DE1925728A1 - Stabilized detergents containing bleach - Google Patents

Description

(Prio 29 »Mal" t968 -

US 712 844, \ yi 875 *

732 678 - 6164)

Colgate-I & Imolive Company

New Yorktjr-Y *, V _: St "A> Hamburg * 19. Shark 1969

Stick! Ii si art β containing bleach Cleaning supplies·,

The invention relates to cleaning agents with an oxidizing effect with a content of bleach and bleach stabilizer and especially for such Relnigongsraittel suitable improved stabilizers.

The use of hypochlorite bleaches in "Reinigungami a tt, as Blelchmlttelmiechungan, 7 / aschmitteln odor Soheuermitteln _t is known wherein basondero advantageous Ergabnisse be achieved with bleaching agents from the N-Chlorimldtyp which have a relatively high Oxyaatlonswlrkuns BIOBE H-chloroimides, jedooh have the The disadvantage is that they are difficult to stabilize against chlorine loss. It is known, for example, that trichlorocyanuric acid, which has a strong oxidizing effect, has three unstable positive chlorine atoms, which are only retained by a bond with nitrogen or oxygen. These chlorine atoms are due to their relatively high reactivity and their relatively weak binding to the trichlorocyanuric acid molecule has a strong tendency to react with other constituents of the product containing the trichlorocyanuric acid or with other trichloroisocyanuric acid molecules with self-decomposition Usually the good bleaching effect of such compounds is of course severely impaired or completely eliminated,

909051/1547

BATH ORIGINAL

In order to eliminate these difficulties, additives for stabilizing bleaching agents of the If-chloride-imide type against chlorine losses have already been proposed, which indeed result in a certain improvement, but still bring considerable harm to them. For example, the known stabilizers have the disadvantage _f that the stabilizing effect in the oxidizing or bleaching products does not last long enough for practical use In addition, many of the stabilizers proposed so far can only be incorporated into diooxidizing products with considerable difficulty. Many of these substances must be handled with extreme care. expanse re substances zususütasn to dia compatibility. ^·: the stabilizer with dor detergent mixture to ensure ,, All of these can as much carry weight, DAFL they speak in many cases against the use of at aioh effective stabilizer.

It is therefore the object of the present invention to propose cleaning agents with an oxidizing effect »which-mlnd ·» at least an If-chloride-type bleaching agent and a bis-dichloride stabilizer contain, the H-CJhlorlmlde effective and sustained stabilization against chlorine losses without exhibiting the disadvantages mentioned,

This object is achieved according to the invention by means of cleaning agents with an oxidizing effect with a content of bleach and ELeichmittalstabilizer dissolved, which are characterized in that they act as a bleaching agent at least one N-C-silorimide and, as a smoke stabilizer, a sufficient amount of sulfur to stabilize the K-chloride

90985T / 1547

BAD ORlGfNAL

containing compound of the general formula

R-SH or " S _w or R ₅ SSI

COR 3

where R stands for an alkyl group with 4 * 12 carbon atoms or a hienyl or Benay group, R. and Rg for the same or different alkyl groups with a total of 2-14 carbon atoms and R * and R for the same upper different alkyl groups are "aryl _f aralkyl or Alkaryigruppen with zusora" men 4-14 carbon atoms contain _f *

In the stabilizers of the formula R-SH, the group R So, for example, from a butyl, Iaobutyl, Bantyl. " Hexyl, Ootyl, Dodecyl, Bxenyl or Benzylgruppe exist. In stabilizers of the formula ■ „can

R ₁ -SR ₂

the radicals R * and R «are formed, for example, by methyl, ethyl, propyl, isopropyl, butyl, leobutyl, benzyl and hyl groups and the like. The stabilizers of the formula RyS-SR. can as R and R. contain, for example, ethyl, propyl = -, isopropyl = -, butyl « _f isobutyl, bntyl, ileacyl, hienyl and benzyl groups, etc.?

