DE2128945A1 - Bleach - Google Patents

Description

NOTHING LAWYERS

DR. JUR. Di Π.-CHEM. WALTER AT

ALFRiO HOi-fVENER

DR. JUR. DiPL-ChEM. H.-J. WOLPP

DR. JUR. HANS CHR. BEIL. L June 9, 197f

623FRANKFUUTAMMAIN-HACHST

AMLONSIIiASSt 38

Our No. 17 171

The Procter & Gamble Company Cincinnati, Ohio, V.St. A.

Bleach

The invention relates to a bleaching agent by a Content of an aroylglutaryl peroxide of the general formula

RCO.OO.CO (CH ₂ ) ₃ CO ₂ H "

where RCO is an optionally ring-substituted benzoyl radical, is characterized as a bleaching component.

The bleaching of tissues and the like with hydrogen peroxide or by inorganic substances that deliver hydrogen peroxide in solution, has long been known and such

1098 51/1864

Substances, especially sodium perborate or percarbonate, have long been common constituents of bleach and detergent mixtures. Although these substances at temperatures near the boiling point of water, for example above about 8J? _T ° C are effective, they show at low temperatures, such as 35 to 65 ° 0, low efficacy.

Certain organic peroxygen compounds are considered Bleaching agents have been described which are effective at these lower temperatures. One class includes the organic aliphatic and aromatic peroxycarboxylic acids and especially the more effective aromatic percarboxylic acids, as described in the British patent Ur. 886,188 are. However, these connections are generally rather " unstable so that they tend to lose their activity rapidly on storage, and in certain cases can they can even be explosive. This makes them difficult to handle during processing and use. aside from that this instability is increased by traces of metals such as iron, nickel, cobalt, copper, etc.

Another class includes the organic peroxides and especially the diacyl peroxides. Some of these compounds are described in Belgian patent specification No. 603,768. These substances hydrolyze in the presence of water with the formation of peroxycarboxylic acids, which can be assumed to that they are those substances which are actually responsible for the bleaching activity. The organic Peroxides are generally also prone to instability and in some cases show a tendency to explode. Many are only sparingly soluble in water and therefore hydrolyze only slowly at moderate washing temperatures. It can therefore only do little be released from the actual bleach during the duration of a standard laundering process. A typical one Connection that suffers from both of these disadvantages is Dibenzoyl peroxide.

109551/1864

In the above Belgian patent, benzoyl succinyl peroxide is mentioned among the preferred diacyl peroxides and this product has the advantage of being soluble in water under neutral or alkaline conditions. Nevertheless, it is unstable in detergent and cleaning agent mixtures and can detonate in the impact test to determine the explosiveness. Although it is unlikely that this Substances are exposed to shocks during normal use, as they are used in the impact test (as it is described in Example 3 below), but shows the detonation tendency in the test that they can be dangerously unstable under other conditions.

It has now been found that the corresponding benzoylglutaryl peroxides according to the invention in detergent and cleaning agent mixtures much more stable and, even in the presence of metal ions such as iron, nickel, cobalt, copper, etc. are not explosive. This is completely surprising; usually a change in a methylene group in a homologous series causes only a minor change the chemical properties of an organic compound. With regard to their improved stability are these benzoylglutary! peroxides in alkaline detergents and Bleaching liquids soluble, hydrolyze rapidly during a washing or lead process, form an aromatic one Peroxyacids as an effective bleaching agent and therefore make very valuable bleaching agents for use at temperatures below about 85 ° C. They are also effective at higher temperatures, but other reagents, such as sodium perborate, available for use at these temperatures and accordingly these represent alternatives for the use of the organic Peroxygen compounds under these special conditions represent.

109851/186 / »

The present invention also relates to Bletehmi loop. which contain the peroxides according to the invention, optionally together with detergent salts and / or organic surface-active Funds included.

The mixtures according to the invention contain, in addition to the peroxides, a neutral or alkaline inorganic Salt or organic complex-forming salt or a compatible one organic surfactant or a mixture of any of these components.

