WO2021191175A1 - Detergent formulation in form of a three dimensional body - Google Patents

Detergent formulation in form of a three dimensional body Download PDF

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Publication number
WO2021191175A1
WO2021191175A1 PCT/EP2021/057339 EP2021057339W WO2021191175A1 WO 2021191175 A1 WO2021191175 A1 WO 2021191175A1 EP 2021057339 W EP2021057339 W EP 2021057339W WO 2021191175 A1 WO2021191175 A1 WO 2021191175A1
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WO
WIPO (PCT)
Prior art keywords
acid
weight
detergent
detergent formulation
composition
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PCT/EP2021/057339
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French (fr)
Inventor
Jochen Eckhard WILLERSINN
Yannick Fuchs
Helmut Witteler
Kevin SEIBEL
Claudia Esper
Original Assignee
Basf Se
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Publication of WO2021191175A1 publication Critical patent/WO2021191175A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0095—Solid transparent soaps or detergents

Definitions

  • the present invention relates to a detergent formulation in form of a three dimensional shaped body.
  • the invention further relates to a process for producing such a detergent formulation in form of a three dimensional shaped body, to various uses of such a detergent formulation and specifically for self-dosing washing machines or dishwashing machines.
  • the invention further relates to a washing and cleaning composition comprising or consisting of such a detergent formulation in form of a three dimensional shaped body and a kit of parts for washing machines or dishwashing machines comprising such a detergent formulation.
  • Formulations for detergents and cleaning agents have to meet a complex property profile. In addition to a large number of technical application properties, this profile also increasingly includes the aesthetic requirements of consumers. In addition to chemical composition, aspects such as external shape, color, consistency, clarity and feel are becoming more important. Thus, a multitude of demands that have to be to be fulfilled simultaneously are made on washing, cleaning and dishwashing compositions, in terms of their cleaning performance, in terms of the manufacturing and their supply forms. In this context, a multitude of dosage forms are already being marketed, including not only the conventional powders and liquid formulations but also tableted products (“tabs"), film-ensheathed individual portions and dosage systems for multiple dosage of washing and cleaning compositions. Current dosage forms may comprise a multitude of separately formulated active ingredients and auxiliaries which are released individually in the cleaning process. However, there is still a great need for new dosage forms to fulfil the actual demands of the market.
  • Machine washing and dishwashing processes in the domestic and commercial sector comprise a plurality of successive steps that are conducted in more or less automated form, the central unit used being a washing machine or machine dishwasher in which at least the cleaning step and generally also the subsequent rinsing step and/or the drying step are conducted.
  • washing machines and machine dishwashers for the domestic sector the soiled laundry or dishware is generally cleaned in a single chamber, and the aforementioned treatment steps proceed successively in a controlled program.
  • Commercial machine dishwashers consist basically of stationary bath tanks from which an essentially aqueous cleaning solution is jetted or sprayed onto the dishware, which moves past these baths on a conveyor belt, such that the used solution flows back into the bath tanks again.
  • polyethers or surfactants containing ether groups are frequently used together with polymers of a,b-ethylenically unsaturated carboxylic acids and especially polyacrylic acid, in which case polyacrylic acid often assumes the role of an incrustation inhibitor or dispersant.
  • the problem is that polyethers and surfactants are frequently of zero or only limited compatibility in liquid form with polyacrylic acid, and so mixing may result in phase separation or the formation of precipitates, which greatly restricts the possible uses of at least one of the components. It is also especially difficult to provide transparent films or coatings or gels based on polyethers or surfactants containing ether groups together with polymers of unsaturated carboxylic acids. However, those products are preferred by the consumer both because of their performance properties and for esthetic reasons.
  • the literature discloses numerous processes for preparing gels from polyacrylic acids. These gels, however, are usually water-insoluble, since they are based on crosslinked polyacrylic acid. Other gels are water-soluble but are based on copolymers of acrylic acid with hydrophobic monomers and therefore have lower performance as incrustation inhibitors or dispersants than pure polyacrylic acid. Furthermore, gels are based on high molecular weight polyacrylic acid, which is likewise not advantageous for use as an incrustation inhibitor or dispersant and increases the processing problems.
  • WO 2015/000969 describes the use of a polymer composition in gel form, obtainable by a process in which a) a monomer composition M1) is provided, consisting of
  • step a) the monomer composition M1) provided in step a) is subjected to a free-radical polymerization in the presence of at least one polyether component PE) selected from polyetherols having a number-average molecular weight of at least
  • WO 2015/000970 refers to a solid polymer composition obtained by polymerizing a monomer containing acid groups in the presence of a polyether compound.
  • the solid polymer composition is especially in the form of a film, a coating on a substrate or a particulate solid.
  • Those polymer compositions can be used in several different dosage forms, e.g. a single portion of a washing, cleaning or dishwashing formulation. They may also be used in the coating or in the sheath of such a dosage form.
  • WO 2015/000971 discloses the use of a polymer composition of WO 2015/000969 in gel form as described in in washing and cleaning compositions, in hygiene products, in cosmetic compositions, in pharmaceutical compositions, in crop protection compositions, in wetting agents, in lacquers, coating compositions, adhesives, leather treatment compositions or textile care compositions, etc.
  • WO 2018/109200 describes a multilayer film comprising at least one layer comprising or consisting of a polymer composition P1), obtainable by free-radical polymerization of a monomer composition M1) comprising at least one monomer A) selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof.
  • a polymer composition P1 obtainable by free-radical polymerization of a monomer composition M1) comprising at least one monomer A) selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and
  • the polymerization is performed in the presence of at least one polyether component PE) selected from polyetherols having a number-average molecular weight of at least 200 g/mol, mono- and di(Ci-C 6 - alkyl) ethers of such polyetherols, surfactants containing polyether groups, and mixtures thereof.
  • PE polyether component
  • WO 2018/109201 describes a multilayer film that can be used as a sheath or coating for a washing or cleaning composition portion.
  • the multilayer film comprises at least one layer of a polymer composition obtained by free-radical polymerization of at least one a,b-ethylenically unsaturated mono- and dicarboxylic acids, or salts, anhydrides or mixtures thereof, in the presence of at least one polyether component.
  • WO 2018/109200 and WO 2018/109201 do not disclose a detergent formulation in form of three dimensional bodies.
  • EP 1134281 relates to a detergent tablet comprising a compressed portion of an active ingredients and a non-com pressed, non-encapsulation portion of an active ingredient.
  • the tablets are compressed powder.
  • State of the art detergent format such as powdered detergent, detergent tabs, or liquid single dose units either display certain challenges in formulation for the formulators (downstream users who produce mixtures and usually market them in the downstream supply chain or directly to consumers), or lack of a convenient handling for the (end)- consumer.
  • the detergent formulation in form of a three dimensional body according to the invention should have at least one of the following properties:
  • the detergent formulation in form of a three dimensional body should possess a good clarity value (clarity).
  • the detergent formulation in form of a three dimensional body should be flexibile (flexibility).
  • the detergent formulation in form of a three dimensional body should retrain its geometrical shape even under thermal influences or humidity influences (free standing).
  • detergent formulations in form of three dimensional shaped bodies having advantageous physicochemical properties and/or having use properties tailored to the respective end use when they comprise or consist of a polymer composition obtainable by free-radical polymerization of a monomer composition comprising at least one monomer selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof, wherein the free-radical polymerization is effected in the presence of at least one polyether component.
  • the detergent compositions according to the invention are clear and transparent, i.e. they have clarity values of at least 70% according to ASTM D1003 and haze values according to ASTM D 1003, which are smaller than 75%. They are typically free- standing and non-sticking three dimensional shaped bodies, typically geometrical bodies.
  • the present invention relates to detergent formulations in form of three dimensional shaped bodies having clarity values of at least 70% according to ASTM D1003 and haze values according to ASTM D 1003, which are smaller than 75%.
  • the three dimensional shaped bodies comprise or consist of a polymer composition P1) that are obtainable by free-radical polymerization of a monomer composition M1) comprising at least one monomer A) selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof, in the presence of at least one polyether component PE) selected from polyetherols having a number-average molecular weight of at least 200 g/mol and the mono- and di-(Ci-C 6 -alkyl ethers) thereof surfactants containing polyether groups and
  • the detergent formulation according to the invention can be obtained by shaping a plastified detergent composition containing or consisting of the polymer composition P1) into the desired shape of a three dimensional shaped body and allowing it to solidify.
  • the invention in particular provides a process for preparing a detergent formulation in form of a three dimensional body as defined herein, which comprises plastifying a detergent composition containing or consisting of the polymer composition P1), shaping the plastified detergent composition into the desired shape of a three dimensional shaped body and solidifying the plastified detergent composition by cooling, in particular by rapid cooling, especially by shock-frosting and deep-cooling.
  • the process comprises the following steps: i) providing a detergent composition comprising or consisting of the polymer composition P1 ) having a water content of at most 25% by weight, e.g. in the range of 1 to 25% by weight or in the range of 5 to 25% by weight, in particular in the range of 10 to 25% by weight, especially in the range of 10 to 20% by weight, based on the total weight of P1); ii) plastifying the detergent composition of step i) by heating the detergent composition to a temperature of at least 50°C, in particular at least 55°C, e.g.
  • step iii) shaping the plastified detergent composition of step ii) into the desired shape of the three dimensional body; and iv) rapid cooling of the shaped detergent composition of step iii) to a temperature of at most -20°C, obtaining the detergent formulation in the shape of a three dimensional body, and v) optionally drying of the obtained detergent formulation.
  • the invention in particular relates to a three dimensional shaped body, which is obtained by this process.
  • the invention further provides a washing and cleaning composition comprising or consisting of the detergent formulation in form of a three dimensional body as defined above and hereinafter or obtainable by the process as defined above and hereinafter.
  • the invention further provides the use of the detergent formulation in form of a three dimensional body as defined above and hereinafter or obtainable by the process as defined above and hereinafter for self-dosing washing mashines or dishwashing mashines.
  • the invention further provides a kit of parts for washing mashines or dishwashing mashines comprising the detergent formulation in form of a three dimensional body as defined above and hereinafter or obtained by the process as defined above and hereinafter and optionally further substance selected from builder, bleach, additives different therefrom and mixtures thereof, for a combined use.
  • a "three dimensional shaped body” in the context of the invention is understood as a shaped body that expands in all three spatial dimensions, i.e., a body that is not substantially flat or planar, respectively.
  • the dimensions of the three dimensional shaped bodies are such that they have dimensions of at least 1 mm, in particular at least 2 mm in all spatial directions.
  • the term “dimension” is understand as the longitudinal extension of the shaped body in one spatial direction. In case of a sphere, the dimensions are the same for all spatial directions. Typically the dimensions in some spatial directions are distinct from dimensions in other spatial directions.
  • two-dimensional is used for defining a body, which is a generally planar, i.e. which in two orthogonal spatial directions have large dimensions and in the third direction orthogonal to the two first ones a very small dimension, such that the ratio of the large dimensions to the small dimension is at least 100 or at least 1000. e.g. including platelets, films and foils.
  • kits of parts is understood as a specific type of composition that contains two or more discrete components, and those components work together for a specific purpose, or to achieve a specific result, e.g. to achieve a particularly good washing effect or to achieve a combination of e.g. a good washing effect and dye-transfer inhibition.
  • the individual components of the kit may be packaged in a single container or in separate containers. The individual components may be used either simultaneously or in sequence. The individual components may be formulated for administration by an end consumer or for the dosing unit of a washing machine or dishwashing machine.
  • a special embodiment is a kit of parts for use in a self-dosing washing machine or dishwashing machine.
  • a kit of parts in the sense of the invention may contain one single detergent formulation in form of a three dimensional body and a component different therefrom.
  • a kit of parts in the sense of the invention may also contain at least two different detergent formulations in form of a three dimensional body and optionally at least one component different therefrom.
  • One single detergent formulation according to the invention in form of a three dimensional body is regarded as one component of the kit. This also applies if the detergent formulation in form of a three dimensional body is composed of two or more active ingredients that are formulated together or comprises two or more separate domains each comprising at least one active ingredient. Even if the ingredients contained within one single three dimensional body work together to achieve a specific result, they are formulated as a single unit and consequently are considered as only one component of the kit.
  • alkyl represents a linear or (over and above 3 carbon atoms) branched saturated aliphatic radical having generally 1 to 40 carbon atoms (“Ci-C4o-alkyl”), preferably 1 to 30 carbon atoms (“Ci-C3o-alkyl”).
  • Ci-C4-alkyl is a linear or branched alkyl radical having 1 to 4 carbon atoms.
  • Examples of Ci-C4-alkyls are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
  • Ci-C7-alkyl is a linear or branched alkyl radical having 1 to 7 carbon atoms.
  • Ci-C7-alkyl are, in addition to those mentioned for Ci-C4-alkyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1 -dimethyl propyl,
  • Ci-Cs-alkyl is a linear or branched alkyl radical having 1 to 8 carbon atoms.
  • Examples of Ci-Cs-alkyl are, in addition to those mentioned for Ci-C7-alkyl, octyl, 2-ethylhexyl and the constitutional isomers thereof.
  • Ci-Cio-alkyl is a linear or branched alkyl radical having 1 to 10 carbon atoms.
  • Ci-Cio-alkyl are, in addition to those mentioned for Ci-Cs-alkyl, nonyl, decyl, 2-propylheptyl and the constitutional isomers thereof.
  • Ci-C2o-alkyl is a linear or branched alkyl radical having 1 to 20 carbon atoms.
  • Ci-C2o-alkyl examples are, in addition to those mentioned for Ci-Cio-alkyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the constitutional isomers thereof.
  • Ci-C3o-alkyl is a linear or branched alkyl radical having 1 to 30 carbon atoms.
  • Ci-C3o-alkyl are, in addition to those mentioned for Ci-C2o-alkyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl and the constitutional isomers thereof.
  • Ci-C4o-alkyl is a linear or branched alkyl radical having 1 to 40 carbon atoms.
  • Ci-C4o-alkyl are, in addition to those mentioned for Ci-C3o-alkyl, the higher homologs having 31 to 40 carbon atoms.
  • Examples of Cs-0 22 -alkyl are octyl, 2-ethyl- hexyl and the constitutional isomers thereof.
  • Cs-Ci 8 -alkyl is a linear or branched alkyl radical having 8 to 18 carbon atoms.
  • Suitable Cs-Ci 8 -alkyls are octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl and the constitutional isomers thereof.
  • they are predominantly linear Cs-Cis-alkyl radicals, as also occur in natural or synthetic fatty alcohols, and oxo process alcohols.
  • Ci2-Ci8-alkyl is a linear or branched alkyl radical having 12 to 18 carbon atoms.
  • Ci2-Cis-alkyls are dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl and the constitutional isomers thereof.
  • they are predominantly linear Ci2-Cis-alkyl radicals, as also occur in natural or synthetic fatty alcohols, and oxo process alcohols.
  • Cg-Cn alcohols represents a mixture comprising alcohols having 9 carbon atoms and alcohols having 11 carbon atoms.
  • C12-C14 alcohols are a mixture comprising alcohols having 12 carbon atoms and alcohols having 14 carbon atoms.
  • C13-C15 alcohols are a mixture comprising alcohols having 13 carbon atoms and alcohols having 15 carbon atoms.
  • C12-C18 alcohols are a mixture comprising alcohols having 12 carbon atoms, alcohols having 14 carbon atoms, alcohols having 16 carbon atoms and alcohols having 18 carbon atoms.
  • alkenyl represents a linear or branched monounsaturated (i.e. comprising one C-C double bond) aliphatic radical having generally 2 to 40 carbon atoms (“C2-C4o-alkenyl”), preferably 2 to 30 carbon atoms (“C 2 -C 30 -alkenyl”).
  • C2-C3-alkenyl examples include ethenyl, 1-propenyl, 2-propenyl or 1-methylethenyl.
  • Examples of C2-C4-alkenyl are, in addition to those mentioned for C2-C3-alkenyl,
  • C2-C6-alkenyl are, in addition to those mentioned for C2-C4-alkenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl- 1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2- butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1 -propenyl, 1,2-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl,
  • C2-Cio-alkenyl examples include, in addition to those mentioned for C2-C6-alkenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 1- nonenyl, 2-nonenyl, 3-nonenyl, 4-nonenyl, 1-decenyl, 2-decenyl, 3-decenyl, 4-decenyl, 5-decenyl and the like.
  • cycloalkyl represents a saturated monocyclic cycloaliphatic radical having generally 3 to 10 carbon atoms (“C3-C10- cycloalkyl”), preferably 3 to 8 carbon atoms (“Cs-Cs-cycloalkyl”), and of course does not have any heteroatoms as ring members (i.e. all ring members are carbon atoms).
  • Examples of C3-C4-cycloalkyl are cyclopropyl and cyclobutyl.
  • Examples of C3-C5- cycloalkyl are cyclopropyl, cyclobutyl and cyclopentyl.
  • Examples of C3-C6-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Examples of C3-C7-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
  • C3-C8- cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Examples of C3-Cio-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
  • Aryl is a mono-, bi- or polycyclic carbocyclic aromatic radical without heteroatoms as ring members.
  • a monocyclic aromatic radical is phenyl.
  • bicyclic aryl radicals two aromatic rings are fused to one another; in other words, they share two adjacent carbon atoms as ring members.
  • Examples of bicyclic aryl groups are 1- and 2-naphthyl.
  • polycyclic aryl groups three or more rings are fused.
  • polycyclic aryl groups are phenanthrenyl, anthracenyl, tetracenyl, 1 H-benzo[a]phenalenyl, pyrenyl and the like.
  • aryl also encompasses bi- or polycyclic radicals in which not all rings are aromatic; it is a prerequisite that at least one ring is aromatic. Examples of these are indanyl, indenyl, tetralinyl, 6,7,8,9-tetra- hydro-5H-benzo[7]annulenyl, fluorenyl, 9,10-dihydroanthracenyl, 9,10-dihydro- phenanthrenyl, 1 H-benzo[a]phenalenyl and the like.
  • the aryl group has generally 6 to 30, especially 6 to 20 and specifically 6 to 10 carbon atoms as ring members.
  • heterocycloalkyl is used without a prefix (C n -C m ) and without specification of the ring heteroatoms, it represents a saturated monocyclic heterocyclic radical having generally 3 to 8 ring members and at least one heteroatom and/or heteroatom- containing group, preferably 1 , 2, 3 or 4 heteroatoms and/or heteroatom-containing groups, as ring members.
  • the heteroatom and the heteroatom-containing group are selected from N, O, S, NO, SO and SO2.
  • Examples of these are oxiran-2-yl, thiiran-2-yl, aziridin-1-yl, aziridin-2-yl, oxetan-2-yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, 1-oxothietan-2-yl, 1-oxothietan-3-yl,
  • heteroaryl or “hetaryl” is used without a prefix (C n -C m ) and without specification of the ring heteroatoms, it represents an aromatic monocyclic heterocyclic radical having 5 or 6 ring members and at least one heteroatom and/or heteroatom- containing group, preferably 1 , 2, 3 or 4 heteroatoms and/or heteroatom-containing groups, as ring members.
  • the heteroatom and the heteroatom-containing group are selected from N, O, S, NO, SO and SO2.
  • Examples of these are 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl,
  • Monoolefins are alkenes; in other words, they are linear or branched aliphatic monounsaturated hydrocarbons having only one C-C double bond. If the term is used without a prefix (C n -C m ), it represents a linear or branched monounsaturated (i.e.
  • C2-C40 monoolefin or "C2-C4o-alkene”
  • C2-C30 monoolefin or "C2-C3o-alkene”
  • C2-C10 monoolefin or "C2-C3o-alkene”
  • C2-C10 monoolefins examples include ethene, propene, but-1-ene, but-2-ene, isobutene, pent-1-ene, pent-2-ene, 2-methyl-but-1-ene, 2-methyl-but-2-ene, 3-methyl-but-1-ene, 3-methyl-but-2-ene, 2,2-dimethylprop-1-ene, hex-1 -ene, hex-2-ene, hex-3-ene, hept-1-ene, hept-2-ene, hept-3-ene, oct-1 -ene, oct- 2-ene, oct-3-ene, oct-4-ene, non-1-ene, non-2-ene, non-3-ene, non-4-ene, dec-1 -ene, dec-2-ene, dec-3-ene, dec-4-ene, dec-5-ene and the positional isomers thereof
  • Nonaromatic hydrocarbons having at least two conjugated double bonds refer to both aliphatic and cycloaliphatic unsaturated hydrocarbons having at least two conjugated double bonds.
  • the cycloaliphatic unsaturated hydrocarbons having at least two conjugated double bonds are either those which do not comprise the maximum number of conjugated C-C double bonds defined by the ring size or those which do comprise the maximum number of conjugated C-C double bonds defined by the ring size but do not satisfy the Huckel rule, whether because the molecule is homoaromatic, antiaromatic or a nonaromatic polyene.
  • Aliphatic hydrocarbons having at least two conjugated double bonds generally comprise 4 to 20 carbon atoms.
  • Examples of aliphatic hydrocarbons having at least two conjugated double bonds are 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene,1,3,5-hexatriene, 1,3-heptadiene, 2,4-heptadiene, 1 ,3,4-heptatriene,
  • Cycloaliphatic hydrocarbons having at least two conjugated double bonds generally comprise 4 to 20 carbon atoms as ring members. Examples are 1 ,3-cyclopentadiene,
  • Alkanols are monohydroxyalkanes, i.e. compounds R-OH in which R is a linear or branched alkyl radical as defined above. If the term is used without a prefix (C n -C m ), it represents a Ci-C3o-alkanol. Examples of Ci-C3-alkanols are methanol, ethanol, n-propanol and isopropanol.
  • Ci-C4-alkanols are, in addition to those mentioned for the Ci-C3-alkanols, n-butanol, sec-butanol, isobutanol and tert-butanol.
  • Ci-C2o-alkanols are, in addition to those mentioned for the Ci-C4-alkanols, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, 2-propyl- heptanol, undecanol, lauryl alcohol, tridecanol, myristyl alcohol, pentadecanol, palmityl alcohol, heptadecanol, stearyl alcohol, nonadecanol, eicosanol and the positional and constitutional isomers thereof.
  • Ci-C3o-alkanols are, in addition to those mentioned for Ci-
  • Alkanediols are dihydroxyalkanes, i.e. alkanes in which two hydrogen atoms have been replaced by OH groups, where at least two carbon atoms must be between the two hydroxyl groups (i.e. hydrates are not encompassed by this term). If the term is used without a prefix (C n -C m ), it represents a C2-C3o-alkanediol. Examples of C2-C3- alkanediols are ethylene glycol (ethane-1 ,2-diol), propane-1 ,2-diol and propane-1 ,3- diol.
  • C2-C4-alkanediols are, in addition to those mentioned for the C2-C3- alkanediols, butane-1 ,2-diol, butane-1 ,3-diol and butane-1 ,4-diol.
  • Examples of C2-C6- alkanediols are, in addition to those mentioned for the C2-C4-alkanediols, pentane-1 ,5- diol and hexane-1 ,6-diol.
  • C2-C2o-alkanediols are, in addition to those mentioned for the C2-C6-alkanediols, heptane-1 ,7-diol, octane-1 ,8-diol, nonane-1 ,9-diol, decane-1 ,10-diol, undecane-1 ,11-diol, dodecane-1 ,12-diol, tridecane-1, 13-diol, tetradecane-1,14-diol, pentadecane-1 ,15-diol, hexadecane-1,16-diol, heptadecane- 1 ,17-diol, octadecane-1 ,18-diol, nonadecane-1,19-diol, eicosane-1 ,20-diol.
  • C2-C3o-alkanediols are, in addition to those mentioned for C2-C2o-alkanediols, the higher homologs having 21 to 30 carbon atoms.
  • the expression Cg-Cn alcohols represents a mixture comprising alcohols having 9 carbon atoms and alcohols having 11 carbon atoms.
  • C12-C14 alcohols are a mixture comprising alcohols having 12 carbon atoms and alcohols having 14 carbon atoms.
  • C13-C15 alcohols are a mixture comprising alcohols having 13 carbon atoms and alcohols having 15 carbon atoms.
  • C12-C18 alcohols are a mixture comprising alcohols having 12 carbon atoms, alcohols having 14 carbon atoms, alcohols having 16 carbon atoms and alcohols having 18 carbon atoms.
  • the polymer composition P1) is prepared by free-radical polymerization of the monomer composition M1) in the presence of at least one polyether component PE). This affords specific polymer compositions P1) having advantageous properties. Without being bound to a theory, hydrogen bonds are able to form between the growing polymer and the polyether component, and these influence the properties of the resultant polymer composition. Thus, polymer compositions P1) having a high content of the polyether component can be attained; these cannot be prepared by mixing the separately prepared polymer with the polyether component. Free-radical polymer degradation advantageously does not take place here.
  • the polymer compositions P1) used for production of the detergent formulation of the invention have a glass transition temperature T G in the range from 0 to 80°C, preferably from 0 to 60°C, especially from 0 to 30°C.
  • the glass transition temperatures (Tg) described in the context of this application can be determined by means of differential scanning calorimetry (DSC). Differential scanning calorimetry (DSC) is typically carried out according to ISO 11357-2:2013, preferably with sample preparation according to ISO 16805:2003.
  • the detergent compositions comprises the polymer composition P1) in an amount of at least 70% by weight, in particular at least 75% by weight, more particularly at least 80% by weight, based on the total weight of the detergent formulation.
  • the detergent compositions comprises the polymer composition P1) in an amount in the range of 70 to 99% by weight, more particular in the range of 75 to 99% by weight or in the range 75 to 95% by weight, in particular in the range of 75 to 90% by weight, especially in the range of 80 to 90% by weight, based on the total weight of the detergent formulation.
  • the amount of the polymer composition P1) in the detergent formulation is at least 90 % by weight, especially at least 95% by weight, based on the total weight of the components in the detergent formulation, which are different from water, and may be up to 100% by weight, based on the total weight of the components in the detergent formulation, which are different from water.
  • the polymer compositions P1 ) used for production of the detergent formulation of the invention have the form of the three dimensional body as defined herein.
  • the monomer composition M1) used for production of the polymer composition P1) comprises at least one monomer A) selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof.
  • the monomer composition M1) consists solely of a,b-ethylenically unsaturated carboxylic acids, salts of a,b-ethylenically unsaturated carboxylic acids and mixtures thereof.
  • the a,b-ethylenically unsaturated carboxylic acid is preferably selected from acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, a-chloroacrylic acid, crotonic acid, citraconic acid, mesaconic acid, glutaconic acid and aconitic acid.
  • Suitable salts of the aforementioned acids are especially the sodium, potassium and ammonium salts, and the salts with amines.
  • the monomers A) can be used as such or as mixtures with one another. The stated proportions by weight all refer to the acid form.
  • the at least one a,b-ethylenically unsaturated carboxylic acid is used for polymerization in non-neutralized form.
  • the acid groups are neutralized preferably to an extent of at most 50 mol%, particularly preferably to an extent of at most 30 mol%.
  • the partial or full neutralization can also be effected during the polymerization or after the polymerization has ended.
  • Suitable bases for neutralization of the a,b-ethylenically unsaturated carboxylic acids, and also the unsaturated sulfonic acids and phosphonic acids mentioned hereinafter are alkali metal hydroxides such as NaOH and KOH, alkaline earth metal hydroxides such as Ca(OH)2 and Mg(OH)2, ammonia and amine bases.
