RU2168578C2 - Process of preliminary treatment of fabric before washing, and bleaching composition - Google Patents

Abstract

FIELD: textile industry. SUBSTANCE: contaminated fabrics are preliminarily treated by liquid composition containing peroxide bleacher and agent removing contaminations and selected from group including ethoxylated monoamine, ethoxylated diamine, ethoxylated polyamine, polymeric ethoxylated amine, and their mixtures. Composition has pH value no higher than 6 and is prepared either in the form of emulsion or in the form of microemulsion. During contact for 5 min with fabric, composition removes different stains. EFFECT: increased cleaning efficiency for wide range of stains and enabled viscosity control. 22 cl, 1 tbl, 6 ex

Description

 The invention relates to whitening compositions, which are particularly suitable for use in pre-treatment, as well as to a method for pre-treatment of fabrics.

 A wide variety of whitening compositions have been described which are particularly suitable for pretreatment of tissues.

 For example, EP-A-598170 discloses such whitening compositions that are aqueous emulsions and constitute a non-ionic surfactant system, further comprising hydrogen peroxide or a water-soluble source thereof and a liquid whitening activator, or any other hydrophobic ingredient that is required separated from the specified hydrogen peroxide.

 European Patent Application 95203330.6 describes such whitening compositions which are aqueous microemulsions and include a whitening activator in an aqueous medium containing hydrogen peroxide and a hydrophilic surface active system.

 However, these emulsions or microemulsions containing peroxide bleach and a bleaching activator, especially when they are used in the pretreatment of various types of fabrics, for example, cotton or synthetic (for example, polyester / polyamides) before washing, have the disadvantage that they do not have such an effective effect on all types of stains, including oily stains, enzyme stains, dirt / clay stains, and bleached stains that would satisfy the consumer's requirements. However, there are still certain opportunities for further improving the process of pretreatment of fabrics using compositions containing bleach, in order to improve their action on stain removal and bleaching.

 Thus, it is an object of the present invention to provide an improved stain-removing action with respect to a wide range of stains, as well as an improved whitening action, especially in conditions of tissue pretreatment before washing, for example, when the composition is applied undiluted to at least part of the fabric before it the wash.

 Further, another problem associated with these emulsions and / or microemulsions containing a relatively high concentration of surfactants, for example, about 8% or higher, is that there is a tendency for significant viscosity to appear, which makes dispersion of these emulsions difficult / microemulsions and makes them unacceptable from the point of view of the consumer.

 Thus, another objective of the present invention is the creation of such liquid emulsions or microemulsions containing peroxide bleach and a surfactant for which the viscosity can be conveniently controlled while maintaining their physical stability.

 It has been found that an improved stain removing effect can be achieved by using a liquid composition containing peroxide bleach and a contaminant removing agent selected from the group consisting of ethoxylated monoamine or ethoxylated diamine or ethoxylated polyamine, polymer ethoxylated amine and a mixture thereof, as described below for preliminarily processed fabrics. Indeed, the addition of such a contaminant removing agent to a liquid composition containing peroxide bleach and optionally a bleaching activator produces an improved stain-removing effect on various types of stains, including grease stains, enzyme stains, dirt / clay stains, as well as bleach stains and the like under preliminary conditions treatment compared to the stain removal action that produces the same composition without said dispersing agent. It was also surprisingly found that liquid formulations containing both peroxide bleach and said contaminant removing agent, when used for tissue pretreatment, provide an improved whitening effect compared to the same formulations not containing a contaminant removing agent. Thus, it has been found that the addition of a single compound, for example, such as a contaminant removing agent, to a composition containing peroxide bleach, results in both an improved stain removal action and an improved bleaching effect. Moreover, it was found that this improved stain-removing effect against various stains persists even in peroxide compositions containing bleach having a long shelf life. Thus, it can be assumed that the oxidized form of an agent that suspends contamination, which can form in the presence of peroxide bleach during prolonged storage and / or elevated temperature, also provides an improved stain-removing effect on various types of stains. In other words, in a broad aspect, the present invention encompasses a process of bleaching fabrics using a liquid composition containing from 0.01 to 15% by weight of the total composition of the peroxide bleach and the contaminant removing agent, said process comprising the steps of applying said liquid composition in undiluted form at least one part of the specified fabric, after which it is optionally left in contact with the specified fabric and then the fabric is washed.

 Further, it was found that the addition of a contaminant removing agent selected from the group consisting of ethoxylated monoamine or ethoxylated diamine or ethoxylated polyamine, polymeric ethoxylated amine and a mixture thereof in a liquid composition made in the form of an emulsion or in the form of a microemulsion containing peroxide bleach and a surface -active substance, reduces its viscosity, whatever this viscosity may be before adding the specified agent that removes pollution. As a rule, it is preferable to prepare liquid compositions in accordance with the present invention either in the form of an emulsion or in the form of a microemulsion, since it is they that produce an improved stain removal effect and an improved whitening action, since they have an acceptable viscosity and do not need to add viscosity controlling additives. In other words, the present invention allows the preparation of emulsions or microemulsions with improved stain-removing / whitening action against all stains and acceptable physical characteristics, as well as with reduced cost, for example, without the introduction of viscosity-controlling additives, which should increase the cost of the composition and its volume, but it does not improve the whitening-cleansing effect of these formulations.

 Another advantage of the present invention is that the stable liquid emulsions or microemulsions obtained in accordance with it are suitable for efficient use by the consumer over a long period of time.

 In addition, another advantage of the composition in accordance with the present invention, obtained in the form of emulsions or microemulsions, is that it also provides excellent cleansing and / or whitening action, when it is used not only for pre-treatment, but also used in other laundry operations in the form of detergents or detergents.

 European Application Description 95870079.1 discloses laundry detergents suitable for pretreatment including polyamines and peroxide bleach. However, ethoxylated amines, ethoxylated polyamines or ethoxylated polymer amines are not disclosed.

 The description of the patent application US 08/663501 discloses compositions suitable for pretreatment of linen, including certain chelates, peroxide bleach and optional ingredients, such as whitening activators, polymer stain removers, such as sulfonated polyethoxy / propoxy oligomers with terminal ether groups. However, ethoxylated monoamines or ethoxylated diamines or ethoxylated polyamines, polymeric ethoxylated amines are not described. EP-A-271312 discloses a fabric washing composition containing peroxyacids as a bleach and stain removing agent such as, in particular, certain alkyl or hydroxyalkyl cellulose ethers, polymers containing ethylene terephthalate and polyethylene oxide terephthalate. Ethoxylated amines, ethoxylated polyamines or polymeric ethoxylated amines are not disclosed.

 WO 96/12004 discloses washing compositions containing lipophilic enzymes and a primary and / or tertiary amine. These compositions provide improved cleaning of greasy or oily stains and stains, especially when used in the pretreatment of fabrics before washing, to clean fabrics from greasy and oily stains. Presented formulations include ethoxylated tetraethylene pentamine (15-18), but not bleach.

 EP-A-112593 describes detergent compositions (pH = 6-8.5) containing ethoxylated mono- or diamines, ethoxylated polyamines and / or ethoxylated aminopolymers as agents for removing / preventing the back sedimentation of clay contaminants. These formulations can be used for pre-treatment during washing. Peroxide bleaches are not disclosed in the description.

(3) этоксилированных полиаминов, имеющих формулу

(4) полимерных этоксилированных аминов, имеющих общую формулу:

(5) и их смесей,

R - H или C₁-C₄ алкил или гидроксиалкил; R¹ - С₂-C₁₂ алкилен, гидроксиалкилен, алкенилен, арилен или алкарилен, или C₂-C₃ оксиалкиленовый остаток, имеющий от 2 до 20 оксиалкиленовых звеньев, предотвращающих образование O-N связей; каждый R² является C₁-C₄ алкилом или гидроксиалкилом, остаток -L-X, или два R² вместе образуют остаток -(CH₂)_r ^-A²-(CH₂)_s-, где A² является - O- или -CH₂-, r 1 или 2, s 1 или 2, и r+s 3 или 4; X - неионная группа, анионная группа или их смесь; R³ является замещенным C₃-C₁₂ алкилом, гидроксиалкилом, алкенилом, арилом или алкарильной группой, имеющей боковые заместители в p положении; R⁴ является C₁-C₁₂ алкиленом, гидроксиалкиленом, алкениленом, ариленом или алкариленом, или C₂-C₃ оксиалкиленовым остатком, имеющим от 2 до 20 оксиалкиленовых звеньев, предотвращающих образование O-O или O-N связей; L представляет собой гидрофильную цепь, которая содержит полиоксиалкиленовый остаток -[(R⁵O)_m (CH₂CH₂O)_n]-, где R⁵ это C₃-C₄ алкилен или гидроксиалкилен и m и n имеют такое численное значение, при котором остаток -(CH₂CH₂O)_n составляет по крайней мере 50 мас.% от указанного полиоксиалкиленового остатка; для указанных моноаминов m имеет значение от 0 до 4, n - по крайней мере 12; для указанных диаминов m имеет значение от 0 до 3, и n имеет значение по крайней мере 6 когда R¹ является C₂-C₃ алкиленом, гидроксиалкиленом или алкениленом и, по крайней мере имеет значение 3, когда R¹ имеет значение, отличное от C₂-C₃ алкилена, гидроксиалкилена или алкенилена; для указанных полиаминов и аминовых полимеров m имеет значение от 0 до 10 и n по крайней мере 3; p имеет значение от 3 до 8; q является 1 или 0; t это 1 или 0, при этом t является 1, когда q имеет значение 1; w это 1 или 0; x+y+z по крайней мере 2; и y+z по крайней мере 2, и указанный способ включает такие стадии, как нанесение указанного состава в неразбавленном виде по крайней мере на часть ткани перед ее стиркой.The present invention encompasses a fabric bleaching process using a liquid composition containing 0.01-15% by weight of the total composition of the bleaching peroxide and the contaminant removing agent selected from the group consisting of
(1) ethoxylated monoamines having the formula
(XL -) - N- (R ² ) ₂
(2) ethoxylated diamines having the formula

(3) ethoxylated polyamines having the formula

(4) polymeric ethoxylated amines having the general formula:

