DE2143010C3 - - Google Patents

Description

The invention relates to phosphate-free washing and cleaning agents, the usual detergents and Contain additives and water-soluble salts of sulfonated straight-chain, saturated aliphatic ω, ω'-dicarboxylic acids as the structural substance.

It is known that the cleaning power of surfactants in detergents and cleaning agents by « Additions of certain substances is increased. Such substances are called structural substances, building materials or builder.

The mode of action of such structural substances has not yet been fully clarified in detail it is assumed, however, that a large number of individual effects affect the special properties of the Determine structural substances:

Increasing the detergency of surfactants, Dispersion of dirt to avoid redeposition, solubilization or emulsification of poorly soluble components, Prevention of the separation of sparingly soluble salts, especially calcium and Magnesium salts, m)

Buffer effect against acidic substances, Regulation of the foaming power of the wash liquor,

Compatibility with the other detergent components, especially with the bleaching agents, erf low corrosion effect.

Another important property is the good biodegradability is not neglected

will.

So far, the inorganic, alkaline substances are particularly well-known as structural substances: Alkali bicarbonates, carbonates, borates, phosphates, polyphosphates and silicates.

In the most common detergents and cleaning agents of the present, however, are used as builder substances almost exclusively polyphosphates, especially pentasodium triphosphate, used Detergents and cleaning agents contain polyphosphates, according to the washing habits of the individual countries, up to 70 percent by weight, based on the total mixture. Despite many advantages it is however, the use of phosphates is also associated with serious disadvantages.

For some years now, monologists have been observing eutrophication with increasing concern. H. Fertilization of water bodies and lakes due to excessive concentration of nutrients that lead to a sensitive disturbance of the biological equilibrium as a result of strong algae growth. The result is a rapid decrease in the oxygen content mainly in the depths of the lakes and an associated one Increase in putrefaction, which ultimately leads to the death of plant and animal life cause. The detergent phosphates are partly held responsible for this damage (Tenside 8 [2], 82 [1971]).

It is also known that polyphosphates also have application-related disadvantages. So subject They easily hydrolyze to form meta- and orthophosphates, the inferior structural substances represent.

The corrosive properties of the polyphosphates towards metals and alloys are also allowed not to go unmentioned (K. L i η d η e r, Tenside-Textilhilfsmittel-Waschrohstoffe, Wissenschaftliche Verlagsgesellschaft MbH, Stuttgart 1964, Volume II, pages 1189 and 1195).

In order to avoid the stated disadvantages of polyphosphates, many attempts have been made to obtain phosphate-free To use structural substances in detergents and cleaning agents. So was z. B. in the USA et al. Nitrilotriacetate (NTA) used in detergent formulations However, it has now been recognized as a disadvantage that NTA does not biologically well under all conditions is degradable. Furthermore, nitrogen is a nuisance as a factor promoting eutrophication. Dubious also agrees with the excellent ability to form complexes with mercury and arsenic could lead to an undesired accumulation of these substances. Finally it was found that NTA and Perborate mutually inactivate, with consumption of the perborate NTA with the formation of Amine oxides and other oxidation products is degraded (Tenside 8 [112 [1971]).

Especially to avoid the problem of eutrophication of water bodies nitrogen- and phosphorus-free substances were examined for their suitability as structural substances. Here However, it was found that the tested monomeric and polymeric compounds either have poor washing properties with good biodegradability (e.g. citric acid) or insufficient biodegradability with usable washing power (e.g. polyacrylates, copolymers) (surfactants 8 [112 [! 37I]).

The invention was therefore based on the object of this

To overcome disadvantages of the relevant prior art.

The phosphate-free detergents according to the invention contain conventional detergents and additives and are characterized by a content of water-soluble salts of sulfonated straight-chain, saturated aliphatic ω, ω'-dicarboxylic acids with 3 to 20, preferably 5 to 12 carbon atoms, as the structural substance.

The compounds to be used according to the invention can be prepared by methods known per se Methods are done. The general procedure is to use a dicarboxylic acid and / or a dicarboxylic acid half-ester and / or a dicarboxylic acid diester the general formula

ROOC- (Ch ₂ K-COOR '

in which R and / or R 'can represent a hydrogen atom or a methyl or ethyl radical and χ stands for an integer from 1 to 18, preferably from 1 to 10,> o sulfonated with sulfur trioxide or chlorosulfonic acid and then the reaction products with a corresponding amount of alkali metal hydroxide or ammonia saponified or neutralized. During the sulfonation, 13 to 2.5, preferably 1.8 to 22 mol, sulfonating agents are used per mole of acid, ester or acid-ester mixture Builders the alkali or ammonium salts of mono- and / or disulfodicarboxylic acid.

