DE2054019A1 - Bleaching detergent - Google Patents

Abstract

A bleaching catalyst includes a combination of a cpd. which liberates H2O2, a low temp. bleach precursor, a metal chelate catalyst and an enzyme able to remove sports and stains. Spec. H2O2 source is Na-perborate, bleach precursor is N,N,N,N'-tetraacetylethylene diamine, enzyme is a proteast obtained from B. subtilis and chelate is a cobalt chelate formed from 1, 10-phenanthroline.

Description

Bleaching detergent and cleaning agent and method for bleaching of textiles.

Priority: March 24, 1970, Luxembourg, No. 60 582 The invention relates on a bleaching detergent and cleaning agent and in particular on a medium with bleaching power at a relatively low temperature, because the agent which may also contain an active detergent ingredient, a hydrogen peroxide releasing one Compound, a low temperature calibration precursor and certain metal catalysts contains.

The preferred hydrogen peroxide releasing compound is sodium perborate, which can be used as either a monohydrate or a tetrahydrate. Other suitable Connections are disclosed in British Patent Specification 836,988.

Sodium perborate is widely used as a bleaching additive for Laundry detergent used in Europe. Detergents such as those used in household laundry sold in some European countries contain up to 30% by weight sodium perborate0 It is known that sodium perborate bleaches effectively at nearby temperatures the boiling point and at boiling, but is much less effective at lower ones Temperatures. A low temperature bleach precursor, hereinafter referred to briefly as a precursor is an organic compound which is supposed to overcome this iwlangel.

Such a precursor can work with hydrogen peroxide in aqueous solution to react at relatively low temperatures, for example at 20 - 600C, with the formation of a bleaching organic peracid. Organic peracids are, as has been known for some time, effective bleaching agents at low levels Temperatures, but their use as such, in contrast to their formation in situ, was caused by the difficulty of isolating and storing the peracid, in particular prevents the difficulty of storing the peracid in a detergent. A Typical precursor molecule contains one or more acyl radicals, which are susceptible to perhydrolysis Acetyl and benzoyl radicals, which are peracetic acid, are preferred and generate perbenzoic acid. The perhydrolysis should proceed sufficiently quickly and the precursor should be sufficiently water soluble that the peracid in a adequate time is formed0 The perhydrolysis must predominate over the simultaneous Hydrolysis reaction. The peracid, if formed, must be sufficiently resistant so that the desired bleaching comes about. These conditions must be specified in the in Considerable milieu, i.e. normal household laundry, at a pH of 9-10.

A check @@@@ process whether a forerunner is suitable or not is in British Patents 836,988, 855,735. The procedure persists therein, a solution of sodium perborate, sodium phosphate and a suitable active detergent to be prepared at 60 0C, the compound to be tested in equimolecular ratio to the active oxygen and stir for 5 minutes. After this time an aliquot is drawn off and immediately piped into glacial acetic acid and ice. Potassium iodide is then added and the liberated iodine in the usual way with sodium thiosulphate titrated The titer depends on the ease of formation of the peracid and its Stability at 600C.

Of course, the titer should be as high as possible.

Low temperature bleach precursors have been described extensively in the patent literature described. An exemplary, but by no means complete, LisX in this regard Patents are given below, along with an indication of the chemical Class of relevant precursors and occasionally preferred compounds.

British Patent 836,988: under. One of the claimed esters, Sodium acetoxybenzenesulfonate (SABS) was found in a household detergent in England used.

British Patent 970,950: Esters.

Belgian patent 621 901: Ester. A preferred connection is chloroacetoxysalicylic acid.

U.S. Patent 3,332,882: acyl-substituted cyanurates.

One of these, triacetyl cyanurate (TACA), has been found commercially available in the USA. offered.

British Patent 855,735: Amide.

British Patent 907 356: Amide. Two of these connections, N, N, N ', N'-tetracetylmethylenediamine (TJND) and N, N, N', N'-tetraacetylethylenediamine (TAED) were used in household detergents in England and the Netherlands.

U.S. Patent 3,061,350: Amide.

South African Patent 68/5685: N-Acylazole.

Two preferred compounds are N-acetylimidazole (AID) and N-benzoylimidazole (BID).

South African Patent 68/6344: Amide.

U.S. Patent 3,425,786: Amide.

In addition to the classes just mentioned, it has been suggested that appropriate members of the following classes could act as precursors: acid chlorides and anhydrides.

The disclosure of the above patents relating to hydrogen peroxide releasing compounds and precursors are hereby included in the present description recorded.

