DE10116021A1 - Detergent composition useful for cleaning hard and/or soft surfaces comprises a nonionic surfactant which is an ethoxylated medium-chain branched alcohol - Google Patents

Abstract

Detergent composition comprises a nonionic surfactant which is an ethoxylated medium-chain branched alcohol (I). Detergent composition comprises a medium-chain branched nonionic surfactant of formula R<1>O(CH2CH2O)pH (I); R<1> = 10-22C alkyl or alkenyl with an average degree of branching of 1.2-2.5; p = 1-9.

Description

The subject of the present application relates to washing or cleaning agents with verbes Serter cleaning performance and their use.

Detergents and cleaning agents for cleaning hard and soft surfaces have been around for a long time well known. Nonionic surfactants known in the prior art, also referred to as nonionic surfactants net, suitable for detergents and cleaning agents, include, for example, alkyl alcohol polyglycols ether, alkyl polyglycosides and nitrogenous surfactants or dialkyl sulfosuccinate or mixtures of the aforementioned substances.

It is known that many detergents or cleaning agents have only a very limited or insufficient amount en Have cold water solubility. The cold water solubility of detergents or cleaning agents, which can be determined, for example, via the so-called Krafft temperature is by variation the components contained in the respective agent, in particular the surfactants, can be influenced. It is also known that the choice of surfactants has a decisive influence on the Reini performance of the respective detergent or cleaning agent.

Furthermore, it has been shown in practice that so far in many detergents and cleaning agents surfactant mixtures used often show unfavorable gel behavior. So washing or detergent particles in the dispersing and dissolving process at the beginning of the dissolution phase in the aqueous medium after a few minutes dissolution time a "corona" around the wash middle particles around. This is a gel phase, often with liquid crystalline phases that further diffusion process and thus can significantly hinder the rate of dissolution (= Ver gelungseffekt). So occurs especially with detergents when dissolving detergent active fen, for example surfactants or the like, in the induction chamber or in the wash liquor Ver success.  

Gelling detergent active ingredients leads to poorer dispersibility, one reduced solubility, an inhomogeneous distribution in the wash liquor, a worsened Cleaning effect and for the formation of detergent residues in the induction bowl and / or on clothing.

It would therefore be very desirable to provide a detergent and cleaning agent which does not clump together when the detergent or cleaning agent is dissolved. It would still be desirable to have detergents and cleaners available that are adequate Have cold water solubility. It would also be of particular interest and cleaning agents with improved cleaning performance. When formulating Washing or cleaning agents, it is desirable from an ecological point of view that the ver the ingredients used are biodegradable.

It is therefore an object of the present invention to provide washing or cleaning agents places that have improved cleaning performance, have good cold water solubility zen and show a residue-free flushing behavior.

Further objects result from the following description of the invention.

Surprisingly, it was found that the use of selected medium-chain branched nonionic surfactants are advantageous instead of the nonionic surfactants customarily used hitherto Way is suitable for the production of detergents or cleaning agents.

The solution to the above-mentioned objects according to the invention consists in the provision of a washing or cleaning agent which comprises medium-chain branched nonionic surfactants which are characterized by the following formula I,

R ¹ -O- (CH ₂ CH ₂ O) _p -H (I);

wherein R ^{1 is} a medium-chain branched alkyl and / or alkenyl radical with 10 to 22 carbon atoms and has an average degree of branching from 1.2 to 2.5 and p stands for numbers from 1 to 9. The degree of branching VG is defined by the number of primary carbon atoms (corresponds to the number of alkyl groups-1).

In a preferred embodiment of the present invention, the washing or cleaning agent contains more than 0% by weight and at most 100% by weight, preferably more than 10% by weight, more preferably more than 20% by weight, particularly preferably more than 40 wt .-% and particularly preferably more than 60 wt .-%, based on the total content of nonionic surfactant, medium chain branched nonionic surfactant according to the formula

R ¹ -O- (CH ₂ CH ₂ O) _p -H (I).

In a particularly preferred embodiment of the present invention, the washing or cleaning agent comprises medium-chain branched nonionic surfactants characterized by the formula I below

R ¹ -O- (CH ₂ CH ₂ O) _p -H (I);

wherein R ^{1 is} a medium-chain branched alkyl and / or alkenyl radical with 8 to 18, preferably with 13 carbon atoms and has an average degree of branching from 1.7 to 2.4 and p represents numbers from 3 to 7.

Further preferred degrees of branching are 1.3; 1.4; 1.6; 1.7; 1.8; 1.9; 2.0; 2.1; 2, 2; 2,3 and 2,4. Preferred values for p are 2, 4, 5, 6 and 8.

In particular, it has been found that detergents or cleaning agents with oxo alcohol ethoxylates according to the invention with an alkyl and / or alkenyl radical R ¹ with a specific chain length range and a degree of branching of 1.2-2.5 have a comparison with detergents or cleaning agents with conventional, essentially unbranched nonionic surfactants have a significantly improved cleaning performance. For example, detergents which were produced using the medium-chain branched nonionic surfactants provided according to the invention show a significantly better cleaning performance in the case of pigment or grease soiling and also in the case of make-up or lipstick contamination.

The use of medium-chain branched surfactants with a ket has proven to be particularly advantageous length of 13 carbon atoms and an average degree of branching in the range of 1.7 to 2,4 in the washing or cleaning agents according to the invention.

Nonionic surfactants suitable according to the invention are preferably produced on the basis of multiply branched olefins with a carbon chain length of C ₉ -C ₂₀ . The aforementioned olefins, which often have branches in positions 4-7, can be prepared, for example, by oligomerization or metathesis from 2 to 5 units of α-olefins. Butene or pentene or corresponding mixtures are preferably used as starting materials. Corresponding higher alcohols, so-called oxo alcohols, can be obtained from the branched olefins by oxosynthesis. The resulting branched primary oxo alcohols are preferred starting materials for the oxo alcohol ethoxylates of the formula R ¹ -O- (CH ₂ CH ₂ O) _p -H (I) provided according to the invention. Oxo alcohol ethoxylates or alkyl alcohol polyglycol ethers can be obtained by adding ethylene oxide to the corresponding oxo alcohols.

