WO1990001534A1

WO1990001534A1 - Low-phosphate builder salt combination

Info

Publication number: WO1990001534A1
Application number: PCT/EP1989/000857
Authority: WO
Inventors: Maria Liphard; Wolfgang Von Rybinski; Uwe Trabitzsch
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1988-07-29
Filing date: 1989-07-21
Publication date: 1990-02-22
Also published as: EP0353562A1; DE3825858A1

Abstract

A builder salt combination for use in washing agents, which improves the secondary detergent power, comprises (A) 40 to 80 parts by weight of a mixture of sodium silicate having the composition Na2O:SiO2=1:0.9 to 1:1.6 and washing soda, the weight ratio of sodium silicate to washing soda being 4:1 to 1:2, (B) 0.2 to 1.5 parts by weight of sodium tripolyphosphate, and (C) 2 to 5 parts by weight of a (co)polymer of 100 to 50 wt.% of acrylic acid or methacrylic acid and 0 to 50 wt.% of maleic acid with a molecular weight of 5000 to 150000 in the form of the sodium salt.

Description

. 4-

"Low-phosphate builder salt combination nation"

The present invention relates to an alkaline, low-phosphate builder salt combination which, when used in detergents, brings about an improvement in the secondary washing capacity. Improved secondary washing capacity means a reduction in tissue incrustation. Such incrustations form after repeated washing and lead to severe graying and hardening. Such an incrustation can be quantitatively determined from an increased ash value.

In a preferred embodiment, the combined salt combination is used in detergents which are used in commercial laundries in conjunction with softened water and are stored as so-called stock solutions. Such agents generally contain larger proportions of metasilicate, soda and phosphates. They are usually for a good primary wash effect, i. H . a high washing performance compared to greasy and mineral. Soiling designed. However, the high alkalinity and the high proportion of alkaline-reacting silicates or soda favor tissue encrustation, especially when the proportion of tripolyphosphate has to be reduced for ecological reasons, for example to a proportion of less than 5% by weight. Usual detergents that are used for such purposes therefore contain significantly more than 5% by weight tripoiphosphate (STP). For example, in the examples according to EP 117 568 it is 18 to 8% by weight. It is also known that good washing results can also be achieved with phosphate substitutes, such as nitriiotriacetate (NTA) or finely divided zeolites. However, the ecological safety of NTA in wastewater and in the sediments of rivers and lakes is controversial, while agents containing zeolites are only of limited suitability for recipe solutions.

A builder salt combination has now been found which contains only minimal proportions of phosphates and - when used in detergents - develops excellent secondary washing power. A further advantage is that such means are suitable for preparing and storing aqueous concentrates (stock solutions, stock solutions), which, as is known, enables considerable rationalization in commercial laundries.

The invention relates to a builder salt combination which can be used in detergents and which improves the secondary washing ability, consisting of (calculated as an anhydrous substance)

A) 40 to 80 parts by weight of a mixture of

AI) sodium silicate with the composition Na ~ 0: SϊC = 1:

0, 9 to 1: 1, 6 and A2) soda with a weight ratio of A1 to A2 of 4: 1 to 1: 2,

B) 0.2 to 1.5 parts by weight of sodium tripolyphosphate,

C) 2 to 5 parts by weight of a (co) polymer from 100 to

50% by weight of acrylic acid or methacrylic acid and 0 to 50% by weight of maleic acid with a molecular weight of 5,000 to 150,000 in the form of the sodium acid.

The builder salt mixture preferably contains 30 to 60 parts by weight of component (AI) and 10 to 50 parts by weight of component (A.2). in a particularly preferred embodiment, the builder salt combination contains 35 to 55 parts by weight of component (A1)

20 to 40 parts by weight of component (A2)

0.3 to 1 part by weight of component (B)

2.5 to 4 parts by weight of component (C), the ratio of (AI) to (A2) preferably being 3: 1 to 2: 3.

