DE2327141B2 - SCAFFOLDING MATERIALS FOR DETERGENTS AND DETERGENTS - Google Patents

Description

The invention relates to the use of copolymers of α-hydroxy acrylic acid and acrylic acid or their water-soluble salts as builders for detergents and cleaning agents.

It is known that the cleaning power of soaps and synthetic detergents in laundry and cleaning? by adding certain water-softening products. Such cleaning enhancers are called "builders". Detergents and cleaning agents containing builders are more effective and yet cheaper than the corresponding builder-free formulations.

In supplements of the non-ionic surfactant component a detergent formulation through which only hydrophobic dirt, such as soot and fat particles, is dispersed and / or is peptized, a detergent must also contain a component that eliminates hydrophilic Dirt is suitable. This is the job of the builder or framework substances. In the absence of it Such a builder is the incrustation of dirt that is detached from the tissue during the washing process only incompletely absorbed by the washing liquor, so that there is a deposit of dirt particles comes on the laundry and no satisfactory washing effect is achieved.

The mechanism and details of the "builder effect" are not yet fully understood. There are several processes that play a role in the function of the builder, such as the stabilization of pigment dirt suspensions, the emulsification of dirt particles, the influencing of the surface and surface properties of aqueous surfactant solutions, the solubilization of water-insoluble components of the cleaning liquor, the peptization of dirt agglomerates, the neutralization of acidic substances and the inactivation of minerals in the washing liquor,
In order to obtain information about the performance and the suitability of individual products as builders, one expediently investigates not only their binding capacity for Ca ions and their ability to form stable dispersions, but also their behavior and their degree of effectiveness in the washing or cleaning process. This ensures that all factors involved in the Euilder effect are qualitatively and quantitatively taken into account.

Conventional builders are the water-soluble alkali ■ > Salts of mineral acids such as alkali carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Of the numerous products proposed as builders, de.i. common detergents and cleaning agents almost exclusively the linear condensed alkali metal phosphates, especially sodium tripolyphosphate, used. The detergents and cleaning agents contain up to about these builders 50% by weight.

As a result of the considerable increase in consumption phos- _> ■> The content of detergents and cleaning agents containing phate both in the household and in the trade has also increased the natural waters of these phosphates increased. When discussing the causes of increasing Water-eutrophication has recently become the property of water-soluble nitrate and phosphate salts awarded to promote the growth of certain algae species under certain conditions and thus on to contribute to the eutrophication of water in this way. Albeit a clear clarification of the proportion of detergents and cleaning agents containing phosphate to the water eutrophication at the moment is not yet possible, it still seems worthwhile to be potentially nitrogen- and phosphorus-free To develop substitutes for the builder substances previously used in detergent formulations.

It is already known to use nitrogen-free and phosphorus-free builder substances in detergent formulations. As such, starch derivatives such as dicarboxyl and carboxy me thy! Starch or

4 ^r ) polymeric carboxylic acids such as polymaleic acid and polyitaconic acid, as well as their copolymers with unsaturated carboxylic acids, olefins or short-chain unsaturated aliphatic ethers or alcohols are used. Oxydi-

· ■) () acetic acid, oxydisuccinic acid, cyclocarboxylic acid, such as Benzene penta- or tetracarboxylic acid, esters of polyethylene glycol and adipic acid, maleic acid, the sulfonate groups contains, as well as esters of ethylene glycol and tri- or tetracarboxylic acids proposed. In the end

v, it is known from German Offenlegungsschriften 21 36 672 and 21 61 727 and from the publication by P. Berth, G. Jakobi and E. Schmadel in Chemiker-Zeitung 95 (1971), pages 548-553, poly-ct- hydroxiacrylic acid or polyacrylic acid or

w) their alkali salts as builders for detergents and cleaning agents to use.

The aforementioned substances have not proven to be satisfactory structural substances in every respect, as these substances are not sufficiently the

b ^r ) have the Buildcr properties explained at the beginning and therefore do not give satisfactory washing results. In addition, there is sometimes a lack of economical processes for the production of these compounds.

fertilize. The aforementioned disadvantages of the known builders are not inherent in the builders of the invention.

It has been found, surprisingly, that a copolymer from oc-hydroxiacrylic acid and acrylic acid or the corresponding sodium salt? a much better ability to sequester than polyvalent ones Has metal ions as, for example, polyoc-hydroxiacrylic acid or polyacrylic acid or its alkali or ammonium salts.

