JP5487103B2 - Detergent or detergent containing polyester antifouling polymer - Google Patents

Description

  The present invention relates to detergents or detergents containing at least one anionic surfactant based on lipochemistry and polyester antifouling polymers and their use in manual or automatic fabric cleaning.

  Furthermore, it relates to the use of polyester-based antifouling polymers in sulfonate ester-containing detergents or detergents to reduce fabric graying in fabric washing. Furthermore, it is related with the washing | cleaning method of the fabric which uses the above-mentioned washing | cleaning agent or detergent at the washing | cleaning temperature of 40 degrees C or less.

In recent years, human societies have a general need to reduce environmental impacts more comprehensively and, as a result, make economic activities more sustainable.
Thus, it is also a requirement of both consumers and industry to create effective formulations that are as environmentally compatible as possible and comply with the principles of sustainability, as well as in the detergent and detergent sectors.

  For this reason, the current developments of common and specific cleaning agents, for example in Europe, are based on legal provisions and standards (eg European Community detergent regulations). Thereby, for all surfactants currently used in detergents, the primary degradation must be at least 80% and complete biodegradation (after 28 days) must be at least 60%.

  A further requirement is not only to comply with legal regulations and standards, but also to contribute as much as possible to environmental conservation factors.

  The fact that the reserves of fossil or petrochemical raw materials are limited is considered a disadvantage for many consumers, and as a result, the protection of such resources is highly preferred. Furthermore, surfactants based on fossil raw materials are often difficult to degrade under anaerobic conditions.

  Thus, in particular, to make available this type of detergent or detergent formulation, which is manufactured on the basis of at least a part, better or most of its surfactants, or completely sustainable ingredients There is a real demand. However, this requirement is further expected by consumers based on systems that are based on at least some, better or most of its surfactants, or based on completely sustainable raw materials, and it is natural nowadays. It is also related to attempts to enable very good primary and secondary cleaning power (primary = soil removal power; secondary = greying suppression).

  However, surfactants based on sustainable raw materials are often more difficult to formulate than surfactant groups (alkyl benzene sulphonates based on petrochemical raw materials) of the greatest economic importance. In addition, usually, at the same input amount, the cleaning power (preferably the soil removing power, particularly the ability to clean stains containing fatty soil) is lower.

  Against this general background, the problem to be specifically achieved by the present invention is that the surfactant component provide a cleaning or cleaning agent that minimizes stress in petrochemical resources. This object is achieved by the method of the present invention.

  The subject of the present invention is a detergent or detergent containing at least one anionic surfactant based on lipochemistry, as well as a polyester-based antifouling polymer.

  “Based on lipochemistry” means for the purposes of the present invention that the surfactants in question (eg anionic surfactants) originate mainly from plants and from animals, oils and / or fats. Is essentially based on. Important vegetable oils are, for example, rapeseed oil, sunflower oil, linseed oil, coconut fat, coconut oil, palm oil, palm kernel oil, soybean oil, peanut oil, castor oil. Important animal fats are, for example, beef tallow and chicken tallow.

  It should be noted that all natural fats and oils mainly contain only linear unsaturated carbon chain fatty acids having an even number of carbon atoms. Here, one exception is beef tallow with 3% C17 fatty acids.

  Fossil, in particular petrochemical feedstocks, that is to say basic substances obtainable in particular from petroleum and natural gas, are clearly distinguished therefrom.

  Substantially (ie, at least partially, better or mostly) anionic surfactants based on lipochemistry, ie, anionic surfactants based on substantially sustainable sources of natural fats and oils The agent is in particular a sulfonic acid ester, preferably sulfonic acid methyl ester (MES), fatty alcohol sulfate (FAS).

Thereby, sulfonic acid esters (substantially based on lipochemistry) can be used particularly preferably in the present invention. Since sulfonate esters are well known to those skilled in the art of cleaning and cleaning agents, the description can be simplified in this respect. Preferably used sulfonate esters usually contain a terminal ester functional group and a sulfonate functional group in the molecule, adjacent to the α-position. These α-sulfonic acid esters can be obtained, for example, by reacting an alkyl ester with a usual sulfonic acid oxidizing agent, preferably air-diluted dry sulfur trioxide (SO ₃ ) at 80 ° C., and then neutralizing. . Coconut oil (C12 / C14 chain), palm kernel oil (palm kernel sulfo fatty acid ester) or tallow methyl ester (C16 / C18 chain) is particularly preferred.

Particularly preferred sulfonic acid esters can be described by the following formula.

In this formula (I), R is the mean _C 6 _{-C 22} alkyl group. Particularly _preferably, C 10 _{-C 18} alkyl _group, C 12 _{-C 14} alkyl _group, C 14 _{-C 16} alkyl _group, C 12 _{-C 15} alkyl _group, C 8 _{-C 10} alkyl _group, C 16 _{-C 18} alkyl It can be a group, a C ₁₆ alkyl group, a C ₁₂ -C ₁₆ alkyl group, or a C ₁₂ -C ₁₈ alkyl group. However most _preferably, a C 16 _{-C 18} alkyl _group, C 12 _{-C 16} alkyl _{group, C 16} alkyl group or a _C 12 _{-C 18} alkyl group.

In this formula (I), R ¹ is an average C ₁ -C ₆ alkyl group, particularly preferably a methyl group.

  In this formula (I), n is a number of 1 or 2, preferably 1.

In this formula (I), M ^{n +} represents a counter ion, and M is preferably Na, K, Ca, Mg, H, monoethanolammonium, diethanolammonium, triethanolammonium, or a mixture thereof. In the present invention, n + is 1+ or 2+ depending on the type of M. As a counter ion, Na ⁺ , K ⁺ , or Mg ⁺ is preferable.

Similarly, fatty alcohol sulfates (substantially based on lipochemistry) can be used particularly preferably in the present invention. Fatty alcohol sulfates are well known to those skilled in the art of cleaning and cleaning agents. Fatty alcohol sulfates that can be preferably used can be described by the formula (II), R ² O—SO ₃ X. These can be obtained, for example, preferably by reaction of saturated fatty acids with concentrated sulfuric acid, gaseous trioxide sulfuric acid, chlorosulfonic acid, amidosulfonic acid.

In formula (II), R ² O—SO ₃ X, R ² is in particular a linear (or branched) aliphatic alkyl group having 6 to 22, preferably 12 to 18 carbon atoms. And / or represents an alkenyl group, X represents an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium, or glucanonium. C _12/14, fatty alcohol sulfates based on _{C 12/18} and _{C 16/18} fatty alcohols, preferably their sodium salts are particularly preferred.

  In the case of branched primary alcohols, these are oxo alcohols, for example oxo alcohols obtained by the reaction of carbon monoxide and hydrogen on α-olefins by the SHOP method. Thus, alkyl sulfates based on oxo alcohols are not anionic surfactants based on lipochemistry.

  Particularly preferred for the present invention are detergents or detergents according to the invention containing sulfonate esters and / or fatty alcohol sulfates (as anionic surfactants based on lipochemistry) and polyester antifouling polymers.

  In the present invention, anionic surfactants based on lipochemistry are anionic surfactants based on petrochemical raw materials, ie alkane sulfonates, preferably secondary alkane sulfonates (SAS), and alkylbenzene sulfones. Differentiated from acid salts, such as preferably linear alkylbenzene sulfonates, as well as α-olefin sulfonates.

  The total amount of anionic surfactant based on petrochemical raw material is advantageously less than 20% by weight, preferably less than 15% by weight, more advantageously less than 10% by weight and even more advantageously 5%, based on the total formulation. Less than 1% by weight, in particular less than 1% by weight. In particular, in fact, anionic surfactants based on petrochemical raw materials are not included in the present invention at all.

  However, if the cleaning or cleaning agent of the present invention contains an alkyl benzene sulfonate (which is possible but not preferred for the present invention), at most less than 20% by weight, based on the total cleaning or cleaning agent For example, in an amount of 0.01 to less than 15% by weight, preferably less than 10% by weight, less than 5% by weight, and even less than 1% by weight. However, in particular in a preferred embodiment of the invention, the formulations of the invention do not contain any alkylbenzene sulfonates.

〔式中、Ｒはアルキル基（原則としてＣ８〜Ｃ１２）を表し、Ｍ^１は１価の陽イオン、好ましくはナトリウムを表す。〕 The alkyl benzene sulfonate has the following general formula.

[Wherein, R represents an alkyl group (C8-C12 in principle), ^{M 1} represents a monovalent cation, preferably sodium. ]

  If the cleaning or cleaning agent of the present invention contains an alkane sulfonate (which is possible but not preferred for the present invention), based on the total cleaning or cleaning agent, at most less than 15% by weight, for example An amount less than 0.01 to 10% by weight, preferably less than 5% by weight or less than 1% by weight.

However, in particular, in a preferred embodiment of the invention, the formulations of the invention do not contain any alkyl sulfonates.

“Alkanesulfonate” has the general formula R—SO ₂ —OM, wherein R represents a (usually secondary) alkyl group, and M is a monovalent cation, preferably sodium. ] Is a general term for the compounds of

  If the cleaning or cleaning agent of the present invention contains an α-olefin sulfonate salt (which is possible but not preferred for the present invention), based on the total cleaning agent or cleaning agent, at most less than 15% by weight For example in an amount of less than 0.01 to 10% by weight, preferably less than 5% by weight or less than 1% by weight.

However, in particular in a preferred embodiment of the invention, the formulations of the invention do not contain any α-olefin sulfonates.

The “α-olefin sulfonate” has the general formula R—CH═CH— (CH ₂ ) _n —SO ₂ —OM [wherein R represents a (primarily linear primary) alkyl group, A monovalent cation, preferably sodium (n = 1 or 2). ] Is a general term for the compounds.

  Technical grade α-olefin sulfonates are usually produced in a 2: 1 ratio of hydroxyalkane sulfonate to alkene sulfonate for manufacturing reasons.

  Fatty alcohol ether sulfate (FAES) can be obtained substantially based on lipochemistry. That is, (substantially) a fatty alcohol alkoxylate is produced by a reaction between a fatty chemical raw material and an alkylene oxide (preferably ethylene oxide), and then reacted with, for example, sulfur trioxide and neutralized to a fatty alcohol ether sulfate. Can be obtained. The alkylene oxide, preferably ethylene oxide, required for the present invention is derived in principle from petrochemical resources. However, it can also be recovered from biomass, for example, by reaction of bioethanol (eg from sugar radish) to ethylene followed by oxidation to ethylene oxide. This is particularly economically useful, especially in countries like Brazil and India, where the corresponding cheap biomass is available. For the purposes of the present invention, the group of fatty alcohol ether sulfates, regardless of the origin of the alkylene oxide, can obtain fatty alcohol components from lipochemical resources anyway, so that the Classified as ionic surfactant.

  Thus, according to a preferred embodiment of the invention, the fatty alcohol ether sulfate is, for example, 0 to 20% by weight, preferably 0.01 to 15%, based on the total detergent or detergent in the formulation of the invention. It is included in an amount of% by weight, preferably 1 to 10% by weight.

  However, according to a further preferred embodiment of the present invention, a very small amount (eg, less than 2% by weight or less than 1% by weight of the total formulation) of fatty alcohol ether sulfate is included or in practice, No fatty alcohol ether sulfate is contained in the preparation of the present invention.

  In a preferred embodiment of the present invention, the polyester-based antifouling polymer is contained in the cleaning agent or detergent of the present invention in an amount of 0.01 to 2% by weight, preferably 0.05 to 1.5% by weight, based on the whole preparation. , Preferably 0.1 to 1% by weight, in particular 0.15 to 0.8% by weight. Applicants have found that this amount of antifouling polymer contributes to achieving good results in terms of primary and secondary detergency of fabric cleaning. In the cleaning agent or cleaning agent of the present invention, it is possible to use a polyester antifouling polymer exceeding 2% by weight.

  If a sulfonic acid ester, preferably sulfonic acid methyl ester (MES), is included as a (substantially) fatty chemistry based anionic surfactant in the detergents or detergents of the invention, 1 to 20% by weight, more preferably 3 to 15% by weight, in particular 5 to 10% by weight, which is a preferred embodiment of the present invention.

  Alkyl benzene sulfonates, preferably linear alkyl benzene sulfonates (LAS), when included in the detergents or detergents of the present invention, are advantageously from 0.01 to 20% by weight, based on the total formulation. An amount of preferably 0.1 to 10% by weight, in particular 1 to 5% by weight, is also a preferred embodiment of the present invention.

  If a sulfonate ester, preferably MES, and a benzene sulfonate, preferably LAS, are used at the same time, for the purposes of the present invention, the amount ratio of sulfonate ester should be at least as great as the alkyl benzene sulfonate. Preferably, more is more advantageous. Thus, in a preferred embodiment, the quantity ratio of sulfonate ester to alkylbenzene sulfonate is preferably at least 1: 1, preferably at least 1.1: 1, in particular 1.2: 1. The quantitative ratio of sulfonate ester to alkylbenzene sulfonate may be equivalent, for example 2: 1 or 3: 1, for example in the range of 1: 1 to 20: 1, or 1.1: 1 to 10: 1. It may be a range.

  However, as already mentioned, the cleaning or cleaning agents according to the invention can contain very small amounts of alkyl sulfonates, for example less than 1% by weight, based on the total formulation, and also contain alkylbenzene sulfonic acids. It does not have to contain any salt.

  When alkylbenzene sulfonates are partially or fully replaced by sulfonate esters, fabrics, especially polyester blended fabrics, and cotton fabrics and graying of the blended fabrics are greatly increased in fabric cleaning, which is a visual problem Can result in consumer dissatisfaction.

  Quite surprisingly, polyester-based antifouling polymers are used in combination with MES (with no LAS present) or in combination with MES (with partial replacement of LAS by MES) In particular, it has been found that fabric graying, in particular polyester and polyester blend fabrics, is significantly reduced. Furthermore, very good primary cleaning power can be achieved.

  It is possible in this way to provide a consumer product with both very good primary and secondary detergency in fabric cleaning and containing a fairly high proportion of sustainable raw materials, ie surfactants based on MES. Conversely, anionic surfactants based on petrochemicals (for example LAS in particular) can be reduced, or in fact can be omitted entirely.

  In particular, very good results in the primary and secondary detergency mentioned above are achieved when polyester-based antifouling polymers as described directly below are utilized in the present invention.

The present invention also includes a polyester-type antifouling polymer including structural units I to III or I to IV substantially consisting of the following, which is also a preferred embodiment of the present invention.
-[(OCHR ¹ -CHR ² ) _a -O-OC-Ph-CO-] _d (I)
^{- [(OCHR 3 -CHR 4)} b -O-OC-sPh-CO-] e (II)
-[(OCHR ⁵ -CHR ⁶ ) _c -OR ⁷ ] _f (III)
-[Multifunctional unit] _g (IV)
[Wherein, a, b, and c each independently represent a number of 1 to 200,
d, e, and f each independently represent a number from 1 to 50;
g represents a number from 0 to 5;
Ph represents a 1,4-phenylene group,
sPh represents a 1,3-phenylene group substituted at the 5-position with a —SO ₃ Me group,
Me is, Li, Na, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, - di -, tri - or represents tetraalkyl ammonium, alkyl ammonium ions _C 1 _{-C 22} alkyl It represents a group or a _C 2 _{-C 10} hydroxyalkyl group, or mixtures thereof,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen or C _1-
Represents a C ₁₈ n- or iso-alkyl group,
R ⁷ is a linear or branched C ₁ -C ₃₀ alkyl group or a linear or branched C ₂ -C ₃₀ alkenyl group, a cycloalkyl group having 5 to 9 carbon atoms, C _6- represents C ₃₀ aryl group or _C 6 _{-C 30} arylalkyl group,
The “multifunctional unit” represents a unit having 3 to 6 functional groups capable of performing an esterification reaction. ]

Among these, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are independently of each other hydrogen or methyl, R ⁷ is methyl, and a, b, and c are independent of each other. 1 to 200, in particular 1 to 20, particularly preferably 1 to 5, very particularly preferably a and b are 1 and c can be a number from 2 to 10 and d is 1 to 25 , In particular 1 to 10, particularly preferably 1 to 5, e is 1 to 30, in particular 2 to 15, particularly preferably 3 to 10 and f is 0.05 to 15, in particular 0. Polyesters having a number of 1 to 10, particularly preferably 0.25 to 3, are preferred. This type of polyester includes, for example, terephthalic acid dialkyl esters, 5-sulfoisophthalic acid dialkyl esters, alkylene glycols, optionally polyalkylene glycols (a, b and / or c is greater than 1), and single-end capped polyalkylenes. It can be obtained by polycondensation of glycol (corresponding to unit III). It should be noted that for numbers a, b, c greater than 1, there is a polymer backbone so that the coefficient can be any value in between as an average. This value reflects the number average molecular weight. Esters of terephthalic acid and one or more difunctional fatty alcohols are suitable as units (I); ethylene glycol having a number average molecular weight of 100 to 2000 g / mol (R ¹ and R ² are each H ) And / or 1,2-propylene glycol (when R ¹ = H and R ² = CH ₃ or vice versa) and / or short chain polyethylene glycol and / or poly [ethylene glycol-co-propylene glycol] It is preferably used in the invention. For example, 1-50 units (I) per polymer chain can be included in the structure. Esters of 5-sulfoisophthalic acid with one or more difunctional fatty alcohols are suitable as unit (II) and the aforementioned are preferably used in the present invention. For example, 1-50 units (II) per polymer chain can be included in the structure. As a nonionic single end-capped polyalkylene glycol monoalkyl ether of structure (III), poly [ethylene glycol-co-propylene glycol] monomethyl ether having an average molecular weight of 100 to 2000 g / mol, and the general formula CH ₃ —O— ( during _{C 2 H 4 O) n -H} [ wherein, n = 1 to 99, especially from 1 to 20, particularly preferably 2 to 10. ] Is preferably used. Since the maximum theoretical average molecular weight that can be achieved by quantitative conversion of the polyester structure is predefined using this type of single-terminal cap ether, the preferred utilization of structural unit (III) is described below. This is considered to be an amount necessary to achieve an average molecular weight. In addition to linear polyesters derived from structural units (I), (II) and (III), crosslinked or branched polyester structures can also be used in the present invention. This is represented by the presence of a multifunctional structural unit (IV) having a crosslinking effect and having a functional group capable of undergoing at least 3 up to 6 esterification reactions. The functional group classification that can be enumerated in the present invention is an acid, alcohol, ester, anhydride or epoxy group. In the present invention, different functionalities may exist in one molecule. Citric acid, malic acid, tartaric acid and gallic acid, particularly preferably 2,2-dihydroxymethylpropionic acid, can be examples thereof. In addition, polyhydric alcohols such as pentaerythritol, glycerol, sorbitol and / or trimethylolpropane may be used. Polyhydric alcohols or aromatic carboxylic acids such as benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid), or benzene-1,3,5-tricarboxylic acid Acid (trimesic acid) is also included. The weight ratio of the crosslinking monomers can be, for example, 10% by weight or less, in particular 5% by weight or less, particularly preferably 3% by weight or less, based on the total weight of the polyester. Polyesters comprising structural units (I), (II) and (III) and optionally (IV) generally have a number average molecular weight in the range of 700 to 50,000 g / mol; number average The molecular weight can be measured by size exclusion chromatography in aqueous solution, specifying a narrow distribution polyacrylic acid sodium salt standard.

