DE1768962A1 - Oxidizing, bleaching, washing and washing aids - Google Patents

Description

PATENT APPLICATION D

Oxidizing, bleaching, washing and washing auxiliaries

Aqueous solutions of inorganic per compounds, in particular of hydrogen peroxide or perborates, have long been used as oxidizing agents, bleaching agents and also washing agents for a wide variety of materials, especially for textiles. However, the active oxygen only becomes effective at temperatures above 70 ° C. and preferably in the range from 80 to 100 ° C. at a rate sufficient for practical purposes, so that these oxidizing, bleaching and washing liquids cannot be used with temperature-sensitive materials. However, such inorganic percompounds and in particular perborates containing washing liquors are often used for washing temperature-sensitive textiles at temperatures of, for example, JO to 50 ° C. remains largely unused in the washing liquor.

109349/1926

The invention relates to the use of certain organic Substances as activators for inorganic per compounds, which are responsible for a practically effective oxidation and / or Bleach required minimum temperature is lowered and / or the oxidation process is accelerated.

The invention also relates to oxidizing agents and bleaching agents, including both the aqueous treatment liquids and the concentrates present in liquid, pasty or solid state .

A particularly interesting field of application for such oxidizing and bleaching agents or for their aqueous ones Solutions is the bleaching and bleaching washing of textiles. The invention also relates to pre- or post-treatment Aids for bleaching textiles or those to be used in the pre- or main wash cycle bleaching detergent.

109849/1926

The according to the invention as activators for inorganic per compounds Substances to be used are trlacylated hydroxylamines and contain the group at least once

- CO - 0 - N ^/

R ₂

in which R is an optionally substituted alkanoyl radical with 1 to 4 carbon atoms or an optionally substituted bonzoyl radical and PU is an optionally substituted alkanoyl radical with 1 to h carbon atoms, an optionally substituted benzoyl radical, an alkylsulfonyl radical with 1 to 4 or an optionally substituted arylsulfonyl radical, where R ^ and Rp can also together form a succinyl or phthalyl radical.

According to the invention come activators for inorganic per compounds preferably Ο, Ν, Ν-triacylated hydroxylamines of the general formula

R - ( ^CH 2) _n -CO-ON

into consideration, in which R is a saturated, straight-chain alkyl radical with 1 to 2 carbon atoms, an optionally by nitro or alkoxy groups substituted aryl radical or the radical

109849/1926

-CO-O- N ^ represent, η an integer from 0 to 1

and R ₁ and PL · can have the meaning given above.

The Ο, Ν, Ν-triacylated hydroxylamines can by reacting Hydroxylamine or hydroxylamine hydrochloride with the corresponding Carboxylic anhydrides, chlorides or esters are obtained. Mixed acylated hydroxylamines are obtained by acylation the corresponding N-acyl- or N, N-diacyl-hydroxyiamines with the relevant acid anhydrides, chlorides or esters. The N-acyl- or Ν, Ν-diacyl-hydroxylamines on which this reaction is based can be prepared by known processes (cf. e.g. Ber. dtsch. Chem. Ges. 29 (1896) 156Ο, J. Amer. Chem. Soc. 86 (1964), 1839). According to the invention as activators for inorganic Some substances which can be used per compounds are already known, but no practical use has yet been made thought of these substances.

The O-substituted Ν, Ν-succinylhydroxylamines used as activators according to the invention are new substances, with the exception of the O-acetyl derivative, as is Ο, Ν-diacetyl-Np-toluenesulfonyl-hydroxylamine. O-Benzoyl-NiN-succinylhydroxylamine must also be considered a new substance. It is true that CC. Hurd and coworkers (J. org. Chemistry _1 £ (195 ² O, H40) obtained a compound of melting point Il6 ° C by cyclization of NiN'-dibenzoxysuccinamide with acetic anhydride, which they took to be O-benzoyl- ^ N-succinylhydroxylamine, and as a by-product they isolated a substance with a melting point of up to 136 ° C., which they call 2-benzoyl-tetrahydro-0-isoxazine - ^, 6-dione

109849/1926

- 4a -

designated. When reacting with N-Hydroxy-succinimide Benzoylchlorid.wurde, however, obtained from the applicant a substance with a melting point of Ij57 to Ij59 ° C, although a has a melting point similar to that of the isomeric 2-benzoyl-tetrahydro-0-isoxazine-3j6-dione, but NMR, IR and mass spectra are similar to those of the other hydroxysuccinimide derivatives, their Structure is clearly secured, so that it can be assumed that it is the 0-benzoyl-N, N-hydroxylamine. Substance protection is therefore claimed for the new substances.

- 5 -109849/1926

In practice, hydrogen peroxide plays the greatest role among the inorganic peroxides to be activated. It can as such, but also in the form of its mostly solid peroxohydrates or addition products to inorganic and organic compounds are used. The latter include, for example, the addition products of hydrogen peroxide on urea or melamine; belong to the peroxohydrates e.g. the perborates, perortho-, perpyro- »perpolyphosphates, percarbonates and persilicates. The activators according to the invention but can also be used together with real peracids, such as Caro'sehen acid (Peroxomonosulfur acid HpSOc) or Peroxodisulfuric acid (HpSpOn) or its salts can be used.

In general, each molecule of activator can have one active oxygen atom activate the respective per connection; for a complete activation of the active oxygen used therefore theoretically to use activator and per compound in equimolar amounts. In many cases, however, one achieves in practice Satisfactory effects even with significantly smaller amounts of activator, while on the other hand one also uses the activator can apply in relatively large excesses;

109849/1926

In general, the amount of activator used will be 0.1 to 5, preferably 0.25 to 2 mol per g atom of active oxygen.

The acceleration of the bleaching or oxidation process is shown both at low temperatures in the range of 20 ° C and when this temperature limit is exceeded, where you can go up to 95 C. Depending on the problem to be solved, the person skilled in the art has the option of using of the activators according to the invention either to lower the treatment temperature and / or to reduce the treatment time at the same time Shorten temperature. Finally, you can also do a low-temperature and high-temperature bleach in one operation combine. In such cases it can be advantageous to use the activator in insufficient amounts; it will then only part of the active oxygen present is activated at low temperatures; the rest stands for the bleach t> egg elevated temperatures available.

The conditions that apply when working with the invention used activators must be observed, such as concentration of the peroxide, temperature, pK value and duration of the Treatment depend essentially on the one to be oxidized

1098-9 / 1926

-X-

or substance to be bleached, possibly also the Carrier material on or in which the substance to be bleached is located. The mostly aqueous oxidation or bleaching liquids can contain 20 to 500, preferably 50 to 250 mg / 1 active oxygen and a pH in the range of 2 to 12, preferably 7 to 11.5 and in particular 8 to 10.5.