  • Preferred amines are alkanolamines such as ethanolamine, diethanolamine and triethanolamine. If desired, partial or full neutralization of the acid groups may also follow after the polymerization.
  • monomer A) is selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, salts of the aforementioned carboxylic acids and mixtures thereof. More particularly, monomer A) is selected from acrylic acid, methacrylic acid, salts of acrylic acid, salts of methacrylic acid and mixtures thereof.
  • exclusively acrylic acid is used as monomer A).
  • Monomer A) is used preferably in an amount of 50% to 100% by weight, more preferably 60% to 100% by weight, based on the total weight of the monomer composition M1).
  • the monomer composition M1) consists to an extent of at least 50% by weight, preferably to an extent of at least 80% by weight and especially to an extent of at least 90% by weight, based on the total weight of the monomer composition M1), of acrylic acid and/or acrylic acid salts.
  • the monomer composition M1) may, in addition to the monomers A), comprise at least one monomer B) selected from unsaturated sulfonic acids, salts of unsaturated sulfonic acids, unsaturated phosphonic acid, salts of unsaturated phosphonic acids.
  • Monomer B) is preferably selected from 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, allylphosphonic acid, salts of the aforementioned acids and mixtures thereof.
  • a preferred monomer B) is 2-acrylamido-2-methylpropanesulfonic acid.
  • Suitable salts of the aforementioned acids are especially the sodium, potassium and ammonium salts, and the salts with amines.
  • the monomers B) can be used as such or as mixtures with one another. The stated proportions by weight all refer to the acid form.
  • the monomer composition M1) in that case consists to an extent of at least 50% by weight, more preferably to an extent of at least 80% by weight and especially to an extent of at least 90% by weight, based on the total weight of the monomer composition M1), of monomers A) and B).
  • the monomer composition M1) comprises at least one monomer B), it is preferably used in an amount of 0.1% to 50% by weight, more preferably 1 % to 25% by weight, based on the total weight of the monomer composition M1).
  • the monomer composition M 1 may thus have the following monomer compositions: A) or A) + B) or A) + C) or A) + B) + C).
  • the monomer composition M 1 ) additionally comprises at least one monomer C) selected from
  • R 1 is hydrogen or Ci-Cs-alkyl
  • R 2 is hydrogen, Ci-C3o-alkyl, C2-C3o-alkenyl or Cs-Cs-cycloalkyl, and X is O or a group of the formula NR 3 in which R 3 is H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl;
  • esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C1-C5- alkanols
  • esters of vinyl alcohol or allyl alcohol with Ci-C30-monocarboxylic acids C5 esters of vinyl alcohol or allyl alcohol with Ci-C30-monocarboxylic acids
  • Preferred nitrogen heterocycles with a free-radically polymerizable a,b-ethylenically unsaturated double bond C1) are selected from N-vinylimidazole (1-vinylimidazole), vinyl- and allyl-substituted nitrogen heterocycles other than N-vinylimidazole, and mixtures thereof.
  • Suitable monomers C1) are also the compounds obtained by protonation or quaternization of 1-vinylimidazole and different vinyl- and allyl- substituted nitrogen heterocycles.
  • Acids suitable for the protonation are, for example, carboxylic acids such as lactic acid or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid.
  • Alkylating agents suitable for quaternization are Ci-C4-alkyl halides or di(Ci-C4-alkyl) sulfates, such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.
  • a protonation or quaternization may generally either precede or follow the polymerization.
  • a protonation or quaternization follows the polymerization.
  • Examples of such charged monomers C1) are quaternized vinylimidazoles, especially 3-methyl-1-vinylimidazolium chloride, methosulfate and ethosulfate.
  • Preferred monomers C1) are also vinyl- and allyl-substituted nitrogen heterocycles other than vinylimidazoles, selected from 2-vinylpyridine, 4-vinylpyridine, 2-allylpyridine, 4-allylpyridine, 2-vinylpiperidine, 4-vinylpiperidine and the salts thereof obtained by protonation or by quaternization.
  • the monomer composition M1) comprises at least one comonomer C1) selected from 1-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, 2-allylpyridine,
  • the monomer composition M1) comprises 1-vinylimidazole as comonomer C1).
  • the monomer composition M1) may additionally comprise at least one monomer C2) selected from compounds of the general formulae (I. a) and (l.b), as defined above.
  • k is preferably an integer from 1 to 500, more preferably 2 to 400, especially 3 to 250.
  • I is an integer from 0 to 100.
  • R 1 in the formula I. a) is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, especially hydrogen, methyl or ethyl.
  • R 2 in the formulae I. a) and l.b) is n-octyl, 1 ,1 ,3,3-tetramethylbutyl, ethylhexyl, n-nonyl, n-decyl, n-undecyl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl, octadecyl, nonadecyl, arachinyl, behenyl, lignoceryl, cerotinyl, melissyl, palmitoleyl, oleyl, linoleyl, linolenyl, stearyl, lauryl.
  • X in the formula I. a) is O or NH, especially O.
  • the monomer composition M1) comprises at least one monomer C2) selected from compounds of the general formulae (I.a1) and (I.b1)
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen, Ci-C4-alkyl.
  • k is preferably an integer from 1 to 100, more preferably 2 to 50, especially 3 to 30.
  • I is an integer from 0 to 50.
  • R 2 in the formulae I.a1) and I.b1) is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • x is preferably 1 or 2.
  • Suitable polyether acrylates I. a) or I.a1) are, for example, the polycondensation products of the aforementioned a,b-ethylenically unsaturated mono- and/or dicarboxylic acids and the acid chlorides, acid amides and acid anhydrides thereof with polyetherols.
  • Suitable polyetherols can be prepared easily by reacting ethylene oxide, propylene 1 ,2-oxide and/or epichlorohydrin with a starter molecule such as water or a short-chain alcohol R 2 -OH.
  • the alkylene oxides can be used individually, alternately in succession, or as a mixture.
  • the polyether acrylates I.a1) can be used alone or in mixtures to prepare the polymers used in accordance with the invention.
  • Suitable allyl alcohol alkoxylates l.b) or I.b1) are, for example, the etherification products of allyl chloride with appropriate polyetherols.
  • Suitable polyetherols can be prepared easily by reacting ethylene oxide, propylene 1 ,2-oxide and/or epichlorohydrin with a starter alcohol R 2 -OH.
  • the alkylene oxides can be used individually, alternately in succession, or as a mixture.
  • the allyl alcohol alkoxylates l.b) can be used alone or in mixtures to prepare the polymers used in accordance with the invention.
  • Monomers C2) used are especially methyl diglycol acrylate, methyl diglycol methacrylate, ethyl diglycol acrylate or ethyl diglycol methacrylate. Preference is given to ethyl diglycol acrylate.
  • Monomer C3) is especially methyl diglycol acrylate, methyl diglycol methacrylate, ethyl diglycol acrylate or ethyl diglycol methacrylate. Preference is given to ethyl diglycol acrylate.
  • the monomer composition M1) may additionally comprise at least one monomer C3) selected from esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C5-alkanols.
  • Suitable esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C5-alkanols are, for example, methyl (meth)acrylate, methyl ethacrylate, ethyl (meth)acrylate, ethyl ethacrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, tert-butyl ethacrylate, n-pentyl (meth)acrylate, and mixtures thereof.
  • the monomer composition M1) may additionally comprise at least one monomer C4) selected from compounds having a free-radically polymerizable a,b-ethylenically unsaturated double bond and at least one cationogenic and/or cationic group per molecule.
  • the cationogenic and/or cationic groups of the monomers C4) are preferably nitrogen- containing groups such as primary, secondary and tertiary amino groups, and quaternary ammonium groups.
  • the nitrogen-containing groups are tertiary amino groups or quaternary ammonium groups.
  • Charged cationic groups can be produced from the amine nitrogens either by protonation or by quaternization with acids or alkylating agents.
  • Examples of these include carboxylic acids such as lactic acid, or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, and examples of alkylating agents include Ci-C4-alkyl halides or sulfates, such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.
  • alkylating agents include Ci-C4-alkyl halides or sulfates, such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.
  • a protonation or quaternization may generally either precede or follow the polymerization.
  • the monomers C4) are selected from esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols which may be mono- or dialkylated on the amine nitrogen, amides of a,b-ethylenically unsaturated mono- and dicarboxylic acids with diamines having at least one primary or secondary amino group, N,N- diallylamine, N,N-diallyl-N-alkylamines and derivatives thereof, and mixtures thereof.
  • esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols which may be mono- or dialkylated on the amine nitrogen preferably derive from C2-C12 amino alcohols mono- or di-Ci-Cs-alkylated on the amine nitrogen.
  • Suitable acid components of these esters are, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof.
  • the acid components used are preferably acrylic acid, methacrylic acid and mixtures thereof.
  • Preferred monomers C4) are N-methylaminoethyl (meth)acrylate
  • Suitable monomers C4) are additionally the amides of the aforementioned a,b-ethylenically unsaturated mono- and dicarboxylic acids with diamines having at least one primary or secondary amino group. Preference is given to diamines having one tertiary amino group and one primary or secondary amino group.
  • Examples of preferred monomers C4) are N-[tert-butylaminoethyl](meth)acrylamide, N-[2-(dimethylamino)ethyl]acrylamide, N-[2-(dimethylamino)ethyl]methacrylamide, N-[3-(dimethylamino)propyl]acrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-[4-(dimethylamino)butyl]acrylamide, N-[4-(dimethylamino)butyl]methacrylamide, N-[2-(diethylamino)ethyl]acrylamide, N-[4-(dimethylamino)cyclohexyl]acrylamide and N-[4-(dimethylamino)cyclohexyl]methacrylamide.
  • the monomer composition M1) may additionally comprise at least one monomer C5) selected from esters of vinyl alcohol or allyl alcohol with C1-C30 monocarboxylic acids.
  • Suitable esters of vinyl alcohol with Ci-C30-monocarboxylic acids are, for example, the esters of vinyl alcohol with C1-C30 monocarboxylic acids such as acetic acid, propionic acid, n-butanoic acid, 2-methylpropanoic acid, n-pentanoic acid, 2,2-dimethylpropanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2,2,4,4-tetramethylpentanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, n-decanoic acid, n-undecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, hepta
  • the monomer composition M1) may additionally comprise at least one monomer C8) selected from esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-alkanediols and amides of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30 amino alcohols having a primary or secondary amino group.
  • monomer C8 selected from esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-alkanediols and amides of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30 amino alcohols having a primary or secondary amino group.
  • Suitable esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-alkanediols are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
  • Suitable amides of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-amino alcohols having a primary or secondary amino group are 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, 2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide,
  • the monomer composition M1) comprises acrylic acid and optionally at least one comonomer selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids other than acrylic acid, salts, anhydrides, esters and amides of such a,b-ethylenically unsaturated mono- and dicarboxylic acids other than acrylic acid, olefinically unsaturated sulfonic acids, salts of olefinically unsaturated sulfonic acids, nitrogen heterocycles having a free-radically polymerizable a,b-ethylenically unsaturated double bond, C2-C10 monoolefins, nonaromatic hydrocarbons having at least two conjugated double bonds, vinyl aromatics, N-vinyllactams and mixtures thereof.
  • a,b-ethylenically unsaturated mono- and dicarboxylic acids other than acrylic acid salts, anhydrides, esters and amides of such a,b-eth
  • the monomer composition M1) comprises acrylic acid and optionally at least one comonomer selected from isobutene, diisobutene, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, maleic acid, maleic anhydride, itaconic acid, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, styrene and mixtures thereof.
  • the monomer composition M1) comprises acrylic acid and optionally at least one comonomer selected from methacrylic acid, 2-acrylamido-2- methylpropanesulfonic acid and mixtures thereof.
  • the monomer composition M1) consists to an extent of at least 80% by weight, preferably to an extent of at least 90% by weight and especially to an extent of at least 95% by weight, based on the total weight of the monomer composition M 1 ), of acrylic acid.
  • the monomer composition M1) may comprise each of the further monomers C1) to C6) preferably in an amount of 0% to 30% by weight, more preferably 0% to 20% by weight and especially 0% to 10% by weight, based on the total weight of the monomer composition M1).
  • the monomer composition M1) comprises at least one monomer selected from C1) to C6), it does so in each case preferably in an amount of 0.1 % to 30% by weight, more preferably 1 % to 20% by weight and especially 1.5% to 10% by weight, based on the total weight of the monomer composition M 1 ).
  • the monomer composition M1) does not comprise any further comonomers except for the monomers A) and B).
  • the monomer composition M1) does not comprise any further comonomers apart from acrylic acid.
  • the polymer composition P1) comprises essentially non-crosslinked polymers.
  • the monomer composition M1) used for production of the polymer composition P1) of the invention thus especially does not comprise any added crosslinking monomers.
  • crosslinking monomers are compounds having two or more than two polymerizable ethylenically unsaturated double bonds per molecule.
  • the monomer composition M1) based on the total weight, comprises less than 0.1 % by weight, more preferably less than 0.05% by weight and especially less than 0.001 % by weight of crosslinking monomers having two or more than two free- radically polymerizable a,b-ethylenically unsaturated double bonds per molecule.
  • the monomer composition M1) does not comprise any crosslinking monomers having two or more than two polymerizable a,b-ethylenically unsaturated double bonds per molecule.
  • Polyether component PE polyether component
  • Suitable polyether components PE are polyetherols having a number-average molecular weight of at least 200 g/mol and the mono- and di(Ci-C 6 -alkyl) ethers thereof.
  • Suitable polyetherols and the mono- and di(Ci-C 6 -alkyl) ethers thereof may be linear or branched, preferably linear. Suitable polyetherols and the mono- and di(Ci-C 6 -alkyl) ethers thereof generally have a number-average molecular weight in the range from about 200 to 100000 g/mol, preferably 300 to 50000 g/mol and more preferably 500 to 40000 g/mol. Suitable polyetherols are, for example, water-soluble or water-dispersible nonionic polymers having repeat alkylene oxide units. Preferably, the proportion of repeat alkylene oxide units is at least 30% by weight, based on the total weight of the compound.
  • Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers.
  • Suitable alkylene oxides for preparation of alkylene oxide copolymers are, for example, ethylene oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide.
  • Suitable examples are copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide.
  • the alkylene oxide copolymers may comprise the copolymerized alkylene oxide units in randomly distributed form or in the form of blocks.
  • the proportion of repeat units derived from ethylene oxide in the ethylene oxide/propylene oxide copolymers is 40% to 99% by weight.
  • Particularly preferred polyether components PE) are ethylene oxide homopolymers and ethylene oxide/propylene oxide copolymers.
  • Suitable polyether components PE are additionally the mono- and di(Ci-C2-alkyl) ethers of the above-described polyetherols. Preference is given to polyalkylene glycol monomethyl ethers and polyalkylene glycol dimethyl ethers.
  • the polyether component PE comprises or consists of at least one polyetherol or a mono- or di-(Ci-C2-alkyl) ether thereof comprising exclusively ethylene oxide units incorporated as alkylene oxide units.
  • Suitable polyether components PE are additionally surfactants containing polyether groups.
  • nonionic and ionic surfactants having at least one nonpolar group and at least one polar group and comprising a polyether group are suitable.
  • the surfactants PE) containing polyether groups are preferably selected from alkyl polyoxyalkylene ethers, aryl polyoxyalkylene ethers, alkylaryl polyoxyalkylene ethers, alkoxylated animal and/or vegetable fats and/or oils, fatty amine alkoxylates, fatty acid amide alkoxylates, fatty acid diethanolamide alkoxylates, polyoxyethylene sorbitan fatty acid esters, alkyl polyether sulfates, aryl polyether sulfates, alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl polyether sulfonates, alkylaryl polyether sulfonates, alkyl polyether phosphates, aryl polyether phosphates, alkylaryl polyether phosphates, glyceryl ether sulfonates, glyceryl ether sulfates, monoglyceride (ether)
  • the preferred nonionic surfactants PE) containing polyether groups include, for example: alkyl polyoxyalkylene ethers which derive from low molecular weight C3-C6 alcohols or from C7-C30 fatty alcohols.
  • the ether component here may be derived from ethylene oxide units, propylene oxide units, 1 ,2-butylene oxide units,
  • Suitable nonionic surfactants comprise, inter alia, surfactants of the general formula (VI)
  • R 10 -O-(CH 2 CH 2 O) x -(CHR 11 CH 2 O) y -R 12 (VI) in which R 10 is a linear or branched alkyl radical having 6 to 22 carbon atoms,
  • surfactants containing hydroxyl groups of the general formula (VII) the sequence of the alkylene oxide units in the compounds of the formula (VII) is arbitrary, s, t, u and v are each independently an integer from 0 to 500, where the sum of s, t, u and v is > 0, R 13 and R 15 are each independently a straight-chain or branched saturated Ci-C4o-alkyl radical or a mono- or polyunsaturated C 2 -C4o-alkenyl radical, and
  • R 14 is selected from methyl, ethyl, n-propyl, isopropyl and n-butyl.
  • the sum of s, t, u and v is preferably a value of 10 to 300, more preferably of 15 to 200 and especially of 20 to 150.
  • t and u are each 0.
  • the sum of s and v is preferably a value of 10 to 300, more preferably of 15 to 200 and especially of 20 to 150.
  • R 13 and R 15 are preferably independently a straight-chain or branched saturated C 2 -C3o-alkyl radical. At the same time, R 13 and R 15 may also be mixtures of different alkyl radicals.
  • R 14 is preferably methyl or ethyl, especially methyl.
  • a preferred embodiment is surfactants containing hydroxyl groups of the general formula (VI 1.1)
  • R 13 -0-(CH 2 CH 2 0) S -(CH 2 CH(CH 3 )0) V -CH 2 CH(0H)R 15 (VII.1 ) where the sequence of the -(CH 2 CH 2 0)- and the (CH 2 CH(CH 3 )0)- units is arbitrary, s and v are each independently an integer from 0 to 500, where the sum of s and v is > 0, and
  • R 13 and R 15 are independently a straight-chain saturated Ci-C3o-alkyl radical or a branched saturated C3-C3o-alkyl radical or a mono- or polyunsaturated C2-C30- alkenyl radical.
  • the sum of s and v is preferably a value of 10 to 300, more preferably of 15 to 200 and especially of 20 to 150.
  • nonionic surfactants includes, for example, hydroxy mixed ethers of the general formula (C6-22-alkyl)-CH(OH)CH 2 O-(EO)20-i20-(C2-26-alkyl).
  • alcohol polyoxyalkylene esters of the general formula (VIII) R 16 -0-(CH 2 CH 2 0) p -(CH 2 CHR 17 0) q -C( 0)R 18 (VIII) where the sequence of the alkylene oxide units in the compounds of the formula (VIII) is arbitrary, p and q are each independently an integer from 0 to 500, where the sum of p and q is > 0,
  • R 16 and R 18 are each independently a straight-chain or branched saturated Ci-C4o-alkyl radical or a mono- or polyunsaturated C 2 -C4o-alkenyl radical, and
  • R 17 is selected from methyl, ethyl, n-propyl, isopropyl and n-butyl.
  • the sum of p and q is preferably a value of 10 to 300, more preferably of 15 to 200 and especially of 20 to 150.
  • R 16 and R 18 are preferably each independently a straight-chain or branched saturated C4-C3o-alkyl radical. At the same time, R 16 and R 18 may also be mixtures of different alkyl radicals.
  • R 17 is preferably methyl or ethyl, especially methyl.
  • alkylaryl alcohol polyoxyethylene ethers e.g. octylphenol polyoxyethylene ethers, alkoxylated animal and/or vegetable fats and/or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates, alkylphenol alkoxylates, for example ethoxylated isooctyl-, octyl- or nonylphenol, tributylphenol polyoxyethylene ether, fatty amine alkoxylates, fatty acid amide and fatty acid diethanolamide alkoxylates, especially ethoxylates thereof, polyoxyalkylene sorbitan fatty acid esters.
  • alkylaryl alcohol polyoxyethylene ethers e.g. octylphenol polyoxyethylene ethers, alkoxylated animal and/or vegetable fats and/or oils, for example corn oil ethoxylates, castor oil ethoxylates,
  • alkyl polyether sulfate sodium dodecyl poly(oxyethylene) sulfate (sodium lauryl ether sulfate, SLES).
  • the detergent formulation according to the invention may comprise at least one further substance selected from polymer compositions P2), which differs from the polymer composition P1), builder, bleach, additives different therefrom and mixtures thereof.
  • detergent formulation according to the invention comprising one or more separate domains comprising at least one further substance selected from polymer compositions P2), which differs from the polymer composition P1), builder, bleach, additives different therefrom and mixtures thereof.
  • the individual detergent formulations of the invention are water-soluble or water-dispersible. According to the field of use of the detergent formulation of the invention, it may be advantageous for the detergent formulation to constist of one single domain or more than one individual separate domains.
  • the individual domains may differ in at least one physical and/or chemical property e.g. their content, their solubility in water etc. For example, it may be desirable for different domains to have different solubility in water. It may also be desirable, for example, for a domain on the outer surface to have a lesser degree of water solubility in order to prevent blocking and/or partial dissolution in the event of high air humidity and/or high contact moisture (e.g. hand moisture).
  • an outer surface domain may also be desirable for an outer surface domain to have high water solubility in order to rapidly release an active ingredient present therein or ensheathed therewith on contact with water. Such a domain may then have water-insoluble outer packaging to prevent unwanted contact with water.
  • the detergent formulations of the invention may also be advantageous for the detergent formulations of the invention to have a temperature-dependent solubility in water.
  • the detergent formulation of the invention comprises at least one polymer P2) different from polymers of the polymer composition P1).
  • the polymer P2) is in the same domain as the polymer composition P1).
  • the polymer P2) may be in at least one separate domain.
  • the detergent formulation of the invention preferably comprises at least one polymer P2) selected from natural and modified polysaccharides, homo- and copolymers comprising repeat units which derive from vinyl alcohol, vinyl esters, alkoxylated vinyl alcohols or mixtures thereof, homo- and copolymers comprising at least one copolymerized monomer selected from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine,
  • N-carboxymethyl-4-vinylpyridium halides and mixtures thereof homo- and copolymers of acrylic acid and/or methacrylic acid, especially copolymers comprising at least one copolymerized acrylic monomer selected from acrylic acid, acrylic salts and mixtures thereof, and at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof, copolymers comprising at least one copolymerized (meth)acrylic monomer selected from acrylic acid, methacrylic acid, salts thereof and mixtures thereof and at least one copolymerized hydrophobic monomer selected from Ci-Cs-alkyl esters of (meth)acrylic acid, C2-C10 olefins, styrene and a-methylstyrene, copolymers comprising at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof and at least one copolymer
  • the detergent formulation of the invention preferably comprises at least one polymer P2) selected from cellulose ethers and cellulose esters, homo- and copolymers comprising repeat units which derive from vinyl alcohol, vinyl esters, alkoxylated vinyl alcohols or mixtures thereof, polymers selected from polyvinylpyrrolidone homopolymers, polyvinylimidazole homopolymers, copolymers comprising copolymerized vinylpyrrolidone and vinylimidazole, polyvinylpyridine N-oxide, poly-N-carboxymethyl-4-vinylpyridium halides, mixtures thereof.
  • polymer P2 selected from cellulose ethers and cellulose esters, homo- and copolymers comprising repeat units which derive from vinyl alcohol, vinyl esters, alkoxylated vinyl alcohols or mixtures thereof, polymers selected from polyvinylpyrrolidone homopolymers, polyvinylimidazole homopolymers, copolymers comprising copolymerized vinylpyrroli
  • the detergent formulation of the invention especially comprises at least one polymer P2) selected from cellulose derivatives, preferably carboxyalkyl celluloses and salts thereof, sulfoalkyl celluloses and salts thereof, acidic sulfuric ester salts of cellulose, alkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses and mixtures of two or more of these cellulose derivatives.
  • cellulose derivatives preferably carboxyalkyl celluloses and salts thereof, sulfoalkyl celluloses and salts thereof, acidic sulfuric ester salts of cellulose, alkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses and mixtures of two or more of these cellulose derivatives.
  • Polysaccharides suitable as polymers P2) are natural polysaccharides, for example cellulose, hemicellulose, xyloglucan, glycogen, starch (amylose and amylopectin), dextran, pectins, inulin, xanthan, chitin, callose, and thermally, hydrolytically or enzymatically degraded starch, e.g. maltodextrin etc.
  • Preferred modified polysaccharides are, for example, cellulose ethers, cellulose esters, cellulose amides, etc.
  • Cellulose ethers are derivatives of cellulose which arise through partial or complete substitution of the hydrogen atoms in the hydroxyl groups of the cellulose. Cellulose ethers from the reaction of cellulose with more than one etherifying agent are also referred to as cellulose mixed ethers.
  • Preferred cellulose ethers are selected from alkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses, carboxyalkyl celluloses and salts thereof, carboxyalkyl alkyl celluloses and salts thereof, carboxyalkyl hydroxyalkyl celluloses and salts thereof, carboxyalkyl hydroxyalkyl alkyl celluloses and salts, sulfoalkyl celluloses and salts thereof.
  • Preferred carboxyalkyl radicals are the carboxymethyl radical and the carboxyethyl radical.
  • a particularly preferred carboxyalkyl radical is the carboxymethyl radical.
  • Preferred sulfoalkyl radicals are the sulfomethyl radical and the sulfoethyl radical.
  • a particularly preferred sulfoalkyl radical is the sulfomethyl radical.
  • Preferred salts are the sodium, potassium, calcium and ammonium salts.
  • Particularly preferred cellulose ethers are selected from carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, ethyl cellulose, n-propyl cellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxybutyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl ethyl cellulose, carboxymethyl methyl cellulose, carboxymethyl ethyl cellulose, carboxymethyl hydroxyethyl cellulose, carboxymethyl hydroxyethyl methyl cellulose, carboxymethyl hydroxyethyl ethyl cellulose, sulfomethyl cellulose and sulfoethyl cellulose.
  • the carboxyalkyl radicals and the sulfoalkyl radicals may also be in salt form.
  • Cellulose esters are derivatives of cellulose which form as a result of esterification of the hydroxyl groups with acids. Preference is given to the sulfuric esters of cellulose. In a specific embodiment, the sulfuric acid is subjected only to a partial esterification, such that the resulting sulfuric esters still have free acid groups or salts thereof. Particular preference is given to using acidic sulfuric ester salts of cellulose. These are notable for their graying-inhibiting effect.
  • Preferred modified polysaccharides are selected from methyl cellulose, ethyl cellulose, propyl cellulose, methyl/ethyl cellulose, ethyl/propyl cellulose, carboxymethyl cellulose, salts of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, etc.
  • the polymers P2) are selected from homo- and copolymers comprising repeat units which derive from vinyl alcohol, vinyl esters, alkoxylated vinyl alcohols or mixtures thereof.
  • Suitable vinyl esters are generally the esters of vinyl alcohol with C1-C15 carboxylic acids, preferably Ci-Cs carboxylic acids, more preferably C1-C4 carboxylic acids.
  • Preferred vinyl acylates are vinyl acetate, vinyl n-propionate, vinyl n-butyrate, vinyl 2-ethylhexanoate, vinyl laurate, etc. Particular preference is given to vinyl acetate.
  • Partly or fully hydrolyzed polyvinyl acetates are generally referred to as "polyvinyl alcohol (PVOH)".
  • Partly hydrolyzed polyvinyl acetates are obtained by incomplete hydrolysis of polyvinyl acetates, meaning that the partly hydrolyzed polymer has both ester groups and hydroxyl groups.