The production of an approximately equal-part mixture of the sodium salts of mono- and Disuifododecandisäure be explained using an example: 645 g (25 mol) of dodecanedioic acid dimethyl ester are heated to 70 to 8O ⁰ C within 5 hours, 5.22 moles of sulfur trioxide, diluted with nitrogen, 23 I or air per minute, gassed in. Then the mixture is left to react for a further 30 minutes and then the acidic sulfonation mixture is lightened by slowly adding 30%. Hydrogen peroxide at 6O ⁰ C on. 2,700 g of an approx. 15% sodium hydroxide solution are then added in small portions to the pale yellow acid and the mixture is heated to the boil for 2 hours for saponification. After removing water and methanol, 950 g of a white substance are obtained, which can be used in the present form as a builder substance.

Although each water-soluble sulfonate of the ω, ω'-dicarboxylic acids with 3 to 20, preferably 5 to 12 Carbon atoms can be used as a structural substance, the alkali or ammonium salts particularly preferred

The alkali and ammonium salts of the following mono- and disulfodicarboxylic acids or their mixtures are particularly effective:

(X-SuIfododecanedioic acid,

ixA'-disulfododecanedioic acid,

(X-sulfoazelaic acid,

aux'-disulfoazelaic acid, bo

Λ-sulfoadipic acid,

ΛΑ'-disulfoadipic acid,

(X-sulfosuccinic acid,

(XA'-disulfosuccinic acid.

The builder substances according to the invention should preferably be used in an amount of 10 to 70 percent by weight 20 to 60, in particular 35 to 60 percent by weight, based on the total mixture of washing and Cleaning agent. The relationship The structural substance to the surfactant is generally 1: 3 to 10: 1.

The phosphate-free detergents and cleaning agents according to the invention can contain all customary anion-active agents and nonionic detergents and additives.

Examples of suitable anionic detergents are: alkyl benzene sulfonates, olefin sulfonates, alkane sulfonates, alkyl sulfates, alcohol oxyethylate sulfates, etc.

Examples of nonionic surfactants are: alkyl polyglycol ethers, alkylphenol polyglycol ethers, acyl polyglycol ethers, oxyethylated fatty acid amides, polyadducts of ethylene oxide and Propylene oxide etc. It is preferable not to add any further structural substances.

The following relevant recipes for some heavy-duty detergents are intended to provide a further explanation of the Invention serve:

Example A.

10.0% n-dodecylbenzenesulfonate, 4.0% Ci6-Ci8 fatty alcohol oxyethylate (11 mol

Ethylene oxide), 3.0% sebum soap,

37.5% sodium salts of sulfonated dodecanedioic acid, prepared according to the production example given on page 4, 5.5% sodium silicate, 20.0% sodium perborate-4H ₂ O, 1.0% sodium cumene sulfonate, 1.0% carboxymethyl cellulose (CMC) , 02 % optical brightener, 17.8% sodium sulfate.

Example B.

14.0% n-dodecylbenzenesulfonate

4.0% sperm oil alcohol oxyethylate (25 mol ethylene oxide), 1.0% sodium toluene sulfonate

1.0% carboxymethyl cellulose (CMC), 44.8% sodium salt of sulfonated dodecanedioic acid, prepared according to the procedure indicated on cable 4 Manufacturing example,

3.0% sodium silicate 12.0% sodium sulfate 20.0% sodium perborate 4 H ₂ O,

0.2% optical brightener.

Example C

10.0% «-olefin sulfonate (Ci5-Ci8), 1.0% sebum soap,

5.5% palmityl alcohol oxyethylate (15 mol ethylene oxide), 1.0% sodium toluene sulfonate,

5.0% sodium silicate,

58.0% sodium salt of sulfonated azelaic acid, prepared according to the preparation example given on page 4, 193% sodium sulfate, 02 % optical brightener.

Example D

16.0% (X-olefin sulfonate (Ci4-Ci ₈ ),

5.6% palmityl alcohol oxyethylate (15 mol ethylene oxide), 3 ^% tallowol soap,

1.0% sodium cumene sulfonate,

1.0% carboxymethyl cellulose (CMCV

3.5% water glass,

35.0% sodium salt of sulfonated adipic acid, prepared according to the procedure given on page 4 Manufacturing example,

34.2% sodium sulfate, 0.2% optical brightener.

The detergency of the anion-active and nonionic detergents mentioned is increased by the addition of the structural substances according to the invention increased in a sparse manner. In addition, these structural substances contribute to the excretion of detergent Substance as poorly soluble salts, e.g. B. calcium salts, so that an incrustation of the tissue is prevented. The substances according to the invention are also characterized by a good suspension capacity (tested on iron oxide), which is a measure of the Represents dirt-carrying capacity, a good buffering effect against acidic dirt, a very good one Compatibility with perborate as a bleaching agent and a comparatively low corrosive effect on metals. Your biodegradability can be described as very good.