You draw connections according to the above formulas are all characterized by the fact that they have a clear stabilizing effect over a long period of time, even under extreme temperature conditions exercise on oxidizing detergents which contain N-chlorimido as a bleaching agent «So show - as can be seen from the following examples - bleaching agents, which contain one or more of the stabilizers described above, after a relatively long time If there is only a minimal or insignificant Ghlorveriuat at temperatures of about 60 °, on the other hand have corresponding Mixtures without a stabilizer have an unacceptable loss of chlorine, which can be so high that that the mixtures are suitable even for mild indigenous treatments are no longer sufficiently effective

909851/1547

BATH

Another advantage of the stabilizers "described is that they themselves have one exceptionally high Stabilisationawirkung against Ghlorvarluste in minimal concentrations. Thus, it was found that Stabilisatorkonaontra" functions in the order of only about 0.001 Με about 0 _f Qew. #, Based on the Bleaching agent mixture, practically excluding the possibility of a substantial chlorine loss * The optimal concentrations are of course dependent on the intended use of the bleaching agent mixture or cleaning agent up to a certain degree , the required StahlIieatorkonzentration correspondingly lower, - ϊΊΙτ other uses in which a stronger dirt removal effect should be obtained _f as it is, for example, with abrasives of the Pail »are with higher K-Ch lorimide concentration also used increasing amounts of stabilizer, - In , - In any case, it has proven to be advantageous for most elevation processes to use the stabilizer in Bolchen Kongen so that the molar ratio of Kercapton to K-Chlorimide is about 1 : 1 Ms about 1 »20 and pre-iigaweise t of about: 2 to 1:10, Ale Examples of stabilizers _f extending erfindungogemäßen for you purposes EIB bsncndero suitable erviiessn have, there may be mentioned, inter alia, the following compounds werdeni

OctylEjeroaptan

Do de cyl mercaptan

Benzy! Mercaptan

Hiethylauloxide
Di-n-propyl sulfoxide
Bi-n-buti'-lsulf oxide
Methyl ethyl sulfoxide
Methylpropylsulfoxyd lü-n-heocylsulfoiyd
9 0 9851/1547

Diieopropyl di-sulfide Mphenyl disulfide Bi-n "propyldlsulfld Di ~ n-butyl disulfide Diethyl disulfide Xthylpropyldisulf1d Di-n-hexyl disulfide,

For the purposes according to the invention, the N-chlorimide bleaching agents are preferably used in the form of particles in a practically dry state, that is, "without free water";"Without free water" means that the products can contain bound water as crystal water. It has been found that the best results are achieved when the N-chloroimides are used in a certain particle size. 07 $ mm (200 mesh) · door pass the erfindungsgemäfien purposes particularly suitable R Ghlorimide are other example trichloroisocyanuric acid, Hchlorieooyanursäure, Hatriumdiohlorisooyanurat and Kaliumdichlorisooyanurat and the like.

The concentration of R-chloride in the products according to the invention can vary in a relatively wide range, the concentration depending in detail on the desired bleaching or soot removal effect of the finished product, since the entire spectrum of possible uses of the products according to the invention is based on the total product. Chlorimidkonzentration co generally in the range of O ₉ I to 90 percent, £ and above, wherein dl ^ "concentration for Textilblelohmittel 10 to 90 OEW" jC and more and for abrasives 0.1 to 5 £

- amounts to.

The stabilizer, in conjunction with the K-chloride bleaching agent, is the critical component of the invention Products represent · The exceptionally high stability of these products against decomposition when stored under relatively

_eM) owe »* ¹ -

unfavorable conditions i.e., conditions under which usually a fairly extensive decomposition of the R-chlorine alumina and a corresponding loss of chlorine occurs » is still of great advantage from another Qrunde, so The decomposition products - many bleaches from Colorimldtyp has a highly corrosive effect; Consequently Substances which tend to form such decomposition products must be stored under strict precautionary measures. In the case of the products made according to the invention «Earths dl · associated with the corrosion of metal containers Problems due to the significant reduction in the loss of chlorine are largely eliminated. In addition, the lower risk of handling is of great importance for the safety of the bar sons involved.

Inventively stabilized B-Chloriaiide can be used in know how all practically dry! products »in which N-chlorine liquids are otherwise advantageously used Whitening agents, bleaching agents, sterilizing agents and Disinfectants are »used«. For example, the system of H-Chlorimide and stabilizer can be im.Gemisch used with detergent or surface-active substances which are practical in the presence of the H-Chlorlmlds are stable

The detergent active substances or surfactants which can be used in the products according to the invention comprise a relatively large number Substance classes, Bs can be soaps or soap-free syndets can be used .. The latter can be described as water-soluble sals · organic reaction products, which in their molecular structure has an anionic solubilizing group such as SO ^ H, SO, H, CJOOH or PO ^ H and one Alkyl or aralkyl radical with 8 to 22 carbon atoms in of the alkyl group contain · Suitable detergents are Long-lasting surfactants with an alkyl substituent 8 to 22 carbon atoms such as the washing-active, water-soluble sulfated «! and sulfonated anlon-active alkali metal and alkaline earth metal salts with a hydrophobic higher alkyl radical such as the salts of mononuclear

