Bleach activators in detergent compositions

• PROCESS FOR PREPARING DETERGENT COMPOSITIONS CONTAINING WHITENING ACTIVATOR AT LEAST ONE CYCLIC TERTIARY AZOTE COMPOUND ί i

that presents ;

i

BP CHEMICALS LIMITED, English, Industrial, based in Belgrai ve House, 76 Buckingham Palace Road, London SW1W OSU, English. !

The invention relates to the process for the preparation of an assembly.

A detergent solution in aqueous solution containing:

I (i) a surfactant chosen from anionic, nonionic, hybrid and cationic surfactants, and their mis? tures; i | (ii) a precursor compound capable of giving rise to a peroxygen compound in the presence of water;

(J) a bleach activating agent capable of enhancing the bleaching activity of the compound of^: peroxygen thus formed;

! l! (iv) a foam suppressing substance; Hey ! !

(v) a detergent forming agent, characterized in that the bleach activating agent comprises one or more detergent forming agents.

<img file="PT89695B_D0001.tif" />

Further cyclic tertiary nitrogen compounds of general formula defined in the claims wherein said activating agent is at least partially water soluble.

The whitening activating agents employed have bleaching activity at relatively low temperatures.

The present invention relates to the use of bleach activators, especially in detergent compositions.

Compounds such as tetracetyl ethylene diamine (hereinafter referred to as ΤΑΕΌ) are well known. Processes for the production of such compounds are described, for example in German Patent Specification No. 2832021. These compounds are said to be effective in activating conventional inorganic salts used as bleach precursors in detergent compositions, and generate peracetic acid. in situ when reacting with alkaline hydrogen peroxide. 0 activating agent for the bleach precursor is the so-called bleach activator. Specific examples of such bleach precursors are sodium perborate and sodium percarbonate. In the absence of activating agents, the bleach precursor e is satisfactorily efficient at high temperatures, and its effectiveness at low temperatures is very low.

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<img file="PT89695B_D0002.tif" />

peratures. The use of compounds such as ΤΑΞΌ enables the pre- bleaching slider operating more efficiently at temperatures around 60 ° C. !

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It has now been found that certain cyclic nitrogen compounds:

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function efficiently as additives in activating the pre-; bleach slider in detergent compositions especially at low temperatures.

Accordingly, the present invention is an aqueous solution detergent composition comprising:

(i) a surfactant chosen from among the agents^:anionic, nonionic, hybrid and cationic surfactants and mixtures thereof; ii) a precursor compound capable of giving a peroxygen compound in the presence of water; I

(iii) a bleach activating agent capable of

tensifying the bleaching activity of the peroxygen compound thus formed; iv) a foam suppressing agent; ej

(v) a detergent bulking agent, characterized in that the bleach activating agent comprises one or more cyclic tertiary nitrogen cyclic compounds of the formula:

<img file="PT89695B_D0003.tif" />

<img file="PT89695B_D0004.tif" />

'^! wherein Q is a bivalent organic grouping such that Q and N i together with the carbonyl and oxygen functions in the compound form one or more cyclic structures and R is H, an alkyl, alkaryl, aryl, aralkyl, alkoxy, haloalkyl, amino, aminoalkyl or a carboxylic acid function or containing a carbonyl group, said activator being at least

Mild partially soluble in water.

¹ Where R is a function comprising an aryl, alkaryl or aralkyl radical, it is essentially that these functions also have a substituent capable of solubilizing the activator in aqueous systems, for example an isulfonic acid group. When R is a function comprising halogen, the halogen is preferably chlorine or bromine.

Examples of such compounds include the compounds of formula

<img file="PT89695B_D0005.tif" />

wherein R has the same meanings as in formula (I), above represented. A specific example of such a compound (R = CHp is 2-methyl- (4H-3,1-benzoxazine-4-one).

Other compounds of this type include those wherein R is an alkylamino group for example a dimethylamino group; a rough, acyl, for example an OH · .00 group; an alkoxy group, for example ethoxy group; a haloalkyl group, for example, a chloromethyl, dichloromethyl or trichloromethyl group;

an alkoxyalkyl ether group, for example an ether group;

<img file="PT89695B_D0006.tif" />

Jinetoxyethylene; or an alkylene carboxylate group, for example, a - (CH₂)₂C00-.

Another compound of this type is a compound of formula III:

<img file="PT89695B_D0007.tif" />

(III) wherein R has the same meanings as in formula I, and

Rg, ^ 3 ^and ^ 4 °ⁱⁿ be identical or different nuclear substituents and may be selected from H, halogen, alkenyl, alkenyl, aryl, hydroxy, alkoxy, amino, alkylamino, COOR (where H is an alkyl group) and carbonyl functions . Specific examples of compounds of this type include those wherein (a) R 4 and R 4 are both H, and R 4 = H and R₂ = OH; R₂ = aceto {; x1 and R2 = H; Rg = R3 = alkoxy, especially methoxy^! xi; Rg = H but R3 = a halogen or haloalkyl, for example a chlorine group or a group. chloromethylene; R₂ = halogen or a haloalkyl group and R 1 = H; hey (I

I; (b) R4, R₂ or R4 = alkyl, for example methyl but the rest are all H.