The invention thus relates to the use of copolymers of ot-Hydroxiac; oic acid and acrylic acid having an acrylic acid content of about 9 to 85 mol% and a relative viscosity of Igewichtsprozentigen solutions of the copolymers in aqueous 2normaler sodium hydroxide solution at 20 ⁰ C of about 0.05 up to about 1.0 as builders for detergents and cleaning agents, the copolymers in the detergents and cleaning agents being contained in an amount of about 10 to 90% by weight.

The lime-carrying capacity of the copolymers according to the invention is considerably higher than that of homopolymers of acrylic acid or ac-hydroxiacrylic acid, i.e. H. that the copolymer gives an unexpected synergistic effect. This result is all the more astonishing according to P. B e r t h, G. J a k ο b i and E. Schmadel, Chemiker-Zeitung95 (1971), pages 548-553, is known, that the lime-carrying capacity of the polyacrylic acid corresponds almost exactly to the stoichiometric ratio. The partial use of cheap acrylic acid for the production of the copolymer reduces its production costs compared to poly-a-hydroxiacrylic acid significantly reduced. The products according to the invention are therefore suitable for use as a structural substance in Detergents and cleaning agents are predestined for their effectiveness and economy.

A preferred feature of the builders according to the invention is that the acrylic acid content was about be from 16 to 50 mol% and the relative viscosity of 1 percent by weight solutions of the copolymers in aqueous 2normaler sodium hydroxide solution at 20 ⁰ C. 0.1 to 0.8.

It has proven to be particularly advantageous to use the water-soluble salts such as. B. to use the alkali or ammonium salts of the copolymers of -hydroxiacrylic acid and acrylic acid as a detergent and cleaning agent component. The builders according to the invention can preferably be used in an amount of about 20 to 60% by weight ^! / o be contained in detergents and cleaning agents.

In addition to the builders according to the invention, conventional detergents and cleaning agents can also be used Builders such as B. Alkalipolyphosphate be included. As a surfactant component in the detergent anionic or nonionic substances preferred.

Among anionic surfactants are the water-soluble salts of higher fatty acids or resin acids, such as sodium or Potassium soaps made from hardened or unhardened coconut, palm kernel or rapeseed oil as well as tallow and the like To understand mixtures of these. Furthermore, among anion-active substances are higher alkyl-substituted, mononuclear aromatic sulfonates, such as alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl radical, alkyl toluene sulfonates, alkyl xylene sulfonates, alkyl phenol sulfonates or Alkyliiaphthalinsulfonate as well as sulfated aliphatic alcohols or alcohol ethers such as sodium or potassium lauryl or hexadecyl sulfate, triethanolamine lauryl sulfal, Sodium or potassium oleyl sulfate

and the sodium or potassium salts of lauryl sulfate ethoxyiated with about 2 to 6 moles of ethylene oxide and the like to understand.

As nonionic surfactants, which in addition to the inventive Builders that may be contained in detergents and cleaning agents are condensation products of alkyl phenols with ethylene oxide or of higher fatty alcohols with ethylene oxide, and also the condensation products of polypropylene glycol with ethylene oxide or propylene oxide and the condensation products of ethylene oxide with the reaction product of ethylene diamine and propylene oxide. Even long-chain tertiary amine oxides belong to the group of compounds mentioned above.

Finally, there are products with ampholytic or zwitterionic substances that are suitable as surfactant components Character to incorporate the following compounds: derivatives of aliphatic, secondary and tertiary Amines or quaternary ammonium compounds with 8 to 18 carbon atoms and one hydrophilic Group in the aliphatic radical, such as. S. Sodium 3-dodecylaminopropionate, Sodium 3-dodecylaminopropane sulfonate, S-iN.N-dimethyl-N-hexadecylamino / propane-1-sulfonate or fatty acid amidoalkyl-N.N-dimethylacetobetaine, the fatty acid containing 8 to 18 carbon atoms and the alkyl radical containing 3 carbon atoms

Further additives which are also part of the detergents containing the builders according to the invention and cleaning agents are, for example, the alkali or ammonium salts of sulfuric acid, silicic acid, Carbonic acid, boric acid, alkylene, hydroxy alkylene or aminoalkylene phosphonic acid and bleaching agents, Stabilizers for peroxide compounds and water-soluble organic complexing agents. Include in detail to the last-mentioned groups of compounds sodium perborate mono- or tetrahydrate, alkali salts of peroximono- or disulfuric acid, peroxohydrates of ortho-, pyro- and polyphosphates, water-insoluble precipitates Magnesium silicate as well as the alkali salts of iminodiacetic acid, Nitrilotriacetic acid and ethylenediaminetetraacetic acid.

