DE2548233A1 - PHOSPHATE-FREE DETERGENT - Google Patents

Description

B it honors ibu η κ for the patent application

Societe Francaise des Silicates Speciaux

"SIFRANCE" 25t Quai Paul Doumer, 92408 Courbevoie / France

Concerning: Phosphate-free detergent

The invention relates to a new powdery, phosphate-free detergent and the method for the same Manufacture and its application.

The detergent according to the invention is for cleaning all types of textiles by immersion in a watery Bath, especially thought of in washing machines of any design and is especially suitable for textiles Synthetic fibers.

The detergents for textiles are generally powders which, when used in water, form an aqueous washing bath be solved; they are removed at the same time as the dirt is rinsed.

It follows that the detergents must meet various requirements. First of all, they should be easy to use and not change adversely over time. You should still not sweat out of the usual packaging, usually made of cardboard.

803813/1222

In the actual washing bath, they should develop a high cleaning power, but not damage the textile material. After all, it should be possible to completely remove them from the laundry when rinsing.

In recent years another requirement has arisen which is related to environmental pollution stands: The detergents should not only be removed when washing, they should also not be used as a detergent present in the wastewater.

These numerous requirements show that an ideal solution is very difficult to find. Numerous Disadvantages arise from the need to use natural water. Natural water always contains Calcium and magnesium salts dissolved in more or less large amounts, the adverse effect of which is due to the Hardness of water is well known.

As a result of various chemical reactions, that is present in natural water in the form of soluble salts Calcium and magnesium precipitated in the form of insoluble salts during the washing process. These are formed "in situ" Precipitation forms encrustations on the laundry, which primarily have a detrimental effect on the handle, give the laundry a gray shimmer and - because they Hold back dirt - the wear and tear or the Increase the speed at which the laundry wears.

Two of these disadvantages are joined by another, namely the precipitation of anionic surfactants such as soap and sodium alkylarylsulfonates. It also leads Iis water hardness to the well-known scale build-up in the Washing machines, especially on the. Heating coils and in the Zi- and derivatives, which also have considerable disadvantages result.

609819/1222

Many attempts have already been made to remedy these known disadvantages.

According to an old solution, sodium carbonate is added to precipitate calcium carbonate and onto it Way to prevent the (unnecessary) consumption of soap. With this treatment, certain incrustations can be traced back to the hardness of the water are, avoid; but there are others as a result of the precipitation of the calcium carbonate formed on the Fiber.

You can still try to soften the water before washing; but this is a very expensive one and therefore uneconomical solution; in addition, the plasticized water has rather troublesome corrosive ones Properties.

Another solution provides for the dissolved calcium with Using a scavenger in a * complex compound too convert and in this way react with the soaps and the anionic surfactants to prevent. This is the best solution known so far and explains the success of certain Phosphorus compounds, such as sodium tripolyphosphate, are excellent at the detergent level has proven itself. Unfortunately, when using this remedy, a new problem arises, namely that it is too plentiful Supply of nutrients or eutrophy of lakes and watercourses.

One has therefore looked for other solutions that avoid phosphates as scavenging agents.

One possibility is to use

609819/1222

surfactants whose activity depends on the Water hardness depends and which are, for example, non-ionic, especially since these non-ionic agents are good for Washing of modern hydrophobic textiles are suitable and their share in the textile sector is constantly increasing. It · but here again difficulties of various kinds arise. One difficulty arises from the fact that the Activity of the nonionic surfactant is not affected by the hardness of the water, but still is the deposition of calcium salts and the corresponding crust formation on the laundry is observed. Another Difficulty stems from the difficulties encountered in shaping the nonionic surfactants Funds yield; these are generally liquid, do not atomize, and tend to get carried away by their powdery carrier to wander away and sweat it out.

Furthermore, it is necessary that the various components of the detergent are compatible and compatible with one another that the detergent as a whole meets the requirements that the dirt is well dissolved that the dirt particles do not settle again and that no crusts form.