_;Another compound of this type is represented by formula IV.

<img file="PT89695B_D0008.tif" />

• Ο &lt;^R6-^Ç7^R7&gt;_no .

(IV) where R has the same meanings as in formula I above ^;Rg e are the same or different groups and may be any of the groups previously defined with respect to R 1 and n has a value of 1 to 3.

tertiary nitrogen cyclic compound may further be represented by formula V, represented below:

<img file="PT89695B_D0009.tif" />

where R has the same meanings as in formula I, and Rg is ¹ 'R_Q are the same or different groups and may be any of the substituent list groups designated above for R, ^! A specific example of such a compound is that. wherein Rg and Rg together form one or more benzene rings i as in formula II above or when together with the two carbon atoms of the hydrocarbyl I have. (ga and nitrogen and carbonyl functions represent a ring of pI (razole, pyrimidine, pyridine or imidazole).

Similarly, Vention bleach activators may have the formulas (VI) or (VII):

<img file="PT89695B_D0010.tif" />

<img file="PT89695B_D0011.tif" />

i ί

I (VI) j (VII); wherein R has the same meanings as in formula I and X is H or a monovalent organic group. A specific example of a compound represented by formula VII is where X = CH₃ and R = Ph.

Compounds of formula II, shown above, may be synthesized by acylation of an isatoic anhydride with an anhydride.

For example, when R = CH 2, the acylating agent is acetic anhydride. The compounds of formulas (VI) and

II (VII) can be synthesized from the corresponding alpha or beta amino acids respectively.

Alternatively, the tertiary nitrogen compound may be prepared by acylation of an amino acid as follows:

<img file="PT89695B_D0012.tif" />

<img file="PT89695B_D0013.tif" />

<img file="PT89695B_D0014.tif" />

Another example of a compound is

<img file="PT89695B_D0015.tif" />

R (IX) i!

wherein R has the same meanings as in formula I above is represented.

The bleach activating agent is at least partially soluble in water. Thus, solubility is at least 0.01% w / w in water at room temperature, for example at 25 ° C.

Activating agents of the present invention are believed to react preferentially with the peroxygen compound, for example hydrogen peroxide generated by contacting the precursor compound with water. It is believed that peroxygen species result in enhanced bleaching activity compared to that initially generated.

The bleach activating agents of the present invention may be used in conjunction with other conventional activators such as TAED, phthalic anhydride, maleic anhydride (succinic anhydride, isononanoyloxybenzenesulfonate (also ^—! known as isonabs) and tetracetyl glycol uryl (also known as TAGU) and the like or with mixtures of such known activators.

Any of the well known surfactants may already be

used with detergent compositions of the present invention. An ; A typical list of these surfactants can be found in European Patent Specification EP 0120591 and US Patent No. 2. 3,663,961.

Examples of water-soluble anionic surfactants include salts of alkyl benzenesulfonates, para-ionsphenic sulfonates, alpha-olefin sulfonates, alkyl glyceryl ether-β-sulfonates and 2-acyloxyalkane-1-sulfonate and beta-alkyloxy. alkane sulfonate. Similarly salts of alkyl sulphates, alkyl polyalkoxy ether sulphates, alpha sulfa carboxylates and¹(Their fatty acid monoglyceride esters, sulfonates and sulfates and alkyl phenol polyalkoxy ether sulfates may be used.

Suitable examples of the aforementioned surfactants are straight chain alkyl benzene sulfonates having 8 to 16 carbon atoms and branched methyl alkyl sulfates having 8 to 16 carbon atoms; which are also efficient. !

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Other anionic detergent compounds suitable for use in; (present invention include alkyl glyceryl ether sulfonates:: tallow derived from coconut oil and tallow; sodium fatty acid monoglyceride sulfonates and derived from coconut oil; and potassium salts or sodium sulfate ether (from alkyl in^Ç8 ^Ç12 alkylene oxide phenol comprising up to 10 alkylene oxide units per molecule. Mixtures of anionic surfactants may already be used.

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( , ^—i^!A substantial list of such compounds can be found.