It has been shown that the washing or cleaning agents or the formulated according to the invention used nonionic surfactants have a significantly better solubility in cold water. Also owned zen the detergents or cleaning agents formulated according to the invention compared to conventional Chen detergents or cleaning agents significantly improved washing-in behavior. This through the  Use of the branched nonionic surfactants provided according to the invention Serte effect comes especially in the production of powder or granular Detergents or cleaning agents, as well as detergents or cleaning agents in tablet form for Wear. It has been found that by partial or total substitution of a conventional chen, essentially unbranched fatty alcohol ethoxylate-based nonionic surfactant by an inventor medium-chain branched oxo alcohol ethoxylate according to the gel behavior of the resulting Detergent or cleaning agent is positively influenced. A clumping or an undesirable Gel formation is largely prevented by using the branched surfactants. This Effect can also be demonstrated by appropriate viscosity measurements.

Another advantage of the washing or cleaning agents according to the invention lies in the good biolo Chemical degradability of the medium-chain branched oxo Alcohol.

According to the present invention, medium-chain branched nonionic surfactants with an alkyl and / or alkenyl radical R ¹ , which predominantly has methyl, ethyl, propyl and / or butyl branches, particularly preferably methyl and / or ethyl branches, are preferably used in the washing or cleaning agents. The medium-chain branched nonionic surfactants provided according to the invention can also have longer alkyl branches.

In a preferred embodiment according to the invention, the washing or Detergent between 0.1 and 30 wt .-%, preferably between 1 and 20 wt .-% and particularly preferably between 2 and 5% by weight of medium chain provided according to the invention branched nonionic surfactants. In gel-like washing or cleaning agents according to the invention agent is a comparatively higher content, preferably above 20% by weight medium-chain branched nonionic surfactants are preferred.

In a further particularly preferred embodiment are in the washing or cleaning medium in addition to the medium-chain branched oxo alcohol ethoxylates, medium-chain branched alkyl contain sulfates and / or alkyl sulfonates. According to the invention, the alkyl sulfates and / or alkyl sulfonates from the group comprising alkyl sulfates and / or alkyl sulfonates with a medium chain branched alkyl radical with 10-22, preferably 8-18, and particularly preferably with 13 Koh lenstoffatomen and an average degree of branching of 1.2-2.5, preferably from 1.7-2.4 selected.

The present invention is further based on the surprising finding that detergent or cleaning agent compositions comprise

• a) at least one medium-chain branched nonionic surfactant of the formula
  R ¹ -O- (CH ₂ CH ₂ O) ₃ -H; and
• b) at least one medium-chain branched nonionic surfactant of the formula
  R ¹ -O- (CH ₂ CH ₂ O) ₇ -H,

have particularly good cleaning properties.

According to the invention, the nonionic surfactant components a) and b) are preferably in a weight ratio from 9: 1 to 1: 9, more preferably in a weight ratio of 7: 3 to 3: 7, particularly preferred in a weight ratio of 3: 2 to 2: 3 and most preferably in a weight ratio of 1: 1 contain.

In a particularly preferred embodiment of the present invention, a) and / or b), preferably a) and b), have a medium-chain branched alkyl and / or alkenyl radical R ¹ with preferably 13 carbon atoms and / or an average degree of branching of 1.7 up to 2.4.

It has surprisingly been found that the medium-chain branched nonionic surfactants a) and b) behave synergistically with respect to the cleaning ability of the particular washing or cleaning agent. If, instead of conventional largely unbranched nonionic surfactants, a medium-chain branched nonionic surfactant according to the formula R ¹ -O- (CH ₂ CH ₂ O) ₃ -H with a degree of toxicity of 3 is used, a clearly improved cleaning performance is observed. The same applies when using a nonionic surfactant according to the invention according to the formula R ¹ O- (CH ₂ CH ₂ O) ₇ -H with an EO degree of 7. An even better cleaning performance can, however, be achieved if the washing or cleaning agents according to the invention a mixture, preferably before a 1: 1 mixture of a) and b). It has been found that the surfactant components a) and b) with an alkyl and / or alkenyl radical R ¹ , which has a chain length of 13 carbon atoms and a degree of branching in the range from 1.7 to 2.4, are particularly advantageous, or the synergistic effect found in relation to the cleaning performance is particularly pronounced.

Furthermore, synergistic combinations of medium-chain branched nonionic surfactants according to the invention with "classic" nonionic found surfactants, which also significantly improve cleaning performance of the respective detergent or cleaning agent. Under "classic" nonionic surfactants in the cream Men of the present invention use non-ionic surfactants with substantially unbranched or understood in the 2-position branched alkyl and / or alkenyl radicals or mixtures thereof. Usual "classic" nonionic surfactants have methyl or higher alkyl branches in the 2-position on.

The present invention is therefore also based on the surprising finding that detergent or cleaning agent compositions comprise

• a) at least one medium-chain branched nonionic surfactant of the formula
  R ¹ -O- (CH ₂ CH ₂ O) _p -H; and
• b) at least one nonionic surfactant of the formula
  R ² -O- (CH ₂ CH ₂ O) _p -H,

where R ²

an essentially unbranched or branched in the 2-position alkyl and / or alkenyl balance with 10 to 22, preferably 8 to 18, particularly preferably 12 to 15 and especially before is with 13 carbon atoms and p stands for numbers from 1 to 9, preferably from 3 to 7.

In a preferred embodiment according to the invention, a) and b) are preferably in Ge weight ratio 9: 1 to 1: 9 and particularly preferably in a weight ratio of 7: 3.

It is particularly preferred according to the invention that a) and / or b), preferably a) and b) have an alkyl and / or alkenyl radical with preferably 13 carbon atoms and / or an ethoxylation degree p of 5 and / or R ^{1 has} an average degree of branching from 1.7 to 2.4, particularly preferably from 2.4.

