CZ16795A3 - The utilization of modified polyesters for removing fatty pollutants from fabrics - Google Patents

Abstract

The present invention relates to the use of selected modified polyesters known for their soil-release properties as cleaning agents for cotton-containing fabrics, thus being able to provide a cleaning effect on such fabrics after only one laundering cycle, as compared to several cycles when functioning in the soil-release agent mode. The present invention also encompasses detergent compositions containing said modified polyesters and a cellulase enzyme, or a co-dispersing agent and/or a soil-antiredeposition agent.

Description

Use of modified polyesters to remove md

Technical field

The present invention relates to the use of modified polymers known for their soil release capacity as cleaning agents to remove greasy stains from fabrics in combination with a nonionic surfactant.

BACKGROUND OF THE INVENTION

The laundry detergent compositions contain a large number of ingredients that provide certain basic benefits. E.g. detergents and detergents are composed of detergent surfactant systems to remove a variety of soiling during washing. These detergents may also include ingredients that treat fabrics during washing, e.g., soften and provide them with an antistatic treatment.

In addition to standard cleaning, softening benefits and antistatic treatment, laundry detergents can also provide other desirable properties. One is to give polyester fiber fabrics the ability to release soiling. The hydrophobic nature of the polyester fabrics makes their washing difficult, particularly in the case of oily soiling and oil paints, which preferably wet the fabric. The result is that oily contamination and oil paints are difficult to remove in aqueous washing processes.

Some polyesters have been found to be particularly useful as soil release agents when incorporated into laundry detergent compositions. During washing, these soil release polyesters are adsorbed onto the surface of fabrics immersed in the wash solution. The adsorbed polyesters form a hydrophilic film which remains on the fabric even after the wash solution is removed and the fabric is dried. This film can be recovered by subsequent washing of the fabric with a detergent composition comprising soil release polyesters.

Such polyesters are described, for example, in U.S. Patent 4,116,885 and 4,711,730.

Improvements in soil release polyesters have been continuously addressed: eg EPA 272 033 describes such improved polyesters, currently EPA 311 372 discloses a further improvement in soil release agents consisting of polyesters with sulfoaroyl ends.

It has now been found that some of the modified polyesters disclosed in EPA 311 342 not only act as soil release agents from polyester fabrics, but are also capable of removing soils from cotton-containing fabrics and dispersing such soils during the main wash cycle of the washing process, as described in our recent application of EP92.202.383.3.

Removing greasy stains is a long-standing problem. When using present detergent compositions, it is difficult to effectively remove said grease from fabrics, especially polyester fabrics.

It has now surprisingly been found that the modified polyesters disclosed in EPA 311,342 in combination with selected nonionic surfactants with a low degree of ethoxylation provide an unexpected improvement in the removal of greasy stains from fabrics.

SUMMARY OF THE INVENTION

The detergent composition of the present invention comprises modified polyesters which are random copolymers of dimethyl terephthalate, dimethylsulfoisophthalate, ethylene glycol and 1,2-propanediol, wherein the end groups consist primarily of sulfobenzoate and secondly of monoesters of ethylene glycol and / or propanediol, and as a nonionic surfactant C ₈ to C _{18 a} primary alcohol ethoxylate comprising 2 to 5 moles of ethylene oxide per mole of alcohol. Most preferred is a detergent composition, wherein the nonionic surfactant is a _C12, primary alcohol ethoxylate ₅ containing about 3 moles of ethylene oxide per mole of alcohol. The presence of such a polyester in the detergent composition in a ratio of from 1: 0.3 to 1: 2.0 provides a surprising thickening effect. This provides a mixture with a potentially effective method by which said selected nonionic surfactant can be formulated as granular detergents.

It has further been found that said modified polyesters can have a thickening effect on said selected nonionic surfactant.

Modified polyesters

The modified polyesters described herein are random copolymers of dimethyl terephthalate, dimethylsulfoisophthalate, ethylene glycol and 1,2-propanediol, wherein the end groups consist primarily of sulfobenzoate and secondly of monoesters of ethylene glycol and / or propanediol. The aim is to obtain a polymer terminated primarily with sulfobenzoate groups at both ends, here in the context most of said copolymers have sulfobenzoate groups at the ends, although some polymers are not fully substituted at their ends with sulfobenzoate groups and may therefore contain ethylene glycol monoesters and / or 1,2 -propanediol.

The polyesters selected here contain about 46% by weight of dimethyl terephthalic acid, 16% of 1,2-propanediol, 10% of ethylene glycol, 13% of dimethylsulfobenzoic acid and 15% of sulfoisophthalic acid and have a relative molecular weight of about 3000. The polyesters and their preparation are described in detail in EPA 311 342.

It has further been found that the use of these modified esters in combination with a cellulase enzyme and / or some codispersing agent and / or some non-ionic surfactant provides a significant improvement in purification.

Nonionic surfactants

The nonionic surfactants of the present invention are C ₈ to C ₁₈ primary alcohol ethoxylates comprising 2 to 5 moles of ethylene oxide per mole of alcohol. Most preferred are: C ₁ to C ₁₅ primary alcohol ethoxylates comprising 3 moles of ethylene oxide per mole of alcohol.

The modified polyesters are present in the detergent composition in a ratio to the nonionic surfactant of from 1: 0.3 to 1:20, preferably from 1: 6 to 1:20.

Detergent mixture

The detergent compositions herein may be in liquid or granular form and are preferably conveyed directly to the drum or indirectly and through the outer shell of the washing machine. This is most easily accomplished by storing the mixture in a bag or container from which it can be released at the start of the wash cycle in response to agitation, temperature rise, or immersion in drum wash water. Such a container may be placed in the drum together with the fabrics to be washed. Alternatively, the washing machine itself can be adapted so that the mixture can be directly added to the drum, for example by means of a dosing device in the entrance door.

