WO2008110318A2 - Anionic soil release polyesters - Google Patents

Abstract

Anionic soil release polyesters are disclosed, comprising terephthalic acid, sulfoisophthalic acid-(poly)alkylene glycol, a non-ionic terminal group and optionally a multi-functional cross-linked monomer. Said polyesters are suitable as soil release components in washing and cleaning agents.

Description

 description

Anionic Soil Release Polymers

The invention relates to the preparation of polyesters from the monomers

Terephthalic acid, 5-sulfoisophthalic acid, alkyl diols or polyalkylene glycols, and polyalkylene glycol monoalkyl ethers and their use in detergents and cleaners, especially in solid dishwashing detergents.

Polyesters of aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, sulfonated aromatic dicarboxylic acids such as sulfoisophthalic acid and diols such as alkylene glycol and their use as "soil release polymer (SRP)" have long been known and described in numerous patents.

In US 4,427,557 are polyester having molecular weights in the range of 2,000 and 10,000 g / mol, prepared from the monomers ethylene glycol (1), polyethylene glycol (2) having molecular weights of 200 to 1000 g / mol, aromatic dicarboxylic acids (3) and alkali metal salts of sulfonated aromatic dicarboxylic acids (4), described and their soil release effect on polyester fabric.

No. 4,702,857 claims polyesters of ethylene glycol, 1,2-propylene glycol or mixtures thereof (1), polyethylene glycol having at least 10 glycol units which is closed at one end by a short-chain alkyl group, in particular by a methyl group (2), a dicarboxylic acid or ester (3) and optionally alkali salts of sulfonated aromatic dicarboxylic acids (4).

No. 4,721,580 discloses polyesters with terephthalate units and sulfo-containing end groups, in particular sulfoethoxylated end groups MO ₃ S (CH ₂ CH ₂ O) _n -H, and praises their use in detergents and fabric softeners. No. 4,968,451 describes polyesters having sulfo-containing end groups, obtained by copolymerization of (meth) allyl alcohol, alkylene oxide, aryldicarboxylic acid and C ₂ -C ₄ glycol and subsequent sulfonation.

In US 5,415,807 it is stated that soil release polymers with sulfonated polyethoxy / propoxy end groups tend to crystallize, resulting in a reduction of the soil release effects. The document teaches that the crystallization tendency of SRP can be suppressed by the addition of hydrotropes.

No. 5,691,298 claims branched backbone soil release polymers comprising diioder polyhydroxysulphonate, terephthalate and 1,2-oxyalkyleneoxy units having nonionic or anionic end groups. In WO 02/18474 non-ionic oligoesters which are flowable at room temperature and their use for cleaning hard surfaces are described. For solid formulations, these oligoesters are unsuitable.

In WO 01/23515, anionic polyesters and their use are claimed for cleaning hard surfaces, characterized in that the polyesters contain sulfo group-containing end groups. These types of polyester are tacky and problematic for solid applications.

In EP 1 035 194, comb-shaped polyesters can be used in detergents and cleaners.

EP 964 015 and US 2002 042 354 describes the use of polyesters, for example of the monomers terephthalic acid, 5-sulfoisophthalic acid, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol and

Polyalkylenglykolmonoalkylether, wherein the Polyalkylenglykolmonoalkylether from Glykoleinheiten> 6 are constructed. These types of polyester are also liquid or sticky. WO 99/09125 discloses detergents and cleaners containing polyesters which contain acetal groups and which are liquid at room temperature.

So far known anionic soil release polymers with sulfo-containing groups are characterized by a good water solubility, but tend to Hygroscopicity and stickiness. A direct grinding of the cooled polyester melt by hammer, sieve or so-called roll mills is not possible. The high intake of water during the grinding process leads to sticking and thus the collapse of the continuous operation. Even though through special, energy-intensive procedures like

Cryo-milling or spray-drying from aqueous solution gives acceptable results, the storage stability of the anionic SRP granules remains limited due to the water absorption capacity.

The object of the present invention was to produce anionic polyesters which are readily soluble in water, exhibit good soil release activity, are compatible with additives and auxiliaries customary in detergents and cleaners, can be incorporated easily into formulations and are resistant to hydrolysis. At temperatures below 60 ^° C., they should be readily and spontaneously soluble in water and fully develop their effect in detergents and cleaners, as well as having an improved cleaning and rinse-aid profile even when the consumption of rinse water is reduced. In addition, they should be able to be assembled without high energy expenditure in the form of storage-stable granules.

It has surprisingly been found that this object is achieved by anionic polyesters which are formally derived from terephthalic acid, 5-sulfoisophthalic acid or the salt of 5-sulfoisophthalic acid, ethylene glycol or polyethylene glycol, propylene glycol or polypropylene glycol and polyalkylene glycol monoalkyl ethers, and optionally of further monomers having 3 to 6 functions capable of polycondensation, in particular acid, alcohol or ester functions.

These anionic polyesters show improved soil release properties, have a very good dissolving behavior and are significantly less susceptible to moisture. It is particularly advantageous that they can be easily obtained by grinding in

Granules are transferred and can be presented in the desired particle size distribution. The invention relates to polyesters containing structural units to 3 or 1 to 4:

(1) PET unit

(2) SIP unit

(3) End plug

- Polyfunctional unit (4) crosslinker

in which

R ¹ independently of one another for H or for a (C ₁ -C -IS) n or iso

Alkyl group, preferably methyl, R ^{2 is} a linear or branched (Ci-C3o) alkyl group or a linear or branched (C ₂ -C ₃₀ ) alkenyl group, for a cycloalkyl group with 5 bis

9 carbon atoms, a (C ₆ -C ₃ o) Arylgruppe- or a (C ₆ -C ₅₀₎

Arylalkyl group, m, n, o independently of one another represent a number from 1 to 200, x, y and z independently of one another represent numbers from 1 to 50, with the proviso that x + y> 2 and z> O, u is a number from 0 to 5, preferably 0 to 0.5 and more preferably from 0 to 0.25, and

Me Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ / 2, Ca ⁺⁺ / 2, Al ⁺⁺⁺ / 3, NH ₄ ⁺ , C ₁ -C ₂₂ -MOnO-, di-, tri- or tetraalkylammonium or C ₂ -C ₁₀ -MOnO-, di-, tri- or

Tetrahydroxyalkylammonium means, with the proviso that the polyesters have a softening point above 40 ⁰ C and a solubility in water with 3 ° German hardness at 20 ⁰ C of more than 6 wt .-%.

A preferred subject of the invention are polyesters, as defined above, wherein R ^{1 is} H and / or methyl, R ^{2 is} methyl, o, m and n is a number from 1 to 200, preferably 1 to 20, particularly preferably 1 to 5, exceptionally preferred o and m = 1 and n can be a number from 2 to 10, x a number between 1 and 30, preferably between 2 and 15, particularly preferably between 3 and 10, y a number between 1 and 25, preferably between 1 to 10, more preferably between 1 and 5 and z is a number between 0.05 and 15, preferably between 0.1 and 10, most preferably between 0.25 and 3 means.

The polyesters according to the invention are obtained by polycondensation of dialkyl terephthalate, dialkyl 5-sulfoisophthalate, alkylene glycols, optionally polyalkylene glycols (at m and / or o> 1) and polyalkylene glycols (end plugs) which are end-capped on one side. It should be pointed out that for numbers m, n, o> 1 there is a polymeric skeleton and thus the coefficients can assume any value in the given interval. This value reflects the number average molecular weight.

For the purposes of the invention, PET unit (1) is understood as meaning the ester of terephthalic acid with one or more difunctional, aliphatic

Alcohols. Preference is given here to ethylene glycol (R ^{1 in} each case H) or 1,2-propylene glycol (R ¹ = H and -CH ₃ ) and / or shorter-chain polyethylene glycols and / or poly [ethylene glycol-co-propylene glycol] with number-average Molecular weights of 100 to 2000 g / mol. Particularly preferred are mixtures of ethylene glycol and propylene glycol. In the structures according to the invention, 1 to 50 PET units can be contained per polymer chain. It is clear to the expert that these are always statistical mean values with a natural distribution that varies from system to system.

For the purposes of the invention, the term "SIP unit (2)" means the ester of 5-sulfoisophthalic acid with one or more difunctional, aliphatic alcohols. Preference is given here to ethylene glycol (R ^{1 in} each case H) or 1,2-propylene glycol (R ¹ = H and -CH ₃ ) or shorter-chain polyethylene glycols having number-average molecular weights of from 100 to 2000 g / mol. Particularly preferred are mixtures of ethylene glycol and propylene glycol. In the structures according to the invention, 1 to 50 SIP units may be present. Here, too, the statements made in the preceding about statistical distributions apply.

As end plug (3) in the context of the invention, all nonionically closed on one side Polyalkylenglykolmonoalkylether according to structural unit (3). Poly [ethylene glycol-co-propylene glycol] monomethyl ethers with average molecular weights of 100 to 2000 g / mol and polyethylene glycol monomethyl ethers of the general formula: CH ₃ -O- (C ₂ H ₄ O) _n -H with n> 1 to 99 are preferably used where n = 1 to 20 is preferably used. Very particular preference is given to polyesters with polyalkylene glycol monoalkyl ethers of the general formula: CH ₃ -O- (C ₂ H ₄ O) _n -H where n = 2 to 10, very preferably n = 3 to 5 as the end group.

Since the theoretical maximum quantitative molecular weight of a polyester structure to be achieved in quantitative conversion is predetermined by the use of end plugs, the amount of structural unit (3) according to the invention is that which is necessary to achieve the average molecular weights according to the invention described above.

In addition to linear polyesters which result from the structural units 1-3 described in the foregoing, are also crosslinked or branched Polyester structures in the context of the invention possible. This is expressed by the presence of a crosslinking polyfunctional structural unit (4) having at least three to a maximum of 6 functional groups capable of esterification reaction. For example, acid, alcohol, ester, anhydride or epoxy groups can be named as functional groups. There are also different functionalities in a molecule within the meaning of the invention.

