DE1617120C3 - Detergents and cleaning agents - Google Patents

Description

3 4

acid groups or 2 dialkanolamine groups bleaching agents, such as alkali perborates, alkali percarbonates, 1 to 2 sulfonic acid groups. Alkali hypochlorites, chlorinated cyanuric acids and their The sulfonic alkali salts and neutral salts such as magnesium silicate acid groups or their salts containing polyesters and sodium sulfate, prepared in the manner indicated. In addition, sequestrants may have a resinous consistency and are insoluble in organic agents, especially alkali salts of aminopoly solvents, but slightly soluble in water, such as the sodium salts of amino acids. They can still contain minor amounts of triacetic acid or the ethylenediaminotetraacetic acid low molecular weight esters or of unreacted and the alkali metal salts of hydroxyalkyldiphosphonic starting materials which are obtained by extraction with acids and aminopolyphosphonic acids, eg. B. removed the organic solvents and optionally io disodium salt of l-hydroxyethane-ljl-diphosphon if necessary can be reacted again. acid or the hexasodium salt of aminotri-Since these compounds have cleaning properties (methylenephosphonic acid), be present,
However, the agent does not have to be separated. In addition, there is generally no need to separate substances. to regulate the pH value in question, such as sodium info Ige the insolubility of the high molecular weight 15 carbonate, sodium bicarbonate, lactic acid and Ci-compounds in organic solvents and tronic acid. ·
Due to their content of low molecular weight, the agents can also contain optical brighteners, as do the usual methods of derivatives of diaminostilbene disulfonic acid or of determining molecular weight. Degree of polymerization Diarylpyrazolinsulfonsäure contain. For the control and molecular weight of the polyesters, therefore, the foam behavior cannot be specified with sufficient accuracy. Foam improvers, such as fatty acid amides or foam detergents can contain any water-soluble contraceptives, in particular trialkylmelamines, containing salts of the sulfonic acid polyesters according to the invention.

^: contain, preferably the alkali metal and am- The new detergents and cleaning agents can contain monium salts. Ammonium salts also include the as are present in solid, in particular powdery, or salts of solutions or pastes derived in the form of organic ammonium bases. Because of the good to understand. The polyesters may be the detergents water solubility of the polyester salts are also be added to ¹ * in the form of the free acids, the preparation of liquid detergent concentrates besonsofern alkaline substances in a DERS suitable for. Such liquid preparations can form a sufficient excess of salt. Apart from the polyester sulfonates, the new tropical substances, such as low molecular weight alkylbenzene detergents and cleaning agents, contain the surface-active substances commonly used in such agents, sulfonates, urea and organic solvents, for example sol. .
Before of the sulfate or sulfonate type, such as primary and In some cases, for example when washing secondary alkyl sulfates and the sulfates of ethoxylated textile materials made of cellulose or regenerated or propoxylated fatty alcohols, also alkylbenzene cellulose, the washing effect can be achieved by adding sulfonates, primary and secondary olefin sulfonates , common graying inhibitors, in particular carb-alkyl sulfonates and α-sulfo fatty acid esters. More oxymethyl cellulose, still to be increased. The compounds of this class to be used, which can optionally be used in amounts of carboxymethyl cellulose, are the higher molecular weight 40 which carry about 0.1 to 3%, based on the total sulfated partial ether and partial ester polyvalent weight of the agent.

