DE1617121C3 - Detergents and cleaning agents - Google Patents

Description

weight determination. Degree of polymerization and mole diarylpyrazoline sulfonic acid included. For controlling

The weight of the polyester cannot therefore be influenced by the foam behavior

specify with sufficient accuracy. Foam improvers, such as fatty acid amides or foam

The detergents can contain any water-soluble contraceptives, in particular trialkylmelamines.

Contain salts of the polyamides according to the invention, hold 5.

preferably the alkali metal and ammonium salts. The new detergents and cleaning agents can be used in

Ammonium salts also include the salts of organic solid, in particular powdery, or in the form of

to understand shear ammonium bases. The polyamides are solutions or pastes. Because of the good ones

The detergents can also be used in the form of the free water solubility of the polyamide salts

Acids are added, provided that the production of liquid detergent concentrates has an alkaline reaction.

Substances suitable in a form sufficient for salt formation. Such liquid preparations can

Excess are present. in addition to the above-mentioned components also hydro-

In addition to the salts of the polyamides, the tropics contain substances such as low molecular weight alkylbenzene

new detergents and cleaning agents in such sulfonates, urea and organic solvents

Agents customary surface-active substances, for example 15 contain. ....'..... ■■

such as those of the sulfate or sulfonate type, such as in some cases, for example when washing

primary and secondary alkyl sulfates as well as the sulfates of textile materials made of cellulose or regenerated

Ethoxylated or propoxylated fatty alcohols, as well as cellulose, can increase the detergency by adding them

Alkylbenzenesulfonates, primary and secondary olefin-customary graying inhibitors, especially carb-

sulfonates, alkyl sulfonates and -sulfo fatty acid esters. “O oxymethyl cellulose, to be increased. The to-

Other compounds of this class, which may be used in amounts of carboxymethyl cellulose,

. Can be used, the higher molecular weight are about 0.1 to 3%, based on the total weight

j laren sulfated partial ethers and partial esters of several of the agents.

valuable alcohols, the ethoxylated sulfates or the new agents are suitable for cleaning

propoxylated fatty acid amides and alkylphenols, as objects of all kinds, but especially for

also fatty acid taurides and fatty acid isethionates and washing of textiles, which are made of synthetic or

their homologues. The alkali soaps are also suitable from cellulose fibers, made from regenerated cellulose or made from

of 'fatty acids as well as the fatty acid condensation mixtures of the fiber types mentioned are made,

products made from amino acids or degraded protein- Compared to known detergents make this easier

fabrics. Ampholytes such as alkyl betaines also add new agents to the washing process and increase the washing process

and alkyl sulfobetaines in question. The means can change the whiteness of the laundry, furthermore non-ionic washing active substances, such as

Alkyl and acyl polyglycol ethers, alkylphenol poly-.

glycol ether, mixed condensates from polyethylene glycol Examples

and polypropylene glycol, fatty acid sugar ester, amine-35

contain oxides and fatty acid alkanolamides. The anti-graying effect of the in the

The compounds mentioned can also be mixed with the compounds described in the following examples

be applied. If the connections have been tested according to known methods (cf.

Aliphatic hydrocarbon residue should have the- H. St up el, "Textil-Praxis", Vol. 3, p. 264 [1954],

ser should preferably be straight-chain and 8 to 22 carbon 40 and J. W. H a η d 1 e y, »Journ. of Amer. Oil Chem.

substance have atoms. In the connections with Soc ", Vol. 42, pp. 993 to 997 [1965]). These are the ones araliphatic hydrocarbon radicals contain the

preferably unbranched alkyl chains on average A) »Redeposition method (also under the name

; ; 6 to 16 carbon atoms. »Backwashing method« known), which means

The new detergents and cleaning agents can wash dirty things together

also according to their respective use. and understand clean textile goods,

intended purpose contain other common constituents, B) "Deposition" method, in which the clean

such as pyrophosphates, polyphosphates and higher con- textiles in an artificially soiled

condensed phosphates and silicates are washed in the form of their liquor.

Alkali salts, also oxygen-releasing or active 50

chlorine-containing bleaches, such as alkali perborates, alkali ·· ■■ »# 'u j

percarbonates, alkali hypochlorites, chlorinated cyanuric A) Redeposition method acids and their alkali salts and neutral salts, such as

Magnesium silicate and sodium sulfate. In addition, 4 lobules were made in the Launder-Ometer

Sequestrants, in particular alkali salts of the synthetic tissue to be examined of 8.3 g

Aminopolycarboxylic acids, e.g. the sodium salts of the total weight together with 1.3 g of an artificial

Aminotriacetic acid or the ethylene diamino tetra soiled cotton yarn 30 minutes up to

acetic acid and the alkali salts of hydroxyalkyl washed five times. Then the reflection

diphosphonic acids and aminopolyphosphonic acids, value determined with a photometer.