It has also been proposed to improve the bleaching effect of sodium perborate by incorporating a metallic catalyst into the bleaching situation, the catalyst being a transition element, for example cobalt. US Pat. No. 3,156,654 describes the use of cobalt chelated with a chalating agent, for example pyridine-2-carboxylic acid. Dutch patent application 67 03189 describes the use of such and similar chelates in connection with the hydrogen peroxide precursor! tx fer system of the type more freely mentioned. The present invention encompasses the use of agents of the type mentioned in Dutch patent application 67 03189, and the disclosure of this application is incorporated into the present by this reference description recorded.

For convenience, the above are hydrogen peroxide releasing agents Compound / precursor / Chekat catalyst combinations in the following occasionally simple referred to as the bleaching component of the invention.

It has become increasingly common to also incorporate enzymes into a detergent. Enzymes are incorporated because of their effect on certain types of dirt and stains, which are resistant to their removal by surfactants or bleaching substances, but are broken down by enzymes. The development of enzymes for use in detergents is described in an article in "fats, soaps, paints", 10, 1968, 743-748, "The Development of Enzymes for Use in Laundry Detergents". The author of this article is Dr J.C. Hoogerheide of Royal Netherlands Fermentation Industries Ltd. The same company also has a technical bulletin in April 1967 issued with the title "Maxatase -proteolytic enzyme product as additive in washing compounds South African patent specification 67/7178 relates, inter alia, to incorporation of enzymes in detergents and describes the general categories of enzymes which come into consideration.

The disclosure of these publications is also supported by this provision included in the present description Tests have shown that the bleaching component of the invention deactivates enzymes found in detergents be used. Accordingly, no benefit should be expected from the combination the mentioned bleaching component and enzyme. Contrary to this expectation however, it was found that agents containing the mentioned bleaching component and Enzyme included, an improvement in the overall stain removal appearance show about that which is obtained by means that either the bleaching component alone, or enzyme alone, or enzyme and the incomplete bleaching Component included.

The invention therefore creates a bleaching detergent and cleaning agent, which comprises a) a hydrogen peroxide releasing compound, b) a low temperature bleach precursor, c) a metal chelate catalyst, d) a stain removal enzyme, and a method of bleaching fabrics using this agent in one watery bath.

A preferred hydrogen peroxide releasing compound is sodium perborate.

The hydrogen peroxide releasing compound is normally used amount to 5-25%, preferably 5-20% by weight of the composition.

A preferred precursor is NNNsNt-etrag gläthylenediamine (TAED). The precursor / hydrogen peroxide releasing compound ratio can vary depending on the precursor and whether it is just one or more reactive than one Has acyl radical in its molecule. In general, the amount of precursor is of the same order of magnitude as the compound releasing hydrogen peroxide in the mean.

The preferred enzyme is a proteolytic enzyme (protease) obtained from b.subtilis. In general, the enzymes are incorporated into the agent in one such an amount that the end product has an activity of 104-106 maltose units per kg if anylolytic enzymes are used, and 5-20 Anson units per kg if proteolytic enzymes are used.

Although improved bleaching can be obtained from a number of transition metal chelates, is the preferred chelate for use in accordance with FIG Invention of a cobalt chelate, e.g., from picolinic acid and its short-chain alkyl derivatives; 5-hydroxypicolinic acid; Pyridine-2,3-dicarboxylic acid; Pyridine-2,6-dicarboxylic acid; 1-1 O-phenanthroline; 8-hydroxyquinoline. A preferred cobalt chelate is one which is formed from 1,1O-phenanthr-line, which inter alia investigated compounds, e.g.

Picolinic acids, which has the lowest inhibiting effect on enzymes. The cobalt chelate is generally used in very small amounts. Because it is catalytic acts, a high concentration in the washing liquid is not required, and high levels of cobalt are disadvantageous. A degree of chelation in the product to one Concentration in the washing liquid of 1 - 5 1 mol per liter is to be achieved ii general optimal.

The detergents and cleaning agents according to the invention are normally especially if they are intended for washing textiles, from 10 - 50% of the Combination of hydrogen peroxide releasing compound, precursor, metal chelate and enzyme, while the remainder of the agent in terms of its cleaning effect is composed according to generally proven principles and essentially consists of active detergent and builder as well as usual additives, e.g. show amplifiers or Foam regulators, fluorescent substances, alkali silicate, tarnishing Substances, dyes, perfumes and the like exist @@.

The surfactant of the agent can consist of anionic (soap or non-soap), non-ionic, ampholytic or zwitterionic compounds, individually or in combination.

From the point of view of stability, the enzyme ingredient becomes a compound on a nonionic basis preferred. The agent is generally from 5-30, preferably Contains 10-25 * surfactant @ Belongs to the surfactant is the same or larger lot of builder. All building materials, both organic and inorganic Builders, which in the past were used in detergents and cleaning agents have been used or proposed can also be used in the agents according to the invention are used, especially sodium tripolyphosphate, potassium pyrophosphate, nitrilotriacetic acid, Ethylenediaminetetraacetic acid, and the like.