  • the hydrolysis of the polyvinyl acetates can be effected in a manner known per se under alkaline or acidic conditions, i.e. with addition of acid or base.
  • polyvinyl alcohols are determined by factors including the polymerization level and the hydrolysis level (level of hydrolysis). With rising hydrolysis level, the water solubility decreases. Polyvinyl alcohols having hydrolysis levels up to about 90 mol% are generally soluble in cold water. Polyvinyl alcohols having hydrolysis levels of about 90 to about 99.9 mol% are generally no longer soluble in cold water but are soluble in hot water.
  • Polyvinyl alcohols suitable as polymers P2) preferably have a hydrolysis level of 50 to 99.9 mol%, more preferably of 70 to 99 mol%, especially of 80 to 98 mol%.
  • Polyvinyl alcohols suitable as polymers P2) preferably have a weight-average molecular weight of 10000 to 300000 g/mol, more preferably of 15000 to 250 000 g/mol.
  • Polyvinyl alcohols suitable as polymers P2) preferably have a viscosity of 2 to 120 mPa-s, more preferably of 7 to 70 mPa-s and especially of 15 to 60 mPa-s, measured to DIN 53015 on a 4% solution in water.
  • the polymers P2) are selected from homo- and copolymers comprising at least one copolymerized monomer selected from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, salts of the three latter monomers, vinylpyridine N-oxide, N-carboxymethyl-4-vinylpyridium halides and mixtures thereof.
  • N-Vinylimidazole, 2-vinylpyridine and 4-vinylpyridine can be converted to the corresponding salts by protonation or quaternization.
  • Suitable acids are, for example, mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and carboxylic acids.
  • Alkylating agents suitable for quaternization are Ci-C4-alkyl halides or Ci-C4-alkyl sulfates, such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.
  • polyvinylpyrrolidone homopolymers and copolymers comprising copolymerized N-vinylpyrrolidone and another different copolymerized ethylenically unsaturated monomer.
  • Suitable N-vinylpyrrolidone copolymers are quite generally uncharged, anionic, cationic and amphoteric polymers.
  • N-vinylpyrrolidone copolymers are selected from copolymers of N-vinylpyrrolidone and vinyl acetate, copolymers of N-vinylpyrrolidone and vinyl propionate, copolymers of N-vinylpyrrolidone, vinyl acetate and vinyl propionate, copolymers of N-vinylpyrrolidone and vinyl acrylate, copolymers of N-vinylpyrrolidone, ethyl methacrylate and methacrylic acid, copolymers of N-vinylpyrrolidone and N-vinylimidazole and the derivatives thereof obtained by protonation and/or quaternization, copolymers of N-vinylpyrrolidone and dimethylaminoethyl methacrylate and the derivatives thereof obtained by protonation and/or quaternization, copolymers of N-vinylpyrrolidone, N-vinylcaprolact
  • the polymer P2) used is an acrylic acid homopolymer.
  • Acrylic acid homopolymers P2) preferably have a number-average molecular weight in the range from 800 to 70 000 g/mol, more preferably 900 to 50000 g/mol, particularly 1000 to 20000 g/mol and especially 1000 to 10 000 g/mol.
  • the term "acrylic acid homopolymer” also encompasses polymers in which the carboxylic acid groups are in partly or fully neutralized form. These include acrylic acid homopolymers in which the carboxylic acid groups are present partly or completely in the form of alkali metal salts or ammonium salts.
  • acrylic acid homopolymers in which the carboxylic acid groups are protonated or are partly or completely in the form of sodium salts.
  • Homopolymers of acrylic acid particularly suitable as polymers P2) are the Sokalan ® PA brands from BASF SE.
  • polymer P2 used is a copolymer comprising at least one copolymerized acrylic acid monomer selected from acrylic acid, acrylic salts and mixtures thereof and at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof.
  • These preferably have a number-average molecular weight in the range from 2500 to 150000 g/mol, more preferably 2800 to 70000 g/mol, particularly 2900 to 50000 g/mol and especially 3000 to 30000 g/mol.
  • copolymers in which the carboxylic acid groups are in partly or fully neutralized form.
  • alkali metal salts are sodium or potassium salts, especially the sodium salts.
  • Preferred polymers P2) are copolymers of maleic acid (or maleic monomers) and acrylic acid (or acrylic monomers) in a weight ratio of 10:90 to 95:5, more preferably those in a weight ratio of 30:70 to 90:10.
  • Preferred polymers P2) are also terpolymers of maleic acid (or maleic monomers), acrylic acid (or acrylic monomers) and a vinyl ester of a C1-C3 carboxylic acid in a weight ratio of 10 (maleic acid):90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester).
  • the weight ratio of acrylic acid to vinyl ester is preferably within a range from 30:70 to 70:30.
  • Particularly suitable polymers P2) based on acrylic monomers and maleic monomers are the corresponding Sokalan ® CP brands from BASF SE.
  • polymer P2 used is a copolymer comprising at least one
  • (meth)acrylic acid monomer selected from (meth)acrylic acid, (meth)acrylic salts and mixtures thereof and at least one hydrophobic monomer.
  • the hydrophobic monomer is especially selected from Ci-Cs-alkyl esters of (meth)acrylic acid, for example the methyl, ethyl, n- and isopropyl, n-butyl and 2-ethylhexyl esters of (meth)acrylic acid and C2-C10 olefins, for example ethene, propene, 1,2-butene, isobutene, diisobutene, styrene and a-methylstyrene.
  • the polymer P2) used is a copolymer of at least one maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof with at least one C2-C8 olefin.
  • copolymers comprising at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof, at least one copolymerized C2-C8 olefin and at least one other different copolymerized comonomer.
  • copolymers comprising at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof and at least one copolymerized C2-C8 olefin as the sole monomers.
  • These preferably have a number-average molecular weight in the range from 3000 to 150 000 g/mol, more preferably 5000 to 70000 g/mol, particularly 8000 to 50000 g/mol and especially 10000 to 30000 g/mol.
  • copolymers in which the carboxylic acid groups are in partly or fully neutralized form.
  • maleic salts for polymerization or for the resulting copolymer to be subjected to partial or complete neutralization.
  • Preferred alkali metal salts are sodium or potassium salts, especially the sodium salts.
  • a specific embodiment is copolymers of maleic acid with C2-C8 olefins in a molar ratio of 40:60 to 80:20, particular preference being given to copolymers of maleic acid with ethylene, propylene, isobutene, diisobutene or styrene.
  • Particularly suitable compounds which contain carboxylic acid groups and are based on olefins and maleic acid are likewise the corresponding Sokalan ® CP brands from BASF SE.
  • a further preferred embodiment is that of copolymers comprising at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof, at least one copolymerized C2-C8 olefin and at least one copolymerized acrylic monomer selected from acrylic acid, acrylic salts and mixtures thereof.
  • a further preferred embodiment is that of copolymers comprising at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof, at least one copolymerized C2-C8 olefin and at least one copolymerized ester of (meth)acrylic acid.
  • the ester of (meth)acrylic acid is especially selected from Ci-Cs-alkyl esters of (meth)acrylic acid, for example the methyl, ethyl, n- and isopropyl, n-butyl and 2-ethylhexyl esters of (meth)acrylic acid.
  • the polymers P2) are selected from homo- and copolymers comprising at least one copolymerized monomer selected from acrylamide, methacrylamide and mixtures thereof. These polymers P2) are preferably water-soluble or water-dispersible. These polymers P2) are especially water-soluble.
  • the polymers P2) are selected from homopolymers of acrylamide or methacrylamide.
  • the polymers P2) are selected from copolymers of acrylamide and/or methacrylamide. These comprise at least one copolymerized comonomer selected from hydrophilic monomers (A1) other than acrylamide and methacrylamide, monoethylenically unsaturated amphiphilic monomers (A2) and further ethylenically unsaturated monomers (A3).
  • Suitable hydrophilic monoethylenically unsaturated monomers (A1) are uncharged monomers such as N-methyl(meth)acrylamide, N,N'-dimethyl(meth)acrylamide or N-methylol(meth)acrylamide, monomers comprising hydroxyl and/or ether groups, for example hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether, hydroxyvinyl butyl ether, polyethylene glycol (meth)acrylate, N-vinylformamide, N-vinylacetamide, N-vinyl- pyrrolidone or N-vinylcaprolactam, and vinyl esters, for example vinyl formate or vinyl acetate.
  • monomers comprising hydroxyl and/or ether groups, for example hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate
  • N-vinyl derivatives may be hydrolyzed to vinylamine units, and vinyl esters to vinyl alcohol units.
  • Suitable hydrophilic monoethylenically unsaturated monomers (A1) are also monomers comprising at least one acidic group or salts thereof.
  • acrylic acid methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acryl- amidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid, 2-acrylamido- 2,4,4-trimethylpentanesulfonic acid, vinylphosphonic acid, allylphosphonic acid, N-(meth)acrylamidoalkylphosphonic acids, (meth)acryloyloxyalkylphosphonic acids and salts and mixtures thereof.
  • the further monoethylenically unsaturated hydrophilic monomers may be hydrophilic cationic monomers.
  • Suitable cationic monomers (A1c) especially include monomers having ammonium groups, especially ammonium derivatives of N-(m-aminoalkyl)(meth)acrylamides or w-aminoalkyl (meth)acrylates.
  • amphiphilic monomers (A2) are monoethylenically unsaturated monomers having at least one hydrophilic group and at least one, preferably terminal, hydrophobic group.
  • the monomers (A3) may, for example, be monoethylenically unsaturated monomers which have a more hydrophobic character than the hydrophilic monomers (A1) and are accordingly water-soluble only to a minor degree.
  • examples of such monomers include N-alkyl- and N,N'-dialkyl(meth)acrylamides, where the number of carbon atoms in the alkyl radicals together is at least 3, preferably at least 4.
  • Examples of such monomers include N-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide or N-benzyl(meth)acrylamide.
  • the polymers P2) are selected from polyamino acids.
  • Suitable polyamino acids are in principle compounds comprising at least one copolymerized amino acid such as aspartic acid, glutamic acid, lysine, glycine, etc.
  • the polyamino acids also include the derivatives obtainable by polymer-analogous reaction, such as esterification, amidation, etc.
  • Preferred polyamino acids are polyaspartic acid, polyaspartic acid derivatives, polyglutamic acid, polyglutamic acid derivatives and mixtures thereof.
  • Polyaspartic acid can be prepared, for example, by alkaline hydrolysis of polysuccinimide (PSI, anhydropolyaspartic acid).
  • PSI polysuccinimide
  • Polysuccinimide can be prepared by thermal condensation of aspartic acid or from ammonia and maleic acid.
  • Polyaspartic acid can be used, for example, as a biodegradable complexing agent and cobuilder in washing and cleaning compositions.
  • Polyamino acids having surfactant properties can be obtained by at least partly converting the free carboxylic acid groups of polyaspartic acid or polyglutamic acid to N-alkylamides and/or to esters.
  • Polyaspartamides can also be prepared by reaction of polysuccinimide with amines.
  • the ring opening of polysuccinimide can be conducted with ethanolamine.
  • DE 3700 128 A and EP 0458079 A describe the subsequent esterification of such hydroxyethyl derivatives with carboxylic acid derivatives.
  • Copolymeric polyaspartic esters are obtainable as described in DE 19545678 A by condensation of monoalkyl esters of maleic or fumaric acid with addition of ammonia.
  • DE 19545 678 A further states that copolymeric polyaspartic esters are obtainable by reaction of polysuccinimide with alcohols, optionally followed by hydrolysis.
  • polyaspartic esters aside from their biodegradability, are notable for excellent properties as stabilizers for O/W and W/O emulsions, as a foam-stabilizing and foam-boosting cosurfactant in washing and cleaning compositions, and as a complexing agent for metal cations.
  • the polymers P2) are selected from polyalkylene glycols and mono- or diethers of polyalkylene glycols.
  • Preferred polyalkylene glycols have a number - average molecular weight in the range from 1000 to 4 000 000 g/mol, more preferably from 1500 to 1 000 000 g/mol.
  • Suitable polyalkylene glycols and the mono- and diethers thereof may be linear or branched, preferably linear.
  • Suitable polyalkylene glycols are, for example, water- soluble or water-dispersible nonionic polymers having repeat alkylene oxide units.
  • the proportion of repeat alkylene oxide units is at least 30% by weight, preferably at least 50% by weight and especially at least 75% by weight, based on the total weight of the compound.
  • Suitable polyalkylene glycols are polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers.
  • Suitable alkylene oxides for preparation of alkylene oxide copolymers are, for example, ethylene oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide. Suitable examples are copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide.
  • the alkylene oxide copolymers may comprise the copolymerized alkylene oxide units in randomly distributed form or in the form of blocks. Preferably, the proportion of repeat units derived from ethylene oxide in the ethylene oxide/propylene oxide copolymers is 40% to 99% by weight. Particular preference is given to ethylene oxide homopolymers and ethylene oxide/propylene oxide copolymers.
  • Suitable mono- and diethers of polyalkylene glycols are the mono-(Ci-Ci 8 -alkyl) ethers and di-(Ci-Ci 8 -alkyl) ethers.
  • Preferred mono- and diethers of polyalkylene glycols are the mono-(Ci-C 6 -alkyl) ethers and di-(Ci-C 6 -alkyl) ethers.
  • Polymer mixtures are suitable, for example, for adjusting the mechanical properties and/or the dissolution properties of the multilayer films of the invention.
  • the polymers used in the polymer mixture may differ in terms of their chemical composition and/or in terms of their physicochemical properties.
  • the detergent formulation of the invention comprises at least one separate domain comprising a mixture of 2 or more polymers.
  • Suitable mixtures may comprise 2 or more different polymer compositions P1) or at least one polymer composition P1) and at least one polymer P2) or 2 or more different polymers P2).
  • a polymer mixture comprising 2 or more polymers which differ in terms of their chemical composition is used.
  • a polymer mixture comprising 2 or more polymers which differ in terms of their molecular weight is used.
  • a polymer mixture comprising at least two polymers P2) comprising repeating units, which derive from vinyl alcohol, is used.
  • this domain comprises the polymer composition P1) and at least one further component selected from polymers P2), builder, bleach, additives and mixtures thereof.
  • the detergent formulation according to the invention consist of two or more domains, at least one domain comprises or consists of the polymer composition P1).
  • each domain may comprise components selected from the polymer composition P1), polymers P2), builder, bleach, additives and mixtures thereof.
  • the detergent formulation of the invention is in form of a three dimensional shaped body which has a clarity value of at least 70% according to ASTM D1003 and a haze value of less than 75% according to ASTM D 1003. If the three dimensional body has two or more domains, the clarity and haze values refer to those domains, which comprise or consist of the polymer composition P1).
  • haze is defined as that percentage transmitted light which in passing through a specimen (plate) deviates from the incident light by more than 2.5° on the average. The haze is determined according to ASTM D 1003.
  • the term "clarity" is defined as that percentage transmitted light which in passing through a specimen (plate) deviates from the incident light by less than 2.5° on the average.
  • the specimen should have substantially plane-parallel surfaces free of dust, grease, scratches and blemishes, and shall be free of distinct internal voids and particles.
  • the clarity is determined according to ASTM D 1003.
  • the detergent formulation according to the invention is preferably characterized by a clarity value of 75 to 100%, more preferably 80 to 100%, especially 85 to 100%, in particular 90 to 99.9%, the clarity value being measured on plaques of 1.1 mm thickness and measured with the method according to ASTM D1003.
  • the detergent formulation according to the invention is preferably characterized by a haze value which is smaller than 75%; the haze value being measured at a plate of 1.1 mm thickness.
  • the detergent formulation preferably is characterized by a haze of 1 to 75%, in particular 2 to 60% is preferred.
  • the haze is determined according to ASTM D 1003.
  • the detergent formulation in form of a three dimensional shaped body is non-tacky.
  • non-tackiness is characterized by low values of the static friction load and/or the sliding friction load. If the a plane surface of a three dimensional body that exhibit low static or sliding friction is in contact with a plane surface of another body the three dimensional body is non-tacky.
  • Stiction or static friction is the friction that needs to be overcome to enable relative motion of stationary objects in contact.
  • Kinetic friction also known as dynamic friction or sliding friction, occurs when two objects are moving relative to each other and rub together.
  • the static friction load is the force that needs to be overcome to achieve relative motion of two stationary objects in planar contact.
  • the dynamic frictional load is the force that must be applied for the relative movement of two bodies in planar contact.
  • the static friction load and/or the sliding friction load are measured with the method according to ISO EN 8295 and are given in Newton (N). Static friction load and static friction value have the same meaning. Likewise, dynamic friction load and dynamic friction value have the same meaning.
  • the detergent formulation according to the invention has a static friction value in the range of 0.5 N to 20.0 N, preferably in the range of 1.0 N to 17 N.
  • the detergent formulation according to the invention has a sliding friction value in the range of 0.1 N to 5.0 N, preferably in the range of 0.2 N to 4.0 N value according to ISO EN 8295.
  • the three dimensional shaped body is characterized in that it has dimensions of at least 1 mm, in particular at least 2 mm, more particularly at least 3 mm, especially at least 4 mm in all spatial directions.
  • the largest dimension of the three dimensional body in a spatial direction is preferably at most 100 mm.
  • the largest dimension of the three dimensional shaped body in one spatial direction is in the range of 20 mm to 100 mm or in the range of 55 to 100 mm.
  • the smallest dimension of the three dimensional shaped body in at least one spatial direction is preferably at least 2 mm, in particular at least 4 mm.
  • the dimensions of the three dimensional shaped body is chosen such that the body cannot be swallowed, e.g. by a child.
  • the dimensions may be the same for all spatial directions, i.e. in case of a sphere. Typically the dimensions in some spatial directions are distinct from dimensions in other spatial directions. Preference given to bodies, wherein the aspect ratios of the largest dimension to the smallest dimension is in in the range from 1:1 to 20:1.
  • the three dimensional shaped body in a first spatial direction has a dimension in the range of 20 to 100 mm, and dimensions in the range of 2 to 100 mm in spatial directions, which are orthogonal to the first direction and to each other and where the aspect ratio of the largeest dimension to the smallest dimesion is preferably in the range of 1 :1 to 20:1.
  • an orthogonal coordinate system can be used to describe three dimensional bodies, whereby the largest longitudinal extension lies on one axis or of the coordinate system or parallel thereto, e.g. on the x-axis or parallel to the x-axis.
  • the base lies in the plane defined by the x-axis and the y-axis, also referred to as the x,y-plane.
  • the z-axis orthogonal to x- and y-axes serves for the description of the material thickness.
  • the dimensions in the x-axis is in the range of 20 to 100 mm, while the dimensions in the y-axis and the z-axis are in the range of 2 to 100 mm.
  • the ratio of the dimension in direction of the x-axis to the dimension in the z-axis is in the range of 1 :1 to 20:1.
  • the shape of the three dimensional shaped body is not of particular importance for the purpose of the invention. It may be regular or irregular.
  • the shape may be a geometrical or non-geometrical shape.
  • geometrical shapes are polyhedrons, including Platonic bodies, Archimedean bodies, Catalan bodies (dual Archimedean bodies), Johnson bodies, including pyramids, and polygonal domes, further prisms, antiprisms, truncated pyramids, cuboids, round-shaped or spherical bodies including spheres, ellipsoids, cylinders, including circular cylinders, ellipsoidal cylinders, cylinders with spherical heads, cones and truncated cones, spherical domes, elliptic domes and ellipsoid domes, and mixed forms having polygonic and round shaped surfaces, including polyhedrons, such as cuboids or prisms, with rounded edges and the like.
  • complex shapes including polyhedrons,
  • the three dimensional shaped body may be hollow or massive.
  • the volume of the three dimensional shaped body is at least 0.001 cm 3 , in particular at least 0.01 cm 3 , more particularly at least 0.033 cm 3 or at least 0.064 cm 3 or at least 0.1 cm 3 and especially at least 1 cm 3 .
  • the volume of the three dimensional shaped body is in the range of 0.01 to 50 cm 3 , in particular in the range of 0.033 to 25 cm 3 or 0.064 to 25 cm 3 or 0.1 to 25 cm 3 , especially in the range of 1 to 20 cm 3 .
  • the volume refers to the massive parts of the body.
  • the detergent formulation according to the invention is flexible/elastic.
  • flexibility/elasticity is the property of a three dimensional body to be deformed (change the shape) under the action of force and to return to its original shape when the force is removed.
  • the detergent formulation according to the invention preferably has a flexibility/elasticity in the range of 15 to 55 N, more preferably in the range of 20 to 45 N, especially in the range of 25 to 40 N determined by TA.XTplus Texture Analyser.
  • the three dimensional body shaped bodies of the detergent composition are prepared by a process which comprises plastifying a detergent composition containing or consisting of the polymer composition P1), shaping the plastified detergent composition into the desired shape of a three dimensional shaped body and solidifying the plastified detergent composition by rapid cooling.
  • the detergent formulation according to the invention can be obtained by mold casting, i.e. by pouring the liquified or plastified detergent composition containing or consisting of the polymer composition P1), e.g. a detergent solution or a molten detergend composition, into a mold with the shape of the respective body and allowing it to solidify.
  • the process in particular comprises the following steps i) to iv) and optionally the drying step iv): i) providing a detergent composition comprising or consisting of the polymer composition P1 ) having a water content of at most 25% by weight, e.g. in the range of 1 to 25% by weight or in the range of 5 to 25% by weight, in particular in the range of 10 to 25% by weight, especially in the range of 10 to 20% by weight, based on the total weight of P1); ii) plastifying the detergent composition of step i) by heating the detergent composition to a temperature of at least 50°C, in particular at least 55°C, e.g.
  • step iii) shaping the plastified detergent composition of step ii) into the desired shape of the three dimensional body; and iv) rapid cooling of the shaped detergent composition of step iii) to a temperature of at most -20°C, obtaining the detergent formulation in the shape of a three dimensional body, and v) optionally drying of the obtained detergent formulation.
  • the process for the prepartion of the detergent formulation in form of a three dimensional body as defined herein comprises the following steps: i) providing a polymer composition P1), having a water content at most of 25% by weight, e.g. in the range of 1 to 25% by weight or in the range of 5 to 25% by weight, in particular in the range of 10 to 25% by weight, especially in the range of 10 to 20% by weight, based on the total weight of P1 ); ii) plastifying the polymer composition P1) provided in step i) by heating to a temperature of at least 50°, in particular at least 55°C and/or at most 100°C, preferably at most 90°C, in particular at most 85°C, e.g.
  • step iii) shaping the plastified polymer composition P1) composition of step ii) into the desired shape of the three dimensional body, in particular by mold casting the plastified polymer composition P1) from step ii), iv) rapid cooling of the shaped, e.g. mold casted product from step iii) to a temperature at most -20°C, obtaining the detergent formulation in form of a three dimensional shaped body and v) optionally drying of the obtained detergent formulation.
  • Step i) providing a detergent composition comprising or consisting of the polymer composition P1)
  • the detergent composition used for producing the three dimensional shaped body can be prepared by analogy to the methods described in the prior art cited in the outset of the instant application. Typically it comprises the production by the polymer composition P1) by the process as described hereinafter, optionally followed by formulating the thus obtained polymer composition with further components, e. g.
  • the detergent compositions used for producing the three dimensional shaped body comprises the polymer composition P1) or a mixture of the polymer composition P1 and the polymer P2) in an amount of at least 70% by weight, in particular at least 75% by weight, more particularly at least 80% by weight, based on the total weight of the detergent formulation.
  • the detergent compositions comprises the polymer composition P1) or a mixture of the polymer composition P1 and the polymer P2) in an amount in the range of 70 to 99% by weight, more particular in the range of 75 to 99% by weight or in the range 75 to 95% by weight, in particular in the range of 75 to 90% by weight, especially in the range of 80 to 90% by weight, based on the total weight of the detergent formulation.
  • the amount of the polymer composition P1 ) or the mixture of the polymer composition P1 ) and the polymer P2) in the detergent formulation is at least 90% by weight, especially at least 95% by weight, based on the total weight of the components in the detergent formulation, which are different from water, and may be up to 100% by weight, based on the total weight of the components in the detergent formulation, which are different from water.
  • the detergent compositions used for producing the three dimensional shaped body comprises the polymer composition P1) or in an amount of at least 70% by weight, in particular at least 75% by weight, more particularly at least 80% by weight, based on the total weight of the detergent formulation.
  • the detergent compositions comprises the polymer composition P1) in an amount in the range of 70 to 99% by weight, more particular in the range of 75 to 99% by weight or in the range 75 to 95% by weight, in particular in the range of 75 to 90% by weight, especially in the range of 80 to 90% by weight, based on the total weight of the detergent formulation.
  • the amount of the polymer composition P1) in the detergent formulation is at least 90% by weight, especially at least 95% by weight, based on the total weight of the components in the detergent formulation, which are different from water, and may be up to 100% by weight, based on the total weight of the components in the detergent formulation, which are different from water.
  • the polymer composition P1) is produced by
  • step B) subjecting the monomer composition M1) provided in step A) to a free-radical polymerization in the presence of at least one polyether component PE) selected from polyetherols having a number-average molecular weight of at least 200 g/mol, mono- and di(Ci-C 6 -alkyl) ethers thereof, surfactants containing polyether groups and mixtures thereof, optionally in the presence of at least one additive.
  • PE polyether component selected from polyetherols having a number-average molecular weight of at least 200 g/mol, mono- and di(Ci-C 6 -alkyl) ethers thereof, surfactants containing polyether groups and mixtures thereof, optionally in the presence of at least one additive.
  • the free-radical polymerization of the monomer composition M1) in step B) is preferably conducted by the feed method. This generally involves metering at least the monomers in liquid form into the reaction mixture. Monomers which are liquid under the metering conditions can be fed into the reaction mixture without addition of a solvent S1); otherwise, the monomers are used as a solution in a suitable solvent S1). It is of course also possible to use monomers that are in solid form.
  • the free-radical polymerization for production of the polymer composition P1) can be effected in the presence of a solvent S1) selected from water, Ci-C 6 -alkanols, polyols other than PE) and the mono- and dialkyl ethers and mixtures thereof.
  • a solvent S1 selected from water, Ci-C 6 -alkanols, polyols other than PE
  • Suitable polyols and the mono- and dialkyl ethers thereof also include alkylene glycol mono(Ci-C4-alkyl) ethers, alkylene glycol di(Ci-C4-alkyl) ethers, oligoalkylene glycols and mono(Ci-C4- alkyl) ethers and di(Ci-C4-alkyl) ethers thereof.
  • the solvent S1) is preferably selected from water, methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol mono(Ci-C4-alkyl) ethers, ethylene glycol di(Ci-C4-alkyl) ethers, 1,2-propylene glycol, 1,2-propylene glycol mono(Ci-C4-alkyl) ethers, 1,2-propylene glycol di(Ci-C4-alkyl) ethers, glycerol, polyglycerols, oligoalkylene glycols having a number-average molecular weight of less than 1000 g/mol and mixtures thereof. Suitable oligoethylene glycols are commercially available under the CTFA names
  • Pluriol E® brands from BASF SE.
  • Suitable alkyl polyalkylene glycols are the corresponding Pluriol A...E® brands from BASF SE.
  • the solvent S1) is more preferably selected from water, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
  • the solvent S1) used is selected from water and a mixture of water and at least one solvent S1) other than water, selected from ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
  • the free-radical polymerization in step B) is effected in the presence of a solvent S1 ) consisting to an extent of at least 50% by weight, preferably to an extent of at least 75% by weight and especially to an extent of at least 90% by weight, based on the total weight of the solvent S1), of water. More particularly, the free-radical polymerization in step B) is effected in the presence of a solvent S1) consisting entirely of water.