E.g. the disodium salt of l-hydroxyethane-l.l-di- 60 The used to soil the cotton yarn

phosphonic acid or the hexasodium salt of the amino-practical dust-sebum-combination consisted of

tri- (methylenephosphonic acid), be present. a mixture of kaolin, iron oxide black, carbon black

^{Substances and synthetic skin oil (from 1} J ₃ fatty acids, ¹ I ₃ fat) are also used as ingredients in the mixture

for regulating the pH value, such as sodium and V3 hydrocarbons). The cotton yarn is

carbonate, sodium bicarbonate, lactic acid and Citro-65 held about 11% pigments after soiling

nenic acid. and about 2% skin fat.

The agents can also contain optical brighteners, such as a detergent composed of

Derivatives of diaminostilbene disulfonic acid or of sedimentation

20% n-dodecylbenzoisulphonate (sodium salt),
2.5% coconut fat alcohol sulfate (Na-Salz),
2.5% tallow alcohol sulfate (sodium salt),

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 incubated at 90 ⁰ C and a liquor ratio of 1: 30 washed 30 minutes (liquor 290 ml): 12 (115 ml liquor), the samples of synthetic tissue at 60 ° C and a liquor ratio of Figure 1. The samples, which had been rinsed four times with distilled water, dried and ironed, were then evaluated photometrically.

B) Deposition method

The test according to this method was carried out with rope in the Terg-O-tometer. 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-dodecylbenzenesulfonate (sodium salt),
1.1 g / l coconut fatty alcohol sulfate (sodium salt),
1.1 g / l tallow alcohol sulfate (sodium salt),

16.0 g / l sodium pyrophosphate,

14.0 g / l sodium sulfate,
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 washed at 6O ⁰ C for 10 minutes at 100 revolutions per minute of the Terg-O-Tometer, then 3 times with distilled water, rinsed, dried and evaluated photometrically.

For example, 1

192 g (1 mole) of anhydrous citric acid, 108 g (1 mole) of hexamethylenediamine and 500 ml of xylene were in a distillation apparatus with a device for separating the water and recycling of the solvent was provided, heated until there is no water of reaction in the template more farewell. The xylene was poured off from the resulting insoluble resin and the residue dried in vacuum. The polyamide dissolved in 2N NaOH with stirring. The excess lye (about 5%) was neutralized with dilute sulfuric acid and the neutral solution was adjusted to a polyester content of 10 g / l. From this solution were Appropriate amounts were added to the washing liquors.

The following were implemented accordingly:

example

2
3
4th
5
6th

acid

Moles of citric acid
Moles of pyromellitic acid
Moles of pyromellitic acid

Moles of nitrilotriacetic acid

Mixture of:
0.5 moles of nitrilotriacetic acid
0.5 moles of maleic acid

Diamine

1 mole of ethylenediamine

1 mole of ethylenediamine

1 mole of hexamethylenediamine

1 mole of hexamethylenediamine

1 mole of ethylenediamine

The results of the washing tests are compiled in the following tables. The graying of polyester fabric was made according to method A

as (redeposition method) after every 5 washes. The washing tests with polyamide fabric were carried out according to method B (deposition method). The abbreviation CMC means carboxymethyl cellulose (Na salt), which was used for comparison.

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

45 Inhibitor % Remission with a conc 0.1 g / l 0.2 g / l ran (like tration of the inhibitor ι 0.5 g / l (Method A) Example) Og / 1 40.7 41.7 46.0 47.0 43.5 polyester CMC 44.1 46.0 46.5 47.5 3 44.1 45.4 45.6 46.5 4th 44.1 45.8 46.0 47.2 5 44.1 47.0 6th 44.1

Substrate
5 ° 55 Inhibitor
(according to % Remission in one
Soot addition of 1.0 g / l 1.5 g / l (Method B) Example) 0.2 g / l 0.5 g / l 55 51 polyamide CMC 70 64 65 60 1 73 67 58 54 2 72 65 58 55 3 70 65 63 60 4th 74 71

Claims (5)