It is well known that silicas and silicates (sand, clay, kaolin, etc.) have been used as Detergent used. You will be mainly because of their abrasive power (powdered sands), their cleaning power (clays), their absorption capacity (Sommieres earth, Talc, etc.), their bactericidal properties (clays) and due to their emulsifier, dispersant, Stabilizer properties and properties that counteract the formation of lumps (magnesium silicate) are valued. Based on these

609819/1222

different properties they are in the most diverse Detergents used.

For example, "an attempt was made to use bentonite because of its plasticizer effect in water? this results from the cation exchanger properties and the colloidal effect of the bentonite, which has a positive effect in the presence of soap. Unfortunately, however, bentonite's detergency leaves something to be desired left over. In addition, it is a natural product that can contain undesirable accompanying substances and is in its composition is not always identical, which gives rise to a certain degree of unreliability the application results. It is also known that detergent effectiveness depends on the presence of surfactants Substances are based, their effect through the presence of the other components of the detergent being affected.

According to FR-PS 514- 928 a connection is used, in which silica and alumina are combined with an alkali base to form a crystalline one that is solid at room temperature Link. In US-PS 2,296,689 grinding and stripping powders are described, which are composed of a insoluble material containing silica. Bentonite has also been linked to detergents described as colloidal clay, either in one of the naturally occurring forms or can be used in modified form in soaps, for example in accordance with US Pat. No. 1 94-3 584. Finally the use of other silicic acid derivatives, such as a magnesium silicate, was also mentioned in US Pat. No. 2,625,513, as well as an anti-lump remedy. In this latter case, that contained in detergents or laundry detergents non-ionic surfactants on diatoms

609819/1222

ever-- _;

adsorbed earth or other similar compounds and converted into solid forms in this way.

Attempts have also been made to sodium tripolyphosphate to be replaced by another compound with a cation exchange effect. For example, FR-PS 2 225 568 as a component of detergents and cleaning agents an Aluminumsilic.at with a small molar ratio SiOp / Al ^ O, and high cation exchange capacity, which replace the phosphates, especially the tripolyphosphate target.

Recently attempts have also been made to use at least one nonionic surfactant at least an insoluble synthetic and amorphous silica support material to absorb and dry the product thus obtained with the other components of the Mixing detergents or cleaning agents. Through this encrustation due to the insoluble carrier material should be avoided.

Unfortunately, it is still difficult to meet the three main requirements mentioned above, removing the dirt, Avoidance of reprecipitation and avoidance of incrustations, to correspond at the same time.

Surprisingly, it has now been found that good results are achieved with a phosphate-free detergent which is characterized in that it is at least one surfactant and at least contains an anti-limescale and anti-tarnish agent consisting of "at least one insoluble in the detergent medium synthetic aluminum silicate of the formula χ Na ^ O, y Al ^ O ^, ζ SiOp, w HpO consists in which for y = 1, χ is less or is equal to 2, ζ is a value from 4 to 15 ", and w is a value of 0.3 to 9 assumes. Advantageously, for y = 1

609819/1222

χ a value from 0.8 to 1.1, ζ a value from 4 to 15 and w a value from 0.5 to 3. Farther is preferably the aluminum silicate used according to the invention amorphous. Furthermore, it forms porous agglomerates due to the agglomeration of primary aggregates those of the diameter of the single particle (last particle) determined in the electron microscope (10 to 50 µm) 100 to 500 Ä. amounts to. The aluminum SiHeat is still marked through a specific surface

BET from 50 to 600 m / g as well as by one in the mercury porosimeter certain porosity for pore sizes from 40 mm up to 2.5 / µm from 50 to 200 ml / 100 g; This matches with essentially an absorption capacity for the surface-active agent which is at least equal to its own weight. The cleansing or washing medium is preferably kept at a pH below 11.