The activators to be used according to the invention can be used anywhere be used where previously peroxo compounds, in particular hydrogen peroxide or perborates, as oxidizing or bleaching agents used. This applies, for example, to the bleaching of oils, fats and waxes, in cosmetic hair and skin treatment, in disinfection or sterilization, in the passivation of aluminum or other light metal surfaces and especially when bleaching all kinds of fibers.

P The desired pH value of the claimed agent is achieved by adding of acidic, neutral or alkaline reacting substances, possibly of buffer g err i see set, above all through those additives that have hitherto been used in the corresponding, customary types of application were also used.

109849/1926?>.>. * ■ - ,, - 8 -

These include, for example, water-soluble or water-insoluble Stabilizers for per compounds to lower the Surface tension of the aqueous oxidizing or bleaching liquids serving anionic, nonionic, cationic or zwitterionic surface-active substances, weakly acidic to alkaline reacting structural substances, including inorganic ones or organic complexing agents for the hardness constituents of water and for heavy metal ions are to be counted, as well inorganic or organic colloidal substances, especially water-soluble ones organic high polymers. This list is not to be regarded as complete; it can all with the respective one Purpose of use commonly used substances are also used. A more detailed list of these substances is located down below.

The oxidizing agents and bleaching agents according to the invention, which can preferably be produced and sold as washing agents and washing auxiliaries, are characterized by a content of a combination of inorganic per compounds, the activators to be used according to the invention and, if appropriate, stabilizers for the per compounds, wherein this combination makes up 10 to 100 % of the total agent and the activators are generally present in an amount of 0.1 to 3, preferably 0.25 to 2 mol per g-atom of active oxygen. The remaining 0 to 90 % of this agent can be the components of such products already listed above and listed in more detail later

109849/1926
Act.

With these solid and especially powdery to granular Oxidizing agents and bleaching agents are not limited to the advantages of the activators to be used according to the invention the activation of the existing per-connection. In particular by adding activators with melting points above 100 ° C., preferably Above 120 ° C and in particular in the range from 130 to 200 C, the oxidation and inventive remain Bleaching agents have a good shelf life, i.e. they show only a very low loss of active oxygen even after long periods of storage and at the same time only a very small decrease in oxygen activation.

Finally, the invention also relates to the bleaching component according to the invention which is of particular practical interest containing detergents, the composition of which is in the general range of the following recipe:

5 - 40, preferably 12 - 30 percent by weight of surfactants or combinations of surfactants, consisting of

0-100, preferably 25-65 percent by weight of surfactants from Sulfonate or sulfate type with preferably 8-18 carbon atoms in the hydrophobic residue,

0 - 100, preferably 5 - 40 percent by weight of nonionic surfactants,

0-100, preferably 10-50 percent by weight soap,

0 - 6, preferably 0.5 - 3 percent by weight foam stabilizers,

0 - 8, preferably 0.5 - 5 percent by weight foam inhibitors,

10-82, preferably 35-75 percent by weight of structural substance, with

109849/1926

- ίο -

at least some of this structural substance is alkaline reacts and wherein the amount of alkaline to neutrally reacting builder substances is preferably the o, 5 to 7 times and especially 1 to 5 times of the total surfactant combination makes up - 50, preferably 15-35 percent by weight of that according to the invention Combination of per compound, in particular perborate, and activator and optionally stabilizers for the per compound, but the amount of this combination is preferably so large that the active oxygen content of the entire detergent is 1-4, preferably 1.5-3 »5 percent by weight.

- 15 * preferably 2-12 percent by weight of other detergent ingredients, such as dirt carriers, brighteners, enzymes, perfume, dyes, water.

The solid activators can be used as powders or granules Mix the other ingredients of the oxidizing agent, bleaching agent, detergent or washing aid. You have, like in the detergent industry It is common practice to use spray drying or other methods to produce a detergent powder that does not contain per compounds prepared, then this is mixed with the per compound and the activator, the powder with the addition of the Activator should preferably have room temperature.

The particles that are liquid at room temperature, but also the solid particles in the oxidizing agent, bleaching agent, detergent or washing aid

1 09849/1 926

- 11 -

Activators to be incorporated can also be mixed with water-soluble or water-insoluble, preferably water-swellable, high-molecular encapsulated or enveloped organic substances. Suitable capsule or shell substances are e.g. gelatin, Methyl, oxethyl or carboxymethyl cellulose, starch and starch derivatives. Also there are solid, water-soluble polyglycol ethers, to which one can also count various types of solid nonionic washing active substances, such as those later Polyethylene glycol-polypropylene glycol mixed ethers described, can be used for this purpose.

- 12 -

109849/1926

The products according to the invention can be used for bleaching and bleaching laundry of a wide variety of fibers of natural or synthetic origin. In addition to the textiles made of cotton, Piegenerat celluloses or linen, which are usually to be treated at temperatures of 70 to 100 ° C., the so-called "prealight" textiles can also be washed and / or bleached according to the invention, which are made from highly refined cotton or from synthetic man-made fibers, such as polyamide. , Polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers or contain at least 30% of these. The textiles referred to as "easy-care", sometimes also as "non-iron", also include those made from synthetic fiber / cotton blended fabrics which can be specially finished.

Temperatures of 20 to 70 ° C., preferably J> 0 to 60 ° C., are suitable for bleaching or washing these easy-care textiles. The high degree of whiteness that can also be achieved according to the invention at these temperatures is advantageous above all with simultaneous or subsequent treatment of the textiles with optical brighteners.

109849/1926

Of the inorganic per-compounds, the in Aqueous solution of neutral to alkaline compounds, especially the perborates, of practical interest.

Among the various perborates, sodium perborate tetrahydrate (NaBO _2. H ₃ O. 3 H ₂ O) is of great practical importance. In its place, partially or completely, ie up to the approximate composition NaBOp. HpOp dehydrated perborate related. Finally, active oxygen-containing borates MaBO _p . H _p 0p usable in which the ratio Na ₅ O: BO- is less than 0.5 ί 1 and preferably in the range of 0.4-0.15: 1 and in which the ratio HpO _? : Na is in the range of 0.5-4: 1. These products are described in German Patent 901 287 and in American Patent 2,49-1,789.

The perborate can be completely or partially replaced by other inorganic per-compounds, in particular by peroxydrates such as the peroxonhydrates of ortho-, Pyro- or polyphosphates and carbonates.

The oxidizing agents, bleaching agents and detergents according to the invention Usual water-insoluble or water-soluble stabilizers for per compounds can be used in amounts of up to 10, preferably from 0.5 to 8 percent by weight.

109849/1926

IVN / OfüO QV8 - 14 -

is

The various magnesium silicates are suitable as water-insoluble perstabilizers. In most cases, these are precipitation products that are formed when aqueous solutions of alkali silicates are combined with solutions of magnesium salts. The ratio MgO: SiO ₂ can be in the range from 4: to 1: h, preferably from 2: 1 to 1: 2. A product with a ratio of MgO: SiO ₀ = 1: 1 is often used. These magnesium silicates can be replaced by the corresponding silicates of other alkaline earth metals, cadmium or tin. Hydrous oxides of tin can also be used as stabilizers. These stabilizers are usually present in amounts from 1 to 8, preferably from 2 to 1 %, of the weight of the entire preparation.