When the compositions are liquid, a solid container such as that described in EPA 151 549 may be used. The detergent compositions herein are preferably granular and flexible containers, sachets or pouches may be used. The bag preferably has a fibrous structure coated with a water-impervious protective material to preserve the internal content as described in EPA 0 018 678, or alternatively the bag may be made of a water-insoluble synthetic polymeric material welded along the edges or provided with a closure so as to welds or seals in the aqueous environment have been opened as described in EPA 0 011 500,0 011 501,0 011 502, 0 011 968. A preferred form of water-opening seal comprises a water-soluble adhesive disposed along the breech and a weld on one side of the pouch made of water-insoluble a polymer film such as polyethylene or polypropylene.

As a variant of containers or bags, laminated sheet products may be used in which the central layer is impregnated and / or coated with the composition and one or more outer layers are applied so as to produce a favorable aesthetic effect of fabric imitation. Uses associated or may be separated upon contact with water to facilitate release of the coated or impregnated material.

As a variant of the laminated containers, a mold comprising one layer embossed or shaped to provide a series of bag-shaped containers, each with a measured amount of detergent, and a second layer overlapping the first layer and welded together in the areas between the container containers where the two layers are in contact. The components may be deposited here in the form of a particulate, paste or melt, and the laminate layers prevent release of the contents from the pouch containers prior to the addition of water. The layers may separate upon contact with water or remain joined together, the only requirement being that this structure should not allow rapid release of the contents of the pouch containers into solution. The number of pouch containers per unit area of the backsheet is optional and is typically from 500 to 25,000 per m ² .

Suitable materials that can be used for the flexible laminate layers in this aspect of the present invention include foam materials, paper, and woven or nonwoven fabrics.

Preferred means for carrying out the washing process of the present invention include the use of reusable dispensing devices having liquid-permeable walls but not solid compositions.

Such devices are described in EPA 0 343 069 and 0 344 070. A later application describes a device comprising a flexible sheet in the form of a bag emerging from a support ring that defines an orifice adapted to allow a sufficient amount of product to be placed in the bag per wash cycle. washing cycle. Part of the wash medium flows through the mouth into the bag, dissolves the product and the solution passes out through the mouth into the wash medium. The support ring is provided with a masking device that prevents the release of the moistened undissolved product, and the device preferably includes radially expanding walls that project radially from the central portion, or a similar structure in which the walls have a helicalform.

The detergent compositions comprise a surfactant

A wide variety of surfactants can be used in the detergent compositions. A list of anionic, nonionic, ampholytic and zwitterionic types of surfactants and their species is described in U.S. Pat. No. 3,961,961 issued to Noris on May 23, 1972.

Particularly preferred are mixtures of anionic surfactants, in particular mixtures of sulphonate and sulphate surfactants in a weight ratio of 5: 1 to 1: 2,

preferably from 3: 1 to 2: 3, more preferably from 3: 1 to 1: 1. Preferred sulfonates include alkylbenzene sulfonates having from 9 to 15, preferably from 11 to 13 carbon atoms in the alkyl chain, and α-sulfonates of fatty acid methyl esters, wherein the fatty acids are derived from carbon moieties having a carbon number of from 12 to 18, preferably from 6 to 16 carbon atoms. up to 18 carbon atoms. An alkali metal, preferably sodium, is used as the cation. Preferred sulfate surfactants are alkyl sulfates having an alkyl chain of 12 to 18 carbon atoms, preferably in admixture with ethoxy sulfates having an alkyl chain of 10 to 20 carbon atoms, preferably 10 to 16 carbon atoms, with an average degree of ethoxylation of from 1 to 18 carbon atoms.

6. Examples of preferred alkyl sulfates of the present invention are tallow alkyl sulfates, coconut alkyl sulfates and C ₁₄ to C ₁₅ alkyl sulfates. An example of a preferred ethoxysulfate is so-called AE3S (three times ethoxylated C ₁₂ to C ₁₅ alkyl sulfate). An alkali metal, preferably sodium, is used as the cation.

A first group of preferred nonionic surfactants of the present invention are condensates of ethylene oxides with a hydrophobic component to form a surfactant having an average hydrophilicity and lipophilicity (PHL) ratio in the range of 5 to 17, preferably 6 to 14, more preferably 7 to 12. The hydrophobic (lipophilic) component is aliphatic or the aromatic nature and the length of the polyoxyethylene group that is condensed with the hydrophobic component can be adjusted to form a water-soluble compound having the desired ratio of hydrophilic and hydrophobic elements.

Further, the compositions herein may contain, in addition to selected nonionic surfactants, other nonionic surfactants such as C ₉ to C ₅ primary alcohol ethoxylates comprising 6 to 8 moles of ethylene oxides per mole of alcohol, particularly preferred surfactants include C ₁₄ to C ₁₅ primary alcohols and 6 to 8 moles of ethylene oxides per mole of alcohol.

The second group of non-ionic surfactants are alkyl polyglucosides of the formula RO-(C ^H ^H ^O) *, wherein Z is a component derived from glucose, R is a saturated hydrophobic alkyl chain containing 12 to 18 carbon atoms, t is a number from 0 to 10 and n is 2 or 3, x is a number of from 1.3 to 4, i.e. a substance comprising less than 10% unreacted hydrophobic alcohols and less than 50% short chain polyglucosides. Substances of this type and their use as detergents are described in EP-B 0070 077,0075 996 and 0094 118.

Another preferred group of nonionic surfactants are the fatty acid polyhydroxyalkylamides of the formula R ² -C (= O) -N (-R ') - Z, wherein R ¹ is H or C ¹ to C 4 alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their % of the mixture, R ² is C 5 to C ₃₁ alkyl and Z is a polyhydroxyalkyl with a linear carbon chain and at least three hydroxyl groups attached directly to the chain or their alkoxy derivatives. Preferably R 1 is methyl, R ² is C ₁ to C ₁₅ alkyl or alkenyl with a linear carbon chain such as coconut alkyl or mixtures thereof, and Z is a residue of an amino reducing sugar derivative such as glucose, fructose, maltose, lactose formed by reductive amination .