  The number average molecular weight is preferably in the range of 800 to 25,000 g / mol, in particular 1,000 to 15,000 g / mol, particularly preferably 1,200 to 12,000 g / mol. According to the invention, it is preferred to use a solid polymer exhibiting a softening point of 40 ° C. or higher as the second type of particle component. They preferably have a softening point of 50-200 ° C., particularly preferably 80-150 ° C., more preferably 100-120 ° C .; The synthesis of the polyester is carried out in a known manner, for example by first heating the above components under standard pressure and heating, followed by distillation of the high stoichiometric amount of glycol used under vacuum. Methods such as building molecular weight can be used. Known transesterification and condensation catalysts such as tetraisopropyl titanate, dibutyltin oxide, alkali or alkaline earth metal alcohol compounds, or antimony trioxide / calcium acetate are suitable for the reaction. For further details, reference can be made to EP442101.

  The polyester preferably used is a polyester of solid consistency that can be easily powdered or compressed or agglomerated into granules of a defined particle size. Granulation is such that the copolymer obtained as a melt by synthesis is solidified into flakes, for example by cooling with a cooling stream of a gas such as oxygen or nitrogen, or by using a flaking roller or a moving belt. Can be done by the method. This crude material can be further pulverized, for example, with a roller frame or a sieve mill, if necessary, and then sieved and rounded as described above. Granulation can be performed by pulverizing the polymer after solidification into a powder, and then compressing or agglomerating as described above, rounding, and processing into granules having a prescribed particle size.

  The partial or complete replacement of the LAS by MES not only maintains the primary and secondary detergency in fabric cleaning very effectively, but in some cases can actually increase the detergency. Soil polymers are particularly preferred. Antifouling polymers preferably used are also described in WO2007 / 0779850A1 (referenced here as it is).

Antifouling polymers used with particular advantage are granular and in particular those having the following particle size distribution:
> 1.6mm < 1%
0.8-1.6mm < 20%
0.4-0.8mm 50-80%
0.1-0.4mm 15-45%
<0.1mm < 5%

  According to a further preferred embodiment of the present invention, the cleaning or cleaning agent of the present invention further comprises a nonionic surfactant and is a nonionic surfactant based on a sustainable raw material, preferably a lipochemical raw material. It is preferred for the present invention to use (substantially) based nonionic surfactants. Among these, nonionic surfactants based on sustainable materials that can be preferably used are in particular sugar structures, such as preferably alkylpolyglucosides (APG), sugar esters, in particular sucrose esters and / or sugar amides, in particular glucamide, fatty acid sarcosinates. , Alkanolamides, protein / fatty acid condensates, and fatty amines.

  Sugar surfactants include, for example, alkyl glucose esters, aldobionamides, gluconamides (sugar amides), glycerol amides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides), and sugars of alkyl polyglycosides It is a known surface-active compound contained in surfactants.

  In the present invention, sugar surfactants that can be particularly preferably used are alkyl polyglycosides, sugar amides (especially glucamide) and sugar esters, for example, preferably sucrose esters, especially alkyl polyglycosides.

Particularly preferred sugar amides have the formula (III): R′C (O) N (R ″) [Z] [wherein R ′ is 5 to 21, preferably 5 to 17, particularly 7 to 15. Represents a straight-chain or branched, saturated or unsaturated alkyl group, preferably a straight-chain unsaturated alkyl group, having preferably 7 to 13 carbon atoms, R ″ is 6 to 22 Linear, branched, saturated or unsaturated alkyl radicals, preferably 6-18, in particular 8-16, particularly preferably 8-14 carbon atoms, preferably linear unsaturated alkyl _{group, C 1 to 5} alkyl groups, in particular methyl, ethyl, propyl, isopropyl, n- butyl, isobutyl, tert- butyl or n- pentyl group or hydrogen, Z is represented sugar group, i.e. a monosaccharide group . ]. Particularly preferred sugar amides are amides of glucose, glucamide, such as lauroylmethyl glucamide.

  Glucamide is an N-alkylated, preferably N-methylated fatty acid amide, which can be obtained by reaction of N-alkyl- (N-methyl) glucosamine with a fatty acid methyl ester.

〔上記式（ＩＶ）中、Ｒ'は、５〜２１個、好ましくは５〜１７個、特に７〜１５個、特に好ましくは７〜１３個の炭素原子を有する直鎖状または分枝状の、飽和または不飽和アルキル基、好ましくは直鎖状不飽和アルキル基、例えばｎ−Ｃ_１２を表し、Ｒ''は、６〜２２個、好ましくは６〜１８個、特に８〜１６個、特に好ましくは８〜１４個の炭素原子を有する直鎖状または分枝状の、飽和または不飽和アルキル基、好ましくは直鎖状不飽和アルキル基、Ｃ_１〜５アルキル基、特にメチル、エチル、プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔｅｒｔ−ブチルまたはｎ−ペンチル基あるいは水素、特に低級アルキル基、通常メチル基を表す。〕 Particularly preferred glucamide can be represented by the following general formula (IV).

[In the above formula (IV), R ′ is linear or branched having 5 to 21, preferably 5 to 17, particularly 7 to 15 and particularly preferably 7 to 13 carbon atoms. , saturated or unsaturated alkyl group, preferably represents a straight-chain unsaturated alkyl group, for example an _{n-C 12,} R '' is 6 to 22, preferably 6 to 18, especially 8 to 16, in particular A linear or branched, saturated or unsaturated alkyl group, preferably having 8 to 14 carbon atoms, preferably a linear unsaturated alkyl group, a C _1-5 alkyl group, especially methyl, ethyl, propyl , Isopropyl, n-butyl, isobutyl, tert-butyl or n-pentyl group or hydrogen, particularly a lower alkyl group, usually a methyl group. ]

Alkyl polyglycoside (APG) is a sugar surfactant that is preferably used. Preferably, general formula (V): RO (AO) _a [G] _x [wherein R is 6 to 22, preferably Represents a linear or branched alkyl group having 6 to 18, in particular 8 to 16, and particularly preferably 8 to 14 carbon atoms, [G] represents a glycosidic linked sugar group, and x is 1 represents a number of 1 to 10, AO represents an alkyleneoxy group, such as an ethyleneoxy group or a propyleneoxy group, and a represents an average degree of alkoxylation of 0 to 20. ] Is shown. The group (AO) _a can contain different alkyleneoxy units, such as ethyleneoxy or propyleneoxy units, where a is the average of the total degree of alkoxylation (ie the sum of the degree of ethoxylation and the degree of propoxylation). It is. Unless otherwise stated or described in detail below, the alkyl group R ^{1 of} APGs is a linear unsaturated group having the indicated number of carbon atoms.

  APGs are nonionic surfactants and are known substances that can be obtained by methods related to preparative organic chemistry. The index x represents the degree of oligomerization (DP) (ie the distribution of mono- and oligoglycosides) and represents a number between 1 and 10 as described above. The x of a particular compound must always be an integer, in which case the value x is mainly 1 to 6, whereas the value x for a particular alkyl glycoside is usually an analytical value represented by a decimal value. It is the calculated value confirmed in. Alkyl glycosides having an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From the viewpoint of applied engineering, alkyl glycosides having an oligomerization degree of less than 1.7, particularly 1.2 to 1.6 are preferred. Xylose, especially glucose, is used as the glycoside sugar.

The alkyl or alkylene group R (in relation to the above formula (V): RO (AO) _a [G] _x ) can be derived from a primary alcohol having 8 to 18, preferably 8 to 14 carbon atoms. . Typical examples are hexanol, octanol, decanol, and undecyl alcohol and their industrial mixtures, which are obtained, for example, by hydrogenation of industrial fatty acid methyl esters or by hydrogenation of aldehydes by Lorenoxo synthesis. It is done. However, the alkyl group or alkylene group R is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, or oleyl alcohol. Also included are elaidyl alcohol, petrocerinyl alcohol, aracidyl alcohol, gadreyl alcohol, behenyl alcohol, erucyl alcohol and industrial mixtures thereof.

Preferred APGs are not alkoxylated (a = 0) and are therefore of the formula (VI): RO [G] _{x wherein} R is a straight chain having 4 to 22 carbon atoms as described above. Represents a chain or branched, saturated or unsaturated alkyl group, [G] represents a glycosidic linked sugar group, preferably a glucose group, and x is 1-10, preferably 1.1-3, especially 1.2. Represents a number of ~ 1.6. ]. Corresponding preferred alkyl polyglycosides are, for example, C _8-10 and C _12-14 alkyl polyglycosides having a DP of 1.4 or 1.5, in particular C _8-10 alkyl-1,5-glucosides and C _{12- 14} alkyl-1,4-glucoside.

Particularly preferred APGs are represented, for example, by the following formula (VI).

  Here, the average degree of oligomerization x is preferably 1.2 to 1.5. The alkyl group is preferably in the range of C8 to C16 (thus, n in the above formula is preferably 7 to 15).

  Sugar esters are also nonionic surfactants that can be preferably used. A sugar ester is an ester (that is, a sucrose ester) of a sugar alcohol (particularly sucrose) and an organic acid or an inorganic acid (particularly a fatty acid or a derivative thereof). For example, sucrose and a fatty acid are reacted in a solution or melt. Or by alkali-catalyzed transesterification using triglycerides. In the present invention, monoesters of short chain fatty acids (for example, monoesters of lauric acid) are preferred.

Non-limiting examples of sucrose esters include, for example, the following formulas VIII-X useful for illustration.

  N in these formulas VIII-X is preferably a number in the range of 1-20. Since sucrose esters are generally complex mixtures (especially those with hydroxy functionality), the above formula is intended primarily to help explain.

  Fatty acid sarcosinate is also a nonionic surfactant that can be preferably used. “Fatty acid sarcosinate” refers to a condensation product of a fatty acid and N-methylglycine. Fatty acid sarcosinate can be produced by reacting N-methylglycine with fatty acid chloride. For example, fatty acid sarcosinates based on C12-C18 fatty acids are particularly preferred. Fatty acid sarcosinate has excellent foaming properties, low water hardness sensitivity and excellent skin affinity.

〔式中、Ｒは、好ましくは８〜２２個の炭素原子を有する直鎖状または分枝状の、飽和または不飽和アルキル基を表す。〕 The fatty acid sarcosinate which can be preferably used can be represented by the following general formula (XI).

[Wherein R represents a linear or branched, saturated or unsaturated alkyl group having preferably 8 to 22 carbon atoms. ]

  Similarly, fatty acid alkanolamides can also be preferably used in the present invention. Fatty acid alkanolamides can be obtained, for example, by reacting alkanolamides with fatty acids, fatty acid methyl esters or fatty acid glycerides.

A preferred fatty acid alkanolamide can be represented by the following formula (XII).

R ¹ —CO generally represents a fatty acid group, in particular a stearin group, a coconut fatty group or an olein group. Di- or monoethanolamine or aminopropanol can be used as alkanolamine, whereby the meaning of R ² and n in the above formula is defined.

  Fatty amines can be used in the present invention as well. The fatty amine can be obtained, for example, by a method in which a fatty alcohol is reacted with ammonia or a short-chain alkylamine or dialkylamine at 210 to 260 ° C. in the presence of a dehydrogenation catalyst. Fatty amine salts are cationized active emulsifiers. These are also encompassed by the term “fatty amine”. Quaternary ammonium compounds can be obtained by alkylation. Quaternary ammonium compounds are also encompassed by the term “fatty amine”. The amine oxide can be obtained by oxidizing a fatty amine with, for example, hydrogen peroxide. These are also encompassed by the term “fatty amine”.

Amine oxides that can be used in the present invention include alkyl amine oxides, particularly alkyl dimethyl amine oxides, alkyl amido amine oxides, and alkoxyalkyl amine oxides. A preferred amine oxide can be represented by the following formula (XIII): R ⁶ R ⁷ R ⁸ N ⁺ —O ⁻ . Where
R ⁶ is a saturated or unsaturated C _6-22 alkyl group, preferably a C _8-18 alkyl group, in particular a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group, and in alkylamidoamine oxides carbonyl In the alkoxyalkylamine oxide, an amidoalkylene group —CO—NH— (CH ₂ ) _z — is bonded to the nitrogen atom N via an oxyalkylene group —O— (CH ₂ ) _z —, and each z is 1 -10, preferably 2-5, especially 3.
R ⁷ and R ⁸ are independently of one another a C _1-4 alkyl group which may be optionally hydroxy-substituted, for example a hydroxyethyl group, in particular a methyl group.

  Examples of suitable amine oxides are the following compounds named according to INCI: almond amidopropylamine oxide, babasamidopropylamine oxide, behenamine oxide, cocamidopropylamine oxide, cocamidopropylamine oxide, cocamamine oxide, Coco-morpholine oxide, decylamine oxide, decyltetradecylamine oxide, diaminopyrimidine oxide, dihydroxyethyl C8-10 alkoxypropylamine oxide, dihydroxyethyl C9-11 alkoxypropylamine oxide, dihydroxyethyl C12-15 alkoxypropylamine oxide, dihydroxy Ethylcocamine oxide, dihydroxyethyl lauramine oxide, dihydroxyethyl stearamine oxide, Hydroxyethyl tallow amine oxide, hydrogenated palm kernel amine oxide, hydrogenated tallow amine oxide, hydroxyethyl hydroxypropyl C12-15 alkoxypropylamine oxide, isostearamidopropylamine oxide, isostearamidpropyl morpholine oxide, lauramidopropylamine oxide , Lauramine oxide, Methyl morpholine oxide, Milkamidopropylamine oxide, Mincamidepropylamine oxide, Myristamidopropylamine oxide, Myristamine oxide, Myristyl / cetylamine oxide, Oleamidopropylamine oxide, Oleamine oxide, Oliveamidopropyl Amine oxide, palmitamidopropylamine oxide, palmitamin oxide, PEG-3 Lau Minoxide, potassium dihydroxyethylcocamine oxide phosphate, potassium trisphosphonomethylamine oxide, sesamide propylamine oxide, soybean amide propylamine oxide, stearamide propylamine oxide, stearamine oxide, tallow amide propylamine oxide, tallow amine oxide , Undecylenamidopropylamine oxide and wheat embryo amidopropylamine oxide. A preferred amine oxide is, for example, cocamidopropylamine oxide.

  Protein / fatty acid condensates can be used in the present invention as well. Protein / fatty acid condensates can be obtained, for example, by acylating protein hydrolysates with, for example, fatty acids, fatty acid methyl esters, preferably fatty acid chlorides or substituted maleic anhydrides.

〔式中、ｎは、好ましくは１〜１３である。〕
例えば、Ｌａｍｅｐｏｎ（登録商標）グレード、Ｇｌｕａｄｉｎ（登録商標）グレード、Ｈｏｓｔａｐｏｎ（登録商標）ＫＣＧ、またはＡｍｉｓｏｆｔ（登録商標）グレードが非常によく知られている。 A particularly preferred protein / fatty acid condensate can be represented by the following formula.

[Wherein, n is preferably 1 to 13. ]
For example, the Lamepon (R) grade, Gladin (R) grade, Hostapon (R) KCG, or Amisof (R) grade are very well known.

  Alkoxylated fatty alcohols can be obtained substantially based on lipochemistry. That is, it can be obtained by reaction of the corresponding fatty acid with an alkylene oxide, preferably ethylene oxide. The required alkylene oxide can be recovered via biomass, but is generally recommended from petrochemical resources. For the purposes of the present invention, alkoxylated fatty alcohols, in any case, are derived from lipochemical resources, so that the surface activity based on (substantially) the fatty chemical raw material, regardless of the origin of the alkylene oxide. Classified as an agent.

Alcohol ethoxylates having a linear residue consisting of 12-18 carbon atoms naturally derived alcohols (e.g., palm, palm, palm kernel, tallow or oleyl alcohol) and having an average of 2-8 EO per mole of alcohol Preferably used. Particularly preferable ethoxylated alcohols are, for example, _C 12 _{-C 14} alcohol having 3EO~6EO, _C 9 ~C ₁₁ alcohol with _{7EO, 3EO, 5EO, C 13} ~C 15 alcohol with 7EO or 8EO, 4 EO, 5 EO , _C 14 _{-C 15} alcohols with 7EO or 9EO, 3EO, _C 12 -C having _C 12 _{-C 18} alcohols with 5EO or 7EO, and mixtures thereof, the _C 12 _{-C 14} alcohol with 7EO having, for example 3EO A mixture of ₁₈ alcohols. The degree of ethoxylation is a statistical average and can be an integer or a fraction in a particular product.

  According to a preferred embodiment of the present invention, the cleaning or cleaning agent of the present invention comprises a nonionic surfactant, in particular a nonionic surfactant based on lipochemistry, from 0.01 to 20 based on the whole formulation. It is contained in an amount of% by weight, preferably 0.1 to 15% by weight, especially 1 to 10% by weight.

  In the present invention, particularly preferred are sustainable raw materials, ie preferably nonionic surfactants based on lipochemistry.

  In the present invention, alkoxylated fatty alcohols can also be preferably used.