The detergent or cleaning agent components according to the invention can be used in a preferred manner Embodiment as a gel, in solid and / or liquid form.

The washing or cleaning agents according to the invention can be preferred in another Embodiment include at least one molded body. Suitable moldings include other granules, extrudates, particles, agglomerates, capsules, tablets, tabs and / or the like chen, as well as mixtures thereof.

The washing or cleaning agent according to the invention can be used to clean hard surfaces and / or soft surfaces can be used.

The washing or cleaning agents according to the invention can in particular be used as dishwashing detergents tel, all-purpose cleaners, bathroom cleaners, floor cleaners, car cleaners, glass cleaners, furniture care products or cleaners, facade cleaners, detergents and / or the like can be used.

Next is the detergent or cleaning agent for cleaning hair, fibers, textiles, carpets chen, clothing, food and / or the like.

The constituents contained in the washing or cleaning agents according to the invention are present preferably selected from the group comprising surfactants, fragrances, dyes, enzymes, En zym stabilizers, builders, substances for adjusting the pH, bleach, bleach activator Ren, silver protection agents, dirt-repellent substances, optical brighteners, graying inhibitor ren, disintegration aids, usual ingredients and / or mixtures thereof.  

The basic composition and formulation of liquid or solid washing or Cleaning agents, such as granular detergents, are known to those skilled in the art. at the production of detergents or cleaning agents are preferably the usually ver used nonionic surfactants, particularly preferably the alcohol ethoxylates, by the invention provided partially or fully medium-branched nonionic oxo alcohol ethoxylates constantly replaced. Of course, the above-mentioned nonionic surfactants and / or erfindungsge In accordance with the intended alkyl sulfates or alkyl sulfonates, they are also additionally used as co-detergents in washing or cleaning agents are used.

In a particularly preferred embodiment, the nonionic surfactants according to the invention according to the formula R ¹ -O- (CH ₂ CH ₂ O) _p -H are used for the production of detergents with improved cleaning performance, preferably for the production of granular, powder and / or gel form Detergents, particularly preferably for the production of detergents or cleaning agents in tablet form.

Oxo alcohol ethoxylates suitable according to the invention, which fall under the formula R ¹ -O- (CH ₂ CH ₂ O) pH, include, for example, Lutensol®, commercially available from BASF AG, Ludwigshafen. Nonionic surfactants, for example, which are available under the name Lutensol TO® from BASF AG, Ludwigshafen, are particularly suitable. Other medium chain branched nonionic surfactants suitable according to the invention are offered under the name Marlipal® by Sasol Germany. According to the invention, Marlipal O13® (Sasol Germany) is particularly suitable.

The following are some washing or cleaning agents suitable according to the invention components explained in detail.

surfactants

As surfactants for the production of detergents or cleaning agents, besides those according to the invention according to the medium-branched nonionic surfactants provided and the medium-chain ver branched alkyl sulfates who used additional anion, cation, ampho- and / or nonionic surfactants the.

For example, other anionic surfactants of the sulfonate and sulfate type can be used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids suitable. Sulfonation products of unsaturated fatty acids, for example oleic acid, are also suitable in small amounts, preferably in amounts not above about 2 to 3% by weight. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Taking fatty acid glycerin esters are to be understood as the mono-, di- and triesters and their mixtures, as in the case of the her position by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the Um esterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. Preferred sulfated fat Acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbons Substance atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid re, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based ge wheel-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.

Fatty acid derivatives of amino acids, for example of, come as further anionic surfactants N-methyl taurine (tauride) and / or N-methyl glycine (sarcoside). In particular be The sarcosides or sarcosinates, and above all sarcosinates of higher ones, are preferred and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate.

Soaps are particularly suitable as further anionic surfactants. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hy third erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or tri-ethanolamine, available. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.  

The anionic surfactants are preferred in the washing or cleaning agents according to the invention as in amounts of 1 to 30 wt .-% and in particular in amounts of 5 to 25 wt .-% th.

In addition to the special medium-chain branched nonionic provided according to the invention Surfactants can also be used in other classes of nonionic surfactants for the production of washing or Detergents are used.

For example, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular methyl acid, such as are described, for example, in Japanese Patent Application JP 58/217598. C ₁₂ -C ₁₈ fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are preferred as nonionic surfactants. In particular C ₁₂ -C ₁₈ fatty acid methyl esters with 10 to 12 EO can be used as surfactants.

Another class of nonionic surfactants that can be used advantageously for the production of detergents or cleaning agents are the alkyl polyglycosides (APG). Alky polyglycosides that can be used satisfy the general formula RO (G) _Z , in which R denotes a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethyl amine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be used for Production of detergents or cleaning agents may be suitable.

Other surfactants used to produce the washing or cleaning agents according to the invention so-called Gemini surfactants. In general, this includes such verbs understood the two hydrophilic groups and two hydrophobic groups per molecule sit. These groups are usually separated from one another by a so-called "spacer". This spacer is usually a carbon chain that should be long enough that the hydrophi groups are sufficiently far apart to act independently of one another can. Such surfactants are generally characterized by an unusually low criticality cal micelle concentration and the ability to greatly reduce the surface tension of the water grace, from. In exceptional cases, however, the term Gemini surfactants does not only include di mere, but also trimeric surfactants understood.  

Gemini surfactants for the production of washing or cleaning agents are, for example, sulfated Hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis- and trimer alcohol tris sulfates and ether sulfates according to German patent application DE-A- 195 03 061. End group capped dimeric and trimeric mixed ethers according to German Pa Tent registration DE-A-195 13 391 are particularly characterized by their bi- and multifunctionality out. The end group-closed surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or Cleaning procedures are suitable.

builders

The washing or cleaning agents according to the invention can all be used as builders or builders Ge usually used in detergents or cleaning agents, in particular in detergents contain builders, in particular zeolites, silicates, carbonates, organic cobuilders and also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used. Amorphous silicates are particularly preferred.

A finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which was developed by CONDEA Augusta S. p. A. Is sold under the brand name VEGOBOND AX® and the formula:

nNa ₂ O. (1-n) K ₂ O Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O,

equivalent.  

Suitable zeolites have an average particle size of less than 10 μm (volume distribution; Measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight of bound water.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular are particularly suitable especially the tripolyphosphates.

Organic cobuilders which can be used in the washing or cleaning agents according to the invention are special polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Po lyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Useful organic builders are, for example, those in the form of their sodium salts settable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, adipin acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acid ren, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these. Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder, the acids possess typically also have the property of an acidifying component and are therefore also used for Setting a lower and milder pH value for detergents and / or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metals tall salts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acid ren, is generally 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and ins special 30,000 to 40,000 g / mol.

Also particularly preferred are biodegradable polymers made from more than two different ones NEN monomer units, for example those which are salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which are preferably monomers acrolein and acrylic have acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing effect Have effect.

Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, can be obtained. Preferred polyacetals are made from dialdehydes such as glyoxal and glutaral dehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. The hydrolysis products are preferably of medium molar mass range from 400 to 500000 g / mol. A polysaccharide with a dextrose  Equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being one common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Both maltodextrins with a DE between 3 can be used and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

A preferred dextrin is described in British patent application 94 19 091. Both Oxidized derivatives of such dextrins are their reaction products with oxides tion agents, which are capable of at least one alcohol function of the saccharide ring to the car to oxidize the acid function. Such oxidized dextrins and methods of their manufacture are for example from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP- A-0 472 042 and EP-A-0 542 496 and international patent applications WO-A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608 be known. A product oxidized at C6 of the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylene diamine disuccinate are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are also glycerol disuccinates and glycerol trisuccinates, as in for example in the US patents US 4,524,009, US 4,639,325, in the euro European patent application EP-A-0 150 930 and Japanese patent application JP 93/339896 to be discribed.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which are at least at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain. Such cobuilders are described, for example, in the international patent application WO A-95/20029.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the hydroxyal Kanphosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt is alkaline (pH 9). Preferred aminoalkane phosphonates are  Ethylene diamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) as well as their higher homologues in question. They are preferably in shape the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta and Octa sodium salt of DTPMP, used. As a builder, the class of phosphonates preferably HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the washing and Detergents also contain bleach, preferably its aminoalkane phosphonates, in particular DTPMP to use, or mixtures of the phosphonates mentioned for the preparation of Means to use.

In addition, all compounds that are able to form complexes with alkaline earth ions to be used as cobuilders.

Suitable polymeric polycarboxylates for the preparation of the agents according to the invention are examples as the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymers Polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic have proven particularly suitable acid with maleic acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% malein contain acid. Their relative molecular weight, based on free acids, is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.

Particularly preferred for the production of the washing or cleaning agents according to the invention are also biodegradable polymers from more than two different monomer units, for example those which according to DE-A-43 00 772 as monomers salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or as described in DE-C-42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those which are described in German patent applications DE-A- 43 03 320 and DE-A-44 17 734 are described and as monomers preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Other suitable builder substances for producing the washing or cleaning agents according to the invention agents are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as described, for example, in international patent application WO-A- 93/08251 are described or their manufacture, for example, in the international Pa tent registration WO-A-93/16110 is described. Oxidized oligo are also suitable saccharide according to German patent application DE-A-196 00 018.  

Other builders suitable for producing the washing or cleaning agents according to the invention Substances are polyacetals, which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained. before Polyacetals are drawn from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid hold.

Means for adjusting the pH

To reduce the pH of detergents or cleaning agents, especially detergents agents, the agents can also contain acidic salts or slightly alkaline salts. Are preferred bisulfates and / or bicarbonates or organic polycar bonic acids, which can also be used as builder substances at the same time. In particular the use of citric acid is preferred.

bleach

The washing or cleaning agents can also contain bleaching agents. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloamine minoperacid or diperdodecanedioic acid.

It is also possible to use bleaches from the group of organic bleaches for the production of Detergents or cleaning agents are used. Typical organic bleaching agents are diacyl peroxides such as B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acid ren, the examples being particularly the alkyl peroxy acids and aryl peroxy acids the.

Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as Al kylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystea rinsic acid, ε-phthalimido-peroxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxy benzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccina te, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassylic acid, the diperoxyphthalate acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can can be used to produce the agents according to the invention.  

Chlorine or. Can also be used as bleaching agents in the washing or cleaning agents according to the invention Bromine-releasing substances are used. Release under the appropriate chlorine or bromine the materials come, for example, heterocyclic N-bromo- and N-chloramides, for example Trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid re (DICA) and / or their salts with cations such as potassium and sodium. Hydantoinverbin Applications such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleach content is preferably 0 to 25% by weight and in particular 1 to 20% by weight, based on the total composition of the detergent and cleaning agent,

Bleach activators

To improve when washing or cleaning at temperatures of 60 ° C and below To achieve bleaching effect, bleach activators can be included.

As bleach activators for the production of the washing or cleaning agents according to the invention NEN compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted result in perbenzoic acid. Suitable substances are O- and / or N- Acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups wear. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine, are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, especially phthal acid anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place can be used to manufacture Washing or cleaning agents according to the invention also use so-called bleaching catalysts be det. These substances are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod Ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Bleach activators which can be used to produce the washing or cleaning agents according to the invention medium also those from German patent applications DE-A-196 16 693 and DE-A-196 16 767 known enol esters as well as acetylated sorbitol and mannitol or their in the euro European patent application EP-A-0 525 239 mixtures described (SORMAN), acylated zuc Kerderivate, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and  Octaacetyl lactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are from the international Patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A- 95/14759 and WO-A-95/17498 are used. The from the German Pa Tent registration DE-A-196 16 769 known hydrophilically substituted acylacetals and those in the German patent application DE-A-196 16 770 and international patent application WO-A- 95/14075 described acyl lactams are also preferred for the preparation of the Invention appropriate detergents or cleaning agents. Even those from the German patent application DE-A-44 43 177 known combinations of conventional bleach activators can be made tion of the washing or cleaning agents according to the invention can be used.