<img file="PT89695B_D0016.tif" />

<img file="PT89695B_D0017.tif" />

—'In, for example, McCutcheon's Dictionary of Emulsifiers an Detergents, International Edition (1981), published by Manu facturing Confectioner Publishing Co. and Surfactants Eu.ro-;

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A: Directory of Surface Active available in Europe, Ed. Gordon L. Hollis, Vol. 1 (1982), published by George Goodwin, Nonionic surfactants that can be used in

I (the present invention are condensed from an alkylene oxide, for example ethylene oxide with a hydrophobic group to form a surface active agent having an appropriate lipophilic hydrophilic balance (HLB) of about 8 to 17, suitably of about 8 to 17%. 9.5 to 13.5, preferably 10 to 12.5 The hydrophobic group may be any aromatic or aliphatic type group and the length of the condensed polyethylene group is:

I can easily be adjusted to produce a composition.¹ water soluble to the desired HLB grade.

Examples of nonionic surfactants include: (a) Alkyl phenol ethylene polyoxide condensates; wherein the alkyl group comprises for example 6 to 12 carbon atoms and in which about 3 to 30 moles, preferably 5 to 14 moles of ethylene oxide are present. Other examples include a mole of dodecyl (-phenol condensed with 9 moles of ethylene oxide and a

1 mole of condensed dinonylphenol with 11 moles of ethylene oxide and 1 mole of nonylphenol and octadecylphenol condensed with 13 moles of ethylene oxide.

(b) The nonionic surfactant may also be formate; as a product of the condensation of one mole of a primary or secondary Cg to C24 aliphatic alcohol with;^; about 2 to 40 moles, preferably from 2 to 9 moles of ethylene oxide.

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<img file="PT89695B_D0018.tif" />

Specific examples of nonionic surfactants; Useful for purposes of the invention include the various grades of Bobanol (Trademark sold by Shell) Lutensol (Trademark traded by BASE) and Synperonics (Trademark traded by ICI). Other useful nonionic surfactants include synthetic nonionic detergents available under the label, Pluronics (Trade Mark) and marketed by

1¹ Wyandotte Chemicals Corporation.

Hybrid compounds such as betaines and sulfobetaines, particularly those having alkyl substituents on Οθ - on the nitrogen atom, may also be used as surfactants.

Examples of cationic surfactants which may be used include, for example, quaternary jamonium salt surfactants and semi-polar nature surfactants, for example amine oxides. Quaternary ammonium salt surfactants are C 1 -C 6 mono N-alkyl or alkenyl surfactants wherein the valences of N are occupied by methyl, hydroxyethyl or

I¹ ;! hydroxypropyl. Suitable examples of amine oxides are the mono- N-alkyl or C6 -C6 alkenyl-amine oxides and pro; pilene-1,3-diamine dioxides wherein the remaining valence are satisfied by methyl, hydroxyethyl or hi (droxyixpropyl) substituents.

Detergent compositions may comprise from 1 to 70% w / w, suitably about 1 to 20 / w / w of the total composition. !

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Mixtures of anionic with nonionic or hybrid surfactants are preferred.

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Inorganic bleaching peroxygen precursors

Suitable for acting as a source of peroxygen compounds,

ÍZ

- e.g. hydrogen peroxide include perborate.

: sodium, monohydrate and tetrahydrate, sodium percarbonate, ^: sodium persilicate and clathrate 4 Na „S0:: 2H„ 0 · 1 NaCl.

ά 4- d ά \

If clathrate materials are used as a peroxygen bleaching precursor a separate alkalinity source is required and, for stability reasons, it is preferable to store it separately from the hydrogen peroxide source. The precursor compound (ii) acting as a source of [hydrogen peroxide] may be present in an amount of from about 1 to 40 w / w, suitably from about 5 to 35 F by weight, preferably from 10 to 30 wt.%. total composition.

In the detergent compositions of the present invention, the molar ratio of the peroxygen compound, e.g. hydrogen generated from a bleach precursor; for the bleach activating agent is generally greater than 1.5: 1, preferably at least 2.0. Under the conditions of use as is generally found in household washing practice, the molar ratio of the branqueat precursor

Bleach activating agent is generally ^:[greater than 5.0: 1 and more preferably greater than 10: 1.

Foam suppressing agents which are useful in the detergent compositions of the invention are suitably selected from silicone, wax, vegetable and hydrocarbide oils and phosphate ester varieties. Silicon foam control agents include polydimethylsiloxanes having a molecular weight of from 200 to 200 ...

200 000 and with a kinematic viscosity of about 20,000,000,000 m3 / s (cSt), preferably from 3,000 to 30,000 mm2 / s (cSt) and mixtures of siloxanes with hydrophobic silanated silica (e.g. trimethylsilanate ) having particle size of about 10 to 20 millimeters and a specific surface area greater than 50 m / g. The appropriate waxes

<img file="PT89695B_D0019.tif" />

include microcrystalline waxes that have a melting point! 65 ° to 100 ° C, a molecular weight of about 4,000 'to 10,000 and a penetration value of at least 0, measured at 77 ° C by the procedure of ASTM-D1321, and also waxes : fines, synthetic waxes and natural waxes. ,

N _z Suitable phosphate esters include (mono- or dialkyl or C2 -C6 alkenyl phosphate esters comprising up to 6 ethoxy groups per molecule.) (Foam suppressors are usually present in an amount of from about 0 to 0.01 and 5% w / w of the total composition, depending on the type of foam suppressor used, and preferably about 0.1 to 2% w / w.