  If the cleaning or cleaning agent according to the invention contains an alkoxylated alcohol in an amount of 0 to 20% by weight, preferably 0.01 to 15% by weight, in particular 1 to 10% by weight, based on the total formulation, Corresponds to a preferred embodiment of the present invention.

  It is also advantageous to use very small amounts of alkoxylated fatty alcohols, for example less than 5% by weight, preferably less than 3% by weight, in particular less than 2% by weight, or even less than 1% by weight, based on the total formulation. obtain. In practice, no alkoxylated fatty alcohols may be included.

  The total amount of surfactant contained in the cleaning or cleaning agent of the present invention generally varies. For example, in the cleaning or cleaning agent of the present invention, a total amount of 5-50% by weight, preferably 10-35% by weight, in particular 15-30% by weight, of surfactants is very advantageous with regard to detergency in fabric cleaning. I found out that

In a further preferred embodiment of the present invention, the cleaning or cleaning agent of the present invention comprises and advantageously comprises an enzyme, preferably amylase, protease, mannase, tannase, carboanhydrase, pectinase, lipase, and / or cellulase. Contains the enzyme in an amount of 0.01 to 5% by weight, based on the total formulation.
Enzymes are also listed below.

It should be noted that in a preferred embodiment of the present invention, the cleaning or cleaning agent of the present invention actually includes:
(A) a sulfonic acid ester in an amount of in particular 1 to 20% by weight, preferably MES,
(B) in particular an alkylbenzene sulfonate in an amount of 0 to 20% by weight, for example 0.01 to 5% by weight, preferably LAS,
(C) a nonionic surfactant advantageously in an amount of 0 to 15% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 5% by weight;
(D) an enzyme preferably in an amount of 0 to 5% by weight;
And optionally further includes detergent or detergent components ("% by weight" are each based on the entire formulation).

  In a preferred embodiment of the invention, the cleaning or cleaning agent of the invention is at least 50% by weight, preferably more than 60% by weight, more than 70% by weight, more than 80% by weight or more than 90% by weight. Contains many, preferably more than 95% by weight, more preferably more than 99% by weight, in particular actually 100% by weight of surfactants based on lipochemical raw materials ("wt%" Based on the amount of total surfactant included).

  According to a further preferred embodiment of the invention, the cleaning or cleaning agent according to the invention comprises a zeolite-containing builder system, preferably a zeolite-containing builder system comprising zeolite, for example 1 to 50% by weight, based on the total formulation. , Preferably more than 5% by weight, more preferably more than 10% by weight, more preferably more than 15% by weight, in particular more than 20% by weight.

  According to another preferred embodiment of the invention, the cleaning or cleaning agent of the invention is a soluble builder system, preferably a soluble builder system comprising sodium, silicate, citrate and / or polycarboxylate. In particular in a total amount of 2.5 to 60% by weight, based on the total formulation.

  According to another preferred embodiment of the invention, the cleaning or cleaning agent of the invention contains a phosphate, preferably 1 to 40% by weight, in particular 5 to 30%, based on the total formulation. Contains a builder system comprising in an amount of% by weight.

  According to a further preferred embodiment of the invention, the cleaning or cleaning agent of the invention has a pH higher than 7.5 (5% solution, measured at 20 ° C.).

  The cleaning or cleaning agent of the present invention may exist in any form, ie solid, liquid, pasty or semi-solid. However, it is preferred that the cleaning or cleaning agent of the present invention is present in solid form. According to a preferred embodiment of the invention, the cleaning or cleaning agent according to the invention is present in solid form, in particular on powder or in the form of granules, preferably in the form of shaped bodies, in particular tablets.

  A further object of the present invention is to provide a cleaning or cleaning agent according to the present invention, preferably a sulphonic ester-containing cleaning or cleaning agent, for reducing fabric graying in manual or automatic fabric cleaning, in particular in fabric cleaning. Is the use of.

  A further subject of the present invention is the use of polyester antifouling polymers, in particular the polyester antifouling polymers mentioned above, in sulphonate-containing detergents or detergents to reduce fabric graying in fabric washing.

  A further subject of the present invention is the use of polyester antifouling polymers, in particular the polyester antifouling polymers mentioned above, in order to increase the primary detergency in sulphonate-containing detergents or detergents.

  The above-mentioned use of the polyester antifouling polymer in a sulfonate ester-containing cleaning agent or cleaning agent is an LAS content of 15% by weight or less, for example 0.01 to 12% by weight, preferably 10% by weight or less, If advantageously 5% by weight or less ("wt%" is based on total detergent or detergent), the LAS content is in particular 0% by weight, and this is therefore a preferred embodiment of the present invention.

  It is also a preferred embodiment of the present invention when the use is used for fabric washing of fabrics based on cotton, synthetic fibers, preferably polyester and / or based on blended fibers, in particular polyester / cotton blended fibers. .

  A further subject of the present invention is a fabric cleaning method using the cleaning agent or cleaning agent of the present invention, in which the cleaning temperature is 40 ° C. or lower, preferably 30 ° C. or lower. It is naturally possible to perform cleaning at a higher cleaning temperature, for example, 60 ° C. or higher. However, very good cleaning results can be obtained at low cleaning temperatures, for example 40 ° C. or lower, more preferably 30 ° C. or lower.

  Some possible components of the cleaning or cleaning agent of the present invention that are not fully claimed are described in more detail below.

  Anionic surfactants such as sulfonate and sulfate type anionic surfactants can be used. Suitable anionic surfactants are already listed. In general, surfactants based on lipochemistry are always preferred for the present invention.

  Further suitable anionic surfactants are, for example, sulfonated fatty acid glycerol esters. “Fatty acid glycerol esters” are understood to be mono-, di- and triesters, mixtures thereof, which are obtained by esterification of monoglycerols having 1 to 3 mol of fatty acids or from 0.3 to 2 mol. Can be obtained by transesterification of triglycerides with glycerol. Preferred sulfonated fatty acid glycerol esters are sulfonated products of saturated fatty acids having 6 to 22 carbon atoms such as hexanoic acid, octanoic acid, decanoic acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. is there.

  The formulations of the present invention may contain sulfonated fatty acid glycol esters, for example, greater than 0.01% by weight based on the total formulation. However, according to a preferred embodiment, the formulations of the invention do not contain sulfonated fatty acid glycol esters. That is, the sulfonated fatty acid glycol ester content is less than 5% by weight, preferably less than 3% by weight, advantageously less than 1% by weight, respectively, based on the total formulation, and in particular does not contain any sulfonated fatty acid glycol ester.

Suitable alkyl (alkenyl) sulfates are C ₁₂ -C ₁₈ fatty alcohols, such as coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or sulfuric acid semiesters of C ₁₀ -C ₂₀ oxo alcohols. And alkali salts, especially sodium salts, of these chain length secondary alcohol semi-esters.

Also suitable are alkyl (alkenyl) sulfates of the above-mentioned chain lengths containing synthetic linear alkyl groups produced on the basis of petrochemistry and having a decomposition behavior similar to suitable compounds based on lipochemical raw materials. For cleaning techniques, C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates, and C ₁₄ -C ₁₅ alkyl sulfates are preferred.

Sulfuric monoesters of linear or branched _C7-21 alcohols ethoxylated with 1-6 moles of ethylene oxide, for example 2-methyl branched _C9-11 with an average of 3.5 moles of ethylene oxide (EO) Also suitable are sulfuric acid monoesters of alcohols or C _12-18 fatty alcohols having 1-4 EO. Because of their high foaming properties, they are preferably used in relatively small amounts, especially in detergents, for example in amounts of 1 to 5% by weight. Preferably, the formulations of the present invention may be free of sulfuric monoesters.

Another class of anionic surfactants is the class of ether carboxylic acids obtained by reacting fatty alcohol ethoxylates with sodium chloroacetate in the presence of a basic catalyst. They are represented by the general formula R ¹⁰ O— (CH ₂ —CH ₂ —O) _p —CH ₂ —COOH [wherein R ¹⁰ is C _{1 to} C ₁₈ and p is 0.1 to 20. ] Have. Ether carboxylic acids do not react with water hardness and exhibit excellent surface active properties.

  Ether carboxylic acids can optionally be included in the formulations of the invention, for example in an amount greater than 0.01% by weight, based on the total formulation. However, according to a further preferred embodiment of the present invention, the formulation of the present invention does not contain an ether carboxylic acid. That is, the content of ether carboxylic acid is less than 5% by weight, preferably less than 3% by weight, advantageously less than 1% by weight, and in particular does not contain any ether carboxylic acid (“wt%” is based on the whole formulation, respectively) .

  Also, for example, di- or polyhydroxyalkanes, mono- and disaccharides, polyethylene glycol, maleic anhydride and at least one unsaturated carboxylic acid having a chain length of 10 to 25 carbon atoms and an acid number of 10 to 140 Partial esters with acid final adducts are also suitable anionic surfactants.

Particularly preferred anionic surfactants are sulfosuccinates, sulfosuccinates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinates, particularly preferred sulfosuccinates. Sulfosuccinate is a mono- and diester salt of sulfosuccinic acid HOOCCH (SO ₃ H) CH ₂ COOH, “sulfosuccinate” is a mono-amide salt of sulfosuccinic acid, and “sulfosuccinamide” is , A salt of diamide of sulfosuccinic acid.

The salts are preferably alkali metal salts, ammonium salts and mono, di and trialkanol ammonium salts, such as mono, di and triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or ammonium. A salt, more particularly a sodium salt.

  In the sulfosuccinate, one or both carboxyl groups of the sulfosuccinic acid are 4 to 22, preferably 6 to 20, especially 8 to 18, more preferably 10 to 16, and particularly preferably 12 to 14. Preferably esterified with one or two identical or different alcohols having one carbon atom, unbranched or branched saturated or unsaturated acyclic or cyclic, optionally alkoxylated . Particularly preferred are unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols, in particular unbranched saturated fatty alcohols, and / or ethylene oxide and / or propylene oxide, preferably alkoxyl with ethylene oxide. And unbranched saturated fatty alcohol esters having a degree of alkoxylation of 1-20, preferably 1-15, especially 1-10, more preferably 1-6, particularly preferably 1-4. In the present invention, monoesters are preferred over diesters. A particularly preferred sulfosuccinate is sulfosuccinic acid lauryl polyglycol ester disodium salt (lauryl-EO sulfosuccinate disodium salt; INCI: Disodium Laureth Sulfosuccinate), for example, a sulfosuccinate content of 30 wt. Is commercially available as Tego® Sulfosuccinate F 30 (Goldschmidt).

  In sulfosuccinamate or sulfosuccinamide, one or both carboxyl groups of sulfosuccinic acid preferably form a carboxylic acid amide with a primary or secondary amine, the amine comprising 4 to 22, Preferably an unbranched or branched saturated or unsaturated acyclic or ring having 6-20, in particular 8-18, more preferably 10-16, particularly preferably 12-14 carbon atoms It has one or two identical or different alkyl groups of the formula, optionally alkoxylated. Particularly preferred are unbranched and / or saturated and / or cyclic alkyl groups, especially unbranched saturated fatty alkyl groups.

The following sulfosuccinates and sulfosuccinates described in detail in the International Cosmetic Ingredient Dictionary and Handbook and named according to the INCI name are also suitable: ammonium dinonyl sulfosuccinate, ammonium lauryl sulfosuccinate, di- Ammonium dimethicone copolyol sulfosuccinate, diammonium lauramide-MEA sulfosuccinate, diammonium lauryl sulfosuccinate, diammonium oleamide PEG-2 sulfosuccinate, diamyl sodium sulfosuccinate, dicapryl sodium Sulfosuccinate, dicyclohexyl sodium sulfosuccinate, diheptyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, diisobutyl sodium sulfos Sinate, dioctyl sodium sulfosuccinate, disodium cetearyl sulfosuccinate, disodium cocamide MEA-sulfo succinate, disodium cocamide glucoside sulfosuccinate, disodium cocoyl butyl gluces-10 sulfosuccinate , Disodium C12-15 palace sulfosuccinate, disodium dec-5 sulfosuccinate, disodium dec-6 sulfosuccinate, disodium dihydroxyethyl sulfosuccinyl undecylenate, disodium dimethicone copolyol Sulfosuccinate, disodium hydrogenated cotton seed glyceride sulfosuccinate, disodium isodecyl sulfosuccinate, disodium isostearamide MEA-sulfosuccinate, dina Rium isostearamide MIPA-sulfosuccinate, disodium isostearyl sulfosuccinate, disodium lanes-5 sulfosuccinate, disodium lauramide MEA-sulfosuccinate, disodium lauramide PEG-2 sulfo Succinate, disodium lauramide PEG-5 sulfosuccinate, disodium laureth-6 sulfosuccinate, disodium laure-9 sulfosuccinate, disodium laureth-12 sulfosuccinate, disodium lauryl Sulfosuccinate, disodium myristamide MEA-sulfosuccinate, disodium nonoxynol-10 sulfosuccinate, disodium oleamide MEA-sulfosuccinate, disodium oleamide MIPA-sulfosuccinate Disodium oleamide PEG-2 sulfosuccinate, disodium oleth-3 sulfosuccinate, disodium oleyl sulfosuccinate, disodium palmitamide PEG-2 sulfosuccinate, disodium palmitole Amido PEG-2 sulfosuccinate, disodium PEG-4 cocamide MIPA-sulfosuccinate, disodium PEG-5 lauryl citrate sulfosuccinate, disodium PEG-8 palmglyceride sulfosuccinate, disodium lys Noreamide MEA-sulfosuccinate, disodium sitosteres-14 sulfosuccinate, disodium stearamide MEA-sulfosuccinate, disodium stearyl sulfosuccinate, disodium stearyl sulfosuccinate Disodium tartamide MEA-sulfosuccinate, disodium tallow amide MEA-sulfosuccinate, disodium tallow sulfosuccinate, disodium tridecyl sulfosuccinate, disodium undecylenamide MEA-sulfo Succinate, disodium undecylenamide PEG-2 sulfosuccinate, disodium wheat germanamide MEA-sulfosuccinate, disodium wheat germanide PEG-2 sulfosuccinate, di-TEA-oleamide PEG-2 sulfos Succinate, ditridecyl sodium sulfosuccinate, sodium bisglycol ricinosulfosuccinate, sodium / MEA laureth-2 sulfosuccinate, tetrasodium dicarboxyethyl stearyl sulfosuccinate Another suitable sulfosuccinamate is disodium _{C16-18-alkoxypropylene} sulfosuccinamate.

  The total anionic surfactant content of the cleaning or cleaning agent of the present invention may vary within wide limits. For example, the formulations of the present invention may contain a very large amount, preferably up to 40, 50, 60% by weight or more of an anionic surfactant. Similarly, the formulations of the present invention may contain very small amounts of anionic surfactants, for example, less than 15 or 10% by weight or less than 5% by weight or less. However, advantageously, anionic surfactants are included in the formulations according to the invention in an amount of 1 to 40% by weight, in particular 5 to 30% by weight; concentrations of 10% or more, even 15% by weight or more. Is particularly preferred. According to a preferred embodiment, the cleaning or cleaning agent according to the invention contains at least 0.1% by weight of an anionic surfactant, based on the total cleaning or cleaning agent.

  In addition to nonionic surfactants, soaps can be included in the cleaning or cleaning agents of the present invention. In particular, saturated fatty acid soaps such as lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid salts, and especially soap mixtures derived from natural fatty acids such as coconut, palm kernel or tallow fatty acid Is appropriate. The soap content of the preparation is preferably 3% by weight or less, in particular 0.5 to 2.5% by weight, based on the whole preparation, irrespective of the anionic surfactant. However, according to other preferred embodiments, the formulations of the present invention do not contain soap.

  Anionic surfactants and soaps can exist in the form of their sodium, potassium or ammonium salts and in the form of soluble salts of organic bases such as mono, di or triethanolamine. They are preferably present in their sodium or potassium salt form, in particular in the sodium salt form. Anionic surfactants and soaps are in-situ, for example, anionic surfactant acids and, if necessary, fatty acids are introduced into the composition to be spray dried and the alkaline carrier in the composition to be spray dried. It is manufactured by neutralizing with.

  Advantageously, the cleaning or cleaning agents according to the invention may also contain nonionic surfactants.

  Their concentration is, for example, 2 or 3 or 5% by weight or less. If useful, they may contain large amounts of nonionic surfactants, for example up to 10% or 15% or 30%, 40%, 50% or more. A suitable lower limit may be a value of 0.01, 0.1, 1, 2, 3, or 4% by weight (“% by weight” is each based on the entire formulation).

  According to a preferred embodiment, the cleaning or cleaning agent according to the invention contains a nonionic surfactant, preferably in an amount of at least 0.1% by weight, based on the total cleaning or cleaning agent. According to another preferred embodiment, the formulation according to the invention does not comprise a nonionic surfactant.

  Although all nonionic surfactants known from the prior art can be included in the formulations of the present invention, nonionic surfactants based on lipochemistry are preferred.

  The cleaning or cleaning agent of the present invention can also contain a cationic surfactant. Suitable cationic surfactants are, for example, surface-active quaternary compounds, in particular surface-active quaternary compounds having ammonium, sulfonium, phosphonium, iodonium or arsonium groups. The use of a quaternary surfactant compound having an antibacterial action can give the formulation an antibacterial action or can improve the antibacterial action already present by other ingredients.

Particularly preferred cationic surfactants have a certain degree of antibacterial activity and have the general formula: (R ^I ) (R ^II ) (R ^III ) (R ^IV ) N ⁺ X ⁻ [wherein R ^{I to} R ^IV _Are the same or different C _1-22 alkyl groups, C _7-28 aralkyl groups or heterocyclic groups, in which two groups or three (in the case of aromatic bonds as in pyridine) three group, a heterocyclic ring together with the nitrogen atom, for example, form a pyridinium or imidazolinium compound, X ^- is a halide ion, a sulfate ion, a hydroxide ion or a similar anion. And a quaternary ammonium compound (QACs, INCI: quaternary ammonium compound). For optimal antibacterial action, the at least one group preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

  QACs can be prepared by reaction of tertiary amines with alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, or ethylene oxide. Alkylation of tertiary amines with one long chain alkyl group and two methyl groups proceeds particularly easily, and quaternization of tertiary amines with two long chain groups and one methyl group is also methyl chloride. Can be performed under mild conditions. Amines having three long chain alkyl groups or hydroxy substituted alkyl groups have low reactivity and are preferably quaternized using dimethyl sulfate.