  • the free-radical polymerization in step B) is effected in feed mode, in which case feeds comprising at least one a,b-ethylenically unsaturated carboxylic acid do not comprise any solvent S1).
  • the metering rates of the monomer feed(s) and any further feeds are preferably selected such that the polymerization is maintained with the desired conversion rate.
  • the addition of the individual feeds here may be continuous, periodical, with constant or changing metering rate, essentially simultaneous or at different times.
  • the addition of all the feeds to the reaction mixture is continuous.
  • the monomer composition M1) and the polyether component PE) are used in a weight ratio of 0.5:1 to 5:1 , more preferably of 0.7:1 to 3:1.
  • the weight ratio of the polyether component PE) to the component S1) is preferably in the range from 0.1 :1 to 5:1 , more preferably from 0.5:1 to 3:1.
  • the free-radical polymerization in step B) is effected at a temperature in the range from 20 to 95°C, more preferably from 30 to 90°C, especially from 40 to 80°C.
  • the free-radical polymerization in step B) can be effected in the presence of at least one additive.
  • Suitable additives are, for example, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, bitter substances, thickeners, solubilizers, organic solvents, electrolytes, antimicrobial active ingredients, antioxidants, UV absorbers and mixtures thereof.
  • the free-radical polymerization in step B) of the process comprises B1) providing an initial charge comprising at least a portion of the polyether component PE), optionally at least a portion of the chain transfer agent CTA) and, if the polymerization is effected in the presence of a solvent S1), optionally at least a portion of S1 );
  • the initial charge is heated to the polymerization temperature before the feeds are added while stirring.
  • the individual reactants are added simultaneously in separate feeds, the flow rates of the feeds generally being kept very substantially constant over the period of addition.
  • the amount of polyether component PE) in the initial charge (step B1)) is 30% to 100% by weight, more preferably 65% to 100% by weight and especially 80% to 100% by weight, based on the total weight of the polyether component PE) used for polymerization.
  • the content of solvent S1) in the initial charge is not more than 70% by weight, based on the total weight of the feedstocks in the initial charge.
  • the content of solvent in the initial charge is not more than 40% by weight, especially not more than 35% by weight, based on the total weight of the feedstocks in the initial charge.
  • the amount of solvent generally changes only by a few percent by weight over the entire course of the process.
  • solvents S1) having a boiling point at standard pressure (1 bar) of below 240°C are used.
  • the solvent is initially charged in its entirety.
  • the initial charge does not comprise any chain transfer agent. If a chain transfer agent is used, this is not added until step B2), via at least one of the feeds.
  • the feeds are added in step B2) over a period of time which is advantageously selected such that the heat of reaction that arises in the course of the exothermic polymerization reaction can be removed without any great technical complexity, for example without the use of a reflux condenser.
  • the feeds are added over a period of 1 to 10 hours.
  • the feeds are added over a period of 2 to 8 hours, more preferably over 2 to 6 hours.
  • the free-radical polymerization in step B) of the process is continuous.
  • the monomer composition M1), the polyether component PE), at least one initiator, optionally at least one chain transfer agent CTA) and optionally at least one solvent S1) are added to the reactor in the form of one liquid stream or preferably at least two liquid streams.
  • the stream comprising the initiator generally does not comprise the chain transfer agent as well. If at least two liquid streams are used, these are typically mixed to obtain the reaction mixture.
  • the polymerization can be effected in one stage or in two or more than two, i.e. in 2, 3, 4, 5 or more, stages.
  • At least one additional stream is mixed in between at least two of the polymerization stages.
  • This may be a monomer-containing stream, initiator-containing stream, solvent- containing stream, chain transfer agent-containing stream, a mixture thereof and/or any other stream of matter.
  • the optionally used solvent and/or any condensation products that form are generally not removed.
  • the polymerization can generally be effected at ambient pressure or reduced or elevated pressure. Preferably, the polymerization is conducted at ambient pressure.
  • the polymerization is generally effected at constant temperature, but it can also be varied during the polymerization if required.
  • the polymerization temperature is kept very substantially constant over the entire reaction period, i.e. steps B2) and B3).
  • the polymerization temperature varies typically within the range from 20 to 95°C.
  • the polymerization temperature varies within the range from 30 to 90°C and especially within the range from 40 to 80°C. If the polymerization is not conducted under elevated pressure and at least one optional solvent S1) has been added to the reaction mixture, the solvent or solvent mixture determines the maximum reaction temperature by virtue of the corresponding boiling temperatures.
  • the polymerization can be effected in the absence or presence of an inert gas.
  • the polymerization is conducted in the presence of an inert gas.
  • Inert gas is generally understood to mean a gas which, under the given reaction conditions, does not enter into any reaction with the reactants, reagents or solvents involved in the reaction or the products which form.
  • the polymerization is conducted in the presence of a solvent, it is selected from the solvents S1) described above.
  • the monomers can be polymerized with the aid of free radical-forming initiators, also referred to hereinafter as free-radical initiators or initiators.
  • free-radical initiators for the free-radical polymerization are in principle all free-radical initiators which are essentially soluble in the reaction medium as exists at the time when they are added and have sufficient activity to initiate the polymerization at the given reaction temperatures. It is possible to introduce one individual free-radical initiator or a combination of at least two free-radical initiators into the process of the invention. In the latter case, the at least two free-radical initiators can be used in a mixture or preferably separately, simultaneously or successively, for example at different times in the course of the reaction.
  • Free-radical initiators which may be used for the free-radical polymerization are the peroxo and/or azo compounds customary for the purpose, for example hydrogen peroxide, alkali metal or ammonium peroxodisulfates (for example sodium peroxodisulfate), diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxymaleate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis(o-tolyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, tert-butyl peroctoate, d
  • initiator mixtures or redox initiator systems for example ascorbic acid/iron(ll) sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodium disulfite, tert-butyl hydroperoxide/sodium hydroxymethanesulfinate,
  • the free-radical initiator is generally provided in the form of a solution in a solvent comprising at least one of the aforementioned solvents S1) and optionally additionally at least one polyether of polyether component PE).
  • the polymerization can be effected without using a chain transfer agent (polymerization chain transfer agent) or in the presence of at least one chain transfer agent.
  • Chain transfer agents generally refer to compounds having high transfer constants which accelerate chain transfer reactions and hence bring about a reduction in the degree of polymerization of the resulting polymers.
  • the chain transfer agents can be divided into mono-, bi- and polyfunctional chain transfer agents, according to the number of functional groups in the molecule that can lead to one or more chain transfer reactions. Suitable chain transfer agents are described in detail, for example, by K. C. Berger and G. Brandrup in J. Brandrup, E. H. Immergut, Polymer Handbook, 3rd edition, John Wiley & Sons, New York, 1989, pp. 11/81 - 11/141.
  • Suitable chain transfer agents are, for example, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde.
  • Further usable chain transfer agents are formic acid and salts or esters thereof, such as ammonium formate, 2, 5-diphenyl-1 -hexene, hydroxyammonium sulfate and hydroxyammonium phosphate.
  • allyl compounds for example allyl alcohol, functionalized allyl ethers, such as allyl ethoxylates, alkyl allyl ethers, or glycerol monoallyl ether.
  • Chain transfer agents used are preferably compounds comprising sulfur in bound form.
  • Compounds of this kind are, for example, inorganic hydrogensulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides and sulfones.
  • di-n-butyl sulfide di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide, dimethyl sulfoxide, dialkyl sulfide, dialkyl disulfide and/or diaryl sulfide.
  • thiols compounds which comprise sulfur in the form of SH groups, also referred to as mercaptans.
  • Preferred chain transfer agents are mono-, bi- and polyfunctional mercaptans, mercaptoalcohols and/or mercaptocarboxylic acids. Examples of these compounds are allyl thioglycolates, ethyl thioglycolate, cysteine, 2-mercaptoethanol,
  • polyfunctional chain transfer agents are compounds which comprise more than two sulfurs in bound form. Examples thereof are trifunctional and/or tetrafunctional mercaptans.
  • the chain transfer agent is more preferably selected from mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid, ethylhexyl thioglycolate and sodium hydrogensulfite.
  • Preferred chain transfer agents are also hypophosphorous acid (phosphinic acid) and salts of hypophosphorous acid.
  • a preferred salt of hypophosphorous acid is the sodium salt.
  • the amount is typically 1 to 40 pphm ("parts per hundred monomer", i.e. parts by weight based on one hundred parts by weight of monomer composition).
  • the amount of chain transfer agents used in the process of the invention is in the range from 3 to 30 pphm, more preferably in the range from 5 to 25 pphm. It is also possible to conduct the polymerization without adding a chain transfer agent.
  • the chain transfer agent is added continuously to the polymerization mixture in its entirety via one of the feeds in step B2).
  • the chain transfer agent either in its entirety to the initial charge, i.e. before the actual polymerization, or to include only some of the chain transfer agent in the initial charge and to add the remainder continuously to the polymerization mixture in step B2) via one of the feeds.
  • the chain transfer agent can be added here in each case without or with solvent S1).
  • the amount of chain transfer agent and the way in which it is added to the reaction mixture have a major influence on the average molecular weight of the polymer composition P1). If no chain transfer agent or only a small amount of chain transfer agent is used and/or if the addition predominantly precedes the polymerization, this generally leads to higher average molecular weights of the polymer formed. If, by contrast, a relatively large amount of chain transfer agent is used and/or the chain transfer agent is added for the most part during the polymerization (step B2)), this generally leads to a smaller average molecular weight. In order to avoid or to reduce unwanted foam formation in the synthesis, in transport (for example in pumping) and in storage, and also in film production, defoamers and foam inhibitors may be used.
  • foam inhibitors or defoamers are useful. Mention should be made here, for example, of (1) oil-based systems based on mineral oil or vegetable oil, which may additionally comprise waxes or silica particles, (2) water-based systems in which oil and waxes are dispersed, (3) silicone-based systems (polysiloxanes), for example in water-soluble form, as oil or water-based emulsion, (4) EO/PO-based polyalkoxylates, (5) alkyl polyacrylates, (6) fatty acids and fatty acid esters, especially mono- and diglycerides of fatty acids, (8) fatty alcohol alkoxylates, (9) defoamers from the class of the phosphoric esters and salts thereof, such as sodium (C6-C2o-alkyl)phosphates, e.g.
  • polysiloxanes can also be used in modified form, for example in alkyl group-modified or polyether group-modified form. These are used with preference.
  • the polymer compositions P1) obtained when the polymerization has finished (step B3)) are transferred to a suitable vessel and optionally cooled directly to ambient temperature (20°C).
  • the polymer compositions P1) obtained in this way are advantageously suitable for production of detergent formulations in form of a three dimensional body, for example for use as a washing or cleaning composition.
  • the production of three dimensional bodies thereon is described in detail hereinafter.
  • the weight-average molecular weight M w of the polymer composition P1) of the invention was determined by means of gel permeation chromatography (GPC) in aqueous solution using neutralized polyacrylic acid as polymer standard. This type of molecular weight determination covers the components of the polymer composition P1) which comprise the monomers M1) in copolymerized form.
  • the polymer composition P1) preferably has a weight-average molecular weight of 2000 to 100000 g/mol, preferably of 3000 to 80000 g/mol.
  • the polymer composition P1) has a sufficiently low glass transition temperature T G suitable for film formation.
  • the polymer compositions P1) have a glass transition temperature T G in the range from 0 to 80°C, more preferably from 0 to 60°C, especially from 0 to 30°C.
  • the water content of the polymer composition P1 provided in step i) is at most 25% by weight based on the total weight of P1), e.g. in the range of 5 to 25% by weight, in particular in the range of 10 to 25% by weight, especially in the range of 10 to 20% by weight.
  • the water content of the polymer composition P1 provided in step i) is in a range of 10 to 25% by weight based on the total weight of P1).
  • the water content of the polymer composition P1 provided in step i) is in a range of 15 to 25% by weight based on the total weight of P1).
  • the water content of P1) can be adjusted by methods known by the skilled person.
  • the polymer composition P1) Prior to use for detergent formulation in form as a three dimensional body production, the polymer composition P1) preferably has a content of acid groups of more than 1 mmol/g, more preferably of more than 1.3 mmol/g. Prior to use for detergent formulation in form as a three dimensional body production, the polymer composition P1) preferably has a content of acid groups of not more than 15 mmol/g. Prior to use for detergent formulation in form as a three dimensional body production, the polymer composition P1) especially has a content of acid groups of 1.5 mmol/g to 10 mmol/g.
  • the acid groups of the polymer composition P1) of the invention are in non-neutralized form.
  • the acid groups of the polymer composition P1) of the invention are partially neutralized. Particularly, 0 to 15% of the acid groups of the polymer composition P1) of the invention are neutralized. Especially, 5 to 10% of the acid groups of the polymer composition P1) of the invention are neutralized.
  • the thus obtained polymer composition P1) may be blended with the polymer P2) and/or with further additives to obtain the detergent composition.
  • the polymer composition P1) or a mixture of the polymer composition P1) and the polymer P2) is used as the detergent composition for subsequent production steps of the three dimensional shaped body.
  • the production of the detergent formulation in form of a three dimensional body comprises plastifying the detergent composition obtained in step i), in particular the polymer composition P1) of step i).
  • the expressions "plastified detergent composition” "plastified polymer composition P1)” relates to polymer composition P1), which is heated to a temperature where its viscosity is sufficiently low that it gets flowable and can e.g. be transported in a pipe by applying pressure, e.g. by pumping, and can be casted in a mold or can be spread on a surface.
  • the detergent composition comprising or consisting of the polymer composition P1) can be plastified by heating it to a temperature of at least 50°C, in particular at least 55°C. Typically, the temperature will be at most 100°C. Preferably, the temperature of the detergent composition comprising or consisting of the polymer composition P1 ) is at most 90°C, in particular at 85°C. More particularly, the detergent composition comprising or consisting of the polymer composition P1) is heated to a temperature in the range from 50 to 100°C, especially in the range of 55 to 90°C or 55 to 85°C.
  • the polymer composition P1 can be plastified by heating it to a temperature of at least 50°C and preferably up to a temperature of at most 100°C in particular at most 90°C or at most 85°C.
  • the polymer composition P1) is heated to a temperature in the range from 50 to 100°C, in particular in the range of 50 to 90°C and especially in the range of 55 to 85°C.
  • the detergent composition comprising or consisting of the plastified polymer composition P1) from step ii) can be shaped into a three dimensional body by conventional molding techniques which include but are not limited to casting plastified detergent composition into a mold or by injection molding the detergent composition comprising or consisting of the plastified polymer composition P1).
  • an injection molding process is employed for the production of a detergent formulation in form of a three dimensional body.
  • Multi-component injection molding may be used to produce injection molded parts consisting of two or more different polymer compositions.
  • the polymer compositions differ only in colour to achieve a specific design.
  • different materials and thus different properties can also be combined in a targeted manner.
  • Composite injection molding requires an injection molding machine with two or more injection units, but only one clamping unit. The parts can thus be produced cost-effectively with only one mold in a single operation.
  • the injection units must work in harmony, but always be controllable independently of each other.
  • the components can be injected through a single special nozzle or introduced into the mold at different points.
  • injection molding parts can be produced which consist of a polymeric carrier comprising or consisting of the polymer composition P1), and a covering material, such as a decorative material.
  • a covering material such as a decorative material.
  • injection techniques such as in-mold decorating (IMD), film insert molding (FIM), in-mold labeling (IML), in-mold coating (IMC) or in-mold painting (IMP).
  • IMD in-mold decorating
  • FIM film insert molding
  • IML in-mold labeling
  • IMC in-mold coating
  • IMP in-mold painting
  • injection molding In mold decoration (IMD), film insert molding (FIM), in-mold labeling (IML), in-mold coating (IMC) or in-mold painting (IMP).
  • IMD In mold decoration
  • FIM film insert molding
  • IML in-mold labeling
  • IMC in-mold coating
  • IMP in-mold painting
  • the in-mold decoration process is a combination of hot pressing and film insert molding. It is used to emboss a functionality from a carrier foil, a special IMD foil, onto a substrate (polymer composition).
  • the functionalized and/or embossed carrier film is placed in the injection mold.
  • the polymer composition is injected.
  • the resulting molded part is removed from the mold and the carrier film is separated. The result is a plastic molding with an embossed functionality.
  • the carrier film becomes part of the finished substrate.
  • the carrier material the stamping foil
  • the foil, cut into shape, is placed in the injection mold and injected with a polymer composition.
  • the exact sequence of the process steps is flexible.
  • the carrier foil may be removed or may form an integral part of the detergent formulation of the invention.
  • the in-mold coating is a combination of spraying and injection molding. First, a coating is applied to the injection mold by means of a spray gun. After the material has dried, the polymer composition is injected.
  • the plastic material is sprayed in the first step, and the coating is sprayed on in the second step, i.e. the process steps are carried out in reverse order to the process steps of the IMC process.
  • Step iv) Cooling In order to solidify the shaped three dimensional body of the plastified shaped product obtained from step iii) is usually subjected to a deep cooling, in particular to a rapid cooling. Rapid cooling is also termed “shock frosting”. Deep cooling means that the shaped product obtained from step iii) to a temperature of at most -20°C, in particular at most -40°C, e.g. in the range of -20 to -200°C or -40 to -200°C. Rapid cooling and shock frosting, respectively, refer to a cooling, where the temperature of the shaped product obtained from step iii) is lowered with in at most 3 minutes, in particular at most 120 seconds to the desired temperature.
  • cooling rates of at least 0.5 K/s, especially at least 0.8 K/s, especially at least 1 K/s, e.g. in the range of 0.5 to 200 K/s or 0.8 to 150 K/s or 1 to 100 K/s are applied.
  • Rapid cooling can be achieved by contacting the shaped product from step iii) with a cooling agent, in particular a liquid or solid cooling agent having a temperature of at most -20°C, in particular at most -40°C, e.g. in the range of -20 to -200°C or -40 to - 200°C, whereby a the detergent formulation in form of a three dimensional body is obtained.
  • a cooling agent in particular a liquid or solid cooling agent having a temperature of at most -20°C, in particular at most -40°C, e.g. in the range of -20 to -200°C or -40 to - 200°C
  • Suitable cooling mediums can be gasous, liquid or solid.
  • Preferred cooling agents are liquid nitrogen, solid carbon dioxide, liquid ethane, liquid propan, liquid perfluorinated alkanes.
  • Suitable perfluorinated alkanes are e.g. perfluorohexane or perfluoro-(2-methyl-3-pentanone).
  • the cooling time required for rapid cooling depends on the size and mass of the detergent formulation according to the invention.
  • the cooling time is in the range of 5 to 120 seconds, in particular in the range of 10 seconds to 30 seconds.
  • the shaped product from step iii) is kept at a temperature of at most -20°C, in particular at most -40°C for a period of at least minutes, e.g. for a period in the range of 5 to 60 minutes to complete solidification.
  • the detergent formulation obtained from step iv) may optionally be dried in order to remove volatile constituents of the detergent formulation, such as water.
  • the detergent formulation obtained from step iv) can be dried by methods known by the skilled person. Typically drying is carried out at temperatures in the range of 0 to > 50°C, in particular in the range of 5 to 40°C.
  • Step vi) Including further additives
  • the shaped detergent formulations obtained from the process of the present invention can be formulated with further additives.
  • a specific embodiment is a process for producing a detergent formulation of the invention comprising at least one additive.
  • an individual separate domain or a plurality of domains but not all the domains or all the domains may each comprise one or more than one additive.
  • at least one additive is present in at least two domains.
  • Additives may, as described above, already be added in the course of the free-radical polymerization in step B) or in the provision of the detergent formulation in form of a three dimensional body. Whether the addition is already effected in step B) or only in the provision of the detergent formulation according the invention depends on the nature and effect of the particular additive.
  • the additives may be auxiliaries for adjustment of the properties of the detergent formulation in form of a three dimensional body or typical additives for the end use of the detergent formulation.
  • Typical additives for the end use of the detergent formulation are especially selected from additives for washing compositions, cleaning compositions, dishwashing compositions, rinse aids, hygiene products, disinfectants, personal care compositions, crop protection compositions, bait traps, wetting agents, etc.
  • detergent formulations which include at least one additive.
  • detergent formulations which include at least one further separate domain including an additive which is a constituent customary for washing and cleaning compositions.
  • the additive is preferably selected from nonionic, anionic, cationic and amphoteric surfactants, builders, complexing agents such as methylglycinediacetic acid, glutaminediacetic acid, glutamic acid diacetic acid and citric acid and the sodium and potassium salts thereof, bleaches, enzymes, enzyme stabilizers, bases, corrosion inhibitors, defoamers and foam inhibitors, wetting agents, dyes, pigments, fragrances, fillers, tableting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, bitter substances, fluorescers, hydrotropes, antiredeposition agents, optical brighteners, graying inhibitors, antishrink agents, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, anti-yellowing agents, corrosion inhibitors, antistats, ironing aids, hydrophobizing and impregnating agents, antiswell and antislip agents, plasticizers, sca
  • Suitable bitter substances are those mentioned hereinafter as components E6).
  • additives and solvents e. g. water
  • solvent S1 e. g. water
  • plasticizer e.g. water
  • plasticizers can be added thereto in the course of production.
  • plasticizers preferably 0.5% to 30% by weight, more preferably 2% to 20% by weight and especially 3% to 10% by weight of plasticizer is used, based on the total weight of the composition.
  • Suitable plasticizers are alkyleneamines, alkanolamines, polyols such as alkylene glycols and oligoalkylene glycols, e.g. 2-methylpropane-1,3-diol, 3-methylpentane-1 ,5- diol, hydroxypropylglycerol, neopentyl glycol, alkoxylated glycerol (for example Voranol® from Dow Chemicals), water-soluble polyesterpolyols (for example TriRez from Geo Specialty Chemicals) and mixtures thereof.
  • Suitable plasticizers are also polyetherpolyols available under the Lupranol® name from BASF SE.
  • alkyleneamines refers to condensation products of alkanolamines with ammonia or primary amines; for example, ethyleneamines are obtained by reaction of monoethanolamine with ammonia in the presence of a catalyst. This results in the following main components: ethylenediamine, piperazine, diethylenetriamine and aminoethylethanolamine.
  • the plasticizers are selected from glycerol, diglycerol, propylene glycols having a weight-average molecular weight of up to 400, ethylene glycol, polyethylene glycols having a weight-average molecular weight of up to 400, diethylene glycol, triethylene glycol, tetraethylene glycol, sugar alcohols such as sorbitol, mannitol, xylitol, isomalt, lactitol, isopentyldiol, neopentyl glycol, trimethylolpropane, diethylenetriamine, triethylenepentamine, triethanolamine and mixtures thereof.
  • scavengers capture molecules
  • Suitable scavengers are polyamines, polymeric polyamines, such as polyethyleneimines, poly(amidoamines) and polyamides.
  • ammonium sulfate, primary and secondary amines having a low vapor pressure such as ethanolamines, amino acid and salts thereof, and also polyamino acid and salts thereof, fatty amines, glucosamines and other aminated sugars.
  • reducing agents such as sulfites, bisulfites, thiosulfites, thiosulfates, iodides, nitrites and antioxidants such as carbamates, ascorbates and mixtures thereof.
  • the detergent formulations of the invention it is possible to add further additives in the form of polymers to the polymer composition P1) and/or the polymers P2) before and/or during the production of the three dimensional body.
  • further additives in the form of polymers to the polymer composition P1) and/or the polymers P2) before and/or during the production of the three dimensional body.
  • 0.05% to 20% by weight, preferably 0.1 % to 15% by weight and more preferably 0.2% to 10% by weight of polymers (based on the total weight of the polymer composition P1), polymers P2) and additional polymers) are used.
  • Such additives can simultaneously improve the washing properties of the detergent formulations, improve the mechanical properties of the detergent formulations, and increase the resistance of the detergent formulations to washing composition components.
  • Suitable further polymers are, for example, oligosaccharides and polysaccharides, starch, degraded starches (maltodextrins), cellulose ethers, specifically hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, microcrystalline cellulose, inulin, carboxymethylcellulose, for example in the form of the sodium salts, alginic acid and alginates, pectin acid and pectins, polyethyleneimines, alkoxylated and especially ethoxylated polyethyleneimines, graft polymers of vinyl acetate onto polyalkylene glycols, especially onto polyethylene glycols, homopolymers of N-vinylpyrrolidone, copolymers of N-vinylpyrrolidone and N-vinylimidazole, copolymers of N-vinylpyrrolidon
  • the surface of the detergent formulations of the invention is possible to subject the surface of the detergent formulations of the invention to at least a partial coating with at least one additive. It is also possible to subject the surface of at least one separate domain of the detergent formulations of the invention to at least partial coating with at least one additive.
  • Such a treatment may serve, for example, to provide the surface with particular properties, such as nonstick action, antistatic action, hydrophilic or hydrophobic properties, etc. It is thus possible to provide the detergent formulations, for example, with better detachment properties from the carrier material used in the production, reduced tack, better compatibility with particular components ensheathed or coated therewith, etc.
  • the application can be effected by standard methods, for example by spraying, dipping, powder application, etc.
  • Suitable additives for coating of the surface of the detergent formulations of the invention are, for example, talc, surfactants such as silicone-containing surfactants, waxes, etc.
  • Printing or milling or engraving of the detergent formulations of the invention is also possible, in order to provide these, for example, with patterns, motifs, or inscriptions.
  • the printing may follow the production of the detergent formulations or be effected in an intermediate step during the buildup of the layers. This printing step preferably follows directly inline after the film production, in a separate printing or converting process, or inline with the pod production.
  • Suitable printing methods are inkjet printing, and also intaglio and planographic printing methods such as flexographic printing, gravure printing, offset printing or inkjet printing.
  • the detergent formulation of the invention may preferably consist of 1 to 10 domains, more preferably 1 to 8 domains, e.g. 1, 2, 3, 4, 5, 6, 7 or 8 domains.
  • the design and arrangement of the domains of the invention is guided by the desired end use.
  • the detergent formulation of the invention comprise a polymer composition P1).
  • one or more separate domains of the detergent formulation of the invention consists of a polymer composition P1).
  • the detergent formulation of the invention comprise a homo- or copolymer P2) comprising repeat units which derive from vinyl alcohol, vinyl esters or mixtures thereof.
  • Preferred polymers P2) are polyvinyl alcohols having a hydrolysis level of 50 to 99 mol%, more preferably of 70 to 98 mol%.
  • the detergent formulation of the invention comprise a cold water-soluble polyvinyl alcohol P2) having a hydrolysis level of not more than 90 mol%.
  • the detergent formulation of the invention comprise at least one cellulose ether P2).
  • Preferred cellulose ethers are selected from alkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses, carboxyalkyl celluloses and salts thereof, carboxyalkyl alkyl celluloses and salts thereof, carboxyalkyl hydroxyalkyl celluloses and salts thereof, carboxyalkyl hydroxyalkyl alkyl celluloses and salts, sulfoalkyl celluloses and salts thereof.
  • Particularly preferred cellulose ethers are selected from carboxymethyl celluloses.
  • the carboxyalkyl radicals may also be in salt form.
  • the detergent formulation of the invention comprise at least one homo- or copolymer comprising at least one copolymerized monomer selected from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, salts of the three latter monomers, vinylpyridine N-oxide, N-carboxymethyl-4-vinylpyridium halides and mixtures thereof.