Alcohols, the sulfates ethoxylated or propoxy- The new agents are suitable for cleaning

Lated fatty acid amides and alkylphenols, also, fatty objects of all kinds, but especially for

acid tauride and fatty acid isethionates and their washing of textiles made from synthetic or cellulose

Homologues. Alkali soaps made from loose fibers, made from regenerated cellulose, are also suitable. or off

Fatty acids and the fatty acid condensation products are mixtures of the fiber types mentioned,

of amino acids or degraded proteins. Compared to known detergents, they make it easier

Ampholytes, such as alkyl betaines and new agents, also add to the washing process

Alkylsulfobetaines in question. The means can further- whiteness of the laundry,

towards non-ionic washing active substances, such as alkyl 50. .

and acyl polyglycol ethers, alkylphenol polyglycol ethers, examples

Mixed condensates of polyethylene glycol and poly- The graying-inhibiting effect of the in the

propylene glycol, fatty acid sugar esters, amine oxides and the following examples

Contain fatty acid alkanolamides. The mentioned ver was tested according to known methods (cf.

bindings can also be used in a mixture.

will. If the compounds have an aliphatic and J.W. Handley “Journ. of Amer. Oil Chem.

Have hydrocarbon radical, this should preferably Soc ", Vol. 42, pp 993 to 997 [1965]). These are the ones

be straight-chain and have 8 to 22 carbon atoms A. "Redeposition" method (also under the name

exhibit. Known in the compounds with araliphatic »backwashing method«), by which one

Hydrocarbon residues contain the preferably 60 shared washing of soiled

understands unbranched alkyl chains on average 6 to 16 carbon and clean textiles,

Atoms of matter. B. »Depositionfr method, in which the clean

The new detergents and cleaning agents can use textiles in an artificially soiled liquor

are also washed according to their respective use,

contain other common ingredients, such as Pyro-65. .

phosphate, polyphosphate and higher condensed ^A · redeposition method

Phosphates as well as silicates in the form of their alkali salts, In the Launder-Ometer 4 lobules were in each case

also oxygen-releasing or active chlorine-containing from the synthetic tissue to be examined by

8.3 g total weight together with 1.3 g of an artificially soiled cotton yarn for 30 minutes washed up to five times. The reflection value was then determined with a photometer.

The practical dust / skin fat combination used to soil the cotton yarn consisted of a mixture of kaolin, black iron oxide, soot and synthetic skin fat (from ¹ ^ fatty acids, ¹ l ₃ fat and hydrocarbons). After the soiling, the cotton yarn contained about 11% pigments and about 2% sebum.

A detergent with the composition. ■ · ': ■ .; '-. "■.; ■ ■ ■ ■■:' ■■■

20% n-Dodecylbenzenesulfonat (Na-Salz),

2.5% coconut fat alcohol sulfate (Na-Salz),

2.5% tallow alcohol sulfate (Na-Salz),

40% sodium pyrophosphate,

0 to 10% graying inhibitor,

35 to 25% sodium sulfate,

'■ ■ "■. ■. · ■ · ■'

The application concentration was 5 g / l and the hardness of the tap water used was 10 ° dH. The cotton samples were washed at 90 ⁰ C and a liquor ratio of 1:12 (liquor 115 ml), the samples of synthetic tissue at 6O ⁰ C and a liquor ratio of 1:30 as (liquor 290 ml) for 30 minutes each. Then the »four times rinsed, dried and ironed samples with distilled water were evaluated photometrically. .. · ■. ■■ · ■ .- ■ · ■■ ■■■

B. Deppsition Method

The test according to this method was carried out with strand material in the Terg-O-tomcter. 10 g skeins of the corresponding substrate were added to 11 wash liquor (liquor ratio 1: 100) of 0.2; 0.5; 1.0 and 1.5 g of standardized carbon black, each with 5% use of the substance to be examined Washed graying inhibitor.

The detergent used consisted of a liquid preparation of the following composition:

7.8 g / l n-Dodecylbenzenesulfonat (Na-Salz),

1.1 g / l coconut fatty alcohol sulfate (Na-Salz),

1.1 g / l tallow alcohol sulfate (Na-Salz),
16.0 g / l sodium pyrophosphate,

14.0g / l sodium sulfate, polyester ..

5.0 g / l graying inhibitor.