Examples of suitable QACs are benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyldimethyl-C ₁₂ -alkyl). Ammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyldodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide), CAS No. 57-09-0), benzethonium chloride (N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium Chloride, CAS No. 121-54-0), dialkyldimethylammonium chloride, such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5) Didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) As well as mixtures thereof. Preferred QACs _are benzalkonium chloride having a C 8 _{-C 18} alkyl group, in particular _C 12 _{-C 14} alkyl benzyl dimethyl ammonium chloride. A particularly preferred QAC is cocopentaethoxymethylammonium methosulfate (INCI: PEG-5 cocomonium methosulfate; Rewoquat® CPEM).

  In order to avoid possible incompatibility between the antibacterial cationic surfactant and the anionic surfactant contained in the cleaning agent or cleaning agent of the present invention, the cationic surfactant used is maximally anionic. It is compatible with ionic surfactants and / or is used in as small an amount as possible, or in particular embodiments of the present invention does not contain any cationic surfactants.

  Additional cationic surfactants, including, for example, quaternary ammonium compounds are described below, particularly with avivage materials. These can also be preferably contained in the preparation of the present invention.

  The cleaning or cleaning agents according to the invention contain one or more cationic surfactants, preferably 0-30% by weight, more preferably 0-20% by weight, based on the total composition. , Preferably 0.01 to 10% by weight, especially 0.1 to 5% by weight. A suitable lower limit may be 0.5, 1, 2, or 3% by weight. According to a preferred embodiment, the cleaning or cleaning agent according to the invention contains a cationic surfactant, preferably in an amount of at least 0.01% by weight, based on the total cleaning or cleaning agent. According to another preferred embodiment, the formulations according to the invention do not contain a cationic surfactant.

  Similarly, the cleaning or cleaning agents of the present invention can also contain amphoteric surfactants. These are described in further detail below.

  The detergents or detergents according to the invention contain one or more amphoteric surfactants, advantageously 0-30% by weight, more advantageously 0-20% by weight, preferably based on the total composition It is contained in an amount of 0.01 to 10% by weight, particularly 0.1 to 5% by weight. According to a preferred embodiment, the formulations according to the invention do not contain amphoteric surfactants.

  A further component of the cleaning or cleaning agent of the present invention is an organic or inorganic builder material. Among the inorganic builder substances are water-soluble or insoluble components such as aluminosilicates, especially zeolites.

  In a preferred embodiment, the cleaning or cleaning agent of the present invention does not contain phosphate. Phosphate-containing preparations are also possible.

  The cleaning agent or cleaning agent of the present invention is at least 10% by weight, at least 15% by weight, or at least 20% by weight or at least 30% by weight or more (eg at least 50% by weight) based on the total cleaning agent or cleaning agent. Having a zeolite content of can be an advantageous condition.

  The detergents or detergents according to the invention contain soluble builders, for example, preferably in an amount of up to 50% by weight, advantageously from 0.1 to 40% by weight, preferably from 5 to 30% by weight, based on the total weight of the whole formulation. %, Particularly preferably 10-20% by weight, sodium carbonate being particularly preferred as a soluble builder. However, it may also be advantageous if the formulation according to the invention contains less than 10% by weight of soluble builder, for example less than 5% by weight. According to a preferred embodiment, the formulations of the invention do not contain soluble builders.

The finely crystalline synthetic zeolite containing bound water that can be used is preferably zeolite A and / or zeolite P. Zeolite MAP® (a product of Crosfield Co.) is particularly preferred, for example as zeolite P. However, zeolite X and mixtures of A, X and / or P are also suitable. Of particular interest is also the co-crystallized sodium / potassium aluminum silicate of zeolite X and zeolite A, which can be purchased as VEGOBOND AX® (product of Condea).

The zeolite can preferably be used as a spray-dried powder or as an undried stabilized suspension that is prepared and still wet. When the zeolite is used as a suspension, the suspension contains a trace amount of nonionic surfactant as stabilizer, for example 1 to 3% by weight, based on zeolite, of 2 to 5 ethylene oxide groups. An ethoxylated C ₁₂ -C ₁₈ fatty alcohol having a C ₁₂ -C ₁₄ fatty alcohol having 4 to 5 ethylene oxide groups or an ethoxylated isotridecanol may be included. Preferred zeolites exhibit 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.

  Further particularly preferred zeolites are faujasite type zeolites. Mineral faujasite, together with zeolites X and Y, belongs to the faujasite type of zeolite structure group 4 characterized by a double six-membered subunit D6R. In addition to the faujasite type, the zeolite structure group 4 also includes the minerals chabazite and gmelinite, and synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. There are no mineral analogues in the last two synthetic zeolites described.

The faujasite type zeolite consists of β cages tetrahedrally bonded via D6R subunits, and the β cages are arranged in the same way as diamond carbon atoms. The three-dimensional network structure of the preferred faujasite type zeolite of the present invention has 2.2 and 7.4 pores. In addition, the basic cell includes 8 cavities of approximately 13 mm in diameter and can be described by the formula: Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] · 264H ₂ O. The network structure of zeolite X has a void volume of about 50% based on anhydrous crystals. The cavity volume is the largest space of all known zeolites (Zeolite Y: cavity volume about 48%, faujasite: cavity volume about 47%).

  In the present invention, the term “faujasite type zeolite” characterizes all three types of zeolite constituting the faujasite subgroup of zeolite structure group 4. Therefore, not only zeolite X, but also zeolite Y and faujasite, and mixtures of these compounds are preferred in the present invention, and pure zeolite X is preferred.

  According to the present invention, a mixture or co-crystallized product of faujasite-type zeolite and another zeolite is also preferred, and the mixture or co-crystallized material does not necessarily belong to zeolite structure group 4, but is at least 50% by weight. The zeolite is preferably a faujasite type.

  Suitable aluminum silicates are commercially available and methods for preparing them are described in standard research papers.

〔式中、ｘは、０〜２７６の数値である。〕
これらのゼオライトの孔径は８．０〜８．４Åである。 An example of a commercial zeolite of type X can be described by the following formula:

[In formula, x is a numerical value of 0-276. ]
These zeolites have a pore size of 8.0 to 8.4 mm.

For example, zeolite A-LSX is also suitable, which corresponds to co-crystallizate of zeolite X and zeolite A, wherein the anhydrous _{form: (M 2 / n O +} M '2 / n O) · Al 2 O 3 · zSiO ₂ [wherein M and M ′ may be an alkali metal or an alkaline earth metal, and z is a number of 2.1 to 2.6. ] Have. This product is manufactured by CONDEA Augusta S. p. A. Is commercially available under the trade name VEGOBOND AX.

〔式中、ｘは、０〜２７６の数である。〕
これらのゼオライトの孔径は８．０Åである。 Y-type zeolite is also commercially available, and can be described by the following formula, for example.

[Wherein, x is a number from 0 to 276. ]
These zeolites have a pore size of 8.0 mm.

  Suitable zeolite particle sizes are advantageously in the range from 0.1 to 100 μm, preferably from 0.5 to 50 μm, in particular from 1 to 30 μm, in each case measured using standard particle size measuring methods. According to another preferred embodiment, the cleaning or cleaning agent according to the invention does not contain zeolite.

  In a preferred embodiment of the present invention, all of the inorganic components included should preferably be water soluble. Therefore, in these embodiments, builder substances other than the zeolites described are used.

  Another suitable builder material is a polyacetal, which can be obtained by reaction of a dialdehyde with a polyol carboxylic acid having 5 to 7 carbon atoms and at least 3 hydroxy groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde, and mixtures thereof and polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

  Other suitable organic builder materials are carbohydrate oligomers or polymers obtainable by partial hydrolysis of dextrins such as starch. This hydrolysis can be performed by a usual method, for example, a method using an acid catalyst or an enzyme catalyst. The hydrolyzate preferably has an average molecular weight in the range of 400 to 500,000 g / mol. Here, polysaccharides having a dextrose equivalent (DE) in the range of 0.5 to 40, in particular 2 to 30, are preferred, in which case DE is the conventional reducing effect of polysaccharides compared to dextrose having a DE of 100. It is a good index. Use of maltodextrins with a DE of 3-20 and dry glucose syrup with a DE of 20-37 and so-called yellow and white dextrins with higher molecular weights in the range of 2,000-30,000 g / mol can do. Preferred dextrins are described in British Patent Application No. 9419091. Such oxidized derivatives of dextrin are reaction products of dextrin with an oxidant capable of oxidizing at least one alcohol function of the saccharide ring to a carboxylic acid function.

  Oxydisuccinate and other disuccinate derivatives, preferably ethylenediamine disuccinate, are also further suitable co-builders. Ethylenediamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salt. In this connection, glycerol disuccinate and glycerol trisuccinate are also preferred. A suitable use amount is, for example, 3 to 15% by weight, based on the total detergent or detergent.

  Other organic co-builders that can be used are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally be present in the lactone form, with at least 4 carbon atoms and at least Contains one hydroxy group and at most two acid groups.

  A further substance with co-builder properties is phosphonate. These are in particular hydroxyalkane phosphonates or aminoalkane phosphonates. For hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a co-builder. 1-Hydroxyethane-1,1-diphosphonate is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Suitable aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues. They are preferably used in the form of the neutral sodium salt, for example as the hexasodium salt of EDTMP or as the heptasodium and octasodium salts of DTPMP. Among the phosphonates used as builders, HEDP is preferred. In addition, aminoalkane phosphonates have significant heavy metal binding capacity. It is therefore preferred to use aminoalkane phosphonates, in particular DTPMP, or mixtures of said phosphonates, especially when the formulation also contains a bleach.

  In cases where it is permissible to contain phosphates, phosphates, in particular pentasodium triphosphate, optionally pyrophosphates and orthophosphates can also be used, which mainly act as precipitants for calcium salts. To do. Phosphate is mostly used in dishwasher formulations, but is sometimes used in detergents.

“Alkali metal phosphates” are alkali metals (especially sodium) that may be distinguished from various phosphoric acids (metaphosphoric acid (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ , and higher molecular weight representatives). And generic term for potassium) salts. Phosphate has a number of advantages: Phosphate acts as an alkaline carrier, prevents limestone deposits on machine parts and lime deposition on fabrics and contributes to detergency.

It exists as sodium dihydrogen phosphate, NaH ₂ PO ₄ , dihydrate (density 1.91 g / cm ³ , melting point 60 ° C.) and as monohydrate (density 2.04 g / cm ³ ). Both salts are white powders that are extremely soluble in water, lose water of crystallization when heated, and become weakly acidic diphosphates (disodium hydrogen phosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200 ° C. It is converted to sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and the Madrell salt (see below) at high temperatures. NaH ₂ PO ₄ reacts acidic; it forms when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide and the suspension is spray dried. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ is a white salt with a density of 2.33 g / cm ³ and a melting point of 253 ° C. (polyphosphorus Potassium acid, decomposed by the formation of (KPO ₃ ) _x ), easily dissolved in water.

Disodium hydrogen phosphate (dibasic sodium phosphate), Na ₂ HPO _4, is a colorless crystalline salt that is extremely soluble in water. Disodium hydrogen phosphate is in anhydrous form and 2 mol water (density 2.066 g / cm ³ , water disappearance at 95 ° C.), 7 mol water (density 1.68 g / cm ³ , melting point 48 ° C. (5 H ₂ O disappeared)) and 12 moles of water (density 1.52 g / cm ³ , melting point 35 ° C. (disappearing 5H ₂ O)), became anhydrous at 100 ° C., and heated more vigorously , Diphosphate, Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with sodium carbonate solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO _4, is a white amorphous salt and is readily soluble in water.

Trisodium phosphate (trisodium phosphate) and Na ₃ PO ₄ are colorless crystals, and this crystal has a density of 1.62 g / cm ^{3 as} a dodecahydrate and a melting point of 73 to 76 ° C. (Decomposition), decahydrate (corresponding to 19-20% P ₂ O ₅ ) has a melting point of 100 ° C., and anhydrous form (corresponding to 39-40% P ₂ O ₅ ) has a density 2.536 g / cm ³ . Trisodium phosphate dissolves readily in water, exhibits an alkaline reaction, and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ is a white deliquescent granular powder with a density of 2.56 g / cm ³ , melting point 1340 ° C., easily dissolved in water And exhibits an alkaline reaction. Tripotassium phosphate is produced, for example, when basic charcoal and potassium sulfate are added to basic slag and heated. It is more soluble, so the higher activity potassium phosphate is highly preferred in the detergent industry compared to the corresponding sodium compound, despite its relatively high price.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O _7, is in anhydrous form (density 2.534 g / cm ³ , melting point 988 ° C., reported as 880 ° C.) and decahydrate ( The density is 1.815 to 1.836 g / cm ³ , the melting point is 94 ° C. (water disappears). Both substances are colorless crystals, which dissolve in water and exhibit an alkaline reaction. Na ₄ P ₂ O ₇ is produced by heating disodium phosphate at a temperature higher than 200 ° C., or by reacting phosphoric acid and sodium carbonate in a stoichiometric ratio, and spray drying the solution. Decahydrate complexes the heavy metal salt with the hardness component, thereby reducing the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ exists in the form of trihydrate and is a colorless hygroscopic powder with a density of 2.33 g / cm ^3. The pH of the 1% strength solution at 25 ° C. is 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ produces high molecular weight sodium and potassium phosphates, which are cyclic representatives (sodium metaphosphate or potassium metaphosphate), and chain type ( A distinction can be made between sodium polyphosphate and potassium polyphosphate. Many names are used in particular for the latter: dissolved or calcined phosphates, Graham salts, crawl salts and Madrell salts. All of the polymeric sodium and potassium phosphates are collectively referred to as “condensed” phosphates.

Industrially important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) is a non-hygroscopic white water-soluble salt, which is anhydrous or contains 6H ₂ O and crystals And has the general formula: NaO— [P (O) (ONa) —O] _n —Na [where n = 3]. At room temperature, about 17 g of anhydrous salt dissolves in 100 g of water, about 20 g at 60 ° C. and about 32 g at 100 ° C .; when the solution is heated at 100 ° C. for 2 hours, hydrolysis causes about 8% orthophosphate and 15 % Diphosphate is formed. In the preparation of pentasodium triphosphate, phosphoric acid is reacted in a stoichiometric ratio with a sodium carbonate solution or sodium hydroxide solution and the solution is spray dried. Similar to Graham salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps). Tripotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate) is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). Potassium polyphosphate is widely used in the detergent and detergent industry. There is also potassium sodium tripolyphosphate which can be used in the present invention as well. These are produced, for example, when sodium trimetaphosphate is hydrolyzed with KOH.

  They can be used in exactly the same way as sodium tripolyphosphate, potassium tripolyphosphate or a mixture of the two according to the invention. A mixture of sodium tripolyphosphate and potassium potassium tripolyphosphate, or a mixture of potassium tripolyphosphate and potassium potassium tripolyphosphate, or a mixture of sodium tripolyphosphate, potassium tripolyphosphate and potassium potassium tripolyphosphate is also used in the present invention. Can do.

  In a preferred embodiment of the invention, carbonates and silicates are used as inorganic builder materials.

In the present specification, in particular, the general formula: NaMSi _x O _{2x + 1} · yH ₂ O [wherein M is sodium or potassium and x is a number of 1.6 to 4, preferably 1.9 to 4.0. , Y is a number from 0 to 20, and preferred values for x are 2, 3 or 4. The crystalline layered sodium silicate is referred to. However, since such crystalline silicates at least partially lose their crystal structure due to the spray drying process, it is preferred to add the crystalline silicate to the treated spray dried product immediately or later. Preferred crystalline layered silicates of the formula shown are those in which M is sodium and x is 2 or 3. In particular, both β-sodium disilicate and δ-sodium disilicate and Na ₂ Si ₂ O ₅ .yH ₂ O are preferable. Such a compound is commercially available, for example, under the name SKS® (Clariant). For example, SKS-6® is primarily δ-sodium disilicate having the formula: Na ₂ Si ₂ O ₅ .yH ₂ O, and SKS-7® is primarily β-2. Sodium silicate. Acid (e.g., citric acid or carbonic) by reaction with, .delta. sodium disilicate than _{kanemite, NaHSi 2 O 5 · yH 2} O is formed, which SKS-9 (R) and SKS-10 (R ) (Clariant). It may also be advantageous to utilize chemically modified versions of these layered silicates. For example, the alkalinity of the layered silicate can be affected appropriately. Compared to δ-sodium disilicate, phosphate-doped layered silicates or carbonate-doped layered silicates have changed crystal forms and dissolve more rapidly, than those of δ-sodium disilicate. High calcium binding ability. For example, general empirical formula: xNa ₂ O.ySiO ₂ .zP ₂ O ₅ [wherein the ratio of x and y corresponds to a numerical value of 0.35 to 0.6, and the ratio of x and z is 1. It corresponds to a numerical value of 75 to 1200, and a ratio of y and z corresponds to a numerical value of 4 to 2800. A layered silicate is known. The solubility of the layered silicate can also be increased by using a finely divided layered silicate. Crystalline layered silicates and other component compounds can also be used. In particular, mention is made of compounds with cellulose derivatives which are advantageous in disintegration effect, and compounds with polycarboxylates (eg citric acid) or polycarboxylate polymers (eg copolymers of acrylic acid).

Preferred builder materials are amorphous in which Na ₂ O: SiO ₂ is from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8, in particular from 1: 2 to 1: 2.6. Also included is sodium silicate, which has secondary cleaning properties. In the present invention, the term “amorphous” is understood to mean “X-ray amorphous”. This is because silicate does not produce the sharp X-ray reflection typical of crystalline materials in X-ray diffraction experiments, but instead the maximum of scattered X-rays with a diffraction angle width of several degrees. Means that one or more are always indicated. However, in electron diffraction experiments, particularly good builder properties can be obtained very easily even if the silicate particles show an indistinct or distinct diffraction maximum. This means that the product has a microcrystalline region with a size of 10 to several hundred nm, and the value is preferably up to 50 nm, in particular up to 20 nm. This type of so-called X-ray amorphous silicate, which dissolves more slowly than ordinary water glass, is known. Compressed amorphous silicate, composite amorphous silicate, and overdried X-ray amorphous silicate are particularly preferred. The content of (X-ray) amorphous silicate, especially in formulations not containing zeolite, is preferably 1 to 10% by weight, which corresponds to a preferred embodiment of the present invention.

