NO753617L - - Google Patents

Description

"DETERGENT MIXTURE".

The present invention relates to a powdered detergent mixture without phosphate content, as well as a method for its production.

The invention relates in particular to detergent mixtures for cleaning textile articles by immersion in an aqueous bath, especially in washing machines of any type,

and especially for synthetic textile items.

Detergent mixtures for cleaning textile items usually take the form of a powder which is dissolved in water during use to form an aqueous bath, and is then removed together with the dirt in a rinsing operation.

It follows that the detergents must satisfy a number of requirements. Above all, they must be easy to handle and not change during storage. Likewise, they must not take out the packaging, which is usually made of cardboard. Furthermore, in the washroom itself, they must have a high washing ability without damaging the toy. Finally, they must be completely removed during the rinse.

A few years ago, however, it became even more so

a requirement in connection with pollution. Not only must the detergent be removed during rinsing, but they must also not constitute any polluting component in the waste water.

It only follows from the number of these requirements that it is very difficult to find an ideal solution. Many disadvantages have been noted in connection with using a natural water. This almost always contains larger or smaller amounts of dissolved salts of calcium and magnesium. However, they are unfortunate sides

by this hardness well known.

As a result of various chemical reactions, calcium and magnesium dissolved in the natural water in the form of their soluble salts will precipitate in the form of insoluble salts during washing. These formations of salts "in situ" cause deposits on the toy which in particular result in its grip becoming uncomfortable and the toy becoming a shade of gray as the dirt is retained and this increases the rate of wear.

To these disadvantages, one can add a further disadvantage arising from anionic surfactants, such as e.g.

soap and sodium alkylaryl sulphonates.

It is noted once again that the hardness of the water leads to damage

in the washing machines, especially the elements for heating and the circulation system, with all the consequent disadvantages.

It goes without saying that numerous solutions have previously been proposed to remedy these disadvantages.

According to a previous proposal, sodium carbonate is added

which is precipitated in the form of calcium carbonate and leads to less consumption of soap. Although the treatment allows the elimination of deposits caused by the hardness of the water, it produces, among other things, precipitates of calcium carbonate formed on the fibres.

You can also make the water bare in advance, but from an economic point of view this is a very expensive solution and the bare water has corrosive properties which are quite annoying.

A further solution consists in complexing with the help of

a complexing agent that complexes calcium in soluble form, unavailable to soap and anionic surfactants. This has been considered the best solution, and can explain the widespread use of certain phosphorus derivatives such as sodium tripolyphosphate, which constitute an excellent solution in terms of detergent technology but have the unfortunate fact that they kill

life in lakes and rivers.

One has consequently looked for other solutions that do not require the use of phosphates as complexing agents.

A solution consists in using surfactants if

activity are less sensitive to water hardness, e.g.

of non-ionic type, and these are well suited to washing hydrophobic modern synthetic textiles which represent an important and decisive part of the laundry.

But here, too, there are shortcomings of many kinds, and even though

the activity of the non-ionic surfactant is not affected by the hardness of the water, precipitation of salts still occurs

of calcium and their deposition påttoyet..

A further difficulty relates to the form of the non-ionic surfactants which are usually present in liquid form, which cannot be atomized and which tend to migrate and penetrate out of the powdered carrier.

Furthermore, they are not miscible with the various components

in the detergent mixture which must still meet the washability requirements, i.e. removal of dirt, non-renewed deposition of the dirt and non-deposition.

Mon^. know that silicon oxide and silicates (sand, clay, kaolin, etc.) have been used as detergents for a very long time. They are known -especially for their abrasive properties (pulverized sand), their cleaning properties (clay), their absorption properties (terre de Sommiéres, talc, etc.), their bactericidal properties (clay), as well as their emulsifying and dispersing properties, as anti -clumping agents and stabilizers (magnesium silicate). These different properties mean that they can be used in different detergents and cleaning agents.