(5) and mixtures thereof,

R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C ₂ -C ₃ oxyalkylene residue having from 2 to 20 oxyalkylene units preventing the formation of ON bonds; each R ² is C ₁ -C ₄ alkyl or hydroxyalkyl, the remainder —LX, or two R ² together form the remainder - (CH ₂ ) _r ^- A ² - (CH ₂ ) _s -, where A ² is —O— or - CH ₂ -, r 1 or 2, s 1 or 2, and r + s 3 or 4; X is a nonionic group, anionic group, or a mixture thereof; R ³ is a substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having side substituents at the p position; R ⁴ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C ₂ -C ₃ oxyalkylene residue having from 2 to 20 oxyalkylene units preventing the formation of OO or ON bonds; L is a hydrophilic chain that contains a polyoxyalkylene residue - [(R ⁵ O) _m (CH ₂ CH ₂ O) _n ] -, where R ⁵ is C ₃ -C ₄ alkylene or hydroxyalkylene and m and n have such a numerical value, in which the residue - (CH ₂ CH ₂ O) _n is at least 50 wt.% from the specified polyoxyalkylene residue; for said monoamines, m has a value from 0 to 4, n is at least 12; for these diamines, m has a value from 0 to 3, and n has a value of at least 6 when R ¹ is C ₂ -C ₃ alkylene, hydroxyalkylene or alkenylene and at least 3 when R ¹ has a value other than C ₂ -C ₃ alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m has a value from 0 to 10 and n is at least 3; p has a value from 3 to 8; q is 1 or 0; t is 1 or 0, with t being 1 when q is 1; w is 1 or 0; x + y + z at least 2; and y + z of at least 2, and said method comprises such steps as applying said composition in undiluted form to at least a portion of the fabric before washing it.

 The present invention encompasses a tissue pretreatment liquid composition comprising peroxide bleach, a surfactant and a dispersion agent selected from the group consisting of ethoxylated monoamine, ethoxylated diamine, ethoxylated polyamine and polymeric ethoxylated amine, and a mixture thereof, as described above, while the specified composition is prepared in the form of an emulsion or microemulsion.

 The pre-treatment process before washing.

 In its broad embodiment, the present invention relates to a tissue pretreatment process using a liquid composition containing a contaminant removing agent as defined above, as well as from 0.01 to 15% of the total weight of the peroxide bleach composition.

 By pretreatment of the fabric, it should be understood that the liquid composition in this case, in its undiluted form, is applied to at least a portion of the contaminated tissue, optionally a portion of the specified tissue is left under the influence, usually for a period of 1 minute to several hours, before the the fabric is washed in accordance with the fabric bleaching process of the present invention.

 Indeed, the present invention is based on the discovery that by adding an agent that removes contaminants, as described above, to a liquid composition containing peroxide bleach, an improved stain-removing effect of the composition is achieved when it is used to pretreat contaminated fabrics before washing, in comparison with the stain removing effect produced by the same composition, but not containing the indicated contaminant removing agent.

 The stain removing action is to be understood in this case as a stain removing effect on a variety of stains / dirt, such as greasy / oil stains and / or enzyme stains, and / or clay / dirt stains, as well as bleached stains.

 Greasy / oily stains mean in this case any stains or stains of greasy origin that can be found on fabrics, for example, from motor fuels, mineral oils, makeup, lipsticks, vegetable oils, spaghetti sauces, mayonnaise and the like. .

 Examples of bleach stains are stains from coffee, tea, wine and the like. Examples of enzymatic stains are grass, chocolate and blood stains.

The stain-removing effect of the proposed compounds on contaminated tissue under pre-treatment conditions can be evaluated using the following test. The composition in accordance with the present invention is first applied to a portion of the contaminated tissue, left to expose the tissue for a period of about 1 to about 10 minutes, usually 5 minutes, after which the pre-treated fabric is then washed under normal washing conditions with a suitable detergent composition under temperature from 30 to 70 ^o C for a period of time sufficient to bleach the specified fabric. For example, the usual contaminated cloth that can be used commercially in a stain removal test is EMC (Empirical Manafacturing Company) underwear from Cincinnati, Ohio, USA, with stains of clay, chocolate, spaghetti sauce, dirty motor oil, makeup , tea, coffee, blood on two different types of fabrics, for example, cotton (CW 120) and poly-cotton (PCW 28).

 The stain removal action can then be evaluated by comparing step by step the contaminated tissue pretreated with the composition of the present invention and treated with other compositions, for example, such as the same composition, but without the contaminant removing agent described in the present invention. A visual calibration scale can be used to determine the difference in the panel with marks (psu) in the range from 0 to 4.

 Thus, the present invention encompasses a fabric bleaching process using a liquid composition containing from 0.01 to 15% by weight of the total composition of the peroxide bleach and the contaminant removing agent as defined above, said process comprising the step of applying said composition in undiluted at least a portion of said fabric is then optionally allowed to be in contact with the fabric, preferably preventing it from drying on the fabric before washing.

 The composition may remain in contact with said tissue, usually for a period of time, preferably from 1 minute to several hours, preferably from 1 minute to 1 hour, more preferably from 1 to 30 minutes, most preferably from 2 to 10 minutes. Typically, when laundry is covered with stubborn stains / dirt that are relatively difficult to remove in another way, they can be more or less intensely wiped or cleaned with a sponge or brush, or simply by rubbing two pieces of fabric against each other.

 By washing, in this case, it is understood that a simple rinse of the fabric in water or laundry can be washed using a suitable composition containing at least one surfactant, and washing can be done either in the machine or manually.

 By definition in its undiluted form, it is to be understood that liquid compositions are applied to the fabric to be pretreated directly without any dilution, for example, liquid compositions in accordance with the present invention are applied as described herein.

 According to the method for pretreatment of contaminated tissues in accordance with the present invention, the liquid compositions used in this process should not remain on the laundry until it dries. Indeed, it was found that the evaporation of water increases the concentration of free radicals on the surface of the tissue and, consequently, the degree of chain reactions. It can also be concluded that when water evaporates, an autooxidation reaction occurs if the liquid composition remains on the laundry before drying. This autooxidation reaction promotes the generation of peroxide radicals, which can cause color degradation and / or tissue damage. Thus, if you do not leave the liquid bleaching composition used in accordance with the present invention, before drying on the linen in the bleaching process of the fabric in accordance with the present invention, then it will be possible to conduct safe pre-treatment using liquid bleaching compositions.

 The essential point is that the compositions used in accordance with the present invention contain peroxide bleach or mixtures thereof.

 The peroxide bleach used here is any peroxide bleach known to those skilled in the art. Such peroxide bleach includes hydrogen peroxide or a water-soluble source thereof, or a mixture thereof. Indeed, the presence of peroxide bleach contributes to the excellent cleaning and bleaching results of these formulations used in accordance with the present invention. In this case, it is understood that the source of hydrogen peroxide refers to any compound that produces peroxide ions, if the specified compound comes into contact with water.

 Suitable water-soluble sources of hydrogen peroxide in this case are percarbonates, persilicates, persulfates such as monopersulfate, perborates, peroxyacids such as diperoxydecanoic acid (DPDA), peroxyphthalic acid, peroxylauric acid, peroxybenzoic acid and hydroxy peroxybenzoic acids. Preferred peroxide bleaches used in this case are hydrogen peroxide, hydroperoxide and / or aliphatic diacyl peroxide.

 Suitable hydroperoxides for use in this case are tert-butyl hydroperoxide, cumene hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene monohydroperoxide, tert-amyl hydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide. Such hydroperoxides have the advantage of being particularly safe from the point of view of the strength of the fabric and its color, and have an excellent whitening effect.

 Suitable aliphatic diacyl peroxides for use in this case are dilauryl peroxide, didecanoyl peroxide, dimyristoyl peroxide and mixtures thereof. Such aliphatic diacyl peroxides have the advantage of being particularly safe in terms of tissue strength and color, and have an excellent whitening effect.

 The compositions used in accordance with the present invention contain from 0.01 to 15% by weight of the total composition of said peroxide bleach or a mixture thereof, preferably from 0.1 to 12%, more preferably from 0.5 to 10% and most preferably from 2 to 8%.

и более предпочтительно линейным

иметь такие значения, как алкилен, гидроксиалкилен, алкенилен, алкарилен или оксиалкилен.The essential point is that the compositions used in accordance with the present invention contain a contaminant removing agent selected from the group of ethoxylated monoamines, ethoxylated diamines, ethoxylated polyamines, polymer ethoxylated amines, as previously defined, and mixtures thereof. Indeed, the presence of said contaminant removing agent provides excellent cleaning and bleaching results with the compositions used in accordance with the present invention. In the above formulas for the contaminant removal agent used, R ¹ may be branched, for example

and more preferably linear

have meanings such as alkylene, hydroxyalkylene, alkenylene, alkarylene or hydroxyalkylene.

R ^{1 is} preferably C ₂ -C ₆ alkylene for ethoxylated diamines and aminopolymers. For ethoxylated diamines, the minimum degree of ethoxylation required for satisfactory removal / reverse deposition of contaminants decreases in the range from C ₂ -C ₃ alkylene (ethylene, propylene) to hexamethylene. However, for ethoxylated aminopolymers, in particular ethoxylated polyalkyleneamines and polyalkyleneimines, in particular if the molecular weights are high, C ₂ -C ₃ alkylene (ethylene, propylene) is preferred for R ¹ , with ethylene being the most preferred. Each R ² preferably represents a residue —LX.

In the above formulas, the L chain is typically an essentially polyoxyalkylene residue - [(R ⁵ O) _m (CH ₂ CH ₂ O) _n ] -. Residues - (R ⁵ O) _m - and (CH ₂ CH ₂ O) _{n of} polyoxyalkylene can be mixed together or preferably form blocks of residues - (R ⁵ O) _m and - (CH ₂ CH ₂ O) _n -. R ⁵ preferably C ₃ H ₆ (propylene). For ethoxylated polyamines and aminopolymers, m is preferably 0 to 5. For all ethoxylated amines in accordance with the present invention, m is most preferably 0, for example, the polyoxyalkylene residue consists essentially of the residue (CH ₂ CH ₂ O) _n . The residue - (CH ₂ CH ₂ O) _n preferably contains at least 85% by weight of the polyalkylene residue and more preferably 100% by weight (m is 0).