  Particularly preferred inorganic water-soluble builders are alkali metal carbonates and alkali metal bicarbonates, and preferred embodiments are sodium carbonate and potassium carbonate, especially sodium carbonate. The content of alkali metal carbonates, especially in zeolite-free formulations, can vary over a very wide range, preferably 1-50% by weight, advantageously 5-40% by weight, in particular 8-30% by weight. The content of alkali metal carbonate is usually higher than the content of (X-ray) amorphous silicate. According to another preferred embodiment, the cleaning or cleaning agent according to the invention does not contain alkali metal carbonates.

  Organic builders that can be used are, for example, polycarboxylic acids that can be used in the form of alkali metal, (especially) sodium salts, for example citric acid, adipic acid, provided that there is no ecological objection to such use. Succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), and mixtures thereof. Preferred salts are salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, and mixtures thereof. These acids can also be used as the acid itself. In addition to its builder action, such acids generally also have the properties of an acidifying component, thus establishing a low pH for detergents and detergents, such as in the case of the granules of the present invention. It is also useful to do. In this regard, mention may be made in particular of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures thereof.

Polycarboxylates are also suitable as organic builders. These are, for example, alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol. For the purposes of this specification, the molecular weight described for the polycarboxylate polymer is the weight average molecular weight _Mw of each acid form, which is in principle by gel permeation chromatography (GPC) using a UV detector. Measured. Measurements are made against an external polyacrylic acid standard and the actual molecular weight value is obtained from its structural similarity to the polymer under investigation. These values are significantly different from the molecular weight data obtained using polystyrene sulfonic acid as a standard. The molecular weight measured using polystyrene sulfonic acid is generally much higher than the molecular weight described herein.

  The cleaning or cleaning agent of the present invention may also include a polymer. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. In this group, short chain polyacrylates having a molecular weight of 2000 to 10,000 g / mol, particularly preferably 3,000 to 5,000 g / mol are preferred because of their excellent solubility.

  Also suitable are salts of polycarboxylate copolymers, especially copolymers of acrylic acid and methacrylic acid, and copolymers of acrylic acid or methacrylic acid and maleic acid. A salt of a copolymer of acrylic acid and maleic acid comprising 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid has proven particularly suitable. Their relative molecular weight is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol, in particular from 30,000 to 40,000 g / mol, based on the free acid.

  The content of organic builder substances in detergents or detergents can vary over a wide range. A content of 2 to 20% by weight is preferred, in particular a content of at most 10% by weight is particularly well accepted. According to another preferred embodiment, the cleaning or cleaning agent according to the invention does not contain organic builder substances.

  At this point, unless otherwise stated, “wt%” is based on total detergent or detergent, respectively.

  The cleaning or cleaning agents of the present invention also contain a component selected from the group of graying inhibitors (anti-redeposition agents), neutral salts and / or fabric softening aids (eg cationic surfactants). Such compositions are preferred.

  The purpose of the anti-graying agent is to keep the soil separated from the fibers suspended in the washing tub. Usually organic water-soluble colloids are suitable for this purpose, examples being water-soluble salts of carboxylic acid polymers, sizes, gelatin, starch or salts of ether carboxylic or ether sulfonic acids of cellulose, or cellulose or starch. The acidic sulfate ester salt is suitable. Water-soluble polyamides containing acid groups are also suitable for this purpose. Furthermore, soluble starch preparations and starch products other than those mentioned above, such as starch degradation products, aldehyde starches, etc. can also be used. Polyvinyl pyrrolidone can also be used. However, cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures thereof, and polyvinylpyrrolidone, for example, are washed. It is also preferred to use them in an amount of preferably 0.1 to 5% by weight, based on the agent or detergent.

  Sodium sulfate is a preferred typical example of a neutral salt. This can be used, for example, in a proportion of 0 to 60% by weight, preferably 2 to 45% by weight.

  Suitable softeners (or finishes) described in more detail below are, for example, the corresponding montmorillonite types, for example swellable layered silicates of bentonite, and cationic surfactants.

  The water content in the cleaning or cleaning agent is preferably 0 to less than 30% by weight, in particular 0.5 to less than 20% by weight, at most 15% by weight, at most 10% by weight, at most 5% by weight, at most 3 A value of% by weight or at most 2% by weight is particularly preferred. These calculations do not include water bound to aluminosilicates such as zeolite that may be present.

  Nonionic surfactants that may be included in the cleaning or cleaning agent as needed are described in further detail below. These nonionic surfactants can be applied to fine particle detergents or detergents in the post-treatment process. However, it can of course be advantageous for all nonionic surfactants to be included directly in the cleaning or cleaning agent according to the invention.

  Nonionic surfactants which can be used are, for example, alkoxylated, advantageously ethoxylated, in particular preferably 8 to 18 carbon atoms, with an average of 1 to 12 per mole of alcohol. A primary alcohol having a molar amount of ethylene oxide (EO), the alcohol group of which may be straight-chain (or methyl-branched at the 2-position, or as normally present in oxoalcohol groups). May contain a linear group and a methyl branching group in a mixed state).

  Preferred alcohol ethoxylates have, for example, a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO can also be used. Examples thereof are (tallow) fatty alcohols containing 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

Preferred nonionic surfactants are, for example, one or more unbranched (or are alkoxylated with ethylene oxide (EO) and / or propylene oxide (PO) and having a degree of alkoxylation of up to 30 (or Branched), saturated or unsaturated _C10-22 alcohol, preferably with a degree of ethoxylation of less than 30, preferably 1-20, especially 1-12, particularly preferably 1-8, more particularly preferably 2-5. _{C 12 to 14} fatty alcohol ethoxylates having certain ethoxylated _{C 10 to 18} fatty alcohols, _{C 12 to 14} fatty alcohol ethoxylates and 4EO having _{C 12 to 14} fatty alcohol ethoxylates or 3EO, having, for example 2, 3 or 4EO Has a 1: 1 ratio by weight to the rate, or 5, 8, or 12 EO It is isotridecyl alcohol ethoxylates.

In addition, classes of nonionic surfactants that can be used are, for example, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably 1 to 4 carbon atoms in the alkyl chain. the a, especially fatty acid methyl esters; for example, the average 3～15EO, especially _C 12 _{-C 18} fatty acid methyl ester having an average 5～12EO, can be used particularly preferably.

  Also preferred are nonionic surfactants of the amine oxide type already mentioned above, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and fatty acid alkanolamide types.

  Alkoxylated amines are also suitable, advantageously ethoxylated and / or propoxylated, in particular having 1 to 18 carbon atoms in the alkyl chain, on average 1 to 12 per mole of amine. Primary and secondary amines with moles of ethylene oxide (EO) and / or 1-10 moles of propylene oxide (PO).

Advantageously, the cleaning or cleaning agent according to the invention may also comprise an antifoaming agent, such as an antifoaming paraffinic oil or an antifoaming silicone oil, such as dimethylpolysiloxane. It is also possible to use mixtures of these active substances. In particular in the case of the specified antifoam actives, suitable additives which are solid at room temperature are paraffin wax, silicic acid which can also be hydrophobized by known methods, and C _2-7 diamines and C _12-22 carboxylic acids. The resulting bisamide.

  Antifoaming paraffin oil is preferably used. They are complex material mixtures which may be mixed with paraffin wax and do not have a clear melting point. For characterization, the melting range and / or freezing point is usually measured by differential thermal analysis (DTA). The freezing point is understood as the temperature at which paraffin transitions from a liquid state to a solid state by slow cooling. Paraffins having fewer than 17 carbon atoms cannot be used in the present invention; therefore, their concentration in the paraffin oil mixture should be as low as possible and conventional analytical methods such as gas chromatography can be used. It is preferably lower than the limit that can be used and measured significantly. It is preferable to use paraffin that solidifies in the range of 20 ° C to 70 ° C. It must be taken into account that paraffin wax mixtures that appear even solid at room temperature may contain different proportions of liquid paraffin oil. In the case of paraffin waxes that can be used in the present invention, the liquid fraction at 40 ° C. is as high as possible, but still does not reach 100% at this temperature. In a preferred paraffin wax mixture, the liquid fraction at 40 ° C. is at least 50% by weight, in particular 55-80% by weight, and at 60 ° C. the liquid fraction is at least 90% by weight. As such, paraffins are fluid and can be pumped at temperatures as low as at least 70 ° C, and preferably as low as at least 60 ° C. Furthermore, it should be noted that paraffin should not contain as much volatile fraction as possible. Preferred paraffin waxes contain less than 1% by weight, in particular less than 0.5% by weight of components that can evaporate at 110 ° C. under atmospheric pressure. Paraffins that can be used in the present invention can be obtained, for example, under the trade names Lunaflex (registered trademark) (manufactured by Fuller) and Deawax (registered trademark) (manufactured by DEA Mineraloel AG).

  The paraffin oil may comprise a bisamide that is solid at room temperature, obtained from a saturated fatty acid having 12 to 22, preferably 14 to 18 carbon atoms and an alkylene diamine having 2 to 7 carbon atoms. Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachidic acid and behenic acid and mixtures thereof, such as can be obtained from natural fats or hardened oils such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylenediamine-1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluylenediamine. Preferred diamines are ethylene diamine and hexamethylene diamine. Particularly preferred bisamides are bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine, and mixtures thereof, and their corresponding derivatives of hexamethylenediamine.

  The cleaning agent or cleaning agent may preferably also contain a UV absorber, which advantageously adheres to the treated fabric and allows the light stability of the fibers and / or the light of other compounding ingredients. Improve stability. A “UV absorber” is understood to mean an organic substance (photoprotective filter) that can absorb ultraviolet radiation and release the absorbed energy again as long wavelength radiant energy, eg heat. The compound having such desirable characteristics is, for example, a compound that becomes active by non-radiation deactivation and a derivative of benzophenone having a substituent at the 2-position and / or 4-position. Furthermore, substituted benzotriazoles, acrylates (cinnamic acid derivatives) phenyl-substituted at the 3-position with or without a cyano group, salicylates, organic Ni complexes and umbelliferone and endogenous urocanins Natural materials such as acids are also preferred. Of particular importance are biphenyl derivatives, in particular stilbene derivatives which are commercially available from Ciba as Tinosorb® FD or Tinosorb® FR. UV-B absorbers to be mentioned are 3-benzylidene camphor or 3-benzylidene norcamphor and their derivatives, such as 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 4- ( Dimethylamino) 2-ethylhexyl benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; cinnamic acid esters, preferably 2-ethylhexyl 4-methoxycinnamate, 4-methoxy Propyl cinnamate, isoamyl 4-methoxycinnamate, 2-cyano-3,3-phenyl cinnamate 2-ethylhexyl (octocrylene); salicylic acid ester, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; benzofe Derivatives, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone; benzalmalonic acid ester, preferably 4- Di-2-ethylhexyl methoxybenzalmalonate; triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyltri Azone, or dioctylbutamide triazone (Uvasorb® HEB) and the like; propane-1,3-dione, such as 1- (4-tert-butylphenyl) -3- (4′-methoxyphenyl) propane- 1,3-dione and the like; ketotricyclo (5.2.1.0) decane derivative. Further suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal salts, alkaline earth metal salts, ammonium salts, alkyl ammonium salts, alkanol ammonium salts and glucamonium salts; sulfonic acid derivatives of benzophenone Preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and Examples include 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid, and salts thereof.

  Suitable typical UV-A filters are in particular derivatives of benzoylmethane, such as 1- (4′-tert-butylphenyl) -3- (4′-methoxyphenyl) propane-1,3-dione, 4 -Tert-butyl-4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione, and enamine compounds. Naturally, the UV-A filter and the UV-B filter can also be used as a mixture. In addition to the soluble materials described above, insoluble photoprotective pigments (ie, finely dispersed, preferably nanonized metal oxides or salts) are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide, as well as oxides of iron, zirconium, silicon, manganese, aluminum and cerium, and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. These oxides and salts are already used as pigments for skin care and skin protection emulsions and decorative cosmetics. These particles should have an average diameter of less than 100 nm, preferably 5-50 nm, in particular 15-30 nm. These may be spherical, but it is also possible to use particles having an elliptical shape or a shape somewhat deviating from the sphere. The pigment may also be surface-treated, i.e. it can be hydrophilized or hydrophobized. Typical examples are coated titanium dioxide, such as titanium dioxide T805 (Degussa) or Eusolex® T2000 (Merck). Here, suitable hydrophobic coatings are primarily silicones, specifically trialkyloxyoctylsilane or simethicone. Preferably, fine zinc oxide is used. Further suitable UV light protection filters can be collected from the relevant prior art.

  The cleaning or cleaning agent comprises a UV absorber, advantageously in a proportion of 0.01 to 5% by weight, preferably 0.03 to 1% by weight. They can also be added later to the cleaning or cleaning agent, for example together with other substances.

  In addition, the cleaning agent or cleaning agent of the present invention can exist as a tablet or a molded body. In the present patent application, “tablet or molded product” refers to a solid material having dimensional stability regardless of the production method thereof. Such objects are produced, for example, by crystallization, casting, injection molding, reaction sintering or thermal sintering, (simultaneous) extrusion, microencapsulation, pelletization, or compression methods such as calendering or tableting. Can do. In this patent application, the production of “tablets” or “molded bodies” by tableting is particularly preferred. Thus, the tablet is preferably made of a compressed particle material.

  The cleaning or cleaning agent of the present invention may preferably contain a disintegration aid. Suitable swellable disintegration aids are, for example, bentonite or other swellable silicates. Synthetic polymers, especially superabsorbents used in the hygiene field or cross-linked polyvinyl pyrrolidone can also be used.

  Polymers based on starch and / or cellulose are particularly preferably used as swellable disintegration aids. These base materials can be made into swellable disintegration aids alone or by processing a mixture with further natural and / or synthetic polymers. In the simplest case, the cellulose-containing material or pure cellulose can be converted into secondary particles by granulation, compression or other pressing methods, and the secondary particles will swell when in contact with water, so they will collapse Acts as an agent. Wood is a proven cellulose-containing material that can be obtained from wood or wood chips (sawdust, sawdust) by thermal or chemical / thermal methods. This cellulosic material by the thermomechanical pulp (TMP) method or the chemical thermomechanical pulp method (CTMP) can be compressed by pressing, preferably compressed by a roll, and converted into particles. Of course, pure cellulose can be used in exactly the same way, but pure cellulose is a more expensive raw material. Here, microcrystalline and amorphous micronized cellulose, and mixtures thereof can be used.

  Another method involves adding a granulation aid to granulate the cellulose-containing material. For example, synthetic polymer or nonionic surfactant solutions have proven results as granulation aids. In order to prevent deposits on fabrics washed with the formulation of the present invention, the primary fiber length of cellulose in the cellulose or cellulose-containing material used should be less than 200 μm, preferably less than 100 μm, especially less than 50 μm. .

  The secondary particles ideally preferably have a particle size distribution in which more than 90% by weight of the particles have a particle size of 200 μm or more. Certain powder ratios can contribute to improved storage stability of the tablets produced thereby. For example, a fines ratio of less than 0.1 mm may be present at a concentration of up to 10% by weight, preferably up to 8% by weight.

  Further, the cleaning or cleaning agents of the present invention may contain finishing materials or conditioning materials or ingredients. For the purposes of the present invention, the term “conditioning” should preferably be understood as referring to finishing of fabrics, garments and textiles. Conditioning is a desirable property of the fabric, such as improved softness, improved gloss and color vibrancy, improved scent effect, reduced felting, ease of ironing due to reduced friction, wrinkles And reduction of static electricity and prevention of color transfer in dyed fabrics.

  In order to improve softness and finishing properties, the formulations of the present invention may contain a softener component. Examples of such compounds are quaternary ammonium compounds, cationic polymers, and emulsifiers, such as those used in hair care agents and fabric finishes. These softener compounds, described in more detail below, can be included in all of the formulations of the invention, but in particular can be included in formulations that are intended to have a softening effect.

〔式（Ａ）中、ＲおよびＲ^１は、１２〜２４個の炭素原子を有する非環状アルキル基を表し、Ｒ^２は、飽和Ｃ_１〜Ｃ_４アルキルまたはヒドロキシアルキル基を表し、Ｒ^３は、Ｒ、Ｒ^１またはＲ^２であり、あるいは芳香族基を表す。Ｘ⁻は、ハロゲン化物イオン、メト硫酸イオン、メトリン酸イオンまたはリン酸イオンあるいはそれらの混合物を表す。〕
式（Ａ）の陽イオン性化合物の例は、ジデシルジメチルアンモニウムクロリド、ジ獣脂ジメチルアンモニウムクロリドまたはジヘキサデシルアンモニウムクロリドである。 Suitable examples are quaternary ammonium compounds of the formulas (A) and (B).

[In the formula (A), R and R ¹ represent an acyclic alkyl group having 12 to 24 carbon atoms, R ² represents a saturated C _{1 to} C ₄ alkyl or hydroxyalkyl group, and R ³ represents , R, R ¹ or R ² or represents an aromatic group. X ⁻ represents a halide ion, a methosulphate ion, a metrate or phosphate ion, or a mixture thereof. ]
Examples of cationic compounds of formula (A) are didecyldimethylammonium chloride, ditallow dimethylammonium chloride or dihexadecylammonium chloride.