The builder substances to be used according to the invention can therefore be used in the detergents and cleaning agents not only fully replace the phosphates, in particular pentasodium triphosphate, which have hitherto mainly been used as structural substances, but show them compared to these even an overall better property profile.

To determine the washing power of detergents in which the phosphate content has been replaced by the structural substances according to the invention, test-soiled WFK cotton fabric is tested in a Launder-O-Meter, a standardized laboratory washing machine 9O ⁰ C for 30 minutes in an aqueous liquor jeweUs washed. For the washing tests, drinking water with a hardness of 12 ° German hardness is used.By comparison with the test-soiled unwashed and the non-soiled fabric, the percentage wash value is calculated according to the following equation:

% Wash value = - ■ - £ 100. c - b

ι η where:

a = remission of the washed fabric, b = remission of the test-soiled fabric, c = remission of the unpolluted fabric.

The remission is a measure of the lightening caused by the washing process and is on dried and ironed fabric measured using an Elrepho photometer from Zeiss, its

Filter B 57 is calibrated against the standard no. 20707 For determining the percentage wash value

24 individual measurements are made on the test fabrics used.

To further explain the subject matter of the invention

The following examples and test results are intended to improve the technical progress that can be achieved with it to serve:

Examples 1 to 5

so The following table shows the percentage washing values that are 1 g / l Sodium dodecylbenzenesulfonate as a detergent substance (WAS) and 1 or 2 g / l builder substance in the Washing liquor were achieved:

example

Washes 1. 2.

1 g / l pentanalrium triphosphate (for comparison)

2 g / l pentasodium phosphate (for comparison)

1 g / l Na salt of sulfonated dodecanedioic acid (Cu), prepared analogously to the preparation example given in column 3

2 g / l Na salt of sulfonated dodecanedioic acid (C] ₂ ), prepared analogously to the preparation example given in Spaite 3

1 g / l Na salt of sulfonated azelaic acid (C9), produced analogously to the production example given in column 3

2 g / l Na salt of sulfonated azelaic acid (C9), produced analogously to the production example given in column 3

1 g / l sodium salt of sulfonated adipic acid prepared analogously to that given in column 3 Manufacturing example

2 g / l Na salt of sulfonated adipic acid (C6), produced analogously to the production example given in column 3

1 g / l Na salt of sulfonated succinic acid (C4), produced analogously to the production example given in column 3

2 g / l Na salt of sulfonated succinic acid (GO, produced analogously to the production example given in column 3

29 30th

20th 29

14th 23

11th 20th

22nd 25th

39 42

36 42

33 40

25th 34

43 42

45 48

50 50 46 50 36 46

52 50

Examples 6 and 7

These two examples show that when the builders according to the invention are used, shown on Example of the sodium salt of sulfonated dodecanedioic acid (Ci.; As with pentanairium triphosphate practically No temperature dependence of the percentage wash values in the range of interest between 60 and 95 ° C can be seen. The wash liquor contained 1 g / l sodium benzene sulfonate as WAS and 2 g / l builder substance.

example

Framework

60 C

Laundry
I. 2

C) ₂ , prepared analogously to the preparation example given in column 3

Pentasodium triphosphate (for comparison)

41

41

95 C

Washes
1. 2.

42

42

Examples 8 to 12

To determine the hardness resistance, the procedure is that differently concentrated solutions of sodium dodecylbenzenesulfonate and structural substance in water with different degrees of hardness? > their cloudiness can be examined. A series of measurements then gives the total value, the between 15 with poor and 75 with very good hardness resistance. After a certain The key can be derived from this as the stability numbers that vary between 1 and 5. In the ideal case, the greatest insensitivity to hardness builders of the water, this value is 5. Further details can be found in DIN regulation 53905 will. As can be seen from the following summary, the builders according to the invention show in combination with sodium dodecylbenzenesulphonate a better hardness resistance than pentasodium triphosphate.

The builder substances according to the invention are in the following compilation by the Examples 2 to 5 introduced abbreviations characterized.

example

Framework

8 C _n , prepared analogously to the preparation example given in the column

9 C ₉ , prepared analogously to the preparation example given in the column

10 C ₆ , prepared analogously to the preparation example given in the column

11 C4, prepared analogously to the preparation example given in the column

12 pentasodium triphosphate (for comparison)

Hardness resistance
age
Stability number According to DlN
53905
Total value 3 42 4th 58 3 43 4th 61 3 37

Examples 13-17

The compatibility of the builder substances according to the invention with the other detergent components was especially checked for sodium perborate, which is often used as a bleaching agent 100% was set. Then, a solution which in addition to 0.004 mol / l perborate was heated for a further 0.004 mol / l skeleton substance and 10 mg / 1 iron (III) chloride containing at 9O ⁰ C and the decrease of the active oxygen content after 30, 90 and 150 minutes were measured. The values obtained were put in relation to the comparison solution; they indicate the increased stabilizing effect of the builder substances according to the invention compared to perborate compared to phosphate.