In the above formula, X may be any compatible non-ionic group, anionic group, or a mixture thereof. A suitable nonionic group includes C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, preferably acetate or methyl ether, respectively; hydrogen (H); or a mixture thereof. A particularly preferred nonionic group is H. PO ₃ ^-2 and SO ₃ ^- are suitable as anionic groups. Particularly preferred is the anionic group SO ₃ ^- . It has been found that the percentage of anionic groups to nonionic groups can be important for the properties determining the removal and prevention of re-precipitation exhibited by ethoxylated amine. A mixture of from 0 to 30% anionic groups and from 70 to 100% nonionic groups provides improved properties. A mixture of from 5 to 10% anionic groups and from 90 to 95% nonionic groups provides the most preferred properties. Typically, a mixture of from 0 to 80% anionic groups and from 20 to 100% nonionic groups provides satisfactory removal properties for reprecipitation.

когда X и n имеют значения, определенные выше, a имеет значение 0 или 1 и b от 1 до 4. Для предпочтительных этоксилированных моноаминов (a=0), n по крайней мере 15, с обычным интервалом от 15 до 35. Для предпочтительных этоксилированных диаминов (a=1), n по крайней мере 12 с обычным интервалом от 12 до 42.Preferred ethoxylated mono- and diamines have the following formula

when X and n are as defined above, a is 0 or 1 and b is from 1 to 4. For preferred ethoxylated monoamines (a = 0), n is at least 15, with a typical range of 15 to 35. For preferred ethoxylated diamines (a = 1), n at least 12 with the usual interval from 12 to 42.

 Methods for preparing ethoxylated amines, for example, are described in EP-A112593.

n предпочтительно по крайней мере 12; с обычным интервалом от 12 до 42; p предпочтительно от 3 до 6. Когда R³ представляет собой замещенную алкильную или арильную группу, q предпочтительно 1 и R⁴ предпочтительно C₂-C₃ алкилен. Когда R³ представляет собой алкил, гидроксиалкил или алкенильную группу и когда q является 0, R¹ предпочтительно C₂-C₃ оксиалкиленовый остаток; когда q 1⁴, R предпочтительно C₂-C₃ алкилен.In the above formula for ethoxylated polyamines, R ³ (linear or branched or cyclic) is preferably substituted C ₃ -C ₆ alkyl, hydroxyalkyl or an aryl group; A ¹ preferably

n preferably at least 12; with the usual interval from 12 to 42; p is preferably from 3 to 6. When R ³ is a substituted alkyl or aryl group, q is preferably 1 and R ^{4 is} preferably C ₂ -C ₃ alkylene. When R ³ is an alkyl, hydroxyalkyl or alkenyl group and when q is 0, R ^{1 is} preferably a C ₂ -C ₃ oxyalkylene residue; when q 1 ⁴ , R is preferably C ₂ -C ₃ alkylene.

Эти этоксилированные полиамины могут быть получены из полиаминопропиленоксидных производных таких как
-(OC₃H₆)_c-NH₂
CH₃---(OC₃H₆)_c-NH₂
-(OC₃H₆)_c-NH₂
где каждый с имеет число от 2 до 20.These ethoxylated polyamines can be obtained from polyaminoamides, such as

These ethoxylated polyamines can be prepared from polyaminopropylene oxide derivatives such as
- (OC ₃ H ₆ ) _c -NH ₂
CH ₃ --- (OC ₃ H ₆ ) _c -NH ₂
- (OC ₃ H ₆ ) _c -NH ₂
where each s has a number from 2 to 20.

где X, w, x, y, z и n определены выше.Preferred polymeric ethoxylated amines are ethoxylated C ₂ -C ₃ polyalkyleneamines and polyalkyleneimines. Particularly preferred ethoxylated polyalkyleneamines and polyalkyleneimines are ethoxylated polyethyleneamines (PEA's) and polyethyleneimines (PEI's). These preferred compounds include units having the general formula

where X, w, x, y, z and n are defined above.

Prior to ethoxylation, PEA's used to prepare the compounds of the present invention have the following general formula
[H ₂ N] _w - - [CH ₂ CH ₂ N] _x - - [CH ₂ CH ₂ NH] _y - - [CH ₂ CH ₂ NH ₂ ] _z ,
where x + y + z is from 2 to 9, y + z is from 2 to 9 and w is 0 or 1 (molecular weight is from 100 to 400). Each hydrogen atom attached to each nitrogen atom represents an active center for sequential ethoxylation. For preferred PEA's, y + z is from 3 to 7 (molecular weight from 140 to 310) and most preferably from 3 to 4 (molecular weight from 140 to 200). These PEA's can be obtained by reactions involving the use of ammonia and ethylene dichloride, followed by fractional distillation. Typical PEA's produced are triethylenetetramine (TETA) and tetraethylene pentamine (TEPA). Above pentamines, for example, hexamines, heptamines, octamines and, possibly, nonamines, the resulting mixture cannot be separated by distillation, and it may include other compounds, such as cyclic amines and especially piperazines. There may also be cyclic amines with side chains in which a nitrogen atom is present (see US 2792372, Dickson, 05/14/57, which describes the preparation of PEA's).

 The minimum degree of ethoxylation required to enhance the removal / prevention of reprecipitation can vary depending on the number of blocks in the PEA. If y + z is 2 or 3, then n is preferably at least about 6. If y + z is from 4 to 9, then a suitable improvement is achieved with n equal to at least 3. For the most preferred ethoxylated PEA's n is at least 12 with a typical range of 12 to 42.

- 30%
Каждый атом водорода, присоединенный к любому атому азота в молекуле PEI, является центром для дальнейшего этоксилирования. Такие PEI's могут быть получены, например, полимеризацией этиленимина в присутствии катализатора, такого как диоксид углерода, бисульфит натрия, серная кислота, пероксид водорода, соляная кислота или уксусная кислота. Определенные способы получения PEI's описаны в US 2182306, Ulrich et al., от 05 12.1939 г.; US 3033746, Mayle et al., от 08.05.1962 г.; US 2208095, Esselmann et al., от 16.06.1940 г.; US 2806839, Crowther, от 17.09.1957 г.; и US 2553696, Wilson, от 21.05.1951 г.The PEI's used to prepare the compounds of the present invention have a molecular weight of at least 440 prior to ethoxylation, which is at least 10 blocks. Preferred PEI's used to prepare these compounds have a molecular weight of 600 to 1800. The polymer backbone structure of these PEI's can be represented by the general formula
N ₂ H - [CH ₂ CH ₂ N] _x - - [CH ₂ CH ₂ NH] _y ] - - [CH ₂ CH ₂ NH ₂ ] _z ,
in which the sum of x, y and z represents a number of sufficient magnitude to obtain a polymer with the molecular weight given above. Although a linear polymer base structure is possible, a branched polymer structure can also be used. The relative ratio of primary, secondary, and tertiary amine groups present in the polymer may vary depending on the preparation method. The distribution of amine groups is usually as follows:
CH ₂ CH ₂ NH ₂ - 30%
CH ₂ CH ₂ NH- - 40%

- thirty%
Each hydrogen atom attached to any nitrogen atom in the PEI molecule is the center for further ethoxylation. Such PEI's can be obtained, for example, by polymerization of ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid or acetic acid. Certain methods for preparing PEI's are described in US 2,182,306, Ulrich et al., 05/12/1939; US3033746, Mayle et al., Dated 05/08/1962; US 2208095, Esselmann et al., Dated June 16, 1940; US 2806839, Crowther, 09/17/1957; and US 2553696, Wilson, 05/21/1951

 As defined in the previous formulas, n is at least 3 for ethoxylated PEI's. However, it should be noted that the minimum degree of ethoxylation for a satisfactory removal / prevention of reprecipitation can increase with increasing molecular weight of PEI, especially significantly above 1800. The degree of ethoxylation of preferred compounds also increases with increasing molecular weight of PEI. For PEI's with a molecular weight of at least 600 n, it is preferably equal to at least 12 with a typical range of 12 to 42. For PEI's with a molecular weight of at least 1800 n, it is preferably equal to at least 24 with a typical range of 24 to 42.

 Typically, the compositions used according to the present invention include from 0.01 to 20% by weight of the total weight of the composition of such an agent, dispersion contaminant or mixtures thereof, preferably from 0.1 to 10%, more preferably from 0.2 to 4%, and most preferably 0.5 to 2%.

 The liquid formulations used in accordance with the present invention are preferably aqueous formulations. The compositions used in the process described herein have a pH of from 0 to 6, preferably from 1 to 5, more preferably from 2 to 5, and most preferably from 3 to 5. Acidified formulations are preferably used due to their stability. The compositions used according to the present invention may include additional components, such as bleach activators, surfactants, flavorings, brighteners, chelating agents, radical quenchers, stabilizers, contaminant suspensions, dye transfer agents, solvents, dyes, other amines, or mixtures thereof.

 Preferred optional components will be described in more detail below.

Compositions
The present invention also encompasses liquid formulations suitable for tissue pretreatment, including peroxide bleaches, dispersing agents, selected from the group consisting of any ethoxylated monoamine, any ethoxylated diamine, any ethoxylated polyamine, any polymer ethoxylated amine and mixtures thereof, as previously defined, and a surfactant, and the composition can be made in the form of either emulsions or microemulsions.

 It is precisely due to the addition of such dispersant contaminant to liquid formulations, including peroxide bleaches, surfactants prepared in the form of either emulsions or microemulsions that achieve not only an improvement in stain removal effects, especially manifested in pretreatment conditions, on various types of stains, including stains of fats, enzymes, clay / dirt, but also an improvement in the whitening effect, while achieving the desired viscosity.

 It has now been found that the dispersant agents of the present invention readily act in formulations made in the form of either an emulsion or a microemulsion, and at the same time provide an appropriate viscosity, that is, the viscosity of said composition is reduced, whatever it is before addition the specified agent dispersing pollution in the specified composition, including peroxide bleach and a surfactant.

 Any surfactant or mixture thereof known to those skilled in the art is suitable for use in the compositions of the present invention, prepared as either emulsions or microemulsions, including anionic, nonionic, cationic, amphoteric, zwitterionic surfactants at concentrations from 0.01 to 50% by weight of the total composition, preferably from 1 to 30%, and most preferably from 2 to 20%.