In particular when used in machine washing processes, it can be of advantage that the The usual foam inhibitors are added to detergents or cleaning agents. As foam inhibitors For example, soaps of natural or synthetic origin are suitable, which have a high proportion have at C18-C24 fatty acids. Suitable non-surfactant foam inhibitors are examples wise organopolysiloxanes and their mixtures with microfine, possibly silanized silica and Paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or Bi stearylethylendiamid.

enzymes

Enzymes are particularly suitable for producing the detergents or cleaning agents the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enes enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All these Hydrolases help remove soiling such as protein, fat or starchy ver stains at.

Oxidoreductases can also be used for bleaching. Particularly suitable for use here Position of the detergents or cleaning agents are those from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic effects obtained from their genetically modified variants substances. Proteases of the subtilisin type and in particular proteases which are preferred Bacillus lentus can be obtained. There are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or from protease, Amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic acting enzymes, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. Examples of such The well-known cutinases are lipolytic enzymes. Also peroxidases or oxidases ha have proven to be suitable in some cases. Suitable amylases include in particular  alpha-amylases, iso-amylases, pullulanases and pectinases. Oxireductases are also suitable net.

For the production of the detergents or cleaning agents come in addition to the above Enzymes are also considered cellulases. Cellulases and other glycosyl hydrolases can by removing pilling and microfibrils to preserve color and increase Contribute to the softness of the textile. Cellobiohydrolases, Endo, are preferably used as cellulases glucanases and glucosidases, which are also called cellobiases, or mixtures of these sen used. Since different cellulase types are characterized by their CMCase and avicelase Differentiate between activities, the desired ones can be achieved by targeted mixtures of the cellulases Activities can be discontinued.

The proportion of the enzymes or enzyme mixtures can, for example, be about 0.1 to 5% by weight preferably 0.5 to about 4.5% by weight, based on the detergent and cleaning composition tongue.

enzyme stabilizers

In addition to phosphonates, the detergents or cleaning agents can also use other enzymes stabilizers included. For example, the washing or cleaning agents can be sodium formate contain. It is also possible to use proteases with soluble calcium salts and a Calcium content of preferably about 1.2 wt .-%, based on the enzyme, are stabilized. Au Calcium salts also serve as stabilizers. It is particularly advantageous but the use of boron compounds, for example boric acid, boron oxide, borax and others Alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7).

graying

The washing or cleaning agents can also contain graying inhibitors. graying Inhibitors have the task of suspending the dirt detached from the fiber in the liquor hold and thus prevent the dirt from re-opening. For this purpose are water soluble Colloids mostly of an organic nature are suitable, for example the water-soluble salts of polymers Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or the cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Wei Furthermore, soluble starch preparations and other starch products than those mentioned above can be used use, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose,  Methylcarboxymethylcellulose and their mixtures, as well as polyvinylpyrrolidone in the inventions detergents or cleaning agents according to the invention.

Silver protectants

According to the invention for the production of detergents or cleaning agents, in particular for machine washing or cleaning agents for dishes to protect the dishes or the ma Schine corrosion inhibitors are used, with silver protection in the machine dishwashing have a special meaning. Can be used to manufacture the washing or cleaning agents are the known substances of the prior art. General to Manufacture of detergents or cleaning agents can be selected from silver protection agents the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylamines notriazoles and the transition metal salts or complexes are used.

Benzotriazole and / or are particularly preferred for the production of the washing or cleaning agents To use alkylaminotriazole. You will also often find ak in cleaner formulations Detergent and cleaning agents containing tivchlorine, which clearly corrode the silver surface can reduce, these are also suitable for the production of detergents or cleaning agents. In the case of chlorine-free cleaners, detergents or cleaning agents are particularly useful for the production of detergents or cleaning agents Organic and redox-active compounds containing oxygen and nitrogen, such as divalent and trivalent Phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyro gallol or derivatives of these classes of compounds are used. Also salt and complex anorga African compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce can be used for the production of detergents or cleaning agents are used. Preferred for the production of washing or Cleaning agents are the transition metal salts that are selected from the group of Manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of Cobalt or manganese and manganese sulfate.

Dirt-repellent substances

In addition, dirt-repellent can also be used to manufacture detergents or cleaning agents Substances are used which have a positive effect on the oil and fat washability from textiles influence (so-called soil repellents). This effect is particularly evident when a textile ver is soiled, previously several times with a detergent according to the invention, this contains oil and fat-dissolving component, was washed. Among the preferred oil and grease solutions the components include, for example, nonionic cellulose ethers such as methyl cellulose and Methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and Hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulo seether, and the polymers of phthalic acid and / or of the known from the prior art Terephthalic acid or its derivatives, in particular polymers of ethylene terephthalates  and / or polyethylene glycol terephthalates or anionically and / or nonionically modified deri vaten of these.

Optical brighteners

These substances, which are also called "whiteners", can be used to make the washing or ri detergent used. Optical brighteners are organic dyes that are part of the invisible convert UV light from sunlight into longer-wave blue light. The emission This blue light complements the "gap" in the light reflected by the textile, so that one with optical Lighter-treated textiles appear whiter and lighter to the eye. Because the mechanism of action A distinction is made between brighteners, which require them to be drawn onto the fibers, depending on the "to be stained benden "fibers, for example brighteners for cotton, polyamide or polyester fibers commercially available brighteners suitable for the production of detergents or cleaning agents essentially five structural groups, namely the stilbene, diphenylstilbene, cumann Quinoline, diphenylpyrazoline group and the group of the combination of benzoxazole or benzi midazol with conjugated systems. An overview of common brighteners is, for example, in G. Jakobi, A. Löhr "Detergents and Textile Washing"; VCH-Verlag, Weinheim, 1987, pages 94 to 100, to find. Are suitable for. B. Salts of 4,4'-bis ((4-anilino-6-morpholino-s-triazin-2-yl) amino] - stilbene-2,2'-disulfonic acid or compounds of the same structure which replace the morpholino A diethanolamino group, a methylamino group, an anilino group or a 2- Wear methoxyethylamino group. Brighteners of the substituted di phenylstyryle may be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4- chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures too the aforementioned brighteners can be used.