Preferred peroxides are those in which the aroyl radical is unsubstituted benzoyl or benzoyl, which is replaced by an or is substituted several chlorine, methyl or methoxy radicals, means.

Usually the peroxides are in the bleach liquor present at a concentration through the 1 to 200 parts by weight per million available oxygen in the liquid, in particular 5 to 150 parts by weight per million. Very good results are obtained with 10 to * J0 parts / million.

The aroyl glutaryl peroxides can be prepared by any effective method. Two general ways can be mentioned, namely the reaction of an aromatic peroxy acid with glutaric anhydride in a suitable solvent ₃ or the reaction of an aroyl chloride

1 Q 9 8 5 1 / T 8 6

with monoperglutaric acid in the presence of one equivalent of a base.

In practice it is usually expedient to incorporate the aroylglutaryl peroxides into a bleaching or bleaching and washing mixture which contains other suitable components. Such mixtures are preferably, but not necessarily, particulate solids. The mixture can contain neutral or alkaline reacting inorganic detergent salts and / or inert diluents. It can contain, for example, alkaline inorganic salts such as alkali metal carbonates, silicates, phosphates and polyphosphates and neutral salts such as alkali metal chlorides or sulfates, for example in an amount of 1 to 99% by weight. Organic complexing agents likewise ^can: optionally be present, such as aminopolycarboxylates, for example Natriumnitrilotriacetate, organic polyphosphonates, e.g. Xthan-i-hydroxy-iji-diphosphonate, sodium citrate, sodium gluconate, etc., for example in an amount up to 99 wt. %. Compatible organic surfactants, particularly anionic, nonionic and zwitterionic detergents, may also be present, for example in an amount up to 90% by weight. The amounts of these components, ie the alkaline inorganic salts, organic complexing agents or organic surfactants, are adjusted depending on both the nature of the organic detergent, if any, and the intended use of the product. Usually, however, the preferred proportions of such components are those commonly used in the products under consideration.

Particularly suitable organic anionic detergents are the water-soluble soaps and the alkylbenzenesulfonates, ■ .in particular linear alkylbenzenesulfonates, alkyl sulfates, olefins * finsulfate and other organic sulfates and sulfonates.

'. 109851/1864

Suitable nonionic detergents include the polyethylene oxide condensates with polypropylene oxides, e.g. the Pluronics (trade name), or with fatty alcohols, alkylphenols, Fatty acids etc .. The mixtures can also contain the usual minor components of the usual bleach and. Detergent mixtures, such as dyes, perfumes, opacification inhibitors, bleach stabilizers, optical brighteners, enzymes, Dust-preventing additives, foam-increasing or-reducing agents, abrasives and the like. Contain.

A primary function of an oxidizing bleach is to chemically react with stains and oxidize the same, whereby their color is reduced and / or their sensitivity to the washing effect is increased. On the other hand such means are said to have dyes (which are considered deliberate - "Spots" mentioned may not discolor or change significantly, or damage the tissue on their own, however, no effective bleach is perfect in this regard. It has now been found that the Tendency of aroyl glutaryl peroxide to damage color or tissue and its tendency to yellow "of super polyamide (nylon) -g'eweben is reduced if an inorganic perhydrate is present in the bleaching liquid.

Inorganic perhydrates are to be understood as meaning compounds which deliver hydrogen peroxide in aqueous solution, such as ^! Sodium perborate, percarbonate, perphosphate, or hydrogen peroxide itself. Potassium and other suitable salts can also be used. This mixture gives a somewhat lower bleaching effect than the aroylglutaryl peroxide alone, but at temperatures below about 85 ° C a considerably higher than perhydrate alone and gives a better combination of bleaching effect and loss of color or tissue damage than with. Application of one of the components occurs alone. ■

According to a further embodiment of the invention a bleaching process and a bleaching mixture like them are described above, created with the modification that an inorganic perhydrate is also present.