The water-insoluble stabilizers can be wholly or partly replaced by water-soluble ones. Suitable as such The organic complexing agents to be discussed later, the amount used depending on the strength of the formed Complexes range from 0.25 to 5 * preferably from 0.5 to 2.5 by weight of the total composition can.

- 15 -

109BA9 / 1926

It is often important to maintain a certain pH value when using the agents according to the invention; therefore, they are often used with weakly acidic, neutral or alkaline substances. The pH value of a liquid solution medium will usually be in the range from 7 to 12, with the fine detergents generally neutral to slightly alkaline (pH value 7 to 9.5), and the cooking detergents more strongly alkaline (pH value 9 * 5 to 12, preferably 10 to 11.5) are set.

- 16 -

109849/1926 .., ..

Those optionally present in the agents according to the invention anionic, zwitterionic or nonionic surfactants contain at least one hydrophobic radical from 8 to 26, preferably 10 to 20 and in particular 12 to in the molecule 18 carbon atoms and one anionic, nonionic or zwitterionic water-solubilizing group. The preferably saturated hydrophobic radical is mostly aliphatic or alicyclic sheer nature; he can do it with the waterless ones Groups can be connected directly or via intermediate links. Benzene rings, carboxylic acid ester or carboxamide groups, ether- or ester-like bonded residues of polyhydric alcohols, such as those of ethylene glycol, of propylene glycol, glycerine or corresponding polyether residues in question.

The hydrophobic radical is preferably an aliphatic hydrocarbon radical with about 10 to 18 carbon atoms, although deviations from this preferred Z number range are possible depending on the nature of the respective surfactant.

Soaps can be used as anionic washing active substances, which are derived from natural or synthetic fatty acids, possibly also from resin or naphthenic acids. Fat, resin or Naphthenic acids of natural origin are often more or less less unsaturated. They are preferably processed in a partially or fully hydrogenated state so that they Iodine numbers of at most 30 and preferably never less

109349/1926

- 17 -

Of the synthetic anionic surfactants, the sulfonates and sulfates in particular are of practical importance. To the suIfonaten include, for example, the alkylarylsulfonates, in particular the alkylbenzenesulfonates, which are, inter alia, preferably straight-chain aliphatic hydrocarbons having 9 to 15, preferably 10 to 14 carbon atoms by chlorination and alkylation of Benzene or from corresponding terminal or internal olefins by alkylating benzene and sulfonating the alkylbenzenes obtained receives. Furthermore, allphatic sulfonates are of interest, for example from preferably saturated, 8 to 18 and preferably Hydrocarbons containing 12 to 18 carbon atoms in the molecule by sulfochlorination with sulfur dioxide and chlorine or Sulphoxidation with sulfur dioxide and oxygen and conversion of the products obtained thereby into the sulphonates are accessible. Mixtures of alkene sulfonates, Hydroxyalkene sulphonates and hydroxyalkane sulphonates can be used, which can be obtained, for example, from terminal or central Cn-C.n- and preferably C.p-C.o olefins by sulfonation with sulfur trioxide and acidic or alkaline hydrolysis of the sulfonation products receives. In the aliphatic sulfonates produced in this way, the sulfonate group is often on a secondary one Carbon atom; but you can also by reacting terminal olefins with bisulfite sulfonates with terminal Produce sulfonate group.

- 18 -

109SA3 / 1926

To the invention to be used also sulfonates salts, preferably dialkali metal salts of Λ-Sulfofettsäüren and salts of these acids include esters with mono- or polyhydric, 1 to k, and preferably 1 to 2 carbon atoms containing aliphatic alcohols.

Further useful sulfonates are the fatty acid esters of oxethanesulfonic acid and dioxypropanesulfonic acid, the fatty alcohol esters of lower aliphatic or aromatic sulfomono- and dicarboxylic acids containing 1 to 8 carbon atoms, the alkyl glyceryl ether sulfonates and the condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

Fatty alcohol sulfates are to be mentioned as surfactants of the sulfate type, in particular those made from coconut fatty alcohols, tallow fatty alcohols or made from oleyl alcohol. Terminal or internal co- to C.o-olefins can also be used Manufacture sulfonation products of the sulfate type. Farther this group of surfactants includes sulfated fatty acid alkylolamides, sulfated monoglycerides and sulfation products of ethoxylated and / or propoxylated fatty alcohols, Alkylphenols with 8 to 15 carbon atoms in the alkyl radical, fatty acid amides, fatty acid alkylolamides, etc., with an Mol of the ethoxylated and / or propoxylated compounds mentioned 0.5 to 20, preferably 1 to 8, in particular 2 to 4 KoI of ethylene and / or propylene dioxide added could be.

109849/1926

- 19 -

The detergents according to the invention can also contain capillary-active synthetic carboxylates, e.g. Fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids and the condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, e.g. with glycocolla, sarcosine or with E. protein hydrolysates.

The nonionic surfactants, here referred to as "nonionics" for the sake of simplicity, include products that make their own Solubility in water of the presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, alkyl oil amide groups as well as an accumulation of hydroxyl groups in general.

Of particular practical interest are those caused by the addition of ethylene oxide and / or glycide to fatty alcohols, Alkylphenols, fatty acids, fatty amines, fatty acid and sulfonic acid amides, these nonionics 4 - 100, preferably 6 - 40 and especially 8 20 May contain ether residues, especially ethylene glycol ether residues per molecule. In addition, polyglycol ether residues can be found in these or, at the end of which propylene or butylene glycol ether residues to be available. . .

- 20 -

109849/1926

The nonionics also include those known under the trade names "Pluronics", "Tetronics" and "Ucon Fluid", water-insoluble polypropylene glycols made water-soluble by the addition of ethylene oxide and addition products of propylene oxide with alkylenediamines or lower, Aliphatic ones containing 1 to 8 and preferably J5 to 6 carbon atoms Alcohols.

Other useful nonionics are fatty acid or sulfonic acid alkylolamides, which are e.g. from mono- or dialkylolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, e.g. derive the Glycaminen. They can be replaced by amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids substitute.

From the group of amine oxides are those of higher tertiary, one hydrophobic alkyl radical and two shorter alkyl and / or alkylol radicals containing up to 4 carbon atoms each Amine-derived nonionics of particular interest.

109849/1926

Zwitterionic surfactants contain at least one acidic or at least one basic hydrophilic group in the molecule. The acidic groups include carboxyl, sulfonic acid, sulfuric acid half-ester, Phosphonic acid and phosphoric acid partial ester groups. Possible basic groups are primary, secondary, tertiary and quaternary ammonium groups.