Advantageously, the surfactant is a synthetic product, namely a surfactant Compound, such as a fatty amine oxide, an alkylolamide, a condensation product of ethylene oxide and a long-chain alcohol or a phenol, a fatty acid, an amine, an amide or a compound from the group consisting of sodium alkylbenzenesulfonate, petalcohol sodium sulfate, Sodium phosphoric acid ester and / or sulfuric acid ester an ethoxylated alcohol and other compounds · more.

Preferably a non-ionic surfactant, for example an ethoxylated compound, in particular a condensation product of ethylene oxide and a polypropylene glycol or an alkylphenol used. The condensation products of 6 to 10 moles of ethylene oxide and one mole of one have proven to be particularly suitable linear aliphatic CLp to C. alcohol proved.

609819/1222

The surfactant can be liquid or solid be.

According to a particular embodiment, the washing or cleaning agent according to the invention contains the same Parts by weight of synthetic alkali aluminum silicate and surfactant.

The agent can consist solely of at least one surfactant and an aluminum silicate exist or contain other compounds.

For example, a detergent or cleaning agent contains * finding (based on weight):

5 to 50% of at least one synthetic alkali aluminum silicate,

Λ up to 30 % of at least one non-ionic surfactant,

1 to 30% of at least one anionic surfactant and

1 to 20 % of a sodium silicate with a molar ratio SiOp / Na ₂ 0 of 1 to 3 ₅ 5 ₅ which acts as a pH buffer substance and as a corrosion inhibitor; aside from that

0.5 to 5 % protective colloid, such as carboxymethyl cellulose, polyvinyl alcohol or vinyl pyrrolidone as an agent against reprecipitation,

0.5 to 5 % of a scavenger, such as ethylenediaminetetraacetic acid (EDTA),

Diethylenetetraminepentaacetic acid (DPTA), nitrilotriacetic acid (NTA) or Sodium citrate, sodium gluconate,

1 to 30%! "Liquid, such as sodium sulfate or sodium borate,

609819/1222

1 to 20 % of a bleach, for example a

Persalz, especially sodium perborate and in the end

0.3 to 2% of an optical brightener or a mixture of optical brighteners.

It has also been found, surprisingly, that the aluminum silicates to be used according to the invention have a exert a synergistic effect on the non-ionic surface-active substances and that these The synergistic effect is enhanced when the ionic character of the Wasdi bath is reduced.

It is known that the nonionic surfactants have a particularly strong effect on the hydrophobic synthetic textiles, for example ethylene glycol polyterephthalate, unfold and that they are also practically insensitive to water hardness.

The invention further relates to a washing process for textiles in an aqueous medium with the aid of a detergent, the water-insoluble agent provided according to the invention as an agent against lime and against crust formation synthetic aluminosilicate and also contains at least one nonionic surfactant; this process is particularly suitable for textiles based on hydrophobic synthetic fibers.

Preferably the wash bath is non-ionic in nature.

According to a preferred embodiment, a nonionic detergent is used which, based on the weight, 1 to 50 % nonionic surface-active

609819/1222

- ίο -

Medium, 5 to 60% aluminosilicate contemplated according to the invention and furthermore, if applicable

0.1 to 5% of an organic scavenger,

0.1 to 5% of an agent against reprecipitation (protective colloidJ,

0.1 to 1% of an optical brightener and 0.1 to 2 % of an organic metal compound as

Corrosion inhibitor.

If a liquid surfactant is used, this is advantageously applied beforehand on a surface-active agent according to the invention to be used synthetic alkali aluminum silicate absorbed.

The product obtained can be used alone or dry mixed with other components of a washing or washing machine Detergent can be used. The proportion by weight of aluminum silicate is advantageously at least equal to the weight fraction of surfactants.

The invention is explained in more detail in the following examples. All washing Iests described were carried out in one commercial, thermo-controlled washing machine, trade name Terg-o-tometer carried out.