Another group of surfactants are semipolar surfactants such as amine oxides. Suitable amine oxides are selected from mono C ₈ to C ₂₀ amine oxides, preferably _C10-C14 N-alkyl or -alkenyloxidy and 1,3-propylendiaminoxidy where N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Another group of surfactants are amphoteric surfactants such as polyamines.

The detergent compositions of the present invention may also be used cationic surfactants and suitable quaternary ammonium surfactants are selected from mono C ₃ to C _lo preferably _C10-C14 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Mixtures of surfactant types are preferred, mixtures of anionic-nonionic surfactants as well as anionic-nonionic-cationic surfactants are particularly preferred. Particularly preferred compositions are described in British Patent No. 5,960,549. The detergent compositions may comprise from 1 to 70% by weight of surfactants, although the surfactant is usually present in an amount of from 1 to 30%, more preferably from 10 to 25% by weight.

The detergent compositions also contain fillers

The filler materials are typically present in an amount of from 5 to 80% of the detergent compositions herein. The compositions described herein do not contain or are almost free of phosphate fillers (wherein, in phosphate-free fillers ί - 1, __, ί 3

LT * cn

Ο ο

The phosphates are present in an amount of less than 1% of the total filler system herein, including water-soluble fillers, water-insoluble fillers, or mixtures thereof.

The water-insoluble fillers may be inorganic ion exchange materials, preferably hydrated inorganic aluminosilicates, more preferably hydrated synthetic zeolites such as hydrated zeolite A, X, B or HS.

Preferred aluminosilicate ion exchange materials have a base cell of the formula M _z ((AlO ₂ ) _z (SiO ₂ ) _y ) xH ₂ O, where M is a calcium exchange cation, z and y are at least about 6, with a molar ratio of z: y ranging from 1 The 0 to 0.5 ax is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate materials are hydrated and are preferably crystalline with a water content of from 10 to 28%, more preferably from 18 to 22% by weight.

The aluminosilicate ion exchange materials are further characterized by a particle diameter of from 0.1 to 10 μΓη, preferably from 0.2 to 4 μηη. As used herein, the particle diameter size is the average diameter of a particular ion exchange material as determined by conventional analytical techniques such as scanning electron microscopy. The aluminosilicate ion exchange materials are further characterized by their calcium exchange ion capacity, which is at least 200 mg CaCO ₃ equivalent of water hardness per gram of aluminum silicate, calculated on the anhydrous basis, and is generally in the range of 300 mg eq / g to 352 mg eq. /G. The aluminosilicate ion exchange materials are further characterized by the rate of their calcium exchange ion, which is described in detail in GB-1 429 143.

. The aluminosilicate ion exchange materials useful in the practice of the present invention are commercially available and also occur in nature, but are preferably synthetically prepared. A method for preparing aluminosilicate ion exchange materials is described in US Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials used herein are available under the designation Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. In a particularly preferred case, the crystalline aluminosilicate ion exchange material is zeolite A and has the general formula:

AND

Na ₁₂ ((AlO ₂ ), ₂ (SiO ₂ ) ₁₂ ) xH ₂ O, wherein x is a number from 20 to 30, preferably 27. Zeolite X of the formula O ₂ O ₂ O ₂ O is also preferred, as is the zeolite HS according to the general formula NaJ (AlO ₂ ) ₆ (SiO ₂ ) _{6 O} · 7.5H ₂ O.

Another preferred water-insoluble inorganic filler is a layered silicate such as SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na ₂ Si ₂ O ₅ ). The high Ca ²⁺ / Mg ²⁺ binding capacity is mainly an ion exchange mechanism. The material is more soluble in hot water.

Water-soluble fillers are usually monomeric or oligomeric carboxylate chelating agents

Preferred carboxylates of this type include one carboxylic group such as lactic acid, glycolic acid, and ether derivatives thereof, as described in Belgian Patent 831 3-8, 821 369 and 821 370. Polycarboxylates containing two carboxyl groups include water-soluble salts of succinic acid, malonic acid, ethylenedioxydiacetic acid, maleic acid , diglycol, wine, tartron and fumaric, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686 and 2,446,687 and US Patent 3,935,257 and sulfinyl carboxylates described in Belgian Patent 840,623. citraconates as well as succinic acid derivatives such as the carboxymethyloxysuccinates described in British Patent 1 379 241, the lactoxysuccinates described in the Netherlands Application 7 205 873 and oxypolycarboxylate materials such as 2-oxa-1,3,3-propanetricarboxylates described in British Patent 1 387 447.

Polycarboxylates containing four carboxyl groups include the oxydisuccinates described in British Patent 1 261 829,1,1,2,2-etantetracarboxylates,

1,1,3,3-propantetracarboxylates and 1,1,2,3-propantetracarboxylates.

Polycarboxylates containing sulfo groups include the sulfosuccinate derivatives described in British Patent 1 398 421 and 1 398 422 and in US Patent 3 936 448 and sulfonated pyrolyzed citrates described in British Patent 1 082 179 and or polycarboxylates containing phosphone substituents as described in British Patent 1 439 000.

Alicyclic α heterocyclic polycarboxylates include cis, cis, cis-cyclopentantetracarboxylates, cyclopentadiene pentacarboxylates,

2.3.4.5- cis, cis, cis-tetrahydrofurantetracarboxylates,

2,5-cis-tetrahydrofuranedicarboxylates, 2,2,5,5-tetrahydrofurantetracarboxylates,

1,2,3,4,5,6-hexane hexacarboxylates and carboxymethyl derivatives of polyols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melitic acid, pyromellitic acid, and phthalic acid derivatives described in British Patent 1,425,343.