Preferred perhydrates are those mentioned above, in particular sodium perborate. Hydrogen peroxide as such can in bleaching liquids and in the method according to the invention be used. Its use in concentrated mixtures leads, although lying within the scope of the invention, often to difficulties in obtaining stable products. The amount of perhydrate is preferably such that the Weight ratio of available oxygen in the aroyl glutaryl peroxide to that of perhydrate is 3: 1 to 1: 6 and in particular is in the range from 1: 1 to 1: 4-.

Although the peroxides according to the invention are more stable when stored in the mixtures described here than previously known water soluble organic peroxy bleach, it may nevertheless be desirable to have protection against atmospheric or other moisture and against at least provide some of the other components of the mixture. This can be done, for example, by coating the peroxides with a inert material, or by mixing it with inert or stabilizing substances, and coating the mixture, or agglomerating or extruding the same in the form of "noodles", or any other suitable means Methods are effected.

The proportion of aroylglutaryl peroxide in these mixtures should be such that an available oxygen concentration is adjusted in the ranges defined above when the mixtures are in the intended concentration can be used in a bleaching or washing liquid. Thus, mixtures suitable for use at usual concentrations are intended for household washing,

BAD ORIGINAL 109851/1864

normally contain enough aroyl glutaryl peroxide to provide 0.1 to 5% by weight of available oxygen, preferably 0.2 to 2 % and more preferably 0.2 to 1 % .

The following examples illustrate the invention:

Example 1: bleaching effect.

Solutions are prepared which contain 4 g / l of a detergent mixture of the following composition, indicated in% by weight: ^;:

linear alkylbenzenesulfonate 17, -6 (alkyl chain C ₁₁ -O ₁₃ );

Sodium toluenesulfonate x 1.8 sodium tripolyphosphate 46.2

Sodium silicate 7 »5

Coconut monoethanolamide 1.8 sodium carboxymethyl cellulose 1.0 Sodium sulfate '12.4

™ ^; · Various smaller compo

nents 1.9

Humidity 10.0

along with

(a) enough sodium perborate, around 100 parts / million adjust available oxygen in the solution;

(b) enough benzoyl glutaryl peroxide to establish 10 parts / million available oxygen in the solution;

(c) enough benzoyl glutaryl peroxide to establish 100 parts / million available oxygen in the solution. .

^: '"^ ^v :" 3 α _: j 10985 1/4664

Cotton towel rags bearing tea stains were treated in each solution at 50 ° C for 10 minutes and then rinsed and dried. When comparing the reflectivity of the untreated and the treated cloths, it was found that 32 % stain removal was present in case (a), 38 % stain removal in case (b) and 6% stain removal in case (c).

Example 2: Stability in the detergent mix.

The stabilities of a typical aromatic peroxyacid and of benzoyl succinyl peroxide and benzoyl glutaryl peroxide in admixture with detergent granules of the composition given in Example 1 were compared. The percentage loss of active oxygen after storage for 14 days at 21 ⁰ O in wax-coated cardboard was as follows:

m-chloroperoxybenzoic acid 85 %

Benzoyl succinyl peroxide. 12 %

Benzoyl glutaryl peroxide 4 %

m-chlorobenzoyl glutaryl peroxide 5%

Example 3: explosiveness.

Samples were tested in an impact test device in which 0.02 g of the substance was distributed on a punch with a 1 GUI '"area, which was limited by a striker with the same surface area. A 2 kg weight was applied to the firing pin". Dropped from a distance of 150 and 200 cm. In the case jedOÄ Benaoylsucuinylperoxid detonated) _during; da ^ ^: Doiisoylgiucarylpsr-oxiä -nxciib detonated :).

BATH

Example 4 ·; Bleaching performance in aqueous solution

alone.

Pieces of cotton towels with tea stains were left for 10 min. washed in solutions of the substances mentioned below, wherein: each was used in such an amount to 100 parts / Llillion to provide available oxygen at 50 ⁰ G. The stain removal values were measured as in Example 1 = and were as follows:

Benzoyl glutaryl peroxide 4-9.5%

Sodium perborate 3 %

Eibenzoyl peroxide no removal,

■ B e i s ρ i e 1 5: Stability in the presence of sodium carbonate.