A highly preferred component of the detergent compositions (according to the invention is one or more of the bulking salts of the detergent, which may constitute more than 90% of the composition, typically about 10 to 70% by weight.). Suitable detergents for the invention may be of the polyvalent organic or inorganic type or mixtures thereof. Examples of bulking salts of inorganic detergents al! Water soluble calines include alkali metal carbonates, borates, phosphates, pyrophosphates, tripolyphosphates and bicarbonates. Suitable examples of alkaline organic detergent builder salts are water-soluble polycarboxylates such as salts of nitrilotriacetic acid, lactic acid, glycolic acid and its derived ethers;_;malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid; citric acid, aconitic acid, citra (conic acid, carboxymethyloxysuccinic acid, lactoxysuccinic acid, 2-oxy-1,3,3-propanomethyloxysuccinic acid, oxysisuccinic acid, 1,1,2,2-ethane tricarboxylic acid, 1,1,3,3l-propane-tetracarboxylic acid, cyclopentane-cis, cis-tetra 14. tracarboxylic acid, cyclopentadiene-pentacarboxylic acid,

2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylic acid, 2,5-tetrahydrofuran-cis-dicarboxylic acid, 1,2,3,4,5,6-hexane-hexacarboxylic acid, melitic acid, pyromelitic acid and phthalic acid derivatives. ί

Internal detergent bulking agents may also be used. soluble in water. A specific example of such bulking agents are zeolites, especially sodium zeolite of Type I marketed as SASI1 (Trade Mark).

Mixtures of organic and / or inorganic bulking agents may also be used.

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Chelating agents, soil suspending and anti-redeposition agents, optical brightening agents, enzymes, colorants and perfumes may also be added to the detergent composition.

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Chelating agents which may be incorporated include nitrilotriacetic and ethylene diamine tetracetic citric acids and their salts derived from organic phosphonates such as those disclosed in U.S. Patent Nos. 3,213,030,

433 021, 3,292,112 and 2,599,807 and bulking salts derived from carboxylic acid such as those described in U.S. Patent No. 3,308,067. Chelating agents may be present in an amount of from about 0.1 to 3%, e.g. preferential- (0.2 to 2% by weight of total composition. Detergent compositions containing bleach activators of the present invention may contain in addition additives (conventional in minor amounts such as perfume flavorings and the like).

read

(1) Thus, the bleach activating agents of the present invention will find wide use in detergent compositions as such.

<img file="PT89695B_D0020.tif" />

- which include inorganic bleach precursors. The fact that these anhydrides activate the bleach precursors at relatively low temperatures, for example from about 20 ° to 60 ° C, compared to those previously used will imply a considerable decrease in the achieved energy consumption. when using detergent. It's not¹ The present invention is further illustrated with reference. to the following Examples. ]

| .Example I! ι

Preliminary wash / bleaching tests were performed on standard stained tissue samples (EMPA * with 1 x 4 red dye) at a constant temperature maintained at 40 ° C using the powder based detergent composition. μ (Table 1) and the various bleach activators

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Described in Tables 2 and 3.

: 2.4 g of base detergent plus 0.45 g of sodium perborate. tetrahydrate and the bleach activating agent (0.15 g, 5.0% w / w) as described in Tables 2 and 3 were added to 600 ml of 40 ° C tap water having [a hardness of about 290 ppm calcium carbonate. The red wine stained tissue samples were then added to the composition and stirred for 30 minutes at 40 ° C after which time the samples were taken, rinsed and dried at 24 ° C. Spot blotting was achieved with each bleach activator was visually examined using standard light conditions (ICS-Texicon Multi-Cabinet, D65) and compared to spot blotting. achieved by TAED (10) and the standard blank assay ((using only perborate, o) in which no bleach activating agent was used and graded).

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II

II

16.

<img file="PT89695B_D0021.tif" />

The following examples were performed using a test technique prescribed by the Swiss Federal Government Testing Agency Eidenossiische Material Erusungs ander Versuchingen sanstalt

Ch-9001, St. Gallen!

Understrasse, PO Box 977, Switzerland.

From here it is referred to as EMPA.