example

13th
14th

Structural substances

% Active oxygen 30 min 90 min

ISO min

C ₁₂ , made analogously to 61.0 41.5 32.5

example given in column 3

C ₉ , produced analogously to 65.5 45.0 33.0

example given in column 3

continuation 21 43
9 010 10 52.5
46.0
7.5 150min I **,., -, Gerüii. ' il-'tiTv.cn % AktivsaucrslofT after
30min 90min 42.0
37.0
4.5 15th
16
17th Cf ,, produced analogously to that in
Example given in column 3
C ₄ , produced analogously to that in
Example given in column 3
Pentasodium triphosphate
(for comparison) 62.0
66.5
29.0

Examples 18-22

As a measure of the dirt-carrying capacity of a structural substance, its suspending capacity, for. B. versus powdered iron oxide. For this purpose, a test method was worked out that includes consists that in a shaking cylinder red AK F iron oxide pigment with an aqueous solution of the Builders with the addition of sodium dodecylbenzenesulfonate shakes vigorously for one minute and after 24 Hours the strength of the turbidity then still to be observed is determined photometrically by measurement The relative numbers obtained for the extinction show that the builder substances according to the invention have at least one have as good suspending properties as pentasodium triphosphate.

example

Framework

Absorbance in
1 cm layer thickness

18 C | 2, manufactured analogously to the 150
indicated in column 3
Manufacturing example

19 C ₉ , manufactured analogously to the 183
indicated in column 3
Manufacturing example

20 C ₆ , manufactured analogously to the 180
indicated in column 3
Manufacturing example

21 C ₄ , prepared analogously to] 75
indicated in column 3
Manufacturing example

22 pentasodium phosphate 160
(for comparison)

Examples 23-27

To determine the corrosive properties of the structural substances according to the invention in relation to steel The procedure was as follows: Degreased steel sheets made of St 37 were placed in a glass flask with With the reflux condenser attached, it is arranged in such a way that it is halfway into a pH value of 10 immersed a percent aqueous solution of the structural substances. The solution was alternated for 8 hours boiled under reflux and left at room temperature for 16 hours. During the shutdown of the equipment air could get to the test panels. After a test period of 8 days, the adhering rust became by treatment for 30 minutes with 2η-hydrochloric acid, which still contains 0.25% lauryl-dimethyl-benzylammonium chloride contained as a corrosion inhibitor, replaced. Then the test panels were with Washed with water, acetone and benzene and dried. The total that occurred during the treatment The weight loss of the sheets, which corresponds to the amount of iron removed, was determined using pentasodium triphosphate shows - as from the following summary

jo position can be seen - the strongest corrosive Effect in comparison with the builder substances according to the invention.

At- structural substance
game

Ablation in
g / m ²

17.1

C12, produced analogously to that in
Preparation example given in column 3

C9, manufactured analogously to that in
Preparation example given in column 3

C ₆ , produced analogously to that in
Production example given in column 3

C ₄ , produced analogously to that in
Preparation example given in column 3

Pentasodium triphosphorus 61.4

(for comparison)

28.3

14.8

26.2

Using the examples and comparative examples mentioned it is shown that the use of the structural substances according to the invention results in high quality Phosphate-free detergents and cleaning agents can be obtained.

Claims (5)

Patent claims: 1. Phosphate-free detergent and cleaning agent, containing conventional detergents and additives, characterized by a content of water-soluble salts of mono- and / or disulfonated straight-chain, saturated aliphatic ω, ω'-dicarboxylic acids with 3 to 20 carbon atoms as the structural substance. ι ο 2. Phosphate-free detergent and cleaning agent according to claim 1, characterized by a Content of water-soluble salts of mono- and / or disulfonated straight-chain, saturated aliphatic ω, ω'-dicarboxylic acids with 5 to 12 carbon atoms as the structural substance. 3. Phosphate-free detergent and cleaning agent according to claim 1 to 2, characterized in that the salts of sulfonated ω, ω'-dicarboxylic acids a mixture of salts SO up to 70 percent by weight are monosulfonated and 30 to 50 percent by weight disulfonated ω ^ u'-dicarboxylic acids. 4. Phosphate-free detergent and cleaning agent according to claim 1 to 3, characterized by a content of 10 to 70 percent by weight, preferably 2-20 to 60, in particular 35 to 60 percent by weight, based on the total amount of the detergent and cleaning agent, of water-soluble sulfonates of straight-chain , saturated aliphatic ω, ω'-dicarboxylic acids with 3 to 20, preferably 5 to 12 χι carbon atoms as the structural substance. 5. Phosphate-free detergent and cleaning agent according to claim 1 to 4, characterized in that no other structural substances are present.