909851/1547

BATH

Alkylaryleulfonates with about 8 to 18 carbon atoms in the straight chain «!! or branched-chain alkyl groups, ss.-Br sodium dodecylbenzenesulfonate _f magnesium trideoylbenzene sulfonate _f lithium or kahumpentapropylenbonssolulfonate, the alkali salts of sulfated ethyleno: scyd “condonylbenzene sulfonate (z, B # those with 3" to 20 and preferably those with 3 "to 10 mol Zthylenojqrd per mol of compound) aliphatisoher alcohols having 8 Ma atoms 18 carbon or * z of alkyl phenols with 6 l> is 18 carbon atoms in the alkyl group * B * Natriumnonylphenolpents & thoxamexTsulfat, the I? ett ~ alkoholaulfatö about 8 bit 18 carbon atoms, ζ, Bo sodium lauryl sulfate and Natriumatearylaiilfat? d5, e Alka3.iaalae higher Fettsttureester niedrigmolakularer Allcylol ~ sulfonsELuren. c _e B <> dea the PettBäureester? 0.triumsalzea the leathioneäure that ifettäthaBolamißaulfats * the Set'taäureamidö of AminoalkylaulfoneSurea _f So-B * .- Ikurinaäureamid or 2aurin _s and the alkali salts of Byöro ^ yalkaneulfonsaurea with 8 "to 1-3 carbon atoms in the alkyl group, see ·, B ^ He xadecyl- oC -ayörosynatriumsulfat? Especially beTorssugte Yerbindtäagsn for erfiadungsgeisägea Zweoke are the Olefinavilfonate "In general, the organic o" b © rfl & cliaaaktiv © n substances irs Fora are verwoadet their AUcali- or Erdalkaliealse as these Sals © the required stability "Wasiserlösliolikeit and Ereiegtinstigkeit for have practical use.

In conjunction with the above. can lensiden wasserlöaliciie salts höhere- Fsttsäursn as the AlkalisalSis-won saturated or unsaturated fatty acids or IVüsohungen thereof with about δ to 18 Sohl®s "material at currents in the molecule, Z, B, KatriTimeapriaat, sodium laurate, Satriusssyristat" Uatrlumpalszitat ₉ Ealiuiaoleat, Katriumatearat _f Sodium and potassium salsa made from fatty acids, sodium and kelium salsa made from coconut oil and the like can be used.

In general, the water-soluble fat and be uresalae dea erfiadttngsgeisSßen Epoäukten 3? Orm of Salse suge- • ow ο However, these salts can äuoli in situ by adding

9 09851/1547

atoichiometric amounts of the usual fatty acids and the desired alkali metal hydroxide is formed directly in the product ι the desired Pettßliurou can also be used or Fettatturengeiniache directly to an ßrobwaaehmittel whose normal alkalinity is similar to that which is water-soluble To form fatty acids aalB.

It is of course void that the established N-Chloride bleaching agents are kept in a practically dry state. As a result, it is recommended to pack the products in fire-proof containers, such as containers made of glass * metal, metal foil *, ifcppa and the like laminated with metal foil “The last-mentioned material has proven to be particularly advantageous because it is light and elastic

Products according to the invention are for the time being in parts with? a thermoset part band size below about 2.0 mm (10 meah). Within this range, the optimal particle size mainly depends on the yerwen ~ dun-gazirck dos productea, "For example, in the case of abrasives, the particle size should be less than about 075 mm (200 meßh}, for spray-dried products, on the other hand, a particle size is preferred which the entire product passes through a sieve with a Maacheii width of 2.0 mm (10 mesh) wad. is held back by a sieve with a Masohenwelte of 0.15 mm (TOO megh) o ^

Which stabilizer and which is IMSiloriaid used in detail in erfindungsgeaäßen Erodukten, itj & ngb Iiauptßäch3.ich from Yerv endußgsj5v;.? Eck of Itoduktes from _F Hach the · -Erfindung prepared _s praktißch dry abrasives consist beißpiölswaisa ä & m SG ^ lorimidf dam stabilizer and a main portion of f one-piece water run-off. kieselsäui ^ lieltigan abrasives wi © Silic-iumdioxyo, feldspar, pumice, volcanic ash, diatomaceous earth, bentonite, falkum and the like or blue mixed materials from si ^ ei or more of these substances,

