DE2149737B2 - LAUNDRY DETERGENT - Google Patents

Description

The present invention relates to detergents, ins- carboxymethylated sucrose, lactose or ratfinose, special textile detergents, and is concerned with new containing _5. Surprisingly, however, the type of additives for those detergents which are suitable for use in accordance with the invention and which have been found to be used in detergent compo-oligosaccharides as builder substances that are significantly more effective in washing detergents are completely or partially suitable. The invention relates to detergents that

In addition to washing-active substances, detergents contain a carboxymethylated oligomer such as anionics, e.g. B. alkylbenzenesulfonates, saccharide degradation product of starch, whose viscosity or nonionics, dirt carriers, such as carboxymethyl in 10 ⁰ _{; o} iger aqueous solution below 250 cP, preferably cellulose and other additives, such as visually below 50 cP and especially below 25 cP, Brighteners, especially large amounts of builder.

substances, which are usually used in amounts of about 35 percent by weight of the detergent composition pre-derivatives used according to the invention are preferably obtained by reaction Cherish. of chloroacetic acid or its salts with oligosaccha

The function of a detergency builder is to ride in the presence of alkali. The implementation can according to L i η d η e r: »Surfactants, textile auxiliaries, detergents, both in an aqueous medium and in a non-aqueous medium raw materials «, Vol. II, Wissenschaftliche Verlagsgesell- 40 Medium. As a preferred team m. B. H. Stuttgart, 1964, p. 129? f., in the action media have water and with water Proven to strengthen the washing effect of washing-active submiscible alcohols. Such alcohols are punch. Known inorganic builders are alkali methanol, ethanol, isopropanol and propanol. metal carbonates, borates, phosphates, polyphosphates, Hydroxides can be used as alkaline components

bicarbonates and silicates. As organic substances 45 or carbonates of alkali metals or ammonium with builder properties are predominantly derivatives that are used.

Ethylenediaminetetraacetic acid, nitrilodiacetic acid and chloroacetic acid or their salts are used

and nitrilotriacetic acid known, as well as polymeric derivatives of acrylic acid, maleic acid and itacone are expediently set in such a proportion that the amount is used to etherify all free acid. Their builder properties are sufficient in the USA.-Pa- 50 OH groups of the saccharide. Different publication 3 308 067. of which higher or lower chlorine

The conventional builder substances, in particular acetic acid amounts, are used, however, it is the phosphates used for this purpose, not expediently, require less than 1 mol of chloroacetic acid serious sewage problems. So has to use for each monosaccharide unit. The emergency excessive use of phosphate, especially in the north- 55 agile amount of alkali, is calculated stoichiomeamerican and Scandinavian area to the eutrophic from the amount of chloroacetic acid used, phation of inland waters (J.Kandier, whereby it is advisable to use a small amount of news from Chemie und Technik, 19 [1971], p. 5). shot is worked.

The use of nitrilotriacetic acid as a phos- As saccharide component are the oligosaccharides

phatersatz in detergents also proved to be 60 suitable which occur during degradation of the starch, that is tricky, since the substance or its derivatives in preferably starch hydrolysates and their viscosity are accumulated organisms and there under in 10 ° / _0: ger aqueous solution under 250 cP, preferential circumstances, harmful side effects can develop below 50 cP and in particular below 25 cP. (Native types of starch show under these conditions

Also the proposed 65 viscosities of about 50,000 to 150,000 cP as builders, while synthetic high polymers are by no means as the viscosity of disaccharides is far below 1), The carbohydrate derivatives, which are used according to the invention as a detergent additive, are characterized by only very low degradability

extremely low viscosity, correspondingly good and cooling-off NaCl parted. The solution could be built into detergent formulations from the fold processability and complete water solubility builder.
the end. They are easily attackable by microorganisms, together with WHAT, magnesium silicate, sodium sulfate

for their part, however, promote algae growth and thus and optical brightener could not result in eutrophication from the solution. They only have a moderate slurry that can easily be sprayed kumplex-forming ability, which is avoided. let. By mixing with 20% perborate, trace elements became a heavy-duty detergent through irreversible complexation from the spray material,
be withdrawn from the ecological balance.
Such oligosaccharides are extremely easily accessible and their production costs come in the usual io B is ρ ie 1 4
Close to phosphate builders.