  • the detergent formulation of the invention comprise a polyvinylpyrrolidone homopolymer.
  • the detergent formulation of the invention comprise a copolymer comprising copolymerized vinylpyrrolidone and vinylimidazole.
  • the detergent formulation according to the invention are suitable as such for use as a washing composition or as a cleaning composition or as a dishwashing composition.
  • the term "dishwashing composition” here also covers rinse aids. Since the detergent formulation according to the invention comprise or consists of a polymer composition P1), they feature dispersing, film-inhibiting, emulsifying and/or surfactant properties, and so the polymer composition P1) also contributes to the washing and cleaning performance.
  • the detergent formulation of the invention do not just improve the washing power, i.e.
  • the detergent formulation of the invention take the form of a three dimensional body, which may comprise one or more separate domains as defined above.
  • the minimum volume of the detergent formulations of the invention for use as a washing composition or as a cleaning composition or as a dishwashing composition is preferably chosen so that the body cannot be swallowed, e.g. by a child.
  • minimum volume of the detergent formulations of the invention for use as a washing composition or as a cleaning composition or as a dishwashing composition is at least 64 mm 3 , more preferably more than 100 mm 3 and especially more than 200 mm 3 .
  • the detergent formulations dissolve at the start of the respective use (for example in the washing or rinse water), thus release the constituents of the washing and cleaning and dishwashing composition and, in dissolved form, because of their dispersing, film- inhibiting, emulsifying and surfactant properties, contribute considerably to the washing and cleaning performance.
  • the detergent formulations of the invention do not just improve the washing power, i.e. actively help to remove soil from the fabric or from hard surfaces such as ceramic, glass, plastic and metal, but also prevent (re)deposition of detached soil and sparingly soluble salts of the water hardness ions on concomitantly washed fabric or hard surfaces, meaning that they have a graying- inhibiting and deposition-inhibiting effect.
  • particulate soil for example clay particles, soot particles and color pigments
  • sparingly soluble salts of the water hardness ions such as the carbonates and silicates of calcium(ll) and magnesium (II) ions. Because of their washing effect, they are especially suitable for formulation of laundry detergents.
  • the washing or cleaning or dishwashing composition portions of the invention comprise, detergent formulations of the invention. They may comprise washing-active or cleaning-active components as additives.
  • the washing or cleaning composition or dishwashing portions of the invention comprise measured amounts of at least one washing-active or cleaning-active composition within the detergent formulations. It is possible here that the washing composition or cleaning composition portions comprise just one individual washing- or cleaning-active composition. It is also possible that the washing composition or cleaning composition portions of the invention comprise two or more than two different washing- or cleaning-active compositions.
  • the different compositions may differ with regard to the concentration of the individual components (in quantitative terms) and/or with regard to the nature of the individual components (in qualitative terms). It is more preferable that the components, in terms of type and concentration, are matched to the tasks that the active ingredient portion packages have to fulfil in the washing or cleaning operation or dishwashing operation.
  • the detergent formulations of the invention are also advantageously suitable for production of dosage forms that resemble a so-called multichamber systems known from the prior art.
  • Those dosage forms have 2, 3, 4, 5 or more than 5 domains which each comprise a single component or a plurality of components of a washing or cleaning or dishwashing composition. This may in principle be a single washing- or cleaning-active ingredient, a single auxiliary or any desired mixture of two or more than two active ingredients and/or auxiliaries.
  • the constituents of the individual domains are preferably in solid form.
  • Those dosage forms are an option, for example, in order to separate components of a washing or cleaning or dishwashing composition that are incompatible or not very compatible from one another.
  • one domain may comprise one or more enzyme(s) and another domain at least one bleach.
  • Those dosage forms are also an option, for example, in order to facilitate controlled release of a particular component, for example at a certain time point in the washing or cleaning or dishwashing operation.
  • each domain may comprise an individual component or a plurality of components of the formulation, or the total amount of any component may be divided between two or more than two domains.
  • the washing composition or cleaning composition or dishwashing composition portions of the invention comprise at least one washing- or cleaning-active composition.
  • These compositions may be any desired substances or substance mixtures that are of relevance in connection with a washing or cleaning or dishwashing operation. These are primarily the actual washing compositions or cleaning compositions or dishwashing compositions with their individual components explained in detail hereinafter.
  • washing compositions are understood to mean those compositions which are used for cleaning of flexible materials having high absorptivity, for example of materials having a textile character
  • cleaning compositions in the context of the present invention are understood to mean those compositions which are used for cleaning of materials having a closed surface, i.e. having a surface which has only few small pores, if any, and as a result has only low absorptivity, if any.
  • Examples of flexible materials having high absorptivity are those which comprise or consist of natural, synthetic or semisynthetic fiber materials and which accordingly generally have at least some textile character.
  • the fibrous materials or those consisting of fibers may in principle be in any form that occurs in use or manufacture and processing.
  • fibers may be in unordered form in the form of staple or aggregate, in ordered form in the form of fibers, yarns, threads, or in the form of three dimensional structures such as nonwoven fabrics, lodens or felt, woven fabrics, knitted fabrics, in all conceivable binding types.
  • the fibers may be raw fibers or fibers in any desired stages of processing. Examples are natural protein or cellulose fibers, such as wool, silk, cotton, sisal, hemp or coconut fibers, or synthetic fibers, for example polyester, polyamide or polyacrylonitrile fibers.
  • Examples of materials having only few and small pores, if any, and having zero or only low absorptivity are metal, glass, enamel or ceramic.
  • Typical objects made of these materials are, for example, metallic sinks, cutlery, glass and porcelain dishware, bathtubs, washbasins, tiles, flags, cured synthetic resins, for example decorative melamine resin surfaces on kitchen furniture or painted metal surfaces, for example refrigerators and car bodies, printed circuit boards, microchips, sealed or painted woods, e.g. parquet or wall cladding, window frames, doors, plastics coverings such as floor coverings made of PVC or hard rubber, or rigid or flexible foams having substantially closed surfaces.
  • metal degreasers glass cleaners, floor cleaners, all-purpose cleaners, high-pressure cleaners, neutral cleaners, alkaline cleaners, acidic cleaners, spray degreasers, dairy cleaners, commercial kitchen cleaners, machinery cleaners in industry, especially the chemical industry, cleaners for carwashing, and also domestic
  • the washing or cleaning composition of the invention in form of a three dimensional body preferably comprises the following constituents:
  • further additive preferably selected from enzymes, enzyme stabilizers, bases, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, fillers, tableting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, bitter
  • the builder C also comprises compounds referred to as sequestrant, complexing agent, chelator, chelating agent or softener.
  • the bleach systems D) comprise, as well as bleaches, optionally also bleach activators, bleach catalysts and/or bleach stabilizers. More preferably, the washing and cleaning composition of the invention comprises at least one enzyme as additive E).
  • a preferred embodiment relates to washing or cleaning compositions in form of a three dimensional body, comprising:
  • At least one further additive preferably selected from enzymes, enzyme stabilizers, bases, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, fillers, tableting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, bitter substances, fluorescers, hydrotropes, antiredeposition agents, optical brighteners, graying inhibitors, antishrink agents, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, anti-yellowing agents, corrosion inhibitors, antistats, ironing aids, hydrophobizing and impregnating agents, antiswell and antislip agents and UV absorbers, and
  • at least one further additive preferably selected from enzymes, enzyme stabilizers, bases, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, fillers, tableting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, bitter substances
  • the percent by weight data relate to the total weight of the washing and cleaning composition.
  • the weight amounts of A) to F) add up to 100% by weight.
  • the washing or cleaning compositions in three dimensional form comprise at the most 25% by weight of water, more preferably at the most 15% by weight of water, especially at the most 10% by weight of water.
  • compositions of the invention comprise at least one surfactant as component B).
  • Suitable surfactants B) are nonionic, anionic, cationic or amphoteric surfactants.
  • surfactants B) which may be used in the context of the present invention include nonionic surfactants (NIS).
  • NIS nonionic surfactants
  • Nonionic surfactants used are preferably alkoxylated alcohols. Preference is given to alkoxylated primary alcohols.
  • Preferred alkoxylated alcohols are ethoxylated alcohols having preferably 8 to 18 carbon atoms in the alkyl radical and an average of 1 to 12 mol of ethylene oxide (EO) per mole of alcohol.
  • the alcohol radical may be linear or preferably 2-methyl-branched or may comprise linear and methyl-branched radicals in a mixture, as typically present in oxo process alcohol radicals.
  • alcohol ethoxylates having linear or branched radicals from alcohols of native or petrochemical origin having 12 to 18 carbon atoms, for example from coconut alcohol, palm alcohol, tallow alcohol or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol.
  • the ethoxylated alcohols are preferably selected from:
  • Ci2Ci4-alcohols with 3 EO, 5 EO, 7 EO or 9 EO,
  • Ci2Ci8-alcohols with 3 EO, 5 EO, 7 EO or 9 EO and mixtures thereof, 2-propylheptanol with 3 EO, 4 EO, 5 EO, 6 EO, 7 EO, 8 EO and 9 EO and mixtures of two or more than two of the aforementioned ethoxylated alcohols.
  • a preferred mixture of nonionic surfactants is a mixture of Ci2Ci4-alcohol (lauryl alcohol/myristyl alcohol) with 3 EO and C ⁇ Cis-alcohol (lauryl alcohol/myristyl alcohol/cetyl alcohol/stearyl alcohol) with 7 EO.
  • Preference is also given to mixtures of short-chain alcohol ethoxylates (e.g. 2-propylheptanol with 7 EO) and long-chain alcohol ethoxylates (e.g. C16C18 with 7 EO).
  • the stated ethoxylation levels are statistical averages (number averages, Mn), which may be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE).
  • NRE narrow range ethoxylates
  • fatty alcohols with more than 12 EO. Examples of these are tallow alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants comprising ethylene oxide (EO) and propylene oxide (PO) groups together in the molecule.
  • block copolymers with EO-PO block units or PO-EO block units, but also EO-PO-EO copolymers or PO-EO-PO copolymers. It is of course also possible to use mixedly alkoxylated nonionic surfactants in which EO and PO units are not in blocks but in random distribution. Such products are obtainable by simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.
  • Surfactants suitable as component B) are also polyetherols, preferably with a number- average molecular weight of at least 200 g/mol.
  • Suitable polyetherols may be linear or branched, preferably linear. Suitable polyetherols generally have a number-average molecular weight in the range from about 200 to 100000 g/mol, preferably 300 to 50000 g/mol, more preferably 500 to 40000 g/mol. Suitable polyetherols are, for example, water-soluble or water-dispersible nonionic polymers having repeat alkylene oxide units. Preferably, the proportion of repeat alkylene oxide units is at least 30% by weight, based on the total weight of the compound. Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers.
  • Suitable alkylene oxides for preparation of alkylene oxide copolymers are, for example, ethylene oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide. Suitable examples are copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide.
  • the alkylene oxide copolymers may comprise the copolymerized alkylene oxide units in randomly distributed form or in the form of blocks. Preferably, the proportion of repeat units derived from ethylene oxide in the ethylene oxide/propylene oxide copolymers is 40% to 99% by weight. Particular preference is given to ethylene oxide homopolymers and ethylene oxide/propylene oxide copolymers.
  • nonionic surfactants which may be used are also alkyl glycosides of the general formula (IV)
  • R 10 is a primary straight-chain or methyl-branched aliphatic radical having 8 to 22 carbon atoms
  • G is a glycoside unit having 5 or 6 carbon atoms, and i is any number between 1 and 10.
  • R 10 is preferably a 2-methyl-branched aliphatic radical having 8 to 22 and preferably 12 to 18 carbon atoms.
  • G is preferably glucose.
  • the oligomerization level i which states the distribution of monoglycosides and oligoglycosides, is preferably within a range from 1.2 to 1.4.
  • a further class of nonionic surfactants which are used with preference in the context of the present invention and are used either as the sole nonionic surfactant or in combination with other nonionic surfactants is that of alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.
  • fatty acid methyl esters as described, for example, in the Japanese patent application JP 58/217598, or those which are preferably prepared by the process described in the international patent application WO 90/13533.
  • nonionic surfactants are amine oxides, for example N-cocoalkyl-N,N- dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides. These nonionic surfactants are preferably used as a mixture with alkoxylated alcohols. Preference is given to the mixture with ethoxylated fatty alcohols. The weight amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • R 12 is hydrogen, an alkyl radical having 1 to 4 carbon atoms or a hydroxyalkyl radical having 1 to 4 carbon atoms
  • R 13 is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can typically be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides includes in this connection also compounds of the formula (VI) in which R 14 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 15 is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene radical having 6 to 8 carbon atoms, and R 16 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to Ci-C4-alkyl or phenyl radicals, and R 17 is a linear polyhydroxyalkyl radical wherein the alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • R 14 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 15 is a linear, branche
  • R 17 is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted to the desired polyhydroxy fatty acid amides, for example according to WO 95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • Suitable surfactants B) are also anionic surfactants.
  • anionic surfactants are soaps, alkylsulfonates, alkylbenzenesulfonates, olefinsulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ethercarboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, for example acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, alkylglucose carboxylates, protein fatty acid condensates and alkyl
  • a first preferred embodiment is that of anionic surfactants of the sulfonate and sulfate types.
  • Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzene sulfonates, olefinsulfonates, i.e. mixtures of alkene- and hydroxyalkanesulfonates, and disulfonates as obtained, for example, from Ci2-Ci8-monoolefins having a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from Ci2-Cis-alkanes, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis and/or neutralization.
  • esters of -sulfo fatty acids estersulfonates
  • anionic surfactants are sulfated fatty acid glycerol esters.
  • Fatty acid glycerol esters are understood to mean, inter alia, the mono-, di- and triesters, and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
  • Preferred sulfated fatty acid glycerol esters here are the sulfation products of saturated fatty acids having 6 to 22 carbon atoms, for example of caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Preferred alk(en)yl sulfates are the alkali metal and especially the sodium salts of the sulfuric monoesters of Ci2-Cis-fatty alcohols, for example of coconut alcohol, tallow alcohol or lauryl, myristyl, cetyl or stearyl alcohol, or of the C10-C20-OXO process alcohols and the monoesters of secondary Cio-C2o-alcohols.
  • alk(en)yl sulfates comprising a synthetic petrochemical-based straight-chain C10-C20- alkyl radical. These have analogous degradation behavior to the equivalent compounds based on oleochemical raw materials.
  • Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates preference is given to the Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates, and also Ci4-Ci5-alkyl sulfates.
  • 2,3-Alkyl sulfates which are prepared, for example, according to US patents 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the DAN® name, are also suitable anionic surfactants.
  • sulfuric monoesters of the straight-chain or branched C7-C21 alcohols which have been ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 to 4 EO.
  • EO ethylene oxide
  • C12-C18 fatty alcohols with 1 to 4 EO Owing to their high foaming level, they are conventionally used in cleaning compositions only in relatively small amounts, for example in amounts of 1 % to 5% by weight.
  • Suitable anionic surfactants in the context of the present invention are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and are the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates comprise Cs-Cis fatty alcohol radicals or mixtures of these.
  • Particularly preferred sulfosuccinates comprise a fatty alcohol radical derived from ethoxylated fatty alcohols.
  • sulfosuccinates wherein the fatty alcohol radicals are derived from ethoxylated fatty alcohols having a narrow homolog distribution. It is likewise also possible to use alk(en)ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.
  • Particularly preferred anionic surfactants are soaps.
  • Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and especially soap mixtures derived from natural fatty acids, for example coconut fatty acids, palm kernel fatty acids, olive oil fatty acids or tallow fatty acids.
  • the anionic surfactants including the soaps may be present in the form of their sodium, potassium or ammonium salts, or as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • Suitable surfactants B) are also cationic surfactants. Particularly preferred cationic surfactants are:
  • N,N-dimethyl-N-(hydroxy-C7-C25-alkyl)ammonium salts mono- and di(C7-C25-alkyl)dimethylammonium compounds quaternized with alkylating agents; ester quats, especially quaternary esterified mono-, di- and trialkanolamines esterified with C8-C22-carboxylic acids; imidazoline quats, especially 1-alkylimidazolinium salts of the formulae VII or VIII where the variables are defined as follows: R 18 is Ci-C 25 -alkyl or C2-C25-alkenyl,
  • R 19 is Ci-C4-alkyl or hydroxy-Ci -C h alky I
  • R 20 is Ci-C4-alkyl, hydroxy-Ci-C4-alkyl or an R 21 -(CO)-R 22 -(CH2)r radical where R 21 is H or Ci-C4-alkyl, R 22 is -O- or -NH- and r is 2 or 3, where at least one R 18 radical is a C7-C22-alkyl radical.
  • the surfactants B) may also be amphoteric surfactants.
  • Suitable amphoteric surfactants are alkyl betaines, alkyl amidobetaines, alkyl sulfobetaines, aminopropionates, aminoglycinates and amphoteric imidazolium compounds.
  • the content of surfactants in detergent formulation of the invention is preferably 2% to 40% by weight and especially 5% to 35% by weight, based in each case on the overall formulation.
  • Builders which are sometimes also referred to as sequestrant, complexing agent, chelator, chelating agent or softener, bind alkaline earth metals and other water-soluble metal salts without precipitation. They help to break up soil, disperse soil particles and help to detach soil, and sometimes themselves have a washing effect.
  • Suitable builders may either be organic or inorganic in nature. Examples are aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, e.g. hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and salts thereof and polymeric compounds containing carboxylic acid groups, and salts thereof.
  • Suitable inorganic builders are, for example, crystalline or amorphous aluminosilicates having ion-exchanging properties, such as zeolites.
  • zeolites are suitable, especially zeolites A, X, B, P, MAP and HS in their sodium form or in forms in which sodium has been partly exchanged for other cations such as Li, K, Ca, Mg or ammonium.
  • Suitable zeolites are described, for example, in US-A-4604224.
  • Crystalline silicates suitable as builders are, for example, disilicates or sheet silicates, e.g. 5- Na2Si2C>5 or B-ls ⁇ ShOs (SKS 6 or SKS 7).
  • the silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as sodium, lithium and magnesium silicates.
  • amorphous silicates for example sodium metasilicate having a polymeric structure, or amorphous disilicate (Britesil® H 20, manufacturer: Akzo). Among these, preference is given to sodium disilicate.
  • Suitable inorganic builder substances based on carbonate are carbonates and hydrogencarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to using sodium carbonates and hydrogencarbonates, lithium carbonates and hydrogencarbonates and magnesium carbonates and hydrogencarbonates, especially sodium carbonate and/or sodium hydrogencarbonate.
  • Customary phosphates used as inorganic builders are alkali metal orthophosphates and/or polyphosphates, for example pentasodium triphosphate.
  • Suitable organic builders are, for example, C4-C3o-di-, -tri- and -tetracarboxylic acids, for example succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acids having C2-C20- alkyl or -alkenyl radicals.
  • Suitable organic builders are also hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids).
  • C4-C20-hydroxycarboxylic acids for example malic acid, tartaric acid, gluconic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid, and sucrosemono-, -di- and - tricarboxylic acid.
  • citric acid and salts thereof preference is given to citric acid and salts thereof.
  • Suitable organic builders are additionally phosphonic acids, for example hydroxy alkylphosphonic acids, aminophosphonic acids and the salts thereof. These include, for example, phosphonobutanetricarboxylic acid, aminotrismethylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, hexamethylenediaminetetramethylene phosphonic acid, diethylenetriaminepentamethylenephosphonic acid, morpholino methanediphosphonic acid, 1-hydroxy-Ci- to -Cio-alkyl-1 ,1-diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid. Among these, preference is given to 1-hydroxyethane-1,1-diphosphonic acid and salts thereof.
  • Suitable organic builders are also aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic dipropionic acid, nitrilotripropionic acid, b-alaninediacetic acid (b-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, propylene-1 ,3-diaminetetraacetic acid, propylene-1 ,2-diaminetetraacetic acid, N-(alkyl)ethylenediaminetriacetic acid, N-(hydroxyalkyl)-ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cyclohexylene-1 ,2-diaminetetraacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid, serinediacetic acid, isoserinediacetic acid, L-as
  • methylglycinediacetic acid Preference is given to methylglycinediacetic acid, glutamic acid diacetic acid and salts thereof.
  • the salts of methylglycinediacetic acid may be in racemic form, meaning that D and L enantiomers are present in an equimolar mixture, or one enantiomer, e.g. the L enantiomer, may be present in excess.
  • Suitable organic builders are also polymeric compounds containing carboxylic acid groups, such as acrylic acid homopolymers. These preferably have a number-average molecular weight in the range from 800 to 70000 g/mol, more preferably from 900 to 50000 g/mol, particularly 1000 to 20 000 g/mol and especially 1000 to 10000 g/mol.
  • acrylic acid homopolymer also encompasses polymers in which the carboxylic acid groups are in partly or fully neutralized form. These include acrylic acid homopolymers in which the carboxylic acid groups are present partly or completely in the form of alkali metal salts or ammonium salts.
  • acrylic acid homopolymers in which the carboxylic acid groups are protonated or are partly or completely in the form of sodium salts.
  • Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids, as described, for example, in EP-A 451 508 and EP-A 396 303.
  • Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated C4-C8 dicarboxylic acids, which may include copolymerized monoethylenically unsaturated monomers from the group (i) mentioned below in amounts of up to 95% by weight, from the group (ii) in amounts of up to 60% by weight and from the group (iii) in amounts of up to 20% by weight as comonomers.
  • Suitable unsaturated C4-C8 dicarboxylic acids here are, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid.
  • Group (i) encompasses monoethylenically unsaturated C3-C8 monocarboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.
  • Group (ii) encompasses monoethylenically unsaturated C2-C22 olefins, vinyl alkyl ethers having Ci-Cs-alkyl groups, styrene, vinyl esters of Ci-Cs carboxylic acids, (meth)acrylamide and vinylpyrrolidone.
  • group (ii) preference is given to using C2-C6 olefins, vinyl alkyl ethers having Ci-C4-alkyl groups, vinyl acetate and vinyl propionate. If the polymers of group (ii) comprise copolymerized vinyl esters, these may also be in partly or fully hydrolyzed form to give vinyl alcohol structural units. Suitable co- and terpolymers are known, for example, from US-A 3887806 and DE-A 4313909. Group (iii) encompasses (meth)acrylic esters of Ci-Cs alcohols, (meth)acrylonitrile, (meth)acrylamides of Ci-Cs amines, N-vinylformamide and N-vinylimidazole.
  • Suitable polymeric compounds containing carboxylic acid groups are also homopolymers of the monoethylenically unsaturated C3-C8 monocarboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, especially of acrylic acid and methacrylic acid, copolymers of dicarboxylic acids, for example copolymers of maleic acid or itaconic acid and acrylic acid in a weight ratio of 10:90 to 95:5, more preferably those in a weight ratio of 30:70 to 90:10 with molar masses of 1000 to 150000 g/mol; terpolymers of maleic acid, acrylic acid and a vinyl ester of a
  • C1-C3 carboxylic acid in a weight ratio of 10 (maleic acid):90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), where the weight ratio of acrylic acid to the vinyl ester may vary within the range from 30:70 to 70:30; copolymers of maleic acid with C2-C8 olefins in a molar ratio of 40:60 to 80:20, particular preference being given to copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50.
  • Suitable polymeric compounds containing carboxylic acid groups are also copolymers of 50% to 98% by weight of ethylenically unsaturated weak carboxylic acids with 2% to 50% by weight of ethylenically unsaturated sulfonic acids, as described, for example, in
  • Suitable weak ethylenically unsaturated carboxylic acids are especially C3-C6 monocarboxyl ic acids, such as acrylic acid and methacrylic acid.
  • Suitable ethylenically unsaturated sulfonic acids are 2-acetylamidomethyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-hydroxy propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1 -sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfo
  • the copolymers may also comprise 0% to 30% by weight of copolymerized ethylenically unsaturated C4-C8 dicarboxylic acids, such as maleic acid, and 0% to 30% by weight of at least one monomer copolymerizable with the aforementioned monomers.
  • the latter monomer comprises, for example, Ci-C4-alkyl esters of (meth)acrylic acid, Ci-C4-hydroxyalkyl esters of (meth)acrylic acid, acrylamide, alkyl-substituted acrylamide, N,N-dialkyl- substituted acrylamide, vinylphosphonic acid, vinyl acetate, allyl alcohols, sulfonated allyl alcohols, styrene and other vinylaromatics, acrylonitrile, N-vinylpyrrolidone, N-vinyl formamide, N-vinylimidazole or N-vinylpyridine.
  • the weight-average molecular weight of these copolymers is in the range from 3000 to 50 000 daltons.
  • Copolymers with about 77% by weight of at least one ethylenically unsaturated C3-C6 monocarboxylic acid and about 23% by weight of at least one ethylenically unsaturated sulfonic acid are particularly suitable.
  • Graft polymers of unsaturated carboxylic acids onto low molecular weight carbohydrates or hydrogenated carbohydrates are likewise suitable.
  • Suitable unsaturated carboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, and mixtures of acrylic acid and maleic acid, which are grafted on in amounts of 40% to 95% by weight, based on the component to be grafted.
  • Suitable modifying monomers are the aforementioned monomers of groups (ii) and (iii).
  • polyglyoxylic acids as described, for example, in EP-B-001004, US-A-5399286, DE-A-4106355 and EP-A-656914.
  • the end groups of the polyglyoxylic acids can have different structures.
  • polyamidocarboxylic acids and modified polyamidocarboxylic acids are known, for example, from EP-A-454126, EP-B-511037, WO-A94/01486 and EP-A-581452.
  • polyaspartic acids and the alkali metal salts thereof or cocondensates of aspartic acid with other amino acids, for example with glycine, glutamic acid or lysine, C4-C25 mono- or dicarboxylic acids and/or C4-C25 mono- or diamines as polymeric compounds containing carboxylic acid groups.
  • polymeric compounds containing carboxylic acid groups preference is given to polyacrylic acids, also in partly or fully neutralized form.
  • Suitable organic builders are also iminodisuccinic acid, oxydisuccinic acid, amino polycarboxylates, alkylpolyaminocarboxylates, aminopolyalkylenephosphonates, polyglutamates, hydrophobically modified citric acid, for example agaric acid, poly- [alpha]-hydroxyacrylic acid, N-acylethylenediamine triacetates such as lauroylethylene diamine triacetate, and alkylamides of ethylenediaminetetraacetic acid such as EDTA tallow amide.
  • oxidized starches as organic builders.
  • the bleach systems D) comprise at least one bleach and optionally at least one further component selected from bleach activators, bleach catalysts and bleach stabilizers.
  • Suitable bleaches are, for example, percarboxylic acids, e.g. diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or -terephthalic acid, salts of percarboxylic acids, e.g. sodium percarbonate, adducts of hydrogen peroxide onto inorganic salts, e.g. sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of hydrogen peroxide onto organic compounds, e.g. urea perhydrate, or of inorganic peroxo salts, e.g.
  • percarboxylic acids e.g. diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or -terephthalic acid
  • salts of percarboxylic acids e.g. sodium percarbonate
  • alkali metal persulfates or peroxodisulfates.
  • Suitable bleach activators are, for example, polyacylated sugars, e.g. pentaacetylglucose; acyloxybenzenesulfonic acids and their alkali metal and alkaline earth metal salts, e.g. sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate; - N,N-diacylated and N,N,N',N'-tetraacylated amines, e.g.