fragrances

Fragrances can be used to produce the detergents or cleaning agents according to the invention be set to improve the aesthetic impression of the resulting means and the In addition to the cleaning performance and the color impression, consumers are "typical and sensory" to provide distinctive washing or cleaning agents. As perfume oils or Fragrances can individual fragrance compounds, e.g. B. the synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. fragrance Compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbene zoat, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and Benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen alde hyd, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, pheny Methyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as  Lime and pinene. However, preference is given to mixtures of different fragrances for the preparation The detergents or cleaning agents according to the invention are used, which together form a generate a speaking fragrance. Such perfume oils can also contain natural fragrance mixtures contain as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, patchouly Rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, Lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galba num oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

disintegration aid

In order to disintegrate the detergents or cleaning agents in solid form, for example in tablet form, To facilitate, it is possible to disintegration aids, so-called tablet disintegrants, in the This must be incorporated to reduce disintegration times. Under tablet disintegrants or disintegration are accelerated according to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of the phar pharmaceutical technology "(6th edition, 1987, pp. 182-184) understood auxiliaries that are suitable for the ra disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in provide resorbable form.

These substances, which are also called "explosives" due to their effect, enlarge their volume in the event of water ingress, with the volume on the one hand increasing (swelling) and the other on the other hand, a pressure can be generated via the release of gases, which the tablet in lets smaller particles disintegrate. Well-known disintegration aids are, for example, carbo nat / citric acid systems, whereby other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrro lidon (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Usual washing and cleaning agents contain 0.5 to 10% by weight, preferably 3 to 7% by weight. and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of detergent or cleaning agent.

Disintegration agents based on cellulose are used as preferred disintegration agents which are suitable for the production of the washing or cleaning agents according to the invention. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants that can be used in the context of the present invention are also cellulose derivatives which are obtainable from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose, which is free of cellulose derivatives, is particularly preferably used as the disintegrant based on cellulose for the production of the washing or cleaning agent according to the invention.

As a further disintegrant based on cellulose for the production of the invention Detergents or cleaning agents can be used in microcrystalline cellulose. This micro crystalline cellulose is obtained by partial hydrolysis of celluloses under such conditions hold on only the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses grasp and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged.

dyes

In order to improve the aesthetic impression of the washing or cleaning agents according to the invention detergents or cleaning agents can be dyed with suitable dyes, preferably the brightener-containing phase (s) ent the total amount of dye (s) ent holding / included. Preferred dyes, the selection of which the expert has no difficulty rides, have a high storage stability and insensitivity to the rest of the content substances of the washing or cleaning agents and against light as well as no pronounced substantivity compared to textile fibers so as not to stain them.

All dyes are preferred for the production of the washing or cleaning agents according to the invention agents that can be oxidatively destroyed in the washing process, as well as mixtures thereof suitable blue dyes, so-called blue tones. It has proven to be a beneficial colorant to produce the detergents or cleaning agents according to the invention, which are in water or are soluble in liquid organic substances at room temperature. Are suitable for for example anionic colorants, e.g. B. anionic nitroso dyes. A possible colorant is for example naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as Han del product is available, for example, as Basacid® Green 970 from BASF, Ludwigshafen, and mixtures of these with suitable blue dyes. Coming as additional colorants Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® patent blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI  74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acidblue 221), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CE Acidyellow 218) and / or Sandolan® Blau (CI Acid Blue 182, CAS 12219-26- 0) for use.

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the coloring agent in the washing or cleaning agents varies. In the case of readily water-soluble colorants, e.g. B. the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range of a few 10 ^-2 to 10 ^-3 wt .-%, each based on the total detergent and cleaning agent. In the pigment dyes particularly preferred because of their brilliance, but less water-soluble, e.g. B. the above-mentioned Pigmosol® dyes, the suitable concentration of the colorant in detergents or cleaning agents, however, is typically a few 10 ^-3 to 10 ^-4 wt .-%, based on the total detergent or cleaning agent.

Examples 1 to 3 below serve to illustrate the invention and are not to be understood as a limitation.  

Examples 1. Use of oxo alcohol ethoxylates according to the invention in a typical gel form Detergent formulation

To determine the washing performance of the washing or cleaning agents according to the invention Corresponding detergent compositions according to the invention have been conventional formulated detergent compared. To the positive influence provided by the invention medium-chain branched nonionic surfactants on the cleaning performance of detergents To demonstrate, a typical gel detergent formulation with conventional, in produced essentially unbranched nonionic surfactants and with corresponding inventive Formulations compared. The detergent compositions according to the invention under differed from the conventional detergent formulation only in terms of the ones used Nonionic surfactants. Instead of the conventional, essentially unbranched nonionic surfactants, they were invented medium-branched nonionic surfactants provided according to the invention in an otherwise identical master recipe used.

The detergent formulation or combination specified in Table 1 was used as the base formulation used composition that corresponds to a common gel formulation. Accordingly, both in the inventive as well as in the conventional detergent formulations as a whole each contain 24% by weight of nonionic surfactant.

Table 1

First, a conventional detergent based on the recipe shown in Table 1 manufactured. A conventional C12-C18 fatty alcohol ethoxylate with a EO grade of 7 (Dehydol LT 7 ®) used. The resulting detergent or its cleaning performance  was used as a standard for comparison in the subsequent investigations pulled

Washing or cleaning agents according to the invention were used according to the invention envisaged oxo alcohol ethoxylates in otherwise identical gel formulations according to Table 1 manufactured. The respective EO degrees or average degrees of branching (= VG) of the used medium-chain branched nonionic surfactants are given in the respective column in Tables 2 and 3 ben. The nonionic surfactants used according to the invention all had an alkyl or alkenyl rest with 13 carbon atoms (= C13).