The substances according to the above composition are calculated to be anhydrous, but can exist as salts containing water of crystallization. The sodium metasilicate can be in anhydrous form or as a pentahydrate. The tripolyphosphate is preferably in the form of a hexahydrate. Since it would hydrolyze too little effective orthophosphate and pyrophosphate under conventional conditions, especially with regard to its small amount, by hot spray drying, it is mixed in dry form with the builder salt or together with the at low temperatures other components granulated in a known manner to form agglomerates

Component (C) preferably consists of polyacrylic acid or a copolymer of acrylic acid and maleic acid in a weight ratio of 95: 5 to 50:50, in particular 90: 10 to 40:60 in the form of the sodium salts. The proportion by weight of the builder mixture is based on sodium salt. Highly suitable polyacrylates have a molecular weight of _. 5,000 to 50,000, particularly suitable acrylic acid-maleic acid copolymers from 25,000 to 100,000. Mixtures of homopolymeric polyacrylate and acrylic acid-maleic acid copolymer are also suitable.

The invention furthermore relates to detergents containing such a builder salt combination, these detergents having the following contents:

40 to 75% by weight of the builder salt combination (A) to (C),

10 to 25 wt .-% of a low-foaming

Surfactant combination (D) and 0 to 40% by weight of other usual detergent constituents, the amount of builder salts in the detergent (based on anhydrous substance) being as follows:

30 to 63.5% by weight of component (AI)

10 to 47.8% by weight of component (A2)

0.2 to 1.5% by weight of component (B)

2 to 5% by weight of component (C).

The composite detergents preferably contain, in addition to the surfactants and other components

35 to 55% by weight of component (AI) 20 to 40% by weight of component (A2) 0.3 to 1% by weight of component (B) 2.5 to 4% by weight of component ( C).

Non-ionic surfactants from the class of polyglycol ethers derived from alcohols are suitable as low-foaming surfactants. with 10 to 22, in particular 12 to 18, carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl branched in 2-position (oxo radical). Their reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation. The number of EO or PO groups given corresponds to a statistical mean for technical alkoxylates.

Examples ^• of suitable ones _. ethoxylated fatty alcohols are C- __ _lg -

Coconut alcohols with 3 to 12 EO, C, _r 10 tallow alcohol with 4 to 16

16-18 ³

EO, oleyl alcohol with 4 to 12 EO and from other native Fatty alcohol mixtures available ethoxylation products with appropriate chain and EO distribution. From the series of ethoxylated oxo alcohols are, for example, those with the composition C. _, .. with 5 to 10 EO and C ^ ^ -C. - Suitable with 6 to 12 EO. Mixtures of low and highly ethoxylated alcohols are characterized by increased detergency against both greasy and mineral soiling, for example those made of tallow alcohol with 3 to 6 EO and tallow alcohol with 12 to 16 EO or C ₁ __ ₁ _-oxo alcohol with 3 to 5 EO and C -oxo alcohol with 8 to 12 EO. Nonionic surfactants with particularly low foaming are those of the general formula R- (EO) - (PO) -OH, in which x is equal to or greater than y and is a number from 5 to 25 and y is a number from 1 to 20.

Also to be considered are ethoxylation products of vicinal diols, amines, thioalcohols and fatty acid amides, which correspond to the fatty alcohol ethoxylates described with regard to the number of carbon atoms in the hydrophobic radical and the glycol ether groups. Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 10 ethylene glycol ether groups can also be used. Finally, block polymers made from ethylene oxide and propylene oxide are also suitable, which are commercially available under the name Pluronics. Alkyl oligoglycosides are also suitable, preferably those with C.-alkyl groups and on average 1.5 to 8 glucose units in the hydrophilic radical.

