DE2057259A1 - Detergents and cleaning agents - Google Patents

Description

The invention relates to detergents and cleaning agents * especially those for textile laundering, and on new ones

Builders and their manufacture.

Usual detergents and cleaning agents are based on active detergent compounds and builders of which the latter the condensed phosphates, e.g. sodium tripolyphosphate, being the most common. It is believed that the use of builders containing phosphorus may be a factor in eutrophication, that is the excessive Fertilization of aquatic plants It has therefore been suggested that to use certain non-phosphorus compounds as builders, but the materials suggested for them suffer from various disadvantages, either in terms of their physical properties, which of their Use in detergent powders or their suitability as builders leaves much to be desired.

Geinäss the invention are phosphorus-free builders for Use in detergents water-soluble or water-dispersible Salts of purane or tetrahydrofuran tetra-

—2—
carboxylic acids, which have the formula (I) or (II)

HOOC-CC-COOH _m HOOC-CH - CH-COOH _{/ ττΛ}

Ii 8 ^U; II- ^(II)

HOOC-C-C-OOOH HOOC-CH CH-COOH

own.

The preferred salts are the alkali salts, especially the sodium salts. But the salts with ammonium and substituted Ammonium cations, for example morpholinium, alkylammonium and mono-, di- and trialkanolammonium, can used if necessary. The alkyl and alkanolammonium cations generally contain lower alkyl groups of 1-3 carbon atoms.

Detergents and cleaning agents can be produced with these furanic or tetrahydrofuran-acidic builders with good cleaning power without containing phosphorus. The tetrahydrofuran tetracarboxylates are the most effective builders.

Examples of suitable salts are tetrasodium, tetrapotassium, tetralithium and tetraammonium tetrahydrofuran-tetracarboxy-

the
translate, txxxlxx monoethanolamine> diethanolamine and Triäthanol amine salts of tetrahydrofurantetracarboxylic, tetra (tetramethylammonium) - and tetra (äthylammonium) tetrahydrofurantetracarboxylate, tetrahydrofurantetracarboxylate Trinatriummonokalium-the Monoisopropanolamin-, Diisopropanolamin- and Triisopropanolaminsalze of Tetrahydrofurantetraoarbonsäure, monosodium tripotassium, Dinatriumdikalium- and Morpholiniumtetrahydrofurantetracarboxylat and un-

BATH ORIGINAL

Of course, the normal salts are, that is the completely neutralized salts, usually applied in the detergents, although neutralization also in the washing liquor can be accomplished if desired. However if the pH of the wash liquor is below about 8.6, some of the salts of furan or tetrahydrofuran tetracarboxylic acid will be be present in the acidic form and some in the normal salt form »

When the builders are used in the detergent compositions, it is also necessary that one or more active detergent compounds be present. Suitable active detergent compounds include anionic (soap and soft soap), nonionic, zwitterionic, and amphoteric compounds which are well known in the art. Specific compounds which can be mentioned, for example, are alkylbenzenesulphonates, alkyl and alkyl ether sulphates, alkylsulphonates, olefin sulphonates (which means the product of sulphonation with sulfur dioxide of an olefin with subsequent neutralization and hydrolysis of the reaction product), N-hydroxyalkylmethyltauronoxides and polykyl alkanesulfonates, trialkyl alkanesulfonates, trialkyl alkanesulfonates with aliphatic alcohols and alkylphenols. Further examples can be calibrated in the literature, for example in "Surface Active Agents' ¹ by Schwartz and Perry and" Surface Active Agents and Detergents "by Schwartz, Perry and Berch.

The weight ratio of the furan or tetrahydrofuran tetracarboxylate ingredients to the active detergent compounds when used in washing and hand dishwashing

098 2 ^ / 203

average is generally in the range of about 1:20 to about 20: 1, preferably from about 1: 3 to 10: 1, and especially from about 2: 1 to 5: 1. However, when these builders in funds are used for mechanical dishwashing, the ratio of builder to the active detergent compound is equal to generally about 10: 1 to about 50: 1 · The amount of builder is generally in the range of about 25 to 75 wt. #.

The furan and tetrahydrofuran tetracarboxylate builders can either be used as the sole builder or if desired are used together with other known builders, e.g. with beta sodium and tetrapotassium pyrophosphates, Pentasodium ". and pentapotassium tripolyphosphates, trisodium and Tripotassium nitrilotriacetates, sodium polyacrylate, sodium copolyethylene maleate etc.