The cleaning performance was used to determine the washing performance of the individual recipes of pigment / fat, make-up and lipstick stains each five times under identical conditions conditions examined. 2.5 kg of laundry were each washed at 40 ° C. in a washing machine of the type Miele W 918 in the Easy Care program using the specified amount of washing medium cleaned.

The numerical values (ΔΔE values) given in Tables 2 and 3 regarding the cleaning performance show the improvement in the washing performance of the specified laundry detergent according to the invention tel formulations compared to the conventional standard recipe described above (with Dehydol LT 7 ® as nonionic surfactant).

Table 2

Table 3

Tables 2 and 3 show that the substitution of a conventional linear C12-18 alcohol thoxylates (Dehydol LT 7) by the indicated medium chain branched oxo alcohol ethoxylates with a degree of branching of 1.7, 2.2 or 2.4 and EO degrees of 5 or 7 in all cases leads to a significantly improved cleaning performance of the detergent. Especially lipstick Soiling can be removed much better with the detergent according to the invention NEN.

Further washing or cleaning agents according to the invention were invented using a inventive surfactant combination of medium-chain branched nonionic surfactant and a mixture of essentially unbranched and branched in the 2-position nonionic surfactant in the invention preferred ratios in otherwise identical gel formulations according to Table 1. The surfactant combinations used were each a mixture of a C13 oxo Alcohol ethoxylate with a degree of branching of 2.4 and a "classic" nonionic surfactant unbranched (40%) and branched (2%) (60%) C14 / C15 oxo alcohol ethoxylate. before The nonionic surfactants mentioned were used in a ratio of 1: 1 and 7: 3.

Show the numerical values (ΔΔE values) given in Table 4 for cleaning performance again the improvement in the washing performance of the washing according to the invention specified formulations compared to the conventional standard recipe described above (with Dehydol LT 7 ® as nonionic surfactant).  

Table 4

Table 4 shows that the use of a surfactant combination according to the invention is sufficient medium-chain branched nonionic surfactant and classic "nonionic surfactant in preferred according to the invention Conditions leads to an improvement in the cleaning performance of the detergent. To the night knows the surprisingly found synergistic effect of the aforementioned inventive In accordance with nonionic surfactant mixtures, an appropriate detergent with 24% by weight C13- Formulated and tested oxo alcohol ethoxylate with a degree of branching of 2.4. It has shown that this detergent formulation also compared to the conventional agent (standard) has a significantly better washing performance. In comparison, this proves to be ß 7: 3 mixture, however, in terms of cleaning ability as even better, which on the synergistic effect of this combination of surfactants is attributable.

2. Synergistic effects when using certain medium-chain branched Oxo-alcohol ethoxylates

To determine the washing performance of the washing or cleaning agents according to the invention with particularly advantageous surfactant combinations according to the invention were again met Detergent compositions according to the invention with conventionally formulated Detergent compared. Instead of the conventional, essentially unbranched nonionic surfactants, the combinations of medium-chain branched nonionic provided according to the invention Surfactants used in an otherwise identical master recipe.

The detergent formulation or combination shown in Table 5 was used as the base formulation used formulation that corresponds to a common detergent formulation. Accordingly both in the inventive and in the conventional detergent formulations each contain a total of 8.23% by weight of nonionic surfactant.  

Table 5

First, a conventional detergent based on that in Table 5 was again given a recipe. A conventional C12-C18- was used as the nonionic surfactant. Fatty alcohol ethoxylate with an EO grade of 7 (Dehydol LT 7 ®) was used. The resulting Detergent or its cleaning performance was used for the subsequent tests Standard used for comparison

For the formulation of the detergents according to the invention on the basis of those given in Table 5 Various oxo alcohol ethoxylate mixtures provided according to the invention were formulated used. Oxo alcohol ethoxylates with EO degrees of 3 or 7 were used. The respective The average degree of branching VG of the medium-chain branched nonionic surfactants used was 1.7 or 2.2. The nonionic surfactants used according to the invention all had an alkyl or alkene nyl radical with 13 carbon atoms (= C13). The corresponding proportions of the under searched nonionic surfactant mixtures are given in Table 6.

The cleaning performance was used to determine the washing performance of the individual recipes of pigment / fat, make-up and lipstick stains each five times under identical conditions conditions examined. 2.5 kg of laundry were each washed at 40 ° C. in a washing machine of the type Miele W 918 in the Easy Care program cleaned using 100 g detergent.  

Show the numerical values (ΔΔE values) given in Table 6 for cleaning performance again the improvement in the washing performance of the washing according to the invention specified formulations compared to a conventional detergent. As a standard recipe (with Dehydol LT 7 ® as nonionic surfactant) the composition given in Table 5 was used.

Table 6

The surprisingly found synergistic effect, which is based on the use of a mixture of a nonionic surfactant according to the formula R ¹ -O- (CH ₂ CH ₂ O) ₃ -H and a non-ionic surfactant according to the formula R ¹ O- (CH ₂ CH ₂ O ) ₇ -H is clearly legible from the test results shown in Table 6. In all cases, a very good, improved cleaning performance was found with a wide variety of soils, which is attributable to the use of the medium-chain branched nonionic surfactants. However, the best cleaning performance was when using mixtures of R ¹ -O- (CH ₂ CH ₂ O) ₃ -H / R ¹ -O- (CH ₂ CH ₂ O) ₇ -H in a ratio of 1: 2 or 2 : 1 to watch. This is undoubtedly due to the synergistic effect of the nonionic surfactants used.

3. Investigation of the gel behavior depending on the surfactant concentration in water

In the investigation described below, the viscosity of the respective surfactants was a water temperature of 15 ° C and different surfactant contents determined.  