100 ml of this stock solution were diluted to one liter with tap water at 10 ° dH. The samples were evaluated for 10 minutes at 100 revolutions per minute of the Terg-O-Tometer washed 3 times then rinsed with distilled water, dried and photometrically at 6O ⁰ C

Temperatures from 150 to 170 ⁰ C heated until the formation of the water of reaction was complete. The polyester was reacted in the molten state at 150 to 160 ^° C. with 130 g (1.06 mol) of propane sultone, part of the reaction product was dissolved in water with the addition of the equivalent amount of sodium hydroxide solution and adjusted to a content of 10 g of ester salt per liter. The amounts of this solution given in the tables below were added to the wash liquors. ■ · ■■ · ■. : τ ■ "■ ':: ■ · -....., - ■ / ·. ·:.

Example 2

116 g (1 mol) of maleic acid, 147 g (1 mol) of N-propyl diethanolamine and 250 g of xylene were together with

1 g of p-toluenesulfonic acid in a distillation apparatus which was provided with a device for separating the water and recycling the solvent, heated until no more water separated in the receiver. The insoluble resin formed was poured off the xylene and the residue was freed from residual solvent in vacuo. The residue was treated with a 10% strength aqueous solution of sodium bisulfite (a total of 190 g Na ₂ S ₂ O ₅ accordingly

2 mol) cooked until completely dissolved. The solution was also to a content of 10 g of ester salt per liter.

The results of the washing tests are compiled in the following tables. The graying polyester fabric was washed according to method A (redeposition method) after every 5 washes certainly. The washing tests with polyamide fabric were carried out according to method B (deposition method) performed. The abbreviation CMC means carboxymethyl cellulose (Na-Salz), which is used for Comparison was used.

The results show that the agents according to the invention are clearly superior to carboxymethyl cellulose.

Substrate (method A) inhibitor

(according to
Example)

CMC

% Retnission at a concentration of the inhibitor of

Og / 1 I 0.1 g / l I 0.2 g / l I 0.5 g / l

44.1
44.1
44.1

40.7
50.0
47.2

41.7
52.5
47.5

43.5 56.0 50.4

■ "'■: ..... Example 1

146 g (1 mole) of adipic acid and 273 g (1 mole) of dodecyl diethanolamine were stirred to Tem

55

Substrate Inhibitor
(according to % Remission in one
Soot addition of 1.0 g / i 1.5 g / l (Method B) Example) 0.2 g / l 0.5 g / l 55 51 Polyamide.. without 68 64 56 51 CMC 68 64 59 55 1 69 68 59 55 2 ::. 72: 67

Claims (2)

