GB2106928A

GB2106928A - Detergent dosage unit

Info

Publication number: GB2106928A
Application number: GB08227987A
Authority: GB
Inventors: Terje Michalsen; Niels Ole Vesterager; Odd Michalsen
Original assignee: Individual
Current assignee: Individual
Priority date: 1981-10-01
Filing date: 1982-09-30
Publication date: 1983-04-20
Also published as: AU8861582A; FR2514025B1; GR77662B; JPS5869299A; BR8205786A; IT8223552A0; ZA827114B; SE8205548L; NO823300L; NL8203840A; GB2106928B; DE3236114A1; NO157903C; IT1196424B; AU558691B2; SE8205548D0; MA19613A1; CA1199549A; BE894544A; LU84401A1

Abstract

A detergent dosage unit comprising tensides and adjuvants whereby the tensides form part as a mixture of up to 99.99% by weight of usual tensides and 0.01-100% by weight of one or more mutually compatible fluorine containing tensides selected among fluorine containing tensides of anionic, nonionic, cationic, and amphoteric nature. The dosage unit combines mechanical strength, storage stability, easy breaking up in water, as well as high cleaning effect in low concentration in the aqueous cleaning liquid. The dosage unit is unsurpassed for use when preparing a detergent solution for high pressure cleaning.

Description

SPECIFICATION A detergent dosage unit, a process for the preparation thereof, and the use thereof The present invention relates to a detergent dosage unit comprising tensides and adjuvants selected for the intended use, as well as a process for the preparation thereof, and the use thereof.

Many proposals have been made for preparing detergent dosage units, cf. for instance the US patent specifications Nos. 4,099,912; 4,234,422; 4,219,435, and Norwegian printed accepted specification No. 130,594. Nevertheless it was not previously possible to present detergent dosage units, such as tablets, in small sizes, which can be used with great effect for solving a wide spectrum of cleaning problems. This is probably due to the fact that it has not yet been possible at a reasonable price to reach a tenside mixture sufficiently efficient even by use in a small amount. In addition, it is usually a problem to prepare tenside containing tablets simultaneously combining mechanical strength, storage stability, easy breaking up in water, and a great cleaning effect in low concentration in the aqueous cleaning liquid.

It turned out surprisingly that it is possible to obtain a highly efficient, detergent dosage unit comprising tensides and adjuvants selected for the intended use by utilizing astenside components a mixture not previously known of usual tensides and one or more mutually compatible fluorine containing tensides selected among fluorine containing tensides of anionic, nonionic, cationic, and amphoteric nature. Such a mixture has a synergistic cleaning effect, the addition of only 0.01% by weight of fluorine containing tensides to a detergent composition of a generally known type providing a quite surprising great cleaning effect, even by use in a concentration unprecedently low for detergent preparations of this type.

In a detergent dosage unit according to the invention the tensides form part as a mixture of up to 99.99% by weight of usual tensides and 0.01-100% by weight of one or more mutually compatible fluorine containing tensides selected among fluorine containing tensides of anionic, nonionic, cationic, and amphoteric nature.

On account of the high price of fluorine containing tensides it is preferred to use an amount as small as possible for the intended use. The optimum amount is determined by tests.

As mentioned a dosage unit according to the invention comprises, if desired, adjuvants, said adjuvants, of course being selected in accordance with the remining ingredients of the dosage unit. An appropriate selection of adjuvants thus ensures achievement of a desired pH-value of an aqueous solution of the dosage unit. The dosage unit may for instance also comprise a colour component selected in accordance with the pH-value (e.g. red colour at a pH-value below 6, green colour at a pH-value of 68, and blue colour at a pH-value above 9, disinfectants, pesticides, and perfume.

Examples of suitable usual tensides appear four instance from the US patent specification No.

4,099,912 and the contents of the specification are incorporated herein by reference. A suitable tenside from BASF is sold under the trade mark "Lutensit AN 10", which is a mixed product comprising an alkylarylpolyglycolether and an organic acid. Other products based on nonylphenol with various degrees of ethoxylation and other organic acids may be used as desired.

Also a mention of many generally used adjuvants furthermore appears from this US patent specification. As examples of acids applicable for the prep aration of an acid powder inactivated on the surface to be used by the preparation of a preferred embod iment of a dosage unit according to the invention polyvalent carboxylic acids may for instance be mentioned such as citric acid, lactic acid, gluconic acid,trinitriloacetic acid, and sulfamic acid, and an inorganic acid such as for instance boric acid.

