DE1617123B2 - - Google Patents

Description

3 4

During the sulfonation, the free sulfonic acids are A) "Redeposition" method (also under the name

these are then neutralized. »Backwashing method« known), which means

The sulfone produced in the given manner understands the common washing of soiled polyesters containing acid groups or their alkali and clean textile goods,
and ammonium salts are in organic solutions. 5 B) »Deposition method, in which the clean textile agents are insoluble, but easily soluble in water. Items in an artificially soiled liquor They can still be washed down in small quantities.

molecular esters or unreacted Aus -.... λ-V

Contain raw materials that are produced by extraction with the A) Redeposition method '·,; :) ■ - ■.

niche solvents removed and again to the um- io ■:

Settlement can be brought. Since this connection- Im Launder-Ometer® (ATLAS, Chicago, USA.)

In order to improve the cleaning properties of the agents, however, 4 lobes were taken from each of the substances to be examined

do not affect, a separation in the general synthetic tissue of 8.3 g total weight together

mean not necessary. ^: -. ■ with 1.3 g of an artificially soiled cotton

Washed up to five times for 30 minutes due to the insolubility of the high molecular weight yarns. Thereafter, bonds in organic solvents and the reflection value was determined with a photometer based on their content of low molecular weight components (Elrepho® from Carl Zeiss, using the usual methods of a molecular filter no. 6 if the failure failed). :
weight determination. Degree of polymerisation and molar weight of the polyester for soiling the cotton yarn can therefore not be specified with a practical dust-sebum combination of sufficient accuracy. was made of a mixture of kaolin, iron oxide

The manufacturing process described above black, soot and synthetic skin oil (from ¹ J ₃ fatty

W is not the subject of the protection request. acids, ¹ I ₃ fat and ¹ J ₃ hydrocarbons). That

The detergents can contain any water-soluble cotton yarn, after soiling, about salts of the sulfonic acid groups according to the invention containing about 2% pigments and about 2% skin oil,
containing polyester, preferably alkali. A detergent made from combined metal and ammonium salts was used. Settlement under ammonium salts

the salts of organic ammonium bases sin-d to _{2Q0 / n} _ _Dod ecylbenzolsulfonat (Na salt)

to understand. The polyesters can add 2.5% coconut fat alcohol sulfate (Na-Salz) to detergents,

can also be added in the form of free sulphonic acids, 30 2.5% tallow fatty alcohol sulphate: (Na-Salz),

if alkaline reacting substances in one for the _40% sodium pyrophosphate,

Sufficient surplus is present. ₀ to 10% graying inhibitor,

The new detergents and cleaning agents can be divided into ₂ 5 to 35% sodium sulfate,

solid, especially powdery form or in the form of '

Solutions or pastes are available. Because of the good 35 with the application concentration 5 g / l and the

The water solubility of the polyester salts is due to the hardness of the tap water used was 10 ° dH,

position of liquid detergent concentrates in particular The cotton samples were at 90 ⁰ C and a

suitable. Such liquid preparations can be used in addition to a liquor ratio of 1:12 (liquor 115 ml), the samples

the above-mentioned components also hydrotropes from synthetic tissue at 60 ° C and a liquor

Substances such as low molecular weight alkylbenzenesulfo- 40 ratio of 1:30 (liquor 290 ml) each 30 minutes

nate, urea and organic solvents. Then the four times with the

keep. rinsed, dried and cleaned water

In some cases, for example when washing ironed samples, evaluated photometrically.

Il textile materials made of cellulose or regenerated _ ,. -. . »,. ,

"Cellulose, the washing effect can be achieved by adding 45 ^B) ^ eposiüon-method

common graying inhibitors, especially carb- The test according to this method was carried out with strand-

oxymethylceÜulose, can still be increased. The goods in the Terg-O-tometer® (United States Testing

using amounts of carboxymethyl cellulose be Company, Hoboken, USA.). 10 g

carry about 0.1 to 3%, based on the total strand of the corresponding substrate were in

weight of the means. 50 11 washing liquor (liquor ratio 1: 100) with addition

The new means are suitable for cleaning values of 0.2; 0.5; 1.0 and 1.5 g of standardized carbon black

Objects of all kinds, but in particular for each 5% use of the item to be examined

Washing of textiles that have been washed from synthetic or cellular graying inhibitors,

loose fibers, made of regenerated cellulose or made of gel. The detergent used consisted of one

mix the types of fibers mentioned are produced. 55 liquid preparation of the following composition:

In comparison with known detergents _{7 8 / n}} facilitate _ _D odecylbenzolsulfonat (Na salt)

w ^U - ^e " ⁿ ^? ¹ χί ^η washing process and increase the _{ug / 1} coconut fatty alcohol sulfate (Na-Salz),

Degree of whiteness of the wash. 1.1 g / l tallow alcohol sulfate (Na-Salz),

16.0 g / l sodium pyrophosphate,

Examples 14.0 g / l sodium sulfate,

50.0 g / l graying inhibitor.