Citric acid, malic acid, tartaric acid and gallic acid, more preferably 2,2-dihydroxymethylpropionic acid, may be named as preferred examples.

Preference is furthermore given to polyhydric alcohols, such as pentaerythrol, glycerol,

Sorbitol and trimethylolpropane used.

Also preferred are polyhydric aliphatic and aromatic carboxylic acids, such as benzene-1, 2,3-tricarboxylic acid (hemimellitic acid), benzene-1, 2,4-tricarboxylic acid (trimellitic acid), particularly preferably benzene-1, 3,5-tricarboxylic acid

(Trimesithsäure).

The proportion by weight of crosslinking monomers, based on the total mass of the polyesters, is preferably 0 to 10 wt .-%, particularly preferably 0 to 5 wt .-% and particularly preferably 0 to 3 wt .-%.

The polyesters of the invention containing structural units 1, 2 and 3 and optionally crosslinking monomers 4 generally have number average molecular weights in the range 700 to 50,000 g / mol, the number average molecular weight being determined by size exclusion chromatography in aqueous solution using close calibration distributed polyacrylic acid Na salt standards. It should be noted at this point that all molecular weight data in this document refer to the number average molecular weight, even if this is not explicitly named. The number-average molecular weights are preferably in the range from 800 to 25,000 g / mol, in particular from 1,000 to 15,000 g / mol, particularly preferably from 1,200 to 12,000 g / mol.

The molar amounts of the structural unit 3 are chosen so that the number average molecular weights mentioned in the invention are achieved.

The polyesters defined above have softening points above 40 ⁰ C, in particular from 41 to 200 ⁰ C. Preferably, the softening point is between 50 and 200 ° C, more preferably between 80 ° C and 150 ° C and extremely preferably between 100 ⁰ C and 120 ⁰ C. In addition, the polyesters of the invention are characterized by a solubility in water with a German hardness of 3 ° at 20 ° C of more than 6 wt .-%. At 30 ° C, 40 ⁰ C and 50 ° C, the solubility is preferably more than 8 wt .-%, more than 40 wt .-% and also more than 40 wt .-%, also measured in water at 3 ° German hardness.

The advantage of these polyesters is that they remain free-flowing for several months during storage at 0 ⁰ C to 40 ⁰ C and show no stickiness. They are also very soluble in water.

The synthesis of the polyesters of the invention is carried out according to known methods by the above components are heated with the addition of a catalyst initially at atmospheric pressure to temperatures of 160 to about 220 ⁰ C using an inert atmosphere. Then, the required molecular weights are built up in vacuum at temperatures of 160 to about 24O ⁰ C by distilling off stoichiometric amounts of the glycols used. Suitable for the reaction are the known transesterification and condensation catalysts of the prior art, such as, for example, titanium tetraisopropylate, dibutyltin oxide, alkali metal or alkaline earth metal alcoholates or antimony trioxide / calcium acetate. For further details on the implementation of the method, reference is made to EP 442 101. A preferred process for preparing the polyesters according to the invention is characterized in that the condensation of the components is carried out in a one-pot process, wherein the transesterification and condensation catalysts is added prior to heating.

The polyesters according to the invention are of solid consistency and can easily be ground into powder or compacted or agglomerated into granules of defined particle sizes.

The granulation of the polyesters according to the invention can be carried out in such a way that the obtained as a melt in the synthesis copolymers by cooling in a cool gas stream, for example air or nitrogen stream or advantageously by applying to a flaking roll or on a treadmill at 40 to 80 ⁰ C. , preferably 45 to 55 ° C to dandruff or flakes are solidified. This coarse material can be ground, for example, in the roll mill or in the screen mill, which can then be screened. The granulation can also be carried out in such a way that the polyesters according to the invention, after solidification, are ground to give powders with particle sizes <400 .mu.m and subsequently converted into granules having defined particle sizes by compaction or agglomeration.

For specific embodiments, it may also be advantageous to dissolve the melt or solidified flakes in water and aqueous solutions with concentrations of 1 to 99 wt .-% of polyester in the spray tower at inlet temperatures of 150 to 180 ⁰ C and outlet temperatures of 80 to granulate to 120 ° C under atmospheric pressure in the fluidized bed.

The grain size of the granules produced in this way is generally in the range of 100 microns - 2000 microns, preferably 200 microns - 1800 microns, more preferably 300 microns - 1000 microns. The bulk density is in the range of 400 to 700 kg / m ³ . The invention furthermore relates to the use of the polyesters according to the invention in detergents and cleaners, textile care agents and agents for finishing textiles. The polyesters according to the invention impart significantly improved soil release properties to the textile fibers and substantially support the soil release properties of the remaining detergent ingredients in relation to oily, greasy or pigmentary stains. It may also be advantageous to use the polyesters according to the invention in after-treatment compositions for the laundry, for example in a fabric softener.

The washing and cleaning agent formulations in which the polyesters according to the invention can be used are pulverulent, granular, paste, gel or liquid.

Examples include heavy duty detergents, mild detergents, color washing medium,

Wool detergents, curtain washes, kit detergents, washing tablets, bar soaps, spot salts, laundry starches and stiffeners, ironing aids. The polyesters of the present invention may also be used in household cleaners, for example all-purpose cleaners, dishwashing detergents, carpet cleaners and impregnators, soil cleaners and conditioners, and other hard surfaces, e.g. made of plastic, ceramic, glass or nanotechnology coated surfaces.

Examples of technical cleaning agents are plastic cleaning and care products, such as for housings and car fittings, as well as cleaning and care products for painted surfaces such as car bodies.

The washing, care and cleaning agent formulations according to the invention contain at least 0.1% by weight, preferably between 0.1 and 10% by weight and more preferably 0.2 to 3% by weight, of the polyesters according to the invention, based on the finished polyester Medium. Depending on their intended use, the formulations should be adjusted in their composition to the type of textiles to be treated or washed.

The detergents and cleaning agents according to the invention can be used commonly

Ingredients, such as surfactants, emulsifiers, builders, bleach catalysts and activators, sequestering agents, grayness inhibitors,

Color transfer inhibitors, color fixatives, enzymes, optical brighteners, softening component. In addition, formulations or parts of the formulation according to the invention can be dyed and / or perfumed by dyes and / or fragrances targeted.

The total concentration of surfactants in the final detergent formulation may be from 1 to 99%, and preferably from 5 to 80% (all wt%). The surfactants used may be anionic, nonionic, amphoteric and cationic. It is also possible to use mixtures of the surfactants mentioned. Preferred washing and cleaning agent formulations contain anionic and / or nonionic surfactants and mixtures thereof with other surfactants.

Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof. Suitable cations here are alkali metals, e.g. Sodium or potassium or alkaline earth metals, such as. Calcium or magnesium and ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, and mixtures thereof. The following types of anionic surfactants are of particular interest:

Alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkane sulfonates, and soaps, as described below.

Alkyl ester sulfonates include linear esters of C ₈ -C ₂ o-carboxylic acids (ie, fatty acids) which are sulfonated with gaseous SO _3, as in "The Journal of the American OiI Chemists Society," 52 (1975), pp. 323-329 becomes. Suitable starting materials are natural fats such as tallow, coconut oil and palm oil, but may also be synthetic in nature. Preferred alkyl ester sulfonates, especially for detergent applications, are compounds of the formula

R ¹ CH COOR

I

wherein R ^{1 is} a C ₈ -C 20 -hydrocarbon radical, preferably alkyl, and R is a C ₁ -C 6 hydrocarbon radical, preferably alkyl. M is a cation which forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine,

Diethanolamine and triethanolamine. Preferably, R ¹ Cio-Ci ₆ alkyl, and R is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates in which R ^{1 is} C ₁₀ -C ₆ -alkyl.

Alkyl sulfates are here water-soluble salts or acids of the formula ROSO ₃ M, where R is a Cio-C ₂₄ hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with Cio-C ₂ o-alkyl, particularly preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl is. M is hydrogen or a cation, eg an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium, e.g. For example, methyl, dimethyl and

Trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. Alkyl chains with Ci ₂ -Ci ₆ are for low washing temperatures (eg below about 50 ⁰ C) and alkyl chains with Ci ₆ -Ci ₈ for higher washing temperatures (eg above about 5O ⁰ C) are preferred.

Alkyl ether sulfates are water soluble salts or acids of the formula RO (A) _m SO ₃ M wherein R is an unsubstituted Cio-C ₂₄ alkyl or hydroxyalkyl group, preferably a C ₂ -C _2O alkyl or hydroxyalkyl, more preferably C ₂ - C ₈ Alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy unit, m is a number greater than 0, preferably between about 0.5 and about 6, more preferably between about 0.5 and about 3 and M is a hydrogen atom or a cation such as. For example, sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples which may be mentioned are C ₂ - to C 18 -fatty alcohol ether sulfates where the content of EO is 1, 2, 2.5, 3 or 4 mol per mol of the fatty alcohol ether sulfate and in which M is sodium or potassium.

In secondary alkanesulfonates, the alkyl group may be either saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group. The sulfo group can be at any position of the C chain, with the primary methyl groups at the beginning and end of the chain having no sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably about 10 to about 20 carbon atoms, and more preferably about 13 to 17 carbon atoms. The cation is, for example, sodium, potassium, ammonium, mono-, di- or

Triethanolammonium, calcium or magnesium, and mixtures thereof. Sodium as a cation is preferred.

In addition to secondary alkanesulfonates, it is also possible to use primary alkanesulfonates in the detergents and cleaners according to the invention.

The preferred alkyl chains and cations are the same as those of the secondary alkanesulfonates.

