LU82125A1 - METHOD FOR WASHING TEXTILES AND THE DETERGENTS TO BE USED FOR THIS - Google Patents

Description

8 'h q' ~~ fC H ^ RAND-duché Dr π> * m bourg L-2480 ù i c. 0 du 01.02.1980 M> n-.eur le Ministre, Ιλ «K -, -, J de l'Éionomie Nationale et des Classes Moyennes T.tre delivre: RV" · K-;

S <:. -e delà Propreté Indu-tr. · Ile 1 Γ> · M BOURG

Demande de Brevet d’invention I. Requête ï SENZOBÄ B «V. Ber.gsingel 2, Deventer.,. Pays-Bas, ........... d) représentée par Jean Waxweiler, 21-25 Allée Scheffer / Luxembourg, agissant en qualité de mandataire ............... .................................................. .................................................. ... (2) dépose ce pr em i er ... f é.vrier .... jni.l neuf .... cent quatr.ev.ingt _______________ (3) 15.00 heures, au Ministèr de l'Économie Nationale et des Classes Moyennes, à Luxembourg: 1. la pré.- '-te requête pour l'obtention d'un brevet d'invention concernant: · -..... ............ .................................................. .................................................. ............................ (4)

Process for washing textiles, as well as the Wai s chirii 11 e 1. ................................. .................................................. ............................

déclare, en assumant la responsabilité de cette déclaration, que Oe-) inventeur (si est (sont): ............................ ......................... ......................... .................................................. .................................... - ........... (5 )

Willem.Puister, Kümperkamp 17, ...... Epse, ...... Pays-Bas 2. la délégation de pouvoir, datée de ................. .................................................. .... le ............................................. ......................

3. la description en langue ............ allemande .............................. de l'invention en deux exemplaires; 4. .. / planches de dessin, en deux exemplaires; K la quittance des taxes versées au Bureau de l'Enregistrement à Luxembourg, 1 {* premier février mil neuf cent quatre-vingt · ....................... .....................

ri ", indique pour la susdite dema .. e de brevet la priorité d’une (des) demande - ci '.

(6) .......... certification ... .... déposée ^ en (7). . Pays-Bas ....... ............................

1o deux février mil neuf cent soixante dix-neuf sous le no.

16 ...... 79008 4 9 ........................................ .................................................. ................. (8> * au nom dSenzora BV ....... ................ ......... (9) élit domicile pour lui (cljti et, si désigne, pour son mandataire, à Luxembourg ..............

Jean Waxweiler, 21-25 Allée Schef fer, Luxembourg (io) sollicite la délivrance d'un brevet d'invention pour l'objet décrit et rej ·: ·. · Ηté dans le · i'inexes s ·? R..i -:> n: «-s, - avec ajournement de cette délivrance à .. / mois.

Lt méir.iataire,. .. .... τ Λ; Π. Procès-verbal de Dépôt

La susdite demande de brevet d'invention a été déposée au Ministère de l’Économie Nationale ft des Gasse> M-> nnts. Service de la Propriété Industrielle à I.uxemVjourg. c date du:> _____ 02/01/1980

Ms. le Ministre - à ^ heures de l’Économie Nationale et des Classes Moyennes, p. d.

Cil J) T) PC I üüïi .. ..........

PRIORITY ASSESSMENT

the patent application in Holland νΟΠ »2.February 1979 under No. 7900849

DESCRIPTION

FOR A PATENT APPLICATION IN

GRAND DUCHY OF LUXEMBOURG

SENZORA B.V.

* METHOD FOR WASHING TEXTILES AND THE DETERGENTS TO BE USED FOR THIS.

- 1 -

The invention relates to the washing of fibers, threads, yarns, fabrics and similar textile goods.

In earlier times, the fabrics mentioned were washed; in the beginning exclusively by the housewife, but gradually more and more operationally. Then came the washing machines, which resulted in the loss of a significant part of the previous manual work

As a result of the above-mentioned development, there was an increasing need for easy-to-use and easy-to-dose detergents, and not only for the company but to an increasing extent also for the housewife. These detergents should meet different requirements. The problems became even more difficult than large quantities, fibers wholly or partly produced synthetically, which were spun and woven, appeared on the market. The new fibers required different, adapted detergents.