It has also been proposed to use bentonite because of its softening ability on the water that is rinsed, its cation-exchange properties and its colloidal action which has a beneficial effect in the presence of soap.

Unfortunately, the washability of bentonite is not very large. Further

as a natural product as such it could contain unwanted contaminants that are not always the same, and this is expressed in a lack of versatility in the applications. It is also known that the washing efficiency due to the presence of surface-active compounds is affected by the presence of other components in the detergent compositions.

In French patent document 514,938, application has been foreseen

of a mixture in which silica and alumina are combined with an alkali base to produce a crystalline compound in the solid state at ordinary temperatures. In US patent 2,296,689 abrasive and scouring powders comprising an insoluble material containing silicon oxide are discussed. Bentonite is also described in detergent compositions, as a colloidal clay usable either in its natural state or modified in soap as in US Patent 1,943,584. Finally, the use of other derivatives of silicon oxide such as, for example, a magnesium silicate in US patent 2,625,513, and as an anti-caking agent has been proposed. In the latter case, as the detergent contains a non-ionic surfactant, this is transferred in solid form by adsorption onto diatomaceous earth or similar substances.

It is also contemplated to replace the tripolyphosphate with another compound capable of cation exchange.

In the French patent document 2,225,568, a silicon oxide aluminate with a low molar ratio SiO 2 /Al 2 O 3 with a high exchange capacity for cations has been proposed for washing purposes to replace the phosphates and especially the tripolyphosphate.

It has recently been proposed to absorb at least one non-ionic surface-active agent on at least one insoluble synthetic absorbent and amorphous carrier of silicon oxide, then carry out a dry mixing of the obtained product with the other components of the detergent mixture. Such a release means that deposits are not produced due to the carrier which is in itself insoluble.

Unfortunately, it is difficult to satisfy them at the same time

three requirements which have been previously mentioned, namely removal of the dirt, anti-renewed deposition of this and anti-scaling.

However, it has surprisingly been found that good results can be achieved using a detergent mixture without phosphates,

in that the mixture comprises at least one surface-active agent and at least one anti-calcifying agent and anti-fouling agent which is made up of at least one synthetic silicon oxide-aluminate insoluble in the washing mixture and which has the formula xNa^O, yA^O^, zSiC^, wf^O ^ YVOr^ y is equal to 1'x is less than or equal to 2, z is between 4 and 15 and w has a value between 0.3 and 9. Advantageously, for y is equal to 1 x varies between 0.8 and 1.1 , z varies between 4 and 15 and w has a value between 0.5 and 3.

Preference is given to the silicon oxide-aluminate used in

according to the invention amorphous.

Furthermore, it exhibits porous agglomerates which are due to agglomeration of primary aggregates with particle diameters measured in an electron microscope between 100 and 500 Å.

The specific surface BET is preferably: 50 to 600 m 2 /g

with a porosity measured by mercury solution porosimetry for pores in the range of 400 Å to 2.5 'ai, corresponding to between 50 and 200 cm/100 g, roughly corresponding to an absorbency for the surfactant of at least its own weight.

The washing environment is preferably kept at a pH lower than 11.

Advantageously, the surface-active agent is made of a synthetic product which can be a surface-active derivative such as fatty amine oxides, alkylolamides, condensation product of ethylene oxide with an alcohol or a phenpl with a long chain, a fatty acid, an amine,

an amide, or a compound of the group:

- sodium alkylbenzene sulfonate,

- sodium fatty alcohol sulfate,

- sodium phosphoric acid ester,

- ethoxylated sulphate alcohol, etc.

Preferably, a non-ionic surfactant is used which

an ethoxylated derivative and especially that formed by the condensation of ethylene oxide on polypropylene glycol, or ethylene oxide on an alkylphenol, but especially a linear aliphatic C'^ to C^ alcohol ethoxylated with 6 to 10 moles of ethylene oxide.

This surfactant can be in the form of a liquid or a solid.

