, but the nonionic agent is an ethoxylated with 9 moles ÄoO ^"G 16"^"C 18 alcohol ο The compound no. 7 (ASP 7) the sulfonated product of the aconitic acid, di the Sulfotricarboxylic acid, of which one carboxyl group was esterified with a nonionic agent, obtained by ethoxylating the nonylphenol with 8.5 mol AoOo and the two other COOH groups and the SO ^ H group were neutralized with potassium hydroxide (see German patent application P 1 803 881.8)

The compound no. 8 (ASP 8) the sulfonated product of maleic acid, d.ie the suif © succinic acid, esterified the carboxyl group with a nonionic agent, obtained by ethoxylation of a linear Ci2 ~ ^C 14 alcohol with 6 moles of A ₀ Oo, and the other carboxyl group and the SO ~ H group were neutralized with potassium hydroxide (see German patent application P 1 803 881.8)

The suIf © polycarboxylic acids, the representatives of which are those just mentioned Compounds Kr. 1 - No. 8 can be used in the inventions, appropriate liquid detergents are applied in

009852/2110

Amounts of 0-35% by weight of total composition, preferably in quantities of 1-20 goats

(d) The anionic surfactant used in the liquid cleaning agents according to the invention is selected in particular from the group of soaps and organic synthetic sulfonates and sulfates. The soaps preferably used are potassium soaps of fatty acids with C ₁ -C ₀₀ , such as coconut oil or tallow fatty acids. The organic synthetic sulfonates and sulfates are preferably selected from the following groups:

1) Sulphonates of olefins having 8-25 carbon atoms, for example Sodium or potassium dodecyl sulfonate,

2) alkylbenzenesulfonates containing 10-16 carbon atoms in the alkyl group, the chain of which can be straight or branched, such as the potassium salts of the decyl, Undecyl, dodecyl, trideeyl, tetradecyl, pentadecyl or hexadecylbenzenesulfonic acid,

3) secondary alkyl sulfates of the type TBEPOL (trade mark),

4) sulfated primary aliphatic alcohols with 8-18 carbon atoms, such as potassium lauryl or hexadecyl sulfate,

5) Potassium alkyl or alkylaryl polyoxyalkylene sulfates, in which the alkyl group contains 8-18 carbon atoms, and the alkylaryl group consists of an alkyl group with Cg ^-0 I2 ^and an aryl group, preferably a phenyl group, and in which the polyoxyalkylene group is preferably a polyoxyethylene group with a content of 1 -4 Mol ÄoO »is _e

The ionic surfactant of the above kind is used in the liquid detergents of the present invention in an amount from 0-20% by weight, preferably 1-15% by weight of the total Applied by means of ©

(β) The nonionic surfactant used in the liquid cleaning agents according to the invention is preferably from the following group selected}

1) Ethoxylated alkylphenols containing 6-12 carbon

0 09852/2110

*; ΐ

% i

atoms in the alkyl chain and 3 - 25 moles of A ₀ Oo per mole of alkylphenol,

2) ethoxylated primary or secondary alcohols, derived from natural or synthetic alcohols with Og-Cp ₂ and with a content of 1 - 50 mol Ä'oOo per mol alcohol,

3) ethoxylated alkanolamides and alkylamides, ZoB · the ethoxylated Diethanolamide of coconut oil fatty acid,

4) copolymers between different alkylene oxides, which are known commercially under the name PLURONIOS, and polymers such as ZoB © polyethylene glycol and polypropylene glycol,

5) esters of polyhydroxyl compounds, e.g. sucrose stearate, Sucrose laurate, etc.

6) tertiary amine oxides, tertiary phosphine oxides, for example dimethyldodecylamine oxide, N-dodecylmorpholine oxide, dodecyldimethylphosphine oxide and the like _e

The nonionic surfactant for which examples were given just enters the compounds of this invention in amounts of 0 - 15 wt ^, preferably 1 -. 10 wt $> _$ of the total composition a *.