An expedient form in which the agents according to the invention are produced is a spray-dried detergent powder, to which solid, finely divided Sodium perborate or other compounds releasing hydrogen peroxide precursors, Enzyme and metal chelate catalyst can be added.

The perborate and precursor can be coated for durability in the package during storage and a desired time-pricing policy get in the washing liquid. The enzyme can, when squeezed, on or in Carrier granules can be glued or incorporated in the manner described in the patent literature is described.

If desired, the enzyme can be stabilized by anchoring to a suitable document according to general principles as it is also in the technical or patent literature.

Generally, the base powder becomes 50 or more of the total composition be. For effective bleaching and stain removal from normal Wash concentrations (0.1-0.8 concentration in the wash liquid) should be at least 10p, preferably more than 20% of the bleaching and stain removing component be present.

Unless otherwise stated, all percentages are by weight.

Example 1 An agent according to the invention is given below.

Component wt.

Sodium dodecylbenzenesulfonate 18 sodium sulfate 7 sodium tripolyphosphate 33 Alkaline sodium silicate (anhydrous) 6 Sodium carboxymethyl cellulose (with 65% Active ingredient) 1 ethylenediaminetetraacetic acid with 100% acid 0.1 fluorescent Substance as received 0.5 For convenience, the above ingredients are used in hereinafter referred to as group A.

Sodium perborate 16 TAED (particle size between 0.251-0.353 mm) 5 Soap 3 Encapsulated Enzymes (Maxatase) 1.7 gobalt chelate catalyst (from picolinic acid) 0.54 Spray-cooled palm kernel monoethanolamide 3 perfume and water to 100 The ingredients in group A were poured over into a slurry and spray dried. The other components some were mixed to make the final product. The end product possessed a special good bleaching and stain-removing pre-composition for the following stains at low levels Temperatures: Blood Tea with Milk Coffee A distinct although less noticeable Effect was obtained @ on beer and soup stains. @ rwünschermassen that should TAED used to be essentially free of material which passed through a 0.178 mm Mesh screen passes through. It has been found to be up to 60% of that from one manufacturer material supplied by TIP passed through a 0.178 mm mesh screen.

A recommended particle size for TAED is between 0.178 and 0.699 mm, mostly between 0.251 and 0.353 mm.

The pH of the agent is desirably between 9 and 9.5, preferably about 9.2 at a 0.4% concentration.

Example 2 The following table summarizes the results which with sodium perborate and two different precursors in different combinations with a cobalt chelate and maxatase enzyme in a base powder with active detergent mixtures from the Italian type "ALL" were obtained.

Table 1%%%%% perborate TAED catalyst maxatase enzyme tea AS.10 BE ~~~~~~~~~~~ ~~~~~~~~~~~~~ BE WE 20 14.8 0.54 1> 4 46.5 54.7 20 14.8 0.54 - 56.1 13.5 20 14.8 - 1.4 29.6 55.2 20 14.8 - - 27.8 15.4 Perborate ASA catalyst Eenzym BE WE 20 23.4 0.54 1.4 48.8 54.9 20 23.4 0.54 - 53.3 11.3 20 23.4 - 1.4 24.7 57.6 20 23.4 - - 28.5 12.4 Conditions: Launderometer laundry / liquid ratio = 1:20 water hardness = 15 ° dH time / temperature = 30 min./400C test wash test pieces with tea stains AS.10: artificial dirt with casein content of catalyst 0.14% COSO4 7H20 0.396% 1.10-phenanthroline molar ratio perborate / TAED 3 perborate / ASA = 1: 1 TAED = Tetraacetylethylenediamine ASA = acetylsalicylic acid BE = bleaching effectiveness WE = Washing effectiveness + enzyme effectO The beneficial overall effect from the addition of both enzyme and cobalt chelate are evident.

Example 3 This example presents the results of practical washing tests gen using test wash. The same test wash was carried out at used in all exams. It is called multi-stained laundry if it has the following stains contains: tea tea / milk tea / milk / sugar # bleachable port wine Burgundy wine Chginati wine @ Stains coffee coffee / milk blackberry # raspberry egg cocoa / milk on enzyme grass Brown beer tomato sauce # appealing brown sauce tomato soup oxtail spots soup The spots are arranged on a scale from 4 to 0 based on visual estimation.

Zero means complete removal of the stain. One rating for each Test garment is obtained by summing the single stain rating.

The washing conditions were as follows. An automatic drum washing machine was used, set for the delicate cycle (program S); the laundry lasted 35 minutes at a temperature rising to 400C.