BATH ORIGINAL

In the production of water-soluble bleaching and Waachmitteln particular good results are achieved when the Tenaid _t, based on the Qeaamtprodukt, in amounts of 0-60 OEW, # vorzugaweiss and about 15 to about 40 weight used _o # is. In addition, the bleaches and detergents according to the invention can contain all additives customary for such products, such as fluorescent brighteners, water-soluble inorganic and organic builder salts and the like 50 to about 95 wt. # Can be used. Suitable builders are, for example, trisodium phosphate, tetrasodium pyrophosphate, acidic sodium pyrophosphate, i-sodium tri-polyphosphate, monobasic sodium phosphate, dibasic sodium phosphate, sodium hexametaphosphate, sodium silicates (SiOp: Na ₂ O sodium carbonate, sodium carbonate, sodium acetic acid, sodium tri-sodium acetate, sodium boron trioxide 3.2: 1ax), sodium carbonate Tetrasodium salts of ethylenediaminetetraacetic acid and the like, as well as mixtures of two or more of these salts.

The water-soluble alkali polyphosphates are particularly preferred. These form salts with those in hard water contained calcium and magnesium ion complexes and thereby prevent the formation of insoluble salts, which otherwise they are deposited on the textiles during washing «Above that In addition, these biosphates improve the cleaning power anionactive surfactants, regulate foam formation and hold the dirt after it has been removed from the textiles Suspended in the wash liquor?

Further substance, which the products according to the invention sugeeetat are, for example, the higher ones Fatty acid amides such as coconut fatty acid or laurinic acid monoethanol amide, isopropanol amide and the like, hydrotropic acidic substances such as lylene and toluene sulphonates, organic substances such as ethanol, Xethylene glycol and Höxylene glycol, Hatrlumoarboxymethylotllulosa and Bolyvinyl alcohol as dirt dispersants,

9098 51/1547

optical and fluorescent brighteners, coloring additives » Corrosion prevention agents, Germicides »Fragrances, Blueing agents and the like.

The detergents according to the invention preferably contain a hydrotropic colloidal cellulosic soil dispersant that is soluble or dispersible in water iet. By using such a cellulose compound together with polyvinyl alcohol, a particularly good one becomes Dirt dispersing effect when washing a wide variety of textiles such as those made of components or synthetic ones Fibers never achieved nylon, dacron or synthetic resin treated cotton * This blend is preferred in Mezigen from 0.1 to 2 wt * #, based on the dry substance, used «Preferred cellulose compounds are the alkali salts of carboxyalkyloelluloaes with up to 3 carbon atoms in the alkyl group, such as the sodium and potassium salts of Carbozymethyloolluloae; Sodium carbonate ethyl cellulose, the oil sulfates and the lower ones are also suitable Alkyl and hydroayalkyloellulose ethers such as methyl, ethyl and HydroJtyäthylcelluloee.

The appropriate products can in particular and advantageously be used for lead-washing and washing of stained and / or soiled fibers such as fabrics, clothes, household linen and the like? For practical use, the stabilized products are dissolved or dispersed in aqueous media so that the individual components are evenly distributed. The aqueous solution obtained is then mixed with the material to be bleached.QLe use of lead smelling is aqueous form offers the advantage that uneven or localized bleaching and fiber damage are largely excluded, while when using lead smelling in dry form, the risk of such damage of the fabric during the treatment - _e To carry out an oxidizing bleaching and waxing treatment according to the present invention, the stabilized 5-chloride product is preferably mixed in

909851/1547

ÖAD original

in an amount sufficient for the desired bleaching with water and then bringing the aqueous treatment obtained together with the material to be bleached. ' The optimal bleaching effect is obtained if, for the Bleiohbehancllung immediately after preparation of the aqueous bleaching solution "* B" within about 3 minutes after the production, makes c Die.oxydierende treatment according to the present invention can be, however, also durehgsführt ao in that the The textiles to be bleached are first introduced into an aqueous medium and then the mixture containing the mercaptan stabilizer and the N-chloroimide lead compound is added.