As is also shown in Example 2, the anionic agents mentioned under point (d) as well as the nonionic agents under point (e) have a much less good resistance to salting out by electrolytes than the agents of the ester of a sulfopolycarboxylic acid type, as under point Therefore, as mentioned in (c), the minimum amount required for the required cleaning ability is used without causing salting out of the liquid cleaning agents according to the invention. If one wishes to use larger amounts of it, ie amounts close to the upper limit of the concentration range given above, one must make do with the use of a hydrotrope or a mixture of the hydrotropic agent with a sulfopolycarboxylic acid of the ipys mentioned under (c) above.
(f) The hydrotropic agent is an organic compound

009852/2110

ORIGINAL INSPECTED

which improved the solubility in water of sparingly soluble substances. Known examples of these agents are xylene- "" sulfonic acid, p-toluenesulfonic acid, p-oumenesulfonic acid and the like, preferably used in the form of their potassium salts the hydrotrope agent to be replaced in particular by a potassium salt of the ester of sulfocarboxylic acid, described in (c), _o This replacement is advantageous' because of the esters of sulfopolycarboxylic acid has excellent detergency, while the hydrotropic agent such properties has not and therefore an inactive ballast in represents the liquid cleaning agents according to the invention «

The hydrotropes agent is applied in an amount of 0-20 wt »$, and preferably from 1 -.12 percent _o #, the entire liquid detergent"

(g) The organic one optionally used according to the invention Sequestrant is an aminopolycarboxylic acid, e.g. ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), or one Hydroxylpolycarboxylic acid and the like, preferably used in the form of its potassium salts o The sequestrant has that Ability to create complexes, soluble in water, with the heavy cations that cause the hardness of the water (calcium, magnesium)

daron

to be formed The agents according to the invention can range from 0-20 ew #, preferably 0.5 - 10 wt. #, of the entire agent contained «

(h) Any per-compound used in the agents according to the invention / is a water-soluble per-compound, ZeBo hydrogen peroxide, a perborate, percarbonate, persulfate, preferably of potassium. The amount of this per compound added can be 0-20% by weight, preferably 1 - 5% by weight of the total mean »

(i) The agents according to the invention can also use the usual wisely used in liquid or solid detergents Contain auxiliary materials. These additives are for example Colorants, perfumes, thickeners, e.g., carboxymethyl cellulose »

009852/2110

Polyvinylpyrrolidone, polyvinyl alcohol and the like, substances preventing corrosion or tarnishing, optical brighteners, etc. <> The amount of all these additives combined can be 0.-5 Gev? ₀ #, preferably 1 - 4 G-ew. #, Make up the total mean «,

(j) The agents according to the invention contain at least the necessary amount of water to produce a liquid detergent

From the foregoing it can be seen that the liquid cleaning agents according to the invention can have very diverse approaches, depending on whether one or more of the various ingredients mentioned above are added _o Their common feature is that they always contain a higher amount of TPP than 164 g / l ( or 14 Gewo #), which has not yet been achieved in liquid cleaning agents, and that they always contain a potassium or ammonium salt of an organic or inorganic acid in sufficient quantity to ensure the solubility of the TPP in water. The other components of the agents according to the invention are optional and are selected according to type and amount as a function of the intended practical application *

In order to produce the agents according to the invention, one can do that Use the following procedure, which is only given as an example for explanation and not as a limitation.

Put about 50 - 60 # of the intended in a container Amount of water, then add the surfactants from Tijp (c), (d) and / or (e), the dye, the perfume, the Thickener, the corrosion inhibitor, the tarnish-preventing substance added «Then you add the hydrotropic agent and the optical brightener hintou and continue stirring until a homogeneous solution is obtained. One then leads always with stirring, add the potassium salts and then water until about 85 # of the total intended amount is reached. The TPP is then added with vigorous stirring and, after it has dissolved, the solution is filtered adding the per compound, adjusts the pH to about 7 - about 9

009852/2110

a, by adding either sulfuric acid or Potassium hydroxide, and then add the remaining amount of water «

Among the fields of application that can be considered for the agents according to the invention, particular mention is made of the softening of water, the cleaning of objects from non-porous surfaces, e.g. Glass, porcelain, enamel, wood, metal and plastics-coated surfaces, for example ₀ Bodies and the like, as well as the washing of the various ΪΧΧΪΣΣΙΚ natural or synthetic textiles, both delicates as coarse scrub ·