Dosage: 20 g / kg in the prewash g average 40 g / kg in of the main wash # concentration 0.75% The agent used according to the table was wAIA "; It is a washing powder with a content of enzymes and sodium perborate base powder and customary in France. "ALA" # is the base powder of "ALA" @ understood without perborate and enzyme. Aicalas is a protease which is used for incorporation in detergents supplied by Novo. The catalyst used is a cobalt / 1,10-phenanthroline chelate, as described in example 2.

Evaluation of many ALL ALL basic powder ALA basic powder blotchy Test laundry + 20% perborate + 20% perborate + 7.5% TAED + 7.5% TAED + 0.8% abalase + 0.54% catalyst + 0.8% Alcalas e tea J 3 2 1 tea + milk # 2 1 1 tea + milk # off- + sugar bleaching- 1 1 1 port wine bare 2 stains 1 1 Burgundy wine 2 3 2 1 Chianti wine # 3 2 1 coffee) 1 1 0 coffee + milk 1 1 1 blackberry juice 2 1 1 1 Himbee juice # 1 1 0 19 13 8 egg 0 0 0 cocoa + milk 2 2 0 grass on en- 2 1 1 zym an-brown beer # 2 2 1 speaking tomato sauce de 1 1 0 brown sauce stains 2 1 1 tomato soup # 3 2 1 ox tail soup 2/14 2/11 1/5 33 24 13 Example 4 From the following table 3 the improved effect is clearly evident, which with the inventive Combination is achieved.

In Table 3, ### the saddle 2 is a middle means according to the invention 1 and 3 are no compositions according to the invention and ii are given for comparison purposes.

Table 3% WE Mean% AS.10 Blood Eakao BE BE stains 1.ALL Base powder + 20% perborate + 7.5 * TAED + 0.8% alicalase 14.5 43.6 74.3 23.3 2.ALL Base powder + 20% perborate + 7.5% TAED + 0.54% catalyst + 0.8% Alcalase 31.9 48.4 79.5 22.4 3rd ALL base powder + 20, 'perborate + 7.5 * TAED + 0.54% catalyst 32.3 16.3 62.0 7.1 CANDY conditions: / washing machine @ program S delicate cycle, 35 Min / 40 ° C Dosage: 20 g / kg in the prewash 40 gjkg in the main wash Catalyst: 0.14% CoSO4 # 7H2O / 0.396% 1,10-phenanthroline ALL base powder: Italian "ALL" base powder without perborate and enzyme.

Example 5 The following Table 4 shows the soaking results Dirty items of laundry with an agent according to the invention compared to items not according to the invention Means.

Table 4%%% catalyst /% Maxatase WE BE (cobalt / 1.10 enzyme AS.10 tea perborate TAED phenanthroline) 20 10 0.54 1.4 37.8 61.0 20 10 - 1.4 37.8 33.0 20 - 0.54 1.4 33.5 6.0 20 10 0.54 8.0 65.0 Conditions: Soaking in the container: 16 hours / 20 ° C wash / liquid ratio: 1:50 water hardness: 15 ° G.H. - Dosage: @@ g / l base powder: French "ALA" without @erborat and @nzym.

Claims (11)

Claims e 1. Bleaching detergent and cleaning agent, thereby It is not noted that it is a combination of a hydrogen peroxide releasing compound, a low temperature bleach precursor, a metal chelate catalyst and an enzyme having stain removing ability. 2. Means according to claim 1, characterized in that g e k e n n z e i c @ n e t d a s s the hydrogen peroxide-releasing compound is sodium perborate. 3. Means according to claim 1 or 2, characterized in that g -e k e n n -z e i c h n e t that the precursor is N, N, N ', ä'-tetraacetylethylenediamine. 4. Means according to one of the preceding claims, characterized g e k Note that the enzyme is a protease obtained from b.subtilis. 5. Agent according to one of the preceding claims, characterized in that g e k e Note that the metal chelate is a cobalt chelate. 6. Means according to claim 5, characterized in that g e k e n n z e i c h n e t, d a s 5 the chelate is formed from 1,10-phenanthroline. 7. Agent according to one of the preceding claims, characterized in that g e k e It should be noted that there is 5-30% by weight of an organic active detergent, 10-50 % By weight of the combination of compound releasing hydrogen peroxide, precursor, includes metal chelate and enzymes. 8. Means according to claim 7, characterized in that the proportion of the compound releasing hydrogen peroxide is 5-25% by weight of the total Means is. 9. Process for bleaching textiles, thereby g e k e n n -z e i n e t that the textiles are treated with water, which is a hydrogen peroxide releasing compound, a low temperature bleach precursor, an metal chelate catalyst and an enzyme having stain removal ability. 10. The method according to claim 9, characterized in that the textile is treated with a solution of an agent according to claim 7. 11. The method according to claim 10, characterized in that g e k e n n -æ e i c h n e t that the means of M claim 8 is used.