In a particular embodiment of the invention, the detergent mixture comprises equal amounts of synthetic alkali metal silicon oxide aluminate and surfactant.

This mixture may consist only of a surfactant and

a silica-aluminate or may include additional products.

A detergent formulation according to the invention comprises the following amounts by weight: - 5 to 50 percent by weight of a synthetic alkali metal silicon oxide aluminate. - 1 to 30 percent by weight of at least one nonionic surfactant.

- 1 to 30 percent by weight of an anionic surfactant.

- 1 to 20 percent by weight of a sodium silicate with a SiO2/Na20 molar ratio between 1 and 3.5, which stabilizes the pH and prevents corrosion.

0.5 to 5 wt pEosenfstav an anti-renew deposition agent such as carboxymethyl cellulose, polyvinyl alcohol polyvinyl pyrrolidone,

- 0.5 to 5% by weight of a complexing agent which

for example:

- EDTA (ethylene diamine tetraacetate)

- EDTA (diethylenetetramine pentaacetate)

- NTA (nitrilotriacetate)

- sodium citrate, sodium gluconate, etc.

- 1 to 30 percent by weight of a filler such as sodium sulfate or sodium borate.

- 1 to 20 percent by weight of a bleaching agent such as e.g. persalts and

then especially sodium perborate,

- and finally, 0.3 to 2% by weight of an optical brightener

or a mixture of optical brighteners.

It has also surprisingly been found that the same silicon oxide aluminates have a synergistic effect in relation to non-ionic surfactants and that. this synergistic effect is further increased if the ionic character of the washing bath is reduced.

It is known that the non-ionic surfactants are particularly active towards synthetic textiles, with a hydrophobic character,

such as ethylene glycol polyterephthalate, and that they are also practically insensitive to the hardness of the water.

The detergent mixture according to the present invention is thus particularly suitable for washing textiles in an aqueous environment, as the detergent mixture comprises at least one anti-lime-forming and anti-scaling agent which is made of a synthetic silicon oxide aluminate insoluble in water, the content of a non- ionic surfactant makes the detergent mixture particularly suitable for washing textile materials based on hydrophobic synthetic fibres.

The washing bath is therefore preferably non-ionic in nature.,

A non-ionic detergent mixture is advantageously used containing <1> to 50% by weight of a non-ionic surfactant, 5 to 60% by weight of a silicon oxide aluminate according to the invention and with any additions of 0.1 to 5% by weight of a organic complexing agent.

0.1 to 5% by weight of an anti-renewable deposit agent,

0.1 to 1% by weight of an optical brightener,

0.1 to 2 percent by weight of an organic type corrosion inhibitor.

In the case of a liquid surfactant,

this is advantageously absorbed in advance on a synthetic alkali metal aluminum oxide silicate according to the invention.

The product obtained can be used alone or dry mixed with

and other components in a detergent mixture.

Advantageously, the amount by weight of silicon oxide aluminate is at least as large as the amount by weight of surfactant.

The invention will be described in more detail in the following with help

of examples of preferred embodiments.

In all the following examples, the washing process was carried out

in a temperature-controlled device sold by US Testing under the designation "Terg-o-tometer".

EXAMPLES 1 to 4.

EXAMPLE,,."!.

This example corresponds to a series of tests with only water passed through to show that the silismum oxide aluminates themselves do not produce any deposit on the toy.

Experiment a): Detergent used.

Nonionic surfactant consisting of a linear C- alcohol ethoxylated with 6 moles of ethylene oxide sold under the name

A similar detergent corresponding to a chemical composition with sodium tripolyphosphite produces a deposit amount of 0.5%.

Experiment b) 4 g/l of a sodium silicon oxide aluminate with formula 14 SiO2, Al^O^, Na2O, I^O is added to the preceding bath.

After 20 washes, the deposit amount was only 0.55% despite the insoluble nature of the sodium silica aluminate. Experiment c) To the bath a) 4 g/l of a sodium silicon oxide aluminate with formula 4 SiO 2 , Al 2 O 3 , Na 2 O, 0.8 H 2 O is added.