The concentration r in which the Bleichroittel & ischung is employed, werden.- varied within a relatively wide range, of course, 3 ^e on the type of bleaching process to be carried out. Pretty much konsentrlerte Lößujngen example, for the treatment of stained ceramic products are used, since in this case there is little risk of damage to the ceramic material * Ia this Pail can · muster the Bleichmittölmiachung as such on the Bahandlungsflache and then indicate enough water _f afld a slurry or Eaete of the desired Eo-nsistens arises , In this process, the aqueous Bieiohaedium forms in Cfegenwart the material to be treated * ·

The invention is illustrated by the following examples but is not limited to the same.

It 5purd © n dr ^ i Trersohiiedeiie abrasives with the following »

Example: 1 2 3 Trichloroisocyanuric acid $ 0.50> $ 0.50> $ 0.50> Sodium bromide 0.70 0.70 0.70 Trisodium phosphate, anhydrous 3.95 3.95 3.95 Detax +), 55 * ig 5.45 5.45 5.45 Heliogen ear stuff 0.25 0.25 0.25 Flint 89.15 88.78 88.85 Octyl meroaptan - - - 0.10 Isobornyl acetate 0.37 0.20

⁺ ) ^tt Detax ^H is a mixture ouch

60 öewr # straight-chain sodium alkylbenzenesulfonate 10% by weight of sodium silicate

0.014 3ew, # Iphol (mixture of o-cresol, isopropyl -

alcohol, H, K), and sodium carbonate)

2.0 wt. # Water
Remainder: sodium sulfate

Isobomyl acetate is not itself a stabilizer, it is ever dooh added to the even and homogeneous Blsperglerung of the constituents and in particular of octyl meroaptan Support SEU ο

To Sestlmaung the stability of the above Bcodukte against Ghlorverluste standing were! Subjected Products bearing testing at a temperature of 6O ⁰ C "The chlorine content was determined in the given in the following table tent intervals, the following results

Table 1
Stability at 60 ^° C

example 1 0 46 3 96 available chlorine 9 days Mr. 2 0, 47 0 well traces 3 0, 42 0 6th traces 0, 0 , 11 traces 0.37 , 18 0.12 , 38 0.38

909851/1547

BAD ORlQfNAL

192S728

■ The amount of available chlorine was determined by two thiosulfate titrations, whereby the samples were initially determined. Addition of potassium iodide or sulfuric acid were left to stand in water for 10 minutes., This method for determining the content of available chlorine is somewhat more reliable, since trichlorocyanuric acid tends to break down with the formation of ineffective compounds., However, in the Despite this degradation, most of them also fall with the normal Thlosulfat-Titratlon the stability of the triohlorisooyanuric acid can be determined, only with this titration » method only records the proportion of trichloroisocyanuric acid that has not been broken down "

As can be seen from the table above, the presence of the stabilizing mercaptan gives the mixture an extremely high stability to chlorine. This could be confirmed by both methods of chlorine determination mirde at storage temperatures in the amount of 6O ⁰ C, achieved, so -The found values are particularly significant, the values show in the stabilized blend after 3 days a chlorine loss of about 9 i> i, however, the available chlorine content thereafter remains virtually constant the amount of 0.38 "Ao. In contrast, an intolerable loss of available chlorine was found with the abrasives without Meroaptan stabilizer within 3 days} In addition, the content of available chlorine decreased significantly when standing for a long time,

Example 4 to 6

Examples 1 to 3 were repeated, but gagaben to all three mixtures Qew 2.7 ^ Hatriumsulfat-Deoahydrat (Ha ₂ SO, '1OHgO), the stability wa against loss of chlorine in the presence of larger Msngen to examine moisture. For this purpose, the water bound in the sodium sulphate was released under the appropriate test conditions * The results

Experiments are summarized in the table below = * 909851/154 7

BATH

- »4 -

(Example 4- »5 and 6 corresponded to the Beihan follow examples 1, 2 and 3) ι

O 46 Table 2 # available
after chlorine ο, 47 Stability at 60 ° C 6th 9 days example
ItTr 0, 42 15 tracks traces 0, 16 tracks traces 4th 0, 37 0.37 0.36 5 0, 6th 0,

From these values, in turn, the great advantage is the use of Me ro apt ana for stabilization against chlorine · - yerluste even under the applied strict test conditions produced "Compared to show the products of Examples 4 and contain 5 'which no mercaptan, a considerable loss of chlorine ?