  • N,N,N',N'-tetraacetylmethylenediamine and -ethylenediamine TAED
  • N,N-diacetylaniline N,N-diacetyl-p-toluidine or 1 ,3-diacylated hydantoins such as 1 ,3-diacetyl-5,5-dimethylhydantoin
  • N-alkyl-N-sulfonylcarboxamides e.g. N-methyl-N- mesylacetamide or N-methyl-N-mesylbenzamide
  • N-acylated cyclic hydrazides acylated triazoles or urazoles, e.g.
  • monoacetylmaleic hydrazide O,N,N-trisubstituted hydroxylamines, e.g. 0-benzoyl-N,N-succinylhydroxylamine, 0-acetyl-N,N-succinyl hydroxylamine or O,N,N-triacetylhydroxylamine; N,N'-diacylsulfurylamides, e.g.
  • oxime esters and bisoxime esters for example O-acetylacetone oxime or bisisopropyliminocarbonate
  • carboxylic anhydrides e.g. acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride
  • enol esters for example isopropenyl acetate
  • 1,3-diacyl-4,5-diacyloxyimidazolines e.g. 1 ,3-diacetyl-
  • 2.5-diketopiperazines e.g. 1,4-diacetyl-2,5-diketopiperazine; ammonium-substituted nitriles, for example N-methylmorpholinioacetonitrile methylsulfate; acylation products of propylenediurea and 2,2-dimethylpropylenediurea, e.g. tetraacetylpropylenediurea; a-acyloxypolyacylmalonamides, e.g. a-acetoxy-N,N'-diacetylmalonamide; diacyldioxohexahydro-1 ,3,5-triazines, e.g.
  • a bleach system composed of bleaches and bleach activators may optionally also comprise bleach catalysts.
  • Suitable bleach catalysts are, for example, quaternized imines and sulfonimines, which are described, for example, in US-A 5360569 and EP-A 453 003.
  • Particularly effective bleach catalysts are manganese complexes, which are described, for example, in WO-A 94/21777.
  • such compounds are incorporated in maximum amounts of up to 1.5% by weight, especially up to 0.5% by weight, and in the case of very active manganese complexes in amounts of up to 0.1 % by weight.
  • the bleach system composed of bleaches, bleach activators and optionally bleach catalysts described the use of systems with enzymatic peroxide release or of photoactivated bleach systems is also possible for the washing and cleaning compositions of the invention.
  • component E1 Suitable enzymes are those as customarily used as industrial enzymes. These include both enzymes with optimal activity in the neutral to alkaline pH range and enzymes with optimal activity in the acidic pH range.
  • component E1) additionally comprises at least one enzyme stabilizer. Suitable enzyme stabilizers E1) are those as customarily used.
  • the enzymes are preferably selected from aminopeptidases, amylases, arabinases, carbohydrases, carboxypeptidases, catalases, cellulases, chitinases, cutinases, cyclodextrin glycosyltransferases, deoxyribonucleases, esterases, galactanases, alpha-galactosidases, beta-galactosidases, glucanases, glucoamylases, alpha- glucosidases, beta-glucosidases, haloperoxidases, hydrolase invertases, isomerases, keratinases, laccases, lipases, mannanases, mannosidases, oxidases, pectinolytic enzymes, peptidoglutaminases, peroxidases, peroxygenases, phytases, polyphenol oxidases, proteolytic enzymes, rib
  • the enzymes are specifically selected from hydrolases, such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannanases, other glycosyl hydrolases and mixtures of the aforementioned enzymes. All these hydrolases contribute to soil dissolution and removal of protein-, grease- or starch-containing soiling. Oxireductases can also be used for bleaching. Of particularly good suitability are enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens.
  • Suitable proteolytic enzymes may in principle be of animal, vegetable or microbial origin. Preference is given to proteolytic enzymes of microbial origin. These also include chemically or genetically modified mutants.
  • Suitable lipases may in principle originate from bacteria or fungi. These also include chemically or genetically modified mutants.
  • Amylases In principle, all a- and/or b-amylases are suitable. Suitable amylases may in principle originate from bacteria or fungi. These also include chemically or genetically modified mutants.
  • Suitable cellulases may in principle originate from bacteria or fungi. These also include chemically or genetically modified mutants.
  • Suitable peroxidases/oxidases may in principle originate from plants, bacteria or fungi. These also include chemically or genetically modified mutants.
  • lyases are suitable. Suitable lyases may in principle originate from bacteria or fungi. These also include chemically or genetically modified mutants.
  • compositions of the invention may comprise further enzymes which are referred to collectively by the term hemicellulases.
  • the washing or cleaning composition of the invention comprises at least one enzyme selected from proteases, amylases, mannanases, cellulases, lipases, pectin lyases and mixtures thereof.
  • the washing or cleaning composition of the invention comprises at least one protease and/or amylase.
  • the washing, cleaning or dishwashing composition of the invention comprises an enzyme mixture.
  • enzyme mixtures comprising or consisting of the following enzymes: protease and amylase, protease and lipase (or lipolytic enzymes), protease and cellulase, amylase, cellulase and lipase (or lipolytic enzymes), protease, amylase and lipase (or lipolytic enzymes), protease, lipase (or lipolytic enzymes) and cellulase.
  • the enzymes can be adsorbed onto carrier substances in order to protect them from premature decomposition.
  • the washing or cleaning composition of the invention may optionally also comprise enzyme stabilizers E1).
  • These include, for example, calcium propionate, sodium formate, boric acids, boronic acids and salts thereof, such as 4-formylphenylboronic acid, peptides and peptide derivatives, for example peptide aldehydes, polyols, such as propane-1 ,2-diol, and mixtures thereof.
  • the detergent formulation of the invention comprises the enzymes preferably in an amount of 0.1% to 5% by weight, more preferably 0.12% to 2.5% by weight, based on the total weight of the detergent formulation.
  • the detergent formulation comprises one or more separate domains comprising at least one enzyme.
  • the enzyme in the separate domains is preferably in an amount of 0.1% to 5% by weight, more preferably 0.12% to 2.5% by weight, based on the total weight of the detergent formulation.
  • they are selected from ethanol, n- or isopropanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or -ethyl ether, diisopropylene glycol monomethyl or -ethyl ether, methoxy, ethoxy or butoxy triglycol, isobutoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, and mixtures
  • Useful foam inhibitors or defoamers are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable bases are alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, ammonium carbonate, alkali metal hydrogencarbonates, alkaline earth metal hydrogencarbonates, ammonium hydrogencarbonates and mixtures thereof. Preference is given to using sodium, lithium and magnesium carbonates or sodium, lithium and magnesium hydrogencarbonates, especially sodium carbonate and/or sodium hydrogencarbonate.
  • the washing or cleaning compositions of the invention may comprise further additives E6) which further improve the performance and/or aesthetic properties.
  • compositions comprise, in addition to the aforementioned components, at least one further additive selected from electrolytes, pH modifiers, perfume carriers, bitter substances, fluorescers, hydrotropes, antiredeposition agents, optical brighteners, graying inhibitors, antishrink agents, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, anti-yellowing agents, corrosion inhibitors, antistats, ironing aids, hydrophobizing and impregnating agents, antiswell and antislip agents, and UV absorbers.
  • at least one further additive selected from electrolytes, pH modifiers, perfume carriers, bitter substances, fluorescers, hydrotropes, antiredeposition agents, optical brighteners, graying inhibitors, antishrink agents, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, anti-yellowing agents, corrosion inhibitors, antistats, ironing aids, hydrophobizing and impregnating agents, antiswell and antislip agents, and UV absorbers.
  • Suitable dye transfer inhibitors are especially homo- or copolymers comprising at least one copolymerized monomer selected from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, salts of the three latter monomers, 4-vinylpyridine N-oxide, N-carboxymethyl-4-vinylpyridinium halides and mixtures thereof.
  • Suitable graying inhibitors and/or washing power boosters are especially: carboxymethylcellulose, graft polymers of vinyl acetate onto carbohydrates, for example onto degraded starch, graft polymers of vinyl acetate onto polyethylene glycol, alkoxylated oligo- and polyamines, e.g. ethoxylated hexamethylenediamine, which may additionally also be in quaternized and/or sulfated form, or alkoxylated polyethyleneimine with 16 to 24 EO per NH, copolymers based on styrene and maleic acid which may additionally also have been modified with end group-capped polyethylene glycol, copolymers based on styrene and acrylic acid.
  • carboxymethylcellulose graft polymers of vinyl acetate onto carbohydrates, for example onto degraded starch
  • graft polymers of vinyl acetate onto polyethylene glycol alkoxylated oligo- and polyamines, e.g. ethoxylated
  • dyes In order to improve the aesthetic impression of the washing, cleaning or dishwashing compositions of the invention, they can be colored with suitable dyes.
  • Preferred dyes the selection of which does not present any difficulty at all to the person skilled in the art, have high storage stability and insensitivity to the other constituents of the compositions and to light, and also no marked substantivity with respect to textile fibers, in order not to stain them.
  • the washing, cleaning or dishwashing compositions of the invention may comprise at least one bitter substance.
  • bitter substances are specially used in order to prevent inadvertent swallowing of the compositions, for example by infants.
  • Suitable bitter substances are known to those skilled in the art. These include, for example, denatonium benzoate (benzyldiethyl-(2,6-xylylcarbamoyl)methylammonium benzoate), the bitterest-tasting substance known to date, which is commercially available under the Bitrex® name.
  • the above-described detergent formulations of the invention are also particularly advantageously suitable for dishwashing detergents, especially of dishwashing detergents for machine dishwashing processes (automatic dishwashing, ADW).
  • the polymer composition P1) present in the detergent formulations exerts a dispersing, film-inhibiting, emulsifying and/or surfactant effect in dishwashing detergents. In addition, they ensure good rinse aid and/or drying performance.
  • formulations of the invention for dishwashing include machine dishwashing compositions, rinse aids and machine dishwashing detergents with rinse aid function.
  • Machine dishwashing processes in the domestic and commercial sector comprise a plurality of successive steps, the first comprising the mechanical removal of loosely adhering food residues and the second the actual cleaning operation with the aid of a machine dishwasher, and the third generally consisting of a rinsing step, which is followed by the drying of the cleaned dishware.
  • These operations are conducted in more or less automated form, the central unit used being a machine dishwasher in which at least the cleaning step and generally also the subsequent rinsing step and/or the drying step are conducted.
  • the soiled dishware is generally cleaned in a single chamber, and the aforementioned treatment steps proceed successively in a controlled program.
  • Fresh water passes through the softening unit to the pump well and is sprayed by means of moving spray arms over the ware to be rinsed.
  • Water-insoluble substances rinsed off are filtered out in the pump well.
  • a generally alkaline cleaning composition is added to the rinse water, heated to the set temperature and distributed over the ware to be rinsed.
  • a rinse aid is added to the treatment liquid, which reduces the surface tension, as a result of which the treatment liquid runs more easily off the ware. After the last rinse cycle, the contents are dried.
  • the components used in the rinse cycle can be used either in the form of individual components or in multicomponent formulations.
  • Multifunctional detergents of this kind comprise surfactants for rinsing and a polymer for water softening. In that case, it is unnecessary to separately dispense a rinse aid and a salt for water softening into the machine dishwasher.
  • Commercial machine dishwashers consist basically of stationary bath tanks from which an essentially aqueous cleaning solution is jetted or sprayed onto the dishware, which moves past these baths on a conveyor belt, such that the used solution flows back into the bath tanks again.
  • the application of a generally highly alkaline cleaning solution generally takes place with the aid of nozzles provided therefor, or of a specific spraying system normally arranged in the middle region of the machine.
  • the detergent formulations of the invention are suitable for dishwashing compositions for machine dishwashing, which especially feature excellent film-inhibiting action.
  • Preferred machine dishwashing composition formulations have inhibiting action with respect to both inorganic and organic film deposits.
  • the inorganic film deposits are especially calcium and magnesium phosphate, calcium and magnesium carbonate, calcium and magnesium silicate and/or calcium and magnesium phosphonate, which arise from the calcium and magnesium salts present in the water and the builders present in standard dishwashing compositions.
  • the organic film deposits are especially soil constituents from the rinse liquor, for example protein, starch and fat deposits.
  • formulations used in accordance with the invention for machine dishwashing are also effective against carry-over deposits, which originate from the residual water in the bottom of the machine dishwasher and comprise, inter alia, dishwashing composition residues and possibly also soil residues from the previous wash cycle of the machine dishwasher.
  • the dishwashing composition in form of a three-dimensonal body of the invention preferably comprises the following constituents:
  • Gb optionally at least one complexing agent
  • Gc at least one builder and/or cobuilder
  • Gd at least one nonionic surfactant
  • Ge optionally at least one component selected from bleaches, bleach activators and bleach catalysts,
  • Gf optionally at least one enzyme
  • Gg optionally at least one further additive, preferably selected from anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, bitter substances, fillers, tablet disintegrants, organic solvents, tableting aids, disintegrants, thickeners and solubilizers,
  • further additive preferably selected from anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, bitter substances, fillers, tablet disintegrants, organic solvents, tableting aids, disintegrants, thickeners and solubilizers,
  • a preferred dishwashing composition in form of a three dimensional body of the invention comprises: Ga) 25% to 98.8% by weight of at least one polymer composition P1 ),
  • Gc 0.1 % to 70% by weight of at least one builder and/or cobuilder
  • Gd 0.1 % to 35% by weight of at least one nonionic surfactant
  • Ge 0% to 30% by weight of at least one component selected from bleaches, bleach activators and bleach catalysts,
  • Gg 0% to 50% by weight of at least one further additive, preferably selected from anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, bitter substances, fillers, tablet disintegrants, organic solvents, tableting aids, disintegrants, thickeners and solubilizers, and Gh) 0% to 20% by weight of water, with the proviso that the weights of the components add up to 100% by weight.
  • at least one further additive preferably selected from anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, bitter substances, fillers, tablet disintegrants, organic solvents, tableting aids, disintegrants, thickeners and solubilizers, and Gh) 0% to 20% by weight of water, with the proviso that the weights of the components add up to 100% by weight.
  • Complexing agents Gb) which may be used are, for example: nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid, aspartic acid diacetic acid, and also salts thereof in each case.
  • Preferred complexing agents Gb) are methylglycinediacetic acid and glutamic acid diacetic acid and salts thereof.
  • Particularly preferred complexing agents Gb) are methylglycinediacetic acid and salts thereof, especially the mono-, di- and trisodium, -potassium, -lithium and -ammonium salts.
  • the salts of methylglycinediacetic acid may be in racemic form, meaning that D and L enantiomers are present in an equimolar mixture, or one enantiomer, e.g. the L enantiomer, may be present in excess. Preference is given in accordance with the invention to 3% to 50% by weight of complexing agent Gb).
  • Builders and/or co-builders Gc) used may especially be water-soluble or water- insoluble substances having the main task of binding calcium and magnesium ions.
  • These may be low molecular weight carboxylic acids and also salts thereof such as alkali metal citrates, in particular anhydrous trisodium citrate or trisodium citrate dihydrate, alkali metal succinates, alkali metal malonates, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate and a-hydroxypropionic acid.
  • a further substance class with cobuilder properties which may be present in the dishwashing compositions of the invention is that of the phosphonates.
  • These are in particular hydroxyalkanephosphonates or aminoalkanephosphonates.
  • 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular significance as cobuilder. It is preferably used in the form of the sodium salt, the disodium salt giving a neutral reaction and the tetrasodium salt an alkaline reaction (pH 9).
  • Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and the higher homologs thereof.
  • the neutral sodium salts for example as the hexasodium salt of EDTMP or as heptasodium and octasodium salts of DTPMP.
  • the builder used in this case is from the class of the phosphonates, preferably HEDP.
  • Aminoalkanephosphonates additionally have a pronounced heavy metal binding capacity. Accordingly, it may be preferable to use aminoalkanephosphonates, particularly DTPMP, or mixtures of the phosphonates mentioned, particularly if the compositions also comprise bleach.
  • Silicates may be used, inter alia, as builders. Crystalline sheet silicates having the general formula NaMSi x C>2 x+i yH 2 0 may be present, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably 0 to 20.
  • amorphous sodium silicates having an S1O2: Na20 ratio of 1 to 3.5, preferably 1.6 to 3 and in particular 2 to 2.8 may be used.
  • builders and/or co-builders Gc) used may be carbonates and hydrogen carbonates, among which the alkali metal salts, particularly sodium salts, are preferred.
  • the cobuilders used may be homopolymers and copolymers of acrylic acid or methacrylic acid preferably having a weight-average molar mass of 2000 to 50000 g/mol.
  • Suitable comonomers are in particular monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and also anhydrides thereof such as maleic anhydride.
  • comonomers containing sulfonic acid groups such as 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid and methanesulfonic acid.
  • Hydrophobic comonomers are also suitable, for example isobutene, diisobutene, styrene, alpha-olefins with 10 or more carbon atoms.
  • Hydrophilic monomers having hydroxyl functions or alkylene oxide groups may also be used as comonomers. Examples include: allyl alcohol and isoprenol and also alkoxylates thereof and methoxypolyethylene glycol (meth)acrylate.
  • the dishwashing formulation of the invention preferably comprise builders and/or cobuilders Gc) in an amount of 5% to 80% by weight, more preferably 10% to 75% by weight, especially 15% to 70% by weight, more especially 15% to 65% by weight, based on the total weight of the dishwashing formulation.
  • Suitable nonionic surfactants Gd) are, for example, weakly foaming or low-foaming nonionic surfactants.
  • the dishwashing formulation of the invention comprise nonionic surfactants preferably in an amount of 0.1 % to 20% by weight, more preferably of 0.1 % to 15% by weight, especially of 0.25% to 10% by weight, especially of 0.5% to 10% by weight, based on the total weight of the dishwashing formulation.
  • Suitable nonionic surfactants include surfactants of the general formula (IX)
  • R 31 -0-(CH 2 CH20)a-(CHR 32 CH 2 0)b-R 33 (IX), in which R 31 is a linear or branched alkyl radical having 8 to 22 carbon atoms,
  • surfactants of formula (X) R 34 -0-[CH 2 CH(CH 3 )0] c [CH 2 CH 2 0] d [CH 2 CH(CH 3 )0] e CH 2 CH(0H)R 35 (X), in which R 34 is a linear or branched aliphatic hydrocarbyl radical having 4 to 22 carbon atoms or mixtures thereof,
  • R 35 is a linear or branched hydrocarbyl radical having 2 to 26 carbon atoms or refers to mixtures thereof, c and e have values between 0 and 40, and d is a value of at least 15.
  • surfactants of formula (XI) are also suitable in the context of the present invention.
  • R 36 is a branched or unbranched alkyl radical having 8 to 16 carbon atoms
  • R 37 , R 38 are each independently H or a branched or unbranched alkyl radical having 1 to 5 carbon atoms
  • R 39 is an unbranched alkyl radical having 5 to 17 carbon atoms
  • f, h are each independently a number from 1 to 5
  • g is a number from 13 to 35.
  • the surfactants of the formulae (IX), (X) and (XI) may be either random copolymers or block copolymers; they are preferably block copolymers.
  • di- and multi-block copolymers constructed from ethylene oxide and propylene oxide can be used, which are commercially available, for example, under the name Pluronic ® (BASF SE) or Tetronic ® (BASF Corporation).
  • reaction products of sorbitan esters with ethylene oxide and/or propylene oxide can be used. Amine oxides or alkyl glycosides are also suitable.
  • An overview of suitable nonionic surfactants are disclosed in EP-A 851 023 and DE-A 198 19 187.
  • the dishwashing compositions of the invention may further comprise anionic or zwitterionic surfactants, preferably in a mixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are likewise specified in EP-A 851 023 and DE-A 198 19 187.
  • Bleaches and bleach activators Ge) used in connection with the dishwashing compositions of the invention may be representatives known to those skilled in the art. Bleaches are subdivided into oxygen bleaches and chlorine bleaches. Oxygen bleaches used are alkali metal perborates and hydrates thereof, and also alkali metal percarbonates. Preferred bleaches in this context are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate. Likewise useable as oxygen bleaches are persulfates and hydrogen peroxide.
  • Typical oxygen bleaches are also organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1 ,12-diperoxydodecanedioic acid, 1 ,9-diperoxyazelaic acid, diperoxoisophthalic acid or2-decyldiperoxybutane-1 ,4-dioic acid.
  • the following oxygen bleaches can also be used in the dishwashing composition: cationic peroxy acids, which are described in the patent applications US 5,422,028,
  • Oxygen bleaches can be used in amounts of generally 0.1 % to 30% by weight, preferably of 1 % to 20% by weight, more preferably of 3% to 15% by weight, based on the overall dishwashing formulation.
  • Chlorine bleaches and the combination of chlorine bleaches with peroxide bleaches can also be used in connection with the dishwashing compositions of the invention.
  • Known chlorine bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N,N ' -dichlorobenzoyl urea, p-toluenesulfonedichloroamide or trichloroethylamine.
  • Chlorine bleaches in this connection can be used in amounts of 0.1 % to 30% by weight, preferably of 0.1 % to 20% by weight, preferably of 0.2% to 10% by weight, more preferably of 0.3% to 8% by weight, based on the overall dishwashing formulation.
  • bleach stabilizers for example phosphonates, borates, metaborates, metasilicates or magnesium salts, may be added.
  • Bleach activators in the context of the present invention can be compounds which, under perhydrolysis conditions, give rise to aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or substituted perbenzoic acid.
  • suitable compounds comprise, inter alia, one or more N- or O-acyl groups and/or optionally substituted benzoyl groups, for example substances from the class of the anhydrides, esters, imides, acylated imidazoles or oximes.
  • TAED tetraacetylethylenediamine
  • TAMD tetraacetylmethylenediamine
  • TAGU tetraacetylglycoluril
  • TAHD tetraacetylhexylenediamine
  • N-acylimides such as N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates such as n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), pentaacetylglucose (PAG), 1 ,5-diacetyl-2,2-dioxohexahydro-1 ,3,5-triazine (DADHT) or isatoic anhydride (ISA).
  • NOSI N-nonanoylsuccinimide
  • acylated phenol sulfonates such as n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS)
  • PAG pentaacetylglucose
  • DADHT 1 ,5-diacetyl-2,2-dioxohex
  • bleach activators are nitrile quats such as N-methylmorpholinium acetonitrile salts (MM A salts) or trimethylammonium acetonitrile salts (TMAQ salts).
  • Preferred suitable bleach activators are from the group consisting of polyacylated alkylenediamines, more preferably TAED, N-acylimides, more preferably NOSI, acylated phenolsulfonates, more preferably n- or iso-NOBS, MM A, and TMAQ.
  • Bleach activators in connection with the present invention can be used in amounts of 0.1 % to 30% by weight, preferably of 0.1 % to 10% by weight, preferably of 1 % to 9% by weight, more preferably of 1.5% to 8% by weight, based on the overall dishwashing formulation.
  • bleach catalysts may also be incorporated in rinse aid particles. These substances are bleach enhancing transition metal salts or transition metal complexes such as salen complexes or carbonyl complexes of manganese, iron, cobalt, ruthenium or molybdenum. Also usable as bleach catalysts are complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper with nitrogen- containing tripod ligands and also amine complexes of cobalt, iron, copper and ruthenium.
  • the dishwashing compositions of the invention may comprise 0% to 8% by weight of enzymes. If the dishwashing compositions comprise enzymes, they comprise them preferably in amounts of 0.1 % to 8% by weight. Enzymes may be added to the dishwashing composition in order to increase the cleaning performance or to ensure the same quality of cleaning performance under milder conditions (e.g. at low temperatures).
  • the enzymes can be used in free form or a form chemically or physically immobilized on a support or in encapsulated form.
  • the enzymes used most frequently in this context include lipases, amylases, cellulases and proteases.
  • esterases, pectinases, lactases and peroxidases Preference is given in accordance with the invention to using amylases and proteases.
  • additives Gg) used may be, for example, anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tablet disintegrants, organic solvents, tableting aids, disintegrants, thickeners, solubilizers or water.
  • the alkali carriers used may be, for example, in addition to the ammonium or alkali metal carbonates already mentioned as builder substances, ammonium or alkali metal hydrogencarbonates and ammonium or alkali metal sesquicarbonates, and also ammonium or alkali metal hydroxides, ammonium or alkali metal silicates and ammonium or alkali metal metasilicates and also mixtures of the aforementioned substances.
  • the corrosion inhibitors used may be, inter alia, silver anticorrosives from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes.
  • glass corrosion inhibitors are, for example, magnesium, zinc and bismuth salts and complexes and polyethyleneimines.
  • Paraffin oils and silicone oils may optionally be used in accordance with the invention as defoamers and to protect plastics and metal surfaces. Defoamers are used preferably in proportions of 0.001% by weight to 5% by weight.
  • dyes for example patent blue, preservatives, for example Kathon CG, perfumes and other fragrances may be added to the cleaning formulation of the invention.
  • An example of a suitable filler in connection with the dishwashing compositions of the invention is sodium sulfate.
  • amphoteric and cationic polymers include amphoteric and cationic polymers.
  • they can be colored using suitable dyes.
  • Preferred dyes the selection of which presents no difficulty whatsoever to the person skilled in the art, have a high storage stability and insensitivity with respect to the other ingredients of the compositions and to light, and do not have any marked substantivity toward textile fibers, in order not to stain them. cleaners
  • the detergent formulations of the invention are also suitable for industrial and institutional cleaners (I & I cleaners).
  • Industrial and institutional cleaners are typically washing compositions, all-purpose cleaners, foam cleaners, CIP (cleaning in place) cleaners for professional and generally automated cleaning operations, for example in industrial laundries, dairies, breweries, the food and drink industry, the pharmaceutical industry or pharmaceutical formulation, or sanitary cleaners.
  • the cleaners may be strongly basic with a high electrolyte content and, if required, comprise bleaches (such as hydrogen peroxide, sodium hypochlorite) or disinfectants and defoamers (for example in bottle cleaning). It is also possible for the standard aforementioned enzymes to be present in the industrial and institutional cleaners.
  • cleaning baths stationary or mobile
  • spray cleaning ultrasound cleaning
  • steam jet cleaning high-pressure cleaning
  • mechanical cleaning for example by means of rotating brushes.
  • compositions for cleaning include those for industry, transport, commerce and industry, and for the private sector. Specific examples include: professional laundries, professional cleaning businesses, ore processing industry, metal and metalworking industry, automobile and automobile supply industry, electrical industry, electronics industry, photographic industry and businesses, leisure industry and businesses, construction material industry, brewing industry and businesses; foods industry (e.g. processing or production of meat, poultry, dairy and fish products), animal nutrition industry, cosmetics industry, pharmaceutical industry, agrochemical industry, gastronomy, the health sector, workshops, and public transport.
  • Examples of objects to be cleaned are institutional laundry, hospital laundry, laundry from laundry collection, buildings containing living spaces, office spaces or commercial spaces of a wide variety of different kinds, and sanitary spaces, warehouses, breweries, small businesses such as bakeries, butcheries and supermarkets; hospitals, care homes, homes for the elderly, administration buildings, factory buildings, doctors' practices; and also motor vehicles (cars and trucks), buses, road tanker vehicles (interior and exterior), rail tanker wagons, passenger vehicles and goods vehicles, and aircraft and ships; and also building facades, tiled or painted walls, wooden floors (parquet, boards) with screed or textile or plastics coverings, signaling and lighting installations, furniture, railings, overhead signage, other signage, safety reflectors, delineating markers, tanks, dishware, glass panes, roads and paths, outside paving, road and railway tunnels.