ここで、Ｒ^２１およびＲ^２２は、互いに独立に、各々、１２〜２２個の炭素原子を有し、０、１、２または３個の二重結合を有する脂肪族基である。 The compound of formula (B) is a so-called esterquat. Ester quart is remarkably excellent in biodegradability. Where R ⁴ is an aliphatic alkyl group having 12 to 22 carbon atoms and having 0, 1, 2 or 3 double bonds; R ⁵ is H, OH or O ( CO) R ⁷ and R ⁶ is H, OH or O (CO) R ⁸ independently of R ⁵ , wherein R ⁷ and R ⁸ are each independently 12-22 An aliphatic alkyl (alkenyl) group having 1 carbon atom and 0, 1, 2 or 3 double bonds. ]. m, n and p may each have a value of 1, 2 or 3 independently of each other. X ⁻ can be a halide ion, a methosulphate ion, a metrate or phosphate ion, and mixtures thereof. Compounds in which R ⁵ is a group O (CO) R ⁷ , R ⁴ and R ⁷ are alkyl groups having 16 to 18 carbon atoms are preferred. Furthermore, compounds in which R ⁶ is OH are particularly preferred. Examples of compounds of formula (B) are methyl-N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate, bis (palmitoyl) ethylhydroxyethylmethylammonium methosulfate or methyl -N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. When using quaternized compounds of the formula (IV) with unsaturated alkyl chains, the corresponding fatty acids have an iodine number of 5 to 80, preferably 10 to 60, in particular 15 to 45, and cis / trans isomers Preference is given to acyl groups in which the ratio (in weight%) is higher than 30:70, preferably higher than 50:50, in particular higher than 70:30. Examples of common commercial products are the methyl hydroxyalkyl dialcoyloxyalkylammonium methosulfate sold by Stepan under the trade name Stepantex®, or the Cognis product known as Dehyquat® Or a product of Goldschmidt-Witco, known as Rewoquat®. Further preferred compounds are diester quats of the formula (C), which are available under the name Rewoquat® W222LM or CR3099, which in addition to softness guarantees stability and anti-coloring.

Here, R ²¹ and R ²² are each independently an aliphatic group having 12 to 22 carbon atoms and having 0, 1, 2, or 3 double bonds.

〔式中、Ｒ^９は、Ｈ、または１〜４個の炭素原子を有する飽和アルキル基であり、Ｒ^１０およびＲ^１１は、互いに独立に、各々、１２〜１８個の炭素原子を有する脂肪族の飽和または不飽和アルキル基であり、Ｒ^１０は、Ｏ（ＣＯ）Ｒ^２０［式中、Ｒ^２０は、１２〜１８個の炭素原子を有する脂肪族の飽和または不飽和アルキル基である。］であってもよく、ＺはＮＨ基または酸素であり、Ｘ⁻は陰イオンであり、ｑは１〜４の整数値であり得る。 In addition to the quaternary compounds described above, other known compounds such as quaternary imidazolinium compounds of the formula (D) can also be used.

[Wherein R ⁹ is H or a saturated alkyl group having 1 to 4 carbon atoms, and R ¹⁰ and R ¹¹ are each independently an aliphatic group having 12 to 18 carbon atoms. R ¹⁰ is O (CO) R ²⁰ , wherein R ²⁰ is an aliphatic saturated or unsaturated alkyl group having 12 to 18 carbon atoms. Z may be an NH group or oxygen, X ⁻ may be an anion, and q may be an integer value from 1 to 4.

〔式中、Ｒ^１２、Ｒ^１３およびＲ^１４は、互いに独立に、Ｃ_１〜４アルキル基、アルケニル基またはヒドロキシアルキル基を表し、Ｒ^１５およびＲ^１６は、それぞれ選択的に独立して、Ｃ_８〜２８アルキル基を表し、ｒは、０〜５までの数である。〕 Further suitable quaternary compounds are described by formula (E).

[Wherein, R ¹² , R ¹³ and R ¹⁴ each independently represent a C _1-4 alkyl group, an alkenyl group or a hydroxyalkyl group, and R ¹⁵ and R ¹⁶ are each independently and independently selected from C _It represents an _8-28 alkyl group, and r is a number from 0 to 5. ]

  In addition to the compounds of formulas (A) and (B), short-chain water-soluble quaternary ammonium compounds such as trihydroxyethylmethylammonium methosulphate or alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, and trialkylmethylammonium chloride For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride can also be used.

  Also suitable are protonated alkylamine compounds having a flexible effect, as well as non-quaternized protonated precursors of cationic emulsifiers.

  Further cationic compounds that can be used in the present invention are quaternized protein hydrolysates.

  Suitable cationic polymers include polyquaternium polymers, especially polyquaternium-6, polyquaternium-7, and polyquaternium-10 polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997). (Ucare polymer IR 400; Amerchol) (also known as Merquat), a polyquaternium-4 copolymer, for example, a graft copolymer having a quaternary ammonium group and a cellulose skeleton linked via allyldimethylammonium chloride. Cationic cellulose derivatives such as cationic guars such as guar hydroxypropyltriammonium chloride, and similar quaternized guar derivatives (eg Cosmedia Guar, manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cations) Sex Rualkylpolyglucoside), for example, the commercial product Glucqat® 100 (according to the CTFA nomenclature “laurylmethylgluces-10hydroxypropyldimonium chloride”), a copolymer of PVP and dimethylaminomethacrylate, vinylimidazole and vinyl Mention may be made of copolymers with pyrrolidone, aminosilicone polymers and copolymers.

  Similarly, polyquaternized polymers (e.g. BASF's Luviquat Care) and chitin-based cationic biopolymers and their derivatives, e.g. under the trade name Chitosan (R) (manufacturer: Cognis) Available polymers can also be used.

  According to the present invention, a cationic silicone oil, such as the commercial product Q2-7224 (manufacturer: Dow Corning; stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (including hydroxylamino-modified silicone, also referred to as amodimethicone). ), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker), Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, quaternium-80 ), And Siliconquat Rewoquat® SQ 1 (Tegopren® 6922, manufacturer: Goldschmidt-Rewo) and the like.

これは、それらの非４級化形態、または、示されるように、それらの４級化形態のアルキルアミドアミンであってよい。Ｒ^１７は、１２〜２２個の炭素原子を有し、０、１、２または３個の二重結合を有する脂肪族アルキル（アルケニル）基であってよい。ｓは、０〜５の値である。Ｒ^１８およびＲ^１９は、互いに独立に、それぞれ、Ｈ、Ｃ_１〜４アルキル基またはヒドロキシアルキルである。好ましい化合物は、脂肪酸アミドアミン、例えばＴｅｇｏ Ａｍｉｄ（登録商標）Ｓ１８の名称のもと入手可能なステアリルアミドプロピルジメチルアミン、またはＳｔｅｐａｎｔｅｘ（登録商標）Ｘ９１２４の名称のもと入手可能な３−獣脂アミドプロピルトリメチルアンモニウムメトスルフェートであり、それらは良好なコンディショニング効果だけでなく、色移り防止効果、特にそれらの優れた生分解性で区別される。 A compound of formula (F) can also be used.

This may be their non-quaternized form or, as indicated, their quaternized form of alkylamidoamine. R ¹⁷ may be an aliphatic alkyl (alkenyl) group having 12 to 22 carbon atoms and having 0, 1, 2, or 3 double bonds. s is a value from 0 to 5. R ¹⁸ and R ¹⁹ are each independently H, C _1-4 alkyl group or hydroxyalkyl. Preferred compounds are fatty acid amidoamines, such as stearylamidopropyldimethylamine available under the name Tego Amid® S18, or 3-tallow amidopropyltrimethyl available under the name Stepantex® X9124. Ammonium methosulfate, which is distinguished not only by a good conditioning effect but also by an anti-color transfer effect, in particular their excellent biodegradability.

  Particularly preferred are alkylated quaternary ammonium compounds in which at least one alkyl chain is interrupted by ester and / or amide groups, in particular N-methyl-N- (2-hydroxyethyl) -N, N- (di- Tallow acyloxyethyl) ammonium methosulfate.

  Suitable nonionic softeners include polyoxyalkylene glycerol alkanoates, polybutylenes, long chain fatty acids, ethoxylated fatty acid ethanolamides, alkyl polyglycosides, especially sorbitan mono-, di- and triesters, and fatty acid esters of polycarboxylic acids It is.

  The preparations according to the invention contain softeners in any case from 0.01 to 80% by weight, usually 0.1 to 70% by weight, preferably 0.2 to 60% by weight, in particular 0.5 It may be contained in an amount of ~ 40% by weight.

  Other surfactants for all of the formulations of the present invention include so-called gemini surfactants. The gemini surfactant generally means a compound having two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from each other by so-called “spacers”. This spacer is usually a carbon chain, which needs to be long enough that the hydrophobic groups are sufficiently separated so that they can act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to significantly reduce the surface tension of water. However, in exceptional cases, the expression “gemini surfactant” is understood to mean not only dimeric surfactants but also trimeric surfactants.

  Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer alcohol tris-sulfates, and ether sulfates. End-capped dimers and trimer mixed ethers are particularly excellent in difunctionality and polyfunctionality. Thus, the end cap surfactants have excellent wettability and low foaming properties, and are therefore particularly suitable for use in automated cleaning, care-providing or cleaning methods.

  However, gemini polyhydroxy fatty acid amides or polypolyhydroxy fatty acid amides can also be used as described in the related prior art.

〔式中、ＲＣＯは、６〜２２個の炭素原子を有する脂肪族アシル基であり、Ｒ^２３は、水素、１〜４個の炭素原子を有するアルキル基またはヒドロキシアルキル基であり、［Ｚ］は３〜１０個の炭素原子と３〜１０個のヒドロキシ基とを有する直鎖状または分枝状ポリヒドロキシアルキル基である。〕
ポリヒドロキシ脂肪酸アミドは既知の物質であり、通常、還元糖を、アンモニア、アルキルアミンまたはアルカノールアミンで還元的アミノ化し、その後、脂肪酸、脂肪酸アルキルエステルまたは脂肪酸クロリドでアシル化することにより得ることができる。 Further suitable surfactants are polyhydroxy fatty acid amides of the formula

[Wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ²³ is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group; [Z] Is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxy groups. ]
Polyhydroxy fatty acid amides are known substances and can usually be obtained by reductive amination of reducing sugars with ammonia, alkylamines or alkanolamines followed by acylation with fatty acids, fatty acid alkyl esters or fatty acid chlorides. .

〔式中、Ｒは、７〜１２個の炭素原子を有する直鎖状または分枝状アルキル基またはアルケニル基であり、Ｒ^２４は、２〜８個の炭素原子を有する直鎖状、分枝状または環状アルキル基あるいはアリール基であり、Ｒ^２５は、１〜８個の炭素原子を有する直鎖状、分枝状あるいは環状アルキル基またはアリール基またはオキシアルキル基であり、Ｃ_１〜４アルキル基またはフェニル基が好ましい、［Ｚ］は、アルキル鎖が少なくとも２つのヒドロキシ基により置換されている直鎖状ポリヒドロキシアルキル基、またはこの基のアルコキシル化、好ましくはエトキシル化もしくはプロポキシル化誘導体である。〕 The group of polyhydroxy fatty acid amides includes compounds of the following formula.

[Wherein R is a linear or branched alkyl group or alkenyl group having 7 to 12 carbon atoms, and R ²⁴ is a linear or branched group having 2 to 8 carbon atoms. Or a cyclic alkyl group or an aryl group, and R ²⁵ is a linear, branched or cyclic alkyl group, an aryl group or an oxyalkyl group having 1 to 8 carbon atoms, and a C _1-4 alkyl group. [Z] is a linear polyhydroxyalkyl group in which the alkyl chain is substituted by at least two hydroxy groups, or an alkoxylated, preferably ethoxylated or propoxylated derivative of this group. is there. ]

  [Z] is preferably obtained by reductive amination of sugars such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compound can then be converted to the desired polyhydroxy fatty acid amide, for example by reaction with a fatty acid methyl ester in the presence of an alkoxide as a catalyst.

  The cleaning agent or cleaning agent of the present invention preferably also contains an amphoteric surfactant. In addition to the large number of mono-, di- and trialkylated amino oxides, betaines are an important class.

〔式中、Ｒ^２６は、６〜２２個の炭素原子を有するアルキル基および／またはアルケニル基であり、Ｒ^２７は、水素または１〜４個の炭素原子を有するアルキル基であり、Ｒ^２８は、１〜４個の炭素原子を有するアルキル基であり、ｎは、１〜６の数値であり、Ｘ^１は、アルカリ金属またはアルカリ土類金属またはアンモニウムである。〕
典型的な例は、ヘキシルメチルアミン、ヘキシルジメチルアミン、オクチルジメチルアミン、デシルジメチルアミン、ドデシルメチルアミン、ドデシルジメチルアミン、ドデシルエチルメチルアミン、Ｃ_{１２／１４}−ココアルキルジメチルアミン、ミリスチルジメチルアミン、セチルジメチルアミン、ステアリルジメチルアミン、ステアリルエチルメチルアミン、オレイルジメチルアミン、Ｃ_{１６／１８}獣脂アルキルジメチルアミン、およびそれらの工業用混合物のカルボキシメチル化生成物である。 Betaine is a known surfactant and is mostly prepared by carboxyalkylation, preferably carboxymethylation, of amine compounds. Preferably, the starting material is condensed with a halocarboxylic acid or salt thereof, particularly sodium chloroacetate, to produce 1 mole of salt per mole of betaine. For example, an unsaturated carboxylic acid such as acrylic acid can be added. With regard to the nomenclature and in particular the distinction between betaines and “true” amphoteric surfactants, reference can be made to the appropriate technical literature. Examples of suitable betaines are represented in particular by carboxyalkylation products of secondary and tertiary amines of the formula (G).

[Wherein R ²⁶ is an alkyl group and / or alkenyl group having 6 to 22 carbon atoms, R ²⁷ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ²⁸ is , An alkyl group having 1 to 4 carbon atoms, n is a numerical value of 1 to 6, and X ¹ is an alkali metal, an alkaline earth metal or ammonium. ]
Typical examples are hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, _{dodecylethylmethylamine} , C12 / ₁₄ -cocoalkyldimethylamine, myristyldimethylamine, cetyl Carboxymethylation products of dimethylamine, _{stearyldimethylamine} , stearylethylmethylamine, _{oleyldimethylamine} , _{C16 / 18} tallow alkyldimethylamine, and industrial mixtures thereof.

〔式中、Ｒ^３１ＣＯは、６〜２２個の炭素原子と０または１または３個の二重結合を有する脂肪族アシル基であり、ｍは、１〜３の数値であり、Ｒ^２９、Ｒ^３０、ｎおよびＸ^２は、前記と同じ意味を有する。〕
典型的な例は、６〜２２個の炭素原子を有する脂肪酸、すなわちヘキサン酸、オクタン酸、デカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、パルミトレイン酸、ステアリン酸、イソステアリン酸、オレイン酸、エライジン酸、ペトロセリン酸、リノール酸、リノレン酸、エレオステアリン酸、アラキジン酸、ガドレイン酸、ベヘン酸およびエルカ酸、ならびにそれらの工業用混合物と、Ｎ，Ｎ−ジメチルアミノエチルアミン、Ｎ，Ｎ−ジメチルアミノプロピルアミン、Ｎ，Ｎ−ジエチルアミノエチルアミンおよびＮ，Ｎ−ジエチルアミノプロピルアミンとの反応生成物であり、これらの反応生成物はクロロ酢酸ナトリウムと縮合される。Ｃ_８／１８−ヤシ油脂肪酸−Ｎ，Ｎ−ジメチルアミノプロピルアミドとクロロ酢酸ナトリウムとの縮合生成物を使用することが好ましい。 Also suitable are the amide amine carboxylation products of formula (H).

[Wherein R ³¹ CO is an aliphatic acyl group having 6 to 22 carbon atoms and 0 or 1 or 3 double bonds, m is a numerical value of 1 to 3, R ²⁹ , R ³⁰ , n and X ² have the same meaning as described above. ]
Typical examples are fatty acids having 6 to 22 carbon atoms, ie hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid , Petroceric acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, and their industrial mixtures with N, N-dimethylaminoethylamine, N, N-dimethylaminopropyl Reaction products of amines, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. Preference is given to using the condensation product of C _{8/18 -coconut} oil fatty acid-N, N-dimethylaminopropylamide and sodium chloroacetate.

〔式中、Ｒ^３２は、５〜２１個の炭素原子を有するアルキル基であり、Ｒ^３３は、ヒドロキシ基、ＯＣＯＲ^３２またはＮＨＣＯＲ^３２基であり、ｍは、２または３である。〕
これらの物質もまた、既知の物質であり、例えば、１または２モルの脂肪酸と、多価アミン、例えばアミノエチルエタノールアミン（ＡＥＥＡ）またはジエチレントリアミンとを環化縮合することにより得ることができる。対応するカルボキシアルキル化生成物は、異なる開鎖ベタインの混合物である。典型的な例は、上述の脂肪酸とＡＥＥＡとの縮合生成物、好ましくは、ラウリン酸またはＣ_{１２／１４}−ココ脂肪酸も、に基づいたイミダゾリンであり、これらは、その後、クロロ酢酸ナトリウムでベタイン化される。 A suitable starting material for betaine that can be used in the present invention is imidazoline represented by the formula (J).

[Wherein R ³² is an alkyl group having 5 to 21 carbon atoms, R ³³ is a hydroxy group, OCOR ³² or NHCOR ³² group, and m is 2 or 3. ]
These substances are also known substances, and can be obtained, for example, by cyclocondensing one or two moles of fatty acid and a polyvalent amine such as aminoethylethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylated product is a mixture of different open chain betaines. A typical example is an imidazoline based on the above-mentioned condensation products of fatty acids with AEEA, preferably also lauric acid or C _{12/14 -coco} fatty acid, which are then betainated with sodium chloroacetate Is done.

  In preferred embodiments, the cleaning or cleaning agents of the present invention may optionally contain one or more complexing agents.

  Complexing agents (INCI: chelating agents), also called sequestering agents, can complex and inactivate metal ions, for example to reduce the appearance stability of the formulation, eg adverse effects on turbidity. It is a possible ingredient. On the other hand, it is important to complex water hardness calcium ions and magnesium ions which are incompatible with many components. Complexation of ions of heavy metals such as iron or copper delays the oxidative degradation of the finished formulation.