 Preferably, the compositions of the present invention use a surfactant system comprising at least one hydrophilic surfactant and at least one hydrophobic surfactant. These two surfactants, in order to form stable emulsions and microemulsions, preferably have different HLB values (hydrophilic-lipophilic balance), and usually the difference in the HLB value of the two surfactants is at least 1, preferably at least 2 and most preferably at least 3.

 By "hydrophobic surfactant" is meant in this description a surfactant having an HLB value of up to 10, or mixtures thereof, preferably having an HLB value of below 10 and more preferably below 9. Of course, a hydrophobic surfactant used according to This invention has excellent grease-removing properties, that is, they have a dissolving effect, which contributes to the removal of hydrophobic contaminants.

 By "hydrophilic surfactant" is meant in this description a surfactant having an HLB value above 10, or mixtures thereof, preferably having an HLB value above 10.5 and more preferably above 11.

 Typically, the compositions of the present invention, formed in the form of an emulsion or microemulsion, include from 1 to 50% by weight of the total composition of said hydrophobic and hydrophilic surfactants, more preferably from 5 to 40% and most preferably from 8 to 30%. Preferred compositions of this invention comprise at least 0.01% by weight of the total composition of said hydrophobic surfactant or mixture thereof, preferably at least 2% and most preferably at least 4% and at least 0.01 % by weight of the total composition of said hydrophilic surfactant or a mixture thereof, preferably at least 2% and most preferably at least 4%.

 Accordingly, non-ionic surfactants are particularly preferred surfactants for use in the compositions of this invention. Of course, nonionic surfactants for use in this invention include alkoxylated fatty alcohols, preferably ethoxylates and / or propoxylates of fatty alcohols. Of course, many such alkoxylated fatty alcohols having very different HLB values (hydrophilic / lipophilic balance) are commercially available. The HLB value of such alkoxylated nonionic surfactants substantially depends on the chain length of the fatty alcohol, the nature of the alkoxylating groups and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to be short chain fatty alcohols and have a high degree of alkoxylation, while hydrophobic surfactants tend to be long chain fatty alcohols and have a low degree of alkoxylation. Directories listing a variety of surfactants, including nonionic ones, with their corresponding HLB values, are available.

 Suitable chemical processes suitable for the production of nonionic surfactants and for use in this invention include the condensation of the corresponding alcohols with alkylene oxide in the desired ratio. Such processes are widely known to specialists in this field and are described in sufficient detail in the literature from this area. A significant amount of alkoxylated alcohols suitable for use in this invention is commercially available from various manufacturers and can be used alternatively.

Preferred hydrophobic non-ionic surfactants for use in the compositions of this invention are surfactants having an HLB of up to 10 and the structural formula RO (C ₂ H ₄ O) _n (C ₃ H ₆ O) _m H, where R represents represents a C ₆ -C ₂₂ alkyl chain or a C ₆ -C ₂₈ alkylbenzene chain, and where n + m is from 0.5 to 5, and n is from 0 to 5, and m is from 0 to 5, preferably n + m has a value from 0.5 to 4.5, and n and m from 0 to 4.5. Preferably, the R chains for use in this invention are C ₈ -C ₂₂ alkyl chains. Accordingly, suitable hydrophobic non-ionic surfactants for use in the compositions of this invention are Dobanol ^R 91-2.5 (HLB = 8.1; R is a mixture of C ₉ and C ₁₁ alkyl chains, n is 2.5 and m is 0), or Lutensol ^R TO3 (HLB = 8; R is a mixture of C ₁₃ and C ₁₅ alkyl chains, n = 3 and m = 0), or Tergitol ^R 25L3 (HLB = 7.7; R is an alkyl chain with length in the range C ₁₂ -C ₁₅ n is 3 and m is 0), or Dobanol ^R 23-3 (HLB = 8.1; R is a mixture of C ₁₂ and C ₁₃ alkyl chains, n is 3 and m is 0) or Dobanol ^R 23-2 (HLB = 6.2; R is a mixture of C ₁₂ and C ₁₃ alkyl chains, n is 2 and m is 0), or mixtures thereof. Preferred in the case of this invention is Dobanol ^R 23-3 or Dobanol ^R 23-2, or Lutensol ^R TOZ, or mixtures thereof. These Dobanol ^R surfactants are commercially available from SHELL. These Lutensol ^R surfactants are commercially available from BASF, and these Tergitol ^R surfactants are commercially available from UNION CARBIDE. Other hydrophobic nonionic surfactants suitable for use in the present invention are non-alkoxylated surfactants. An example of such substances is Dobanol ^R 23 (HLB <3).

Preferred hydrophilic non-ionic surfactants for use in the compositions of this invention are surfactants having an HLB of higher than 10 and the structural formula RO- (C ₂ H ₄ O) _n (C ₃ H ₆ O) _m H, where R represents a C ₆ -C ₂₂ alkyl chain or a C ₆ -C ₂₈ alkylbenzene chain and where n + m is from 5 to 11, and n is from 0 to 11, and m is from 0 to 11, preferably n + m is from 6 to 10, and n and m are from 0 to 10. In this description, n and m refer to the average degree of ethoxylation / propoxylation. Preferably, the R chains for use in the present invention are C ₈ -C ₂₂ alkyls. Accordingly, suitable hydrophilic nonionic surfactants for use in the compositions of this invention are Dobanol ^R 23-6.5 (HLB = 11.9; R is a mixture of C ₁₂ and C ₁₃ alkyl chains, n is 6.5 and m is 0) or Dobanol ^R 25-7 (HLB = 12; R is a mixture of C ₁₂ -C ₁₅ alkyl chains, n = 7 and m = 0), or Dobanol ^R 45-7 (HLB = 11.6; R is a mixture of C ₁₄ -C ₁₅ alkyl chains, n = 7, m = 0), Dobanol ^R 91-5 (HLB = 11.6; R is a mixture of alkyl chains with a length in the range of C ₉ -C ₁₁ , n is 5 and m is 0), or ^{Dobanol R 91-6 (HLB = 12,5;} R is a mixture of C ₉ -C ₁₁ alkyl 's chains, n is 6 and m is 0), or ^{Dobanol R 91-8 (HLB = 13,7;} R is a mixture of C ₉ -C ₁₁ alkyl chains, n is 8 and m is 0), Dobanol ^R 91- 10 (HLB = 14.2; R is a mixture of C ₉ -C ₁₁ alkyl chains, n is 10 and m is 0), or mixtures thereof. Preferred in the case of this invention is Dobanol ^R 91-10 or Dobanol ^R 45-7, or Dobanol ^R 23-6.5, or mixtures thereof. These Dobanol ^R surfactants are commercially available from SHELL.

In addition to hydrophilic nonionic surfactants, hydrophilic surfactants such as polyhydroxylated fatty acid amides or mixtures thereof corresponding to the formula can also be used in the compositions of this invention
R ² —C (O) —N (R ¹ ) —Z,
where R ¹ is H or C ₁ -C ₄ hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R ² is C ₅ -C ₃₁ hydrocarbon, and Z is a polyhydroxy hydrocarbon containing a linear hydrocarbon chain of at least c 3 hydroxyls directly connected to the chain, or their alkoxylated derivatives.

Preferably R ¹ is C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, and most preferably methyl, R ² is C ₇ -C ₁₉ unbranched alkyl or alkenyl, preferably unbranched C ₉ -C ₁₈ alkyl or alkenyl , more preferably unbranched C ₁₁ -C ₁₈ alkyl or alkenyl, and most preferably unbranched C ₁₁ -C ₁₄ alkyl or alkenyl, or mixtures thereof. Z will preferably be a derivative of reducing sugars obtained by the reductive amination reaction; more preferably Z is glycidyl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. High dextrose corn syrup, high fructose corn syrup and high maltose corn syrup, as well as the individual sugars listed above, can be used as starting material. These corn syrups may yield a mixture of sugars, components for Z. It should also be understood that there are no reasons that preclude the use of other suitable starting materials. Z will preferably be selected from the group consisting of -CH ₂ - (CHOH) _n -CH ₂ OH, - CH (CH ₂ OH) - (CHOH) _n-1 -CH ₂ OH, -CH ₂ - (CH ₂ OH) ₂ - (CHOR ') (CHOH) -CH ₂ OH, where n is from 3 to 5 inclusive and R' is H or a cyclic or aliphatic monosaccharide and their alkoxylated derivatives. Most preferred are glycityls in which n is 4, especially CH ₂ (CHOH) ₄ —CH ₂ OH.

In the formula R ² C (O) -N (R ¹ ) -Z, R ¹ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, N-2-hydroxypropyl. R ² C (O) -N may be a compound such as, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, thalloamide and the like. Z may be 1-deoxyglycidyl, 2-deoxyphructityl, 1-deoxymaltityl, 1-deoxyylactityl, 1-deoxygalactity, 1-deoxymannithyl, 1-deoxy maxotriotityl and the like.

Suitable polyhydroxy fatty acid amide surfactants for use in the present invention may be commercially available from Hoechst under the trade name HOE ^® ..

 Methods for producing amide polyhydroxy fatty acid surfactants are well known in the art. In general, they can be prepared by reacting an alkylamine with a reducing sugar during a reductive amination to form the corresponding N-alkyl polyhydroxy amine, and then reacting the N-alkyl polyhydroxy amine with a fatty aliphatic ether or triglyceride in the condensation / amidation step to form N- alkyl, N-polyhydroxy-amide fatty acid as a product. Processes for the production of mixtures containing polyhydroxy fatty acid amides are described, for example, in GB 809060, 02/18/1959, Thomas Hedley & Co., Ltd; US 2965576, 12.20.1960, E.R. Wilson; US 2703798, March 8, 1955, Anthony M. Schwartz; US 1985424, 12/25/1934, Piggot and WO92 / 06070, each of which is incorporated into the description by reference.

 Other suitable hydrophilic surfactants for use in the compositions of this invention include anionic surfactants and mixtures thereof.

Suitable anionic surfactants for use in the compositions of this invention include water-soluble salts of acids or acids of the formula ROSO ₃ M, where R is preferably a C ₁₀ -C ₂₄ hydrocarbon, preferably an alkyl or hydroxyalkyl having C ₁₀ -C ₂₀ alkyl components, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, and M represents H or a cation, for example, an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl, dimethyl and trimethylammonium thions and quaternary ammonium cations, such as tetramethylammonium, and dimethylpiperidinium cations and quaternary ammonium cations, derivatives of alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like). Typically, C ₁₂ -C ₁₆ alkyl chains are preferred for low temperatures (for example, below about 50 ^° C) and C ₁₆ -C ₁₈ alkyl chains are preferred for high washing temperatures (for example, above about 50 ^° C).