Equal amounts of 'sodium carbonate and the following peroxides were mixed and stored for 2 weeks in a wax-coated paperboard in a laboratory (at about 24 ⁰ G) .. The oxygen losses, based on the amount originally present were (in wt. ~%) As follows:

(a) Benzoyl glutaryl peroxide 3%

(b) la-chlorobenzoylglutaryl peroxide 3 ° / a

(c) Benzoyl succinyl peroxide 39%

(d) dibensoyl peroxide 13 %.

Example 6;

Ä.ls typical Hochleistungadotergeris zav ÖU ^ ^ -insams-n use with eiriwa Bieiciiaitirel was a granular laisftixu A foLsö ^ the "Zusararaenset; z-UIIs hargöstellb;

BAD ORfGiNAL

- ■ - ■, · :. z 10 985! / I8B4 : -

Sodium linear alkylbenzene
sulfonate 9 Sodium tallow alkyl sulfate 5 Sodium toluene sulfonate 1 Soap (tallow / coconut oil) 4- Sodium tripοlyphοsphat 45 Sodium silicate 10 Coconut ethanol amides 2 Sodium carboxymethyl cellulose 1 Sodium sulfate 11 humidity 10 various impurities,
Perfume etc. 2

100

Washing and bleaching solutions were put into tap water (about 175 parts / million card as calcium carbonate) , which per liter contained:

(1) 4.75 6 A mixture of 0.25 E BGP.

(2) 4.55 g mixture A 0.25 g BGP 0.2 g P34- '

(3) 4.45 g Mixture A 0.25 S BGP 0.3 g PB4

(4) 4.25 S Mixture A 0.25 S BGP 0.5 g PB4

(5) 4.15 g mixture A 0.25 6 BGP 0.6 g PBA-

BGP "means benzoyl glutaryl peroxide;
PB4 means sodium perborate tetrahydrate.

Stain removal:

Cotton cloth with tea stains were used in this in a Miniaturwaschnaschine at 50 ⁰ C for 10 minutes

109851 / 1-864 BAD ORIGINAL

The rags were then removed, rinsed in cold tap water, dried, and their reflectance measured and compared with that before washing, the percentage stain removal was determined as follows:

100 χ

Reflection after bleaching - reflection before bleaching.

100 - reflection before bleaching

The values obtained were: ■

Solution (1) "71 ° / o stain removal

Solution (2). 65 % stain removal

Solution (5) 64 % stain removal

Solution (4) 68 % stain removal

Solution (5) 68 % stain removal.

Tissue damage: "

Test pieces of superpolyamide (UyIon) ', cotton and terylene-cotton blend were 10 times in the solutions (1), washed at 5O ⁰ C (5) and (5)'. After each washing, they were rinsed with cold tap water and dried. The tissue damage was reported as loss of tensile strength and the numerical values below indicate average percentages of tensile strength loss for all fabrics.

Solution: ' ° / o Loss of tensile strength:

(5) io - :. ■ .:

109851/1 86

Superpolyami aver yellowing:

Test pieces of superpolyamide, which had been treated with optical brighteners during the preparation were placed in solutions (1), (2), (3) and (4) at 50 ⁰ C and soaked spurred on!, Wherein a natural cooling to room temperature took place. Fresh solutions were then heated to 50 ° C. and the fabrics were washed at this temperature for 10 minutes. They were then rinsed in cold tap water and dried. This cycle was repeated 10 times each time. The whiteness or yellowness of the fabrics before and after the treatment were measured by a Hunter color difference meter (manufactured by Hunter Associates Laboratory's Inc.) using a yardstick, with more negative values indicating increasing yellowness.

..The values obtained were:.

Solution (1) , -38 (2) -23 (3) --11 f4} ' -8th

Example 7:

Washing and bleaching solutions were used as in Example 6 indicated produced, however, per liter

(6) 4.25 g mixture A 0.25 S BGP 0.5 g PB4 or

(7) 4.8g Mixture A contained 0.20g BGP.