  Suitable complexing agents are, for example, the following complexing agents described in more detail in the International Cosmetic Ingredient Dictionary and Handbook and named by INCI: aminotrimethylene phosphonic acid, β-alanine diacetate, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexanediaminetetraacetic acid, diammonium citrate, diammonium EDTA, diethylenetriaminepentamethylenephosphonic acid, dipotassium EDTA, disodium azacycloheptane diphosphonate, disodium EDTA, disodium pyrophosphate, EDTA, Etidronic acid, galactaric acid, gluconic acid, glucuronic acid, HEDTA, hydroxypropylcyclodextrin, methylcyclodextrin, pentapotassium triphosphate, pentasodium aminotrimethyle Phosphonate, pentasodium ethylenediaminetetramethylenephosphonate, pentasodium pentateate, pentasodium triphosphate, pentenoic acid, phytic acid, potassium citrate, potassium EDTMP, potassium gluconate, potassium polyphosphate, potassium trisphosphonomethylamine oxide, ribbon acid , Sodium chitosan methylene phosphonate, sodium citrate, sodium diethylenetriamine pentamethylene phosphonate, sodium dihydroxyethyl glycinate, sodium EDTMP, sodium glucoceptate, sodium gluconate, sodium glyceres-1-polyphosphate, sodium hexametaphosphate, sodium metaphosphate, Sodium metasilicate, sodium phytate, sodium polydimethyl Glycinophenol sulfonate, sodium trimetaphosphate, TEA-EDTA, TEA-polyphosphate, tetrahydroxyethylethylenediamine, tetrahydroxypropylethylenediamine, tetrapotassium pyrophosphate, tetrapotassium pyrophosphate, tetrasodium EDTA, tetrasodium etidronate, tetrasodium pyrophosphate Sodium, tripotassium EDTA, trisodium dicarboxymethylalaninate, trisodium EDTA, trisodium HEDTA, trisodium NTA and trisodium phosphate.

  Preferred complexing agents are tertiary amines, especially tertiary alkanolamines (amino alcohols). An alkanolamine has both an amino group and a hydroxy group and / or an ether group as functional groups. Particularly preferred tertiary alkanolamines are triethanolamine and tetra-2-hydroxypropylethylenediamine (N, N, N ', N'-tetrakis- (2-hydroxypropyl) ethylenediamine). Particularly preferred combinations of tertiary amines with zinc ricinoleate and one or more ethoxylated fatty alcohols and optionally solvents as nonionic dissolution promoters are described in the prior art.

  Particularly preferred complexing agents are etidronic acid (1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, HEDP, acetophosphonic acid, INCI: etidronic acid) including salts thereof. is there. Accordingly, in a preferred embodiment, the cleaning or cleaning agent of the present invention comprises etidronic acid and / or one or more salts thereof as a complexing agent.

  In certain embodiments, the cleaning or cleaning agents of the present invention comprise one or more tertiary amines and one or more other complexing agents, preferably one or more complexing. Combinations of complexing agents with the acid or salts thereof, in particular triethanolamine and / or tetra-2-hydroxypropylethylenediamine with etidronic acid and / or one or more of its salts Contains combinations.

  The detergents or detergents according to the invention contain complexing agents, advantageously from 0 to 20% by weight, preferably from 0.1 to 15% by weight, in particular from 0.5 to 10% by weight, based on the total formulation. It is particularly preferably contained in an amount of 1 to 8% by weight, more particularly preferably 1.5 to 6% by weight.

  In a further preferred embodiment, the cleaning or cleaning agent according to the invention optionally comprises one or more of the abovementioned enzymes.

  Suitable enzymes are in particular those of the hydrolase species, such as proteases, carboanhydrases, tannases, esterases, lipases and lipolytic active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of said enzymes. All these hydrolases contribute to the removal and graying of soils (eg proteinaceous, greasy or starchy soils) during washing. Cellulases and other glycosyl hydrolases can also help to retain color and increase fabric softness by removing pilling and microfibers. Oxidoreductase can also be used to prevent bleaching and color transfer.

  Particularly suitable are enzyme active substances obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens, which exhibit particularly good suitability. It is preferred to use a subtilisin type protease, in particular a protease obtained from Bacillus lentus. In this regard, an enzyme mixture, for example an enzyme mixture of protease and amylase or protease and lipase or lipolytic active enzyme, or an enzyme mixture of protease and cellulase, or an enzyme mixture of cellulase and lipase or lipolytic enzyme, or protease, amylase Of particular interest are enzyme mixtures of lipase or lipolytic active enzyme or protease, lipase or lipolytic active enzyme and cellulase, in particular protease and / or lipase-containing or lipolytic active enzyme-containing mixtures. An example of such a lipolytic active enzyme is the known cutinase. Peroxidase or oxidase has also been found to be suitable in some cases. Suitable amylases include in particular α-amylase, isoamylase, pullulanase and pectinase. Β-glucosidase, also called cellobiohydrolase, endoglucanase and cellobiase, or a mixture thereof can be preferably used as cellulase. Since different types of cellulose differ by CMCase activity and avicelase activity, the desired activity can be achieved by a conditioned mix of cellulases.

  The enzyme may be adsorbed or coated on the support material as a shaped body to protect the enzyme from premature degradation. The proportion of enzyme, enzyme mixture or enzyme granule can be, for example, about 0.1 to 5% by weight, preferably 0.12 to about 2% by weight, based on the total formulation.

The cleaning agent or cleaning agent of the present invention may contain a bleaching agent if necessary. Of the compounds that generate H ₂ O _{2 in} water and act as bleaches, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Additional bleaching agents which can be used are, for example, a peroxypyrophosphates, citrate perhydrate, and peracid salts or peracids generates H ₂ O _2, for example, persulfates or persulfuric acid. Urea peroxohydrate percarbamide, which can be described by the formula: H ₂ N—CO—NH ₂ .H ₂ O _2, can also be used. In particular, if, for example, the formulations are used to clean hard surfaces in automatic dishwashing, they may optionally contain bleach from the group of organic bleaches, such bleaches being In principle, it can also be used in laundry detergents. Typical organic bleaching agents are diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are peroxo acids, with specific mention being made of alkyl peroxo acids and aryl peroxo acids. Preferred representatives are perbenzoic acid and ring substituted derivatives thereof such as alkyl perbenzoic acid, but peroxy-α-naphthoic acid and magnesium monoperphthalate, aliphatic or substituted aliphatic peroxo acids such as perlauric acid, peroxyphosphoric acid, Stearic acid, ε-phthalimidopercaproic acid (phthalimidoperhexanoic acid, PAP), o-carboxybenzamide percaproic acid, N-nonenylamide peradipic acid and N-nonenylamide persuccinate, and aliphatic and araliphatic peroxydicarboxylic acids Acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelineic acid, diperoxysebacic acid, diperoxybrassic acid, diperoxyphthalic acid, 2-decyldiperoxybutane-1,4-dicarboxylic acid, N, N-terephthaloyl di- (6-Aminopercaproic acid) can also be used.

  The bleaching agents may preferably be coated to prevent their premature degradation.

  Dyes can be used in the cleaning or cleaning agents of the present invention; the amount of one or more dyes should be selected low so that no visible residue remains after use of the formulation . The formulations of the present invention preferably do not contain a dye.

  The cleaning or cleaning agents according to the invention preferably contain one or more antimicrobial active substances or preservatives, usually 0.0001 to 3% by weight, preferably 0.0001 to 2% by weight, in particular 0.0002. May be included in an amount of ˜1 wt%, particularly preferably 0.0002 to 0.2 wt%, more particularly preferably 0.0003 to 0.1 wt%.

  Antibacterial active substances or preservatives are classified into bacteriostatic and fungicides, fungistatic and fungicides, etc., depending on the antibacterial area and mechanism of action. Important materials from these groups include, for example, benzalkonium chloride, alkylaryl sulfonates, halophenols, and phenylmercuric acetate. Within the scope of the teachings of the present invention, the concepts “antimicrobial action” and “antimicrobial active substance” have a general technical meaning. Suitable antimicrobial active substances are preferably alcohols, amines, aldehydes, antimicrobial acids or salts thereof, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyl, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, Benzamidine, isothiazoline, phthalimide derivative, pyridine derivative, antibacterial surfactant compound, guanidine, antibacterial amphoteric compound, quinoline, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propylbutylcarbamate, iodine, iodophor, peroxo compound , Halogen compounds, and any mixture of the above.

Here, the antibacterial substance is ethanol, n-propanol, isopropanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydroacetic acid, o-phenylphenol, N-methylmorpholinoacetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2′-methylenebis (6-bromo-4-chlorophenol), 4,4′-dichloro-2′-hydroxydiphenyl ether (diclosan) 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N '-(1,10- Decandiyldi-1-pyridinyl-4-ylide ) Bis (1-octaneamine) dihydrochloride, N, N′-bis (4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecanedimidoamide, glucoprotamine, antimicrobial surface activity 4 Class compounds such as 1,6-bis (2-ethylhexyl biguanide hexane) dihydrochloride, 1,6-di (N ₁ , N ₁ ′ -phenyldiguanide-N ₅ , N ₅ ′) hexane tetrahydrochloride, 1 , 6- di _{(N 1,} N 1 '- phenyl _-N 1, _{N 1} - Mechirujiguanido _{-N 5, N} 5') hexane dihydrochloride, 1,6 _{(N 1,} N 1 _'-o- chlorophenyl jig Enid _{-N 5, N} 5 ') hexane dihydrochloride, 1,6 _{(N 1,} N 1' -2,6- dichlorophenyl jig biguanide _{-N 5, N} 5 ') f San dihydrochloride, 1,6 _{(N 1, N 1 '-β} (p- methoxyphenyl) Jiguanido _-N 5, _{N 5')} hexane dihydrochloride, 1,6 _{(N 1,} N 1 '- α-methyl-β-phenyldiguanide-N ₅ , N ₅ ′) hexane dihydrochloride, 1,6-di (N ₁ , N ₁ ′ -p-nitrophenyldiguanide-N ₅ , N ₅ ′) hexane dihydrochloride, omega: .omega.-di _{(N 1,} N 1 '- phenyl jig biguanide _{-N 5, N} 5') - di -n- propyl ether dihydrochloride, omega: omega .'- di - _(N 1, N ₁ '-p-chlorophenyl jig biguanide _{-N 5, N} 5') - di -n- propyl ether tetrahydrochloride, 1,6 _{(N 1,} N 1 '-2,4- dichlorophenyl jig biguanide - _{N 5,} N ₅ ') hexane tetrahydrochloride, 1,6 _{(N 1,} N 1 _'-p- methylphenyl jig biguanide _{-N 5, N} 5') hexane dihydrochloride, 1,6 _{(N 1,} N 1 '-2,4,5 - trichlorophenyl jig biguanide _-N 5, _{N 5} ') hexane tetrahydrochloride, 1,6 _{[N 1, N 1' -α-} (p- chlorophenyl) Echirujiguanido _{-N 5, N} 5 '] hexane dihydrochloride , Ω, ω-di (N ₁ , N ₁ ′ -p-chlorophenyldiguanide-N ₅ , N ₅ ′) -m-xylene dihydrochloride, 1,12-di (N ₁ , N ₁ ′ -p- chlorophenyl jig biguanide _{-N 5, N} 5 ') dodecane dihydrochloride, 1,10-di _{(N 1,} N 1' - phenyl jig biguanide _{-N 5, N} 5 ') decane tetrahydrochloride, 1,12-di _{(N 1, N} 1 '- Fenirujigua De _{-N 5, N} 5 ') dodecane tetrahydrochloride, 1,6 _{(N 1,} N 1' _-o- chlorophenyl jig biguanide _{-N 5, N} 5 ') hexane dihydrochloride, 1,6-di ( _{N 1,} N ₁ '-o- chlorophenyl jig biguanide _-N 5, _{N 5')} hexane tetrahydrochloride, ethylene-bis (1-tolylbiguanide), ethylene bis (p- tolylbiguanide), ethylene bis (3,5 Dimethylphenylbiguanide), ethylenebis (p-tert-amylphenylbiguanide), ethylenebis (nonylphenylbiguanide), ethylenebis (phenylbiguanide), ethylenebis (N-butylphenylbiguanide), ethylenebis (2,5-di Ethoxyphenyl biguanide), ethylene bis (2,4-dimethylphenyl biguanide), Such as tylene bis (o-diphenylbiguanide), ethylene bis (mixed amylnaphthyl biguanide), N-butylethylene bis (phenyl biguanide), trimethylene bis (o-tolyl biguanide), N-butyl trimethylene bis (phenyl biguanide) Biguanidine and guanidine including polyguanidine, and acetate, gluconate, hydrochloride, hydrobromide, citrate, bisulfite, fluoride, polymaleate, n-cocoalkyl sarcosine, phosphorus Acid salt, hypophosphite, perfluorooctanoate, silicate, sorbate, salicylate, maleate, tartrate, fumarate, ethylenediaminetetraacetate, iminodiacetate, cinnamate, Thiocyanate, alginate, pyromellitic acid salt, tetracarboxybutyrate, It can be selected from the corresponding salts such as benzoate, glutarate, monofluorophosphate, perfluoropropionate, and desirable mixtures thereof. Also suitable are halogenated xylene and cresol derivatives, such as p-chlorometacresol or p-chlorometaxylene, and natural antimicrobial actives of plant origin (eg, from herbs or wildflowers), animal origin, or microbial origin. From the group comprising antibacterial surfactant quaternary compounds, natural antibacterial active substances of plant origin and / or natural antibacterial active substances of animal origin, particularly preferably caffeine, theobromine and theophylline, and essential oils such as eugenol, thymol and geraniol At least one natural antibacterial active substance of plant origin selected and / or at least one natural antibacterial active substance of animal origin selected from the group comprising enzymes such as milk protein, lysozyme and lactoperoxidase, and / or ammonium, sulfonium It is preferred to use at least one antibacterial surfactant quaternary compound having a phosphonium, iodonium or arsonium group, a peroxo compound and a chlorine compound. Substances of microbial origin, so-called bacteriocin, can also be used. Preference is given to using glycine, glycine derivatives, formaldehyde and compounds which readily liberate formaldehyde, formic acid and peroxides.

  Quaternary ammonium compounds (QACs) suitable as antibacterial active substances have already been described above. Particularly suitable is, for example, benzalkonium chloride. Benzalkonium halides and / or substituted benzalkonium halides are, for example, Lonza Barquat®, Mason Marquat®, Witco / Sherex Variquat®, and Lonza Hyamine. (Registered trademark), and Bardac (registered trademark) manufactured by Lonza. Another commercially available antimicrobial active is N- (3-chloroallyl) hexanium chloride such as Dowicide® and Dowicil® from Dow, benzethonium chloride, such as Hyamine® 1622 from Rohm & Haas. Methylbenzethonium chloride such as Hyamine (registered trademark) 10X manufactured by Rohm & Haas, and cetylpyridinium chloride such as Cepacol chloride manufactured by Merrell Labs.

  The cleaning or cleaning agent of the present invention may optionally contain an ironing aid to improve the rewet of the treated fabric and facilitate ironing of the treated fabric. For example, silicone derivatives can be used in the composition. Since these exhibit anti-foaming properties, they further improve the rinsability of formulations having cleaning activity. Preferred silicone derivatives are, for example, polydialkylsiloxanes or alkylarylsiloxanes in which the alkyl group has 1 to 5 carbon atoms and is wholly or partially fluorinated. A preferred silicone is polydimethylsiloxane, which may optionally be derivatized, amino functional, or quaternized, or Si—OH, Si—H and It may have a Si-Cl bond. Preferred silicones have a viscosity at 25 ° C. in the range of 100 to 100,000 mPas, and the silicone can be used in an amount of 0.2 to 5% by weight based on the total formulation.

The powder (strong) detergent of the present invention preferably contains a component selected from the following, for example.
An anionic surfactant advantageously in an amount of 1 to 35% by weight, preferably 5 to 25% by weight, in particular 10 to 20% by weight, preferably a sulfonic acid ester, in particular a sulfonic acid methyl ester,
Non-ionic surfactants advantageously in an amount of 0.1 to 20% by weight, preferably 2 to 15% by weight, in particular 6 to 11% by weight, such as alkyl glucosides, fatty acid glucamides, fatty alcohol ethoxylates, etc.
-Cleaning builders, such as zeolites, polycarboxylates, sodium citrate, etc., in amounts of 5-60% by weight, preferably 10-55% by weight, in particular 15-40% by weight,
An alkali in an amount of advantageously 1 to 30% by weight, preferably 2 to 25% by weight, in particular 5 to 20% by weight, such as sodium carboxylate,
A bleaching agent advantageously in an amount of 5 to 25% by weight, preferably 10 to 20% by weight, such as sodium perborate, sodium percarbonate, etc.
A corrosion inhibitor in an amount of advantageously 1 to 6% by weight, preferably 2 to 5% by weight, in particular 3 to 4% by weight, such as sodium citrate,
-Stabilizers, preferably in amounts of 0 to 1% by weight, such as phosphonates,
An antifoaming agent in an amount of advantageously 0.1 to 4% by weight, preferably 0.2 to 3% by weight, in particular 1 to 2% by weight, such as soap, silicone oil, paraffin, etc.
Advantageously 0.01 to 2% by weight, preferably 0.1 to 1% by weight, in particular 0.3 to 0.8% by weight of enzymes such as proteases, amylases, cellulases, lipases, tannases, pectinases, carboan Such as hydrase,
-Preferably 0 to 1% by weight of an anti-graying agent, such as carboxymethylcellulose,
An anti-discoloring agent, preferably in an amount of 0 to 2% by weight, such as polyvinylpyrrolidone derivatives,
A polyester antifouling polymer, preferably in an amount of 0.01 to 2% by weight,
-Advantageously 0 to 60% by weight, preferably 1 to 40% by weight, in particular 5 to 20% by weight of a regulator, such as sodium sulfate,
A fluorescent bleaching agent in an amount of preferably 0.1 to 0.3% by weight, in particular 0.1 to 0.4% by weight,
-Perfume-water,
-Soap,
-Bleach activators,
-Cellulose derivatives,
-Antifouling agents.

  The cleaning or cleaning agent of the present invention may preferably also contain a perfume oil (fragrance).