The following examples serve to illustrate the invention liquid funds, but not to limit them *

example 1 Effect of potassium salts on the solubility of TPP in

Water"

Solutions are prepared which contain increasing amounts of solubilizing it Containing salt (potassium or ammonium salt) Add to 100 ml of each of these solutions while stirring vigorously, Add sodium tripolyphosphate in such an amount that one Part of it does not dissolve. The suspension obtained in this way is stirred for one hour by means of a magnetic Agitator β Then you leave it overnight at the usual Temperature. It is then filtered and the amount of sodium tripolyphosphate in solution is determined with the aid the following analytical methods:

a) Determination of the dissolved sodium by flame photometry,

b) colorometric determination of the phosphate ion using ammonium molybdate and ammonium monovanadate using a spectrophotometer o

The other substances are determined by the usual methods of chemical analysis »

The sodium tripolyphosphate used has the hexahydrate form, because the anhydrous form gives rise to the formation of supersaturated solutions, which subsequently crystallize,

0 0 9 8 5 2/2110

For the TPP of NaCl and 1 of Na ₂ SO ₄ , are Contents , H ₂ O ₂ . V 2029598 0 163 anhydrous form NaCl Nar- N ^a 5 ^P 3 ° 10 the quantities expressed H ₂ O ₂ Na ₅ P ₅ O ₁ expressed 205 Influence 0 163 KCl 164 in g / l of 238 - 13 - 50 152 ^P 3 ° 10 230 271 In all of the following examples, the 101 138 63 KCl 289 in g / 1. 201 112 86 0 Na ₅ P ₅ O ₁₀ 219 Influence 46 35 163 Na ₂ SO ₄ 34 74 194 0 K ₂ SO ₄ 195 202 Na ₅ P ₅ O ₁₀ 42 of Na ₂ CO ₅ , K ₂ SO ₄ and (NH, J ₂ S 185 164 82 Na ₅ P ₅ O ₁₀ 0 Na ₅ P ₅ O ₁₀ 230 145 164 8th, 163 (NH ₄ ) ₂ S0 ₄ Na ₅ P ₅ O ₁₀ 301 . 111 17th 7 174 0 288 80 33 193 19th 41 51 205 41 Influence from KBO ₂ and 68 227 74 Na ₂ CO ₅ Na ₅ P ₅ O ₁₀ 88 247 213 0 164 KHCO ₅ 252 340 54 198 KHCO ₅ and K ₂ CO ₅₀ 105 0 Na ₅ P ₅ O ₁₀ 264 45 164 K ₂ CO ₅ Influence 92 212 0 KBO ₂ 230 235 44 0 KBO ₂ 270 222 15th KBO ₂ . 435 0 22nd

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223 259 291

KBO ₂ .H ₂ O ₂ Na ₅ P ₃ 52 285 1 00 336

65 114 262 543

17th

45

87

218

Influence of sodium _{citrate 2H 2} O and potassium citrate 1H ₂ O.

164 185 220 240 264

Well ₅ ^P 3 ° 10 1 64 1 30th 102 54 22nd

Influence of potassium aconitate and maleate,

Aconitate

40 83

207 412

Na ₅ P ₃ O ₁₀ maleate

164 207 224 245 231

39

79

201 164

193 '215 221

Influence 3E & K of the potassium eels of Β, Ώ.Τ.Α « and !.!

EoD.TA »K. Na ₅ P ₃ O ₁₀

25 70

140 270

164

176 182 188 179

25th

70

140 164

185 187

(+) E.D. »Τ.A. j Ethylenediamine tetra © asigeäur®

(++) N.T.A. : Nitrilotriacetic acid β "

The gates in the table indicate that the sodium salt is inevitable the Lb'alichkeit dee Hatriuntripolyphoapliate he "

009852/2110

low "and that the potassium and ammonium salts _β increase they can be seen also that some of the salts used in the present invention exceed the potassium far in his lösliehmachenden effect on the TPP ©