1 2 ten polyesters were produced by known processes. Aliphatic, cycloaliphatic and aromatic, saturated or 1. Detergents and cleaning agents, g e k e η n-unsaturated dicarboxylic acids are used, the characterized by a content of 0.1 to 5 up to 20 carbon atoms, esp-20 Percentage by weight, based on the total special weight of malonic, amber, glutar, adipine, seba the means of water-soluble salts of mono-, maleic and fumaric acid or benzene dicarboxylic polyesters, their acid component from an acid and their mixtures. The ones in question Dicarboxylic acid residue and their ^ alcohol dialkanolamines are derived from alcohols with 1 to 6, component is from dialkanolamines or io preferably 2 to 3 carbon atoms and can the N-substituted derivatives thereof and the straight-chain or branched, saturated or unsaturated by introducing sulfonic acid groups or, on the nitrogen atom, by means of aliphatic, cyclo-alkylsulfonic acid groups water-solubilized aliphatic or aromatic, are 1 to 18 carbon, substituted hydrocarbon radicals containing atoms 2. Means according to claim 1, characterized to be 15. Examples of such substituted alkanolamines due to a content of soluble alkali salts which are N-methyldiethanolamine, N-methyldipropanol-carboxymethyl cellulose. amine, N-ethyl diethanolamine, N-propyldipropanol- amine, N-propylenediethanolamine, N-butyldiethanolamine, N-dodecyl diethanolamine, N-oleyl diethanol 20 amine, N-cyclohexyldipropanolamine and N-phenyl- diethanolamine. The esterification of the reaction components, which are preferably used in a molar ratio of 1: 1, It is known that detergents and cleaning agents are carried out in a known manner, for. B. by several hours contain surface-active compounds, substances 25 heating under normal pressure in a vacuum or in add that the dirt-carrying capacity of the washing presence of a solvent with which the reac- improve speed. Such, in the following can be distilled off azeotropically as conversion water. By substances designated as graying inhibitors prevent the addition of conventional esterification catalysts, in particular an absorption of the detached dirt on the other strong inorganic or organic acids, cleaned surfaces. Most of the time, the implementation can be accelerated. Instead of around polyanionic polymers, which either consist of natural or free dicarboxylic acids can also react with substances, such as cellulose, gelatin or glue or through derivatives capable of movement, such as anhydrides and halides, Polymerization of vinyl compounds, such as acrylic, are used as starting materials. Likewise can acid, methacrylic acid, maleic acid and their gel the dicarboxylic acids in the form of their dimethyl or mixing with copolymerizable olefins produced 35 diethyl esters with the alkanolamines in the presence will. The polysulfonates of vinyl polymers are also conventional transesterification catalysts in a known manner have already been interesterified as graying-inhibiting additives. recommended for detergents and cleaning agents. From the introduction of the sulfonic acid groups takes place however, the compounds in question are also made according to known methods. Unsaturated only the carboxymethyl cellulose is a larger tech- 40 polyester, for example those made from maleic acid and niche importance, especially since they are dialkanolamines or those in which the am graying-inhibiting effect of all known hydrocarbon residues in nitrogen atom synthetic polymers. The carboxy-saturated can be caused by the addition of alkali methyl cellulose and also the synthetic bisulfites mentioned on the double bonds in the sulfonates However, polymers have the disadvantage that their 4S are converted. Also the sulfonation of the double graying reducing agent Effect on cellulose bonds with complex compounds from sulfur fibers is limited, while they are trioxide and an organic compound, such as when washing of synthetic fiber material, especially such pyridine, dioxane or Ν, Ν-dimethylaniline, is possible Polyamides, polyesters and polyolefins, practically borrowed. In the same way, saturated PoIytisch are ineffective. This disadvantage turns out to be sulfonated as esters in which the acid residue, such as especially compared to white textiles made from synthetic malonic acid residue, a reactive methylene fiber or mixed fabrics from synthesis and cellu groups. Loose fibers noticeable in spite of use can also be unsaturated or saturated frequent washing irreversibly graying and thus polyester with quaternizing agents, which 2 to 6 carbon become unsightly. 55 carbon atoms and a sulfonic acid or sultone The task was to develop a means, included group, to be implemented. examples for which does not have the disadvantages mentioned above. such quaternizing agents are haloalkyl The invention relates to a washing and sulfonic acids or their salts such as 1-bromopropane ■ Cleaning agent characterized by a content of 3-sulfonic acid and 1-chloroethane-2-sulfonic acid or from 0.1 to 20 percent by weight, based on the 60 their alkali salts, furthermore alkane sultones such as propane Total weight of the means, of water-soluble salts sultone or butane sultone. It is formed at this one of polyesters, the acid component of which results from a reaction of polymeric sulfobetaines or salts of Dicarboxylic acid radical and their alcohol com-N-alkylsulfonic acids. The sulfobetaines can be used as component is derived from dialkanolamines or theirs or after neutralization of the sulfonic acid group Derived from N-substituted derivatives and which are used by 65 in the detergents and cleaning agents. Introduction of sulfonic acid groups or alkyl- The ratio of sulfonation or quatre- sulfonic acid groups are made water-soluble. Nating agent to polyester is preferably so The salt contained in the new detergents selected so that after the reaction to 2 dicarbon