Other suitable anionic surfactants for use in the compositions of this invention are water soluble acid salts or acids of the formula RO (A) _m SO ₃ M, where R is unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl having C ₁₀ -C ₂₄ an alkyl component, preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A represents an ethoxy or propoxy group, m is greater than 0, usually between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M representing T is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium. Ethoxylated alkyl sulfates, as well as propoxylated alkyl sulfates are also intended. Specific examples of substituted ammonium cations include methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium, and dimethylpiperidinium cations and cations derived from alkanolamines, such as ethylamine, diethylamine, triethylamine, mixtures thereof. Examples of surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylate (1,0) sulfate, C ₁₂ -C ₁₈ E (1,0) M, C ₁₂ -C ₁₈ alkyl polyethoxylate (3,0) sulfate C ₁₂ -C ₁₈ E (3.0), and C ₁₂ -C ₁₈ alkylpolyethoxylate (4.0) sulfate C ₁₂ -C ₁₈ E (4.0) M, where M is selected from sodium or potassium.

где M представляет собой водород или катионную частицу и где R представляет собой алкильную группу длиной от 11 до 15 атомов углерода, предпочтительно от 11 до 13 атомов углерода. Предпочтительными M являются водород и соли щелочных металлов, особенно натрий и калий. Указанные ацилсаркозинатные поверхностно-активные вещества являются производными природных жирных кислот и аминокислоты саркозина (N-метилглицин). Они удобны для использования в виде водных растворов их солей или в виде порошка в их кислотной форме. Являясь производными природных жирных кислот, названые ацилсаркозинаты быстро и полностью подвергаются биодеградации и имеют хорошую совместимость с кожей.Other anionic surfactants suitable for dispersion may also be used in this invention. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as salts of mono-, di- and triethanolamines) soaps, C ₉ -C ₂₀ linear alkylbenzenesulfonates, C ₈ -C ₂₂ primary or secondary alkanesulfonates, C ₈ -C ₂₄ olefinsulfonates, sulfonated polycarboxylic acids obtained by sulfonation of pyrolysis products of alkaline earth metal citrates, for example, as described in GB 1082,179; C ₈ -C ₂₄ alkyl esters of polyglycol sulfates (containing up to 10 mol of ethylene oxide); alkilefirsulfonaty such as C ₁₄ -C ₁₆ metilefirsulfonaty, acyl, fatty oleilglitserinsulfaty, etilenoksidsulfonatov alkylphenol ethers, paraffin sulfonate: alkyl phosphates, isocyanates such as atsilizotsianaty, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), sulfosuccinate diesters (especially saturated and unsaturated C ₆ -C ₁₄ diesters), alkyl polysaccharide sulfates such as alkyl polyglucoside sulfates (non-ionic, non-sulfonated x compounds described below), branched primary alkyl sulfates, alkyl polyethoxycarboxylates satisfying the formula RO (CH ₂ CH ₂ O) _k CH ₂ COOM ⁺ , in which R is C ₈ -C ₂₂ alkyl, k has integer values from 0 to 10, and M is a soluble salt forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids contained in (or isolated from) tall oil. Further examples are given in “Surface Active Agents and Detergents” (vol. 1 and II, Schwartz, Perry and Berch). Many such surfactants are also described in US Pat. No. 3,929,678, published December 30, 1975, Laughlin, et al., At column 23, line 58 through column 29, line 23 (incorporated by reference). Other suitable anionic surfactants for use in the compositions of this invention also include acyl sarcosinates or mixtures thereof in their acid or salt form, preferably long chain acyl sarcosinates, having the following formula

where M represents hydrogen or a cationic particle and where R represents an alkyl group with a length of from 11 to 15 carbon atoms, preferably from 11 to 13 carbon atoms. Preferred M are hydrogen and alkali metal salts, especially sodium and potassium. These acyl sarcosinate surfactants are derivatives of natural fatty acids and the amino acid sarcosine (N-methylglycine). They are convenient for use in the form of aqueous solutions of their salts or in the form of a powder in their acid form. Being derivatives of natural fatty acids, the named acyl sarcosinates quickly and completely undergo biodegradation and have good skin compatibility.

Accordingly, the long chain acyl sarcosinates used in this invention are particularly preferred, including C ₁₂ acyl sarcosinate (e.g., acyl sarcosinate corresponding to the structural formula above, where M is hydrogen and R is an alkyl group of 11 carbon atoms) and C ₁₄ acyl sarcosinate (e.g. acyl sarcosinate corresponding to the structural formula above, where M represents hydrogen and R represents an alkyl group of 13 carbon atoms). C ₁₂ acyl sarcosinate is commercially available, for example as Hamposyl L-30 ^®, supplied by Hampshire. C ₁₄ acyl sarcosinate is commercially available, for example as Hamposyl M-30 ^®, supplied by Hampshire.

 It has been found that a further improvement in the stain removing effect is achieved with a surfactant system comprising a hydrophilic nonionic surfactant and a hydrophobic nonionic surfactant, as well as a hydrophilic surfactant similar to amide polyhydroxy fatty acid surfactant substances and / or ethoxylated alkyl sulfates.

The whitening compositions of the present invention may also include an amine oxide surfactant according to the formula R ₁ R ₂ R ₃ NO, where each of R ₁ , R ₂ , R _{3 is} independently C ₁ -C ₃₀ , preferably C ₁ -C ₂₀ , and more preferably a C ₁ -C ₁₆ hydrocarbon chain.

 In an embodiment of the invention, in which the compositions are formulated as emulsions, they are opaque. In a centrifuge study, it was found that these emulsions did not phase out after 15 minutes of centrifugation at 6000 rpm. A microscopic examination showed that these emulsions exist as a dispersion of droplets in a medium.

где HLB(X) относится к HLB ингредиента для эмульсификации, если имеется несколько ингредиентов, чтобы эмульсифицировать, X относится ко всем ним (средневзвешенный, основанный на % каждого ингредиента в формуле), HLB(A) относится к значению HLB гидрофильного поверхностно-активного вещества или их смеси, и HLB(B) относится к HLB гидрофобного поверхностно-активного вещества или их смеси.In an embodiment of the present invention, in which the compositions are prepared as microemulsions, said compositions are transparent in the absence of opaque additives and dyes. In a centrifuge study, it was found that these microemulsions did not phase out after 15 minutes of centrifugation at 6000 rpm. A microscopic examination showed that the named microemulsions exist as a dispersion of droplets in a medium. We found that the particles have a diameter usually of about or less than 3 microns, preferably less than 2 microns. In a preferred embodiment of the invention relating to an emulsion, in which it also includes water-insoluble ingredients, for emulsification, like a bleaching activator, as described hereinafter, the emulsification system satisfies the equation

where HLB (X) refers to the HLB emulsification ingredient, if there are several ingredients to emulsify, X refers to all of them (weighted average, based on% of each ingredient in the formula), HLB (A) refers to the HLB value of the hydrophilic surfactant or mixtures thereof, and HLB (B) refers to the HLB of a hydrophobic surfactant or mixtures thereof.

In a particularly preferred embodiment of the emulsion of the present invention, in which the emulsion may also include a bleaching activator like acetyl triethyl citrate, an adequate surfactant system will include a hydrophobic non-ionic surfactant, for example with an HLB value of 6, such as Dobanol ^R 23- 2, and a hydrophilic non-ionic surfactant, for example with an HLB value of 15, such as Dobanol ^R 91-10. Other suitable non-ionic surfactant systems include, for example, Dobanol ^R 23-6.5 (HLB about 12) and Dobanol ^R 23 (HLB below 6) or Dobanol ^R 45-7 (HLB is 11.6) and Dobanol ^R 23 -3 (HLB is 8.1).

The bleaching compositions of the present invention, prepared in the form of emulsions or microemulsions, are chemically stable. "Chemical stability" means in this description that the indicated compositions of this invention, including peroxide bleach, do not undergo more than 10% loss of available oxygen at 50 ^° C. for 2 weeks. The concentration of available oxygen can be measured by chemical titration methods known in the art, such as the iodometric method, permanganometric method, or cerimetric method. These methods and selection criteria for the appropriate method are described, for example, in Hydrogen Peroxide, WC Schumb, CN Satterfield and RL Wentworth, Reinhold, New York, 1955 and Organic Peroxides, Daniel Swern, Editor, Wiley Int. Science, 1970. Alternatively, the stability of these formulations can also be evaluated by the bulging test.

 Accordingly, said whitening compositions of the present invention can be packaged in deformable containers / bottles without compromising the stability of said containers / bottles containing them for storage over an extended period of time.

 The liquid compositions of the present invention, prepared either as emulsions or as microemulsions, are usually aqueous and are prepared in an acidic pH range of up to 6, preferably at a pH of 1 to 5, more preferably at a pH of 2 to 5, and most preferably at pH from 3 to 5. The formation of the compositions of the present invention in the acidic pH range contributes to the stability of these compositions. The pH of the compositions of the present invention can be established using organic or inorganic acids.

 Optional additives.

 The compositions of the present invention may also include additional ingredients, such as whitening activators, stabilizers, chelating agents, radical quenchers, structurants, stain suspensions, colorants, solvents, brighteners, flavorings, foam suppressants, colorants or mixtures thereof.

 As an additional, but very preferred component, the compositions of the present invention include a bleach activator or a mixture thereof. The term “bleach activator” means, as used herein, a compound that reacts with hydrogen peroxide to form peroxyacids. Peroxyacids thus formed constitute activated bleach. Particularly suitable bleach activators for use in the present invention are hydrophobic bleach activators, for example, a bleach activator that does not substantially and continuously mix with water. Typically, such whitening activators have a secondary HLB (hydrophilic lipophilic balance) value below 11, preferably below 10. The secondary HLB value is known to those skilled in the art and is defined, for example, in "Emulsions theory and practice", P. Becher, Reinhold, New- York, 1957, or in "Emulsion science", P. Sherman, Academic Press, London, 1969.