;;; table go

Sodium linear H-alkylbenzenesulfonate (average length of C1-5 alkyl chain) _:Ethoxylated tallow alcohol with 14 units of ethylene oxide)

Sodium Soap (Cp2 Î · 16 · chain length: 13-26% j 0 j_q "0 22 '74 ~ 87%) Sodium triphosphate Sodium silicate (SiO2.3: 1)

Magnesium silicate 1'Carboxymethylcellulose 'Sodium ethylenediaminetetraacetate

Sodium Sulphate

Water

8,0

2,9

3.5 43,8

7.5 1,9 1,2 0,2

21,2

9,8

100

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<img file="PT89695B_D0022.tif" />

TABLE 2 Visual Spot Removal Rating j, 2-Methyl (4H) 3,1-benzoxazine-4-one derivatives

I (Glass, red wine stained tissue samples, 30 minutes, 40 ° C, 5% activating agent)

<td>R ... . . _. . ...</td><td>X</td><td>Method of preparation</td><td>Classification visual</td>

<td>2-methyl</td><td>H</td><td>ref 1</td><td> 11</td>

<td>2-Chloromethyl</td><td>H</td><td>ref 2</td><td> 11</td>

<td>2-Dichloromethyl</td><td>H</td><td>ref 2</td><td> 3</td>

<td>2-Trichloromethyl</td><td>H</td><td>ref 2</td><td> 3</td>

<td>2-Methoxymethyl</td><td>H</td><td>ref 2</td><td> 11</td>

<td>2-Amino</td><td>H</td><td>ref 3</td><td> 2</td>

<td>2-Dimethylamino</td><td>H</td><td>ref 4</td><td> 11</td>

<td>2-Acetyl</td><td>H</td><td>ref 2</td><td> 10</td>

<td>: 2-Ethoxy</td><td>H</td><td>ref 2</td><td> 7</td>

<td>2-Methyl</td><td>6,7-Dimethoxy</td><td>ref 5</td><td> 11</td>

<td>2-methyl</td><td>7-Chlorine</td><td>ref 5</td><td> 11</td>

<td>2-methyl</td><td>6-Chlorine</td><td>ref 5</td><td> 11</td>

<td>2-methyl</td><td>8-Methyl</td><td>ref 5</td><td> 11</td>

<td>| 2-Methyl</td><td>6-methyl</td><td>ref 5</td><td> 11</td>

<td>2-methyl</td><td>5-methyl</td><td>ref 5</td><td> 11</td>

<td>2-methyl</td><td>6-Acetoxy</td><td>ref 6</td><td> 9</td>

<td>| 2-Methyl</td><td>6-hydroxy</td><td>ref 7</td><td> 8</td>

<td>'2-Methyl</td><td>7-Nitro</td><td>ref 5</td><td> 10</td>

t

<img file="PT89695B_D0023.tif" />

i, TABLE 3 jί (Visual Stain Removal Classification (Glass; Red Wine Stained Tissue Samples,

<img file="PT89695B_D0024.tif" />

<img file="PT89695B_D0025.tif" />

ref 5

<img file="PT89695B_D0026.tif" />

ref 8 - TABLE 3 (continued)

Visual Stain Removal Rating (Glass; Red Wine Stained Tissue Samples, Minutes, 40 ° C, 5% Activator)

Activator

Method of Preparation

Visual rating

<img file="PT89695B_D0027.tif" />

References:

jíl. LA Errede, J. Org. Chem., 1976, 41, 1763; North Patent;

i) American 3,989,698. ii;

x 2. British Patent GB-A-1389128;

3 K. Lempert and G. Doleschall, Monatsh, 1974, 95 (3), 950.

4. GV Boyd and RL Monteil, J. Chem. Soc. Perkin 1.,!

; 1978, 1388.

5 DR Desai. VS Patel, and SR Patel, J. Indian Chem.

Soc., 1966, 43 (5), 351.

6 See the summaries described below.

7- See the summaries described below ii

8. M. Crawford and V. '. T. Little, J. Chem. Soc., 1959, 729. 19. CNC Drey and RJ Ridge, J. Chem. Soc. Perkin 1, 1980, 378!

<img file="PT89695B_D0028.tif" />

References 2 and 5 contain general preparation methods that have been adapted to prepare each compound using the given conditions and appropriate starting materials.

Synthesis of bleach activators. 1. Preparation of 6-Acetoxy-2-methyl- (4H) 3,1-benzoxazine-4-one)

5-Hydroxy anthranilic acid (30.6 g, 0.2 mol) was heated at reflux in acetic anhydride (100 ml) for 3 hours. After cooling a solid formed which was removed by filtration, washed with diethyl ether and dried. 6-Acetoxy-2-methyl- (4H) 3,1-benzoxazine-4-one was isolated as white crystals. (11.2 g, 26%)._; /2. Preparation of 6-hydroxy-2-methyl- (4H) 3,1-benzoxazine-4-one.