Example 2

Resistance to the salting out of the surfactants by the electrolytes «

The method of determining resistance to salting out is following

For each studied surfactant Three aqueous solutions are prepared at the $ 1, $ 5 and 10 percent by "# contain the active substance · It can also be prepares an aqueous solution containing 900 g / l to Kaliumcitratmonohydrat, and to use them to _s to titrate the three solutions of the active material. '
(Phase separation) ο The three quantities of citrate corresponding to the three concentrations of active material are plotted on a curve. A straight line is obtained, which is extrapolated in order to get to know the fictitious concentration of citrate corresponding to 0 $ of active material, in order to be able to compare the resistance to salting out through electrolysis of the various active materials investigated »*

The results obtained are in the table below reproduced:

009852/2110

Surfactant

Resistance to salting out «concentration in g / l of anhydrides Potassium citrate extrapolates when there is an active material

ASP 1. Potassium salts ASP 8 555 ASP 2 of esters of Linear potassium alkylbenzenesulfonate 620 ASP 3 ', * SuIf opolycarbon- Lauryl ether sulfate with 3.5 mol Ä.Oo 330 ASP 4 . acids ethoxylated with 6 moles EOO « 482 ASP 5 (ASP 5 = sodium salt) Nonylphenol 425 ASP 7 ethoxylated with 8.5 mol 292 secondary O ₁₁ -O ₁ C ₅ alcohol 316 ...- ■ ..- with 7 1 too little soluble Get AoOe 180 70 25; 50

The table shows that the ester salts of sulfopolycarboxylic acids of class (c), as they are preferably used as surfactants, resistance to salting out due to electrolytes that are significantly higher than that of the anionic and nonionic surfactants of class (d) and (e) e

These results are obtained by the following experience bestä _T Untitled, in which the maximum amount (in g / l) of is determined to be examined active agent which is introduced into an aqueous detergent solution containing 200 g / l TPi 20 g / l potassium pyrophosphate and Contains -20 g / l of potassium sulphate without phase separation (see table below).

009852/2110

ASP 2 J potassium salts of esters of ASP 3 / sulfopolycarboxylic acids ASP 5! (ASP 5 = sodium salt)

linear potassium _{alkyl (C 10} -O ^) - benzenesulfonate lauryl ether sulfate with 3 »5 mol I ₀ O ₀
Potassium alkyl (O ₁ 2 "C _1. ) Sulfate

^Ö 12 "~ ^G 14 ^Allj: alcohol ethoxylated with 6 mol 1 * 0 _β nonylphenol ethoxylated with 8.5 mol iUOe

220 g / l 200 g / l 220 g / l

<30 g / l <80 g / l <20 g / l

<20 g / l <20 g / l

Example 3 Hydrotropic power of the ester salts of sulfopolycarboxylic acids »

In example 2 it was shown that the usual anionic and nonionic surfactants have a tendency to break down through electrolytes To be salted out at. Relatively low concentrations of the surfactants. To combat this tendency a hydrotropic agent must be added to the detergents

In the present examples, a liquid cleaning agent is used, which is a potassium salt of an ester of a SuIfopolycarboxylic acid (ASP 1), a commercially known nonionic agent, Tergitol 15S3, which is the condensation product of a secondary C-j - | --O ^ ^ alcohol with 3 mol 1.0 » is, furthermore TPP, potassium pyrophosphate and potassium xylene sulfonate (P »XeS ·), contains which latter represents the hydrotropic agent ·

In the following table Ϊ it is shown that in order to separate to prevent detergent leaching in two phases, man the concentration of P.X. must increase if the concentration of Tergitol 15S3 is increased

In Table II it is shown that the content of P ₀ XS, can be reduced under the condition that the content of ASP 1 is increased in parallel, which proves the hydrotropic activity of this compound »

In the following two tables the numerical values mean g / l «

009852/2110

Table I.
Trial ASP 1 Tergitol TPP Potassium

No"