 Suitable bleach activators for use in the compositions of this invention include those bleach activators that belong to the classes of esters, amides, imides or anhydrides. Examples of suitable compounds of this type are described in GB 1586769 and GB 2143231 and a method for their preparation in a suitable form is described in EP-A-62523. Suitable examples of such compounds for use in the present invention are tetraacetylethylenediamine (TAED), sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, diphenoxydecanoic acid as described in US Pat. No. 4,818,425 and peroxyadipic acid nonylamide as described, for example, in US Pat. NOBS). Also suitable are N-acylcaprolactams selected from the group consisting of substituted or unsubstituted benzoylcaprolactam, octanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecanoylcaprolactam, formylcaprolactylprolactam, formylcaprolactylpropylactyl, A particular family of bleach activators of interest has been described in European Patent EP 624154, and acetyl triethyl citrate (ATS) is particularly preferred in this family. Acetyl triethyl citrate has the advantage of being non-polluting, since it decomposes over time into citric acid and alcohol. Moreover, acetyl triethyl citrate has good hydrolytic stability in the product during storage and is an effective bleach activator. Finally, it provides the composition with high activity.

 The compositions in accordance with this invention may include from 0.01 to 20% of the specified bleach activator by weight of the total composition, or mixtures thereof, preferably from 1 to 10% and more preferably from 3 to 7%.

 Suitable chelating agents for use in this invention include chelating agents selected from the group of phosphonate chelating agents, aminocarboxylate chelating agents, multifunctionally substituted aromatic chelating agents and, in addition, chelating agents such as glycine, salicylic acid, aspartic acid, glutamines acid and mixtures thereof. Chelating agents, if used, are usually present in an amount ranging from 0.001 to 5% by weight of the total composition, and preferably from 0.05 to 2% by weight.

Suitable phosphonate chelating agents for use in the present invention may include edronic acid, as well as aminophosphonate compounds, including aminoalkylene poly (alkylene phosphonates), alkane metal ethane-1-hydroxydiphosphonates, nitrile trimethylene phosphonates, ethylenediaminetetramethylene-phosphonates. Phosphonate compounds may be present either in their acid form or in the form of salts with various cations in some or all of their acid groups. Preferred aminophosphonate chelating agents for use in the present invention are diethylene triamine pentmethylene phosphonates. Such phosphonate chelating agents are commercially available in the Monsanto company under the trade name DEQUEST ^®.

в жидких составах по настоящему изобретению, значительно уменьшает разрушение, обычно ассоциируемое с предварительной обработкой тканей пероксидсодержащими отбеливающими составами, особенно тех тканей, которые содержат ионы металлов, такие как медь, железо, хром и марганец.The most preferred phosphonate chelating agents for use in the present invention are aminotri (methylenephosphonic acids), designated ATMMPs in this specification. Of course, it was found that the addition of ATMMP, for example, compounds of the formula

in the liquid compositions of the present invention, significantly reduces the degradation commonly associated with pretreatment of fabrics with peroxide-containing whitening compositions, especially those that contain metal ions such as copper, iron, chromium and manganese.

 Multifunctionally substituted aromatic chelating agents may also be useful in the compositions of this invention (see US 3812044, 05.21.1974, Connor et al.). Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, for example 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylene diamine-N, N'-disuccinic acid or a salt thereof of alkali metals, alkaline earth metals, ammonium or substituted ammonium, or a mixture thereof. Ethylene diamine-N, N'-disuccinic acids, especially the (S, S) isomer, are described in detail in US 4704233, 11/03/1987, Hartman and Perkins. Ethylenediamine-N, N-disuccinic acid, for example, is commercially available under the tradename ssEDDS ^® in Palmer Research Laboratories.

 Suitable amino carboxylates for use herein include ethylenediaminetetraacetates, diethylenetriaminepentaacetate, diethylenetriaminepentaacetate (DTPA), N-gidroksietiletilendiamintriatsetaty, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexaacetates, ethanoldiglycines, propilendiamintetrauksusnaya acid (PDTA) and methyl acid (MGDA), are both in their acid form or in the form of their salts of alkali metals, ammonium and substituted ammonium. Particularly suitable aminocarboxylates for use in this invention are diethylene triamine pentaacetic acid, propylene diamine tetraacetic acid (PDTA), which, for example, are commercially available from BASF under the trade names Trilon FS_ and methyl glycidiacetic acid (MGDA).

где R₁, R₂, R₃ и R₄ независимо выбирают из группы, состоящей из -H, алкил, алкокси, арил, арилокси, -Cl, -Br, -NO₂, -C(O)R' и SO₂R''; где R' выбирают из группы, состоящей из -H, -OH, алкил, алкокси, арил и арилокси; R'' выбирают из группы, состоящей из алкила, алкокси, арила и арилокси; и R₅, R₆, R₇ и R₈ независимо выбирают из группы, состоящей из -H и алкила.Other preferred chelating agents for use in this invention are of the formula

where R ₁ , R ₂ , R ₃ and R _{4 are} independently selected from the group consisting of —H, alkyl, alkoxy, aryl, aryloxy, —Cl, —Br, —NO ₂ , —C (O) R ′ and SO ₂ R ''; where R 'is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl and aryloxy; R ″ is selected from the group consisting of alkyl, alkoxy, aryl and aryloxy; and R ₅ , R ₆ , R ₇ and R _{8 are} independently selected from the group consisting of —H and alkyl.

 Particularly preferred chelating agents for use in the present invention are ATMMP, diethylene triamine methylene phosphonate, ethylene N, N'-disuccinic acid, diethylene triamine pentaacetate, glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid and mixtures thereof, and M is particularly preferred.

 Suitable radical quenchers for use in this invention include well-known substituted mono- and dihydroxybenzenes and their analogs, alkyl and aryl carboxylates, and mixtures thereof. Preferred similar radical quenchers for use in the present invention include di-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butylhydroquinone, mono-tert-butylhydroquinone, tert-butylhydroxyanisole, benzoic acid, toluic acid, benzenechol, catechol 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, n-propyl gallate or mixtures thereof, and di-tert-butyl hydroxytoluene is particularly preferred. When used, radical quenchers are typically present in amounts ranging from 0.001 to 2% by weight of the total composition and preferably from 0.001 to 0.5% by weight.

 The presence of chelating agents, especially ATMP and / or radical quenchers, can contribute to the tissue-preserving properties of the compositions of the present invention, suitable for pre-treatment of contaminated stained fabrics in contact for a long time before washing said fabric.

 The compositions of the present invention may also include up to 20%, preferably from 2 to 10%, of the total weight of the composition, solvent, or mixture thereof. It has been found in more detail that the addition of a solvent system comprising at least one hydrophobic solvent and at least one hydrophilic solvent to the liquid composition of the present invention further contributes to the usefulness of said composition, for example, further improving the removal action for all contaminants on various types of stains, including oily stains, enzyme stains, as well as bleached stains.

 Suitable hydrophobic solvents for the present invention include terpenes, such as mono- and bicyclic monoterpenes, especially hydrocarbon-type terpenes, which include terpinene, terpinolene, limonene and pinene and mixtures thereof. Particularly preferred materials of this type are d-limonene, dipentene, alpha-pinene, and / or beta-pinene. Other hydrophobic solvents include all types of paraffins, both linear and non-linear, containing from 2 to 20 carbon atoms, preferably from 4 to 10, more preferably from 6 to 8. Octane is preferred in the present invention. Another hydrophobic solvent for use in this invention is benzyl alcohol. Particularly preferred hydrophobic solvents of this invention are d-limonene, dipentene, alpha-pinene, beta-pinene, octane, benzyl alcohol, or mixtures thereof.

 Suitable hydrophilic solvents for use in this invention include alkoxylated aliphatic alcohols, such as methoxypropanol, ethoxypropanol, propoxypropanol, butoxypropanol, as well as alkyl glycols, such as ethoxy ethoxyethanol, aliphatic or aromatic alcohols, such as ethanol, such as propanol and glycols, such as propanediol, and mixtures thereof.

 Any polymeric contaminant removing agent known to those skilled in the art may be further included in the compositions and methods of this invention. The stain-removing polymeric agents are characterized by the presence of both hydrophilic segments necessary for hydrophilizing the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, for binding to and retaining hydrophobic fibers on them until the end of the washing and rinsing cycles, and acting as such thus, as anchors for hydrophilic segments. This makes it possible, during subsequent treatment of stains, with agents that remove contaminants, to more easily wash them in subsequent washing operations.

Polymeric contaminant removing agents suitable for the present invention especially include those contaminant removing agents which have: (a) one or more hydrophilic components consisting mainly of (i) polyoxyethylene segments with a degree of polymerization of at least 2 or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization from 2 to 10, in which said hydrophilic segment does not cover any oxypropylene block as long as it is connected with neighboring moieties blocks for each end with ester bonds, or (iii) a mixture of oxyalkylene blocks comprising oxyethylene and from 1 to about 30 oxypropylene blocks, and the mixture contains a sufficient amount of oxyethylene blocks so that the hydrophilic component has a hydrophilicity large enough to increase the hydrophilicity of the surface conventional polyester synthetic fibers over a precipitated decontaminant on such a surface, said hydrophilic segments preferably include at least about 25% hydroxyethyl ilene blocks and more preferably, especially for those components that contain about 20 to 30 oxypropylene blocks, at least about 50% oxyethylene blocks; or (b) one or more hydrophobic components comprising (i) C ₃ -oxyalkylene terephthalate segments, wherein if said hydrophobic components also include oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C ₃ -oxyalkylene terephthalate is about 2: 1 or lower, (ii) C ₄ -C ₆ alkylene or C ₄ -C ₆ oxyalkylene segments, or a mixture thereof, (iii) poly (vinyl ether) segments, preferably polyvinyl acetate having a polymerization degree of at least 2 or (iv) C ₁ -C ₄ alkyl esters, or C ₄ hydroxyalkyl ether substituents, or impurity, wherein said substituents are present in the form of C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives, or mixtures thereof, and such cellulose derivatives are amphiphilic, thus they have a sufficient number of C ₁ -C ₄ alkyl ether and / or C ₄ hydroxyalkyl ether blocks to deposit on the surface of a conventional synthetic polyester fiber and retain a sufficient amount of hydroxyls already bonded to the surfaces of a conventional synthetic fiber in order to increase hydrophilicity fibers, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a) (i) should have a degree of polymerization of from about 1 to about 200, although higher degrees can also be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable C ₄ -C ₆ hydroxyalkylene hydrophobic segments include, but are not limited to, end groups of contaminating polymer agents, such as MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O-, where M is sodium and n is 4 to 6, inclusive as described in US 4721580, 01/26/1988, Gosselink.