4 g (0.1 mmol) of sodium hydroxide were dissolved in 4 ml of water and 50 ml of methanol. 6-Acetoxy-2-methyl- (4H) 3,1-benzoxazine-4-one (8.2 g, 0.04 mol), prepared above, was added to 30 ml of methanol and the mixture was refluxed for 3 hours. The solvent was removed by evaporation and the resulting sodium salt was dissolved in water and the solution acidified with hydrochloric acid. 5-hydroxy-N-acetyl acid_x ,

Anhydranilic acid was collected as a beige solid and dried under vacuum. The dried solid (7.8 g, 0.04 mol) was then dissolved in dry THF (50 ml). The mixture was stirred at room temperature for 18 hours and insoluble urea removed by filtration. The filtrate was evaporated to dryness evenly by 6-hydroxy-2-methyl- (4H) 3,1-benzoxazine-4-one (2.7 g, 38%).

Example 2

<img file="PT89695B_D0029.tif" />

/

Other wash / bleach tests were performed on! Standard stained fabric samples (2 x 6 ”red wine stained EMPA) using the base detergent powder composition (Table 1) and the various bleach activators described in Table 4 in a Terg-o-tometer. The temperature (meter was kept at a constant temperature of 40 ° C and performed at 75 rpm.

g of the basic detergent plus 0.75 g of sodium perborate tetrahydrate and the bleach activating agent (0.25 g,

5.0% w / w) as described in Table 4 was added to one liter of tap water at 40 ° C, which has a hardness of about 290 ppm calcium carbonate. Red wine stained tissue samples were added and then the composition was stirred for 20 minutes at 40 ° C, after which samples were rinsed and dried at 24 ° C. Sample reflectance was measured before and after washing. using a Micromatch ICS reflectometer and percent stain removal (^ RS) was calculated by applying the following formula, where L represents the whiteness parameter generated by the reflectometer (black = 0 and white = 100).

ji li ii ji% SR = L sample - 1 red wine x 100

L white - L red wine tl ι

I'm

Three repeated trials were performed and the average result! !

if was calculated.

<img file="PT89695B_D0030.tif" />

TABLE 4

Stain elimination percentage

2-Methyl (4H) 3,1-benzoxazine-4-one derivatives

Terg-o-tometer; tissues stained with red wine, 20 minutes, 4 ° C, 5% activating agent)

<td>ί R</td><td>X</td><td>% elimination of stains</td>

<td>2-methyl</td><td>H</td><td> 83,7</td>

<td>2-methyl</td><td>8-Methyl</td><td> 71,5</td>

<td>: 2-Methyl</td><td>6-methyl</td><td> 82,4</td>

<td>_;2-methyl</td><td>5-methyl</td><td> 77,5</td>

<td>2-methyl</td><td>6-Chlorine</td><td> 81,5</td>

<td>2-methyl</td><td>7-Chlorine</td><td> 80,6</td>

<td>2-methyl</td><td>6,7-Dimethoxy</td><td> 70,5</td>

<td>2-methyl</td><td>7-Nitro</td><td> 77,0</td>

<td>2-Chloromethyl |</td><td>H</td><td> 81,9</td>

<td>2-Dichloromethyl</td><td>H</td><td> 64,2</td>

<td>2-Trichloromethyl</td><td>H</td><td> 70,5</td>

<td>2-Me t oxime t ilo</td><td>H</td><td> 80,8</td>

<td>2-Dimethylamino</td><td>H</td><td> 81,1</td>

<td>[2-Acetyl</td><td>H</td><td> 70,4</td>

<td>h? aed</td><td></td><td> 77,0</td>

<td>Perborate</td><td></td><td> 60,6</td>

<img file="PT89695B_D0031.tif" />

<img file="PT89695B_D0032.tif" />

2-methyl- (4H) 3,1-benzoxazine-4-one bleach activator (hereinafter referred to as 2MB4) has been selected as a representative example of this series for extensive wash / bleach assays.

[Example 3 il (Comparison of percentage stain elimination achieved by 2-methyl- (4H) 3,1-benzoxazine-4-one (2MB4) and tetracetyl ethylene diamine (TAED) at various temperatures ( Table 5).

Washing / bleaching assays were performed using the same method as described in Example 2. In this Example, 4.155 g of base detergent, 0.75 g of sodium perborate Itetrahydrate plus bleach activator ( 0.125 g, i

2.5 7 ° w / w) θ Tissue samples stained with red wine were added to 1 liter of water at various temperatures (Table

5) and were stirred for 20 minutes. I will

The data clearly show the best washing performance of the

2MB4 compared to TAED at low temperatures 20 ° C, 30 ° C and 40 ° C.

ί

TABLE 5!

———— |

Comparison of 2MB4 with TAED at various temperatures (Terg-o-tometer; tissues stained with red wine; 20 min.