The preparation of primary alkanesulfonic acid, from which the corresponding sulfonates effective as surfactant are obtained, is described, for example, in EP 854 136-A1. Other suitable anionic surfactants are alkenyl or alkylbenzenesulfonates. The alkenyl or alkyl group may be branched or linear and optionally substituted with a hydroxyl group. The preferred alkylbenzenesulfonates contain linear alkyl chains having about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation is sodium, potassium, ammonium,

Mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. For mild surfactant systems, magnesium is preferred as a cation, whereas sodium is preferred for standard washing applications. The same applies to alkenylbenzenesulfonates.

The term anionic surfactants also includes olefin sulfonates obtained by sulfonation of C ₁₂ -C ₂₄ , preferably Cu-C-iβ-α-olefins with sulfur trioxide and subsequent neutralization. Due to the preparation process, these olefin sulfonates may contain minor amounts of hydroxyalkanesulfonates and alkanedisulfonates. Specific mixtures of α-olefin sulfonates are described in US-3,332,880.

Other preferred anionic surfactants are carboxylates, e.g. Fatty acid soaps and comparable surfactants. The soaps may be saturated or unsaturated and may contain various substituents such as hydroxyl groups or α-sulfonate groups. Preferably, linear saturated or unsaturated carbons are hydrogen radicals as the hydrophobic portion having from about 6 to about 30, preferably about 10 to about 18 carbon atoms.

Also suitable as anionic surfactants are salts of acylaminocarboxylic acids which are acylsarcosinates formed by reaction of fatty acid chlorides with sodium sarcosinate in an alkaline medium; Fatty acid-protein condensation products obtained by reaction of fatty acid chlorides with oligopeptides; Salts of alkylsulfamidocarboxylic acids; Salts of alkyl and alkylaryl ether carboxylic acids; C ₈ -C ₂₄ olefinsulfonates, sulfonated

Polycarboxylic acids prepared by sulfonation of the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB-1, 082,179; Alkyl glycerol sulfates, oleyl glycerol sulfates, alkyl phenol ether sulfates, primary paraffin sulfonates, Alkyl phosphates, Alkyϊetherphosphate, isethionates such as the acyl isethionates, N-Acy tauride!, Alkyl succinates, sulfosuccinates, Monoester of sulfosuccinates (especially saturated and unsaturated Ci2-Ci ₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₈ diesters ), Acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and

Alkylpolyethoxycarboxylates such as those of the formula RO (CH ₂ CH ₂ ) _k CH ₂ COO ^" M ⁺ , wherein R is C ₈ to C ₂₂ alkyl, k is a number from 0 to 10 and M is a cation, resin acids or hydrogenated resin acids, such as Rosin or hydrogenated rosin or tall oil resins and tall oil rosin acids.

As non-ionic surfactants, for example, the following compounds come in

Question:

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.

These compounds include the condensation products of alkylphenols having a C ₆ to C ₂ o alkyl group, which may be either linear or branched, with alkene oxides. Preference is given to compounds having about 5 to 25 mol of alkene oxide per mole of alkylphenol. Commercially available surfactants of this type include Igepal ^® CO-630, Triton ^® X-45, X-114, X-100 and X102, and the ^® Arkopal N trademarks of Clariant (Germany) GmbH. These surfactants are referred to as Alkylphenolalkoxilate, eg Alkylphenolethoxilate.

Condensation products of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide.

The alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of C ₁₀ - to C ₂ o-alcohols with about 2 to about 18 moles of ethylene oxide per mole of alcohol. The alkyl chain can be saturated or unsaturated. The alcohol ethoxylates may have narrow ("narrow range ethoxylates") or a broad homolog distribution of ethylene oxide ("broad range ethoxylates"). Examples of commercially available nonionic surfactants of this type are Tergitol ^® 15-S-9 (the condensation product of a linear secondary Cn-Cis-alcohol with 9 moles ethylene oxide), Tergitol ^® 24-L-NMW (the condensation product of a linear primary C ₂ -C ₄ alcohol with 6 mol Ethylene oxide with narrow molecular weight distribution). Also included in this product class are the Genapol ^® brands from Clariant Products (Germany) GmbH.

Condensation products of ethylene oxide having a hydrophobic base formed by condensation of propylene oxide with propylene glycol.

The hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800. The addition of ethylene oxide to this hydrophobic part leads to an improvement in water solubility. The product is liquid up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to a condensation with up to about 40 moles of ethylene oxide. Commercially available examples of this product class are the Pluronic ^® brands from BASF and the ^® Genapol PF brands from Clariant Products (Germany) GmbH.

Condensation products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.

The hydrophobic moiety of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of about 2500 to 3000. Ethylene oxide is added to this hydrophobic unit to a content of about 40 to about 80 wt .-% polyoxyethylene and a molecular weight of about 5000 to 11000. Commercially available examples of this class of compounds are the ^® Tetronic brands of BASF and the ^® Genapol PN brands of Clariant Products (Germany) GmbH. Semipolar nonionic surfactants

This category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides, and water-soluble sulfoxides each having an alkyl group of about 10 to about 18 carbon atoms. Semi-polar nonionic surfactants are also amine oxides of the formula

O

▲

R (OR?) _Χ N (R ¹⁾ ₂

R here is an alkyl, hydroxyalkyl or alkylphenol group having a chain length of about 8 to about 22 carbon atoms, R ² is an alkylene or hydroxyalkylene group having about 2 to 3 carbon atoms or mixtures thereof, each R ¹ is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms or a polyethylene oxide group having about 1 to about 3 ethylene oxide units and x represents a number from 0 to about 10. The R ¹ groups may be bonded to each other via an oxygen or nitrogen atom be and thus form a ring. Amine oxides of this type are especially C 1 -C ₈ -alkyldimethylamine oxides and C 6 -C 12 -alkoxyethyl-dihydroxyethylamine oxides.

fatty acid amides

Fatty acid amides have the formula o

RCN (R ¹ ) ₂

wherein R is an alkyl group having about 7 to about 21, preferably about 9 to about 17 carbon atoms and each radical R ^{1 is} hydrogen, Ci-C ₄ alkyl, CVC ₄ - hydroxyalkyl or (CaH ₄ O) _x H means where x varies from about 1 to about 3. Preferred are

monoethanolamides, diethanolamides and isopropanolamides.

Further suitable nonionic surfactants are alkyl and alkenyl oligoglycosides and also fatty acid polyglycol esters or fatty amine polyglycol esters each having 8 to 20, preferably 12 to 18 C atoms in the fatty alkyl radical, alkoxylated triglycamides, mixed ethers or mixed formyls, alkyl oligoglycosides, alkenyl oligoglycosides, fatty acid N-alkylglucamides, phosphine oxides, dialkyl sulfoxides and protein hydrolysates.

Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amide betaines, aminopropionates, aminoglycinates, or amphoteric imidazolinium compounds of the formula

R ³

R ¹ CON (CH ₂ ), ^ ⁺ -CH ₂ Z

4 2

R R

wherein R ^{1 is} C ₈ -C ₂₂ alkyl or alkenyl, R ^{2 is} hydrogen or CH ₂ CO ₂ M, R ^{3 is} CH ₂ CH ₂ OH or CH ₂ CH ₂ OCH ₂ CH ₂ CO ₂ M, R ^{4 is} hydrogen, CH ₂ CH ₂ OH or CH ₂ CH ₂ COOM, Z is CO ₂ M or CH ₂ CO ₂ M, n is 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonium or alkanolammonium.

Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples of these are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate) and cocoamphoacetate.

Further preferred amphoteric surfactants are alkyldimethylbetaines and alkyldipolyethoxybetaines having an alkyl radical of from about 8 to about 22 carbon atoms, which may be linear or branched, preferably having from 8 to 18 carbon atoms and more preferably from about 12 to about 18

Carbon atoms. These compounds are marketed, for example, from Clariant (Germany) GmbH under the trade name ^® Genagen LAB. Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R ¹ N (CH ₃ ) ₃ ^p X ^σ , R ¹ R ² N (CH ₃ ) ₂ ^p X ^σ , R ¹ R ² R ³ N (CH ₃ ) ^p X ^σ or R ¹ R ² R ³ R ⁴ N ^p X ^σ . The radicals R ¹ , R ² , R ³ and R ⁴ may preferably independently of one another unsubstituted alkyl having a chain length between 8 and 24 carbon atoms, in particular between 10 and 18 carbon atoms, hydroxyalkyl having from about 1 to about 4 C Atoms, phenyl, C ₂ - to C ₈ -alkenyl, C ₇ - to C ₂₄ -aralkyl, (C ₂ H ₄ O) _x H, where x is from about 1 to about 3, one or more ester groups-containing alkyl radicals or cyclic quaternary ammonium salts. X is a suitable anion.

In preferred embodiments, the detergents and cleaners of the invention comprise linear alkylbenzene sulfonate. The preferred alkylbenzenesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation being sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. For mild surfactant systems, magnesium is preferred as a cation, whereas sodium is preferred for standard washing applications.

In likewise preferred embodiments, the detergents and cleaners according to the invention contain secondary alkanesulfonates having linear alkyl chains with about 9 to 25 carbon atoms, preferably about 10 to about 20 carbon atoms and more preferably about 13 to 17 carbon atoms. The cation is, for example, sodium, potassium, ammonium, mono-, di- or

Triethanolammonium, calcium or magnesium, and mixtures thereof. Sodium as a cation is preferred

In equally preferred embodiments, the inventive washing and cleaning agents contain alkyl ether sulfates of the formula RO (A) _m SO ₃ M wherein R is an unsubstituted C _O -C ₂₄ alkyl or hydroxyalkyl group, preferably a C ₂ - C ₂ o alkyl or Hydroxyalkyl, more preferably C | C ₂ -C ₈ alkyl or hydroxyalkyl. A is an ethoxy or propoxy moiety, m is a number greater than 0, preferably between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is a hydrogen atom or a cation such as, for example, , For example, sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples which may be mentioned are C _12- to cis-fatty alcohol ether sulfates where the content of EO is 1, 2, 2.5, 3 or 4 mol per mol of the fatty alcohol ether sulfate and in which M is sodium or potassium.