Of the above-mentioned polycarboxylates, polycarboxylates containing up to three carboxyl groups per molecule, particularly citrates, are preferred.

Preferred filler systems in preferred granular detergent compositions include a mixture of a water-insoluble aluminosilicate builder such as Zeolite A or layered silicate (SKS / δ) and a water-soluble carboxylate chelating agent such as citric acid.

Other filler materials that can be used as part of the filler system for use in the present invention include inorganic materials such as alkali metal carbonates, bicarbonates and silicates.

Other suitable water-soluble organic salts are homo- or copolymeric acids or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by no more than two carbon atoms.

Polymers of this type are described in GB-A1 596 756. Examples of such salts are polyacrylates having a relative molecular weight of from 2000 to 5000 and their copolymers with maleic anhydride and such copolymers have a relative molecular weight of from 20,000 to 70,000, preferably about 40,000 .

In a preferred embodiment of the present invention, the detergent compositions comprise a cellulase enzyme as described above in a content of from 0.025 to 10% of the composition.

In another preferred embodiment of the present invention, the detergent compositions or detergent ingredients comprise an anti-redeposition agent or a soil-suspending agent in combination with the modified polyesters described herein.

Suitable antiredeposition agents and soil suspending agents include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethyicellulose, homo- or copolymers of polycarboxylic acids or salts and polyamino acids thereof. Polymers of this type include polyacrylates and copolymers of maleic anhydride and acrylic acid previously mentioned as fillers, as well as copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, wherein the maleic anhydride represents at least 20 mol% of the copolymers. Polyamino acids such as aspartic acid-derived polyamino acids are described, for example, in British Patent 9226942.2.

These materials are commonly used in a content of from 0.5 to 10% by weight of the composition, more preferably from 0.75 to 8%, most preferably from 1 to 6% by weight of the composition.

The present detergent compositions are preferably in granular form, and more preferably in a compact form, i.e. have a density that is greater than that of a conventional detergent composition. The preferred density of the mixture is from 550 to 950 g / L, preferably from 650 to 850 g / L, measured at 20 ° C.

The compact ¹ form of the present invention most preferred compositions is best described in terms of the composition by the amount of inorganic filler salts which are common ingredients of powdered detergent compositions, wherein in conventional detergent compositions the filler salts are present in amounts typically from 17 to 35% by weight mixtures.

In the most preferred compositions of the present invention, the filler salt is present in an amount not exceeding 15% of the total weight of the composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition.

The inorganic filler salt in the compositions of the present invention is selected from alkaline earth metal sulphates and chlorides.

The preferred filler salt is sodium sulfate.

The compositions of the present invention typically include suitable ingredients that are typically part of detergent compositions. Enzymes, optical brighteners, bleaches, bleach activators, suds suppressors, anti-wrinkle agents, dyes and pigments are examples of such suitable ingredients and can be added in varying amounts as desired.

Enzymes such as proteases, celluloses, lipases or amylases are particularly preferred ingredients of the compositions of the present invention, preferably cellulose.

Any bacterial cellulose or fungal cellulase having a pH optimum between 5 and 9.5 can be used as cellulose here in combination with the modified polyesters.

Suitable celluloses are disclosed in GB-A-2 075 028; GB-A-2,095,275 and DE-OS-2447,832.

Examples of such celluloses are cellulases produced by Humicola insolens (Humicola grisea var. Thermoidea), in particular Humicola DSM 1800, and cellulose 212 produced by an Aeromonas sponge and cellulose extracted from the mollusc hepatopancreas (Dolabella Auricula Solander).

The cellulose added to the composition of the present invention may be in the form of a non-dusty granulate, eg, a crystalline, or in liquid form, in which the cellulose is present as a cellulase concentrate suspended eg in a nonionic surfactant or dissolved in an aqueous medium.

Preferred cellulases used herein are characterized in that they provide at least 10% removal of immobilized radiolabeled carboxymethylcellulose according to the C14CMC method described in EPA 350 098 at 25.10 ⁶ % cellulose protein in a test wash solution.

The most preferred cellulases are described in International Patent Application WO 91/17243. E.g. The cellulase composition useful in the composition of the present invention may consist essentially of a homogeneous endoglucanase component that is immunoreactive with an antibody against highly purified 43 kD cellulose derived from Humicola insolens, DSM 1800, or which is a homologue of said 43 kD endoglucanase.

The modified polyesters herein on cotton-containing fabrics typically achieve their advantageous cleaning properties by incorporating them into a detergent composition comprising additional cleaning ingredients, ranging from 0.025% to 10% by weight of the composition.

Alternatively, the modified polyesters may be added separately, during the wash cycle, in the form of detergents, which may contain other selected detergent active agents such as anti-redeposition anti-fouling and codisperse agents, and / or cellulose enzyme. In particular, the modified polyesters may be used for pretreating cotton-containing fabrics prior to the main wash cycle of the washing process.

Preferred optical brighteners are anionic in nature, for example: sodium 4,4'-bis- (2-dietanolamino-4-anilino-s-triazin-6-yl-amino) stilbene-2: 2 ^1- disulfonate, 4,4 ' sodium bis (2-morpholino-4-anilino-s-triazin-6-yl-amino) stilbene-2: 2'-disulfonate, 4,4'-bis- (2,4-dianilino-s-triazine-) O-ylamino) stilbene-2: 2 ¹ disulphonate, sodium, 4 ', 4-bis (2,4-dianilino-s-triazin-o-yl-amino) stilbene-2-sulfonate,

Sodium 4,4'-bis- (2-anilino-4- (N-methyl-N-2-hydroxyethylamino) -s-triazin-6-yl-amino) stilbene -2: 2'-disulfonate, 4,4 ' sodium bis (4-phenyl-2,1,3-triazol-2-yl) stilbene-2: 2'-disulfonate,

4,4 ¹ -bis- (2-anilino-4- (l-methyl-2-hydroxyethylamino) -s-triazine-o-yl-amino) stilbene-2: 2'-disulfonate and sodium 2- (stilbyl-4 Sodium (naphtho-1 ', 2': 4,5) -1,2,3-triazole-2-sulfonate.