If the detergents according to the invention are intended for the preparation of base liquors, the use of such nonionic surfactants or surfactant mixtures is recommended, the HLB value of which is in the range from 11 to 1 6, preferably 1 1, 5 to 15. These have sufficient resistance to phase separation. Other suitable low-foaming surfactants are sodium soaps, possibly also potassium soaps, of fatty acids with 10 to 22, preferably 12 to 18, carbon atoms. The fatty acids on which these soaps are based can be derived from natural fatty acid mixtures, for example coconut, palm kernel, tallow or rapeseed oil fatty acids, and saturated as well as monounsaturated, e.g. B. Containing oleic acid. Soaps with a high proportion of C. - - fatty acids and / or a high proportion of oleic acid are particularly suitable for detergent solutions. Soaps with a high proportion of tallow fatty acids or saturated C _ __ fatty acids have a foam-suppressing effect. "

In addition, synthetic anionic surfactants can also be present, preferably those of the sulfonate type, such as linear alkylbenzenesulfonates with essentially 10 to 13 carbon atoms in the alkyl group. Other suitable sulfonate surfactants are olefin sulfonates and secondary alkyl sulfonates with 12 to 18 carbon atoms as well as alpha sulfo fatty acids and alpha sulfo fatty acid esters, derived from saturated C ₁ __- »fatty acids or their methyl, ethyl or propyl esters. Optionally, sulfate surfactants may also be present, e.g. B. Alkyl sulfates derived from linear C. __. "-Fatty alcohols. The synthetic anionic surfactants are usually used as sodium salts. Alkylbenzenesulfonates (dodecylbenzenesulfonate) are preferred, since they make a comparatively small contribution to the development of foam, but make a high contribution to the washing power.

The total proportion of surfactants is 10 to 25% by weight, based on the composition, of which 5 to 25% by weight is based on nonionic surfactants, 0 to 15% by weight on soaps and 0 to 10% by weight on synthetic anionic surfactants omitted. The proportion of nonionic surfactant is preferably 8 to 22% by weight, the proportion of soap is 0 to 10% by weight and that of synthetic anionic surfactant, in particular in the form of the alkylbenzenesulfonate defined above, 0.5 to 5% by weight. -%. Further constituents which can be contained in the composite detergents are: bleaching agents, such as per compounds, activators for per compounds, such as tetraacetylethylene diamine; Stabilizers for per compounds, such as polyaminopolycarboxylates and in particular polyaminopolyphosphonates; Enzymes such as proteases and amylases; Graying inhibitors, such as cellulose ethers, for example carboxymethyl cellulose, hydroxyethyl methyl cellulose and methyl cellulose and mixtures of the cellulose ethers mentioned; optical brighteners, in particular those of the substituted bis- (1,3,5-amino-sym-triazinyl) -stilbene disulfonic acid type; Solubilizers, such as toluene or xylene sulfonates; Neutral salts such as sodium sulfate. In addition, if the agents are not intended for stock liquors, water-insoluble detergent constituents may also be present, such as finely crystalline, water-containing zeolites of the NaA type with a calcium binding capacity of 100 to 200 mg CaO / g determined according to DE 24 12 837. May further addition of foam inhibitors such as organopolysiloxanes and mixtures thereof with finely divided SiO_, paraffins or Mikroparaf- fine long-chain, bis-acylalkylendiamine, saturated C_ ₀ _ ₂ "-Fett- acids as well as their mixtures in amounts of between 0.05 and 0.5 Gew. Be used.

The application concentrations of the composite detergents are generally 3 to 10 g / l, those of the builder salt combination 2 to 8 g / l, the use of moderately hard to soft water, ie a water with less than 12 ° dH (89 mg Ca / liter), preferably 10 ° dH or less is preferred. Examples

1. A detergent was used with a content of (in% by weight) based on anhydrous substance:

1.5% linear sodium dodecylbenzenesulfonate

0.5% Na soap (tallow soap)

8.0% nonionic surfactant (6% C _l2 _ ₁₄ alcohol + 3 EO,

2% tallow alcohol + 7 EO 0.3% optical brightener 46.0% Na ₂ Sϊ0 ₃ (metasilicate) 29.0% soda 3.5% builder additive rest of water