Suitable emulsifiers are adducts of 0 to 30 mol

Alkylene oxide, in particular ethylene, propylene and / or butylene oxide to linear or branched, saturated or unsaturated fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms, to alkylphenols having 8 to 15 carbon atoms in the Alkyl group and sorbitan ester;

(Ci ₂ -Ci ₈ ) fatty acid mono- and diesters of addition products from 0 to 30

Moles of ethylene oxide with glycerol;

Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and optionally their ethylene oxide addition products;

Addition products of 5 to 60 mol, preferably 15 to 60 mol, of ethylene oxide with castor oil and / or hydrogenated castor oil;

Polyol and especially polyglycerol esters, e.g. Polyglycerol polyricinoleate and polyglycerol poly-12-hydroxy stearate.

Preference is given to liquid fatty acid esters which may be both ethoxylated (PEG-10 polyglyceryl-2 laurate) and non-ethoxylated (polyglyceryl-2 sesquiisostearate).

Further preferred mixtures according to the invention contain sorbitol esters prepared by reaction of sorbitol with fatty acid methyl esters or fatty acid triglycerides. The fatty acid residue in the fatty acid methyl esters and fatty acid triglycerides generally contains 8 to 22 carbon atoms and may be straight-chain or branched, saturated or unsaturated. Examples of these are palmitic acid, stearic acid, lauric acid, linoleic acid, linolenic acid, isostearic acid or oleic acid. Suitable fatty acid triglycerides are all native animal or vegetable oils, fats and waxes, for example Olive oil, rapeseed oil, palm kernel oil, sunflower oil, coconut oil, linseed oil, castor oil, soybean oil, optionally also in a refined or hydrogenated form. Since these natural fats, oils and waxes are usually mixtures of fatty acids with different chain lengths, this also applies to the fatty acid residues in the sorbitol esters used according to the invention. The sorbitol esters used according to the invention may also be alkoxylated, preferably ethoxylated. In addition, it is possible to use anionic emulsifiers, such as ethoxylated and nonethoxylated mono-, di- or tri-phosphoric esters, but also cationic emulsifiers, such as mono-, di- and tri-alkyl quats and their polymeric derivatives.

Also suitable are mixtures of compounds of several of these classes of substances.

Other detergent and cleaner ingredients used in the present

The invention may include inorganic and / or organic builders to reduce the degree of hardness of the water.

These builders can be included in the detergent and cleaner compositions at levels of from about 5 to about 80 percent by weight. Inorganic builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.

Examples of silicate builders are the alkali metal silicates, in particular those having a SiO ₂ : Na ₂ O ratio of between 1.6: 1 and 3.2: 1, and phyllosilicates, for example sodium phyllosilicates, as described in US Pat. No. 664,839, available from Clariant Products (US Pat. Germany) GmbH under the brand SKS ^® . SKS- ^6® is a particularly preferred phyllosilicate builder. Aluminosilicate builders are particularly preferred for the present invention. These are, in particular, zeolites of the formula Na _z [(AIO ₂ ) z (SiO 2) y] x H 2 O, where z and y are integers of at least 6, the ratio of z to y is between 1, 0 and about 0, 5, and x is an integer from about 15 to about 264.

Suitable aluminosilicate-based ion exchangers are commercially available. These aluminosilicates may be of crystalline or amorphous structure, and may be naturally occurring or synthetically produced. Methods for the preparation of aluminosilicate-based exchangers are described in US-3,985,669 and US-4,605,509 Preferred ion exchange resins based on synthetic crystalline aluminosilicates are available under the designation zeolite A, zeolite P (B) (including those described in EP-AO 384,070) and zeolite X. Preference is given to aluminosilicates having a particle diameter of between 0.1 and 10 μm.

Suitable organic builders include polycarboxylic compounds such as ether polycarboxylates and oxydisuccinates as described, for example, in U.S. 3,128,287 and U.S. 3,635,830. Reference should also be made to "TMS / TDS" builders from US 4,663,071.

Other suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as e.g. Ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylic acids such as mellitic acid, succinic acid, oxydibemic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.

Citrate-based builders, eg, citric acid and its soluble salts, especially the sodium salt, are preferred polycarboxylic acid builders can also be used in granulated formulations, in particular together with zeolites and / or sheet silicates.

Other suitable builders are the 3,3-dicarboxy-4-oxa-1, 6-hexanedioates and the related compounds disclosed in US 4,566,984.

If phosphorus-based builders can be used, and particularly if laundry soap bars are to be manually formulated, various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate can be used. Also, phosphonate builders such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates such as disclosed in U.S. 3,159,581, U.S. 3,213,030, U.S. 3,422,021, U.S. 3,400,148 and U.S. 3,422,137 can be used ,

The detergent compositions of the present invention may optionally contain one or more conventional bleaching agents, as well as activators or stabilizers, especially peroxyacids, which do not react with the inventive polyesters. The peroxyacid can be either a free peroxyacid, or a

A combination of an inorganic persalt, for example, sodium perborate or sodium percarbonate and an organic peroxyacid precursor, which is converted to a peroxyacid when the combination of the persalt and the peroxyacid precursor is dissolved in water. The organic peroxyacid precursors are often referred to in the art as bleach activators.

Examples of peroxyacids preferred for use in this invention include peroxydodecanedioic acid (DPDA), nonylamide of peroxysuccinic acid (NAPSA), nonylamide of peroxyadipic acid (NAPAA) and decyldiperoxy succinic acid (DDPSA). The peroxyacid is preferably contained in a soluble granule, according to the method of US 4,374,035. A preferred bleach granule contains, in weight percent, 1% to 50% of a exothermic soluble compound such as boric acid; 1% to 25% of a peroxyacid-compatible surfactant such as C13LAS; 0.1% to 10% of one or more chelate stabilizers, such as sodium pyrophosphate; and 10% to 70% of a water-soluble salt, such as sodium sulfate.

The peroxyacid bleach is used in amounts that provide an amount of available oxygen between about 0.1% to about 10%, preferably between about 0.5% to about 5%, more preferably from about 1% to 4%. The percentages are based on the total weight of the detergent composition.

Suitable amounts of peroxyacid bleach, based on a unit dose of the detergent compositions of the present invention used for a typical wash liquor comprising about 65 liters of water at 15 to 60 ^° C, will produce between about 1 ppm to about 150 ppm available oxygen, preferably between about 2 ppm to about 20 ppm of available oxygen. The wash liquor should have a pH between 7 and 11, preferably between 7.5 and 10.5, to achieve a sufficient bleaching result. Reference is made to column 6, lines 1 to 10 of US 4,374,035.

Alternatively, the bleach composition may contain a suitable organic peroxyacid precursor which produces one of the above peroxyacids when reacted with hydrogen peroxide in aqueous alkaline solution. The source of hydrogen peroxide may be any inorganic peroxide that releases hydrogen peroxide in aqueous solution, such as sodium perborate (monohydrate and tetrahydrate) and sodium percarbonate.

Available as bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxy-benzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU). , Tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxine (ADMG) and 1-phenyl-3-acetylhydantoin (PAH), Nonanoylcaprolactam phenylsulfonate ester (APES), nonanoylphenylsulphonate ester (NOPS), nitrilotriacetate (NTA) and ammonium nitriles.

The detergent and cleaner compositions of the invention may contain one or more conventional enzymes. Such enzymes include lipases, amylases, proteases, cellulases. Pullinases, cutinases, peroxidases. Proteases available BLAP ^®, Opti Clean ^®, Maxacal ^®, Maxapem ^®, Esperase ^®, Savinase ^®, Purafect ^®, OxP and / or Duraxym ^®, of amylases Termamyl ^®, amylase LT ^®, Maxamyl ^®, Duramyl ^® and / or Pruafect ^® OxAm to lipases, Lipolase ^®, Lipomax ^®, Lumafast ^® and / or Lipozym ^®.

A preferred enzyme is cellulase. The cellulase used here can be obtained from bacteria or fungi and should have an optimum pH range between 5 and 9.5. Preferred cellulases are described in WO-91/17243.

Likewise preferred enzymes are lipases, which, as fat-splitting enzymes, allow a better detachment of native oils and fats from soiled fabrics and thus support the effect of the polyesters according to the invention, it generally being possible to achieve additive as well as synergistic effects.

The enzymes can be adsorbed to carrier substances and / or embedded in encapsulating substances.

Based on the weight of the detergent compositions containing the polyesters according to the invention, the proportion of enzymes is at least 0.001% by weight, preferably between about 0.001 to about 5% by weight, in particular from about 0.001 to about 1% by weight. %, especially from about 0.01 to about

1% by weight.

Sodium tripolyphosphate (STPP), ethylenediaminetetraacetic acid (EDTA), salts, nitrilotriacetic acid (NTA) are available as sequestering agents.

Polyacrylate, phosphonate, oxalic acid, salt, citric acid, zeolite, condensed

Phosphates, carbonates, polycarbonates. Suitable graying inhibitors are carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and polyvinyl pyrrolidone.

Color transfer inhibitors are also suitable, for example polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), eg Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, eg Sokalan ^® HP 50 / Fa. BASF, and copolymers of N-vinylpyrrolidone with N-vinylimidazole, and optionally other monomers

The invention includes detergents and cleaning agents containing color fixing agents as active substances, for example color fixing agents obtained by reacting diethylenetriamine, dicyandiamide and amidosulfuric acid, amines with epichlorohydrin, for example dimethylaminopropylamine and epichlorohydrin or dimethylamine and epichlorohydrin or dicyandiamide, formaldehyde and ammonium chloride, or dicyandiamide , Ethylenediamine and formaldehyde or cyanamide with amines and formaldehyde or polyamines with cyanamides and amidosulfuric acid or cyanamides with aldehydes and ammonium salts, but also polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), eg Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, eg Sokalan ^® HP 50 / Fa. BASF, and copolymers of N-vinylpyrrolidone with N-vinylimidazole, and optionally other monomers.