The stain removal tests and super polyamide yellowing tests were carried out as indicated in Example 6.

109851/1864

The results of the test were as follows: Removal of stains:

Solution (6) 68 %

(7) 67 %

Super polyamide yellowing:

Solution (6) -4- (7) -22

Thus, a concentration of benzoyl glutaryl peroxide results in the same or slightly less stain removal than a mixture of benzpylglutaryl peroxide / perborate , - delivers, nevertheless, a yellowing of super polyamide.

109851/1864

Claims (18)

Patent claims: 1. bleach, characterized in that it contains an aroylglutaryl peroxide of the general formula RCO.00.CO (CH ₂ ) 3CO ₂ H wherein RCO is an optionally ring-substituted benzoyl radical, as a bleaching component. 2. Bleaching agent according to Claim 1, characterized in that the benzoyl radical of the aroylglutaryl peroxide is uhsubstituiert or contains one or more -Cl-, -OCH, - or -CH, - radicals in the core. 3. bleach according to claim 1 or 2 in the form of an aqueous solution, characterized in that the peroxide in one Concentration is present that is sufficient to 1 to 200 parts by weight / Million available oxygen in the solution. *}. Bleaching agent according to Claim 3 *, characterized in that the peroxide is present in a concentration sufficient to provide 10 to 40 arrows by weight / million available oxygen in the solution. 5. bleaching agent according to claim 1 or 2, characterized in that it is also a neutral or alkaline inorganic Salt or organic complex-forming salt or a compatible one organic surfactant or a mixture of any of these components. 6. Bleaching agent according to claim 5, characterized in that it contains an alkali metal carbonate, silicate, phosphate or polyphosphate as the alkaline inorganic salt. 51/18 6 / * ORIGINAL BATHROOM 7. bleaching agent according to any one of claims 5 or 6, characterized characterized in that it contains an alkali metal chloride or sulfate as the neutral inorganic salt. 8. bleach according to one of claims 5 to 7 »characterized in that that the amount of inorganic salt is 1 to 99 wt .- #. . ". · 9. bleaching agent according to any one of claims 5 to 8, characterized characterized in that the organic complexing agent is an aminopolycarboxylate, an organic polyphosphonate nitrium citrate, or sodium gluconate. 10. bleach according to claim 9 *, characterized in that it contains the organic complexing agent in an amount up to 9-9% by weight. 11. bleaching agent according to any one of claims 5 to 10, characterized characterized in that the organic surfactant is an anionic, nonionic or zwitterionic Petergens is. 12. bleach according to claim 11, characterized in that the organic surface-active agent is a water-soluble Soap, an alkyl benzene sulfonate, an alkyl sulfate, an olefin sulfate, a polyethylene oxide condensate with polypropylene oxide or with a fatty alcohol, an alky! phenol or a Fatty acid is. 13. Bleaching agent according to one of Claims 5 to 12, characterized in that it contains enough aroyl glutaryl peroxide to set 0.1 to 3 % by weight of available oxygen in the mixture. 109851/1884 14., bleach according to claim 13, characterized in that it contains enough aroylglutaryl peroxide to be 0.2 to 1% by weight adjust the available oxygen in the mixture. 15 · bleaching agent according to one of the preceding claims, characterized characterized in that it also contains an inorganic perhydrate. 16. A bleaching agent according to claim 15, characterized in that it is sodium perborate or sodium petearbonate as the inorganic perhydrate contains. 17. Bleaching agent according to claim 15 or 16, characterized in that that the weight ratio of available oxygen in the aroyl glutaryl peroxide to that in the perhydrate is 3: 1 to 1: 6 amounts to. 18. bleach according to claim 17, characterized in that the weight ratio of available oxygen in the aroyl glutaryl peroxide to that in the perhydrate is 1: 1 to 1: 4. For The Procter & Gamble Company Cincinnati, Ohio, V.St.Ä, (Dr H.J. Wolff) Lawyer 109851/1864