2
3
4th
5

80 80 80 80 80

1533

0 10 20 30 40

pyrophosphate

180 '20 180 SO 180 20

180
180

20 20

ΓοΛ ob ι

20 50 60

Try ASP 1 Tergitol

No,

3
4th
5

0 20

40 60 80

15S3

40

40

40 40 40

Table II

TPP potassium

pyrophosphate

180
180

180
180
180

20 20

20 20 20

108 82

72 70 60

Example 4

Inhibiting effect of potassium pyrophosphate on hydrolysis of . TPPo

The aqueous solutions of sodium tripolyphosphate develop rapidly by hydrolysis to an equilibrium which is about 2 $ sodium orthophosphate and about 15 $ sodium pyrophosphate, based on the total concentration of phosphates (see GHABEREK & MARTELL, "Organic Sequestring Agents", New York, John Wiley Inc , S · 304), includes " ^:

In order to show the inhibiting effect of the pyrophosphate on the hydrolysis of TPP, the following detergent solution was used prepared:

100 g / l ASP 4

10 g / l Tergitol 15S3 (secondary O ₁ C alcohol ethoxylated with

7 mol 1.0ο) '

4 g / l potassium diethylenetriamine pentaacetate (Versenex 80,

Trade name)

200 g / l TPP containing 2.5 # sodium pyrophosphate and 1 $ Na-

009852/2110

trium orthophosphate 20 g / l potassium pyrophosphate
50 g / 1 potassium xylene sulfonate
20 g / l potassium sulfate (pH = 8.62).

This agent is kept at 25 ° G and the contents (in wt. _O #) of tripolyphosphate, pyrophosphate and orthophosphate of the agent _β are determined at various time intervals. The results are shown in the following table:

Time orthophosphate pyrophosphate tripolyphosphate

After 0 days 0.9 11.4 87.7

after 11 days 1.0 11.3 87.7

after 20 days 0.9 11.4-87.7

after 27 days 1.0 11.8 87.2

after 57 days 1.2 12.7 86.1

It can be seen "that the TPP content has fallen from 87.7 1 ° to 86.1 # after 57 days, which proves that the hydrolysis was practically prevented by the presence of potassium pyrophosphate."

Example 5

Liquid cleaning agents with a content of surfactants of type (d) and (e)

In these cleaning agents, which all contain:

200 g / l TPP

20 g / l potassium pyrophosphate

20 g / l potassium sulfate
150 g / l potassium xylene sulfonate,

were the amounts given in the following table Surfactants of type (d) and (e) incorporated:

(d) KaIiUBBaIlCyI (C ₁ QC ₁₅ ) .benzenesulfonate; 200 g / l of lauryl ether sulfate with 3.5 moles of Ä.O. ι 200 g / L

(e) G ₁₂ -G ₁₄ AlkOhOl ethoxylated with 3 mol AoO. : 100 g / l nonylplienol ethoxylated with 6 mol A- · - ■: 100 g / l

0098 52/2110

Example 6 .

Liquid cleaning agents containing surfactants Type (c) together with surfactants of type (d) or (e) »

The following table shows the concentrations of the various Components expressed in g / l "

Type .ic) Type (d) K- or NH, - Hydrotrope K _A P ₉ 0 ₇ TPP, _ or (e) «·» ">» ⁴ · ⁴ '

salt

80 ASP 4 10 alk.sec, 50 K ₉ SO (C ₁₅ ) - 3 ÄO. V

70..P.I.S ·

80 ASP 4 10 alk.sec. 75 K ₉ SO. 70 PT ₀ S (C ₁₅ ) -? Ä0 ⁴

50 ASP 2 10 Alk.sec _o 75 (NH _A ) 2S0, 125 P _O X * S (Cj- 7 10 4 * 4

100 ASP 7 10 (C ₁₉ -C ₁ J 20 K ₉ SO.Alk ¹ 2 6 ¹⁴ AO ^{2 4}

100 ASP 8 10 (C ₁

100 ASP 2 20 K soap 20

20 K ₂ SO ₄

25 250

25 250

25 250

25 250

20 ASP 6

+ 10 nonyl 120 P ₀ XoS ₀

30 ASP 2 phenol - 6 A'O 75 KHCO ₃

100 ASP 2 20 nonyl- 50 K ₃ citr. 100 P ₀ XoS. 20 phenol - 6 lO IH ₉ O

150 P ₀ XoS ₀ 20 200 150 P ₀ X ₀ So 20 200

50 PX _o S ₀ 20 200

(x) PeT.S. = Potassium toluenesulfonate

i a.spiel 7

Liquid detergents for fabric washing "at high temperature".