The washing and cleaning agents according to the invention may complexing agents, for example aminocarboxylates, such as ethylenediaminetetraacetate,

N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediamine tetrapropionate,

Triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate,

Cyclohexanediaminetetraacetate, phosphonates, for example

Azacycloheptane diphosphonate, Na salt, pyrophosphates, etidronic acid (1-hydroxyethylidene-1, 1-diphosphonic acid, 1-hydroxyethane-1, 1-diphosphonic acid, acetophosphonic acid) and their salts, aminophosphonates, such as

Ethylenediaminetetrakis (methylenephosphonate),

Diethylene triamine pentakis (methylene phosphonate), amine trimethylene phosphonic acid, Cyclodextrins, as well as polyfunctionally substituted aromatic complexing agents, such as dihydroxydisulfobenzene or ethylenediaminedisuccinates.

Cyclic hydrocarbons such as distyrylbenzenes, distyrylbiphenyls, diphenylstilbenes, triazinylaminostilbenes, stilbenyl-2H-triazoles, for example stilbenzyl-2H-naphthol [1,2-d] triazoles and bis (1,2,3-triazole-2-yl) can be used as optical brighteners -yl) stilbenes, benzoxazoles, for example stilbenylbenzoxazole and bis (benzoxazole), furans, benzofurans and benzimidazoles, for example bis (benzo [b] furan-2-yl) biphenyl and cationic benzimidazoles, 1,3-diphenyl-2-pyrazoline, coumarin , Naphthalimides, 1,3,5-2-yl derivatives, methine cyanine and dibenzothiophene-5,5-oxide.

Preference is given to anionic optical brighteners, in particular sulfonated compounds.

Also suitable are triazinylaminostilbenes, distyrylbiphenyls and mixtures thereof, 2- (4-styrylphenyl) -2H-naphtho [1,2-d] triazole, 4,4'-bis (1,2,3-triazole-2-ol) yl) stilbene, aminocoumarin, 4-methyl-7-ethylaminocoumarin, 1, 2-bis (benzimidazol-2-yl) ethylene, 1, 3-diphenyl-phrazoline, 2,5-bis (benzooxazol-2-yl) -thiophene, 2- Strylnaphtho [1,2-d] oxazole, 2- (4-styryl-3-sulfophenyl) -2H-naphtho [1,2-d] triazole and 2- (stilben-4-yl) -2H-naphthol 1, 2-d] triazole

The detergents according to the invention may contain optical brighteners in amounts of 0.001% by weight to 2% by weight, preferably 0.002% by weight to 0.8% by weight, particularly preferably 0.003% by weight to 0.4% by weight. % contain.

As softening components are quaternary ammonium salts of the type

R, R '

, N ^"1

X ^'

R ³ R ⁴

where R ¹ = C ₈ -C ₂₄ n- or iso-alkyl, preferably C ₁₀ -C ₈ n-alkyl R ² = C ₁ -C ₄ alkyl, preferably methyl

R ³ = R ¹ or R ²

R ⁴ = R ² or hydroxyethyl or hydroxypropyl or their oligomers

X ^" = bromide, chloride, iodide, methosulfate, acetate, propionate, lactate.

Examples thereof are distearyldimethylammonium chloride, ditallowalkyldimethylammonium chloride, ditallowalkylmethylhydroxypropylammonium chloride, cetyltrimethylammonium chloride or the corresponding benzyl derivatives such as dodecyldimethylbenzylammonium chloride. Cyclic quaternary ammonium salts such as alkyl morpholine derivatives can also be used.

In addition, besides the quaternary ammonium compounds, imidazolinium compounds (1) and imidazoline derivatives (2) can be used.

N ^ N-CH ₂ -CH ₂ -AR (2)

I R

wherein

R = C ₈ -C ₂₄ n- or iso-alkyl, preferably Ci ₀ -Ci ₈ n-alkyl

X = bromide, chloride, iodide, methosulfate

A is -NH-CO-, -CO-NH-, -O-CO-, -CO-O-.

A particularly preferred class of compounds are the so-called ester quats. These are reaction products of alkanolamines and Fatty acids which are then quaternized with conventional alkylating or hydroxyalkylating agents.

Preferred alkanolamines are compounds according to the formula

R ² R ⁱ - N

* With

R ¹ = Ci-C ₃ hydroxyalkyl, preferably hydroxyethyl and

R ² , R ³ = R ¹ or C ₁ -C ₃ alkyl, preferably methyl.

Particularly preferred are triethanolamine and methyldiethanolamine.

Further particularly preferred starting materials for esterquats are

Aminoglycerol derivatives, e.g. Dimethylaminopropanediol.

Alkylating or hydroxyalkylating agents are alkyl halides, preferably

Methyl chloride, dimethyl sulfate, ethylene oxide and propylene oxide.

Examples of esterquats are compounds of the formulas:

O ∈ RC- (OCH ₂ CH ₂ ) _n OCH ₂ CH _{2 CH} n N © ^ ci Θ

/ \

RC- (OCH ₂ CH ₂ ) _n O-CH ₂ CH ₂ ^CH 3

II RC- (OCH ₂ CH ₂ ) _n O-CH ₂ CH ₂ CH ₂ CH ₂ O (CH ₂ CH ₂ O) -CR

Il / \

RC- (OCH ₂ CH ₂ ) _n O-CH ₂ CH ₂ ^/ CH ₃ CH ₃ -O-SO ₃ © RC- (OCH ₂ CH ₂ ) - O-CH -

wherein RCO is derived from C ₈ -C ₂ 4 fatty acids, which may be saturated or unsaturated. Examples of these are caproic acid, caprylic acid, hydrogenated or not or only partially hydrogenated tallow fatty acids, stearic acid, oleic acid, linolenic acid, behenic acid, palminstearic acid, myristic acid and elaidic acid. n is in the range of 0 to 10, preferably 0 to 3, particularly preferably 0 to 1. Further preferred fabric softener raw materials with which the inventive polyesters can be combined are amidoamines based on, for example, dialkyltriamines and long-chain fatty acids, and their ethoxylates or quaternized variants. These compounds have the following structure:

R ¹ - A - (CH _{2) n} - N - (CHa) _n - A - R ²

I (CH ₂ -CH ₂ -O-) _m -H

in which R ¹ and R ² independently of one another are Cs - C ₂ 4 n- or iso-alkyl, preferably Ci ₀ -

Ciδ n-alkyl,

A is -CO-NH- or -NH-CO-, n is 1-3, preferably 2, m is 1-5, preferably 2-4.

By quaternization of the tertiary amino group may additionally be a radical R ³ , which may be C 1 -C ₄ -alkyl, preferably methyl, and a counterion X, which

Chloride, bromide, iodide or methyl sulfate can be introduced.

Amidoaminooxethylate or their quaternized secondary products are among the Trade names Varisoft ^® 510 ^® Varisoft 512 ^® Rewopal V 3340 and ^® Rewoquat W 222 LM offered.

The preferred use concentrations of the polyesters used in the softener formulations according to the invention correspond to those mentioned for detergent formulations.

The detergents and cleaning agents according to the invention preferably contain dyes and fragrances or perfumes.

Preferably used are solutions or emulsions of the abovementioned fragrances and perfume oils, which can be prepared by customary methods.

Another object of the invention are solid dishwashing detergents containing the above-defined polyester. These are means for cleaning glass, porcelain, cutlery, metal and plastic items in the machine. The polyesters according to the present invention cause a very good flow behavior of the rinse or rinse water on the surfaces of said article. This shortens the drying time in the

Dishwasher and one reaches a residue-free and stain-free dishes. In addition, these polyesters are very soluble in water and thus allow a reduction in the amount of rinse water.

The content of the polyester used in solid according to the invention

Dishwashing detergent formulations for the machine can vary within wide limits and is generally from 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, particularly preferably 1 to 3 wt .-% based on the respective formulation.

The solid dishwashing detergents according to the invention for the machine can be presented as powders, granules or in the form of tablets. The preparation of the solid dishwashing detergents according to the invention presents no difficulties and can be carried out in a known manner. The powders or granules according to the invention can be prepared by simply mixing the powdered or granulated polyester with the other ingredients of the dishwashing detergent formulation in the appropriate amounts.

The solid dishwashing detergents according to the invention can also be presented as extruded shaped bodies. In this case, a solid and substantially free-flowing mixture of the ingredients or a part of the ingredients of the dishwashing formulation is extruded under pressure strand and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension.

A preferred embodiment of the invention are dishwashing detergents in tablet form, which may be single-phase or multi-phase, single-color or multi-color and in particular consist of one or more layers, in particular two layers.

It is preferably such that all components - optionally one layer - mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric presses or

Pressed rotary presses. Particularly in the case of multilayer tablets, it can be advantageous if at least one layer is pre-compressed. Preferably, a tablet produced in this way has a weight of from 10 g to 50 g, in particular from 15 g to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of rectangular or cuboid-shaped tablets, which are predominantly introduced via the metering device, for example the dishwasher, is dependent on the geometry and the volume of these

Dosing. Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26 x 36 mm or 24 x 38 mm. The dishwashing detergents according to the invention in tablet form may contain tablet disintegrating agents. Suitable substances such as starch, cellulose and cellulose derivatives, alginates, dextrans, cross-linked polyvinylpyrrolidones, and systems of weak acids and carbonate-containing agents, such as citric acid and tartaric acid in combination with bicarbonate or carbonate, but also finely divided and swellable phyllosilicates of the type Bentonites and smectites. Also contributing to gas formation substances such as citric acid, bisulfate, bicarbonate, carbonate and percarbonate can be used as a possible disintegrants.