The Srfindungsgemässen detergent agents may include conventional additives such as soil suspending agents, hydrotropes, corrosion inhibitors, dyes, perfumes, fillers, optical bleaching agents, enzymes, foam boosters, ^ chaumdrücker, germicides, tarnishing inhibiting substances, cationic Aktivdetergensverji compounds, plasticizers, bleaching ^ü toffe etc. When using the detergents according to the invention for washing laundry, the washing liquors should normally have a pH of about 7 to about 12, preferably of about 9 to about 11. Therefore, it is usually desirable to incorporate a pH buffer, for example sodium silicate, carbonate, or sodium into the detergent

109824/7037

-biearbonat · »· The rest of the agents according to the invention is water.

physical The agents according to the invention can be any conventional / 3? form such Own means, e.g. powder, Kiigelehen, flakes, bars, Pieces, noodles, liquids, pastes, etc. The agents can be produced and used in a conventional manner.

The tetrahydrofuran tetracarboxylates serving as framework salts can easily be prepared by neutralizing tetrahydrofuran tetracarboxylic acid with the appropriate base. For example, the pure tetrasodium salt can be prepared by dissolving the commercially available acid in a slight excess of dilute NaOH. About four volumes of ethanol are added and a white precipitate is formed, which is filtered off. The precipitate is redissolved in water and ice, precipitated in a ^V, which is repeated three times, is dried whereupon the salt in a vacuum oven at 1œ5 ° C. The product is an essentially pure tetrasodium tetrahydrofuran tetraearboxylate, as shown by the titration of a sample with perchloric acid in glacial acetic acid.

Mixed salts of tetrahydrofuran tracarboxylic acid can be obtained in a similar manner become the desired by neutralizing the acid with the required proportional amounts of basic th cation-containing compounds.

The tetrasodium salt of tetrahydrofuran tetraoarboxylic acid has no melting point, but decomposes before melting. Differential thermal analysis dee material to showed that the decomposition starts above 400 ⁰ O. This material

1'Ö 9 8 2 4 /? 0 3 7

-6- can therefore withstand high processing temperatures.

The furan tetracarboxylates can be prepared in a similar manner are made by neutralizing furan tetracarboxylic acid. The extraction of the acid is described in HeIv. Chem. Acta, J [6.276 (1933) and includes condensation of two molecules of Sodium diethyl oxalacetate with bromine in chloroform, with formation a tetraester compound which is cyclized in concentrated sulfuric acid to form tetraethylfurantetracarboxylate, which can then be hydrolyzed to the acid. * Tetrahydrofuran tetracarboxylic acid can be produced by reducing furantetracarboxylic acid, or it can

4-ia -, - u synthesized
immediately gy «t _/ eg by oxidation of endoxotetrahydrophthalic acid or its anhydride with nitre

acidic

The detergents according to the invention are illustrated in the following examples, which include comparative agents, in which the parts and percentages are by weight, unless otherwise stated. The detergents of the various agents are included in the examples. Unless otherwise stated, the tests of the cleaning ability were carried out in a Terg-O-Tometer, in which a "Dacron" (RTM) polyester 65 # / cotton 35 # test item, soiled with ^ vacuum cleaner dirt ^ ei 49 ⁰ O in a 0.1 # solution of eans ppm to be tested ^M in water with a content of 180 Caloium and magnesium ions (2: 1) average at a AnfangapH 10 washed wmrde.Die units detergency (DU's) of the center is calculated as the Endreflektani the washed piece minus the initial reflectant

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of the stained piece (average of two attempts), whereby, the Reflectant with a Gardner Automatic Color Difference Meter, Model AC-3 is measured

Examples 1-11

A number of detergents have been manufactured by Mixing of the ingredients and their washing and cleaning power was determined »The batches and their washing and Cleaning power follow in Table I,

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Table I. Components approach τοη example

j __2 __3_ 4 _Y> 6 _Y 8 __9_ 10 11

Nat r ium-line ar βΒ-s elcun-

aäres-alkyl (C ₁₀ -C ^ c) - /

■ b | nzolsulfonax ^

Sodium silicate

(| i0 ₂ : Na ₂ 0 2.4: 1) / _

Sodium sulfate ^ _: 20 #

Tetrasodium tetrahydro 50-40 30-20-10 furant e tracarboxylate

rv Sodium tripolyphosphate - 50 - 40 - 30 - 20 10

Water 4 to 100

Washing and cleaning power units

(Average) 31.8 33.4 32, Ό 32 ,? 31.4 31.1 29.7 29.4 25.4 23.3 14.5

These examples show that the tetrahydrofuran tetracarboxylate generally equivalent to sodium tripolyphosphate, especially with low builder concentrations, is.