Examples 1 to 4

Number of washes 20th temperature 20 ° - * 80 ⁰ C in 20 min Washing time 20 min Bath volume 250 ml water soft water O ° th or
hard water 20 th
French standard Ni ¹ 90003 tissue white cotton standard
tissue
4 samples per bath

603819/1222

Motion rinse

Determination of the trusts

75 rpm

3 times for 2 minutes each time in the same water as used for washing

by ashing the cotton samples in the oven "

Example 1_

This example describes a series of tests in soft water which show that the aluminosilicates do not cause any precipitation on the laundry.

Experiment a) : Washing liquor used

Nonionic surfactant consisting of the condensation product of a linear G ^ alcohol and 6 moles of ethylene oxide (trade name
Cemulsol DB 512) '4 g / l

Sodium disilicate 2 g / l

Sodium sulfate 4 g / l

Sodium perborate 4- g / l

Sodium tripolyphosphate 6 g / l

various additives 0.2 g / l

This wash liquor, which corresponded to a formulation with sodium tripolyphosphate, caused encrustation of 0.5%

Experiment b)

4 g / l sodium _{aluminum silicate of the formula 14 SiO 2} , AlpO ,, Na ^ O, H ^ O was added to the above bath.

609819/1222

To. 20 washes "was the degree of encrustation only 0.55%, despite the insoluble nature of the sodium aluminum silicate.

Experiment c)

4 g / l sodium aluminum silicate of the formula 4 SiO ₂ , Al ₂ O ₅ , Na ₂ O, 0.8 H ₅ O were added to bath a).

After 20 washes, the degree of encrustation was only 0.5%.

It must be emphasized here that the total concentration detergent was 20 to 24 g / l; this concentration is higher than usual in practice and was chosen to carry out the experiment under the toughest or most difficult conditions possible.

Experiment d)

A wash liquor was used which contained 4 g / l of the same nonionic surfactant and 4 g / l aluminum silicate of the formula 14 SiOp, AlpO ₇ ,, NapO, HpO; Degree of incrustation 0.5%

Example 2

This example was carried out like the previous one, The only difference is that in hard water, degree of hardness 20, in accordance with the French standard NF T 90003 was worked.

Test a): resulted in a degree of incrustation of 1.0%;

Experiment b): resulted in a degree of encrustation of 1.1%;

Experiment c): resulted in a degree of incrustation of 1.0%;

Experiment d): resulted in a degree of incrustation of 1.65%

609819/1222

A slight increase in the degree of incrustation is observed here as a result of the use of hard water.

Example 3

This example shows the effect of the aluminum silicate to be used according to the invention in hard water.

Try abcdefgh

Non-ioni see s

Surfactant acc.

Example 1 4 g / l 4g / l 4g / l 4g / l 4g / l

Na dodecylbenzene

sulfonate. 4g / l 4g / l 4g / l

Na disilicate 4g / l 4g / l

TPP (Na tripoly

phosphate) 4g / l 4g / l

14 SiO ₀ Al ₀ O ^ Na ₀ O

4g / l 4g / l

Degree of incrustation

% 5.4 6.8 4.8 3.2 0.2 1.65 0.2 1.9

This example shows that the aluminum silicate to be used according to the invention prevents incrustations, however in its effect lags somewhat behind the TPP (tripolyphosphate) used in the same amounts.

B. Example 4

This example shows the effect of the aluminum silicate to be used according to the invention in hard water (20 NP)

109819/1222

as part of a wash liquor of the following composition:

surfactant 4 g / l

Sodium disilicate 4 g / l

Sodium sulfate 4 g / l

Sodium perborate 4 g / l

various additives 0.3 g / l

In a first experiment, the surfactant according to Example 1 was used as the surface-active agent and 4 g / l Sodium tripolyphosphate added. The degree of incrustation was 1.2% after 20 washes.