  • Acidic sanitary cleaners are also suitable for the sanitary sector comprising at least one organic acid.
  • Acidic sanitary cleaners are especially suitable for WC cleaning, for cleaning of washbasins, shower cubicles, shower trays and swimming baths, and sinks in the kitchen sector. They are effective, for example, in the removal of limescale and urine scale deposits and in the removal of bacteria which typically form on the limescale and urine scale deposits. They ensure cleanliness and effectively prevent malodors. It has now been found that, surprisingly, the multilayer films of the invention have high compatibility with acidic surfactant compositions and are particularly advantageously suitable for use in acidic sanitary cleaners.
  • a preferred acidic sanitary cleaner in form of a three dimensional body preferably comprises the following constituents: at least one polymer composition P1 ) as defined above, or obtainable by a process as defined above, at least one organic acid, optionally water, - optionally at least one thickener, and optionally at least one further additive.
  • the acidic sanitary cleaner is in solid form.
  • Suitable organic acids are formic acid, acetic acid, citric acid or methanesulfonic acid. Particular preference is given to acetic acid or citric acid.
  • the cleaner of the invention comprises the organic acid preferably in an amount of 1 % to 40% by weight, especially of 5% to 15% by weight, based on the total weight of the cleaner.
  • the cleaner of the invention preferably comprises at least one surfactant in an amount of 0.5% to 50% by weight, especially of 1 % to 15% by weight, based on the total weight of the cleaner.
  • Suitable thickeners in principle are any known thickeners (rheology modifiers), provided they do not have any adverse effect on the action of the washing and cleaning composition. Suitable thickeners may either be of natural origin or synthetic in nature.
  • thickeners of natural origin examples include xanthan, carob seed flour, guar flour, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches, such as hydroxyethyl starch, starch phosphate esters or starch acetates, dextrins, pectins and cellulose derivatives, such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose and the like.
  • Thickeners of natural origin are also inorganic thickeners, such as polysilicic acids and clay minerals, e.g. sheet silicates, and also the silicates specified under the builders.
  • synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partly) crosslinked homopolymers of acrylic acid, for example homopolymers, crosslinked with an allyl ether of sucrose or pentaerythritol or with propylene, of acrylic acid (carbomer), e.g. the Carbopol® brands from BF Goodridge (e.g. Carbopol® 676, 940, 941 , 934 or the like) or the Polygel® brands from 3V Sigma (e.g.
  • Polygel® DA copolymers of ethylenically unsaturated mono- or dicarboxylic acids, for example terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl or ethyl acrylate and a (meth)acrylate derived from long-chain ethoxylated alcohols, for example the Acusol® brands from Rohm & Haas (e.g. Acusol® 820 or 1206A), copolymers of two or more monomers selected from acrylic acid, methacrylic acid and their Ci-C4-alkyl esters, e.g.
  • copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of butyl acrylate and methyl methacrylate e.g. the Aculyn® and Acusol® brands from Rohm & Haas (e.g. Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular weight acrylic acid copolymers, for example copolymers, crosslinked with an allyl ether of sucrose or pentaerythritol, of Cio-C3o-alkyl acrylates with one or more comonomers selected from acrylic acid, methacrylic acid and their Ci-C4-alkyl esters (e.g. Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas).
  • Ci-C4-alkyl esters e.g. Carbopol® ETD 2623, Carbopol
  • Examples of synthetic thickeners are also reaction products of maleic acid polymers with ethoxylated long-chain alcohols, e.g. the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119 from ISP; polyethylene glycols, polyamides, polyimines and polycarboxylic acids. Also suitable are mixtures of the aforementioned thickeners.
  • Preferred thickeners are xanthans and the aforementioned polyacrylic and polymethacrylic compounds.
  • Suitable additives are those mentioned above as component E) for the washing and cleaning compositions of the invention, to which reference is made here in full. These especially include stabilizers, dyes and fragrances.
  • Figure 1 shows the flexibility measurement of P1-1 , P1-2 and ADW tablet.
  • Figure 2 shows the flexibility measurement of an ADW tablet.
  • the initial charge was heated to 75°C while stirring at 100 rpm. Then feeds 1 , 2 and 3 were metered in within 4 h and the reaction mixture was polymerized for a further hour. The mixture was then allowed to cool down to room temperature.
  • the polymer composition is obtained in the form of a transparent and viscous solution.
  • the weight-average molecular weight M w of the polymer composition P1) obtained was determined by means of gel permeation chromatography (GPC) in aqueous solution using neutralized polyacrylic acid as polymer standard. In this type of molecular weight determination, the components of the polymer composition which comprise the aforementioned monomers M) in copolymerized form are ascertained.
  • the weight-average molecular weight Mw of the polymer composition P1-1) obtained was 10000 g/mol.
  • the weight-average molecular weight Mw of the polymer composition P1-2) obtained was 12700 g/mol.
  • the polymer compositions P1-1 and P1-2 were plastified in an oven at 85-90°C. Subsequently, the plastified compositions were casted into silicone molds specificly designed for the friction measurement after DIN53375.
  • the plastified composition casted inside the silicon mold was allowed to cool to 30°C. Subsequently the mold was covered with a plastic bag to avoid water condensation ontop of the body and placed into solid carbon dioxide granules, where it rapidly cooled to about -80°C, and allowed to rest for 30-45 minutes at this temperature. The mold was taken from the solid carbon dioxide and allowed to warm to ambient temperature. The casted body of the polymer composition was removed from the mold and stored in a climate chamber at 25°C and 50% rel. humidity to avoid evaporation of water until the measurement was conducted.
  • the plastified composition casted inside the silicon mold was allowed to cool to ambient temperature.
  • the body of the polymer composition was kept inside the silicon mold overnight. Subsequently the body was removed from the mold, dried for three days under ambient temperature and stored in a climate chamber at 25°C and 50% rel. humidity to avoid further evaporation of water until the measurement was conducted.
  • Friction measurement The measurements are conducted according to the standard DIN EN ISO 8295:2004. The standard is used to measure the friction coefficient between two materials under specific conditions. A fixed normal load (1 ,96 N) is applied (controlled by the weight of a metallic block), a fixed contact surface (40 cm 2 ) and the testing speed (100 mm/min) is also set. During this test, the static friction load (statischen Reibungskraft FS) (also called adhesive friction (Haftreibungskraft) in a predecessor standard to DIN EN ISO 8295:2004 (DIN 53375) which is not valid anymore since 11/1986) is measured as well as the dynamic friction load (dynamisch Reibungskraft FD) also called sliding friction (Gleitreibungskraft) in DIN 53375. The data a summarized in table 1.
  • the flexibility of the three dimensional embodiments was determined with a TA.XTplus Texture Analyzer by Stable Micro Systems. A 5 kg measurement cell was used and a spherical measurement probe with a diameter of 0.25 inch was applied for the penetration test. A spherical ring with a diameter of 70 mm and a wall thickness of 5 mm was used as a foundation for the three dimensional embodiment.
  • the embodiment P1-1 or P 1-2 plastified as described above and the plastified embodiment was casted in a cylindrical mold in such a way that the resulting final three dimensional body had a diameter of 70 mm and a length in z-direction of 7 mm. The respective embodiment was allowed to cool and stored in a climate chamber at 25°C and 50% humidity for equilibration.
  • the flexibility of the embodiments was determined by the respective force necessary to deform the center of the embodiment by 12 mm with the spherical probe.
  • the probe was moved 12 mm in z-direction with a speed of 0.2 mm/s to deform the embodiment.
  • An exponential increase in the force up to the described maximum could be detected.
  • the deformation force declines in an exponential fashion, however with a higher slope.
  • a common dishwashing detergent tablet with the dimension of 55 mm x 35 mm x 10 mm displays the following force-way curve (figure 2).
  • the tablet does not display the exponential increase and decay with a hysteresis-like behavior, it can be regarded as nonflexible.
  • the maximum force applicable with this setup is already reached after a penetration distance of 0.6 mm, which is 5% of the total penetration distance applied to the dishwashing detergent tablet.
  • the experimental data are summarized in table 2, figure 1 and figure 2.
  • Specimens of the polymer compositions P1-1 and P1-2 were prepared by plastifying the polymer compositions P1-1 and P1-2, respecitively, by the procedure described above casting the plastified polymer composition in a cylindrical mold in such a way that the resulting final three dimensional body had a diameter of 70 mm and a length in z-direction of 4 mm.
  • the respective product was allowed to cool and stored in a climate chamber at 25°C and 50% humidity for equilibration as described for protocol B above.
  • a sheet of polyvinyl alcohol (PVA) having a thickness of 1.5 mm was also analyzed.
  • the measurements of haze and clarity were carried out as described in ASTM D1003. The results are summarized in the following table 3:
  • the washing effect of the detergent formulation according to the invention was determined as follows: Selected soiled fabrics were washed in the presence of ballast fabric made from cotton at 30°C with the addition of the detergent formulation P1-1A according to the invention in cylindrical shape with a diameter of 70 mm and height of 6 mm. After the wash cycle, the fabrics were rinsed, spun and dried. To determine the washing effect, the reflectance of the soiled fabric was measured before and after the washing using a photometer from Datacolor (Elrepho 2000) at 460 nm. The higher the reflectance value, the better the washing ability. Washing conditions:

Abstract

The present invention relates to a detergent formulation in form of a three dimensional body. The invention further relates to a process for producing such a detergent formulation in form of a three dimensional body, to various uses of such a detergent formulation and specifically for self-dosing washing machines or dishwashing machines. The invention further relates to a washing and cleaning composition comprising or consisting of such a detergent formulation in form of a three dimensional body and a kit of parts for washing machines or dishwashing machines comprising such a detergent formulation.

Description

Detergent formulation in form of a three dimensional body BACKGROUND OF THE INVENTION The present invention relates to a detergent formulation in form of a three dimensional shaped body. The invention further relates to a process for producing such a detergent formulation in form of a three dimensional shaped body, to various uses of such a detergent formulation and specifically for self-dosing washing machines or dishwashing machines. The invention further relates to a washing and cleaning composition comprising or consisting of such a detergent formulation in form of a three dimensional shaped body and a kit of parts for washing machines or dishwashing machines comprising such a detergent formulation.
PRIOR ART
Formulations for detergents and cleaning agents have to meet a complex property profile. In addition to a large number of technical application properties, this profile also increasingly includes the aesthetic requirements of consumers. In addition to chemical composition, aspects such as external shape, color, consistency, clarity and feel are becoming more important. Thus, a multitude of demands that have to be to be fulfilled simultaneously are made on washing, cleaning and dishwashing compositions, in terms of their cleaning performance, in terms of the manufacturing and their supply forms. In this context, a multitude of dosage forms are already being marketed, including not only the conventional powders and liquid formulations but also tableted products ("tabs"), film-ensheathed individual portions and dosage systems for multiple dosage of washing and cleaning compositions. Current dosage forms may comprise a multitude of separately formulated active ingredients and auxiliaries which are released individually in the cleaning process. However, there is still a great need for new dosage forms to fulfil the actual demands of the market.
Machine washing and dishwashing processes in the domestic and commercial sector comprise a plurality of successive steps that are conducted in more or less automated form, the central unit used being a washing machine or machine dishwasher in which at least the cleaning step and generally also the subsequent rinsing step and/or the drying step are conducted.
In washing machines and machine dishwashers for the domestic sector, the soiled laundry or dishware is generally cleaned in a single chamber, and the aforementioned treatment steps proceed successively in a controlled program. Commercial machine dishwashers consist basically of stationary bath tanks from which an essentially aqueous cleaning solution is jetted or sprayed onto the dishware, which moves past these baths on a conveyor belt, such that the used solution flows back into the bath tanks again. There is a demand for new dosage forms that are suitable for machine assisted washing and dishwashing processes in the domestic and the industrial sector. In detergents, washing compositions, dishwashing compositions, rinse aids, etc. polyethers or surfactants containing ether groups are frequently used together with polymers of a,b-ethylenically unsaturated carboxylic acids and especially polyacrylic acid, in which case polyacrylic acid often assumes the role of an incrustation inhibitor or dispersant. The problem is that polyethers and surfactants are frequently of zero or only limited compatibility in liquid form with polyacrylic acid, and so mixing may result in phase separation or the formation of precipitates, which greatly restricts the possible uses of at least one of the components. It is also especially difficult to provide transparent films or coatings or gels based on polyethers or surfactants containing ether groups together with polymers of unsaturated carboxylic acids. However, those products are preferred by the consumer both because of their performance properties and for esthetic reasons.
The literature discloses numerous processes for preparing gels from polyacrylic acids. These gels, however, are usually water-insoluble, since they are based on crosslinked polyacrylic acid. Other gels are water-soluble but are based on copolymers of acrylic acid with hydrophobic monomers and therefore have lower performance as incrustation inhibitors or dispersants than pure polyacrylic acid. Furthermore, gels are based on high molecular weight polyacrylic acid, which is likewise not advantageous for use as an incrustation inhibitor or dispersant and increases the processing problems.
WO 2015/000969 describes the use of a polymer composition in gel form, obtainable by a process in which a) a monomer composition M1) is provided, consisting of
A) at least one a,b-ethylenically unsaturated acid and
B) 0% to 0.1 % by weight, based on the total weight of the monomer composition M1), of crosslinking monomers having two or more than two polymerizable a,b-ethylenically unsaturated double bonds per molecule, b) the monomer composition M1) provided in step a) is subjected to a free-radical polymerization in the presence of at least one polyether component PE) selected from polyetherols having a number-average molecular weight of at least
200 g/mol and the mono- and di(Ci-C6-alkyl) ethers thereof, surfactants containing polyether groups, and mixtures thereof, in formulations for machine dishwashing (ADW). There is no description of a detergent formulation in form of a three dimensional body.
WO 2015/000970 refers to a solid polymer composition obtained by polymerizing a monomer containing acid groups in the presence of a polyether compound. The solid polymer composition is especially in the form of a film, a coating on a substrate or a particulate solid. Those polymer compositions can be used in several different dosage forms, e.g. a single portion of a washing, cleaning or dishwashing formulation. They may also be used in the coating or in the sheath of such a dosage form.
WO 2015/000971 discloses the use of a polymer composition of WO 2015/000969 in gel form as described in in washing and cleaning compositions, in hygiene products, in cosmetic compositions, in pharmaceutical compositions, in crop protection compositions, in wetting agents, in lacquers, coating compositions, adhesives, leather treatment compositions or textile care compositions, etc.
WO 2018/109200 describes a multilayer film comprising at least one layer comprising or consisting of a polymer composition P1), obtainable by free-radical polymerization of a monomer composition M1) comprising at least one monomer A) selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof. The polymerization is performed in the presence of at least one polyether component PE) selected from polyetherols having a number-average molecular weight of at least 200 g/mol, mono- and di(Ci-C6- alkyl) ethers of such polyetherols, surfactants containing polyether groups, and mixtures thereof.
WO 2018/109201 describes a multilayer film that can be used as a sheath or coating for a washing or cleaning composition portion. The multilayer film comprises at least one layer of a polymer composition obtained by free-radical polymerization of at least one a,b-ethylenically unsaturated mono- and dicarboxylic acids, or salts, anhydrides or mixtures thereof, in the presence of at least one polyether component.
Again, WO 2018/109200 and WO 2018/109201 do not disclose a detergent formulation in form of three dimensional bodies.
EP 1134281 relates to a detergent tablet comprising a compressed portion of an active ingredients and a non-com pressed, non-encapsulation portion of an active ingredient. The tablets are compressed powder. State of the art detergent format, such as powdered detergent, detergent tabs, or liquid single dose units either display certain challenges in formulation for the formulators (downstream users who produce mixtures and usually market them in the downstream supply chain or directly to consumers), or lack of a convenient handling for the (end)- consumer.
It is an object of the present invention to provide a convenient and easy to handle detergent formulation, which also may provide new dosage experiences for the (end)- consumer. Further, it is an object to provide a detergent format, which can overcome formulation problems for the formulators trying to harmonize technical and aesthetic characteristics. Additionally, it is an object to provide new format for self-dosing laundry mashines and automated dishwashers should provided.
The detergent formulation in form of a three dimensional body according to the invention should have at least one of the following properties:
The detergent formulation in form of a three dimensional body should possess a good clarity value (clarity).
The detergent formulation in form of a three dimensional body should be flexibile (flexibility).
The detergent formulation in form of a three dimensional body should retrain its geometrical shape even under thermal influences or humidity influences (free standing).
The tackiness between two of the detergent formulations in form of a three dimensional body being in contact with each other is diminished (non-sticking).
SUMMARY OF THE INVENTION
It has now been found that, surprisingly, it is possible to provide detergent formulations in form of three dimensional shaped bodies having advantageous physicochemical properties and/or having use properties tailored to the respective end use when they comprise or consist of a polymer composition obtainable by free-radical polymerization of a monomer composition comprising at least one monomer selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof, wherein the free-radical polymerization is effected in the presence of at least one polyether component.
The detergent compositions according to the invention are clear and transparent, i.e. they have clarity values of at least 70% according to ASTM D1003 and haze values according to ASTM D 1003, which are smaller than 75%. They are typically free- standing and non-sticking three dimensional shaped bodies, typically geometrical bodies.
Therefore, the present invention relates to detergent formulations in form of three dimensional shaped bodies having clarity values of at least 70% according to ASTM D1003 and haze values according to ASTM D 1003, which are smaller than 75%. The three dimensional shaped bodies comprise or consist of a polymer composition P1) that are obtainable by free-radical polymerization of a monomer composition M1) comprising at least one monomer A) selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof, in the presence of at least one polyether component PE) selected from polyetherols having a number-average molecular weight of at least 200 g/mol and the mono- and di-(Ci-C6-alkyl ethers) thereof surfactants containing polyether groups and mixtures thereof.
The detergent formulation according to the invention can be obtained by shaping a plastified detergent composition containing or consisting of the polymer composition P1) into the desired shape of a three dimensional shaped body and allowing it to solidify.
The invention in particular provides a process for preparing a detergent formulation in form of a three dimensional body as defined herein, which comprises plastifying a detergent composition containing or consisting of the polymer composition P1), shaping the plastified detergent composition into the desired shape of a three dimensional shaped body and solidifying the plastified detergent composition by cooling, in particular by rapid cooling, especially by shock-frosting and deep-cooling.
In particular, the process comprises the following steps: i) providing a detergent composition comprising or consisting of the polymer composition P1 ) having a water content of at most 25% by weight, e.g. in the range of 1 to 25% by weight or in the range of 5 to 25% by weight, in particular in the range of 10 to 25% by weight, especially in the range of 10 to 20% by weight, based on the total weight of P1); ii) plastifying the detergent composition of step i) by heating the detergent composition to a temperature of at least 50°C, in particular at least 55°C, e.g. in the range of 50 to 100°C, in particular in the range of 55 to 90°C or 55 to 85°C; iii) shaping the plastified detergent composition of step ii) into the desired shape of the three dimensional body; and iv) rapid cooling of the shaped detergent composition of step iii) to a temperature of at most -20°C, obtaining the detergent formulation in the shape of a three dimensional body, and v) optionally drying of the obtained detergent formulation.
This preferred process yields a three dimensional shaped body having a very low tackiness. Therefore, the invention in particular relates to a three dimensional shaped body, which is obtained by this process.
The invention further provides a washing and cleaning composition comprising or consisting of the detergent formulation in form of a three dimensional body as defined above and hereinafter or obtainable by the process as defined above and hereinafter.
The invention further provides the use of the detergent formulation in form of a three dimensional body as defined above and hereinafter or obtainable by the process as defined above and hereinafter for self-dosing washing mashines or dishwashing mashines.
The invention further provides a kit of parts for washing mashines or dishwashing mashines comprising the detergent formulation in form of a three dimensional body as defined above and hereinafter or obtained by the process as defined above and hereinafter and optionally further substance selected from builder, bleach, additives different therefrom and mixtures thereof, for a combined use.
DETAILED DESCRIPTION OF THE INVENTION
A "three dimensional shaped body" in the context of the invention is understood as a shaped body that expands in all three spatial dimensions, i.e., a body that is not substantially flat or planar, respectively. The dimensions of the three dimensional shaped bodies are such that they have dimensions of at least 1 mm, in particular at least 2 mm in all spatial directions. The term “dimension” is understand as the longitudinal extension of the shaped body in one spatial direction. In case of a sphere, the dimensions are the same for all spatial directions. Typically the dimensions in some spatial directions are distinct from dimensions in other spatial directions.
In contrast to the term “three dimensional” the term “two-dimensional” is used for defining a body, which is a generally planar, i.e. which in two orthogonal spatial directions have large dimensions and in the third direction orthogonal to the two first ones a very small dimension, such that the ratio of the large dimensions to the small dimension is at least 100 or at least 1000. e.g. including platelets, films and foils.
A "kit of parts" is understood as a specific type of composition that contains two or more discrete components, and those components work together for a specific purpose, or to achieve a specific result, e.g. to achieve a particularly good washing effect or to achieve a combination of e.g. a good washing effect and dye-transfer inhibition. The individual components of the kit may be packaged in a single container or in separate containers. The individual components may be used either simultaneously or in sequence. The individual components may be formulated for administration by an end consumer or for the dosing unit of a washing machine or dishwashing machine. A special embodiment is a kit of parts for use in a self-dosing washing machine or dishwashing machine. A kit of parts in the sense of the invention may contain one single detergent formulation in form of a three dimensional body and a component different therefrom. A kit of parts in the sense of the invention may also contain at least two different detergent formulations in form of a three dimensional body and optionally at least one component different therefrom. One single detergent formulation according to the invention in form of a three dimensional body is regarded as one component of the kit. This also applies if the detergent formulation in form of a three dimensional body is composed of two or more active ingredients that are formulated together or comprises two or more separate domains each comprising at least one active ingredient. Even if the ingredients contained within one single three dimensional body work together to achieve a specific result, they are formulated as a single unit and consequently are considered as only one component of the kit.
In the context of this application, some compounds which can be derived either from acrylic acid or from methacrylic acid or from mixtures of the two are referred to by insertion of the "(meth)" syllable into the compound derived from acrylic acid. The organic radicals of the variables mentioned above and below constitute an individual enumeration of individual group members. The prefix Cn-Cm denotes the possible number of carbon atoms in the respective group.
If the term "alkyl" is used without a prefix (Cn-Cm), it represents a linear or (over and above 3 carbon atoms) branched saturated aliphatic radical having generally 1 to 40 carbon atoms ("Ci-C4o-alkyl"), preferably 1 to 30 carbon atoms ("Ci-C3o-alkyl").
In the context of the present invention, Ci-C4-alkyl is a linear or branched alkyl radical having 1 to 4 carbon atoms. Examples of Ci-C4-alkyls are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl. Ci-C7-alkyl is a linear or branched alkyl radical having 1 to 7 carbon atoms. Examples of Ci-C7-alkyl are, in addition to those mentioned for Ci-C4-alkyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1 -dimethyl propyl,
1.2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1 -dimethyl butyl, 1,2-dimethyl butyl, 1,3-dimethylbutyl,
2.2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
1.1.2-trimethylpropyl, 1,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl, 1 -ethyl-2- methylpropyl, heptyl and the constitutional isomers thereof.
Ci-Cs-alkyl is a linear or branched alkyl radical having 1 to 8 carbon atoms. Examples of Ci-Cs-alkyl are, in addition to those mentioned for Ci-C7-alkyl, octyl, 2-ethylhexyl and the constitutional isomers thereof.
Ci-Cio-alkyl is a linear or branched alkyl radical having 1 to 10 carbon atoms.
Examples of Ci-Cio-alkyl are, in addition to those mentioned for Ci-Cs-alkyl, nonyl, decyl, 2-propylheptyl and the constitutional isomers thereof.
Ci-C2o-alkyl is a linear or branched alkyl radical having 1 to 20 carbon atoms.
Examples of Ci-C2o-alkyl are, in addition to those mentioned for Ci-Cio-alkyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the constitutional isomers thereof.
Ci-C3o-alkyl is a linear or branched alkyl radical having 1 to 30 carbon atoms.
Examples of Ci-C3o-alkyl are, in addition to those mentioned for Ci-C2o-alkyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl and the constitutional isomers thereof.
Ci-C4o-alkyl is a linear or branched alkyl radical having 1 to 40 carbon atoms.
Examples of Ci-C4o-alkyl are, in addition to those mentioned for Ci-C3o-alkyl, the higher homologs having 31 to 40 carbon atoms. Examples of Cs-022-alkyl are octyl, 2-ethyl- hexyl and the constitutional isomers thereof.
Cs-Ci8-alkyl is a linear or branched alkyl radical having 8 to 18 carbon atoms. Suitable Cs-Ci8-alkyls are octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl and the constitutional isomers thereof. In a preferred embodiment, they are predominantly linear Cs-Cis-alkyl radicals, as also occur in natural or synthetic fatty alcohols, and oxo process alcohols.
Ci2-Ci8-alkyl is a linear or branched alkyl radical having 12 to 18 carbon atoms.
Suitable Ci2-Cis-alkyls are dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl and the constitutional isomers thereof. In a preferred embodiment, they are predominantly linear Ci2-Cis-alkyl radicals, as also occur in natural or synthetic fatty alcohols, and oxo process alcohols.
In the context of the present application, the expression Cg-Cn alcohols represents a mixture comprising alcohols having 9 carbon atoms and alcohols having 11 carbon atoms. C12-C14 alcohols are a mixture comprising alcohols having 12 carbon atoms and alcohols having 14 carbon atoms. C13-C15 alcohols are a mixture comprising alcohols having 13 carbon atoms and alcohols having 15 carbon atoms. C12-C18 alcohols are a mixture comprising alcohols having 12 carbon atoms, alcohols having 14 carbon atoms, alcohols having 16 carbon atoms and alcohols having 18 carbon atoms.
If the term "alkenyl" is used without a prefix (Cn-Cm), it represents a linear or branched monounsaturated (i.e. comprising one C-C double bond) aliphatic radical having generally 2 to 40 carbon atoms ("C2-C4o-alkenyl"), preferably 2 to 30 carbon atoms ("C2-C30-alkenyl").
Examples of C2-C3-alkenyl are ethenyl, 1-propenyl, 2-propenyl or 1-methylethenyl. Examples of C2-C4-alkenyl are, in addition to those mentioned for C2-C3-alkenyl,
1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1-propenyl, 1-methyl-2- propenyl or 2-methyl-2-propenyl. Examples of C2-C6-alkenyl are, in addition to those mentioned for C2-C4-alkenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl- 1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2- butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3- butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1 -propenyl, 1,2-dimethyl-2-propenyl,
1 -ethyl-1 -propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl-1 -pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1- pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2- pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3- pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4- pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1 -butenyl,
1 ,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1 , 3-d im ethyl- 1 -butenyl, 1 ,3-dimethyl-2- butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2, 3-dimethyl-1 -butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3, 3-dimethyl-1 -butenyl, 3,3-dimethyl-2- butenyl, 1 -ethyl-1 -butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1 -butenyl,
2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2- propenyl, 1-ethyl-2-methyl-1 -propenyl, 1 -ethyl-2-methyl-2-propenyl and the like. Examples of C2-Cio-alkenyl are, in addition to those mentioned for C2-C6-alkenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 1- nonenyl, 2-nonenyl, 3-nonenyl, 4-nonenyl, 1-decenyl, 2-decenyl, 3-decenyl, 4-decenyl, 5-decenyl and the like.