Examples 12-17

A series of detergents were prepared as in US Pat Examples 1-11, however, the sodium silicate was omitted from the product. The approaches and their washing and cleaning assets follow in Table 2 II.

Table II Components approach of example ($)

12 15 14 15 16 17

Sodium linea

res-secondary- Alkyl (C ₁₀ -C ₁₅ ) -

benzenesulfonate

Sodium Sulphate ^ $ 20 Tetrasodium tetra-

hydrofurantetra- 50 - 40 - 10 -

carboxylate

Sodium tripolyphosphate 50-40-10

Water ^ to 100

Washing and cleaning power units (average) 31.2 33.7 30.9 32.3 16.2 18.4

The results show that tetrahydrofuran tetracarboxylate only slightly inferior to Watciumbripolyphoijphab in Pehlen den Ha briuma Llilcatpu ff et'ö Irf fc j

Example 18

The agent of Example 1 and 2 were tested for ^ash-w and Reinigungsvennögen in water of different degrees of hardness with the Table III in the following results.

Table III

middle 1
2 Washing and Detergent Power UnitsC Avg 2 °. 1 £ ° -
31.8 31.8
34.2 33.4 300
27.2
29.5 at different water hardnesses ppm. example
example jO
36.5
37.3

The results show that the means of Example 1 with Tetrasodium tetrahydrofuran tetracarboxylate almost equivalent in terms of washing and cleaning power within the range of degrees of hardness that with sodium tripolyphosphate means built up as a builder.

Examples 19-26

A number of detergents were made using various active detergent compounds, as in table IV, which also contains the results with regard to washing and cleaning performance.

Table IV

Components

Tetrasodium tetrahydrofuran tetracarboxylate Sodium tripolyphosphate

Sodium silicate (SiO ₂ * 2.4: 1)

Sodium sulfate
Nedol 45-11 *

Cocodimethylsulfopropyl betaine

Sodium hydroxyalkyl - (C ₁ ^ -C ₁₆ ; N-methyl taurate

water

19th

40.

20th

Approach of example ($)

21

23

40

■ 40 - · 40 10 10 - - 20th 20th 20th 20th 20th 20th 20th 20th

40

10

20th

20th

24

25th

40 40

10 10 20 20

26th

40 10

20th

20th

-to 100-

Wascla- and cleaningBYermö-

gen units (average) ** 27.9 31.4 27.1 29.9 29.2 30.8 24.7 27.3

* A non-ionic active detergent compound which is an adduct of a modified »» 0X0 ⁿ

° 14 ~ " ^C 15 - ^^ ^{01101 mi-fc is} an average of 11 moles of ethylene oxide

** Measured for Examples 19-22 at 0.256 concentration and for Examples 23-26 at
0.1596 concentration,

ro ο cn

These results show that the tetrahydrofuran tetracarboxylate an effective builder for nonionic, zwitterionic and amphoteric active detergent compounds is·

Examples tfrti 27-32
A number of detergents have been prepared using mixtures of tetrasodium tetrahydrofuran tetracarboxylate and sodium nitrilotriacetate as building materials. The preparations of the agents and the agents with each of the materials as the sole builder and with sodium tripolyphosphate as the builder and the results of the washing and cleaning performance test follow in Table V.