Carboxy, sulfate, and sulfonate betaines have because of them good compatibility with other surfactants of particular practical interest. Suitable sulfobetaines are obtained, for example by reacting tertiary amines containing at least one hydrophobic alkyl radical with sultones, for example propane or butane sultone. Appropriate Carboxybetaine is obtained by reacting the tertiary amines mentioned with chloroacetic acid, its salts or with Chloroacetic acid esters and cleavage of the ester bond.

- 22 -

1098A9 / 1926

The foaming power of the surfactants used can be determined Increase or decrease the combination of suitable surfactants. The foaming power can also be achieved by other than surfactant-like Change additions. As is known, the above-mentioned nonionics of the alkylolamide type are suitable as foam stabilizers; in addition, fatty alcohols or higher terminal diols can be used for this purpose.

The foaming power of synthetic anionic or nonionic surfactants can be reduced by adding soaps; With certain combinations of synthetic anionic surfactants, nonionics and soap, the foaming power is still reduced more diminished. Furthermore, the addition products of propylene oxide with the capillary-active polyethylene glycol ethers described above are characterized by a low foaming power by varying the number of ethylene glycol and propylene glycol residues present in the molecule can produce the various cloud points. These nonionics work at temperatures above their cloud point to nonionics other than foam inhibitors; however, they can also be combined with other surfactants or mixtures of different surfactants combine.

109849/1926

Mixtures of anionic surfactants, especially those des Sulfate and / or sulfate type, of nonionic surfactants and von Seifeh have acquired great practical importance, considering the foam intensity of such combinations the choice of soaps can vary. If these soaps contain e.g. 12 to 18 carbon atoms in the fatty acid residue, then the surfactant mixtures show A certain amount of foam suppression, which is often not sufficient if the detergents are used at temperatures of 60 to 100 C. to be used in drum washing machines. In such cases, a strong foam dampening is achieved with synthetic ones anionic, zwitterionic and nonionic surfactants by adding soaps made from fatty acid mixtures with 20 to 30, preferably 20 to 26 carbon atoms in the fatty acid residue.

However, the surfactants can also be combined with foam inhibitors known per se which are not surfactants. This may include ' N-alkylated aminotriazines containing chlorine, which one by reacting one mole of cyanuric acid chloride with 2 to

Moles of a mono- and / or dialkylamine with 6 to 20, preferably 8 to 18 carbon atoms in the alkyl radical. Paraffins, halogen paraffins, aliphatic Co- to C _2Q- ketones can also be used as foam inhibitors, especially in combination with soaps.

- 24 109849/1926

By choosing suitable foam inhibitors it can be achieved that the foam-suppressing effect only when exceeded A certain temperature sets in, so that detergents can be produced in the medium temperature range Foam up to 65 ° C, for example, but less when moving to higher temperatures Develop foam. You can even combine foam stabilizers and temperature-dependent foam inhibitors combine.

The temperature-dependent foam inhibitors include the above-mentioned N-alkylated aminotriazines, as well as paraffins, haloparaffins, ketones, etc., whose foam-inhibiting effect is particularly strong above their melting point. But the higher _} of fatty acids with 20 to 50 carbon atoms, soaps derived in the molecule, show a similar effect. These soaps can be added in different amounts; Their proportion can be 5 to 100 # of the total soap content present in the surfactant component.

- 25 109849/1925

The framework present in the products according to the invention Substances are weakly acidic, neutral and alkaline reacting inorganic or organic salts, in particular • inorganic or organic complexing agents.

According to the invention usable, weakly acidic, neutral or alkaline salts are, for example, the bicarbonates, carbonates or silicates of alkalis, mono- , di- or trialkali metal orthophosphates, di- or tetraalkali metal pyrophosphates, metaphosphates known as complexing agents, alkali metal sulfates and the alkali metal salts of organic, non-capillary-active, 1 to 8 carbon atoms containing sulfonic acids, carboxylic acids and sulfocarboxylic acids. These include, for example, water-soluble salts of benzene, toluene or xylenesulphonic acid, water-soluble salts of sulphoacetic acid, sulphobenzoic acid or the salts of sulphodicarboxylic acids and the salts of acetic acid, lactic acid, citric acid and tartaric acid.

The water-soluble salts of higher molecular weight polycarboxylic acids can also be used as builders, in particular Polymers of maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Copolymers of these acids with one another or with other polymerizable substances, such as with Ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid

1 0 9 8 A 9/1 9 2 6 ^? '" ^l

- 26 -

3-butene carboxylic acid, 3-methyl-J-butene carboxylic acid and with Vinyl methyl ether, vinyl acetate, isobutylene, acrylamide and styrene are useful.

As complexing builders are the weakly acidic metaphosphates and the alkaline polyphosphates, especially the tripolyphosphate are suitable. They can be completely or partially replaced by organic complexing agents.

The organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-oxethyl-ethylenediamine triacetic acid, Polyalkylene-polyamine-N-polycarboxylic acids and other known organic complexing agents, it is also possible to use combinations of different complexing agents, to the other known Complexing agents also include di- and polyphosphonic acids of the following constitution:

, 0H

Marg

.0H

'H

.0H

OH OH

'HO

109849/1926

.OH • Ο

.OH

wherein R is alkyl and R ^{1 is} alkylene radicals having 1 to 8, preferably having 1 to 4 carbon atoms, and X and Y are hydrogen atoms or alkyl radicals having 1 to 4 carbon atoms. Carboxymethylene phosphonic acid (HOOC-CHp-PO (OH) ₂ ) can also be used as a complexing agent according to the invention. All of these complexing agents can be present as free acids, but preferably as alkali salts.

109849/1926

- 28 -

In the preparations according to the invention can also Contain dirt carriers that keep the dirt detached from the fiber suspended in the liquor and so on prevent the graying. Water-soluble colloids of mostly organic nature are suitable for this, such as, for example the water-soluble salts of polymeric carboxylic acids,

Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids the starch or the cellulose or salts of acid sulfuric acid esters of the cellulose or the Strength. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Farther can starch and other starch products than those mentioned above be used, such as degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

- 29 -

109849/1926

INSPECTED

SO

Examples

on the preparation of the activators according to the invention

Example H 1 .

Ο, Ν-diacetyl-Np-toluenesulfonyl-hydroxylamine 46.2 g (0.25 mol) of Np-toluenesulfonyl-hydroxylamine are mixed with 75 * 6 g (0.75 mol) of acetic anhydride with stirring, the temperature rises within one hour to 65-70 ⁰ C at. The mixture is allowed to stir for a further 14 hours, the reaction solution is evaporated in vacuo and the remaining crude product is recrystallized from isopropanol; Yield: 47.5 g (64 # of theory) 0, N-diacetyl-Np-toluenesulfonylhydroxylamine; F 65-67 ° C

Analysis t

C _n H ₁ → NO ₅ S calcd C 48.70 % \ H 4.80 %; ν 5 * 17 % i S 11.8l % (M0: 271.30) found C 48.55 % \ H 4.79 %; N 5.54 %; S 11.56 %

Example H 2

O-propionyl-Ν, Ν-succinylhydroxylamine

(N-propionyloxy-succinimide) ...