Example 7 and 8

Example 3 was repeated, but alo stabilizer was used in one case all dodecyl mercaptan and in the other case Benzyl meroaptan used. The results are in the reproduced in the following table:

Table 3

Stability at 60 ° C

Example stabilizer # Ciilor available

Mr. after

jog

7 Dodeoy! Mercaptan 0.45 0.24 0.24 0.23

8 Benzyl meroaptan 0.43 0.36 0.36 0.35

The chlorine content was determined by titration in the same way as in Beiepi. *! 1 to 3 determines »The results zaig3n again the superior stabilizing effect of the meroaptan compounds p The one with the addition of Dodocylnaroapton The results obtained are somewhat lower than those found with the addition of benzylmarcaptan, but show

909851/1 547

bath

it was also a significant improvement over a comparison sample, which after 6 days of storage had only an insignificant chlorine content 4 to 6 described in the manner described with sodium sulfate and examined *

Example 9 Ms 11

Three different abrasives were made with the following compositions:

Example: 9 10 11th Trichloroisocyanuric acid 0.50? 6 0.50 i * 0.50 ^ Sodium bromide 0.70 0.70 0.70 Trisodium phosphate, anhydrous 3.95 3.95 3.95 Detax ⁺ ), 55 # ig 5.45 5.45 5.45 HeIiogeη colorant 0.25 0.25 0.25 Flint 89.15 88.95 88.89 Diisopropyl disulfide - - 0.06 Isobornyl acetate - · 0.20 0.20

⁺ ) Composition see example 1-3

To test the stability of the above products to chlorine losses during storage samples were stored these products at a temperature of 6O ⁰ C ,. The chlorine content was examined at the time intervals indicated in the following table, the following results being obtained: Table 4

Stability at 60 ° C

example 9 0 , 46 0 »11 $> available \ 5 chlorine Mr. 10 0 , 46 0 , 11 after traces 11th 0 , 42 0 .38 traces 6 days 0 0.38 traces traces 0.38

909851/1547 ..- ,.

: BAD ORIGINAL

From the above it can be seen that by adding the disulfide stabilizer, an extraordinarily good chlorine rate was achieved in the product. Thus the mixture stabilized with the sulfide had only a very small loss of available chlorine of the order of magnitude after 3 days from about 9 i> up; It is noteworthy that afterwards the content of available chlorine remained constant at the value of 0.38 ^ set after 3 days. The total loss of available chlorine was therefore no higher than 9 ^ - Days an intolerable loss of chlorine was found; in addition, the content of available chlorine fell significantly further after further storage. In view of the relatively strict test conditions, i.e. a storage temperature of 60 ° C., the improvement in stability through the addition of disulfide is particularly significant.

Example 12 to 14

Examples 9 to 11 were repeated, however, were added to all three mixtures 2.7 wt _a # Hatriumsulfat decahydrate (NagSO.'IORjO) to the stability of the products to test moisture in the presence of larger amounts "To this was added, the bound water in the sodium sulfate The results clearly showed that the bisulfide had an excellent stabilizing effect even in the presence of moisture *

Example 15 and 16

Example 11 was repeated, but instead of diopropyl diulfide, diphenyl diulfide was used as the stabilizer used. The results are shown in the following table, in which Example 16 the disulfide-containing Product and Example 15 a comparative product without Dieulfid iat:

90 9851/1547

Table ^ Stability at 6O ⁰ C.

Example f * available Oil or

No, after

β days

15 0.50 0.12 tracks

16 0.46 0.40 0.38

As the values show, the addition of biphenyldisulfId again achieved a significant improvement in the stability against chlorine loss «

Example 17 and 18

Examples 11 and 16 were repeated, however, was the content of disulfide in each case, based on the total mixture, increased by 0.1 wt. Both cases gave excellent results in terms of chlorine stability A slight decrease in the stabilizing effect was observed for diisopropyl disulfide. This decrease can be within the experimental margin of error, however it is more likely that this stabilizer will have a Concentration limit has been reached, above which the stabilizing effect no longer increases. So v / urde found » that the stabilization effect is within certain Limits with the increase in the stability increases, but then above certain concentra-tion words decreases again or is otherwise adversely affected. "

Example 19 to 21

Three different abrasives were then followed Compositions made:

BATH ORIGINAL 90 9 8 5 1/15 Λ 7

Example: 19 20

Trichloroisocyanuric acid $ 0.50> 0.50 % ι mßm -mil a *
0.50 Sodium bromide 0.70 0.70 0.70 Trisodium phosphate, anhydrous 3.95 3.95 3.95 Detax ⁺ ), 55 #ig 5.45 5.45 5.45 HeIogen paraffin 0.25 0.25 0.25 Silei 89.15 88.78 88.68 Dimethyl sulfide - - 0, JO Isobornyl acetate - 0.37 0.37