The detergent was also not allowed to act on the machine elements ^ with which the laundry came into contact ^. It was also shown that the foam formation had to be controlled.

One and the other caused the detergent to become increasingly complicated. The latter were also often tailored to certain fabrics and / or certain parts of the washing process.

*

So now we know detergents for prewash, delicate detergents, colored detergents, white and wool detergents, which generally have an analogous composition, but are adapted in a certain way to the intended use. The adjustment can take place by omitting or replacing certain components, but it can also be achieved by choosing the washing process of the machine, for example due to differences in temperature, switching on the prewash or other processing.

- 2 -

So far, phosphorus compounds, in particular polyphosphates, play a special role in the washing process. Initially, they served as plasticizers for water. They kept the substances that caused the hardness of the water in dissolution and prevented the precipitation of lime on vital parts of the washing machine and at the same time the formation of lime deposits on and in the laundry was prevented. The latter resulted in less wear on the laundry. Surprisingly, the phospha also showed a favorable influence on the washing itself.

v

A disadvantage of the phosphates, however, is that after use they drain into the drain and pass through the cleaning system unchanged. In this way, these phosphates also end up in the surface water and cause excessive / excessive growth of the algae, which requires large amounts of oxygen and thus makes the surface water low in oxygen. The latter in particular puts the biological cleaning process of the water at a disadvantage and thus causes the fish to rot and die.

The task is therefore to replace the phosphates to a large extent or completely with other substances or other mixtures without adversely affecting the cleaning effect on the laundry and the machines used in the process.

According to the invention, this problem is solved by partially or completely replacing the phosphates in textile detergents by a combination of three components which belong to the following chemical groups:

Group 1: polyvalent, possibly substituted, saturated carboxylic acids. These are also specified as component Z.

Group 2: Polymerysates of methyl vinyl ethers with maleic acid hydrides. These are indicated with PV.

- 3 -

Group 3: Polymerized mono- or polyvalent unsaturated carboxylic acids of the acrylate type with an average molecular weight of approximately 12000-20000. These are still given as AC.

The components of the combination according to the invention are preferably added in the form of water-soluble salts, in particular alkali metal or ammonium salts. Incidentally, salt formation can also take place in the water itself, by reaction with the alkalis present in the further composition of the detergent, provided that the alkalinity of the washing liquor does not decrease too far.

The Z component can be, for example, citric acid, tartaric acid, oxalic acid, malic acid, preferably in the form of their salts. The sodium salt is generally used.

The PV component is known per se. They can be represented by the following formula: (-CH (0CH) -CH, “) (-CH (NOONa -)

Methyl vinyl ether group di-Na salt of maleic acid

The AC component is also known per se and is represented by the formula (-CH (COONa) -CH2 “).

In connection with the desired solubility, a polymer with an average molecular weight below 15000 is preferably chosen. The substances mentioned can be eliminated completely biologically by the DECO method.

In general, it can be said that the phosphate has a good calcium binding capacity for pigments and a good effect to support the washing process.

Of the Z components, especially the citrates have a good one

Calcium binding capacity, but the opposite / very massive effect on laundry processing.

The PV component has a good calcium binding capacity and a good dispersibility for pigments, but has a massive influence on the washing process.

The AC component has a massive calcium binding capacity, a massive dispersibility for pigments and a massive support for the washing process. Surprisingly, it has now been shown that the combination of the components mentioned under 1, 2 and 3 led to a good and balanced result which is equivalent to the action of the tri-polyphosphate.

This result is discussed in more detail below using a number of wash samples.

The following was used as the basic composition:

Air dry, free-flowing powder, containing: g

Soda (anhydrous) 30

Na dodecylbenzenesulfonate 2

Optical white fabric (Tinopal DMS-x, CIBA product) 0.2

Na disilicate 11

Perfume 0.3

Ci2_i4fatty alcohol ethylate 1.5

Sodium sulfate 13

Mg silicate 0.7

Na perborate 4 aq 9 CMC 2.5

Proteolytic enzyme 0.5

Na tallow fatty acid soap 14

Total 84.7

Balance polyphosphate and / or combinations of components Z, PV and AC.