In a second experiment, the iripolyphosphate was replaced by an equal amount by weight of aluminum silicate of the formula 14 SiO ₂ , Al ₅ O ₅ , ^ H ₅ O. The degree of encrustation was 1.70 %. * Na ₂ O

In a third attempt, the non-ionic surfactant from the first attempt was carried out an anionic surfactant replaced with sodium dodecylbenzenesulfonate; the Degree of encrustation was 1.10%.

In a fourth experiment, the same sodium aluminum silicate as before was used in the preceding formula used instead of TPP (tripolyphosphate). The degree of incrustation was 2%.

The preceding examples show that the usual sodium tripolyphosphate can be used in a simple and unexpected manner in detergents and cleaning agents simply by means of an aluminum silicate, as provided according to the invention

609819/1222

see can replace. Contrary to what was expected, this remedy settles in spite of its insolubility not on the textile fibers a "b and also largely prevents the incrustations caused by lime and thus acts in the same way and comparable to sodium tripolyphosphate.

Examples 5 "to 10

The washing tests were carried out in the same washing machine as in the previous examples under the following Conditions carried out:

Fabric: Dirty ethylene glycol polyterephthalate (Dacron)

White ethylene glycol polyterephthalate

Washing or cleaning attempts:

Washing time: 10 min at 70 ° C Movement: '100 RPM

Rinsing with cold water: 2 min. Water: hardness 22 ° th (NF 90003).

The determination of the whiteness or degree of whiteness (reflectance) was carried out using the ELEEPHO device from Zeiss with a filter No. 10. The numerical values given are the mean value from eight determinations.

Redeposition Degree: In this experiment white (clean) textile samples were washed at the same time as the soiled samples, namely under the same Conditions as above and also in hard water, degree of hardness 22 ° th (NF 9000J).

The decrease in whiteness is a measure of the redeposition.

609819/1222

- -16 - '

The incrustation tests were also carried out using a Terg-o-tometer. The incrustations were determined by ashing the samples.

An amorphous aluminum silicate of the formula Na ₂ O, Al ₂ (X, 14 SiO ₂ , 2.5 H ₂ O, with a BET specific surface area of 52 m / g and a porosity determined in the mercury porosimeter for pore sizes of 40 nm ( 400 S) up to 25 μm of 90 ml / 100 g and a cation exchange capacity of 45 mg OaO / g, which was determined as follows:

1 g (as active substance) of aluminum silicate were added to 1 liter of aqueous solution containing 0.594 g of CaCl _{2 (corresponding to 300 mg CaO / 1 or 53-50 ° hardness) adjusted to pH 10 with dilute sodium hydroxide solution.} The solution was stirred for 15 min vigorously at a temperature of 22 i 2 ⁰ C. After filtering off, the hardness of the filtrate was determined in accordance with French standard T 90003.

The nonionic surfactant consisted of a mixture of the condensation products of linear C ^ ₂ - C ^ - alcohols (1 mole) and 6 moles of ethylene oxide.

The individual conditions and the results obtained are summarized in the table below. The specified Concentration (application) is the concentration in the wash liquor; the specified differences in concentration are based on maintaining the same concentration for each reaction partner from one experiment to the other became, i.e., nonionic surfactant (surfactant) 1.2 g / l; Aluminum silicate 1.8 g / l,

609819/1222

Sodium disilicate 2 g / l.
The table shows:

In Examples 5 and 8 that the detergent action on polyester fabric is reinforced by the presence of the aluminum silicate to be used according to the invention, on the other hand, it is reduced by the tripolyphosphate present (Example 7);

in example 10, which is a detergent containing sodium disilicate has an equivalent washing or cleaning ability, but gives poor redeposition values.

Me encrustation or crusting is common in all cases small amount. The tests carried out with cotton show that the aluminum silicate works just as well in terms of cleaning action and in terms of redeposition is slightly higher.