The builder additive consisted of a) 3.0% acrylic acid-maleic acid copolymer as Na salt, molecular weight = 70,000 (Sokalan CP5) 0.5% Na-P-O .., anhydrous (degree of conservation 98%)

b) 3.0% polymer according to (C) 0.5% sodium sulfate

c) 0.5% Na ₅ P ₃ 0 _1Q 3.0% sodium sulfate

d) 3.5% sodium sulfate

The washing tests were carried out in a launderometer on textile samples made from bleached nettle. Dosage: 4.0 g / l, temperature 90 ° C, washing time 30 minutes (heating period 15 minutes), rinsing three times, water hardness 10 ° dH at a Ca: Mg ratio of 5: 1. After 25 washing treatments, the textile samples were ashed. The ash values (mean values from 3 control samples) are summarized in the following table.

g / l OOg tissue

The results show that small amounts of phosphate (test c) do not reduce the fiber incrustation, but actually favor it. Small amounts of copolymer bring about minimal improvement (experiment b). A combination of both substances leads to a considerable increase in the secondary washing ability.

Claims

Patent claims

1. Use of builder salt combination to improve the secondary washing ability, consisting of (calculated as anhydrous substance)

A) 40 to 80 parts by weight of a mixture of

A1) Sodium silicate with the composition Na_0: SiO_ = 1: 0.9 to

1: 1, 6 and A2) soda with a weight ratio of A1 to A2 from 4: 1 to 1: 2

B) 0.2 to 1.5 parts by weight of sodium tripolyphosphate

C) 2 to 5 parts by weight of a (co) polymer of 100 to 50% by weight of acrylic acid or methacrylic acid and 0 to 50% by weight of maleic acid with a molecular weight of 5,000 to 150,000 in the form of the sodium salt.

2. builder salt mixture according to claim 1, characterized by ei¬ NEN content

30 to 60 parts by weight of component (A1), 10 to 50 parts by weight of component (A2).

3. builder salt mixture according to claim 1 and 2, characterized by

35.0 to 55 parts by weight of component A1

20.0 to 40 parts by weight of component A2

0.3 to 1 part by weight of component B

2.5 to 4 parts by weight of component C.

4. Detergent with improved secondary washing ability, characterized by a content of

40 to 75% by weight of an alkaline builder salt combination (A) to (C), 5 to 25% by weight of a low-foaming surfactant combination 0 to 40% by weight of other usual

Detergent ingredients, characterized in that the builder salt combination (water-free substance based on detergent) is composed as follows: A1) 30.0 to 63.5% by weight sodium silicate of the composition

Na ₂ 0: Si0 ₂ = 1: 0.9 to 1: 1.6, A2) 10.0 to 47.8% by weight of soda,

B) 0.2 to 1.5% by weight of sodium tripolyphosphate,

C) 2.0 to 5.0% by weight of a (co) polymer from 100 to 50

% By weight of acrylic acid or methacrylic acid and 0 to 50% by weight of maleic acid with a molecular weight of 5,000 to 150,000 in the form of the sodium salt.

5. Composition according to claim 4, characterized by a content of 35.0 to 55 wt .-% of component AI

20.0 to 40% by weight of component A2 0.3 to 1% by weight of component B 2.5 to 4% by weight of component C.

6. Composition according to claims 4 and 5, characterized by a content of a surfactant combination consisting of

5 to 25% by weight of nonionic surfactants,

0 to 15% by weight of soap,

0 to 10% by weight of synthetic anionic surfactants.

7. Composition according to claim 6, characterized by a surfactant combination of the following composition:

8.0 to 27.0% by weight of nonionic surfactants,

0 to 10.0% by weight of soap in the form of the sodium salt,

0.5 to 5 wt .-% of linear C-alkylbenzenesulfonates in the form of the sodium salt.