The solution of 33 g (approx. 0.3 mol) of N-hydroxysuccinimide in 340 ml of proponic acid anhydride is stirred at 80 ° C. for 4 hours. After the reaction solution has been evaporated in vacuo, the residue crystallizes through. After recrystallizing once from isopropanol, 42.4 g (85.6 % of theory) of N-propionyl oxy-succinimidj P. 47-48 ° C. are obtained.

analysis

C ₇ H _Q N0 ₄ calculated C 49.20 % -, H 5 * 26 % \ H 8.19 %

(MW: 171.15) found C 49.89 %, H 5 * ^ 0 ¹ Pl N 7 * 90 %

109849/1928

- 30 -

ORIGINAL INSPECTED Example H 3

O-Benzoyl-NjN-suceinyl-hydroxylamine
(N-benzoxy-succinimide)

To the suspension of 17.3 g (0.15 mol) of N-hydroxysuccinimide in 200 ml of ether and 60 ml of pyridine, a solution of 17.5 ml (0.15 Mol) benzoyl chloride in 50 ml of ether zu.Man allowed to stir for a further 2 hours at room temperature, mixed with 200 ml of water and sucks off the colorless, crystalline product. After two recrystallizations from isopropanol, 19 * 8 g (60.2 % of theory) of analytically pure N-benzoxysuccinimide are obtained;

137-39 ° C.

analysis

C ₁₁ H ₉ NO ₄ calcd C 60.27 %, H 4.14 %; N 6.39 % (MW: 219.20) found C 60.69 %, H 3.76 & N 6.50 % . .

Example H 4

O-p-methoxybenzoyl-NiN-suecynyl-hydroxylamine (N-p-methoxybenzoxy-succinimide)

The preparation of the p-methoxybenzoyl derivative takes place analogously the information in Example 3 above · From 46.0 g (0.4 mol) of N-hydroxysuccinimide and 68.24 g (0.4 mol) p-Ktithoxybenzoylchlorid is obtained after recrystallization

1098A9 / 1926

. 31 -

from isopropanol 79.8 g (80 % of theory) Np-methoxybenzoxy- "succinimidj F. 142-4 ° C... ·

analysis

C ₁₂ H _n NO ₅ calcd C 57.80 %; H 4.45 %, N 5.62 % (MW: 249.23) found C 57.73 %; H 4.09 % \ N 5.55 %

Example H 5

O-p -nitrobenzoyl-NjN-succinyl-hydroxylamine (N-p-nitrobenzoxy-succ inimide)

In analogy to the procedure of Example 3, from 27.5 g (0.24 mol) of N-hydroxy succ inimide and .41.0 g (0.24 mol) of p-nitrobenzoyl chloride, after recrystallization from acetonitrile, 28.0 g ( 44.4 % of theory) Np-nitrobenzoxy-succinimide F, 212-15 ° C.

Analysis:. . ·

C ₁₁ HgN ₂ O ₆ calcd C 50.00 %; H 3.06 % ', N 10.60 % (MW 264.20) found C 50.52 %; H 2.72 % \ N 10.89 %

Example H 6

0,0'-malonyl-bis- [n, N-succinyl-hydroxylamine] (N-malonyl-disuucinimide )

The suspension of 79.0 g (0.68 mol) of N-hydroxy-succinimide in 500 ml of dry benzene and 48.0 g (0.34 mol) of malonyl chloride is 15 hours at 40-45 ° C and then another 2 hours at

- 32 -

109849/1 926

Stirred boiling temperature until the evolution of HCl has ended. The crude N-MaI on yloxydisuccinimide which has precipitated in almost quantitative yield is filtered off with suction, washed with ether and recrystallized once from acetonitrile; Yield: 66.7 g (65.7% of theory.) Of analytically pure N-MaIonyloxy-disecinimid of melting point 244 ⁰ C (dec.).

Analysis :

C ₁₁ H ₁₀ N ₂ Og calculated C 44.31 % i H 3.38 %>, N 9.39 %

(MW: 298.22) found C 44.60 Ji5, H 3.29 %; N 9.72 %

Example H 7

OiO'-succinyl-bis- ^ NiN-succinyl-hydroxylamineJ (N-succinyloxy-disuccinimld )

The suspension of 115.0 g (1.0 mol) of N-hydroxysuccinimide in 1 l of dry toluene and 77.5 g (0.5 mol) of succinyl chloride is refluxed for 10 hours until the evolution of HCi has ended. The precipitated product is filtered off with suction and washed with ether; Yield: 149 g (95.5 % of theory) of N-succinyloxy-disuccinimide, melting point 279-83 ° C. (decomp.).

Analysis :

C ₁₂ H ₁₂ N ₂ Og calcd C 46.16 $; H 3.87 & N 8.97 %

(MW: 312.24) found C 46.14 %; H 3.93 % ', N 8.97 %

All compounds produced were also clearly characterized by their IR, NMR and mass spectra.

109849/1926

Jt

Examples

on the use according to the invention of the products described as activators for inorganic per compounds.

Examples V 1 - V 7

The usefulness of the activators used according to the invention was demonstrated by the following experiment:

Solutions containing 0.6l5 g of NaBO ₂ -HgOgO H ₃ O (4 mol) and 2.5 g of Na ^ P ₃ O ₇ . 10 HpO per liter were heated to 45 ° C. or 60 ° C. after the addition of 4 mmol of activator and kept at the specified temperature with stirring throughout the experiment. At certain time intervals 100 ml were pipetted off, immediately added to a mixture of 250 g ice and 15 ml glacial acetic acid and then, after the addition of approx. 0.35 g potassium iodide, titrated with 0.1 η sodium thiosulfate solution and starch as an indicator.

Under the specified conditions, a 100% activation of the peroxo compounds used consumes 8.0 ml Thiosulfate solution. In the tables is both the thiosulphate consumption as well as the percentage of the activated peroxo compound released.