Substances that reduce the dirt-carrying capacity of washing liquors increase, such as carboxymethyl cellulose, polyvinyl alcohol, polyvinyipyrolidone or as foam regulators are suitable, such as mono- and dialkyl phosphoric acid esters with 16-20 carbon atoms in the alkyl radical and whiteners, Disinfectants and / or proteolytic enzymes can be additional components of the detergents and cleaning agents be.

The builders according to the invention or the detergents and cleaning agents containing them are considered technical To be called progressive, as it causes the precipitation of calcium ions in the wash liquor to a considerable extent prevent or delay and also with both hydrophilic and hydrophobic dirt particles Form stable dispersions. Another advantage is that these structural substances do not contain phosphorus or contain nitrogen and thus do not favor the eutrophication of natural waters. The lime-carrying capacity of the copolymers in the detergents and cleaning agents according to the invention is exceeded Surprisingly, by more than double the stoichiometrically calculable value, while in the case of the polyacrylic acid or its sodium salt is the value of the stoichiometrically calculable lime-carrying capacity almost coincides with the actual value. Somewhat more favorable ratios than with polyacrylic acid in the case of poly-A-hydroxiacrylic acid, but also

compared to the builder according to the invention, a table I

there is a glaring difference.

The invention is to be explained in more detail by the following examples, Examples 1-6 Describe the preparation of the builder substances according to the invention, while Examples 7 and 8 show the effectiveness of the structural substances with regard to the lime-bearing capacity or in the washing test in the presence further detergent components is explained.

in

example 1

A mixture of 213 g (2 mol) «-chloroacrylic acid and Heated 1.5 liters of benzene in a polymerization vessel to 80 ° C and the mixture with 1 g of benzoyl peroxide offset. Then 72 g (l mol) were added to the mixture with vigorous stirring within 30 minutes Acrylic acid added dropwise. After adding a further 2 g of benzoyl peroxide, the mixture was at for a further 5 hours Leave 80 ° C, then cooled and the polymer filtered off and dried. There were 286 g of copolymer obtained with a chlorine content of 24.1%. Taking into account the fact that during the polymerization Traces of HCl gas were released, the acrylic acid content of the copolymer was 34 mol%. the relative viscosity of a 1 percent strength by weight solution of the polymer in dimethylformamide at 25 ° C was 0.63.

For the production of a copolymer from Λ-hydroxiacrylic acid and acrylic acid, 80 g of the above-described chlorine-containing copolymer in 800 ml of boiling Stir in water and boil for 3 boilers with constant vigorous stirring. The resulting fine powdery hydrolyzate was filtered off and dried. The yield was 55 g.

A 1 percent strength by weight solution of the polymer in aqueous two-normal NaOH had a solution at 20 ° C relative viscosity of 0.34.

Example 2

A mixture of 213 g (2 mol) oc-chloroacrylic acid, 144 g (0.2 mol) of acrylic acid and 2 l of a mineral oil fraction with the boiling point 144 to 175 ° C in a polymerization vessel heated to 80 ° C and then mixed with 2.13 g of benzoyl peroxide. The mixture became 5th Stirred for hours at 80 ° C. and after cooling the polymer isate filtered off. The polymer was washed with low-boiling petroleum ether and dried. There were 222 g of polymer with a chlorine content of 28.6% and an acrylic acid content of 9 mol% were obtained.

140 g of the above-described polymer were stirred into 1.5 l of boiling water and, as in Example 1, converted into a polymer containing α-hydroxiacrylic acid. The yield was 86 g. The relative viscosity of a 1 weight percent solution of the polymer in two normal NaOH was at 2O ⁰ C 0.15.

Λ B C D E F G H

A ■■ BC

D = E = 28.8
2.13
236.0

26.7

17.0
0.57

89.0
0.20

72.0

3.0

280.0

22.5

34.0 0.48

97.0 0.30

144.0

3.6 353.0

18.3 50.0

0.52 104.0

Examples 3 - 5

The procedure of Example 2 was repeated, except that h5 only the amount of acrylic acid used and the amount of starter were varied. The obtained test results c are summarized in Table I.