<td colspan="6">products; 2.5% activator</td>

<td rowspan="2">'Temperature</td><td colspan="2">% elimination</td><td colspan="2">7th elimination</td><td rowspan="2">7th Elimination stain with perborate</td>

<td>gives</td><td>stain with 2MB4</td><td>gives</td><td>stain with TAED</td>

<td>20 ° C</td><td></td><td> 65,9</td><td></td><td> 60,0</td><td> 57,4</td>

<td>: 30 ° c</td><td></td><td> 75,9</td><td></td><td> 69,7</td><td> 64,8</td>

TABLE 5 (continued)

Comparison of 2MB4 with TAED at various temperatures

<td rowspan="3">(Ter rg-ot ometr; O/ Z ° gives Temperature</td><td colspan="3">fabrics stained with red wine; 20 minutes</td>

<td colspan="2">products; 2.5% activator</td><td rowspan="2">ί l % eliminates t stain í with perborate</td>

<td>of elimination stain with 2MB4</td><td>% elimination stain with DAED</td>

<td>40 ° C</td><td> 79,8</td><td> 77,5</td><td>i 67.9</td>

<td>50 ° C</td><td> 85,9</td><td> 84,9</td><td> 76,3</td>

<td>60 ° C</td><td> 90,1</td><td> 88,1</td><td> 84,1</td>

<td>80 ° C</td><td> 92,7</td><td> 91,6</td><td> 90,2</td>

Example 4 I; I i

(Comparison of percent stain elimination achieved with 2-methyl- (4H) 3,1-benzoxazine-4-one (2MB4) and tetracetyl ethylene diamine (TAED) at various levels of activator treatment (Table 6).

The wash / bleach assays were performed using the same method as for Example 2. In this Example (4 g of the base detergent and 0.75 g of sodium perborate tetrahydrate were added). together with samples I (from red wine stained tissue to one liter of water at 40 ° C and stirred for 20 minutes. The amount of activator used was varied (Table 6) and in each case made up the total of 1/5 g using sodium sulfate. (Results obtained indicate that 2MB4 exceeds TAED at different levels of activator treatment. Adding more: | TAED does not cause a significant increase in elimination of

<img file="PT89695B_D0033.tif" />

—Spots than achieved at lower levels of 2MB4

P TABLE 6 ¹ , X

Comparison of 2MB4 with TAED at various treatment levels (Terg-o-tometer, red wine stained tissue samples!&gt; 20 minutes at 40 ° C) ¹ -X - ~ ~

<td>activator</td><td>Stain elimination% with 2MB4</td><td>% elimination of stains with TAED</td>

<td> 0,0</td><td> 66,5</td><td> 66,5</td>

<td> 1,0</td><td> 76,9</td><td> 73,2</td>

<td> 2,5</td><td> 81,1</td><td> 77,3</td>

<td> 5,0</td><td> 85,5</td><td> 82,0</td>

Example 5

Washing / bleaching assays were performed on tea stained tissue samples (2 ”x 6 EMPA) and the stain elimination percentage with 2-methyl- (4H) 3,1-benzoylazinobenzamide was measured. 4-one (2MB4) and tetracetyl ethylene diamine (TAED) at (different temperatures and treatment levels (Table 7).

(Assays were performed using the same method as described in Example 2. However, in this example, tea stains were used and the results evaluated after 30 min. The temperatures and amount of activator used are indicated. in Table 7.

I

These results again demonstrate the improvement of the behavior^: • Im 2MB4 in relation to TAED.

TABLE 7

<img file="PT89695B_D0034.tif" />

Comparison of 2MB4 with TAEB (Tea Stained Fabric)

<td></td><td>T e rg- ο- ϊ om eter,</td><td>30 minutes)</td>

<td>4 Activator 0 of</td><td>stain removal at 30 ° C</td><td>% stain removal at 40 ° C</td>

<td>j 2% 2MB4</td><td> 83,7</td><td> 90,8</td>

<td>1 2% TAEB</td><td> 79,1</td><td> 88,3</td>

<td>3% 2MB4</td><td> 86,1</td><td> 91,5</td>

<td>3% TAEB</td><td> 82,2</td><td> 91,3</td>

<td>Perborate</td><td> 72,5</td><td> 81,8</td>

EXAMPLE 6 A percentage comparison of blotting was performed using 2-methyl- (4H) 3,1-benzoxazine-4-one (2MB4) with other bleach activators, tetracetyl ethylene-day (mine (TAEB ), isononanoyl oxybenzenesulfonate (ISONOBS), magnesium mooperoperphthalate hexahydrate (ex Interox H48) and diperoxidodecanedioic acid (BPLDA) (Table 8).