As examples of suitable fluorine containing tensides can especially be mentioned fluorine containing tensides selected among fluoro-carbon containing tensides having from 4to 20 carbon atoms in the fluorine containing carbon chain comprising 7 to 25 fluorine atoms and of one of the formulae CnF2n+tC6H4X, CnF2n+tSO2X CnF2n+tX CnF2nt1C2H4X, and CnF2n+tC6H4SO2X, in which in case of anionic tensides X represents -OH,-NRt R2, -NHR3,-NCH2COOH, SO3,-SH-CSSH, R2PO4,- etc., in case of nonionic tensides X represents NlR4)CO(OCH2CH2)n(OCH3CH2)nOC4Hg and -(OCH2-CH2)n-OH,-CN,-SCN, etc., in case of cationic tensides X represents -NHC2H4(C2Hs)2=R+Y-, where Y preferably represents a halogen, and in case of amphoterictensides X represents-N H C2H4N+ (Rt R2(C2H4= COOetc.

Suitable anionic, fluorine containing tensides are sold by 3M under the Trade Marks "Fluorad-FC 128", "Fluorad-FC 170 C", and "Fluorad-FC 430", which tensides have the chemical formulae C8Ft7SO2N(C2Hs)CH2COOK, C8Ft7SO2N(C2Hs) (CH2CH20)14H, and C8Ft7SO3N(C2Hs)4.

The fluoride containing tensides suitable for the invention are either already known compositions or new compositions which can be prepared analogously to processes known per se.

It was previously considered impossible to obtain a useful textile softener unless it was prepared in a liquid state according to the traditional methods.

However, itturned out surprisingly to be possible in a tablet according to the invention to incorporate a usual softener, which at the breaking up of the tablet in water is as efficient as conventional softeners. A particularly advantageous embodiment of the invention is thus a dosage unit in which a textile softener forms part as adjuvant.

Efficient, wax-containing wash and care products were not previously prepared in tablet form. Previously it was necessary to prepare such compositions in a traditional manner in the form of liquid products.

It turned out surprisingly that it is possible to obtain an efficient, wax-containing wash and care product dosage unit, e.g. in tablet form, by incorporating a dosage unit according to the invention. When such a wax- containing tablet according to the invention is placed in hot water, the tablet breaks up easily, and an aqueous wax emulsion is formed as a matter of course, which in use provides a perfect film or coating of wax without formation of stripes on the su rface treated.

A dosage unit according to the invention is preferably given in the form of a tablet or a powder, which for instance is filled in capsules, bottles, sachets, packets or pads. A preferred tablet size is from 5100 g of a volume of 3-800 ml. The tablets may be cylindrical of a diameter of from 5-30 mm and a height of from 5-150 mm, or rectangular for instance of a dimension in the range of from 5 x 5 x 5 mm to 30 x 30 x 150 mm. Forthe preparation of a dosage unit according to the invention it is usually necessary to use a particular technique in order to avoid problems during the preparation in the form of attacks by the moisture of the air, deliquescence or formation of a hydrated hard, almost insoluble shell on the surface of the tablet.

The process according to the invention for the preparation bf a detergent dosage unit comprising tensides and adjuvants selected for the intended use is characterised by preparing while excluding moisture a mixture of up to 99.99% by weight of usual tensides and 0.01-100% by one or more mutually compatible fluorine containing tensides selected among fluorine containing tensides of anionic, nonionic, cationic, and amphoteric nature, and dis tributingthis mixture uniformly on a mixture of the selected adjuvants in such a mannerthatthe adjuvant particles are coated with a layer of the tenside mixture, and mixing the thus stabilized powder with an acid powder inactivated on the surface, whereafterthe resulting powder, if desired, istabletted or filled in capsules, bottles, sachets, packets or pads.

By the process according to the invention it is surprisingly possible to incorporate a very high amount of liquid active material without causing a caking into a water-insoluble composition.

A particular embodiment of the process according to the invention for preparing a detergent dosage unit in the form of a tablet having a long dissolving period is characterised by preparing while excluding moisture a mixture of up to 99.99% by weight of usual tensides and 0.01-100% of one or more mutually compatible fluorine containing tensides selected among fluorine containing tensides of anionic, nonionic, cationic and amphoteric nature, and distributing this mixture uniformly on the adjuvant mixture comprising slowly water-soluble binders in such a manner that the adjuvant particles are coated with a layer ofthetenside mixture, and subsequently tabletting the thus stablized powder into a preferably oblong tablet.