1 2 of polyamides containing free carboxyl groups, claims: the acid component of which consists of a tricarboxylic acid residue and / or tetracarboxylic acid residue and in which 1. Detergents and cleaning agents, known to contain diamines 2 to 18 carbon atoms, characterized by a content of 0.1 to 5. Such polyamides can also be used 20 percent by weight, based on the total, in which up to 50 mol percent of the tri- or weight of the means, in water-soluble salts tetracarboxylic acids are replaced by dicarboxylic acids, of poly containing free carboxyl groups. their acid component from a tri-hold polyamides are known Vercarbonsäurerest and / or tetracarboxylic acid residue produced. The starting materials are all and in which the diamines 2 to 18 carbon-phatic, cycloaliphatic and aromatic tri- or Contain material atoms. Tetracarboxylic acids in question, especially citric 2. Agent according to claim 1, in which up to acid, tricarballylic acid, nitrilotriacetic acid, ethylene-50 Mole percent of the tri- or tetracarboxylic acids diaminotetraacetic acid, cyclohexane tricarboxylic acid, are replaced by dicarboxylic acids. 15 trimesic acid, oxytrimesic acid and pyromellitic 3. Composition according to claim 1 and 2, in which the acid. The acids mentioned can contain up to 50 mol diamines Contain 2 to 12 carbon atoms. percent by aliphatic or cycloaliphatic, 4. Means according to one or more of the pre-saturated or unsaturated as well as aromatic Diaausgabe Claims in which the molar carboxylic acids, such as malonic, amber, glutar, adi ratio from polyvalent carboxylic acid to ao pin, sebacic, maleic and fumaric acid as well as benzene diamine 1.1: 0.9 to 0.9: 1.1. dicarboxylic acids. The ones to use 5. Agents according to one or more of the pre-polybasic carboxylic acids generally contain outgoing claims, characterized by up to 20 carbon atoms. a content of soluble alkali salts of the carb- The eligible, preferably 2 to oxymethyl cellulose. as diamines containing 12 carbon atoms can straight-chain or branched, saturated or unsaturated, cycloaliphatic as well as aromatic and hetero- Atoms, such as O, N, and S, may be interrupted. Examples * 'for such diamines are ethylene diamine, propylene 30 diamine, tetramethylene diamine, pentamethylene diamine, It is known that detergents and cleaning agents contain hexamethylenediamine, p-phenylenediamine, benzidine, contain surface-active compounds, substances piperazine, 4,4'-diaminodiphenylsulfone and 4,4'-dizueto add, the dirt-carrying capacity of washing aminodiphenyl ethers. improve speed. Such, hereinafter referred to as Ver. The representation of the polyamides takes place in a known manner The substances designated as graying inhibitors can be prevented in ways, for example by heating for several hours a resorption of the detached dirt on that of the mixture consisting of acid and diamine cleaned surfaces. It is usually in a vacuum or in the presence of a solvent, to polyanionic polymers, either from which the water of reaction is distilled off azeotropically Natural substances such as cellulose, gelatine or glue can be. Instead of the free di, tri or or by polymerizing vinyl compounds, 40 tetracarboxylic acids can also react like them Acrylic acid, methacrylic acid, maleic acid and capable derivatives, e.g. B. the anhydrides as their starting point Mixtures, substances with copolymerizable olefins, are used. getting produced. Even the polysulfonates of vinyl- By the choice of the molar ratio of poly- polymers have already been recommended as graying-inhibiting carboxylic acids for diamine within a preferred additive for detergents and cleaning agents. In the range from 1.1: 0.9 to 0.9: 1.1, the degree of polymerization of the compounds in question varies within certain limits; in its effect, however, a high degree of polymerisation graying-inhibiting effect is all known to be aimed for. Exceeds synthetic polymers to avoid premature chain ends. The carb- 50 termination is therefore preferred a molar ratio, oxymethylcellulose and also the mentioned synthetic- which is as close as possible to 1: 1,
However, see polymers have the disadvantage that the prepared in the manner indicated, free their graying-reducing effect on polyamides containing cellulose carboxyl groups are of fibers is limited, while washing them resinous consistency, in water and in organic of synthetic fiber material, especially sol- 55 insoluble in solvents, in dilute alkaline solutions chem made of polyamides, polyesters and polyolefins, but easily soluble. They can still be underpractical ineffective. This disadvantage makes decent amounts of low molecular weight amides in particular compared to white textiles made from syn or unreacted raw materials, theses fibers or blended fabrics from synthetic fibers and those produced by extraction with organic solvents Cellulose fibers are noticeable, which are removed during use despite 60 and possibly again for implementation frequent washing irreversibly gray and can therefore be brought. Because these connections become unsightly. but not the cleaning properties of the agents The task was to develop a means that is detrimental to separation in general which does not have the disadvantages mentioned above. not mandatory. The invention relates to a washing and 65 Due to the insolubility of the high molecular weight cleaning agent, characterized by a content of bonds in organic solvents and on from 0.1 to 20 percent by weight, based on their content of low molecular weight fractions Total weight of the agents, the usual methods of molecular weighting of water-soluble salts fail