Any inorganic peroxygen bleach may be used in an amount of from 3 to 40% by weight, preferably from 8 to 25% by weight, and most preferably from 12 to 20% by weight of the composition. Preferred examples of such bleaches are sodium perborate monohydrate and tetrahydrate, perhydrate and mixtures thereof.

Another preferred ingredient separately mixed is a carboxylic acid precursor as a bleach, commonly referred to as a bleach activator, which is added to granular detergents in the form of a crystallizate or agglomerates. Peroxygen bleaches (peroxygen) are preferably combined with bleach activators, which in situ results in the formation of an aqueous solution (i.e. during the washing process of the peroxyacid corresponding to the bleach activator). Examples of suitable materials of this type are described in British Patent 1 586 769 and 2,143,231 and a method for forming their crystallizates is disclosed in EPA 0 062 523. Examples of such preferred materials are tetraacetylethylenediamine and the like.

Sodium 3,5,5-trimethylhexanoylbenzenesulfonate, diperoxydodecanoic acid as described in, eg, US 4,818,425 and peroxyadipic acid nonylamide as described in, eg, US 4,259,201 and n-nonanoyloxybenzenesulfonate (NOBS) and acetyltriethyl citrate (ATC) as described in European patent application

91.870207.7.

Bleach activators are commonly used in a content of from 0.5 to 10% by weight, more typically from 1 to 8% and preferably from 2 to 6% by weight of the composition.

Metallocatalysts / MnPC may also be used, preferably in a proportion of 0.2 to the total detergent composition of the present invention.

Another suitable ingredient is a suds suppressor such as silicones and silicone-silicone mixtures. For example, alkylated polysiloxane materials can be used as silicones, while silica gel is commonly used in the form of very fine forms such as aerogel and xerogel and hydrophobic silica gels of various types. These materials are used in particulate form in which the suds suppressor is preferably releasably incorporated in a water-soluble or water-dispersible, substantially non-surfactant detergent impermeable carrier. Alternatively, the suds suppressor may be dissolved or dispersed in a liquid carrier and spray applied to one or more components.

As mentioned above, silicone suds suppressors may include a mixture of alkylated siloxanes of the type described herein and solid silica gel. Such mixtures are prepared by attaching silicone to the surface of solid silica gel particles. A preferred silicone suds suppressor is, for example, a hydrophobic silylated, most preferably trimethylsilylated, silica gel having a particle size in the range of 10 to 20 millimicrons with a specific surface area above 50 m ² / g well mixed with dimethyisilicone fluid of relative molecular weight in the range of 500 to 200,000 a silicone: silanized silica gel ratio of from 1: 1 to 1: 2.

A preferred silicone suds suppressor is described in US Patent 3,933,672 (Bartollotta et al.). Other particularly preferred suds suppressors are the self-emulsifying silicone suds suppressors described in German Patent Application DTOS 2,646,126, which was published on April 28, 1977. An example of such materials is DC-544, commercially available from Dow Corning which is a siloxane-glycol copolymer.

The suds suppressors described herein are commonly used in ranges of from 0.001 to 2% by weight of the composition, preferably from 0.01 to 1% by weight of the composition. The incorporation of suds suppressors is preferably in the form of a separate particulate, allowing for the inclusion of additional suds suppressors such as C ₂₀ to C ₂₄ fatty acids, microcrystalline waxes, and high molecular weight copolymers of ethylene oxide and propylene oxide that might otherwise adversely affect matrix dispersibility. Techniques for preparing such particulates as suds suppressors are mentioned in U.S. Patent 3,933,672 (Bartolotta et al.).

Fabric softeners, which may be organic or inorganic in nature, may also be included in the detergent compositions of the present invention. Inorganic plasticizers such as fuller's clays are described in GB-A-1 400 898.

Organic fabric softeners include the water-soluble tertiary amines as disclosed in GB-A-1 400 898, the water-insoluble tertiary amines described in GB-A-1 514 276 and EP-B-0 011 340, and combinations thereof with mono C ₁₂ to C ₁₄ quaternary ammonium salts described in EP-B-0 026 527 and EP-B-0 0260528, and double chain amides as described in EP-B-0 242 919. Other preferred organic components of fabric softener systems include high molecular weight polyethylene oxides as described in EP-A-0 299 575 and 0 313 146.

Preferred granular detergent compositions of the present invention comprise fuller clays in the range of from 5 to 20%, more preferably from 8 to 15% by weight of the material added as a mixed dry component to the remainder of the composition. Organic plasticizers such as water-insoluble tertiary amines or double chain amides are included in the composition in a content of from 0.5 to 5% by weight, usually from 1 to 3% by weight, and high molecular weight polyethylene oxide materials and water-soluble cationic materials are included in the mixture 0.1 to 2%, usually from 0.15 to 1.5% by weight. These materials are typically added to the spray dried portion of the mixture, although in some cases it may be preferable to add them as a dry mixed particulate or spray them as a molten liquid onto the second solid component of the mixture.

The compositions of the present invention may also include a dye transfer inhibitor such as polyvinylpyrrolidones having a relative molecular weight of from 5000 to 2200, which are typically present in the granular detergent compositions in a content of from 5 to 500 mg / l of polyvinylpyrrolidone in the wash solution. PVPVI can also be used as a dye transfer inhibitor in the detergent composition.

The compositions of the present invention may comprise a chelant (heavy metal masking agent) in a content of at least 0.05 to 5% by weight of the composition, preferably from 0.05 to 1%, most preferably from 0.1 to 0.5% by weight of the composition.