Dosage units prepared by the process according to the invention are mechanically strong, but may nevertheless, if desired, be shaped so as to break up easily in water. A pressure of about 30-800 kg/m2 may be used for the preparation of tabletted dosage units, which results in a density of from 0.7-2.0 g/cm3.

Numerous fields of application exist for the dosage units according to the invention, including for instance private homes, hospitals and laundries, farm work, foodstuff industry, as well as the iron and metal industries. The dosage units according to the invention are especially in tablet form suited for use by the preparation of detergent solutions for high pressure cleaning. Previously it was not possible to provide a detergent product in tablet form for high pressure cleaning.

The following examples are provided to illustrate the present invention in somewhat greater detail and to show the specific embodiments of the invention, but these should not be construed as limiting.

Example 1 A detergent composition for washing of cars is prepared having the following approximate formulation: Ingredients Parts by weight "Fluorad-FC 128" 2.2 "LutensitAN 10"t 20.0 Sodium trinitriloacetate 33.3 Sodium hydrogen carbonate 13.3 Citric acid 20.0 Polyvinyl pyrrolidone 2.5 Diethanolamine 6.7 Polyethylene glycol 2.0 The product is prepared in the following manner: 2.2 kg of powdered "Fluorad-FC 128" are mixed with 6.7 kg of diethanolamine, and 20 kg of "Lutensit AN 10". are added to the resulting mixture.Subse quently, the entire mixture is heated to 50"C and then sprayed on a powder mixture of 33.3 kg of sodium trinitriloacetate, 13.3kg of or sodium hydrogen carbo- nate, and 2.5 kg of polyvinyl pyrrolidone to obtain a homogeneous, stable powder which is air-cooled, said latter mixture being prepared in advance.

2.0 kg of polyethylene glycol are heated to melting and sprayed onto 20 kg of finely crystalline citric acid in order to obtain an acid powder inactivated on the surface. This powder is subsequently mixed with the above tenside containing mixture. The producttre- ated to completion is applicable as such ortabletted or filled in capsules, bottles, sachets, packets or pads in order to obtain appropriate dosage units.

A dirty car with a so-called traffic film, which is difficult if not impossible to remove by high pressure cleaning in the traditional manner, is high pressure washed using the product according to the invention, and the result is a surprisingly clean car without a traffic film.

The efficiency of a tablet of 13.5 g prepared in this manner is extremely good. The tablet possesses an excellent mechanical strength and breaks up easily in water.

By way of comparison it may be mentioned that the efficiency of a corresponding tablet not compris ing fluorine containing tenside is approximately 20 times less efficient In order to obtain a correspond ing effect as by the above tablet according to the invention it would thus be necessary to use a tablet according to the known art which is approximately 20 times bigger, viz. a tablet of about 290 g.

In this manner the composition according to the invention permits new fields of application, e.g. for high pressure cleaning, whereby it was not previously possible in practice to dosage the detergent composition by means of a tabletted product.

Example 2 A slowly soluble detergent composition for car wash is prepared comprising the components stated below: Ingredients Parts by weight "Fluorad-FC 128" 2.2 "LutensitAN 10" 20.0 Sodium trinitriloacetate 33.3 Diethanolamine 6.7 Polyethylene glycol, molecular weight 6.800 2.0 Nonylphenol (30 moles E.O.) 35.8 The product is prepared in the following manner: 2.2 kg of powdered "Fluorad-FC 128" are mixed with 6.7 kg of diethanolamine, and 20 kg of "Lutensit AN 10" are added to the resulting mixture. Subse quentlythe entire mixture is heated to 50"C and then sprayed onto 33.3 kg of sodium trinitriloacetate powder.

2.0 kg of polyethylene glycol are heated together with 35.8 kg of nonylphenol (30 moles E.O.) to melting. The latter mixture is atomized onto the powder prepared above. The product mixed to completion is then tabletted into a cylindrical tablet. Such a tablet is particularly suited for use in high pressure cleaners without tanks for chemicals and injector.