⁺ ) Composition see example 1 bia 3

To determine the stability of the above products against Clhlorverluat during storage, the products prolonged storage at einar temparature of 49 ⁰ C were exposed ο The chlorine content was determined in the conditions shown in the following table intervals:

Table _6

Stability at 49 ⁰ C

Example ^c ß> available chlorine

No, after

0 7 14 21 25 days

19 0 _f 44 0.20 0.14 tracks tracks

20 0.45 0.18 0.12 lanes lanes

21 0.12 0.39 0.39 0.39 0.39

As is apparent from the above values have dio Mischun- '. "]"'"Gen in the presence of Diinethylaulfoxyd excellent chlorine stability _f which duroh balde Uhlorbestimmungainethoden was naohgawiesen ο After a storage period of 7 days, the stabilized with dimethyl sulfoxide mixture has a low chlorine loss which lies in the ßröSonordnung of about 7 f "" However, the content of available chlorine remained after Ubar a period of 18 days kon accumulates at the level reached after 7 days Wart 0.39 # - the total loss of available Chloi so 'was only At about 7 $, on the other hand, the abrasives without methyl sulfoxide showed a "better" after 7 days

9 0 "9851 / 1547-

BAD ORIG | _NAL

tolerable loss of available chlorine * also went down the chlorine content drops considerably with further storage. Ee is also interesting that the content of available Chlorine in the mixtures according to Examples 1 and 2, if determined by the more reliable titration method was practically zero. This suggests that trichloroisocyanuric acid has a considerable effect It has undergone degradation to compounds with no bleaching action * However, with the normal titration procedure it becomes apparent not between the effective and the degraded ineffective Differentiated form of trichloroisocyanuric acid

Example 22 to 24

Examples 19 to 21 were repeated, but 2.7% by weight of sodium sulfate decahydrate (lfegSO. "1OHgO) was added to all three mixtures in order to test the stability of the products in the presence of large amounts of moisture . This was done in sodium sulfate Bound water released by appropriate test conditions. The results are compiled in the table below, in which Examples 22, 23 and 24 correspond to Examples 19 »20 and 21 in the order given

Table 7 Stability at 49 ⁰ C

Example # available chlorine

No α after

14th 25 days

22 0.44 0.19 0.15 0.13

23 0 »44 0.16 0.17 0.08

24 0.42 0.34 0.34 0.34

These results in turn show the excellent effect of dimethyl sulfoxide in achieving a significant stabilization against chlorine loss among those used Treatment conditions. In contrast, the comparison products of Examples 22 and 23 show without dimethyl sulfoxide a significant loss of chlorine,

51/15 4 7 .V /

· - ORIGINAL BATHROOM

* 20 -

Example 25 mid 26

The same mixtures were used as in Example 21 and 24 and stored under the same storage conditions, but with the storage period extended to 34 days «The results are given in the following table:

Table e .8 Stability at 49 ⁰ O

Example # available chlorine

No. after

3 8 27 34 days

25 0.43 0.39 0.39 0.39 0.36

26 0.41 0.37 0.36 0.32 0.31

The above figures show that the dimethyl sulfoxide aueh during prolonged storage excellent consistent stabilizing effect exerted Thus only a minimal loss of chlorine was found after a storage period of 34 days, "

In practice, the values shown in the examples above result in considerable advantages. As already on As outlined above, it is essential for the effectiveness of any given bleach mixture to: that they are sufficient for prolonged storage under changing conditions in terms of temperature, humidity, etc. remains stable against chlorine losses. For example, it is unavoidable that a detergent is used during transport Storage and / or use is exposed to conditions under which it absorbs moisture «This will also be the case not avoided by precautionary measures in handling, packaging and the like «. A particular advantage of the The present invention is therefore the fact that the products according to the invention have high stability against chlorine losses even in the presence of moisture Bine offers improved stability against chlorine loss from economic point of view numerous advantages «This is how the effectiveness of Blelchmlttelmiechungen«, their effect depends on their content of available chlorine, In absence more powerful stabilizers even at short