A suitable chelant for incorporation into the detergent compositions of the present invention is ethylenediamine-N, N'-disuccinic acid (EDDS) or alkali metal, alkaline earth metal salt, ammonium salt or substituted ammonium salt or mixtures thereof. Preferred EDDS compounds are the free acid and its sodium or magnesium salts. Examples of such preferred sodium salts of EDDS include Na ₂ EDDS and Na ₄ EDDS. Examples of such preferred magnesium EDDS salts include MgEDDS and Mg ₂ EDDS. Magnesium salts are most preferred for inclusion in the compositions of the present invention.

Other chelants include organic phosphonates including aminoalkylene polyphosphonates (alkylenephosphonates), alkali metal ethane-1-hydroxydiphosphonates, nitrilotrimethylene phosphonates, ethylenediaminetetramethylene phosphonates, and diethylenetriaminepentamethylene phosphonates. The phosphonates may be present either as an acid or as a complex of either an alkali or an alkali metal ion and the molar ratio of said metal ion to said phosphonate is at least 1: 1. Such complexes are described in US-A-4,259,200. Preferably, the organic phosphonates, if present, are in the form of their magnesium salt. The content of chelants in the phosphorus-containing compositions of the present invention is preferably minimized, most preferably completely excluded from the compositions. Other suitable chelants include aminopolycarboxylate chelants such as EDTA and HEDTA.

The compositions of the present invention can be prepared by a variety of methods including dry mixing, spray drying, agglomeration and granulation, and combinations of these techniques. With the compositions of the present invention, it can be prepared with different bulk densities, from conventional granular products to so-called concentrates (i.e. bulk densities of about 600 g / l).

DETAILED DESCRIPTION OF THE INVENTION

The following examples illustrate the present invention and facilitate its understanding.

The abbreviations of the individual ingredients mean:

LAS: sodium salt of linear dodecyl benzene sulfonate AS: sodium salt or C _{with C15} alkyl sulfate TAS: sodium salt of alkyl sulfate, tallow

FA45E7: long chain alcohol (C ₁₄ to C ₁₅ ) ethoxylated with 7 moles of ethylene oxide

FA25E3: long chain alcohol (C _{12 to} C ₁₅ ) ethoxylated with 3 moles of ethylene oxide

CAT: C ₁₂ alkyltrimethylammonium chloride Aluminum: fuller clay

Zeolite A4: zeolite sodium 4A with an average particle size ranging from 1 to 10 μίτι

SKS-6: crystalline layered silicate (Hoechst)

Copolymer AA / MA: copolymer of acrylic acid and maleic PAA: polyacrylate polymer

CMC: carboxymephylcellulose

Phosphonate: Ethylenediaminetetraethylenephosphonic acid sodium EDTA: Ethylenediaminetetraacetic acid sodium salt PB1: NaBO ₂ .H ₂ O

TAED: tetraacetylethylenediamine PVP: polyvinylpyrrolidone Silicate (R = n): SiO ₂ / Na ₂ O = n

Cellulose: 43 kD species corresponding to the description given above Amylase: Termamyl 60T (Novo-Nordisk)

Lipase: Lipolase 100T (Novo-Nordisk)

Protease: Savinase 4T (Novo-Nordisk)

SSS: foam suppressor system (silica gel / silicone mixture)

X

The modified polyesters used in the following examples correspond to the species described in claim 2 of the present invention.

The method of preparation is as follows:

The process for preparing polyesters involves mixing all the monomers in a round-bottomed flask, stirring at 180 ° C until the resulting mixture is clear and stirring continuously for 24 hours. Transferring the contents of the round-bottomed flask to another flask (typically 11), heating under vacuum at 200 ° C for 45 minutes, removing from the flask and cooling. A solid clear glass is obtained which is then finely pulverized.

Example 1

The following detergent composition was prepared:

% by weight LAS 9 TAS 3 FA45E7 2.5 Zeolite 33 Sodium citrate 21 Sodium carbonate 3 Sodium sulfate 5 PAA 3.5 Protease 1.6 Cellulose 0.5 Modified polyester 0.5

Test procedure

A bundle of soiled fabrics containing fibers that have been soiled by a set of soils such as particulate matter, greasy soils, enzymatic soils and bleachable soils on cotton and polywoven fabrics, the fabrics were washed with a compact detergent composition as above. Half of each bundle was washed with the detergent composition as above and the other half was washed with the same cellulose-free composition. Testing was performed at 40 ° C in water with a hardness of 4,475 mmol / l. All tests were repeated four times.

The removal of contamination was evaluated relative to the reference contamination of each of the types previously washed under the same conditions. The compositions used for washing the reference fabrics did not contain modified polyester or cellulose,

Pollution removal was evaluated using the known schefe scale using the results on the surface units assessed by two assessors according to the following criteria:

= I think there is a difference between the two

2 = There is a difference between the two

3 = There is a big difference between the two

4 = There is a difference between the two soiling as between black and white.

Mean data was calculated compared to the reference fabric. The results for the greasy contamination on polycotton material were as follows.

Pollution Preference for Example 1 mixture versus reference Dirty engine oil +1.1 * Make up + 0,5 *

* = statistically significant

Example 2

A detergent composition similar to that of Example 1 was used to wash a bundle of soiled fabrics that were soiled by a set of soils such as particulate matter, greasy soils, enzymatic soils and bleachable soils. Half of each bundle was washed with the composition of Example 1 and the other half was washed with the same composition without modified polyester. Testing was performed at 40 ° C in water with a hardness of 4,475 mmol / l. All assays were repeated four times, and the samples were scaled according to the percentage of contamination removal calculated using a McBeth colorimeter using a conventional 1 a b system. Tests were carried out at different casts

modified polyesters ranging from 0.025 to 10% by weight of the detergent composition.