The graying-inhibiting effect of the from this stock solution were in each case 100 ml with

The compounds described in the following examples tap water diluted at 10 ° dH to one liter,

was tested according to known methods [cf. 6 ₅ The samples were stored at 60 ° C for 10 minutes at 100

H. St up el "Textil-Praxis" Vol. 3, p. 264 (1954) and rotations per minute of the Terg-O-tometer washed,

J. W. Ha η d 1 e y »Journ. of Amer. Oil Chem. Soc. «Then rinsed 3 times with distilled water,

Vol. 42, pp. 993 to 997 (1965)]. These are the dried ones and evaluated photometrically.

Inhibitor A

196 g (2 mol) of maleic anhydride, 125 g (2 mol) of anhydrous ethylene glycol and 500 ml of xylene were together with a drop of concentrated sulfuric acid in a distillation apparatus equipped with a Reflux condenser and a device for separating the water and recycling the solvent was provided, heated until no more water of reaction separated in the template. To Distilling off the xylene, the polyester was treated with a solution of 230 g of anhydrous sodium pyrosulfite (corresponds to 2.4 mol of sodium hydrogen sulfite) in 400 ml of water until completely dissolved under reflux cooked. By boiling with 140 ml of 10% hydrogen peroxide and neutralization with sodium hydroxide solution any excess sodium hydrogen sulfite still present was converted into sodium sulfate. the The solution was adjusted to a polyester content of 10 g / l and the detergent mixtures described below added in appropriate amounts.

Inhibitor B

According to the information in Example 1, a was made from 98 g (1 mol) of maleic anhydride and 107 g (1 mol) diethylene glycol produced polyester with 76 g of sodium pyrosulphite (corresponding to 0.8 mol of sodium hydrogen sulphite) partially sulfonated.

Inhibitor C

As described in Example 1, a polyester was prepared from 1 mol of 1,2-propylene glycol and 1 mol of maleic anhydride and completely sulfonated with excess sodium hydrogen sulfite (1.3 mol). - ^: - ■ '-

"^; " ~ ^{J ;; v} ; Inhibitor D ::: -;:!

A sulfonated polyester was obtained from 1 mol of 1,4-butaldiol and 1 mole of maleic anhydride using 1.3 moles of sodium hydrogen sulfite.

A sulfonated polyester was also prepared from maleic acid and 1,2-hexanediol (compound E) for comparison.
The results of the washing tests are given in the following

compiled in the same tables. The graying polyester fabric was washed using method A (redeposition method) after every five washes determined, while the experiments with Perlori fabric according to method B (deposition method) were made. The abbreviation CMC means carboxymethyl cellulose.

Table 1

example Substrate Inhibitor % Remission at a concentration of the inhibitor of 0.2 g / l 0.5 g / l (Method A) Og / 1 0.1 g / l 41.7 43.5 polyester CMC 44.1 40.7 56.0 58.1 1 polyester A. 44.1 50.0 56.2 58.5 2 polyester B. 44.1 52.0 54.6 55.0 3 polyester C. 44.1 51.0 50.2 51.1. 4th polyester D. 44.1 48.8 44.2 47.0 - polyester E. 44.1 44.7

Table 2

example Substrate Inhibitor 0.2 g / l ό remission at a soot addition of 1.5 g / l (Method B) 68 51 polyamide without 68 51 - polyamide CMC 71 55 5 polyamide A. 73 56 6th polyamide B. 71 54 7th polyamide C. 70 55 8th polyamide D. 68 52 - polyamide E. 0.5 g / l 1.0 g / l 64 55 64 56 65 58 68 60 66 59 67 57 63 55