The tablet disintegrants are mixed in very finely divided form either before pressing with the other tablet ingredients, which may be finely divided or granular, but also liquid to pasty, or the other tablet ingredients are coated or powdered with the tablet disintegrant.

The solid dishwashing detergents according to the invention comprise the customary constituents selected essentially from surfactants, preferably nonionic surfactants, enzymes, amino acids and salts, builders, co-builders, bleaches, organic acids, hydrotropes, colorants and perfumes, further specific auxiliaries and additives such as antioxidants, zeolites, salts, bleach activators, bleach catalysts, photoactive metal oxides, photoactive nanoparticles, photoactivators, enzyme stabilizing additives, fungicides, bactericides, scale inhibitors, antistatic additives, foam regulators, dye transfer inhibitors, odor scavengers, polymers, pigments, pH control agents, agents for UV absorption, optical brighteners, dispersing, complexing, preserving and glass corrosion agents.

In the Geschirreinigungsmitteln for the machine low-foam connections are preferred. These are especially nonionic surfactants, preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 22 carbon atoms and an average of 1 to 25 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in the 2-position may be methyl branched or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 10 to 20 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 18 EO per mole of alcohol are preferred. The degree of ethoxylation represents a statistical average, which may be a whole or fractional number for a particular product. The alcohol ethoxylates may have a narrowed or broad homolog distribution of ethylene oxide (narrow rank ethoxylates or broad rank ethoxylates). This class of product includes the Genapol ^® TM grades from Clariant (Germany) GmbH.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Another class of nonionic surfactants that can be used advantageously are alkyl polyglycosides (APG), for example those of the general formula RO (G) ₂ , in which R is a linear or branched, in particular 2-methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a glycose unit having 5 or 6 carbon atoms, preferably for glucose. Of the

Glycation z is between 1 and 4, preferably between 1 and 2. Preferably used are linear alkyl polyglycosides, ie alkyl polyglycosides which consist of a glycerol residue and an n-alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and fatty acid alkanolamides may also be suitable. The amount of this nonionic Surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half thereof.

Also suitable are nonionic surfactants of the general formula

the alternating ethylene oxide and Alkylenoxideinheiten, preferably propylene oxide units and the EO and AO units may be randomly distributed or arranged in blocks. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows and the indices x and y independently stand for integers from 1 to 10. Nonionic surfactants that can be used with particular preference are available, for example under the tradename Genapol ^® ED products from Clariant (Germany) GmbH.

Further suitable surfactants are polyhydroxy fatty acid amides of the general formula

R1 R-CO N- [Z]

in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxy groups. The polyhydroxy fatty acid amides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent Acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained.

The group of polyhydroxy fatty acid amides also includes compounds of the following formula

O-R2

R1 I R -CO N- [Z]

R is a linear or branched alkyl or alkylene radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or a Oxy-alkyl radical having 1 to 8 carbon atoms, wherein C ' _M alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical , [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units, preferably propoxylene oxide units, and the EO and AO units can be randomly distributed or arranged in block form have proven to be particularly preferred nonionic surfactants. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here, rinse aids are preferred which as nonionic (s) surfactant (s) surfactants of the general formula R _{1 is} -O- (CH ₂ -CH ₂ -O) _W - (CH ₂ -CH-O) _x (CH ₂ -CH ₂ -O) _y - (CH ₂ -CH-O) ₂ - H

R2 R3

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-3 o-alkyl or alkenyl radical; each group R ² or R ^{3 is} independently -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , and the indices w, x, y and z are independently stand for integers from 1 to 10. The preferred nonionic surfactants of the formula (IV) can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R1 in the general formula (IV) may vary depending on the origin of the alcohol. When native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 22 carbon atoms, for example lauryl, coconut, palm fat, palm kernel , Stearyl, isostearyl, oleyl, capron, capryl, caprine, 2-ethylhexyl, isotridecyl, myristyl, cetyl, elaidyl, petroselinyl, arachyl, gadoleyl, behenyl, erucyl , Brassidylalkohol are preferred. Alcohols which are accessible from synthetic sources are, for example, Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. The radical R ¹ in formula (IV) preferably represents an alkyl radical having 6 to 30, preferably 8 to 18 carbon atoms. As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² and R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preferably, R ² and R ^{3 are} a methyl radical. Nonionic surfactants that can be used with particular advantage, for example, under the name Genapol ^® EP 2564 and Genapol ^® EP 2584 from Clariant Products (Germany) GmbH.

As preferred additional surfactants, low foaming nonionic surfactants are used. With particular preference is a nonionic surfactant containing a melting point above room temperature. Accordingly, preferred compositions are characterized in dass.sie nonionic (s) surfactant (s) having a melting point above 20 ⁰ C, preferably between 25 and 50 ⁰ C and in particular between 25 and 45 ° C included. In addition to the nonionic surfactants having melting or softening points in the above-mentioned temperature range, nonionic surfactants which may be solid or highly viscous at room temperature are suitable. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably 35 Pas and in particular above 40 Pas. Nonionic surfactants which have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants solid at room temperature are from the alkoxylated nonionic surfactant groups, especially the ethoxylated primary alcohols, and blends of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment, the nonionic surfactant is with a

Melting point above room temperature an ethoxylated nonionic surfactant, which has arisen from the reaction of a monohydroxy alcohol or alkylphenol having 6 to 20 carbon atoms with at least 12 moles, preferably 15 moles and especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol. A particularly preferred nonionic surfactant is solid at room temperature from a straight chain Ci ₆ - received ₂ o-fatty alcohol, preferably a C ₈ alcohol and at least 12 moles, preferably 15 moles and especially at least 20 moles of ethylene oxide. Accordingly, particularly ethoxylated nonionic surfactant (s) are preferred, the / of C ₅ . ₂₀ - Monohydroxyalkanolen or C ^ o-alkylphenols or C ₆ - ₂ o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n). The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, in particular up to 15% by weight, of the total molecular weight of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes up more than 30% by weight, preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the propylene units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants are included.

Further particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. a block copolymer of polyoxyethylene and polyoxypropylene, initiated with

Trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Non-ionic surfactants that can be used with particular advantage, for example, under the name Genapol ^® PF 10 or Genapol ^® PF 20 from Clariant (Germany) GmbH.

Also preferred is a nonionic surfactant of the formula

R ₁ O [CH ₂ CH (CH ₃ ) O] X [CH ₂ CH ₂ OMCH ₂ CH (OH) R ₂ ]

in which R _{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R _{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x represents values between 0.5 and 1.5, and y represents a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ₁ O [CH ₂ CH (R ₃ ) O] X [CH ₂ IkCH (OH) [CH ₂ IjR ₂ ]

in the R ₁ and R ₂ for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30

Carbon atoms, R _{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl radical, x is values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R ₃ in the above formula may be different. Ri and R ₂ are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ₃ , H, methyl or ethyl are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As already described, each R ₃ in the general formula (VI) may be different if x> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the group R _{3 may form} ethylene oxide (R ₃ = H) or propylene oxide (R ₃ = CH ₃ ) units which may be joined in any order, for example (EO) (PO) (EO ), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO ). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa , Particular preference is given to end-capped poly (oxyalkylated) alcohols of the general formula

R ₁ O [CH ₂ CH (R ₃ ) O] XCH ₂ CH (OH) CH ₂ R ₂ ■

In this formula, Ri, R ₂ and R _{3 are defined} as in the previous general formula. X is from 1 to 30, preferably from 1 to 20 and in particular from 4 to 16. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 have} 8 to 18 C atoms, R ^{3 is} H and x Takes values from 6 to 15. Nonionic surfactants that can be used with particular advantage, for example, under the name Genapol ^® BE 2410, Genapol ^® BE 2810 or Genapol ^® BE 2805 Clariant Products (Germany) GmbH.

In the context of the present invention, surfactant-capped surfactants and nonionic surfactants with butoxy groups are preferably also usable as nonionic surfactants. In particular, representatives of the general formula belong to the first group

R ₁ O [CH ₂ CH (R ₃ ) O] _x R ₂

in the R _{1 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms, R _{2 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms which is optionally substituted by 1, 2, 3, 4 or 5 hydroxy groups and optionally by further ether groups, R _{3 is} hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl or tert. Butyl stands and x can take values between 1 and 40. R ₂ may optionally be alkoxylated, wherein the alkoxy group is preferably selected from ethoxy, propoxy, butoxy groups and mixtures thereof.

In this case, preference is given to surfactants of the general formula (VIII) in which R _{1 is} a C ₉ - _H or Cn- _15- alkyl, R ₃ = H and X assumes a value of 8 to 15, while R _{2 is} preferably a straight-chain or branched saturated alkyl radical. Particularly preferred surfactants can be represented by the formulas C _9-1! (EO) ₈ C (CHa) ₂ CH ₂ CH _3, C _11-15 (EO) ₁₅ (PO) ₆ -C _2-14, C _9- I ₁ (EO) ₈ (CHz) ₄ CH ₃ .

Also suitable are mixed alkoxylated surfactants, preference being given to those having butyloxy groups. Such surfactants can be defined by the general formula

R ₁ (EO) ₃ (POMBO) _C

in which R _{1 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c is between 1 and 30, preferably between 1 and 20. Alternatively, the EO and PO groups in this general formula may also be reversed.