909851 / 15A7

Storage under relatively mild temperature and humidity conditions significantly impaired. To compensate for the resulting loss of available chlorine, In practice one then has to use the bleach in larger sizes Apply quantities «, as the non-stabilized bleach-containing Cleaning agents therefore have a lower effect relative to their volume, and their costs often exceed their costs the economically permissible level "

Results similar to those in the examples given above are obtained if one or more of the compounds dichloroisocyanuric acid, sodium dichloroisocyanurate and potassium dichloroisocyanurate are used instead of triochloroisocyanuric acid from 0.001 to 0.1 wt. The stabilizer concentration is only critical insofar as a sufficient amount of the stabilizer has to be used to stabilize it against chlorine losses. Within these limits, the concentration can be varied "On the other hand, should unusual size quantities D * H _ff in is order of. about $ 10> of the total product, vterde avoided * n *, * tya the UQg- liohkeit a harmful effect on the HkCfalorimidirex'bindung from zusehließen "

Good stabilization effects against chlorine losses also achieved if in the above examples, instead of the stabilizers mentioned there, compounds such as n-butyl mercaptan, Isobutyl meroaptan, n-hexyl mercaptan »n ~ I ^ ntyl · - marcaptan, see «Pentylmercaptan, n-Decylmex ^ eapt & n, methyldiaulfide, di-n-butyl disulfide, diisobutyl disulfide, Di «n -axyl disulfide or dibenzyl disulfide can be used, being particularly good results in conjunction with tfem Alkaüsalzeii of dichloroisocyanuric acid were obtained ι however, these stabilizers are also used in isocyanuric acid or dichloroisoojaiiursäürö ont &alf; f nrl

ο η q $ ι /

BATH ORIGINAL

Products achieved significant improvements compared to comparable products?

The erfiodungsgemäßen products may optionally from a simple Misohung an IT Chloriiaidö with one of said Stabiliaatoren in the above Molverhält- consist bite - In this way äußeret effective bleach, disinfectant and the like are obtained in such products, the excellent Stabiliaationawirkung the mercapto shows particularly clear, which was proven by appropriate tests in which, under the conditions described above at storage temperatures of 49-60 ° O after 6 to 9 days, only CSilor losses of 10-12 # and below were found.

^8AD

Claims (1)

Claims _Λ Detergents with an oxidizing effect containing bleach and bleaching agents StaMTÜaatoi ·; characterized in that it contains as a bleaching agent xaiPö at least an N-Gloriraid and as a lead agent a sufficient amount of a sulfur-containing compound of the general formula to stabilize the N-CStilorimide against Ohloryerluate - 0
R-SH or "3 -d odor Ry-S -i> - R, λ ^ -ο-ΊΙλ i -1- wherein R is group with 4 ¹ 2 Eohleii3toffatomen or a V Hienyl- or benzyl group is an alky!, H ^ and B ₂ are identical or different alkyl groups FLIR .with susunKen 2 "" \ ± Kohlenstoffatomen'und R ^ and R, the same or various alkyl, aryl, aralkyl or alkaryl groups. with a total of 4 "· H carbon atoms, contain- f cleaning agent according to claim 1, characterized nuzeichnet goke-, ES as a bleaching agent trichloroisocyanuric acid, liichlorisocyanursäure, sodium dichloroisocyanurate or Kalitrmdichlorisocyanurat or a mixture of sr ^ ei or my · containing these compounds, - Cleaning agent according to claims 1 vnä. 2 _? characterized in that it is octyl nercaptan _r dodecyl mercaptan, benzyl mercaptan, n- * butyl ⁿ iiBro3? tan _; . l-so '' butyl mercaptan, n-Penty! mercaptan, BLißopropyldisulfid, mphenyldisulfld, mn-'outyldisulfid, diisopropyl "butyldisu.lfid _r mbenzyldisulfid, dimethyl sulfoxide" Diäthylsv.lfoxya, di-n-propylsulfoxyd, mn-butylsulfoxyd, "Kathyläthylsulfoxyds Methylpropylöuifoxyd or Contains Oi-n-he ^ lsulfoxide or a mixture of two or more of these compounds, 9098 5 1/1 ZWl 4. Procedure Eum StabiliBiereD of Bleaching Agents from Ιϊ-Chloriiaidtyp against chlorine losses, thereby marked. ' net, daÄ aan dae bleach mil; one the loss of chlorine for the H-chloride preventive amount of a stabilizer gealfi Anepruoh 1 and 3 brings together » hbisn 9 0 9851/1547 ORIGINAL BATHROOM *