Amount of acrylic acid used (g) Amount of benzoyl peroxide used (g) Yield of chlorine-containing copolymer (g) Chlorine content of the copolymer (%) Acrylic acid content in the chlorine-containing polymer (mol%) F = relative viscosity of a 1% by weight solution of the chlorine-containing polymer in dimethylformamide at 25 C

G = yield of hydrolyzed copolymer (g) Il = Relative viscosity of a solution of the lgewichtsprozentigen hydrolyze the polymer in aqueous zweinor- ₂ -, painter NaOH at 20 C.

Example 6

213 g (2 mol) of a-chloroacrylic acid were in a

jo polymerization vessel ir 7.5 l of a mineral oil fraction with the boiling point 144-175 ° C dissolved and heated ^{to SO 11 C.} After adding 3.5 g of benzoyl peroxide, 720 g (10 mol) of acrylic acid were added dropwise over the course of 3 hours with vigorous stirring. In addition, four times 1.5 g of benzoyl peroxide were added with an interval of 1 hour each time. After a reaction time of 8 hours, the polymer was filtered off, washed with low-boiling petroleum ether and dried. 938 g of polymer with a chlorine content of 7.5% were obtained.

The proportion of Acryicäurebeuug 84 mol%. The viscosity a *% solution of the copolymer in dimethylformamide at 25 ° C. was 0.79.

For hydrolysis, 80 g of the copolymer were boiled in 1 l of water for 3 hours. Then the Solution evaporated to dryness. The yield of hydrolyzate was 69 g. The viscosity of a 1 percent by weight The solution of the polymer in 2N aqueous NaOH at 20 ° C. was 0.55.

B e i s ρ i e I 7

The lime carrying capacity (KTV) of the hydrolysis products prepared according to Examples 1-6 was durd Titration of an aqueous solution containing sodium carbonate containing 0.2% by weight of the hydrolysis product held and adjusted to pH 10 mi an aqueous 0.05norinal calcium acetate solution bi: determined for the permanent turbidity that occurs. Tue < The measure of the lime-bearing capacity brings about the end

bo pressure, how many milligrams of calcium ions from I g de: Hydrolysis product are held in solution.

The stoichiometric calcareous capacity of the Hydro lysis products can be calculated using the following formula

^{/ Allorn} B ^cw ' ^c * ^{11 approx}
2 xX

20,000 A

rmgl

LgJ

where Ä is the equivalent weight of the hydrolysis product

t it means. The latter was determined by acidimetric titration certainly.

In Table 2 below, the obtained Values for the lime-bearing capacity of the products according to the invention in comparison with the corresponding ones Values of polyacrylic acid or poly-n-hydroxiacrylic acid set.

Table 2 Ä Lime carrier possibilities effectively 81.4 theoretically 310 j product 82.9 246 409 j
i According to example 1 82.8 241 425 I According to example 2 81.5 242 464 According to example 3 84.5 245 684 \ According to example 4 74.7 237 507 I According to example 5 72.3 268 274 ■ According to example 6 82.5 277 265 Poly-acrylic acid c 242 l'oly-a-hydroxy- i acrylic acid

Table 2 shows the superiority of the products according to the invention over the comparison products with regard to the lime-carrying capacity, in that the first-mentioned products keep far more Ca ' ⁴ ions in solution than the comparison substances.

The polyhydroxiacrylic acid shown in Table 2 as a comparative product was prepared as follows:

a) In a round-bottom flask equipped with a stirrer and reflux cooler, a mixture of 100 g rx-chloroaryl acid, 400 ml benzene and Ig Bcn / oyl peroxide was heated to boiling for 3 hours under a nitrogen atmosphere. The precipitated polymer was separated off and ^{dried at 40 °} C. in a vacuum. The yield of polychloroacrylic acid was 100% of theory.

b) It was an aqueous solution saturated at 30.degree manufactured by poly-iX-chloroacrylic acid and this Solution heated to boiling for 2 hours. The precipitated hydrolyzate was washed chloridfrci and dried in vacuo at 60 "C. The yield of poly-a-hydroxiacrylic acid was 77 g or 100% the theory. The hydrolyzate had a molecular weight of 2800 and a lime binding capacity of 265 mg Ca / g.

c) By neutralizing 25 g of the poly-rx-hydroxiacrylic acid with 25 g of a 50% sodium hydroxide solution and evaporation of the water, the sodium salt / obtain.