Table V Components

Sodium-linear-secondary

Approach by example

28

50 51

benzenesulfonate sodium silicate

2.4: 1)

Sodium sulfate sodium nitrilotriacetate

Tetrasodium tetrahydrofurante tracarboylate

Sodium tripolyphosphate

50
10

20 20

10 40

40 -

Washing and cleaning power units (average)

34.5 32.2 31.8 31.6 32.0 32.7

10Ö824 / 2037

2QB725R

-13- Example 35

A detergent was prepared with the following

Approach:

Components j »

Sodium-linear-secondary-alkyl-

(CQ-O ₁ j-) benzenesulfonate 16

Alkaline sodium silicate 8

Tetrasodium tetrahydrofuran tetracarboxylate 50

The cleaning ability of this agent and a comparative agent A with sodium tripolyphosphate as the cleaning agent instead of the tetrasodium tetrahydrofuran tetracarboxylate was determined at different concentrations.In the method for determining the washing and cleaning ability, a LoSUn _{1 of} the compound in water of 18 ° hardness (Ca: Mg 2: 1 ) at 45 ⁰ C used for washing a cotton test piece, impregnated; Synthetic sebum marked with a carbon-14, in a Terg-O-Tometer for 10 minutes, whereby the radioactive number of the piece was measured before and after washing The washing and cleaning capacity is the change in the radioactive number in percent

The results for example 33 and the comparative agent A follow in labeile VI

Table VI

Approach & washing and cleaning power with different

product concentrations

0.05 »0.075 0.1 0.125 0.15 0.20 0.30"" Example 33 _{32> 1 43>? 55> 8} ^ _{6 66> 2? 0> 4} ^ ₉

Comparative mean A 15.6 14.0 38.7 54.6 67.6 77.0 83.5

10 ^ 824/2037

-4Φ-

These results show that tetrahydrofuran tracarboxylate is generally equivalent to sodium tripolyphosphate
Removal of greasy dirt, especially with a low product concentration, is ₀

Example 34

A detergent and cleaning agent was prepared according to the following Approach:

Components j »

Sodium linear secondary alkyl (CjQ-C..c) benzenesulfonate 16

Tetrasodium tetrahydrofuran tetracarboxylate 50 Alkaline sodium silicate 8

Sodium carboxymethyl cellulose 0.5

Fluorescent fabric 0.5

Water to 100

This remedy was used to wash dirty ones
Pillowcases, tea towels and towels in one
Household HotpointiRTMjEmpress Washer Using
of water of 18 ° hardness (Ca: Mg 2: 1) at 45 ° C. The same tests were carried out using a detergent of the same composition but in which the builder
Was sodium tripolyphosphate. Each item was cut in half and each half washed with a different agent. the
Washed articles were visually evaluated for appearance, and in the majority of cases no difference was noticed, but when there was a difference, the articles washed with the composition of the present invention were preferred.

10982A / 2037

Example 35

A detergent and cleaning agent was produced according to the following approach
Components %

Sodium-line ar es-secondary s-alkylT
(C,. QC .jc) benzenesulfonate on 18th T e tranatriumfurante tracarb oxylate 50 water 100

The washing and cleaning power of each agent was determined by the method described above using a Terg-0-Tometer im. Compared to a similar agent, wherein the Tetranatriumtetracarboxylat had been replaced by sodium tripolyphosphate · It has been found that at 0 concentration, the builder effect 4 ^ ^uf the Reinigungsvermögei ^ of Purantetracarboxylatsl only 67 # of those of the sodium tripolyphosphate was, but still a significant improvement over the Depicted use of the active detergent compound without any builder.

1 0 HB 2 UI 7 η 3 7

Claims (6)

7057753 claims 1. Washing and cleaning agents, comprising a water-soluble organic active detergent compound and a builder, characterized in that the builder is a water-soluble or water-dispersible alkali,
The ammonium or substituted ammonium salt of furan or tetrahydrofuran tetracarboxylic acid, the weight ratio of the active detergent compound to the builder being from about 20: 1 to 1:50. 2. Means according to claim 1, characterized in that that the weight ratio of active detergent compound to builder is from about 3: 1 to about 1:10. 3. Agent according to one of the preceding claims, characterized in that the builder is an alkali or the ammonium salt of tetrahydrofuran tetracarboxylic acid is 4. Means according to claim 3, characterized in ic h net, that the salt is tetrasodium tetrahydrofuran tetracarboxylate is. 5. Agent according to one of the preceding claims, characterized in that it comprises about 25-45 wt. ^ Of an anionic, zwitterionic or amphoteric detergent compound. 6. Agent according to one of the preceding claims, characterized in that there is about 25-75 wt Comprises salts of tetrahydrofuran tetracarboxylic acid.