Particularly preferred representatives of this group of surfactants can be distinguished by the formulas C _9-11 (PO) ₃ (EO) ₁₃ (BO) ₁₅ , C _9-11 (PO) ₃ (EO) ₁₃ (BO) ₆ , C _{9- 11} (PO) ₃ (EO) ₁₃ (BO) ₃ , C _9-11 (EO) ₁₃ (BO) ₆ , C _9-11 (EO) ₁₃ (BO) ₃ , C _9-11 (PO) (EO) ₁₃ (BO) ₃ , C _9-11 (EO) ₈ (BO) ₃ , C _9-11 (EO) ₈ (BO) ₂ , C _12-15 (EO) ₇ (BO) ₂ , C _9-11 ( EO) ₈ (BO) ₂ , and C _9-11 (EO) ₈ (BO). A particularly preferred surfactant of formula C _13-15 (EO) _9-10 (BO) _1-2 is commercially available under the name Plurafac LF ^® 221st It is also possible to use a surfactant of the formula C _12-13 (EO) 10 (BO) ₂ . Foam inhibitors can be used to suppress foaming during the rinsing process. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci ₈ -C ₂₄ fatty acids. Suitable non-surfactant

Foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally signed silica and paraffins, waxes, microcrystalline waxes and their mixtures with signed silica or Bisfettsäurealkylendiamiden. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

In the context of the present invention, dishwashing detergents are preferred which contain the nonionic surfactant (s) in amounts of from 0.5 to 10% by weight, preferably from 1 to 5% by weight, and particularly preferably 1, 5 to 4 wt .-%, each based on the finished agent included.

It is also possible to use anionic, cationic and / or amphoteric surfactants in conjunction with the abovementioned nonionic surfactants, these having only minor importance owing to their foaming behavior in automatic dishwashing, and in most cases only in amounts below 10% by weight, in most cases even below 5 % By weight, for example from 0 to 2.5% by weight, based in each case on the agent.

Enzymes such as proteases, amylases, lipases or cellulases, for example proteases such as BLAP.RTM. 140 from Henkel, Optimase.RTM. M-440, Optimase.RTM. M-330, Opticlean.RTM. TM, may preferably be used for better detachment of proteinaceous or starchy food residues -375, Opticlean ™ - M-250 from Solvay Enzymes, Maxacal ™ CX 450,000, Maxapem ™ from Ibis, Savinase ™ 4.0 T, 6.0 T, 8.0 T from Novo or Experase ™ T from Company Ibis; Amylases such as Termamyl ™ 60 T, Novo, Amylase-LT ™ from Solvay Enzymes or Maxamyl ™ P 5000, CXT 5000 or CXT 2900 from Ibis; Lipases such as Lipolase ™ 30 T from Novo; Cellulases such as Celluzym TM 0.7 T from Novo Nordisk. Enzymes may be present in the compositions according to the invention in an amount of from 0.1 to 5% by weight, preferably from 1 to 3% by weight, based on the total dishwashing detergent. As amino acids are synthetic or naturally occurring amino acids in question, the z. B. by hydrolysis of plant or animal proteins such as collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein are available.

Preferred are alpha-amino acids, e.g. Serine, threonine, ornithine, arginine, lysine, asparagine, glutamine, phenylalanine or tyrosine, but especially glycine, alanine, valine, leucine and isoleucine. Particularly preferred is glycine or its alkali or ammonium salts, e.g. Sodium glycinate.

In addition to the amino acids, their alkali metal, alkaline earth or ammonium salts, in particular the sodium salts, can also be used in the dishwashing compositions according to the invention.

By varying the ratio of the amino acids to their salts, a certain desired pH value can be set just as easily as with the bicarbonate / carbonate system. With regard to limescale inhibition, however, the alkali carrier system amino acid / amino acid salt is clearly superior to the bicarbonate / carbonate system.

Amino acids or amino acid salts are present in the compositions according to the invention in amounts of from 0.5 to 60% by weight, preferably from 10 to 50% by weight. It is also possible to use mixtures of different amino acids or amino acid salts. Optionally, carbonate and / or bicarbonates, in particular alkali carbonates and / or bicarbonates in amounts of up to 15 wt .-%, based on the total dishwashing detergent, be included. However, the dishwasher detergents according to the invention are preferably free of carbonates and / or bicarbonates. Also, the use of highly alkaline metasilicates, such as sodium metasilicate, is preferably omitted; In contrast, disilicates may optionally be present in the form of their alkali metal salts in amounts of from 0.1 to 20% by weight, based on the dishwashing detergent. As builder components, which have the actual function of complexing hardness of water and keeping precipitated Ka in dispersed form in the wash liquor, so as to prevent limescale come, for example, organophosphonic acids or their salts, crystalline phyllosilicates, zeolites, di- and polyfunctional organic Carboxylic acids or their salts, oxidized starch and polycarboxylic acids or polycarboxylates in question. On the previously used phosphates, such as pentasodium triphosphate, which may in principle also be included, is preferably omitted for environmental reasons.

Preferred builder components are di- or polyfunctional organic

Carboxylic acids or their salts, in particular citric acid or its salts and / or synthetic polycarboxylic acids or polycarboxylates, in a total amount of 1 to 60 wt .-%, preferably 10 to 40 wt .-%, based on the total dishwashing detergent are.

Synthetic polycarboxylic acids or polycarboxylates are to be understood as meaning the synthetic polymers or their salts of the polymerization products of unsaturated carboxylic acids or their salts, to which are e.g. Polyacrylic acid, polymethacrylic acid, polymaleic acids or copolymers of acrylic acid with maleic acid or maleic anhydride belong.

Suitable polyacrylates are, for. Alcosperse ™ 102, 104, 106, 404, 406 from Alco, Acrysole ™ A N1, LMW 45 N, LMW 10 N from Norsohaas, Degapas ™ from Degussa; suitable copolymers of polyacrylic acid and maleic acid are, for. Sokalan ™ cP 5, CP 7 from BASF, Acrysol ™ QR 1014 from Norsohaas, Alcosperse ™ 175 from Alco.

The dishwashing compositions according to the invention may further contain oxygen-based bleaching agents, in particular perborates and / or percarbonates, in an amount of from 0.5 to 20% by weight, preferably up to 10% by weight, based on the total dishwashing detergent.

Of particular importance are the sodium perborate tetrahydrate (NaBO2, H2O2. 3 H2O), the sodium perborate monohydrate (NaBO2.H2O2) and the peroxycarbonate (Na2CO3.1.5 H2O2). Other useful bleaching agents are, for example, pers acid salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid. In addition, optional bleach activators are included. Suitable bleach activators are in particular N-acyl and O-acyl compounds, preferably tetraacylated diamines such as tetraacetylethylenediamine (TAED). The compositions of the invention contain such conventional bleach activators in an amount of 0.1 to 10 wt .-%, preferably 1 to 5 wt .-%. The agents of the invention may optionally also contain active chlorine-releasing agents such as trichloroisocyanuric acid; however, they are preferably free of active chlorine-releasing agents.

Particularly preferred acids are organic acids, preferably short-chain aliphatic monocarboxylic acids, hydroxycarboxylic acids and dicarboxylic acids. Examples of aliphatic monocarboxylic acids and dicarboxylic acids are C ₁ to C ₅ -alkyl and -alkenyl acids, such as glutaric acid, succinic acid, propionic acid, adipic acid and acetic acid. As examples of hydroxycarboxylic acids are hydroxyacetic acid and citric acid.

The polyesters according to the invention can also be used in separate rinse aid formulations.

A particularly preferred embodiment are solid dishwashing detergent formulations with integrated rinse aid comprising, in addition to the polyesters according to the invention, 0 to 50% by weight of phosphates, preferably pentasodium triphosphate, 0 to 5% by weight of phosphonates, 0 to 50% by weight of sodium citrate, 0 to 10 % By weight of sodium polycarboxylates, 0 to 40% by weight of sodium carbonate, 0 to 25% by weight of sodium bicarbonate, 0 to 30% by weight of sodium disilicate, 5 to 15% by weight of bleaching agent, preferably sodium perborate, 1 to 5% by weight. % Bleach activator, preferably TAED, 1 to 5% by weight of enzymes, preferably proteases and amylases, 1 to 10% by weight of nonionic surfactants, preferably fatty alcohol alkoxylates and polyethylene glycol 0 to 2% by weight paraffins, 0 to 1% by weight % Silver protection, fragrances and dyes. The following examples are intended to illustrate the subject matter of the invention without limiting it thereto.

Example 1: Polyester 1

281.5 g of 1,2-propanediol, 229.6 g of ethylene glycol, 250 g of PEG 250 monomethyl ether, 970.9 g of terephthalic acid dimethyl ester and 236 g were obtained in a 2 l four-necked flask with KPG stirrer, internal thermometer, gas inlet tube and distillation head , 98 g of 5-Sulfoisophthalsäuredimethylester Na salt presented and the reaction mixture then inertized by the introduction of N ₂ . In countercurrent then 1 g of titanium tetraisopropylate and 0.8 g of sodium acetate was added to the reaction mixture. The mixture was heated slowly on an oil bath, starting from about 120-150 ⁰ C internal temperature, the solid components began to melt. While stirring was then heated to 190 ⁰ C within 30 min. At about 173 ° C, the transesterification or distillation began. Over the course of 2 hours, the internal temperature was raised to 210 ^° C. until the required stoichiometric amount of condensate was reached. Thereafter, the oil bath temperature was increased to about 240 to 250 ⁰ C and lowered the internal pressure within 30 minutes to best oil pump vacuum. During the three hour vacuum phase, the condensation was completed by distilling off the excess amount of alcohol. During this time, the internal temperature of the polyester melt slowly increased to about 220 ⁰ C at the end of the reaction. Subsequently, it was aerated with N ₂ and discharged the melt on sheets.

Example 2: Polyester 2

In a 3-liter four-necked flask equipped with KPG stirrer, internal thermometer, gas inlet tube and distillation still 418.5 g of 1, 2-propanediol, 279.3 g of ethylene glycol, 212.4 g of tetraethylene glycol monomethyl ether, 1359.3 g

Terephthalsäuredimethylester and 296.22 g 5-Sulfoisophthalsäuredimethylester- Na-SaIz and 250 g of polyethylene glycol 250 presented and the reaction mixture then inertized by the introduction of N ₂ . In countercurrent was then added 1.5 g of sodium methylate and 0.5 g of sodium carbonate to the reaction mixture. The mixture was heated slowly on an oil bath, starting from about 120-150 ⁰ C internal temperature, the solid components began to melt. While stirring was then heated to 190 ⁰ C within 30 min. At about 173 ° C, the transesterification or distillation began. Over 2 hours, the internal temperature was increased to 210 ° C until the stoichiometric amount of condensate required was reached. Thereafter, the oil bath temperature was increased to about 240-250 ⁰ C and the internal pressure within 30 minutes lowered to best oil pump vacuum. During the three hour vacuum phase, the condensation was completed by distilling off the excess amount of alcohol. During this time, the internal temperature of the polyester melt slowly increased to about 220 ⁰ C at the end of the reaction. Subsequently, it was aerated with N ₂ and discharged the melt on sheets.