'j;¹ Bleach activators were compared on an equal activity basis and sufficient amount of the supplied commercial activator was added to provide a level of 2% activity. The actual weights of the bleach activator as supplied by the manufacturer used in the wash tests are given in Table 8. The compositions_;total were diluted with sodium sulfate to 5 grams; í ”^- But.

<img file="PT89695B_D0035.tif" />

• Assays were performed using the same method as described in Example 2. In this Example, 3,4-g of base detergent, 0.75 g of sodium perborate tetrahydrate, bleach activator and stained tissue samples with red wine were added to one liter of tap water at 40^uC and stirred for 20 minutes.

!

Bleaching performance with 2MB4 is more efficient than with all other bleach activators under these conditions except DPDDA.

However, other wash tests which serve to compare 2MB4 and DPDDA on an equal available oxygen basis (Example 7) and on an equal weight basis indicate that ο 2MB4 is greater than DPDDA under other conditions.

TABLE 8

Equal Activity (Terg-o-tometer, red wine stained fabrics, 20 minutes

% Stain Elimination Activator

Used activator weight

2MB4

75,0

0.1 g

TAED

73,6

ISONO.BS

71,1

0.1 g

H48 il

DPDDA

77,1

0.83 g

Perborate

0.0 g

I

Example 7

Washings for canedioic til- (4H) 3,1-benzoxazine-4-one (2KB4) with canedioid (DPDDA) were performed on an oxygen basis

<img file="PT89695B_D0036.tif" />

diperoxide acid available.

Assays were performed using the same method as Example 2. In this Example, 3.05 g of Ibase detergent, 0.75 g of sodium perborate tetrahydrate, bleach activator and tissue stained samples Red wine was added to one liter of tap water at 40 ° C and stirred for 20 minutes. Sufficient amount of bleach activator was used to provide an available oxygen content of 1.09 x 10-4 mol. 0 Weight ! The actual bleach activator as supplied by the manufacturer used in the wash assay is given in Table 9.

Total compositions were diluted to 5 g using sodium sulfate.

The data showed that 2MB4 is higher in yield than DPDDA under these conditions.

TABLE 9

Comparison of 2MB4 with DPDDA ((Equal Available Oxygen)! (Terg-o-tome ter, red wine stained tissues, 20 minutes, 40 ° C (Activator% elimination

<td></td><td>of stains</td><td>Used activator weight</td>

<td>2MB 4</td><td> 85,4</td><td>0.125 g</td>

<td>DPDDA</td><td> 83,8</td><td>1.129 g</td>

<td>TAED</td><td> 81,8</td><td>0.125 g</td>

Example_8

<img file="PT89695B_D0037.tif" />

A comparison was made of the percentage elimination of stains obtained with 2-methyl- (4H) 3,1-benzoxazine-4-one (2MB4) and diperoxidodecanedioic acid (DPDDA) on an equal weight basis (Table 10).

Assays were performed based on the same method as described in Example 2. In this Example, 4.125 g of the base detergent, 0.75 g of sodium perborate, tetrahydrate, the bleach activator (0.125 g 2.5% w / w) and the samples ί! Red wine stained fabrics were added to a cloth. O !

tap water at 40 ° C and stirred for 20 min. . !

Again, 2MB4 clearly outperforms DPDDA under these conditions. tions. J

TABEDA 10 '(Equal Weight) (Terg-o-tometer, red wine stained tissues; 20 minutes; 2.5% activator;

% elimination

<td>Activator</td><td>stain</td><td colspan="2">Used activator weight</td>

<td>i 2MB4</td><td> 75,2</td><td> 0,125</td><td>g</td>

<td>DPDDA</td><td> 62,5</td><td> 0,125</td><td>g</td>

<td>Perborate</td><td> 61,5</td><td> 0,0</td><td>g</td>

<img file="PT89695B_D0038.tif" />

ι:

Example 9 Wash / bleaching tests were performed to compare 2-methyl- (4H) 3,1-benzoxazine-4-cna (2MB4) with isononoyloyloxybenzenesulfonate (ISONOBS) under washing conditions used in the United States of America (Table 11).

1.2 g of the basic detergent, 0.15 g sodium perborate tetrahydrate and the bleach activator (0.15 g, 10% w / w) were added to one liter of tap water at 25 ° C. Red wine stained tissue samples were added and the composition stirred for 20 minutes at 25 ° C after which time the samples were removed, rinsed and dried at 24 ° C. The percentage of spots was then measured and calculated in the same manner as described for Example 2.

The data in Table 11 demonstrate the best 2MB4 yield over ISONOBS under these conditions. The difference in stain elimination is even more pronounced than in the tests performed under the washing conditions used in Europe (Table 8).

TABLE 11

Comparison of 2MB4 with ISONOBS US Washing Conditions (Terg-o-tometer, red wine stained tissues; 20 minutes; 25 ° C; 10% activator)