The washing results were evaluated by using a normalized washing process, with dirty rags in the form of test strips being subjected to the washing process in a known, reproducible manner. Finally, the strips were ironed smooth and dry. The degree of whiteness of the washed samples was determined with a colorimeter.

The figures achieved served as a cleaning value indicator.

The test pieces were made of white Katun strips of 45x15 cm, to which test rags of 6x10 or 6x20 were connected on both sides by sewing; produced. The color measurement is a reflection measurement and thus higher digits represent better color tones, ie better dirt removal.

The same composition was used for evaluating the detergents for prewash, delicates and colored laundry, except that magnesium silicate and perborate were omitted. Red wine, cocoa, normal dirt, blood and berries were chosen as "polluters". For this purpose, the dirt strips were supplied by well-known institutes (EMPA, Switzerland and TNO / Netherlands).

The washing program was as follows:

Prewash duration in minutes

Inlet 75 1 water 3/4

Heating up to 40 ° C 2

Prewash 3

Spout 3 / 4_ total 6.5

Main wash

Inlet 20 1 water 3/4

Heating up to 85 ° C 6.5

Main wash 8.5

Spout 3 / 4_ total 16.5 - 6 -

do the washing up

Inlet 75 1 water 3/4

Rinse (temp. 35-40 ° C) 2.5

Spout _3 / 4_ in total 4

Inlet 3/4

Rinse (25-27 ° C) 7

Spout _3 / 4_ 8.5 in total

Inlet 75 1 water 3/4

Rinse (15-20 ° C) 23.5

Spout 3 / 4_ in total 4

Inlet 75 1 water 3/4

Rinse (15-20 ° C) 2

Spout 3 / 4_ in total 3.5

Whole white laundry program including prewash and rinse 43 minutes When using a bleaching process, 150 ml concentrated bleaching solution (activity 150 g / l) is added to the second rinse and 25 g Na bisulfite to the third rinse.

During the tests, together with two test strips, the weight was always 10 kg. Washed clean towels.

Example 1.

Comparison of a tpp-containing detergent with the same composition / in which the tpp was replaced by citrate and AC component and with the same composition ^ in which the tpp was replaced by citrate and PV component.

"TAMOL" (a brand of the Baden aniline and soda factory, abbreviated to BASF below) was chosen as the AC component, - 7 - which is a polyvalent polycarboxylic acid of the acrylate type.

"SOKALIN" (also a BASF brand) was chosen as the PV component, which is a polymer of methyl vinyl ether and maleic hydride.

Detergent A contained 84 g of the basic composition 9 g of citrate and 3 g of TAMOL.

= Detergent B contained 9 g citrate and 2 g SOKALAN on 84.7 g of the basic composition.

Detergent C contained 84 g of the basic composition ’20 g tpp.

150 g of washing powder was added for the prewash and 200 g for the main wash. The result is shown in the following table:

TABLE A

Types of test cloth: _EMPA EMPA EMPA EMPA EMPA TNO TNO TNO_

Detergent A Wine Cocoa Std Blood Blood std Berries Cocoa Medium White A 64 26 29 47 49 16 23 68 40 B 56 22 17 43 39 14 23 48 33 C_62 34 45 56 55 59 48_72_ · 54

Std = standardized dirt.

The significantly better effect of the phosphate-containing detergent is clearly evident.

The product with the composition C was now compared with a washing powder of the same composition in which 84.7 g of 9 g of citrate, 2 g of SOKALAN and 3 g of TAMOL were added. This mixture is further indicated as a St mixture.

The result was an average whiteness of 53! was exactly the same as the tpp result in view of the observation error.

- 8th -

Example II

In this example, ST mixture was used for white laundry / in which the Na citrate was replaced by an equal amount by weight of Na tartral. Average of the result 51.

Example III

ST mixture in which the Na citrate was replaced by an equal amount by weight of Na oxalate. Average with white laundry 56.

If the CMC in detergent was replaced by an equal amount by weight of CMZ (carboxymethyl starch), the mean value was 53.

Example IV

Here, in St mixture, SOKALAN SC 9357 was added instead of Sokalan PC-1 (which was used in the previous examples). The latter substance has a different ratio than SOKALAN PC-1. Average with white laundry 55.