The results are detailed below:

Content 0.025% 0.1% 0.5% 10% Average removal of greasy contamination from polycotton 52% 64% 69% 73%

Contaminated engine oil, shoe polish and make up have been considered and used as typical greasy contamination.

The data in the tables describe the average increase in the percentage of soil removal compared to the reference samples.

Example 3

Increase the removal of greasy soils using a combination of modified polyester and carboxymethylcellulose.

The multi-cotton samples have been pre-treated many times with a detersive mixture containing carboxymethylcellulose (CMC) to form CMC deposits on cotton poly-cotton fabrics. The cotton was then dried and contaminated with contaminated engine oil (DMO). One half of the soiled fabric was washed with a detersive composition similar to that of Example 1 for reference, while the other half was washed with the same composition containing modified polyesters. Samples were scaled according to calculated percent removal of pollution from each sample using a hunter color lab system. The data was also compared to samples that were subjected to the same treatment as above, only the detersive mixture contained a soil removal polymer but not CMC. The results are shown below.

Reference (CMC only) Only modified polyester CMC / modified polyester Average% removal pollution 21% 43% 79%

rrw

Test conditions: 40 ° C / hardness 4,475 mmol / l, performed four times.

Example 4

Pre-treatment solution containing modified polyester prepared according to data see below:

Mixture 1 2 3 4 5 O Modified polyester 0.5 1 3 5 6 O LAS 40 50 75 75 - - FA45E7 13 17 17 - 30 22nd Copolymer of maleic and acrylic acid 46.5 32 5 20 May 64 72

All of the solutions were used to pre-treat the cotton fabrics prior to washing to remove a number of previous greasy contaminants such as contaminated engine oil, sunscreen and lipstick.

All fabrics were pretreated with each of the blends that showed an improvement in the removal of soiling from the cotton as compared to the untreated soiling.

The following compact detergent compositions were also prepared:

Compact detergent compositions (all contents expressed in% by weight)

Examples 5 6 7 8 9 10 11 LAS 11 - 6.5 - 6.5 - - TAS - - 3.25 3.9 2.25 - - AS 5 12 - - - 6 6.5 FA45E7 4 1 2.2 6 2.2 3 - FA25E3 - - - - - 6 7 CAT - - - 2.45 - - - Glucosamidzloje - 10 - - - - - Sodium citrate / acid lemon 18 5 12 15 Dec 12 4 4 Zeolite 4A 32 15 Dec 16 20 May 15 Dec 13 13 SKS-ó - 12 - - - 12 12 Copolymer AA / M A 4.1 5 3.5 3.5 - 5 3 Poiypeptid 3 - 2 Phosphonate 0.19 1 - - 1 - - EDTA - - 0.32 0.32 - - - Na ₂ CO ₃ / NaHCO ₃ 3 2.5 10 10 10 9 10 Silicate (R2) 3 2 2.5 2.5 2.5 3.5 3.5 CMC - 0.5 - - 0.5 0.3 - Hlinka - - 8.6 8.6 - - - PB1 - - 11.5 - 12 - 12 Percarbonate - - - 12 - 23 - TAED - - 3.2 - 4 6 4 Protease 1,2 1.6 1.4 1.4 1.4 1.4 1.4 Cellulose 0.5 - 0.3 0.1 0.1 0.1 0.1 Lipase 0.4 0.3 0.3 0.3 0.3 0.3 0.3 Amylase 0.2 0.3 - - - - - Na ₂ SO ₄ 2 2.5 3.5 3.5 4 3.5 4 PVP - 0.5 1 - - - - PVNO - - - - - - 0.5 SSS 0.4 0.4 0.5 0.5 0.5 0.5 0.5 Modifik. polyester 0.3 0.4 0.3 0.5 0.5 0.5 0.5 Minority ingredients + water Refill up to 100%

Example 5

Increase the removal of greasy soils using a combination of modified SRP and C25E3 (= AE3 in this example).

The combination of SRP and C25E3 has been tested against the products available under the names Skip Micro System (SMS) and Skip Regular.

The following significant results have been obtained for the removal of greasy contamination: a) SMS

Removal of greasy soils Refsherence - SMS (same dose 140 g) Cotton Polybotton Polyester Ariel Ultra-D + 0.3% CFP - 40 ° C -0.4 -0.34 -1.02s Ariel Ultra-D + 0.3% CFP + 4.7% AE3 - 40 Ό -0.16 0.21 0.06 Ariel Ultra-D + 5% AE7-60 'C -l, 13p -l, os on Ariel Ultra-D + 0.3% CFP - 60 Ό -1,15s -1,70s -LóOs Ariel Ultra-D + 8% AE3 ZERO AE7-60 Ό -0.41 0.01 on Ariel Ultra-D + 0.3% CFP + 4.7 AE3 - 60 'C -0.1 -0.49s -0.44s

(b) Skip Regular

Removal of greasy soils, Refresher - Skip Regular (215 g vs 140 g) Cotton Polybotton Polyester Ariel Ultra-D + 4.7 AE3-40 * C -0.57 -0.7 ls -l, 8o Ariel Ultra-D + 0.3% CFP + 4.7% AE3 - 40 'C -0.2ó 0.23 0,83s

Comparison with Skip Regular clearly shows that SRP + AE3 performs better than AE3 alone. This is not the case with SMS.

Ř

The addition of Ae3 also improves the efficacy of the oils with grease. AE3 and SRP added together with Ariel Ultra-D:

I) increases the effect of AE3 (against Skip Regular) or

II) shows an improvement over AE3 alone (against SMS).

Example 6

SRP synergism with non-ionic C25E3 (= AE3).

Introduction

The polypropylene material of the granulate has a very hydrophobic surface, to which oily contaminants such as DMO are very attracted and quickly attached to it.

Summary

1) The effect of CFP on granulate purification is dependent on the ratio of CFP to surfactant. A low SRP to surfactant ratio shows an improvement in purification, a high SRP to surfactant ratio shows a deterioration in purification.