The effectiveness of the agents according to the invention for the G-robwäache is in the Launder-O-Meter at a temperature of 85 ° C tested for 20 minutes at a concentration of 5 ml / l in water of French hardness of 17 ° Standard soiled tapes were supplied by TEST FABRICS Inc. STANDARD (abbreviated TF) and from US TESTING Cy

009 852/2 110

STANDARD (abbreviated UoSoT ₀ ) _o This test measures the percentage of the dirt "removed by the laundry" from the belts

In the following table, the tests Hr ₀ 1 - 3 were carried out with agents according to the invention, all of which contained:

100 g / l ASP 2

6 g / l tetrasodium E.D.ToA.

2 g / l polyvinylpyrrolidone
100 g / l potassium iylene sulfonate

20 g / l K ₄ P ₂ O ₇
200 g / l TPPo

In addition, the agent for experiment no. 1 contained 20 g / l nonylphenol, ethoxylated with 6 Ä _e 0 _e , 50 g / l boric acid and 12.5 g / l KOH; the means for the Run No. ₀ 2 contained 20 g / l of nonylphenol ethoxylated with 6! "Ο. and 50 g / l potassium citrate; the means for XIXIiS experiment no. 3, contained 20 g / l C ₁₆ -O ₂₀ -alcohol, ethoxylated with 6 I ₀ O. and 50 g KHCO _5, Experiments No. ₀ 4 and no. 5 were with powdered commercially available heavy-duty detergents, namely "ALL" (No. 4) and "Prodixan" (No. ₀ 5) carried out using 5 g / l «

Experiment number ₀ Tl U ₀ SoT ₀ 1 64.7 18.1 2 64.5 18.7 3 65.1 18.0 4th 54.9 15.6 VJI 56.0 16.9

One becomes the superiority of the experiments nos. 1 - 3 over determine the tests no. 4 and 5

Example 8

Interest in increasing the concentration of TPP in liquid cleaning agents .

The effectiveness test of this example is the same as that of example T _9, with the tapes TP and USI also being compared with results with the washing

009852/2110

powders "ALL" and ¹¹ PHODIXAl "were used«, The water used had a French hardness of 40 ° _e

The experiments UTr. 1-5 were with liquids according to the invention Detergents carried out which contained growing amounts of TPP, namely (in g / l) i 0, 50, 100, 150, 200 ^ where the Remainder of the agent was the following

100 g / l ASP 2

20 g / l nonylphenol ethoxylated with β 1 »O® 2 g / l polyvinylpyrrolidone
6 g / l tetrasodium IDTA
100 g / l potassium xylene sulfonate
20 g / l K ₄ P ₂ O ₇
20 g / l K

The experiments Br ₀ 6 and 7 were carried out with «« ALL "and" PHODIXAiP ¹ *

Experiment No. ₀ Tf UcS ₀ T ₆

1 23.2 3.7 2 32.2 5.5 3 53.9 7.4 4th 64.6 ■ 11.5 5 67.6 16.0 β 52.7 14.6 7th 56.2 15.7

The table above clearly shows the increasing effectiveness of the agents with increasing levels of TPP®

Example 9

Liquid detergents for coarse washing at low temperatures

temperature «

The means are given in g / l «

009 852/2 110

50 50 40 - - 25th - 25th 4th 4th 1 1 100 100 20th 20th 20th
180 20th
180

Medium Medium I ___II

ASP 3

Nonylphenol ethoxylated with 6 mol 1 · 0 · sec. (θ _ΛΛ - <ί _Λ alcohol ethoxylated with 3 mol A \

Ethoxylated with 7 moles of pentasodium DTPA polyvinylpyrrolidone potassium xylene sulfonate K ₄ P ₂ O ₇
K ₂ SO ₄
T.PoP

Example 10 Liquid detergents for delicate laundry »

The experiments were performed in a Tergometer for 10 minutes at a temperature vcn 4O ⁰ C using 5 ml of detergent per liter of water of 17 ° French hardness of running "

Standard artificially soiled tapes were used, supplied from TESTFABRICS Ine «, USA. They are made of nylon (K), also polyester-cotton 65/35 (P) and wool (L) *

Four detergents according to the invention were used, all of which contained?