The carbohydrate 8 kg of seasoned potato starch used according to the invention were converted into 25 liters

derivatives can usually be suspended in water in detergents. 2.5 1 of an alkaline hypochlorite-used builder completely or partially - replacing the solution that contained 123.4 g / l active chlorine was added to - The amount used in detergents is therefore 15 and first 2 hours at 50 \ then * up to 70, preferably 25 to 45 Gev.ichtspruz.eiu, for 1 hour at 80 ^: stirred.

Drew on di (. detergent composition. A detergent according to the invention was added in portions to this starch solution Stirring under heavy washing active substances and other usual additives. The temperature was kept at 70 to 71 ^: Maintained.

The invention is reacted in the following examples were again 21 hypochlorite solution explained in more detail. The quantities are based on added and stirred for 30 minutes at 80 °, on weight. The resulting product showed in a washing test

25 good builder properties. example 1

Example 5

Native corn starch was _10/0 solution A / brought by hydrolytic degradation to a viscosity of 20.3 cP / ° 30 ° _o aqueous suspension of corn starch. 30 was adjusted to pH 2 with concentrated HCl and 80 parts of this was broken down. Starches were stirred with at room temperature. Samples were taken from the batch in 180 parts of sodium chloroacetate at 400 parts hot at regular intervals. As soon as water and treated with 120 parts of 50 ° / _o aqueous sodium hydroxide solution a 1: 2 diluted with water decoction of the alkalized. The mixture was boiled in a viscose flow for 4 hours under re-starch suspension after rapid cooling. The reaction process was then 43.8 cP, the hydrolyzed product was spray-dried and used as a builder. granular starch filtered off. 1 mole (based on anhydrous

glucose) this starch was in aqueous solution with 3 mol NaHO and 3.1 mol chloroacetic acid sodium

Example 2 _sa l _z according to Example 1 implemented. The product showed

40 excellent builder properties similar to those of the

The reaction according to Example 1 was repeated, the product from Example 1 corresponded, but with the difference that only half of them Amounts of sodium chloroacetate and caustic soda are used became. B e i s ρ i e 1 6

The reaction product was dried in an analogous manner

application process used as a builder. Potato starch was used in an analogous manner

1 nH ₂ SO ₄ hydrolyzed in 40 ° / ₀ aqueous suspension at 40 ° until a 10 ° / _o strength boiled 23.3 cP

Example 3 had. The degraded starch was analogous to

50 game 5 etherified. The oligosaccharide ether showed good In a 2-1 three-necked flask, the one with stirrer and washing action. Reflux condenser, 440 ml of water and 10 ml of 35 ° / _o strength H ₂ O ₂ were added. Example 7

In a beaker, 132 g

Caustic soda in 180 ml of water prepares a lye. 55 In a mixer (brand Drais), 400 kg 0,3 ml of this liquor was SUS stoffperoxyd in the Dieihalskolben overall potato starch with a solution of 2.5 kg of water, type and 160 g native corn starch with stirring (30 ° / _o solution) and 5.0 kg of ammonia (27%) suspended. The suspension was mixed intensively for 1 hour at 50 ° in 80 liters of water and slowly stirred at 60 °. Then 20 ml of the lye were draw-dried. The product showed in 10% aqueous give, with gelatinization occurred. The paste has a viscosity of 200 to 240 cP. lor viscosity rapidly; the degradation was 2 hours The reaction of the starch with sodium chloroacetate and

continued at 70 °. The entire sodium hydroxide solution was then carried out analogously to Example 1. This was obtained Lye added. an excellent detergent builder.

Every 15 minutes were total

360 g of sodium monochloroacetate in portions of 65 examples

90 g each and after the last addition

Stirring at 80 ° for 1 hour. The washing tests carried out are

almost colorless, thin-bodied solution, from which the following is tabulated when standing:

Test method

Deposinon test:

5 dirty washes on BW 10 mg carbon black I, 1 gi ASB

2 g / l test sub-liquor liquor 1:50 20 minutes / 90 degree of whiteness (Elrepho)

Lightening test:

Remission (in ° / ₀ ) of test soiled BW after

3 washes / 90 liquor 1:80 with lg / 1 ABS and

2 g / l test substance

the same., ohae ABS (self-washing ability)

Calcium deposit (ppm Ca) on BW after 5 washes Cu complexation (potentiometric) ⁰ Z ₀ Cu / 100 mg PS) \