Polymeric contaminant removing agents suitable for the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, copolymers from ethylene terephthalate or propylene terephthalate blocks with terephthalate polyethylene oxide or terephthalate polypropylene oxide, and the like. Such agents are commercially available and include cellulose hydroxyesters such as METHOCEL (Dow). Contaminant removing cellulosic agents for use in the present invention also include agents selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyalkyl celluloses (see US 4000093, 12/28/1976, Nicol et al. )

Pollution agents containing poly (vinyl ester) hydrophobic segments include grafted copolymers of poly (vinyl ester), for example C ₁ -C ₆ , vinyl esters, preferably poly (vinyl acetate), grafted onto polyalkylene oxide bases such as polyethylene oxide bases (cm EP-A-O219048, 04/22/1987, Kud et al.). Commercially available contaminant removing agents of this type include SOKALAN, a type of material, for example, SOKALAN HP-22, manufactured by BASF (West Germany).

 One type of preferred contaminant removing agent is a copolymer having a random arrangement of ethylene terephthalate and polyethylene oxide (PEO) terephthalate blocks. The molecular weight of this polymeric contaminant removing agent is in the range of from about 25,000 to about 55,000 (see US 3959230, 05.25.1976, Hays and US 3893929, 07/08/1975, Basadur).

 Another preferred contaminant removing polymer is a repeating ethylene terephthalate block polyester that contains 10-15% by weight of ethylene terephthalate blocks together with 90-80% by weight of polyoxyethylene terephthalate blocks, polyoxyethylene glycol derivatives with an average molecular weight of 300-5000. Examples of such polymers include the commercially available products ZELCON 5126 (Dupont) and MILEASE T (ICI) (see also US 4702857, 10.27.1987, Gosselink).

 Another preferred contaminant removing polymeric agent is a sulfonated product of a substantially linear ether oligomer comprising an ether oligomer chain of repeating terephthalate and oxyalkylene oxide blocks and chain end groups covalently linked to the chain. These contaminant removing agents are fully described in US Pat. No. 4,968,451, 11/06/1990, J.J. Scheibel and E.P. Gosselink. Other suitable polymeric contaminant removing agents include terephthalic acid polyesters according to US 4711730, 08/08/1987, Gosselink et al., Anionic end-group oligomeric esters according to US 4721580, 01/26/1988, Gosselink and block polyester oligomeric compounds according to 4702857, 10.27.1987, Gosselink.

 Preferred polymeric contaminant removing agents also include contaminant removing agents according to US 4,877,896, 10/31/1989, Maldonado et al. which describes anionic, especially sulfoaroyl, terephthalate esters with terminal groups.

 Further preferred contaminant removing polymeric agents are oligomers with repeating terephthaloy blocks, sulfoisoterephthaloy blocks, oxyethylene and oxy-1,2-propylene blocks. The repeating blocks form an oligomer chain and are preferably terminated with modified isothionate end groups. Particularly preferred contaminant removing agents of this type include about one sulfoisophthaloyl block, 5 terephthaloyl blocks, hydroxyethylene and oxy-1,2-propylene blocks in a ratio of about 1.7 to about 1.8 and two end groups of 2- (2- hydroxyethoxy) ethanesulfonate sodium. These contaminant removing agents also include from about 0.5 to about 20% by weight of the oligomer, a crystallization reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluenesulfonate and mixtures thereof (see US 5415807, 05.16.1995, , Gosselink et al.).

 When used, contaminant removing agents will comprise from about 0.01 to about 10% by weight of the mixture of surfactant compounds of this invention, usually from about 0.1 to about 5%, preferably from about 0.2 to about 3 %

 The compositions of the present invention may also include one or more components effective to inhibit the transfer of dyes from one painted surface to another during the cleaning process. Typically, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. When used, these agents typically comprise from about 0.01 to about 10% by weight of the composition, preferably from about 0.01 to about 5%, and more preferably from about 0.05 to about 2%.

More specifically, the polyamine-N-oxide polymers preferred for use in this invention comprise blocks having the following structural formula: RA _x -P; where P is a polymerizable block to which an NO group can be attached, or an NO group can form part of a polymerizable block, or an NO group can be attached to both blocks; A represents one of the following structures: —NC (O) -, C (O) O—, —S—, —O—, N =; x is 0 or 1; and R represents aliphatic, ethoxylated aliphatic, aromatic, heterocyclic groups, or any combination thereof, to which nitrogen of the NO group can be attached, or the NO group is part of these groups. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and their derivatives.

где R₁, R₂, R₃ представляют собой алифатические, ароматические, гетероциклические или алициклические группы или их комбинацию; x, y, z имеют значения 0 или 1; и азот N-O группы может быть присоединен или образует часть любой из вышеуказанных групп. Аминоксидный блок полиамин-N-оксидов имеет рКа < 10, предпочтительно рКа < 7, наиболее предпочтительно рКа < 6.The NO group can be represented by the following general structures

where R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups, or a combination thereof; x, y, z are 0 or 1; and nitrogen of the NO group may be attached or form part of any of the above groups. The amine oxide block of polyamine N-oxides has a pKa <10, preferably pKa <7, most preferably pKa <6.

 Any polymer chain can be used as long as the formed amine oxide polymer is water soluble and possesses dye transfer inhibiting properties. Examples of such suitable polymer chains are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include randomly located or block copolymers in which one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. Amine-N-oxide polymers typically have an amine to amine-N-oxide ratio of from 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be different according to the copolymerization parameters or the degree of N-oxidation, respectively. Polyamine oxides can be obtained with almost any degree of polymerization. Typically, the average molecular weight is in the range of 500 to 1,000,000; more preferred from 1000 to 500000; more preferred from 5,000 to 100,000. This preferred class of products may be referred to as PVNO. The most preferred polyamine-N-oxide useful in the surfactant mixture of this invention is poly (4-vinylpyridine-N-oxide), the average molecular weight of which is about 50,000 and the ratio of amine to amine-N-oxide is about 1: 4.

 Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as PVPVI class) are also preferred for use in this invention. Preferably, the PVPVIs have an average molecular weight in the range of 5,000 to 1,000,000, more preferably 5,000 to 2,000,000, and most preferably 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described by Barth, et al., Chemical Analysis, vol. 113, "Modern Methods of Polymer Characterization", text incorporated herein by reference). PVPVI copolymers usually have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0, 4: 1. These copolymers can be either linear or branched.

 The compositions of the present invention may also include polyvinylpyrrolidone (PVP) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVP's are known to those skilled in the art of surfactants ( see, for example, EP-A-262897 and EP-A-256696, incorporated herein by reference). Compositions containing PVP may also contain polyethylene glycol (PEG) having an average molecular weight of from about 500 to about 100,000, preferably from about 1000 to about 10,000. Preferably, the ratio of PEG to PVP in parts per million (ppm) adopted for washing solutions, is from about 2: 1 to about 50: 1, and more preferably from about 3: 1 to about 10: 1.

If high soap formation is desired, soap-forming additives, such as C ₁₀ -C ₁₂ alkanolamides, can be included in the compositions usually in an amount of from 1 to 10%. C ₁₀ -C ₁₄ monoethanol and diethanolamides represent a typical class of such soap-forming additives. The use of such soap-forming additives with high soap-forming surfactants, such as the amine oxides, betaines and sultaines noted above, is also advantageous. If desired, soluble magnesium salts, such as MgCl ₂ , MgSO ₄ and the like, may also be added, to a concentration of, for example, 0.1-2%, to provide additional soap formation and enhance the grease-removing effect.

 Any optical brighteners, fluorescent whitening agents or other brighteners and whitening agents known in this field can be included in the active formulations, if they are created for factory processing or laundries, with the content usually from about 0.05 to about 1.2% of masses of surfactants in the compositions of the present invention. Commercial optical brighteners that may be useful for the present invention can be classified into several subgroups, which include, but are not necessary limitation, derivatives of stilbene, pyrazoline, coumarin, carboxylic acids, mesincyanins, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered heterocyclic brighteners; This list is illustrative but not restrictive. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, John Wiley & Sons, New York (1982).

 Specific examples of optical brighteners useful for the compositions of this invention are brighteners described in US 4790856, 12/13/1988, Wixon. These brighteners include the Verona PHORWHITE range of brighteners. Other brighteners described in this link include Tinopal UNPA, Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis in Italy; 2- (4-styryl-phenyl) -2H-naphthol- [1,2-d] triazoles; 4,4-bis- (1,2,3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bisphenyls; and aminocoumarins. Specific examples of such brighteners include 4-methyl-7-diethylaminocoumarin; 1,2-bis (benzimidazol-2-yl) ethylene; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphth- [1,2-d] -oxazole and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] triazole (see also US 3646015, 02/29/1972 , Hamilton). Typically, anionic brighteners are preferred in the present invention.

 Although the preferred use of the compositions described in the present invention is laundry pretreatment, as noted above, the compositions of the present invention can also be used as surfactants for laundries, improving surfactants in laundries, household cleaning products for bathrooms or kitchens.

 Compositions of the present invention suitable for pretreatment of fabrics can be packaged in various containers, including ordinary bottles, bottles equipped with a spray ball, sponges, brushes, or nebulizers.

 The present invention will be illustrated by examples (see table).

 An excellent stain-removing effect was obtained on various stains, including clay-like greasy / oily stains, stains from dirty motor oils, make-up, lipsticks, carotenoid stains like spaghetti sauce, bleached stains like tea, and enzymatic ones like grass, blood, pre-treating the contaminated fabric with any of the compositions I to VI, as described above, for example, when the composition is applied to the fabric for a contact time of about 5 minutes, before washing the specified fabric with water or washing with conventional surface compositions non-active substances, such as Tide laundry detergent at dilution levels, for example, from 1 to 400.