By the use of such a tablet the high pressure cleaner can reach a higher pressure, no drop in pressure occuring above the injector, and besides chemicals do not enterthrough the pump and consequently not through the machine. The tablet according to the invention is intended for positioning within the washing pipe mounted on the machine. In this manner it is possible to keep the tablet ingredients away from the machinery whereby the risk of corrosion is reduced.

Example 3 A neutral universal cleaning composition is prepared having the following approximate formulation: No. Ingredients Parts by weight 1 "Fluorad-FC 170 C" 0.6 2 "Fluorad-FC 430"g 1.6 3 Ethoxylated tridecylalcohol (7 moles E.O.) 2.5 4 Ethoxylated tridecylalcohol (10 moles E.O.) 3.0 5 Sodium trinitriloacetate 5.8 6 Sodium hydrogen carbonate 6.5 7 Trinitroloacetic acid 5.6 8 Polycarboxylic acid 2.0 9 C,2-C14 diethanolamide 3.0 10 Sodiumtripolyphosphate 2.8 The ingredients Nos. 1-1 and 9 are mixed and sprayed onto a powdered mixture prepared in advance of the ingredients Nos. 5,6, 8, and 10 and being in continuous movement, and the resulting mixture for half an hour, whereafter ingredient No. 7 is incorporated before the resulting product stands during the night.Subsequently, the product is formed in dosage units, e.g. bytabletting. The entire procedure is carried out without the presence of moisture. Such tablets are suitable for oil degreasing purposes.

Example 4 An alkaline heavy duty detergent is prepared of the following composition: No. Ingredients Parts by weight 1 "Fluorad-FC 170 C" 3.0 2 Ethoxylated tridecylalcohol (10 moles E.O.) 15.0 3 Sodium tripolyphosphate 20.0 4 Polycarboxylicacid Na-salt 3.0 5 Potassium Hydroxide 66.0 By proceeding analogously with Example 3, the ingredients Nos. 1 and 2 are mixed, and the resulting mixture is then sprayed onto a powdered mixture prepared in advance of the remaining ingredients Nos.3-5. Finally dosage units are formed, e.g. by tabletting. Such tablets are particularly suitable for use within thefoodstuffindustry.

Example 5 A tablet of 15 g prepared in accordance with Example 3 is placed in a beaker whereafter 11 of water is added. The self-acting dissolving velocity at various temperatures appears from the following table:

Min 0 1 2 3 4 5 PC % 0 17 37 60 85 100 45"C % 0 39 75 100 6BC % 0 57 100 The pH-value of the solution is 7.1.

A tablet of 15 9 prepared in accordance with Example 4shows the following self-acting dissolving velocity (breaking up course):

Min. 0 1 2 3 4 5 6 7 7oC % 0 8 44 50 65 80 96 100 45"C % 0 44 65 97 100 65"C % 0 47 98 100 The pH-value of the solution is here 12.6.

As it appears the tablets according to the invention have very quick dissolving periods per se. By way of comparison it may be mentioned that the tablets known on the market and sold under the name "splendor SprinklerTablet" which are prepared in accordance with Danish patent application No.

5503/79, requires about 820 minutes for the dissolving.

Now both a tablet according to Example 3 and according to Example 4 is dissolved in 11 of water.

By using a 6% dosage ofthis cleaning composition in high pressure cleaners for car wash, an outstanding effect is obtained on cars. The car is completely clean and without anytrafficfilm. Thus a soft white rag can be carried across the paint without being discoloured.

Example 6 A wax-containing wash and care product of the following composition is prepared in tablet form: No. Ingredients Parts by weight 1 "Fluorad-FC 170 C" 0.2 2 Tridecylalcohol (10 moles E.O.) 4.0 3 C12-C14diethanolamide 2.0 4 KSI wax 8.0 5 Sodium hydrogen carbonate 25 6 Sodium trinitriloacetate 9.0 7 Tridecylalcohol (25 moles E.O.) 2.0 8 Trinitriloaceticacid 12.1 The ingredients Nos. 1, 2, and 3 are heated to 90 C, whereafterthe ingedient No. 4 is melt and incorporated into said mixture. The resulting hot substance is distributed during half an hour on a mixture prepared by mixing in advance the ingredients Nos. 5, 6, 7,and8.

A wax tablet of 15 g prepared as stated above is placed in a beaker whereafter 11 of 60"C hot water is added. The pH-value of the solution is 7.5. It appears that the tablet is easily soiuble in the hot water during formation of a completely homogenous wax solution, which in use provides a perfect wax film.