109849/1926 _ _

SS

Table for example V 1:

Activation of perborate with Ο, Ν, Ν-triacetyl-hydroxylamine

sampling
after
χ minutes at
ml
0.1 η Na ₂ S ₂ C Scored
45 ⁰ C
% 0
), activated activation
at 60
ml
0.1 η Na ₂ S ₂ O, ⁰ C
% 0
activated X = I 7.57 94.6 7.17 89.5 5 7.75 96.9 6.69 83.6 10 7.49 93.6 5.54 69.2 15th 7.26 90.8 4.65 58.1 30th 6.59 82.4 3.65 45.7 45 6.02 75.4 2.24 28.0 60 5.34 66.7 (0.35) (4.4)

Table for example V 2:

Activation of perborate with N-benzoxysuccinimide

sampling
after
χ minutes at
ml
0.1 η Na ₂ S ₂ ( Scored
45 ° C
% 0
), activated activation
at
ml
0.1 η Na ₂ S ₂ C 60 ⁰ C
% 0
), activated X = I 0.63 7.9 1.21 15.1 5 1.25 15.6 2.27. 28.4 10 2.05 25.6 3.11 38.9 15th 2.74 34.2 3.51 43.8 30th 3.92 49.1 3.40 42.5 45 4.13 51.7 1.68 21.0 60 3.40 42.5 0.80 10.0

109849/1 926

Table for example V J5:

Activation of perborate with N-acetoxy-succinimide

sampling
after
χ minutes at 45
ml
0.1 η Na ₂ SgO, Scored
⁰ C
% 0
activated activation
at
ml
0.1 η Na ₂ S ₂ 60 ° c
* 0
0, activated X = 1 7.32 91.5 6.86 , 85.7 5 7.50 93.8 6.33 79.2 10 7.22 90.3 5.58 69.7 15th 6.97 87.3 4.86 60.8 30th 6.45 80.7 3.23 40.4 45 5.72 71.5 2.17 27.1 60 5.14 64.2 1.39 17.4

Table for example V 4:

Activation of perborate with N-propionyloxy-succinimide

sampling
after
X minutes at
ml
0.1 η Na ₂ S ₂ C Scored
45 ° C
% o
), activated activation
at
ml
0.1 η Na ₂ S ₂ C 60 ° C.
% ο
), activated X * = 1 7.29 91.2 6.40 80.0 5 7.23 90.5 5.21 65.2 10 6.65 83.2 4.18 52.2 15th 6.39 79.9 3.09 38.6 30th 5.69 71.0 1.58 19.8 45 4.95 61.8 0.61 7.6 60 4.39 54.8 0 0

109849/1926

Table for example V 5 *

Activation of perborate with 0, N-diacetyl-N-benzölsulfony / hydroxylamine .

sampling
after
χ minutes at
ml
0.1 η Na ₂ S ₂ < _o Scored
45 C
% 0
) _ activated activation
at
ml
0.1 η Na ₂ S ₂ C 60 ° c
) -. activated χ - 1 2.72 34.0 . 5.34 66.7 5 4.45 55.6 3.46 43.2 10 4.62 57.7 2.55 31.9 15th 4.13 51.7 1.73 21.6 30th 1.97 24.6 1.27 15.9 45 1.07 13.4 0.26 3.3 60 0.26 3.3 0 0

Table for example V 6:

Activation of perborate with Ο, Ν-diacetyl-p-toluenesulfonyl-hydroxylamine

sampling
after
χ minutes at
ml
0.1 η Na ₂ S ₂ ( Scored
45 ° C
% o
) activated activation
at
ml
0.1 η NagSgi 60 ° C
* 0
D, activated X = 1 2.08 26.0 2.75 34.4 5 4.14 51.7 3.30 41.2 10 4.62 57.7 .. 2.03 ■ 25.4 15th 4.18 52.2 1.61 20.1 30th 2.01 25.2 0 0 45 0.65 8.1 0 0 60 0 0 0 0

109849/1926

- 37 -

Table for 3 example V 7:

Activation of perborate with N-succinyloxy-disuecinimld

sampling
after
χ minutes at
ml
0.1 η Na ₂ S Achieved activation
45 ⁰ C at 60
% 0 ml
₂ 0, activated 0.1 η Na ₂ S ₂ O-, 4.45 ⁰ C
% 0
activated x = l 3.72 46.5 6.81 55.6 VJl 5.60 70.0 6.13 • 85.2 10 6.51 81.4 5.66 76.7 15th 6.42 80.0 4.25 71.0 30th 6.22 77.9 2.94 53.2 45 5.63 70.4 2.03 36.8 60 5.46 68.3 25.4

109849/1926

S3

As can be seen from the tables, the substances examined show a good activation of the perborate, albeit the course of activation differs from case to case. The compounds Ο, Ν, Ν-triacetyl-hydroxylamine, N-acetoxysuccinimide and N-propionyloxy-succinimide (cf. Examples V 1, V 3, V 4) show both at 45 ° and at 60 ° C immediately after the start of the experiment a maximum activation, which lasts above all at 45 ° C for a longer period of time. The connection N-Benzoxy-succinimide (Example V2) reached at 45 ° C their maximum activation only after about 45 minutes to then to maintain a relatively high degree of activation until the end of the experiment. The maximum occurs at 60 C. activation occurs after about 15 minutes, after which the activation drops faster than at 45 ° C. The connection CN-diacetyl-N-benzenesulfonyl-hydroxylamine (Example V 5) shows at 45 ° C the strongest activation after about 10 minutes, at 60 ° C the activation maximum occurs immediately in the course of Minutes then the activation drops to zero. Ο, Ν-diacetyl-ptoluenesulfonylhydroxylamine (Example V 6) activates most strongly at 45 ° C. after 10 minutes and then leaves the effect quickly after; at 60 ° C is activated moderately for about 15 minutes. N-Succinyloxy-disuccinimide (Example V 7) shows both at 45 ° C as well as at 60 ° C an initially increasing and then only slightly decreasing ability to activate. This different behavior the timing of the activation gives the person skilled in the art the opportunity to choose an activator, the effect of which depends on the particular Bleaching or oxidation process is optimally adapted.

109849/1926 - 39 -

to

Example V 8

For bleaching hair, for coloring hair with the help of oxidative dyes and for the oxidative treatment of hair after shaping under the influence of reducing agents Thio compounds (Kaltwell method) are usually used aqueous ones containing 10 to 200 g / l HgOg Solutions.

If you carry out this treatment after adding 20 to 500 g / l one of the activators according to the invention, in particular one of the activators according to Examples V 1-V 7, is a considerable strengthening of the oxidizing effect of the HgOg observe so that, if desired, you can also work at lower HpOp concentrations.