60 g / l ASP 2

6 g / l tetrasodium EDTA 90 g / l potassium xylene sulfonate

1 g / l polyvinylpyrrolidone 20 g / l K ₂ SO ₄ 20 g / l K ₄ P ₂ O ₇ 200 g / l TPP,

but which differ from each other by the presence of the following compounds "

009852/21

Means for experiment no ₀ 1

20 g / l secondary C ^ alcohol ethoxylated with 3 mol i «0« 20 g / l secondary alcohol (Cj ₅ ) ethoxylated with 7 mol I ₀ O ₀ 20 g / l ethoxylated diethanolamide of coconut oil fatty acid

Funds for experiment no 2

40 g / l nonylphenol ethoxylated with 6 mol A ₀ O ₀ 20 g / l monoethanolamide of coconut oil fatty acid «

Means for the experiment Ir ₀ 5
40 g / l nonylphenol ethoxylated with 6 mol AoO »

Means for experiment Ur ₀ 4

40 g / l nonylphenol ethoxylated with 6 mol A '0 * 10 g / l diethanolamide of lauric acid 10 g / l lauryl ether sulfate with 2.5 mol I ₉ O ₉

Experiments Nos. 5 and 6 were carried out using commercially available liquids Delicates detergents, namely "OSA" (No. 5) and "SOLILAINB" (No. 6) carried out, which were also used in the tests at a concentration of 5 ml / l «

The results obtained are given in the following table:

Attempt no. N P. L. 1 80.3 36 _a 2 90.1 2 80.1 41.1 92.9 3 75.5 41.8 92.3 4th 81.7 40.0 76.4 5 71.1 23.5 25.2 6th 64.6 30.9 65.9

The superiority and versatility of the liquid detergents according to the invention (experiments No. 1 - 4) are thus evident, although the commercially available remedies (Trials No. 5 and 6) contain a higher content of Tenaiden (over $ 25) The agents according to the invention are just as suitable for washing by hand as with a machine «

009852/2110

Claims (1)