Example 3: Polyester 3

In a 3-liter four-necked flask equipped with KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, 281.5 g of 1,2-propanediol, 223.4 g of ethylene glycol, 202 g of triethylene glycol monomethyl ether, 582.5 g

Terephthalsäuredimethylester and 296.22 g 5-Sulfoisophthalsäuredimethylester- Na-SaIz presented and the reaction mixture then inertized by the introduction of N ₂ . In countercurrent, 1.02 g of titanium tetraisopropylate and 0.8 g of sodium acetate were then added to the reaction mixture. The mixture was heated slowly on an oil bath, starting from about 120-150 ⁰ C internal temperature, the solid components began to melt. With stirring is now heated to 195 ° C within 45 min. At about 173 ⁰ C began the transesterification or distillation. Over 3 hours, the internal temperature was increased to 210 ⁰ C until the stoichiometry required amount of condensate was reached. Thereafter, the oil bath temperature was increased to about 240-255 ⁰ C and lowered the internal pressure within 60 minutes to <20 mbar. During the four hour vacuum phase, the condensation was completed by distilling off the excess amount of alcohol. During this time increases the internal temperature of the polyester melt slowly up to 225 ° C at the end of the reaction. Subsequently, it was aerated with N ₂ and discharged the melt on sheets.

Example 4: Polyester 4

Reaction procedure according to Example 2 Components: 281.5 g of 1,2-propanediol

223.4 g of ethylene glycol 776.7 g of terephthalic acid dimethyl ester

355.5 g of sodium 5-sulfoisophthalate salt 295.5 g of tallow fatty alcohol with 8 units of ethylene oxide (Genapol T080)

1, 00 g of titanium tetraisopropylate 0.8 g of sodium acetate

Example 5: Polyester 5

Reaction procedure according to Example 3 Components: 620.6 g of ethylene glycol

970.9 g of terephthalic acid dimethyl ester

444.3 g of sodium 5-sulfoisophthalate Na salt

162 g of triethylene glycol monobutyl ether

1, 00 g of titanium tetraisopropylate 0.8 g of sodium acetate

Example 6: Polyester 6

Reaction procedure according to Example 1 Components: 152.2 g of 1,2-propanediol

124.1 g of ethylene glycol 388.3 g of terephthalic acid dimethyl ester 177.7 g of 5-sulfoisophthalic acid Li salt 100 g of lauryl alcohol with 7 units of ethylene oxide

(Genapol LA 070)

1.00 g of titanium tetraisopropylate

Example 7: Polyester 7

Reaction procedure according to Example 1 Components: 422.3 g of 1,2-propanediol

335.1 g of ethylene glycol 873.8 g of terephthalic acid dimethyl ester

177.7 g of 5-sulfoisophthalic acid Na salt 100 g of triethylene glycol monomethyl ether 50 g of polyethylene glycol 500

50 g of polyethylene glycol 1500 1.00 g of titanium tetraisopropylate

Example 8: Polyester 8

Reaction procedure according to Example 1 Components: 380.5 g of 1,2-propanediol

186.2 g of ethylene glycol

873.8 g of terephthalic acid dimethyl ester

444.3 g of 5-sulfoisophthalic acid Na salt 125 g of tripropylene glycol monomethyl ether 150 g of ethylene oxide-propylene oxide copolymer (Genapol PF 20)

1.00 g of titanium tetraisopropylate

Example 9: Polyester 9

Reaction procedure according to Example 1

Components: 280.0 g of 1,2-propanediol 241, 0 g of ethylene glycol 582.0 g of terephthalic acid dimethyl ester 296.0 g of sodium 5-sulfoisophthalate Na salt 143.0 g of tetraethylene glycol monomethyl ether

0.6 g of sodium acetate 1.00 g of titanium tetraisopropylate

formulation Examples

Phosphate-containing machine dishwashing detergent powder:

Sodium tripolyphosphate 43.5%

SKS-6 HD-D (phyllosilicate) 10.0%

Soda heavy 29.5%

Polyester 1 1, 00%

Percarbonate 10.0% TAED (Peractive CB) 2.0%

Nonionic surfactant (Genapol EP 0244) 1, 5%

Protease (Savinase 8.0 T (Novozymes)) 1, 5%

Amylase (Termamyl 120 T (Novozymes)) 1, 0%

Low-phosphate machine dishwashing detergent (Tab, multifunctional)

Sodium tripolyphosphate 24.0%

Soda 33.0%

Polyester 4 1, 00%

Disilicate 5.0%

Sodium citrate 7.2%

Percarbonate 10.0%

TAED 2.0%

Nonionic surfactant (Genapol EP 2584) 1, 5%

Polyglycol 8.5%

Polycarboxylate 5.0%

Enzymes 2.5%

Perfume 0.3% Phosphate-free machine dishwashing detergent (Tab, multifunctional)

SKS-6 HD 10.0%

Soda heavy 27.5%

Sodium citrate 29.5%

Polyester 3 1, 00%

Percarbonate 10.0%

TAED 3.0%

Polycarboxylate 5.5%

Enzymes (protease, amylase) 3.0%

Genapol EP 2584 4.0%

Polyglycol 5.2%

Perfume 0.3%

Chlorinated machine dishwashing detergent for USA:

Sodium tripolyphosphate 33.5%

Soda 26.5%

Disilicate, amorphous or crystalline 9.0% sodium sulphate 26.5%

Polyester 1, 5%

Nonionic surfactant (Genapol EP 0244) 1, 5%

Sodium dichlorocyanurate 1, 5%

The polyesters according to the invention were compared with respect to their hygroscopicity with soil release polymers of the prior art.

Hygroscopicity of a copolymer of the invention compared to other anionic soil release polymers. Open storage at 25 ^° C. and 65% atmospheric humidity; the uptake of water g H ₂ O / per kg SRP was measured SRP 30 min 60 min 90 min 120 min

Polyester 3 1 4 5 5

Polyester 10 20 30 40 55

SRA 200 30 60 78 92

The result shows that the polyester according to the invention (polyester 3) has a significantly lower hygroscopicity than analogous polyesters with sulfo-containing end groups (polyester 10 and SRA 200).

The polyester 10 corresponds to the polyester 3 with the difference that in the synthesis of the polyester 10 50 mol% of triethylene glycol monomethyl ether was replaced by Na isethionate, so that the polyester contains partially terminal sulfo groups.

SRA 200 is a polyester of ethylene glycol, polyethylene glycol, terephthalic acid and Na isethionate.

Claims

claims:

1. Polyester consisting of structural units 1 to 3 or 1 to 4

- Polyfunctional unit- u

(4)

in which

R ^{1 is} independently of one another H or a (Ci-Ci ₈ ) n or iso-alkyl group, preferably methyl,

R ² is a linear or branched (Ci-C ₃ o) alkyl group or a linear or branched (C ₂ -C ₃ o) alkenyl group, a cycloalkyl group having 5 to 9 carbon atoms, a _(C6 -C30) Aryl group or for a (C ₆ -CsO) arylalkyl group m, n, o independently represent a number from 1 to 200, x, y and z independently of one another represent numbers from 1 to 50, with the proviso that x + y> 2 and z> 0, u for a number from 0 to 5, preferably 0 to 0.5 and more preferably from 0 to 0.25 and

Me Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ / 2, Ca ⁺⁺ / 2, Al ⁺⁺⁺ / 3, NH ₄ ⁺ , Ci-C ₂₂ -mono-, di-, tri- or tetraalkylammonium or

Di-tri- or

Tetrahydroxyalkylammonium means, with the proviso that the polyesters have a softening point above 40 ⁰ C and a solubility in water with 3 ° German hardness at 20 ⁰ C of more than 6 wt .-%.

2. A polyester according to claim 1, wherein R ^{1 is} H and / or methyl, R ^{2 is} methyl, o, m and n are numbers from 1 to 200, x is a number from 1 to 30, y is a number from 1 to 25 and z are a number from 0.05 to 15.

3. Polyester according to claim 1 or 2, wherein o, m and n are numbers from 1 to 20.

4. Polyester according to claim 1 or 2, wherein o, m and n is a number from 1 to 5.

5. A polyester according to claim 1 or 2, wherein o and m are 1 and n is a number from 2 to 10.

6. A polyester according to claim 1 or 2, wherein x is a number from 2 to 15.

7. A polyester according to claim 1 or 2, wherein x is a number from 3 to 10.

8. Polyester according to claim 1 or 2, wherein y is a number from 1 to 10.

9. Polyester according to claim 1 or 2, wherein y is a number from 1 to 5.

10. A polyester according to claim 1 or 2, wherein z is a number from 0.1 to 10.

11. A polyester according to claim 1 or 2, wherein z is a number from 0.25 to 3.

12. Polyester according to claim 1 or 2, wherein u is the number 0.

13. Polyester according to claim 1 having a softening point between 41 and 200 ⁰ C.

14. Polyester according to claim 1 with a softening point between 50 and 200 ⁰ C.

15. Polyester according to claim 1 with a softening point between 80 and 150 ° C.

16. Polyester according to claim 1 with a softening point between 100 and 120 ° C.

17. Solid dishwashing detergent containing a polyester according to claim 1.

18. Washing and cleaning compositions containing a polyester according to claim 1.