DE2149737A1 - LAUNDRY DETERGENT - Google Patents

Description

DR. ING. A. VAN DERWERTH DR. FRANZ LEDERER

21 HAMBURG 90 β MUNICH 80

WILSTORrER STR. 33 ■ TIU (04 III 77 08 61 LUCILE-CRAHN-STR. S3 · TlL. ΙΟβΙΙ) 440 «4«

"Munich, October 1, 1971 L / My

Applicant: Diamalt Aktiengesellschaft, Munich 13> Friedrichstrasse 18th

laundry detergent

The present invention relates to detergents, in particular laundry detergents, and is concerned with novel additives for those detergents which are suitable, the builder substances usually used in detergent compositions completely or partially to replace.

In addition to detergents such as anionics, detergents contain e.g. alkylbenzenesulfonates, or nonionics, dirt carriers such as carboxymethyl cellulose and other additives such as optical Brighteners, especially larger amounts of builder substances, usually in amounts of about 40 wt .- ^ of the detergent composition are present.

The function of a detergent builder is according to Lindner: "Tenside Textile ^{Auxiliaries Washing Raw Materials 11} , Volume II, Wissenschaftliche Verlagegesellschaft mbH Stuttgart, 19 ^ 4, p. 1299 *". » in

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the enhancement of the washing effect of washing-active substances. Known inorganic builders are alkali metal carbonates, -borates, -phosphates, -polyphosphates, -bicarbonates and -silicates. As are organic substances having a builder property mainly derivatives of ethylenediaminetetraacetic acid, the NitriJadiessigsäure and the nitrilotriacetic acid known, as well polymeric derivatives of acrylic acid, maleic acid and itaconic acid. Its builder properties are in USP 3,308,067 described.

The conventional builders, in particular the phosphates used for this purpose, cause serious k wastewater problems. Thus, for example, excessive phosphate application, especially out in the North American and Scandinavian countries to the eutrophication of Binnengewässarn (J.Kandier, news from chemistry and technology, 22 * O97 ¹⁾ 5 x) · ^Th e use of nitrilotriacetic as a replacement for phosphate in detergents proved also as treacherous, since the substance or its secondary products are accumulated in organisms and can develop harmful side effects there under certain circumstances.

Also the synthetic ones proposed as builders High polymers are by no means to be regarded as environmentally neutral, as they only because of their chemical character have very little degradability and therefore may cause unpredictable damage in bodies of water.

Attempts have therefore been made to find builder substances that are biodegradable and can already be destroyed in modern sewage treatment plants. For example, DOS 2 040 9Λ8 describes a derivative of starch or cellulose which, as a result of oxidative action, carries carboxyl groups and aldehyde functions. These products are each characterized by more or less good biodegradability. Disadvantageous for the use of such high molecular weight products as

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2U9737

Builder in ash detergents, however, is their relatively high level Viscosity, especially when you consider the high level of builder used in detergent formulations.

It has now been found that carboxymethylated mono-, di- and oligosaccharides, especially the reaction products of chloroacetic acid with mono-, di- and / or oligosaccharides possess excellent builder properties, nevertheless have an extremely low viscosity and are completely biodegradable. '

The invention thus relates to detergents which contain carboxymethylated mono-, di- and / or oligo-accharides exhibit.

The carbohydrate derivatives used according to the invention are preferably obtained by reacting chloroacetic acid or their salts with mono-, di- and oligosaccharides in the presence of alkali. The reaction can be carried out either in an aqueous medium or in a non-aqueous medium. Water and water-miscible alcohols have proven to be preferred reaction media. Such alcohols are methanol, ethanol, isopropanol, propanol.

Hydroxides or carbonates of alkali metals or ammonium can be used as alkaline components.

The chloroacetic acid or its salts are expediently used in such a quantitative ratio that the amount is sufficient to etherify all free OH groups of the saccharide. Deviating from this, higher rates can also be used or lower amounts of chloroacetic acid are used, but it is not expedient to use less than 1 mol of chloroacetic acid to be used per monosaccharide unit. The necessary The amount of alkali is calculated stoichiometrically from the amount of chloroacetic acid used, advantageously with a small excess is used.

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2U9737

All mono-, di- and oligosaccharides are used as saccharide components suitable. Sorbitol, glucose and, in particular, sucrose are preferred, with the optional hydrogenated technical precursors for the production of these sugars, such as breakdown products of the Starch e.g. a starch hydrolyzate, or cellulose or sugar syrup can be used with advantage.

The viscosity of a 10 $ aqueous solution of the starting point saccharide should be below 250 cp, preferably below 50 cp and especially below 25 cp. (Native starch

* types show viscosities of under these conditions approx. 50,000 - 150,000 cp.)