0.025 g SRP / 5 g Ariel 0.05 g SRP / 3 g Ariel Ult. Share CFP: NI surfactant (1: 6 0 - 6 (1: 2 0: 2) Pollution degree polyprop. Net Dirty Very Dirty Dirty

2) The critical factor of this phenomenon is the presence and type of nonionic surfactant. The surfactant and the water itself give the granulate dirty, just like the CFP and the water itself.

CFP content in ppm 0 50 100 ALIGN! 0 0 Product content in ppm 0 0 0 6 000 10 000 Pollution degree Fabric {Very Dirty Dirty Dirty Very Dirty Dirty

3) Significant is the finding that the CFP and no nonionic Ariel surfactant also give a soiled fabric

CFP content in ppm 0 50 0 50 Content of non-ionic surf. in ppm 0 0 500 500 Product content in ppm 10 000 10 000 10 000 10000 Pollution degree fabric Dirty Dirty Dirty Net

4) The use of the non-ionic surfactant C25AE3 requires better cleaning and further enhances the effect of SRP.

CFP content in ppm 0 50 Content of non-ionic surf. in ppm 500 AE3 500 AE3 Product content in ppm 10000 10000 Pollution degree fabric Net Very clean

5) Synergism with a nonionic surfactant shows improved shoe polish cleaning when both CFP and C25e3 are used to prewash and wash polyester fabric.

Ariel Ultra 3.26% 45E7 Ariel 45E7 + 0.5% CFP ARiel + 3.26% C25E3 Ariel + 0.5% CFP + 3.26% C25E3 % Removing shoe polish 29 28 35 44 (significant)

The result is a synergistic effect when both SRP and nonionic surfactant (AE3) are used together, and the improvement of the effect is dependent on the proportion of SRP to the nonionic surfactant (AE3) as expressed below.

CFP: nonionic surfactant Improved effect 1: 2 No 1: 6 Yes 1:10 Yes 1:20 Yes (but a little less)

Example 7

With limited success, numerous attempts have been made to thicken C25E3 with a variety of detergent ingredients. The use of the modified soil removal polymers of the present invention provides a method of thickening C25E3.

By mixing C25E3 with the soil removal polymer solution in a ratio of one part of C25E3 to 0.3 parts of the soil removal polymer at room temperature with gentle stirring, a thick viscous paste is prepared which does not separate on standing.

Different soil removal polymers can provide the same thickening effect.

Higher contaminant removal contents provide a denser paste.

Share C25E3 Pollutant removal polymer Thickening effect 3 0.3 None 2 0.3 Somewhat dense, but separates on standing 1 0.3 Thick stable white paste 1 2 Thick stable white paste

Conditions: room temperature, gentle stirring.

These results describe the thickening of the non-ionic C25E3 surfactant after addition of the soil removal polymer solution as described in the present invention. This disclosure provides a potentially effective way in which C25E3 can be incorporated into granular detergents.

Industrial applicability

The compositions for removing greasy soils from fabrics according to the present invention are advantageous for the industrial manufacture of laundry and / or prewash compositions.

Claims (11)

PATENT CLAIMS A detergent composition of modified polyesters for removing greasy soils from fabrics, comprising a modified polyester which is a random copolymer of dimethyl terephthalate, dimethylsulfoisophthalate, ethylene glycol and 1,2-propanediol, wherein the end groups consist primarily of sulfobenzoate and secondly of monoesters. etyienglykolu and / or propane-diol and a nonionic surfactant which is _a C to C ₁₈ primary alcohol ethoxylate containing 2 to 5 moles of ethylene oxide per mole of alcohol. 2. A detergent composition according to claim 1, claim wherein the nonionic surfactant is a C ₂ to C ₁₅ primary alcohol ethoxylate containing 3 moles of ethylene oxide per mole of alcohol. 3. A detergent composition according to claim 2 wherein the weight ratio of the nonionic surfactant to the modified polyester is in the range of 1: 0.3 to 1: 2.0. A method of using a modified polyester, characterized in that the polyester is a randomic copolymer of dimethyl terephthalate, dimethylsulfoisophthalate, ethyleneglycol and 1,2-propanediol, wherein the end groups consist primarily of sulfobenzoate and secondly monoesters of ethyleneglycol and / or propanediol in admixture with nonionic surfactant. which is a C ₈ to C ₈ ethoxylated primary alcohol comprising from 2 to 5 moles of ethylene oxide per mole of alcohol is used as a cleaning agent to remove fatty impurities from fabrics, which fabrics are in contact with an aqueous washing liquid containing said fabrics. The method of claim 4, wherein the modified polyester comprises 4% by weight of dimethyl terephthalic acid, 16% by weight. 1,2-propanediol, 10% ethyleneglycol, 13% sulfobenzoic acid and 15% sulfoisophthalic acid and has a relative molecular weight ranging from 2500 to 3000. The method of claims 4 or 5, wherein the nonionic surfactant is a C ₁₂ to C ₁₅ ethoxylated primary alcohol comprising 3 moles of ethylene oxide per mole of alcohol. The method of claim 4,5 or 6, wherein the weight ratio of the nonionic surfactant to the modified polyester is in the range of 1: 6 to 1:20. The process according to any one of claims 4 to 7, wherein the modified polyester is mixed with a cellulase enzyme. The method of any one of claims 4 to 8, wherein the modified polyester is incorporated in a detergent additive composition comprising additional detersive ingredients in a content of 0.025 to 10% by weight of the composition. The method of any one of claims 4 to 8, wherein the modified polyester is incorporated in a detergent additive composition for prewashing fabrics. Method according to any one of claims 4 to 8, characterized in that the detergent composition or detergent additive composition is placed in a container capable of releasing the composition at the beginning of the wash cycle or the prewash cycle and that container is placed in the drum of the washing machine together with the fabrics to be washed and / or prewashed. .