Claims (22)

1. The method of bleaching tissue using a liquid composition containing from 0.01 to 15% by weight of the total composition of the bleaching peroxide and an agent that removes impurities selected from the group consisting of (1) ethoxylated monoamines having the formula
(XL -) - N- (R ² ) ₂
(2) ethoxylated diamines having the formula

(3) ethoxylated polyamines having the formula

(4) polymeric ethoxylated amines having the general formula

(5) and mixtures thereof,

R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C ₂ -C ₃ oxyalkylene residue having from 2 to 20 oxyalkylene units preventing the formation of O-N bonds; each R ² is C ₁ -C ₄ alkyl or hydroxyalkyl, the remainder is -L-X, or two R ² together form the remainder - (CH ₂ ) _r ^- A ² - (CH ₂ ) _s -, where A ² is —O- or —CH ₂ -, r 1 or 2, s 1 or 2, and r + s 3 or 4; X is a nonionic group, anionic group or a mixture thereof; R ³ is a substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having side substituents at the p position; R ⁴ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C ₂ -C ₃ oxyalkylene residue having from 2 to 20 oxyalkylene units preventing the formation of O — O or O — N bonds; L is a hydrophilic chain that contains a polyoxyalkylene residue - [(R ⁵ O) _m (CH ₂ CH ₂ O) _n ] -, where R ⁵ is C ₃ -C ₄ alkylene or hydroxyalkylene and m and n have such a numerical value, in which the residue - (CH ₂ CH ₂ O) _n is at least 50 wt.% of the specified polyoxyalkylene residue; for said monoamines, m has a value from 0 to 4, n is at least 12; for these diamines, m has a value from 0 to 3, and n has a value of at least 6 when R ¹ is C ₂ -C ₃ alkylene, hydroxyalkylene or alkenylene and at least 3 when R ¹ has a value other than C ₂ -C ₃ alkylene, hydroxyalkylene or alkynylene; for said polyamines and amine polymers, m has a value of from 0 to 10 and n is at least 3; p has a value of from 3 to 8; q is 1 or 0; t is 1 or 0, with t being 1 when q is 1; w-1 or 0, x + y + z, at least 2; and y + z, at least 2, and the composition used has a pH of not higher than 6 and it is applied undiluted to at least a portion of the fabric before washing.  2. The method according to claim 1, characterized in that the tissue is treated for 1 minute to 1 hour, preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, before washing the fabric.  3. The method according to any one of claims 1 and 2, characterized in that said peroxide bleach is hydrogen peroxide or a water-soluble source thereof, preferably selected from the group consisting of percarbonate, persilicate, persulfate, perborate, peroxyacids, hydroperoxides, diacyl peroxides and mixtures thereof preferably hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene monohydroperoxide, tert-amyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, dilauryl peroxide d, didecanoyl peroxide, dimyristoyl peroxide or mixtures thereof.  4. The method according to any one of the preceding paragraphs, characterized in that the composition contains peroxide bleach from 0.1 to 12%, more preferably from 0.5 to 10%, and most preferably from 2 to 8%. 5. The method according to any one of the preceding paragraphs, characterized in that said contaminant removing agent is a polymeric ethoxylated amine in which R ¹ is C ₂ -C ₃ alkylene, preferably ethylene, and wherein L mainly consists of a residue - (CH ₂ CH ₂ O) _n - and n has a value of at least 12.  6. The method according to claim 5, characterized in that the polymer ethoxylated amine is ethoxylated polyethyleneamine having a molecular weight of from 140 to 310 to ethoxylation.  7. The method according to claim 5, characterized in that said polymer amine is ethoxylated polyethyleneimine having a molecular weight of from 600 to 1800 to ethoxylation.  8. A method according to any one of the preceding paragraphs, characterized in that said composition comprises from 0.01 to 20% by weight of the total composition of said contaminant removing agent, or a mixture thereof, preferably from 0.1 to 10%, more preferably from 0 , 2 to 4% and most preferably from 0.5 to 2%.  9. The method according to any one of the preceding paragraphs, characterized in that the composition contains a whitening activator, preferably in a concentration of from 0.01 to 20% by weight of the total composition, more preferably from 1 to 10% and most preferably from 3 to 7%.  10. The method according to claim 9, characterized in that said whitening activator is selected from the group consisting of acetyl triethyl citrate, tetraacetylethylenediamine, sodium 3,5,5 trimethylhexanoylbenzenesulfonate, diperoxydecanoic acid, peroxyadipic acid nonylamide, non-nonanoyloxybenzene, n-nonanoyloxy-benzene, benzoylcaprolactam, octanoylcaprolactam, nonanoylcaprolactam, hexananoylcaprolactam, decanoilcaprolactam, undecanoilcaprolactam, formylcaprolactam, acetylcaprolactam, propanoilcaprolactam, b tanoylcaprolactam, pentanoylcaprolactam and mixtures thereof, preferably acetyl triethyl citrate.  11. The method according to any one of the preceding paragraphs, characterized in that said composition is aqueous and has a pH from 1 to 5, preferably from 2 to 5, and most preferably from 3 to 5. 12. A liquid whitening composition suitable for pretreatment of fabrics, containing peroxide bleach in an amount of from 0.01 to 15% of the total weight of the composition, a surfactant and a contaminant removing agent selected from the group consisting of (1) ethoxylated monoamines, having the formula
(XL -) - N- (R ² ) ₂
(2) ethoxylated diamines having the formula

or
(XL-) ₂ -NR ¹ - (R ² ) ₂
(3) ethoxylated polyamines having the formula

(4) polymeric ethoxylated amines having the general formula

(5) and mixtures thereof,

R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C ₂ -C ₃ oxyalkylene residue having from 2 to 20 oxyalkylene units preventing the formation of O-N bonds; each R ² is C ₁ -C ₄ alkyl or hydroxyalkyl, the remainder is -L-X, or two R ² together form the remainder - (CH ₂ ) _r ^- A ² - (CH ₂ ) _s -, where A ² is —O- or —CH ₂ -, r 1 or 2, s 1 or 2, and r + s 3 or 4; X is a nonionic group, anionic group or a mixture thereof; R ³ is a substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having side substituents at the p position; R ⁴ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C ₂ -C ₃ oxyalkylene residue having from 2 to 20 oxyalkylene units preventing the formation of O — O or O — N bonds; L is a hydrophilic chain that contains a polyoxyalkylene residue - [(R ⁵ O) _m (CH ₂ CH ₂ O) _n ] -, where R ⁵ is C ₃ -C ₄ alkylene or hydroxyalkylene and m and n have such a numerical value, in which the residue - (CH ₂ CH ₂ O) _n is at least 50 wt.% of the specified polyoxyalkylene residue; for said monoamines, m has a value from 0 to 4, n is at least 12; for these diamines, m has a value from 0 to 3, and n has a value of at least 6 when R ¹ is C ₂ -C ₃ alkylene, hydroxyalkylene or alkenylene and at least 3 when R ¹ has a value other than C ₂ -C ₃ alkylene, hydroxyalkylene or alkynylene; for said polyamines and amine polymers, m has a value of from 0 to 10 and n is at least 3; p has a value of from 3 to 8; q is 1 or 0; t is 1 or 0, with t being 1 when q is 1; w is 1 or 0; x + y + z of at least 2; and y-z, at least 2, while the composition has a pH of not higher than 6 and it is prepared either in the form of an emulsion or in the form of a microemulsion.  13. The composition according to p. 12, characterized in that said peroxide bleach is hydrogen peroxide or a water-soluble source thereof, preferably selected from the group consisting of percarbonate, persilicate, persulfate, perborate, peroxyacids, hydroperoxides, diacyl peroxides and mixtures thereof, preferably hydrogen peroxide , tert-butyl hydroperoxide, cumene hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene monohydroperoxide, tert-amyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, dilauryl peroxide, didecanoi l peroxide, dimyristoyl peroxide or mixtures thereof.  14. The composition according to p. 12 or 13, characterized in that it contains from 0.1 to 12% of the specified peroxide bleach, more preferably from 0.5 to 10%, and most preferably from 2 to 8%. 15. The composition according to PP.12 to 14, characterized in that the specified agent that removes contaminants, is a polymeric ethoxylated amine in which R ¹ has the meaning C ₂ -C ₃ alkylene, preferably ethylene, and L mainly consists of residue - (CH ₂ CH ₂ O) _n - and n has a value of at least 12.  16. The composition according to p. 15, characterized in that the polymer ethoxylated amine is ethoxylated polyethyleneamine having a molecular weight of from 140 to 310 to ethoxylation.  17. The composition according to p. 15, characterized in that the polymer amine is ethoxylated polyethyleneimine having a molecular weight of from 600 to 1800 to ethoxylation.  18. The composition according to any one of paragraphs.12 to 17, characterized in that said composition comprises from 0.01 to 20% of the total weight of the composition of the specified agent that removes impurities, or a mixture thereof, preferably from 0.1 to 10%, more preferably from 0.2 to 4% and most preferably from 0.5 to 2%.  19. The composition according to any one of paragraphs.12 to 18, characterized in that it contains a whitening activator, preferably in a concentration of from 0.01 to 20% by weight of the total composition, more preferably from 1 to 10% and most preferably from 3 to 7 %  20. The composition according to claim 19, characterized in that said whitening activator is selected from the group consisting of acetyl triethyl citrate, tetraacetylethylenediamine, sodium 3,5,5 trimethylhexanoylbenzenesulfonate, peroxide adipanoic acid nononamide, non-nonanoyloxy-benzene, n-nonanoyloxy-benzene, benzoylcaprolactam, octanoylcaprolactam, nonanoylcaprolactam, hexananoylcaprolactam, decanoilcaprolactam, undecanoilcaprolactam, formylcaprolactam, acetylcaprolactam, propanoilcaprolactam, b tanoilkaprolaktam, pentanoilkaprolaktam and mixtures thereof, preferably acetyl triethyl citrate.  21. The composition according to any one of paragraphs.12 to 20, characterized in that it contains at least a hydrophobic surfactant having a hydrophilic-lipophilic balance of HLB not higher than 10 or a mixture thereof, preferably below 10, more preferably below 9 and at least a hydrophilic surfactant having an HLB above 10 or a mixture thereof, preferably above 10.5, more preferably above 11.  22. The composition according to any one of paragraphs.12 to 21, characterized in that it is aqueous and has a pH from 1 to 5, more preferably from 2 to 5, and most preferably from 3 to 5. Priority on points:
03/04/96 according to claims 3 and 13;
07.24.96 according to claims 10 and 20;
07/31/96 according to item 21;
09/13/96 other items.

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