If the total percentage of the three additional components is assumed to be 100%, the combination of the Z component is preferably 50-70%, the PV component 10-20% and the AC component 15-30%. The components can be added in the form of a mixture or separately in a suitable phase of washing powder production *. Addition to liquid or solid detergent compositions is straightforward; the components can be used in any composition customary in detergent technology, including those detergents which, by adding activating agents, exert their cleaning and, in particular, also bleaching action at low temperatures. In order to maintain the cleaning effect of a phosphate-free product, it is not necessary to replace the amount of fosfate in an ordinary detergent with an equal amount of the combination according to the invention. Usually the best results are obtained if the phosphate is replaced by not more than 50-70% of its weight in the new combination.

- 9 -

The following example explains the results when the phosphate is partially replaced by the combination of the invention.

Example V

The following compositions were assumed in this example. Component weight percent

Na carbonate 20 optical white 0.2 - dodecylbenzenesulfonate 2

Na disilicate 11.0

Fatty alcohol ethoxylate 2.0

Perfume 0.04

Mg silicate 0.5

Na perborate 10.0 CMC 2.0 fatty acid soap (tallow). 14.0

Tripolyfosfate (tpp) 37.9

In this composition, after 37.9% tpp reduced to 18.9% with the addition of: Na citrate 12% * Sokalan CP-1 3.0%

Tamol PA 4%

This composition is further indicated as E.

Also in composition D the tpp was reduced to 10.9% with the addition of:

Na citrate 17.0%

Sokalan CP-1 5.0% TAMOL PA 5.0%

This gave the composition F.

- 10 -

The washing tests are carried out in a manner analogous to that described in the first example. The numbers are shown in Table B below, with the remark that all numbers are the average of 12 wash attempts.

Table B.

»

Washing material result and composition _D_E_P_

X XX

Wine stains (EMPA) 83.8 63.5 63.5 COCOA (EMPA) 41.8 43.3 41.9

Std dirt (EMPA) 53.0 52.5 52.1

Blood (EMPA) 69.2 69.8 68.0

Blood (EMPA) 69.9 69.9 68.5

Std dirt (TNO) 70.5 69.2 64.3

Cocoa (TNO) 76.0 76.5 76.1

Berries (TNO) 44.0 44.7 44.7

Mean 61.0 61.2 59.8 x Do not compare numbers with numbers from other examples.

From the above it can be seen that the partial substitution of phosphate with a mixture of Na citrate, SOKALAN and TANOL leads to a practically equivalent product. If one chooses the other components in such a way that there is no nitrogen-containing component in the finished washing powder / it is possible in this way to obtain a practically nitrogen-free product. Any plant growth influence on the process is avoided.

Claims (7)

1. Detergent for textiles with a reduced phosphate content characterized by the presence of at least one component from each of the three following groups: 1 / salts of polyvalent, water-soluble, optionally substituted carboxylic acids 2 / water-soluble salts of polymers from methyl vinyl ethers and maleic anhydrides 3 / water-soluble salts of a polymerized, unsaturated , polyvalent carboxylic acid of the acrylate type with an average molecular weight of about 12000 to 200001 2. Detergent according to claim 1, characterized by a phosphate content of 0-20% calculated on total weight of the detergent. 3. Detergent according to claim 1 and 2, characterized in that the mutual weight ratio of the components according to the groups, 2 and 3 is such that for 100 parts by weight 60-70 parts by weight of group 1, 15-30 parts by weight of group 2 and 10-20 parts by weight of group 3 are present. 4. Nitrogen-free detergent according to claim 1, 2 and 3 characterized in that the other constituents of the detergent are chosen such that the detergent contains at most 0.1% nitrogen. 5. Air-dry, free-flowing washing preparation for addition to conventional detergents, consisting of a mixture according to claim 1, 2 and 3, if desired mixed with one or more substances known from the detergent industry, in particular also fillers. 6. A method of washing textiles, characterized in that care is taken to ensure that the combination of substances characterized in the first claim, preferably in the ratio mentioned in claim 2, is present in the washing liquor. , - 12 - 7. The method according to claim 6, characterized in that it is ensured that less than 0.1% by weight nitrogen of the detergent, calculated on the amount of dry substance present in the wash liquor, is simultaneously present in the wash liquor. * 1