After 20 washes, the deposit amount was only 0.5%. It is noted

that the total concentration in the washing bath is 20 to 24 g/l, which corresponds to a higher concentration than usual in practice, but one would also try more stringent conditions.

Experiment d) A composition containing:

- 4 g/l of the same non-ionic surfactant

- 4 g/l of the silicon oxide aluminate with formula 14 Si02, Al^^, Na20, H20

- the deposit amount 0.5%.

EXAMPLE 2.

This example is identical to the previous one with the exception of

that the trial is carried out with hard water (hardness 20° according to French standard NF T 90003).

trial a) gives a deposit amount of 1.0%

- attempt b) gives a deposit amount of 1.1%

attempt c) gives a deposit amount of 1%

- attempt d) gives a yield amount of 1.65%.

A minor increase in the amount of deposits is noted here.

EXAMPLE 3.

The purpose of this example is to measure the impact of the silica aluminate in hard water. This example shows the role the silicon oxide aluminates play as an inhibitor for the deposits, even if its effect is less pronounced than for TPP used in the same quantities.

EXAMPLE 4.

This example is _1 to show the effect of the silica aluminate in hard water (hardness 20° French standard) in a detergent mixture of composition

In a first attempt, the surfactant is made of "Cefhulsol DB 312" and 4 g/l TPP is added.

The deposit amount after 20 washings is 1.2%.

In another attempt, TPP is replaced with the same weight of

a silicon oxide aluminate of formula 14 SiO 2 , Al^^ , Na 2 O,

2 H 2 O, the deposit amount being 1.70%.

In the third attempt, in the composition for the first attempt, the non-ionic surface-active agent is replaced by an anionic surface-active agent which is made up of sodium dodecylbenzene sulphonate and the deposit amount is 1.10%.

In a fourth attempt, the previous composition is replaced by the sodium silicon oxide aluminate as before

TPP.

The content of deposits is found to be equal to 2%.

in

The previous examples then clearly show that TPP can be replaced in a simple and unexpected way in the detergent mixtures with a silicon oxide aluminate, since, contrary to what one would expect, no deposit is obtained on the fibers despite the insolubility, the deposit of calcareous deposits is prevented in large scale so that the silica-aluminate plays a role comparable to the sodium tripolyphosphate.

EXAMPLES 5 to 10.

The washing tests were carried out in a "terg-o-tometer" type device (US Testing) under the following conditions: Textile: Polyethylene glycol terephthalate "Dacron" soiled, supplied by USbTest Fabric.

White "Dacron" supplied by US Test Fabric.

Washing test: Washing conditions: 10 minutes at 70°C.

Agitation: rotation speed 100 revolutions per minute.

Rinsing in cold water: 2 minutes.

Water - hardness 22° (French standard 90003)

The reflex ion measurements are carried out using a Zeiss "ELREPHO" device equipped with filter no. 10. The numbers are the mean value of 8 numbers.

Degree of renewed deposition: this attempt consists in washing the test pieces at the same time as the soiled test pieces.

Conditions: hard water 22° (French standard 90003): same conditions as for washing.

The loss in reflectivity is a measure of the renewed deposit.

The deposition tests were also carried out during use

of a "Terg-o-tometer" apparatus.

The silicon oxide aluminate used is an amorphous composition

which correspond to formulas Na2O, hl^ O^, 14 SiC^, 2, 5 H2O. It has a surface BET of 52 m^/g and a porosity measured by mercury solution porosimetry for the pores between 400Å and 25^u of 90 cm/100 g and a cation exchange capacity of 45 mg CaO/g determined as follows:

To 1 liter of an aqueous solution containing 0.594, g CaCl2

(300 mg CaO/l or hardness 53.50) adjusted to pH 10 using diluted caustic soda add 1 g (as active substance)

of silica-aluminate.