As many possible embodiments can be made of this invention without departing from the broad scope thereof, it is to be understood that all matter herein set forth is to be interpreted as illustrated and not as unduly limiting the invention.

Claims

1. A detergent dosage unit comprising tonsides and adjuvants selected for the intended use, characterised by the tensides forming part as a mixture of up to 99.99% by weight of usual tensides and 0.01-100% by weight of one or more mutually compatible fluorine containing tensides selected among fluorine containing tonsides of anionic, nonionic, cationic and amphoteric nature.

2. A dosage unit according to claim 1, characterised by wax forming part as adjuvant.

3. A dosage unit according to claim 1, characterised by a textile softener forming part as adjuvant.

4. A dosage unit according to claims 1 to 3, characterised by its content of fluorine containing tensides being selected among fluoro-carbon containing tonsides of 4to 20 carbon atoms in the fluoride containing carbon chain containing 7to 25 carbon atoms and of one of the formulae CnF2n+1C6H4Xx CnF2n-1SO2X, CnF21COX, CnF2n+1Xt CnF2n+ 1C2H4X, and CnF2n+ 1C6H4-SO2X, in which in case of anionic tensidos X represents -OH, -NR' R2,-NHR3,-NCH2COOH, SO3,-SH, -CSSH, R2PO4, etc., in case of nonionic tensidos X represents N(R4)CO(OCH2CH2)n (OCH3CH2)nOC4H9 and -(OCH2-CH2)n-OH,-CN,-SCN, etc.

In case of cationic tensides X represents -NHC2H4= (C2H5)2R+ Y-, where Y preferably represents a halogen, and in case of amphoteric tensides X represents-NHC2H4N+=(R'R2) C2H4COO etc..

5. A dosage unit according to claims 1 to 4 characterised by the tonsides forming part as a mixture of 30% of usual tensides and 70% of fluorine containing tensides.

6. A dosage unit according to claim 1, characterised by comprising 0.5 - 5% by weight of a material comprising the compound of the formula CaFi7SO2N(C2H5) CH2COOK 15 - 25% by weight of a mixed alkylarylpolyg lycolether and an organic acid 30- 40% by weight of sodium nitriloacetate 10 - 20% by weight of sodium hydrogen carbonate 15- 30% by weight of citric acid 2- 5% by weight of polyvinyl pyrrolidone 5- 10% by weight of diethanolamine and 1 - 3% by weight of polyethylene glycol.

7. A process for preparing a detergent dosage unit comprising tensides and adjuvants selected for the intended use, characterised by preparing while excluding moisture a mixture of up to 99.99% by weight of usual tensides and 0.01-100% by weight of one or more mutually compatible fluorine containing tensides selected among fluorine containing tensides of anionic, nonionic, cationic, and amphoteric nature, and distributing this mixture uniformly on a mixture of the selected adjuvants in such a manner that the adjuvant particles are coated with a layer of the tenside mixture, and mixing the thus stabilized powder with an acid powder inactivated on the surface, whereafter the resulting powder, if desired, is tabletted or filled in capsules, bottles, sachets, packets or pads.

8. A process for preparing a detergent dosage unit in the form of a tablet having a long dissolving period and comprising tensides and adjuvants selected for the intended use, characterised by preparing while excluding moisture a mixture of up to 99.99% by weight of usual tensides and 0.01-100% by weight of one or more mutually compatible fluorine containing tensides selected among fluorine containing tensides of anionic, nonionic, cationic, and amphoteric nature, and distributing this mixture uniformly on the adjuvant mixture containing slowly water-soluble binders in such a manner that the adjuvant particles are coated with a layer of the tenside mixture and subsequently by forming the thus stabilized powder into a preferably oblong tablet.

9. The use of a detergent dosage unit as claimed in claims 1-6 for a simple dosing and preparation of a detergent solution.

10. The use of a detergent dosage unit as claimed in claims 1-6 for the preparation of a detergent solution for high-pressure cleaning.

11. A detergent dosage unit substantially as described above and disclosed in the accompanying specification.

12. A process for preparing a detergent dosage unit substantially as described above and disclosed in the accompanying specification.

13. A use of a detergent dosage unit substantially as described above and disclosed in the accompanying specification.