109849/1926

Examples

about laundry detergents and auxiliary washing agents according to the invention

In the detergents or auxiliary washing agents according to Examples W 1
up to W 5 numerous Ο, Ν, Ν-triacylated hydroxylamines were incorporated as activators; accordingly had the funds depending on
the activation characteristics of the activator have different application properties. For example, agents with Ο, Ν, Ν-triacetyl-hydroxylamine showed a maximum activation both at 45 ° and at 60 ° C immediately after the start of the experiment, which lasted for a long time above all at 45 ° C. Agents with N-benzoxysuccinimide only reached their maximum degree of activation after about 45 minutes at 45 ^, but this decreased only relatively little over the course of an hour. At 60 C
the maximum of the activation occurred already after about 15 minutes, but dropped thereafter faster than at 45 ° C. 0, N diacetyl-N-benzenesulfonyl-hydroxylamine was at 45 ° C after about 10 minutes · the strongest activation, at 6O ⁰ C, on the other hand, the activation maximum occurred immediately and dropped to zero in the course of an hour. 0, N, -Diacetyl-p-toluenesulfonylhydroxylamine activated most strongly at 45 ° C. after 10 minutes and then quickly ceased to act

-" after. At 60 ° C the activation effect lasted about 15 minutes

j £ long. N-Sjccinyloxy-disuccinimide showed at both 45 ° C and to an initially increasing and then only slightly decreasing

- »Letting activation.
co

*** This different behavior of the activators in the course of the activation process gives the specialist the opportunity to
To manufacture or dispose of detergents and washing auxiliaries

- 41 -

choose the effect of which is optimally adapted to the respective washing and bleaching process.

Example W 1
A mixture of

50 % fine-grain perborate

50 % activator

is suitable as a rinse aid for washed laundry. It is advisable to replace 5% of the perborate with MgSiO.

Example W 2

A rinse aid for washed laundry, which at the same time dissolves fiber incrustations, especially calcareous fiber incrustations, has the following composition:

30 % perborate

20 % hydroxyethane diphosphonate 15 % Na ₂ SO ₄

35 % activator

Here, too, you can incorporate 5 % MgSiO and reduce the Na ₃ SO ₄ content accordingly.

Example W 3

A bleaching auxiliary washing agent, which can be used in the commercial laundry, possibly together with active washing substances and / or complexing agents, in particular together with tri-polyphosphate in the pre-wash or main wash , is produced in the following way:

ν ^; _ Ji? -

109849/1926

A mixture of 30 parts by weight of perborate, 25 parts by weight of tripolyphosphate and 5 parts by weight of MgSiO ₅ is sprayed on a granulating plate while agitating with 10 parts by weight of finely atomized water. While the water is being sprayed on and afterwards, cold air is passed over the moving material until the heat of hydration released when the water is absorbed is dissipated. Then 30 parts by weight of activator are mixed in.

Example W 4

A mixture of 15 parts by weight of perborate and 60 parts by weight of a voluminous tripolyphosphate is placed on a granulating plate with a bulk density of 500 g / l, 5 parts by weight of a proteolytic enzyme and 10 parts by weight of activator with 10 parts by weight of an atomized liquid deposit It is produced from 10 moles of ethylene oxide to one mole of oleyl alcohol sprayed. This liquid nonionic washing active substance causes the particles to agglomerate, with binding of the enzymej however, the voluminous tripolyphosphate absorbs so much of the nonionic washing active substance that the product always appears dry on the outside.

Example W 5

A cooking detergent is made by spray drying and then adding a mechanical mixture of 66.0 % sodium perborate and 34 % activator

109849/1926 '^'

Composition made: (amounts in percent by weight) 12 % alkylbenzenesulfonate)

as in example W 6 4 % soap)

J>% C ₁₂ _ _l8 fatty alcohol + 10 EO 38% Na ₅ P ₃ O ₁₀

1 % ethylenediamine tetraacetate

1.5 % CMC
18 % perborate

9 % activator

0.2 % optical brightener
Remainder sodium sulfate and water

The ethylenediamine tetraacetate present in this detergent serves to stabilize the perborate against catalytic decomposition through traces of heavy metals that could get into the detergent solution.

Example W 6

A detergent taken from the atomizing tower was divided into five portions after cooling. While the fifth portion received only an addition of perborate and sodium sulfate, four of these portions were transformed by addition of the activator, perborate and an activator according to the reduced amount of sodium sulphate in _& aktivatorhaltx d bleaching detergent. These four detergents had the following composition:

10 9 8 4 9/1 926

9S

Alkyl benzene sulfonate 4.9 Nonylphenol + 9 A'O 2.3 Soap (sat. C ₁ g_ ₂₂ -Fettsäur.e) 6.0 ^Na 5 ^P 3 ° 10 35.7 Na ₂ O. 3 SiO ₂ 5.3 MgSiO ^ 1.3 CMC 1.2 Perborate 15.4 Activator 0 Sodium sulfate, brightener
water rest

Weight percent Weight percent Weight percent Weight percent Weight percent Weight percent Weight percent Weight percent -25.3 percent by weight

A technical straight-chain alkylbenzenesulfonate was used as the alkylbenzenesulfonate, its alkyl chain on average Contained 12 carbon atoms; Alkyl benzene sulfonate and soap were present as sodium salts.

The following activators were used:

(I) 0, N, N-triacetyl-hydroxylamine

(II) N-benzoxysuccinimide

(III) Ο, Ν-diacetyl-M-benzenesulfonyl-hydroxylamine

(IV) CN-diacetyl-N-p-toluenesulfonyl-hydroxylamine

With the five detergents of the recipe given above was a series of bleaching tests. carried out, the four containing activator Detergents were also subdivided by different amounts of the activator used in each case and varied in such a way that the Kol ratio activator: perborate ranged from 0.25 to 1.5. The perborate concentration was a constant 5 mmol / l.

109849/1926

- 45 -

it

Using these detergents, test rags made of raw nettle, as well as those with tea and forest berry stains were made on cotton at a detergent concentration of 5 g / l and a liquor ratio of 1:10 in water of 16 ° dH Washed at 45 ° C for 15 minutes. The activator-free detergent served as a comparative product; this comparative detergent was also used for washing at 90.degree.

The lightening was measured with a reflectance photometer at 460 μm and 620 μm and those on all test patches averaged values obtained. This resulted in the following remissions:

Table I (Ο, Ν, Ν-triacetyl-hydroxylamine)

Activator
conc.
(mmol / 1) Relationship
nis
Activator
Perborate Scored
We bleach
kung
($ Remission) Relative
Whiteness
increase % 0 65.3 0 1.25 0.25 70.7 47.8 2.50 0.50 72.7 65.5 3.75 0.75 74.5 81.3 5.00 1.00 76.1 95.6 7.50 1.50 75.3 88.5 o ² ) 76.6 100.0

109849/1926

- 46 -

Table II (N-Benzoxy-succinimide)

Activator
conc.
(mmol / 1) Relationship
nis
Activator
Perborate Scored
We bleach
kung
(Remission %) Relative 1
Whiteness
increase % 0 65.6 0 1.25 0.25 70.1 37.8 ' 2.50 0.50 72.3 56.3 3.75 0.75 75.6 84.0 5.00 1.00 77.6 101.0 7.50 1.50 78.2 106.0 o ² ) 77.5 100.0

Table III (Ο, Ν-diacetyl-N-benzenesulfonyl-hydroxylamine

Activator
conc.
(mmol / 1) Relationship
nis
Activator
Perborate Scored
We bleach
kung
{% Remission) Relative
Whiteness
increase 1 0 64.5 0 1.25 0.25 66.1 12.2 2.50 0.50 70.0 42.0 3.75 0.75 (70.4) (45.0) 5.00 1.00 73.6 69.5 7.50 1.50 72.3 59.5 ° ²⁾ 77.6 100.0

109849/1926

-AT -

le

Table IV (O, N-Diacetyl-N-p-toluenesulfonylhydroxylamine)

Activator
conc.
(rnMol / 1) Relationship
nis
Activator
Perborate Scored
We bleach
kung
{% Remission) D.
Relative
Whiteness
increase % 0 65.6 0 1.25 0.25 69.0 28.6 2.50 0.50 70.6 42.0 3.75 0.75 72.0 53.7 5.00 1.00 73.1 63.2 7.50 1.50 73.1 63.2 o ² ) - 77.5 100.0

1) Based on the respective difference (11.3 % or 11.9 % remission) of the bleaching effects without activator at 45 and 90 ° C.