Example 8

The washing power was determined by means of washing tests of wash liquors with a constant concentration of known detergent components. however different Amounts of inventive builder A or B or C determined and the results obtained shown in the figure. Under scaffolding open Λ, Β and C are the sodium salts / .e of the examples 1, 3 and 6 to understand hydrolysis product produced. For comparison, analogue Wüschversuche were under Use of the known scaffolding pins I) and L carried out and the values obtained in this way for the washing claw are also shown in the figure in the form of curves. Under structural substance I) is the sodium salt of a l'ol \ acrylic acid / u, whose 40 weight pn> / enligc aqueous solution at 25 "CeJnC viscosity of 1900 cents ipoise owns. Builder L relates to the sodium salt of poly-hydroxiacrylic acid. its manufacture before was described standing.

The washing insurances were made with a standard Cotton fabric with Krelder soiling in one Launder-O-meter at a wash liquor temperature 95 'C implemented standard fabric with Krefeldcr An In the book by Kurt L i η d η e ι »Tenside. Textilhilfsmillcl - washing raw materials «, knowledge shaft!. Vcrlagsgesellschaft Stuttgart (1964). Volume Il page 1837. defined.

The Wascli water possessed 20 German degrees of hardness a pH value of 10. The washing time was 30 minutes! and the tile relationship. characterized by: Ratio of (kg) laundry to (liter) washing liquor 1:50 in the presence of 10 Slahlkugeln.

After the prescribed washing time has elapsed, the Slandard cotton webc rinsed once hot and cinma cold with water of the same hardness and then rinsed in the remission photometer ί-lrepho from Zeiss the whiteness measured using the R 53 filter. The detergency was determined by the difference method determined, which results from the following equation:

K = Wu WG, -% WC ₁ ,

in which mean

% WK - 'Vu washing power

% Whiteness of the washed fabric /, =% whiteness of the unwashed fabric.

To carry out the washing tests, a washing liquor with the following composition was used applies:

0.45 g / l dudecylbenzenesilfonate

0.15 g / 1 ethoxylating tallow alcohol with one-half mol

Ethylene oxide per mole of alcohol

0.15 g / l hardened sebum cile

0.15 g / l magnesium silicate

0.15 g / l sodium silicate

1.25 g / l sodium perboral teirahydrate

0.45 g / l sodium sulfate

0.05 g / L Tylose

0.2-2 g / l builder A. B, C. D or F.

ad 1000 ml of water.

The washing power achieved with the individual wash liquors is demonstrated by the curves of the curves Λ to J, the curves / VßundC'dicIIrgebnissi of washing tests with the inventive builders A, B and C and the K.irven wound /: 'the results of Show washing tests with known Gcrüsi fabrics D and II. It can be seen that in the case of spiclsweisc with a Gcrüslsloffmcngc of 1.8 g / wash liquor with the scaffolding \. B and C a detergency of 35.5% or j. |, B% or 34.4% is achieved, while under the same conditions the structural fabrics D and L only eiiu; Washing power of 32.6 "/ or 33.0" / (i result. These results are also inherent in the technical superiority of the scaffolds according to the invention compared to the known scaffolds in the standard washing test.

1 lihill /.ciehnunuen

Claims (5)

Patent claims: 1. Use of copolymers of oc-hydroxiacrylic acid and acrylic acid with an acrylic acid content of about 9 to 85 mol% and a relative viscosity of the 1 percent by weight solutions of the copolymers in aqueous 2 normal sodium hydroxide solution at 20 ⁰ C of about 0.05 to about 1, 0 as builders for detergents and cleaning agents, the copolymers being contained in the detergents and cleaning agents in an amount of about 10 to 90% by weight. 2. Use of the copolymers according to claim 1, characterized in that the acrylic acid portion of 16 to 50 Mo -% and the relative viscosity of 1 percent by weight solutions of the copolymers in aqueous 2norma he Natriumhydroxidlösüng at 20 ⁰ C for about 0.1 to 0.8! be. 3. Use of the copolymers according to claim I or 2, characterized in that the water-soluble salts of the copolymers are used as detergent and cleaning agent components. 4. Use of the copolymers according to claim 3, characterized in that the Alkali or ammonium salts of the copolymers are used as detergent and cleaning agent components. 5. Use of the copolymers according to claim 1-4, characterized in that they are in Detergents and cleaning agents are contained in an amount of about 20 to 60% by weight.