Those used according to the invention as an ash additive Carbohydrate derivatives are characterized by an extremely low viscosity, correspondingly good and simple processability and complete water solubility. They are easily attackable by microorganisms, but in turn promote algae growth and thus eutrophication are not. They only have a moderate ability to form complexes, as a result it is avoided that trace elements are deprived of the ecological equilibrium through irreversible complexation will. Due to the abundance of sugar and the ease with which they are made, such products are extremely high

f Easily accessible and their production costs come close to the usual phosphate builders.

The carbohydrate derivatives used according to the invention can the builders usually used in detergents completely or partially replace. Your use menjju in detergents is therefore at 5-70, preferably 25- ^ 5 wt .- ^, based on the detergent composition. An inventive Detergents can be used as active washing substance, e.g. alkylbenzene sulfates and / or contain nonionic washing active substances and other common additives.

309816/0953

214973?

The invention is explained in more detail in the following examples. The quantities given are based on weight.

example 1

68.5 parts of sucrose were in

^ 50 parts of water dissolved. 5 5 parts of sodium chloroacetate and the aqueous solution of 6 hours of caustic soda were added to the diosor solution.

The mixture was kept at about 95 ° for 5 hours. That The product was spray dried and used as a builder used.

Example 2

68.5 parts of sorbitol and
185 parts of sodium chloroacetate were in

450 parts of water dissolved. This solution became the. aqueous solution of

Gh divide caustic soda in
Given 100 parts of water.

The mixture was refluxed for 5 hours. Afterward the reaction product was spray-dried and used as a builder.

Example 3

Native corn starch was brought to a viscosity of 20.3 cp / 10% solution by hydrolytic degradation.

80 parts of this mined starch were with

180 parts of sodium chloroacetate in

400 parts of hot water and dissolved with

120 parts of 50% sodium hydroxide solution made alkaline. The mixture was boiled h hours under reflux. The reaction product was then spray-dried and used as a builder.

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Example 4

The reaction according to Example 3 was repeated, however with the difference that only half the amounts of sodium chloroacetate and caustic soda were used.

The reaction product was dried using an analogous method used as a builder.

Example 5

In the same way as in Example 2, mannitol was reacted with sodium chloroacetate and the reaction product as Builder used.

Example 6

170 parts of a hydrogenated, 40 $ strength glucose syrup were with 200 parts of water and diluted with

185.6 parts of sodium chloroacetate are added. Then 215 parts of 30% sodium hydroxide solution were added and the mixture was refluxed cooked. The reaction product was brought to dryness on heated cylinders and used as an additive in Detergents used.

Example 7

103 parts of mannitol,

278.4 parts of sodium chloroacetate and 96 parts of caustic soda were made into a mixture Share isopropanol and

15O parts of water entered and refluxed for 3 hours cooked. The reaction product was filtered, washed with isopropanol, and under vacuum at 60 dried. The colorless reaction product was used as a builder in detergent formulations.

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Example 8

In the same way as in Example 7, sucrose was made with sodium chloroacetate reacted in isopropanol / water and the reaction product used as a builder.

Example 9

The reaction products of Examples 1-8 were mixed with half the amount by weight Prepares alkylbenzenesulfonate test formulations. With the respective test formulations were cotton swabs with the addition of standard dirt (Depositions process s) washed in the usual way for comparative purposes. In parallel, cotton swabs with comparative formulations were produced washed, the ABS / tripolyphosphate or only ABS and only tripolyphosphate and sucrose or Contained sorbitol in addition to ABS. The assessment was made after 5 vials on the basis of the optical whiteness. The results of the vase tests show the full equivalence of most of the builders of the invention with that which is customary used tripolyphosphate. They also show that sucrose and sorbitol do not have any builder property. The results are summarized in the table below:

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Detergent formulation SECTION Grayish Builder with ... without + + + Tripolypho sphat with + + Tripolyphosphate with O Sucrose ' with + + + Sorbitol with + + + example 1 with + - Example 2 .with O Example 3 with O Example M- with + + Example 5 with O Example 6 with O Example 7 with + Example 8 O

Graying scale:

ο ■ none

+ «Hardly

+ + » Venig

+ + + ■ strong

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Claims (7)

Claims 1. Detergent characterized by a content of carboxymethylated mono-, di- and / or oligosaccharides. 2. Detergent according to claim 1, characterized in that there are reaction products of chloroacetic acid with Contains mono-, di- and / or oligosaccharides. 3. Detergent according to Claim 1 or 2, characterized in that it contains carboxymethylated sucrose, k. Detergent according to Claim 1 or 2, characterized in that it contains carboxymethylated starch hydrolyzate. 5. Detergent according to Claims 2 and k, characterized in that it contains reaction products of chloroacetic acid with a saccharide whose viscosity in 10% aqueous solution is less than 250 cp, preferably less than 50 cp and in particular less than 25 cp. 6. Detergent according to one of claims J-5> characterized in that that it is 5-70, preferably 25- ^ 5% by weight of carboxymefchylated saccharide. 7. Detergent according to claim 6, characterized in that the carboxymefchylated saccharide completely or partially replaces the builder usually used in detergents. ii \ öF EGTEO 309816 / 09S3