Hydrophilic suspension against Fe ₂ O ₃ . Absorbance measured at E _{45 OiS}

According to the invention
ca rbox ymeihy I ized
Oligosaccharide
according to example 1

76.3

47

15th

130 to

99

62 Carboxy methyliei te

Sucrose loudly

Dutch

Disclosure document

002 714

75.1

46

up to 200

35
5

TPP

77.1

47

15th

20 to

100 184

This clearly shows that the washing values of the carboxymethylated oligo builders according to the invention

saccharide both in the deposition experiment with soot as

are always better even with normal soiled fabric

than with the comparable sucrose derivative. She ,

in many cases reach the value of tripolyphos without

phat approach. Also the self-washing ability of the carboxymethylated oligosaccharide according to the invention is significantly better than that of carboxymethylated

Sucrose. The complex-forming properties of the

carboxymethylated oligosaccharide according to the invention are higher than that of the sucrose derivative, what from the values for the calcium deposit and the

Copper complexing ability is clearly evident. Mined maize-Das The ability to form complexes for calcium is unetherified and roughly in the range of values for citric acid, however the substance according to the invention shows a clear retarding effect on calcium incrustation

in the tissue. The hydrophilic suspending capacity of Example 1

substance of the invention, ie the ability to hold hydrophilic particles in suspension, is as compared with phosphates not particularly excluded 45 _R.

shapes, but u, n orders of magnitude higher than example l

of carboxymethylated sucrose, according to Dutch laid-open specification 7 002 714.

_. . , "," Example 3

Example9 So ^v

The reaction products of Examples 1 to 7 were mixed with half the amount each

weight amount of ABS test formulations. With example 4

Washing tests were carried out according to the following scheme for the respective test formulations:

Cotton was in a liquor, which per liter Ig

Alkylbenzenesulfonic acid sodium salt and 2 g test example 5

substance (builder) contained, washed for 20 minutes at 90 °. The liquor ratio was 1:50, each Washing process became soot (lampblack 100 with

Lömg / lFlotte) added. The flaps were after Betspiel 6

Each wash is rinsed thoroughly in cold running water and dried. After 5 washes the optical white ground of the rag on the Zeiß-Elrepho- 65.

Device folded 4 times and underlaid with black example 7

Disk measured at 460 nm. Each measurement was carried out four times and the values were averaged.

More optical impression

black

White

Whiteness

Average

of whiteness

sure

32.3 29.6 30.6 31.2 76.9 76.9 77.2 / 7.4

29.6

30.8

30.3

28.9

76.4

76.4

76.1

76.1

74.0

74.6

74.8

74.8

76.4

75.9

76.4

76.5

75.0

75.5

74.8

75.1

76.1

76.3

75.8

76.2

75.5

76.1

76.3

75.6

77.2

77.1

76.8

76.6

30.9

77.1

29.9

76.3

74.6

76.3

75.1

76.1

75.9

Claims (3)

and therefore, under certain circumstances, patent claims in bodies of water: can cause damage that is not yet foreseeable. 1 j ^ an | la, therefore trying to use builders 1. Find detergents marked with that are biodegradable and already in -len a content of a carboxymethylated Oliso 5 modern sewage treatment plants can be destroyed. So saccharide degradation product of starch, whose vis- describes the German Offenlegungsschrift 2 041) -MR viscosity in 10%, a watery solution below 250 cP, a derivative of starch or cellulose, which as a result of oxyvorzuesweise under 50 cP "and especially under the influence of carboxyl groups and aldel -> 5 CP is carrying functions. These products stand out respectively 2. Detergent according to claim 1, characterized by more or less good biodegradability, that there are 5 to 70, preferably 25 to wedge off. Disadvantageous for the use of such 45 percent by weight of carboxymeth-based oligo- high-molecular-weight products as builders in detergents However, saccharide "contains" is their relatively high viscosity, in particular 3. Detergent according to claim 1 and 2, characterized when the high amount used for Bunder m don ^ indicates that the carboxymethylated oil iso 15 concerns detergent formulations. saccharide which is commonly found in washing seeds. It has now been found that carboxy, neth> hoard »Ended builder completely or partially replaced. Oligosaccharides, in particular the reaction products of chloroacetic acid with oligosaccharides, have excellent builder properties, however 2o have an extremely low viscosity and are volatile are constantly biodegradable. From the Dutch patent application 7 002 714 detergents are already known that