2) Bleaching effect without activator at 90 ° C.

The products according to Examples W 1, W 3, W 5 and W 6 were left on The effect of laundry items that were contaminated by pathogenic germs or microorganisms was also evident at temperatures in the Range from 45 to 60 ° C caused by the addition of activator Killing these microorganisms. The same observation was made when, in experiments V 1 to V 7, in the presence of such microorganisms worked.

- 48 -

109849/1926

Claims (19)

PATENT CLAIMS l) Use of triacylated hydroxylamines that at least once the grouping - CO - 0 - N contain, in which R _{1 is} an optionally substituted alkanoyl group with 1 to 4 carbon atoms or an optionally substituted benzoyl group and Rp is an optionally substituted alkanoyl group with 1 to K carbon atoms, an optionally substituted benzoyl group, an alkyl group with 1 to 4 carbon atoms or an optionally substituted arylsulfonyl group , where R. and R _{2 can} also together form a succinyl or phthalyl radical, as activators for inorganic per compounds. 2) Use of 0, N, N-triacylated hydroxylamines of the general formula ^ * ^R i R - (CH ₂ ) _n - co - ο - \\ C R ₂ in which R is a saturated, straight-chain alkyl radical with 1 to 2 carbon atoms, an aryl radical which can be substituted by nitro or alkoxy groups, or the radical 109849/1926 -CO-O-N ^, η an integer from 0 to 2. R. a optionally ¹ s substituted alkanoyl radical with 1 to 4 carbon atoms or a given ^r all substituted benzoyl radical and Bp an optionally substituted alkanoyl radical
"with 1 to 4 carbon atoms, an optionally substituted benzoyl radical. an alkylsulfonyl radical with] up to 4
Carbon atoms or an optionally substituted one
Arylsulfonyl radical, where R. and R «can also together form a succinyl or phthalyl radical, as activators for inorganic per compounds. 3) O.N-Dia'etyl-K-p-toluenesulfonalhydroxylamine 4) O-propionyl-N, N-surr-ynyl-hydroxylamine 5) O-Benzoyl-N. N-sucinyl-hydroxylamine
C) Op-methoxy-N, N-succynyl-hydroxylamine 7) O-p -nitrobenzoyl-N, N-succinyl-hydroxylamine 8) O ^ O'-Malonyl-bis-NiN-succinyl-hydroxylamine 9) 0,0'-succinyl-bis-N, N-succinyl-hydroxylamine 10) Use of triacylated hydroxylamines according to claims 1-9 as activators for inorganic per compounds in an amount of 0.1 to 3, preferably 0.25 to 2 mol of activator per g atom Active oxygen. 11) Use.von triacylated hydroxylamines according to claims 1-9 as activators for inorganic per compounds in oxidation 109849/1926 _BAD ORIGINAL _ _{50 m} and bleaching liquids containing 20 to 500, preferably 50 to 250 mg / 1 'active oxygen. 12) Use of triacylated hydroxylamines according to claims 1-9 as activators for inorganic per compounds in aqueous solutions with a pH of 2 to 12, preferably 7 to 11.5 and especially from 8 to 10.5. Ij5) Use of triacylated hydroxylamines according to claims 1-9 as activators for inorganic per compounds in oxidizing hair treatment. 14) Use of triacylated hydroxylamines according to claims 1-9 as activators for inorganic per compounds in solid, powdery to granular oxidation, bleaching, washing and ash auxiliaries. 15) Use of triacylated Hydroxylamines according to claim 1 - 9 « as activators for inorganic per compounds according to claim 1 to J5 in possibly containing disinfectants, liquid, solid, powdery oxidation, bleach, detergents and washing aids. . 16) Inorganic percompounds and activator containing oxidation bleaching, Washing and washing auxiliaries characterized in that they are triacylated hydroxylamines as activators according to claim 1 • to 9 included. 109 * 49/1926 BAD ORIGINAL Patent department 17) Oxidizing, bleaching, washing and washing aids, characterized in that the combination of inorganic per compound, activator and optionally stabilizer for the per compound makes up 10 to 100% of the agent, preferably in oxidizing, bleaching and washing aids more than 50-90 and in particular 55-75 and in detergents preferably 10 50, in particular 15-35 % of this combination is present. 18) Oxidizing, bleaching, washing and washing auxiliaries according to claim characterized in that the activators in an amount of 0.1 - J5> preferably from 0.25 to 2 mol per g-atom of active oxygen are present. 19) Oxidizing, bleaching, washing and washing auxiliaries according to claim 9 and 10, characterized in that they are composed as follows: 5 - 40, preferably 12 - 50 percent by weight of surfactants or Combinations of surfactants consisting of 0-100, preferably 25-65 percent by weight of sulfonate and / or sulfate type surfactants, 0 - 100, preferably 5 - ² ^ O percent by weight of nonionic surfactants, 0-100, preferably 10-50, percent by weight soap, 0 - 6, preferably 0.5 - 3 percent by weight of foam stabilizers, 0 - 8, preferably 0.5 - 5 percent by weight foam inhibitors, 109849/1926. Patent department D 3461 • Io - 82 preferably 35 - 75 percent by weight of structural substances wherein at least some of these builder substances react alkaline and wherein the amount of alkaline to neutral reacting Builder substances preferably 0.5 to 7 times and in particular 1 to 5 times the total washing active substance matters - 50, preferably 15-35 percent by weight of the invention Combination of per compound, in particular perborate and activator and possibly stabilizers for the per compound, however, the amount of this Korabination is preferably so large that the active oxygen content of the entire bleach the mean is 1-4, preferably 1.5-3.5 percent by weight, - 15 * preferably 2-12 percent by weight of other detergent ingredients, such as dirt carriers, brighteners, enzymes, perfume, dyes, water. HENKEL & CIE. GmbH / ^ / iV Ί <^^ '. J / ii (Dr. Haas) (Dr. fctgel) 109849/1926