Claims (5)

which are converted into sulfonates by reaction with alkali bisulfites. These polyesters can be used as detergents and cleaning agents, they have 1. Detergents and cleaning agents, geke η η- but practically no graying-inhibiting properties are characterized by a content of 0.1 to 5 properties compared to textiles made from synthetic fibers. 20 percent by weight, based on the total. Polyesters made from diols, the polyesters containing sulfonic acid groups, the acid component of which is less than the specified number of carbon atoms and consists of maleic acid residues, because of their constitution is too hydrophilic and whose alcohol component is different from glycols and is therefore wetting, but not satisfactory with 2 to 4 Carbon atoms or their polygons could have cleaning properties,
ether derives, where the ratio of the number of 2. Means according to claim 1, in which the 15 substances is effective. Polyester of ethylene glycol and / or propylene object of the invention is a washing and cleaning Derive glycol ......... agent, characterized by a content of 3. Composition according to claim 1, in which the polyesters 0.1 to 20 percent by weight, based on the total of polyethylene glycols or polypropylene weight of the means, of water-soluble salts of su / glycols with 2 to 10 glycol ether groups. 20 polyesters containing formic acid groups, the acidic 4. Means according to claim 1 to 3, in which the component consists of maleic acid residues and their Molar ratio of maleic acid to dihydric alcohol component differs from glycols with 2 to alcohol 1.1: 0.9 to 0.9: 1.1. 4 carbon atoms or their polyethers derived, (_ 5. Means according to one or more of the preceding- wherein the ratio of the number of maleic acid residues to going claims, characterized by one of the number of sulfonic acid groups is 2: 1 to 1: 1. Content of soluble alkali salts of the carboxy-die in the new detergents in salt form pre-methylcellulose. Hanging polyester containing sulfonic acid groups * _t are manufactured using known processes. as Glycols suitable for starting materials are ethylene glycol, 30 1,2-propylene glycol, 1,3-propylene glycol and the various Isomers of butylene glycol. There are also di-, tri- and polyglycols, in which the glycols Contains 2 to 4 carbon atoms and the number of It is known that detergents and cleaning agents containing glycol ether groups from 2 to 10 can be used. Even contain surface-active compounds, substances as well as the aforementioned glycols or glycol ethers add that the dirt-carrying capacity of the washing can be used. Preferably from improve speed. Such, hereinafter referred to as ethylene glycol and propylene glycol or their graying inhibitors designated substances prevent ether run out. The esterification of the glycols or polyglycols with cleaned surfaces. It is mostly about maleic acid or maleic anhydride takes place in the case of polyanionic polymers, which are either made from natural, for example, by heating the manure substances for several hours, such as cellulose, gelatin or glue, or by mixing, optionally in the presence of conventional polymerisation of vinyl compounds, such as acrylic esterification catalysts the water of reaction acid, methacrylic acid, maleic acid and their mixture produced by the application of reduced pressure or by mixing with copolymerizable olefins, which forms an azeotrope with water, are eliminated. Even the polysulfonates can be removed from vinyl polymers. The production of polyglycols as graying-inhibiting additives to polyester can also be carried out in such a way that detergents and cleaning agents are recommended. Of the compounds initially involved in 50 mole percent of maleic acid with alkylene, however, only the oxides, such as ethylene oxide, propylene oxide or butylene carboxymethyl cellulose, a larger technical 50 oxide, have been converted in the usual way, whereupon the resulting ones gain significance, especially since they are in Their graying-inhi- polyglycol esters with a further 50 mole percent maleic acid effect, all known synthetic acid or maleic anhydride are esterified,
table polymers. The carboxymethyl- The molar ratio of glycol to acid or acid cellulose and the synthetic polyanhydride mentioned should be 1.1: 0.9 to 0.9: 1.1. The mers have the disadvantage, however, that their reduction in the molar ratio within this range, which reduces graying on cellulose fibers, limits the degree of polymerisation within certain limits, while they vary when washing from syn. In the interest of a good graying-aesthetic fiber material, in particular those with a protective effect, however, a high degree of polymeri-polyamides, polyesters and polyolefins, practically a degree of sations, should be aimed for. To avoid a pre-ineffective. This disadvantage makes itself - 60 early chain termination, therefore a molar ratio is preferred especially compared to white textiles from synthetic, which is as close as possible to 1: 1,
fibers or blended fabrics from synthetic and cellular The introduction of sulfonic acid groups is expedient Loose fibers are noticeable, which, despite frequent, moderately due to the build-up of alkali metal washing irreversibly gray and thus unsightly sulfite on the double bond or even under verenlich will. 65 preparation of common sulfonating agents, such as chlorosulfone US Pat. No. 2,454,546 discloses upper acid or sulfur trioxide in the presence of inert ones Surface-active polyesters made from maleic acid and 6 bis solvents, in particular from dioxane and pyridine Diols containing 18 carbon atoms known, or Ν, Ν-dimethylene aniline, made. So far