Solution one < pmrores. vigorously for 15 minutes at a temperature of

22 - 2°C. After filtration, the hardness of the filtrate is determined according to French standard T 90003.

The non-ionic surfactant is made up of a

mixture of linear C^2-<C>^<->alcohols ethoxylated with 6 mol of ethylene oxide and which is sold under the name "Cemulsol DB 311".

The conditions and the results achieved are reproduced in it

following table. The specified concentration is the concentration in the solution, as the apparent differences in their concentration wash. es that from one trial to the next the same concentration has been maintained for each chemical reagent, resp. 1.2 g/l for the nonionic surfactant, 1.8 g/l for the silica aluminate and 2 g/l for the sodium disilicate.

The following table shows:

The examples. 5. u and 8 show that the detergency for polyester is increased by the presence of the silicon oxide aluminate but is decreased by TPP ;(-example 7]

It is further shown that a mixture containing disilicate (Example 10) has an equivalent washing ability, but a worse renewed deposit.

It is noted that the deposits are small in all cases. The experiments carried out with cotton show that the silicon oxide aluminate works well with regard to washability and is slightly superior with regard to renewed deposition.

Claims (9)

Based on the results for the deposit on cotton, these are slightly less good than with TPP, but better than what could be expected to be achieved, according to the results in the previous examples. The previous examples also show the interesting thing about a composition of non-ionic or weakly ionic type, containing a silicon oxide aluminate and its unexpected effect corresponding to the requirements set for a detergent mixture for hydrophobic fibres. PATE CLAIMS 1. Detergent mixture without phosphates, characterized in that it includes at least one surfactant and at least one anti-calcifying and anti-fouling agent, consisting of at least one synthetic silicon oxide aluminate which is insoluble in the washing medium and corresponds to the formula x Na 2 O , y Al 2 O 3 , z SiO 2 » w H 2 0, wherein y is equal to 1, x is less than or equal to 2, z is from 4 to 15, and w has a value between 0.3 and 9. 2. Detergent mixture as stated in claim 1, characterized in that the silica alumina corresponds to the formula x Na2 0, y A12O3, z SiO2, w H2 0 in which y is equal to 1, x varies between 0.8 and 1.1, z varies between 4 and 15 and w has a value between 0.5 and 3. 3. Detergent mixture as stated in claim 1 or 2, characterized in that the sodium silicon oxide aluminate has a porosity measured by mercury solution porosimetry, for pores in the range 400Å o to 2.5 ai, of between 50 and 200 cm 3/ 100 and a specific surface BET of between 50 and 600 m 2 /g. 4. Detergent mixture as specified in claims 1 to 3, characterized in that the surface-active agent is made up of a synthetic product. 5. Detergent mixture as stated in claims 1 to 4, characterized in that it comprises at least one surfactant. 6. Detergent mixture as stated in claims 1 to 5, characterized in that it comprises at least one non-ionic surfactant. 7. Detergent mixture as stated in claims 1 to 6, characterized in that it comprises equal amounts of synthetic silicon oxide aluminate and surfactant. 8. Detergent mixture as stated in claims 1 to 7, characterized in that it comprises 5 to 50 percent by weight of at least one synthetic silismum oxide aluminate. - 1 to 30 percent by weight of at least one nonionic surfactant. - 1 to 30 percent by weight of at least one anionic surfactant. - 1 to 20 percent by weight of a sodium silicate with a SiO 2 / Na 2 0 molar ratio between 1 and 3.5. - 0.5 to 4% by weight of an anti-renewed deposit agent. - 0.5 to 5% by weight of a complexing agent. - 1 to 30 percent by weight of a filler. 0.3 to 2 weight percent of at least one optical brightener. 9. Process for producing the detergent mixture specified in claims 1 to 8, characterized in that a surface-active agent in liquid form is first absorbed on a carrier extensively a synthetic aluminum oxide silicate so that a powdered product is obtained.