  The viscous flavors that can be advantageously used in the present invention are Angelica oil, Anise oil, Arnica flower oil, Basil oil, Bay oil, Champaca flower oil, Silver fir oil, Silver fir seed oil, Elemi oil, Eucalyptus oil, Fennel oil, Pine needle oil, galvanum oil, geranium oil, gingergrass oil, guayak tree oil, balsam garjan oil, helichrysum oil, ho oil, ginger oil, iris oil, kayap oil, ginger oil, camomile oil, camphor oil, canoga (Canoga) Oil, cardamom oil, cassia oil, pine needle oil, copaiba balsam oil, coriander oil, carved peppermint oil, caraway oil, cumin oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, amblet seed oil, myrrh oil , Clove oil, neroli oil, near uri oil, olive oil, orange oil, oregano oil, Marosa oil, Patchouli oil, Peru balsam oil, Petit grain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Star anise oil, Scented oil, Thyme oil, Verbena oil, vetiver oil, juniper berry oil, mugwort oil, winter green oil, ylang ylang oil, ysop oil, cinnamon oil, cinnamon leaf oil, and cypress oil.

  However, higher-boiling or solid fragrances of natural or synthetic origin can also be advantageously used in the present invention as viscous fragrances or fragrance mixtures in fragrance oils. These compounds include the compounds shown below and mixtures thereof: ambridolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, benzoic acid Ethyl acetate, benzophenone, benzyl alcohol, borneol, bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fencheon, fenkylacetate, geranyl acetate, geranyl formate, Heliotropin, heptine carboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, Droxycinnamyl alcohol, indole, Iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methyl Methyl anthranilate, p-methylacetophenone, methylchavicol, p-methylquinoline, methyl β-naphthylketone, methyl-n-nonylacetaldehyde, methyl n-nonylketone, muscone, β-naphtholethylether, β-naphtholmethylether, Nerol, nitrobenzene, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol , Phenylacetaldehyde dimethylacetal, phenylacetic acid, pregon, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymen, thymol, γ-undelactone, vanillin, veratramaldehyde, cinnamaldehyde , Cinnamyl alcohol, cinnamic acid, ethyl cinnamate, and benzyl cinnamate.

  In the present invention, more volatile perfumes that can be advantageously introduced into perfume oils are in particular low-boiling perfumes of natural or synthetic origin that can be used alone or in mixtures. Examples of more volatile perfumes include alkyl isothiocyanate (alkyl mustard oil), butanedione, limonene, linalool, linalyl acetate and linalyl propionate, menthol, menthone, methyl n-heptenone, ferrandrene, phenylacetaldehyde, terpinyl acetate, Citral and Citronellal.

  Perfumes that can be used are, for example, condensation products of amines and aldehydes. Preferred examples of condensation products of amines and aldehydes include anisaldehyde methyl anthranilate, auran thiol (hydroxy citronellal methyl anthranilate), verdane thiol (4-tert-butyl-α-methyldihydrocinnamaldehyde methyl anthranilate). ), Berthocin (2,4-dimethyl-3-cyclohexenecarbaldehyde), hydroxycitronellal ethyl anthranilate, hydroxycitroneral linalyl anthranilate, methyl-N- (4- (4-hydroxy-4-methylpentyl) ) -3-Cyclohexenylmethylidene) anthranilate, methyl naphthyl ketone methyl anthranilate, methyl nonyl acetaldehyde methyl anthranilate, methyl-N- (3,5,5-trimethylhexylidene Anthranilate, there is vanillin methyl anthranilate and / or mixtures thereof. The perfume oil of the present invention may preferably contain a condensation product of an amine and an aldehyde.

  For example, adoxal (2,6,10-trimethyl-9-undecene-1-al), amyl acetate, anisaldehyde (4-methoxybenzaldehyde), bacdanol (2-ethyl-4- (2,2,3-trimethyl-) 3-cyclopenten-1-yl) -2-buten-1-ol), benzaldehyde, benzophenone, benzyl acetate, benzyl salicylate, 3-hexen-1-ol, cetarox (dodecahydro-3A, 6,6,9A-tetramethyl) Naphtho [2,1B] furan), cis-3-hexenyl acetate, cis-3-hexenyl salicylate, citronellol, coumarin, cyclohexyl salicylate, simal (2-methyl-3- (p-isopropylphenyl) -propionaldehyde) , Decylaldehyde, Ethylbani , Ethyl-2-methylbutyrate, ethylene brushate, eucalyptol, eugenol, exaltolide (cyclopentadecanolide), fluorhydride (3- (3-isopropylphenyl) butanol), galaxolide (1,3,4,4) 6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran), γ-decalactone, γ-dodecalactone, geraniol, geranyl nitrile, helional (α- Methyl-3,4- (methylenedioxy) hydrocinnamaldehyde), heliotropin, hexyl acetate, hexylcinnamaldehyde, hexyl salicylate, hydroxyamblanc (2-cyclododecylpropanol), hydroxycitroneral, iso-E super (7- Acetyl-1,2,3 , 4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene), isoeugenol, isojasmon, Koavone (acetyldiisoamylene), lauryl aldehyde, IRG201 (2, 4-dihydroxy-3,6-dimethylbenzoate), Liral (4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde), Majantol (2 , 2-dimethyl-3- (3-methylphenyl) propanol), Mayor (4- (1-methylethyl) cyclohexanemethanol), methyl anthranilate, methyl β-naphthyl ketone, methyl cedrilone (methyl Drenylketone), methylcavicol (1-methyloxy-4,2-propen-1-ylbe) Zen), methyldihydrojasmonate, methylnonylacetaldehyde, muskindanone (4-acetyl-6-tert-butyl-1,1-dimethylindane), nerol, nonalactone (4-hydroxynonanoic acid, lactone), norrin Vanol (1- (2,2,6-trimethylcyclohexyl) -3-hexanol), pt-bucinal (2 methyl-3- (para-tert-butylphenyl) propionaldehyde), p-hydroxyphenylbutanone, patchouli , Phenylacetaldehyde, phenylethyl acetate, phenylethyl alcohol, phenylethylphenyl acetate, phenylhexanol / phenoxanol (3-methyl-5-phenylpentanol), polysanthol (3,3-dimethyl-5- (2,2 3-trimethyl-3-cyclopenten-1-yl) -4-penten-2-ol), rosafen (2-methyl-5-phenylpentanol), sandalwood, α-terpinene, tonalide / musk plus (7- Acetyl-1,1,3,4,4,6-hexamethyltetralin), undecalactone, undecavertol (4-methyl-3-decen-5-ol), undecylaldehyde, undecenaldehyde, vanillin It is particularly advantageous if perfumes such as and / or mixtures thereof are included in the perfume oils of the present invention.

  In a preferred embodiment, the cleaning or cleaning agent of the present invention contains a certain minimum perfume oil. That is, at least 0.01 wt%, preferably at least 0.1 wt%, very preferably at least 0.15 wt%, more preferably at least 0.2 wt%, based on the total detergent or detergent. %, More preferably at least 0.25% by weight, more preferably at least 0.3% by weight, particularly preferably at least 0.35% by weight, more particularly preferably at least 0.4% by weight, even very highly Preferably at least 0.45% by weight, more preferably at least 0.5% by weight, even more preferably at least 0.55% by weight, even more preferably at least 0.6% by weight, even more advantageous Is at least 0.65% by weight, even more preferably at least 0.7% by weight, even more preferably at least 0.75% by weight, even more preferably at least 0. Wt%, more highly preferably at least 0.85% by weight, especially at least 0.9% by weight of the perfume oil. The upper limit is, for example, 5, 3 or 1% by weight, based on the entire formulation.

  In a preferred embodiment, the perfume oil comprises amylcinnamal, amylcinnamyl alcohol, benzyl alcohol, benzyl salicylate, cinnamyl alcohol, cinnamal, coumarin, eugenol, geraniol, hydroxycitronal, hydroxymethylpentylcyclohexenecarboxaldehyde, isoeugenol, anisyl alcohol. , Benzyl benzoate, benzyl cinnamate, citronellol, farnesol, hexylcinnamaldehyde, lyial, d-limonene, methylheptin carbonate, 3-methyl-4- (2,6,6-trimethyl-2-cyclohexen-1-yl ) -3-buten-2-one, oak moss extract, scented extract of moss, less than 8, preferably less than 7, more advantageously Less than 6, more preferably less than 5, more preferably less than 4, even more advantageously less than 3, preferably contains less than 2, in particular it does not contain.

  Different detergent formulations were subjected to cleaning tests on primary and secondary cleaning power (40 ° C., Miele W308, main wash cycle 75 minutes, 16 ° dH, laundry volume 3.5 kg). Whiteness was compared for various types of fabrics (cotton, cotton / polyester blended fabric, polyester).

  The following detergent formulations were tested.

Cleaning agent 1 (comparative example) :
4 wt% C12-C14 fatty alcohol with 7EO
C9-13 alkylbenzene sulfonate, sodium salt 10% by weight
Sodium percarbonate 18% by weight
TAED 3% by weight
C12-18 fatty acid, sodium salt 1.5% by weight
2% by weight of PVA / maleic acid copolymer
Phosphonic acid, sodium salt 0.5% by weight
Sodium carboxylate 20% by weight
Zeolite A 25% by weight
CMC, sodium salt 1% by weight
Antifoam 1.3% by weight
Enzyme (Amylase, Protease, Cellulase) +
Fragrance 0.5% by weight
Fluorescent bleach 0.3% by weight
Until sodium sulfate reaches 100

Cleaning agent 2 (comparative example) :
4 wt% C12-C14 fatty alcohol with 7EO
C9-13 alkylbenzene sulfonate, sodium salt 5% by weight
C16-18 sulfonic acid methyl ester 5% by weight
Sodium percarbonate 18% by weight
TAED 3% by weight
C12-18 fatty acid, sodium salt 1.5% by weight
2% by weight of PVA / maleic acid copolymer
Phosphonic acid, sodium salt 0.5% by weight
Sodium carboxylate 20% by weight
Zeolite A 25% by weight
CMC, sodium salt 1% by weight
Antifoam 1.3% by weight
Enzyme (Amylase, Protease, Cellulase) +
Fragrance 0.5% by weight
Fluorescent bleach 0.3% by weight
Until sodium sulfate reaches 100

  Cleaning agent 2 differs from cleaning agent 1 in that half of LAS (C9-13 alkylbenzene sulfonate, sodium salt) is replaced with MES (C16-18 sulfonic acid methyl ester). The total amount of surfactant included is the same.

Cleaning agent 3 (comparative example) :
4 wt% C12-C14 fatty alcohol with 7EO
C16-18 sulfonic acid methyl ester 10% by weight
Sodium percarbonate 18% by weight
TAED 3% by weight
C12-18 fatty acid, sodium salt 1.5% by weight
2% by weight of PVA / maleic acid copolymer
Phosphonic acid, sodium salt 0.5% by weight
Sodium carboxylate 20% by weight
Zeolite A 25% by weight
CMC, sodium salt 1% by weight
Antifoam 1.3% by weight
Enzyme (Amylase, Protease, Cellulase) +
Fragrance 0.5% by weight
Fluorescent bleach 0.3% by weight
Until sodium sulfate reaches 100

  Cleaning agent 3 differs from cleaning agent 1 in that the entire amount of LAS (C9-13 alkylbenzene sulfonate, sodium salt) is replaced with MES (C16-18 sulfonic acid methyl ester). The total amount of surfactant included is the same.

Cleaning agent A:
4 wt% C12-C14 fatty alcohol with 7EO
C9-13 alkylbenzene sulfonate, sodium salt 5% by weight
C16-18 sulfonic acid methyl ester 5% by weight
Sodium percarbonate 18% by weight
TAED 3% by weight
C12-18 fatty acid, sodium salt 1.5% by weight
2% by weight of PVA / maleic acid copolymer
Phosphonic acid, sodium salt 0.5% by weight
Sodium carboxylate 20% by weight
Zeolite A 25% by weight
CMC, sodium salt 1% by weight
Antifoam 1.3% by weight
Enzyme (Amylase, Protease, Cellulase) +
Antifouling polymer ^* 0.2% by weight
Fragrance 0.5% by weight
Fluorescent bleach 0.3% by weight
Sodium sulfate until 100 * Antifouling polymer: As the antifouling polymer, a polyester antifouling polymer that meets the conditions indicated in claim 8 was used.

  Cleaning agent A differs from cleaning agent 1 in that half of LAS (C9-13 alkylbenzene sulfonate, sodium salt) is replaced with MES (C16-18 sulfonic acid methyl ester). The total amount of surfactant included is the same. Furthermore, cleaning agent A contains 0.2% by weight of an antifouling polymer (the only difference from cleaning agent 2).

Cleaning agent B:
4 wt% C12-C14 fatty alcohol with 7EO
C16-18 sulfonic acid methyl ester 10% by weight
Sodium percarbonate 18% by weight
TAED 3% by weight
C12-18 fatty acid, sodium salt 1.5% by weight
2% by weight of PVA / maleic acid copolymer
Phosphonic acid, sodium salt 0.5% by weight
Sodium carboxylate 20% by weight
Zeolite A 25% by weight
CMC, sodium salt 1% by weight
Antifoam 1.3% by weight
Enzyme (Amylase, Protease, Cellulase) +
Antifouling polymer ^* 0.2% by weight
Fragrance 0.5% by weight
Fluorescent bleach 0.3% by weight
Sodium sulfate until 100 * Antifouling polymer: As the antifouling polymer, a polyester antifouling polymer that meets the conditions indicated in claim 8 was used.

Cleaning agent B differs from cleaning agent 1 in that the entire amount of LAS (C9-13 alkylbenzene sulfonate, sodium salt) is replaced with MES (C16-18 sulfonic acid methyl ester). The total amount of surfactant included is the same. Furthermore, cleaning agent B contains 0.2% by weight of antifouling polymer (the only difference from cleaning agent 3 ).

  In each case, after 5 washing cycles, the washing results were evaluated (average of 5 tests is shown respectively).

The following results were obtained with detergent 1:

The following results were obtained with detergent 2 (with LAS partially replaced by MES):

The following results were obtained with detergent 3 (with complete replacement of LAS with MES):

  Comparison of cleaning agents 1-3 revealed that partial or complete replacement of LAS with MES without other changes in formulation resulted in soil removal and reduced laundry whiteness. In particular, the whiteness of the polyester has dropped dramatically.

The following results were obtained with Cleaning Agent A (with LAS partially replaced by MES and antifouling polymer added):

  Compared to Cleaning Agent 1, despite the partial replacement of LAS by MES, surprisingly, there was an improvement in both soil removal and whiteness as a result of the addition of antifouling polymer. . There was a significant improvement in both soil removal and laundry whiteness compared to Cleaning Agent 2, which differs only in that it did not contain an antifouling polymer. The improvement in whiteness is particularly noticeable in cotton / polyester blends and even more so in polyester.

The following results were obtained with detergent B (with complete replacement of LAS with MES and addition of antifouling polymer):

  Surprisingly, as a result of the addition of the antifouling polymer, soil removal and whiteness of the laundry (cotton and cotton / polyester blends) as a result of the addition of the antifouling polymer, despite the complete replacement of LAS with MES as compared to cleaning agent 1 There was an improvement in both degrees. The whiteness of the polyester was slightly poor. There was a significant improvement in both soil removal and laundry whiteness compared to Cleaning Agent 3, which only differed in not incorporating an antifouling polymer. The improvement in whiteness is particularly noticeable in cotton / polyester blends and even more so in polyester.

  These experiments confirm that partial or complete replacement of LES with MES can be made without the adverse effects on primary and secondary detergency when the antifouling polymers of the present invention are added. If not added, dramatic reductions may occur, especially with respect to the whiteness of the polyester.

Claims (13)

The following structural units (I), (II) and (III):
-[(OCHR ¹ -CHR ² ) _a -O-OC-Ph-CO-] _d (I)
^{- [(OCHR 3 -CHR 4)} b -O-OC-sPh-CO-] e (II)
-[(OCHR ⁵ -CHR ⁶ ) _c -OR ⁷ ] _f (III)
[Where,
a and b are numbers from 1 to 5, c is a number from 2 to 10, d is a number from 1 to 5, e is a number from 3 to 10, and f is a number from 0.25 to 3. Number,
Ph represents a 1,4-phenylene group,
sPh represents a 1,3-phenylene group substituted at the 5-position with a —SO ₃ Me group,
Me represents Li, Na, K, Mg / 2, Ca / 2, Al / 3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, and the alkyl group of the ammonium ion is C ₁ -C ₂₂ alkyl or _C 2 _{-C 10} hydroxyalkyl group, or mixtures thereof,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen or a methyl group,
R ⁷ is a methyl group ]
Polyester antifouling polymer containing and the following formula:

[Wherein, R _is a C 6 _{-C 22} alkyl group,
R ¹ is a C ₁ -C ₆ alkyl group,
n is a number of 1 or 2,
M ^{n +} represents a counter ion, M is Na, K, Ca, Mg, H, monoethanolammonium, diethanolammonium, triethanolammonium or a mixture thereof, and n + is 1+ or 2+ depending on the type of M ]
A detergent or detergent comprising a sulfonate derived from natural fats and oils and having a content of alkylbenzene sulfonate of 5% by weight or less based on the total weight of the agent. The polyester Le antifouling polymer, based on the weight of the whole agent, in an amount of 0.01 to 2% by weight, the detergent or cleaning agent according to claim 1. The sulfonic acid ester le, based on the weight of the whole agent, in an amount of 1 to 20% by weight, the detergent or cleaning agent according to claim 1 or 2. The cleaning agent or detergent in any one of Claims 1-3 which does not contain an alkylbenzene sulfonate . The cleaning agent or detergent in any one of Claims 1-4 which does not contain the anionic surfactant based on a petrochemical raw material . The cleaning agent or cleaning agent according to any one of claims 1 to 5 , comprising an alkoxylated fatty alcohol in an amount of 0.01 to 20% by weight based on the weight of the whole agent . The cleaning agent or detergent in any one of Claims 1-6 containing an enzyme . The cleaning agent or cleaning agent according to any one of claims 1 to 7 , which is present in a solid state . Use of a cleaning or cleaning agent according to any of claims 1 to 8 in manual or automatic fabric cleaning . Use according to claim 9 for reducing fabric graying in fabric washing . 11. Use according to claim 9 or 10, wherein the amount of linear alkylbenzene sulfonate in the cleaning or cleaning agent is not more than 5% by weight, based on the total weight of the agent . 12. Use according to any of claims 9 to 11, in a fabric based on cotton, a fabric based on synthetic fibers and / or a fabric based on blended fabrics . A method for cleaning a fabric, wherein the cleaning agent or cleaning agent according to any one of claims 1 to 8 is used, and the cleaning temperature is 40 ° C or lower .