Claims 1 · Liquid homogeneous washing and cleaning agent with one content by weight (a) H - 35 wt. $ sodium tripolyphosphate, (b) 0.1-50% by weight of at least one potassium and / or Ammonium salt of an organic or inorganic acid, (c) 15 - β5.9 Gew _e $ water « 2e Liquid homogeneous detergent and cleaning agent according to claim 1, characterized by a weight content of (a) 14 - 35 wt% sodium tripolyphosphate, (b) 0.1-50 Gewe # of at least one potassium and / or Ammonium salt of an organic or inorganic acid, (c) 0-35% by weight of at least one ester salt of a sulfopolycarboxylic acid ₉ (d) 0-20% by weight of at least one anionic surfactant, (e) 0 - 15 Gewejö at least one nonionic surfactant, (f) 0-20 Gewo # at least one hydrodrop, (g) 0-20 Gewo # at least one organic sequestrant, (h) 0-20 wt. ^ of a perforation, (i) 0-5 Gew _e ? 6 total of dye, perfume, thickener, optical brightener, corrosion inhibitor, tarnishing substance (j) Heet of water to make up to 100 3 · Liquid, homogeneous detergent and cleaning agent according to the preceding claims, g ekennze i c hn et by a weight-wise content (a) 18-28 wt. # sodium tripolyphosphate, (b) 1-10 wt. # of at least one potassium and / or Ammonium salt of an organic or inorganic acid, (o) 1-15% by weight of at least one ester salt of a sulfopolycarboxylic acid, (d) 1-15% by weight of at least one anionic surfactant, (e) 1 - 10 wt.? * at least one nonionic surfactant, 0 0 9 8 5 2/2110 (f) 1-12 Gen. # at least one hydrotrope » (g) 0.5 - 10 wt. of at least one organic sequestrant ₉ (h) 1-5% by weight of at least one per compound j, (i) 1-4 weight _e $ total preventing of dye, perfume ,, thickeners, optical brightener ,, corrosion inhibitor, the starting substance, (j) Remaining water to make up to 100 4o agent according to claim 1, characterized in that it is used as a potassium and / or ammonium salt the potassium pyrophosphate in a meage of 5 - 25 percent by weight, based on the sodium tripolyphosphate ! 5 "means according to claim 1, ge'kenn- characterized" is characterized in that the potassium and / or ammonium salt from the group consisting of potassium sulfate, ammonium sulfate, -Kaliumcarbonat, potassium ₉ £ aliumorthoborat> - potassium metaborate, potassium tetraborate, potassium perborate, potassium maleate and potassium citrate, is selected » 6 »means according to claims 2 and 3» characterized .ge--characterizing η et ₉ that it contains as potassium and / or ammonium salt in a Kaliumpjrophosphat Menge.von 5 - on which contains 25 wt latriumtripolyphosphat based © ^ » 7o means according to claims 2 and 3 $ da du rchg; β «indicates that the potassium and / or ammonium salt is selected from group ₉ consisting of potassium sulfate, ammonium sulfate, potassium carbonate, potassium carbonate, potassium orthoborate, potassium metaborate, potassium tetraborate, potassium perborate, potassium maleate and potassium citrate ₉ » θ ", means according to claims 1 - 7, dadu r chge indicates that the potassium and / or ammonium salt is formed in situ from an organic or inorganic acid" 0 0 9 8 5 2/2110 9 «Agent according to claims 2-8, characterized in that the ester salt of a sulfopolycarboxylic acid the salt of the sulfonated derivative is one or more alpha-dicarboxylic acids which are beta-unsaturated and with the hydroxyl group one or more nonionic Surfactants are esterified * 10 * Agent according to claims 2-8, characterized in that the ester salt of a sulfopolycarboxylic acid the salt of the sulfonated derivative of one or of several alpha-tricarboxylic acids, which is beta-unsaturated and one or more nonionic surfactants are esterified with the hydroxyl group » 11. Means according to claims 2-8, thereby marked draws that the ester salt of a sulfopolycarboxylic acid is the salt of the unsaturated polyearboxylic acid, which is obtained by pyrolysis of calcium citrate and by sulfonation the double bond, acidification, esterification with the hydroxyl group of one or more nonionic surfactants and Salt formation is preserved " 12. Composition according to claims 2-11, characterized in that the ester salt of a sulfopoly · = - carboxylic acid is a salt of sodium, potassium or an amine, preferably the potassium salt _o 13. Means according to claims 2 - 12, d a d u r c h g e indicates, that the anionic surfactant from the group consisting of sulfonates of olefins, alkylbenzenesulfonates, primary alkyl sulfates, secondary alkyl sulfates, and alkyl or alkylaryl polyoxyalkylene sulfates is· 14. Means according to claim 13, characterized in that that the anionic surfactant is in the form of a salt of sodium, potassium or an amine, preferably the has the form of a potassium salt 009852/2110 15 »Means according to claims 2-14, characterized that the nonionic surfactant off the group consisting of ethoxylated alkylphenols, ethoxylated primary or secondary alcohols, ethoxylated Alkanolamides or alkylamides, polymers or copolymers of alkylene oxide, esters of polyhydroxylated compounds and tertiary amine oxides or tertiary phosphine oxides is selected « 16. Means according to claims 2-15, characterized in that that the hydrotrope from the group consisting of xylene sulfonic, p-toluenesulfonic and p-cumene sulfonic acid, is preferably selected in the form of a potassium salt « 17 «Means according to claims 2-16, characterized in that that the organic sequestrant from the group consisting of aminopolycarboxylic acids and hydroxylpolycarboxylic acids, is preferably selected in the form of their potassium salts « 18o means according to claims 2-17 »thereby marked indicates that the per compound is selected from hydrogen peroxide and potassium perborate. 19 · sequestering agent according to claim 1 _e 20 · Means for washing textiles according to claims 2-18. 21 · Means for cleaning objects with non-porous Surface according to any one of claims 2-18. 009852/2110