TABEL:

609819/1222

Examples 5 6 7 8 9

Surfactant (%) 100 40 40 40 24 24

Calcium

carbonate (.%) 60

Ha-disilicate (%) 16 16

Na tripolyphos

phat (J ₀ ) fluid 0.45 5.3 60 3 60 30th 3 5 60 Aluminum silicate
fii0 ₂ / Al ₂ 0 ₅ = 14% 1.2 28.5 10.7 30th 30.3 17.4- Laundry detergent-
nature 25.2 Re-elimination ₂ , -
on cotton '^ sticky
powder -21.2 flowable
powder -1.8 -17.5 5 Application g / 1 Re-elimination
on polyester -4.0 Encrustation
cotton 3 0.47 0.55 0.57 30.6 V / ash effect at
polyester Encrustation
Polyester bag 26.8 30.2 32.5 31.5 -11.8 Washing effect at
cotton -1.5 -2.7 -0.8 -2.2 0.61 0.50 0.55 1.90 1.08 32.1 29.0 -1.2 -2.3 1.90 1.60

The results for crusting on cotton are not quite as good as when using sodium tripolyphosphate, however, noticeably better than expected, in accordance with the previous examples.

These examples show the importance of a detergent that is non-ionic or only weakly ionic, containing an aluminum silicate provided according to the invention and the unexpected effects, especially with regard to the requirements for a detergent for hydrophobic fibers.

72XXIV 809819/1222

Claims (1)

PATENT CLAIMS (1) Phosphate-free detergent, characterized in that it contains at least one surface-active agent and at least one agent against lime and. contains against crust formation, which consists of at least one synthetic aluminum silicate insoluble in the washing medium and _{corresponds to the formula χ Na 2} O, y Al ₂ CU, ζ SiO ₂ , w HpO, in which for y = 1, χ ^ - 2, ζ one Number from 4 to 15 and w corresponds to a number from 0.3 to 9. (2) Detergent according to claim 1, characterized in that the aluminum _{silicate corresponds to the formula χ Na 2} O, y AlpO ,, ζ SiOp, w HpO, in which for y = 1, χ a value of 0.8 to 1.1 and ζ corresponds to a number from 4 to 15 and w corresponds to a number from 0.5 to 3. (3) Detergent according to one of claims 1 or 2, characterized in that the sodium aluminum silicate has a porosity determined in the mercury porosimeter of 50 "to 200 ml / 100 g for pore sizes from 40 nm to 2.5 / µm and a specific surface area according to BET from 50 to 600 m ² / g. (4) detergent according to one of claims 1 to 3, characterized in that the sodium aluminum silicate is amorphous. 609819/1222 (5) detergent according to one of claims 1 to 4, characterized in that it is as surfactant contains a synthetic product. (6) detergent η sch one of claims 1 to 5, characterized in that it contains at least one non-ionic surfactant contains. (7) detergent according to one of claims 1 to 6, characterized in that it is the same Contains parts by weight of synthetic aluminosilicate and surfactant. (8) detergent according to one of claims 1 to 7, characterized in that it is based by weight, contains: 5 to 50% at least one synthetic aluminum silicate, 1 to 30 % of at least one non-ionic surfactant, 1 to 30% of at least one anionic surfactant,
1 to 20 % sodium silicate with a molar ratio SiOg / Na ^ O = 1 to 0.5 to 5% means to prevent redeposition, 0.5 to 5% scavenger, 1 to 30 % filler, 0.3 to 2% optical brightener. (9) Process for the preparation of the detergent according to one of claims Λ to 8, characterized in that the liquid surface-active agent is first adsorbed on a synthetic aluminum silicate as a carrier and the powdery product obtained is optionally mixed with the other components. 609819/1222 - 3 - ; oh - (10) Use of the detergent according to one of Claims 1 to 7 "at a pH value of - = 11 of the aqueous Detergent solution. (11) Use of the detergent according to claim 6 for textiles based on hydrophobic synthetic fibers. 609819/1222