Table 7

Table 7 can clearly be seen that a conventional, essentially un branched fatty alcohol ethoxylate (Dehydrol LT 7) or the corresponding solution for surfactant Held in the range of 40-60% has a pronounced highly viscous phase. This ungün permanent gel behavior would, for example, when dissolving detergent granules or ent Talking tablets lead to clumping or gel formation. A clump or one strong gel formation has an extremely disadvantageous effect on the induction behavior of the corresponding one Detergent.

The nonionic medium-chain branched surfactant A (iso-C-13-ethoxylate + 7E0; degree of branching 2, 2), however, does not form a significant, highly viscous phase. The surfactant solutions obtained are significantly less viscous than comparable non-ver. even with surfactant contents of over 60% branched surfactants. Detergents that are produced using surfactants A and / or B, therefore show a significantly improved gel behavior or a significantly better induction ratio th.

Claims (15)

1. washing or cleaning agents comprising medium-chain branched nonionic surfactants characterized by the following formula 1
R ¹ -O- (CH ₂ CH ₂ O) _p -H (I);
wherein R ^{1 is} a medium-chain branched alkyl and / or alkenyl radical having 10 to 22 carbon atoms and has an average degree of branching from 1.2 to 2.5 and p represents numbers from 1 to 9. 2. washing or cleaning agent according to claim 1 comprising medium-chain branched non-ionic surfactants characterized by the following formula I.
R ¹ -O- (CH ₂ CH ₂ O) _p -H (I);
wherein R ^{1 is} a medium-chain branched alkyl and / or alkenyl radical with 8 to 18, preferably with 13 carbon atoms and has an average degree of branching from 1.7 to 2.4 and p represents numbers from 3 to 7. 3. Washing or cleaning agent according to claim 1 or 2, characterized in that the medium-chain branched alkyl and / or alkenyl radical R ^{1 has} predominantly methyl, ethyl, propyl and / or butyl branches, preferably methyl and / or ethyl branches. 4. washing or cleaning agent according to one of claims 1 to 3, characterized in that between 0.1 and 30% by weight in the washing or cleaning agent, preferably between 1 and 20% by weight and particularly preferably between 2 and 15% by weight of medium-chain branched nonionic surfactant are contained. 5. washing or cleaning agent according to one of claims 1 to 4, characterized in that branched medium-chain in the detergent or cleaning agent Alkyl sulfates and / or alkyl sulfonates are selected from the group comprising Alkyl sulfates and / or alkyl sulfonates with a medium chain branched alkyl radical with 10 to 22, preferably 8 to 18 and in particular, preferably with 13 carbon atoms and one average degree of branching from 1.7 to 2.4. 6. washing or cleaning agent according to one of claims 1 to 5, characterized in that in the washing or cleaning agent

• a) at least one medium-chain branched nonionic surfactant of the formula
  R ¹ -O- (CH ₂ CH ₂ O) _p -H; and
• b) at least one medium-chain branched nonionic surfactant of the formula
  R ² -O- (CH ₂ CH ₂ O) _p -H

is contained, with a) and b) preferably in a weight ratio of 9: 1 to 1: 9, more preferably in a weight ratio of 7: 3 to 3: 7, particularly preferably in a weight ratio of 3: 2 to 2: 3 and most preferably in a weight ratio 1: 1 are included. 7. washing or cleaning agent according to claim 6, characterized in that a) and / or b), preferably a) and b) a medium-chain branched alkyl and / or alkenyl radical R ¹ preferably having 13 carbon atoms and / or an average degree of branching of 1.5 to 2.3, particularly preferably 1.7 or 2.2. 6. washing or cleaning agent according to one of claims 1 to 5, characterized in that in the washing or cleaning agent

• a) at least one medium-chain branched nonionic surfactant of the formula
  R ¹ -O- (CH ₂ CH ₂ O) _p -H; and
• b) at least one nonionic surfactant of the formula
  R ² -O- (CH ₂ CH ₂ O) _p -H,

is contained, wherein R ^{2 is} an essentially unbranched or branched in the 2-position alkyl and / or alkenyl radical having 10 to 22, preferably 8 to 18, particularly preferably 12 to 15 and particularly preferably having 13 carbon atoms and p for numbers of 1 to 9, preferably from 3 to 7. 9. washing or cleaning agent according to claim 8, characterized in that a) and b) in a weight ratio of 9: 1 to 1: 9 and in particular which are preferably contained in a weight ratio of 7: 3. 10. washing or cleaning agent according to claim 6 or 7, characterized in that a) and / or b), preferably a) and b) an alkyl and / or alkenyl radical having preferably 13 carbon atoms and / or a degree of ethoxylie p of 5 have and / or R ^{1 has} an average degree of branching of 1.7 to 2.4, particularly preferably of 2.4. 11. washing or cleaning agent according to one of the preceding claims, characterized in that the medium-chain branched nonionic surfactants of For mel I are biodegradable. 12. washing or cleaning agent according to one of the preceding claims, characterized in that the washing or cleaning agent as a gel, in solid and / or in liquid form.   13. washing or cleaning agent according to one of the preceding claims, characterized in that the washing or cleaning agent as a shaped body, before preferably as granules, extrudate, particles, agglomerate, capsule, tablet, tab and / or same, as well as mixtures thereof. 14. washing or cleaning agent according to one of the preceding claims, characterized in that the detergent or cleaning agent components are selected are from the group comprising surfactants, fragrances, dyes, enzymes, enzyme stabilizers Ren, builders, substances for adjusting the pH, bleach, bleach activators, sil protective agents, dirt-repellent substances, optical brighteners, graying inhibitors ren, disintegration aids, usual ingredients and / or mixtures thereof. 15. Use of the washing or cleaning agent according to one of the preceding claims Cleaning hard surfaces and / or soft surfaces, preferably for cleaning of hair, fibers, textiles, carpets, clothing, food and / or same and particularly preferred as dishwashing detergent, all-purpose cleaner, bathroom cleaner, Floor cleaners, car cleaners, glass cleaners, furniture care products, furniture cleaners, facades cleaner, detergent and / or the like.