If the term "cycloalkyl" is used without a prefix (Cn-Cm), it represents a saturated monocyclic cycloaliphatic radical having generally 3 to 10 carbon atoms ("C3-C10- cycloalkyl"), preferably 3 to 8 carbon atoms ("Cs-Cs-cycloalkyl"), and of course does not have any heteroatoms as ring members (i.e. all ring members are carbon atoms).
Examples of C3-C4-cycloalkyl are cyclopropyl and cyclobutyl. Examples of C3-C5- cycloalkyl are cyclopropyl, cyclobutyl and cyclopentyl. Examples of C3-C6-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of C3-C7-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Examples of C3-C8- cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of C3-Cio-cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
"Aryl" is a mono-, bi- or polycyclic carbocyclic aromatic radical without heteroatoms as ring members. A monocyclic aromatic radical is phenyl. In bicyclic aryl radicals, two aromatic rings are fused to one another; in other words, they share two adjacent carbon atoms as ring members. Examples of bicyclic aryl groups are 1- and 2-naphthyl. In polycyclic aryl groups, three or more rings are fused. Examples of polycyclic aryl groups are phenanthrenyl, anthracenyl, tetracenyl, 1 H-benzo[a]phenalenyl, pyrenyl and the like. In the context of the present application, the term "aryl" also encompasses bi- or polycyclic radicals in which not all rings are aromatic; it is a prerequisite that at least one ring is aromatic. Examples of these are indanyl, indenyl, tetralinyl, 6,7,8,9-tetra- hydro-5H-benzo[7]annulenyl, fluorenyl, 9,10-dihydroanthracenyl, 9,10-dihydro- phenanthrenyl, 1 H-benzo[a]phenalenyl and the like. The aryl group has generally 6 to 30, especially 6 to 20 and specifically 6 to 10 carbon atoms as ring members.
If the term "heterocycloalkyl" is used without a prefix (Cn-Cm) and without specification of the ring heteroatoms, it represents a saturated monocyclic heterocyclic radical having generally 3 to 8 ring members and at least one heteroatom and/or heteroatom- containing group, preferably 1 , 2, 3 or 4 heteroatoms and/or heteroatom-containing groups, as ring members. The heteroatom and the heteroatom-containing group are selected from N, O, S, NO, SO and SO2.
Examples of these are oxiran-2-yl, thiiran-2-yl, aziridin-1-yl, aziridin-2-yl, oxetan-2-yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, 1-oxothietan-2-yl, 1-oxothietan-3-yl,
1 ,1-dioxothietan-2-yl, 1 ,1-dioxothietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1-oxotetrahydrothien-2-yl, 1 ,1-dioxotetrahydrothien-2-yl, 1-oxotetrahydrothien-3-yl, 1.1-dioxotetrahydrothien-3-yl, pyrrolidin-1-yl, pyrrol i d i n-2-y I , pyrrol i d i n-3-y I , pyrazolidin- 1-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin-5-yl, imidazolidin-1-yl, imidazolidin-2- yl, imidazolidin-4-yl, oxazolidin-2-yl, oxazolidin-3-yl, oxazolidin-4-yl, oxazolidin-5-yl, isoxazolidin-2-yl, isoxazolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl, thiazolidin-2-yl, thiazolidin-3-yl, thiazolidin-4-yl, thiazolidin-5-yl, isothiazolidin-2-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazolidin-5-yl, 1,2,4-oxadiazolidin-2-yl, 1,2,4-oxadiazolidin-3-yl,
1.2.4-oxadiazolidin-4-yl, 1 ,2,4-oxadiazolidin-5-yl, 1 ,2,4-thiadiazolidin-2-yl,
1.2.4-thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin-4-yl, 1 ,2,4-thiadiazolidin-5-yl,
1.2.4-triazolidin-1 -yl, 1 ,2,4-triazolidin-3-yl, 1 ,2,4-triazolidin-4-yl, 1 ,3,4-oxadiazolidin-2-yl,
1.3.4-oxadiazolidin-3-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-3-yl,
1.3.4-triazolidin-1 -yl, 1 ,3,4-triazolidin-2-yl, 1 ,3,4-triazolidin-3-yl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan- 5-yl, 1,4-dioxan-2-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-1 -yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1 -yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-yl, 1,3,5-hexahydrotriazin-1-yl,
1.3.5-hexahydrotriazin-2-yl, 1 ,2,4-hexahydrotriazin-1-yl, 1 ,2,4-hexahydrotriazin-2-yl,
1.2.4-hexahydrotriazin-3-yl, 1 ,2,4-hexahydrotriazin-4-yl, 1 ,2,4-hexahydrotriazin-5-yl,
1.2.4-hexahydrotriazin-6-yl, morpholin-2-yl, morpholin-3-yl, morpholin-4-yl, thiomorpholin-2-yl, thiomorpholin-3-yl, thiomorpholin-4-yl, 1-oxothiomorpholin-2-yl,
1 -oxothiomorpholin-3-yl, 1 -oxothiomorpholin-4-yl, 1 , 1 -dioxothiomorpholin-2-yl,
1.1-dioxothiomorpholin-3-yl, 1,1-dioxothiomorpholin-4-yl, azepan-1-, -2-, -3- or -4-yl, oxepan-2-, -3-, -4- or -5-yl, hexahydro-1,3-diazepinyl, hexahydro-1,4-diazepinyl, hexahydro-1 ,3-oxazepinyl, hexahydro-1 ,4-oxazepinyl, hexahydro-1 ,3-dioxepinyl, hexahydro-1,4-dioxepinyl, oxocanyl, thiocanyl, azocanyl, [1 ,3]diazocanyl, [1,4]diazocanyl, [1 ,5]diazocanyl, [1 ,5]oxazocanyl and the like.
If the term "heteroaryl" or "hetaryl" is used without a prefix (Cn-Cm) and without specification of the ring heteroatoms, it represents an aromatic monocyclic heterocyclic radical having 5 or 6 ring members and at least one heteroatom and/or heteroatom- containing group, preferably 1 , 2, 3 or 4 heteroatoms and/or heteroatom-containing groups, as ring members. The heteroatom and the heteroatom-containing group are selected from N, O, S, NO, SO and SO2.
Examples of these are 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl,
3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 1-imidazolyl, 2-imidazolyl,
4-imidazolyl, 5-imidazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl,
5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-iso- thiazolyl, 1 ,3,4-triazol-1 -yl, 1,3,4-triazol-2-yl, 1,3,4-triazol-3-yl, 1 ,2,3-triazol-1 -yl,
1.2.3-triazo l-2-yl , 1,2,3-triazol-4-yl, 1,2,5-oxadiazol-3-yl, 1,2,3-oxadiazol-4-yl,
1.2.3-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,5-thiadiazol-3-yl, 1,2,3-thiadiazol-4-yl, 1.2.3-th i ad iazo l-5-yl , 1 ,3,4-thiadiazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl,
1-oxopyridin-2-yl, 1-oxopyridin-3-yl, 1-oxopyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl,
2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1 ,3,5-triazin-2-yl, 1 ,2,4-triazin-3- yl, 1,2,4-triazin-5-yl, 1 ,2,3,4-tetrazin-1-yl, 1 ,2,3,4-tetrazin-2-yl, 1 ,2,3,4-tetrazin-5-yl and the like.
Monoolefins are alkenes; in other words, they are linear or branched aliphatic monounsaturated hydrocarbons having only one C-C double bond. If the term is used without a prefix (Cn-Cm), it represents a linear or branched monounsaturated (i.e. comprising one C-C double bond) aliphatic hydrocarbon having generally 2 to 40 carbon atoms ("C2-C40 monoolefin" or "C2-C4o-alkene"), preferably 2 to 30 carbon atoms ("C2-C30 monoolefin" or "C2-C3o-alkene"), especially 2 to 10 carbon atoms ("C2-C10 monoolefin" or "C2-C3o-alkene"). Examples of C2-C10 monoolefins are ethene, propene, but-1-ene, but-2-ene, isobutene, pent-1-ene, pent-2-ene, 2-methyl-but-1-ene, 2-methyl-but-2-ene, 3-methyl-but-1-ene, 3-methyl-but-2-ene, 2,2-dimethylprop-1-ene, hex-1 -ene, hex-2-ene, hex-3-ene, hept-1-ene, hept-2-ene, hept-3-ene, oct-1 -ene, oct- 2-ene, oct-3-ene, oct-4-ene, non-1-ene, non-2-ene, non-3-ene, non-4-ene, dec-1 -ene, dec-2-ene, dec-3-ene, dec-4-ene, dec-5-ene and the positional isomers thereof. Nonaromatic hydrocarbons having at least two conjugated double bonds refer to both aliphatic and cycloaliphatic unsaturated hydrocarbons having at least two conjugated double bonds. The cycloaliphatic unsaturated hydrocarbons having at least two conjugated double bonds are either those which do not comprise the maximum number of conjugated C-C double bonds defined by the ring size or those which do comprise the maximum number of conjugated C-C double bonds defined by the ring size but do not satisfy the Huckel rule, whether because the molecule is homoaromatic, antiaromatic or a nonaromatic polyene.
Aliphatic hydrocarbons having at least two conjugated double bonds generally comprise 4 to 20 carbon atoms. Examples of aliphatic hydrocarbons having at least two conjugated double bonds are 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene,1,3,5-hexatriene, 1,3-heptadiene, 2,4-heptadiene, 1 ,3,4-heptatriene,
1.3-octadiene, 2,4-octadiene, 3,5-octadiene, 1 ,3,5-octatriene, 2,4,6-octatriene,
1 ,3,5,7-octatetraene and the like.
Cycloaliphatic hydrocarbons having at least two conjugated double bonds generally comprise 4 to 20 carbon atoms as ring members. Examples are 1 ,3-cyclopentadiene,
1.3-cyclohexadiene, 1 ,3-cycloheptadiene, 1 ,3,5-cycloheptatriene, 1 ,3-cyclooctadiene,
1 ,3,5-cyclooctatriene, 1 ,3,5,7-cyclooctatetraene and the like. Alkanols are monohydroxyalkanes, i.e. compounds R-OH in which R is a linear or branched alkyl radical as defined above. If the term is used without a prefix (Cn-Cm), it represents a Ci-C3o-alkanol. Examples of Ci-C3-alkanols are methanol, ethanol, n-propanol and isopropanol. Examples of Ci-C4-alkanols are, in addition to those mentioned for the Ci-C3-alkanols, n-butanol, sec-butanol, isobutanol and tert-butanol. Examples of Ci-C2o-alkanols are, in addition to those mentioned for the Ci-C4-alkanols, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, 2-propyl- heptanol, undecanol, lauryl alcohol, tridecanol, myristyl alcohol, pentadecanol, palmityl alcohol, heptadecanol, stearyl alcohol, nonadecanol, eicosanol and the positional and constitutional isomers thereof. Examples of Ci-C3o-alkanols are, in addition to those mentioned for Ci-C2o-alkanols, the higher homologs having 21 to 30 carbon atoms and the positional and constitutional isomers thereof.
Alkanediols are dihydroxyalkanes, i.e. alkanes in which two hydrogen atoms have been replaced by OH groups, where at least two carbon atoms must be between the two hydroxyl groups (i.e. hydrates are not encompassed by this term). If the term is used without a prefix (Cn-Cm), it represents a C2-C3o-alkanediol. Examples of C2-C3- alkanediols are ethylene glycol (ethane-1 ,2-diol), propane-1 ,2-diol and propane-1 ,3- diol. Examples of C2-C4-alkanediols are, in addition to those mentioned for the C2-C3- alkanediols, butane-1 ,2-diol, butane-1 ,3-diol and butane-1 ,4-diol. Examples of C2-C6- alkanediols are, in addition to those mentioned for the C2-C4-alkanediols, pentane-1 ,5- diol and hexane-1 ,6-diol. Examples of C2-C2o-alkanediols are, in addition to those mentioned for the C2-C6-alkanediols, heptane-1 ,7-diol, octane-1 ,8-diol, nonane-1 ,9-diol, decane-1 ,10-diol, undecane-1 ,11-diol, dodecane-1 ,12-diol, tridecane-1, 13-diol, tetradecane-1,14-diol, pentadecane-1 ,15-diol, hexadecane-1,16-diol, heptadecane- 1 ,17-diol, octadecane-1 ,18-diol, nonadecane-1,19-diol, eicosane-1 ,20-diol. Examples of C2-C3o-alkanediols are, in addition to those mentioned for C2-C2o-alkanediols, the higher homologs having 21 to 30 carbon atoms. In the context of the present application, the expression Cg-Cn alcohols represents a mixture comprising alcohols having 9 carbon atoms and alcohols having 11 carbon atoms. C12-C14 alcohols are a mixture comprising alcohols having 12 carbon atoms and alcohols having 14 carbon atoms. C13-C15 alcohols are a mixture comprising alcohols having 13 carbon atoms and alcohols having 15 carbon atoms. C12-C18 alcohols are a mixture comprising alcohols having 12 carbon atoms, alcohols having 14 carbon atoms, alcohols having 16 carbon atoms and alcohols having 18 carbon atoms.
In the context of the present invention, the terms “plastify” and “plasticise” have the same meaning. Polymer composition P1)
The polymer composition P1) is prepared by free-radical polymerization of the monomer composition M1) in the presence of at least one polyether component PE). This affords specific polymer compositions P1) having advantageous properties. Without being bound to a theory, hydrogen bonds are able to form between the growing polymer and the polyether component, and these influence the properties of the resultant polymer composition. Thus, polymer compositions P1) having a high content of the polyether component can be attained; these cannot be prepared by mixing the separately prepared polymer with the polyether component. Free-radical polymer degradation advantageously does not take place here.
For production of the detergent formulation of the invention, preference is given to using polymer compositions P1) having a low glass transition temperature TG. Preferably, the polymer compositions P1) used for production of the detergent formulation of the invention have a glass transition temperature TG in the range from 0 to 80°C, preferably from 0 to 60°C, especially from 0 to 30°C.
The glass transition temperatures (Tg) described in the context of this application can be determined by means of differential scanning calorimetry (DSC). Differential scanning calorimetry (DSC) is typically carried out according to ISO 11357-2:2013, preferably with sample preparation according to ISO 16805:2003.
Preferably, the detergent compositions comprises the polymer composition P1) in an amount of at least 70% by weight, in particular at least 75% by weight, more particularly at least 80% by weight, based on the total weight of the detergent formulation. In particular, the detergent compositions comprises the polymer composition P1) in an amount in the range of 70 to 99% by weight, more particular in the range of 75 to 99% by weight or in the range 75 to 95% by weight, in particular in the range of 75 to 90% by weight, especially in the range of 80 to 90% by weight, based on the total weight of the detergent formulation. In particular, the amount of the polymer composition P1) in the detergent formulation is at least 90 % by weight, especially at least 95% by weight, based on the total weight of the components in the detergent formulation, which are different from water, and may be up to 100% by weight, based on the total weight of the components in the detergent formulation, which are different from water.
In a particular group embodiments, the polymer compositions P1 ) used for production of the detergent formulation of the invention have the form of the three dimensional body as defined herein. Monomer composition M1)
Monomer A)
The monomer composition M1) used for production of the polymer composition P1) comprises at least one monomer A) selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof.
In a specific embodiment, the monomer composition M1) consists solely of a,b-ethylenically unsaturated carboxylic acids, salts of a,b-ethylenically unsaturated carboxylic acids and mixtures thereof.
The a,b-ethylenically unsaturated carboxylic acid is preferably selected from acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, a-chloroacrylic acid, crotonic acid, citraconic acid, mesaconic acid, glutaconic acid and aconitic acid. Suitable salts of the aforementioned acids are especially the sodium, potassium and ammonium salts, and the salts with amines. The monomers A) can be used as such or as mixtures with one another. The stated proportions by weight all refer to the acid form.
Preferably, the at least one a,b-ethylenically unsaturated carboxylic acid is used for polymerization in non-neutralized form. If the a,b-ethylenically unsaturated carboxylic acids are used for polymerization in partly neutralized form, the acid groups are neutralized preferably to an extent of at most 50 mol%, particularly preferably to an extent of at most 30 mol%. The partial or full neutralization can also be effected during the polymerization or after the polymerization has ended.
Suitable bases for neutralization of the a,b-ethylenically unsaturated carboxylic acids, and also the unsaturated sulfonic acids and phosphonic acids mentioned hereinafter, are alkali metal hydroxides such as NaOH and KOH, alkaline earth metal hydroxides such as Ca(OH)2 and Mg(OH)2, ammonia and amine bases. Preferred amines are alkanolamines such as ethanolamine, diethanolamine and triethanolamine. If desired, partial or full neutralization of the acid groups may also follow after the polymerization.
More preferably, monomer A) is selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, salts of the aforementioned carboxylic acids and mixtures thereof. More particularly, monomer A) is selected from acrylic acid, methacrylic acid, salts of acrylic acid, salts of methacrylic acid and mixtures thereof.
In a specific embodiment, exclusively acrylic acid is used as monomer A).
Monomer A) is used preferably in an amount of 50% to 100% by weight, more preferably 60% to 100% by weight, based on the total weight of the monomer composition M1).
In a preferred embodiment, the monomer composition M1) consists to an extent of at least 50% by weight, preferably to an extent of at least 80% by weight and especially to an extent of at least 90% by weight, based on the total weight of the monomer composition M1), of acrylic acid and/or acrylic acid salts.
The monomer composition M1) may, in addition to the monomers A), comprise at least one monomer B) selected from unsaturated sulfonic acids, salts of unsaturated sulfonic acids, unsaturated phosphonic acid, salts of unsaturated phosphonic acids.
Monomer B) is preferably selected from 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, allylphosphonic acid, salts of the aforementioned acids and mixtures thereof.
A preferred monomer B) is 2-acrylamido-2-methylpropanesulfonic acid.
Suitable salts of the aforementioned acids are especially the sodium, potassium and ammonium salts, and the salts with amines. The monomers B) can be used as such or as mixtures with one another. The stated proportions by weight all refer to the acid form.
Preferably, the monomer composition M1) in that case consists to an extent of at least 50% by weight, more preferably to an extent of at least 80% by weight and especially to an extent of at least 90% by weight, based on the total weight of the monomer composition M1), of monomers A) and B). When the monomer composition M1) comprises at least one monomer B), it is preferably used in an amount of 0.1% to 50% by weight, more preferably 1 % to 25% by weight, based on the total weight of the monomer composition M1). Monomers C)
The monomer composition M1) may additionally comprise at least one further monomer other than the monomers containing acid groups and salts thereof (= monomer C).
The monomer composition M 1 ) may thus have the following monomer compositions: A) or A) + B) or A) + C) or A) + B) + C). Preferably, the monomer composition M 1 ) additionally comprises at least one monomer C) selected from
C1) nitrogen heterocycles having a free-radically polymerizable a,b-ethylenically unsaturated double bond,
C2) compounds of the general formulae (I. a) and (l.b)
Figure imgf000018_0001
in which the sequence of the alkylene oxide units is arbitrary, x is 0, 1 or 2, k and I are independently an integer from 0 to 100, where the sum of k and I is at least 2, preferably at least 5,
R1 is hydrogen or Ci-Cs-alkyl,
R2 is hydrogen, Ci-C3o-alkyl, C2-C3o-alkenyl or Cs-Cs-cycloalkyl, and X is O or a group of the formula NR3 in which R3 is H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl;
C3) esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C1-C5- alkanols,
C4) compounds having one free-radically polymerizable a,b-ethylenically unsaturated double bond and at least one cationogenic and/or cationic group per molecule,
C5) esters of vinyl alcohol or allyl alcohol with Ci-C30-monocarboxylic acids,
C6) esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30- alkanediols, amides of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30 amino alcohols having a primary or secondary amino group, and mixtures of two or more than two of the aforementioned monomers C1) to C6).
Monomer C1)
Preferred nitrogen heterocycles with a free-radically polymerizable a,b-ethylenically unsaturated double bond C1) are selected from N-vinylimidazole (1-vinylimidazole), vinyl- and allyl-substituted nitrogen heterocycles other than N-vinylimidazole, and mixtures thereof.
The amine nitrogens of the aforementioned compounds can be used to produce charged cationic groups either by protonation with acids or by quaternization with alkylating agents. Suitable monomers C1) are also the compounds obtained by protonation or quaternization of 1-vinylimidazole and different vinyl- and allyl- substituted nitrogen heterocycles. Acids suitable for the protonation are, for example, carboxylic acids such as lactic acid or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid. Alkylating agents suitable for quaternization are Ci-C4-alkyl halides or di(Ci-C4-alkyl) sulfates, such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. A protonation or quaternization may generally either precede or follow the polymerization. Preferably, a protonation or quaternization follows the polymerization. Examples of such charged monomers C1) are quaternized vinylimidazoles, especially 3-methyl-1-vinylimidazolium chloride, methosulfate and ethosulfate.
Preferred monomers C1) are also vinyl- and allyl-substituted nitrogen heterocycles other than vinylimidazoles, selected from 2-vinylpyridine, 4-vinylpyridine, 2-allylpyridine, 4-allylpyridine, 2-vinylpiperidine, 4-vinylpiperidine and the salts thereof obtained by protonation or by quaternization.
More particularly, the monomer composition M1) comprises at least one comonomer C1) selected from 1-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, 2-allylpyridine,
4-allylpyridine and the salts thereof obtained by protonation or by quaternization. Specifically, the monomer composition M1) comprises 1-vinylimidazole as comonomer C1). Monomer C2)
The monomer composition M1) may additionally comprise at least one monomer C2) selected from compounds of the general formulae (I. a) and (l.b), as defined above. In the formulae I. a) and l.b), k is preferably an integer from 1 to 500, more preferably 2 to 400, especially 3 to 250. Preferably, I is an integer from 0 to 100.
Preferably, R1 in the formula I. a) is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, especially hydrogen, methyl or ethyl.
Preferably, R2 in the formulae I. a) and l.b) is n-octyl, 1 ,1 ,3,3-tetramethylbutyl, ethylhexyl, n-nonyl, n-decyl, n-undecyl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl, octadecyl, nonadecyl, arachinyl, behenyl, lignoceryl, cerotinyl, melissyl, palmitoleyl, oleyl, linoleyl, linolenyl, stearyl, lauryl.
Preferably, X in the formula I. a) is O or NH, especially O.
More preferably, the monomer composition M1) comprises at least one monomer C2) selected from compounds of the general formulae (I.a1) and (I.b1)
1
R O
H2C=C — C — O — (CH2-CH2-0)k(CH2-CH(CH3)-0)|R2
(I.a1)
Figure imgf000020_0001
in which the sequence of the alkylene oxide units is arbitrary, x is 0, 1 or 2, k and I are independently an integer from 0 to 100, where the sum of k and I is at least 2, preferably at least 5,
R1 is hydrogen or methyl,
R2 is hydrogen, Ci-C4-alkyl.
In the formulae I.a1) and I.b1), k is preferably an integer from 1 to 100, more preferably 2 to 50, especially 3 to 30. Preferably, I is an integer from 0 to 50.
Preferably, R2 in the formulae I.a1) and I.b1) is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
In the formula I.b1), x is preferably 1 or 2.
Suitable polyether acrylates I. a) or I.a1) are, for example, the polycondensation products of the aforementioned a,b-ethylenically unsaturated mono- and/or dicarboxylic acids and the acid chlorides, acid amides and acid anhydrides thereof with polyetherols. Suitable polyetherols can be prepared easily by reacting ethylene oxide, propylene 1 ,2-oxide and/or epichlorohydrin with a starter molecule such as water or a short-chain alcohol R2-OH. The alkylene oxides can be used individually, alternately in succession, or as a mixture. The polyether acrylates I.a1) can be used alone or in mixtures to prepare the polymers used in accordance with the invention.
Suitable allyl alcohol alkoxylates l.b) or I.b1) are, for example, the etherification products of allyl chloride with appropriate polyetherols. Suitable polyetherols can be prepared easily by reacting ethylene oxide, propylene 1 ,2-oxide and/or epichlorohydrin with a starter alcohol R2-OH. The alkylene oxides can be used individually, alternately in succession, or as a mixture. The allyl alcohol alkoxylates l.b) can be used alone or in mixtures to prepare the polymers used in accordance with the invention. Monomers C2) used are especially methyl diglycol acrylate, methyl diglycol methacrylate, ethyl diglycol acrylate or ethyl diglycol methacrylate. Preference is given to ethyl diglycol acrylate. Monomer C3)
The monomer composition M1) may additionally comprise at least one monomer C3) selected from esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C5-alkanols.
Suitable esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C5-alkanols are, for example, methyl (meth)acrylate, methyl ethacrylate, ethyl (meth)acrylate, ethyl ethacrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, tert-butyl ethacrylate, n-pentyl (meth)acrylate, and mixtures thereof.
Monomer C4)
The monomer composition M1) may additionally comprise at least one monomer C4) selected from compounds having a free-radically polymerizable a,b-ethylenically unsaturated double bond and at least one cationogenic and/or cationic group per molecule.
The cationogenic and/or cationic groups of the monomers C4) are preferably nitrogen- containing groups such as primary, secondary and tertiary amino groups, and quaternary ammonium groups. Preferably, the nitrogen-containing groups are tertiary amino groups or quaternary ammonium groups. Charged cationic groups can be produced from the amine nitrogens either by protonation or by quaternization with acids or alkylating agents. Examples of these include carboxylic acids such as lactic acid, or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, and examples of alkylating agents include Ci-C4-alkyl halides or sulfates, such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. A protonation or quaternization may generally either precede or follow the polymerization.
Preferably, the monomers C4) are selected from esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols which may be mono- or dialkylated on the amine nitrogen, amides of a,b-ethylenically unsaturated mono- and dicarboxylic acids with diamines having at least one primary or secondary amino group, N,N- diallylamine, N,N-diallyl-N-alkylamines and derivatives thereof, and mixtures thereof.
The esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols which may be mono- or dialkylated on the amine nitrogen preferably derive from C2-C12 amino alcohols mono- or di-Ci-Cs-alkylated on the amine nitrogen. Suitable acid components of these esters are, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. The acid components used are preferably acrylic acid, methacrylic acid and mixtures thereof.
Preferred monomers C4) are N-methylaminoethyl (meth)acrylate,
N-ethylaminoethyl (meth)acrylate, N-(n-propyl)aminoethyl (meth)acrylate, N-(tert-butyl)aminoethyl (meth)acrylate, N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminomethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate and N,N-dimethylaminocyclohexyl (meth)acrylate.
Suitable monomers C4) are additionally the amides of the aforementioned a,b-ethylenically unsaturated mono- and dicarboxylic acids with diamines having at least one primary or secondary amino group. Preference is given to diamines having one tertiary amino group and one primary or secondary amino group.
Examples of preferred monomers C4) are N-[tert-butylaminoethyl](meth)acrylamide, N-[2-(dimethylamino)ethyl]acrylamide, N-[2-(dimethylamino)ethyl]methacrylamide, N-[3-(dimethylamino)propyl]acrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-[4-(dimethylamino)butyl]acrylamide, N-[4-(dimethylamino)butyl]methacrylamide, N-[2-(diethylamino)ethyl]acrylamide, N-[4-(dimethylamino)cyclohexyl]acrylamide and N-[4-(dimethylamino)cyclohexyl]methacrylamide.
Monomer C5)
The monomer composition M1) may additionally comprise at least one monomer C5) selected from esters of vinyl alcohol or allyl alcohol with C1-C30 monocarboxylic acids. Suitable esters of vinyl alcohol with Ci-C30-monocarboxylic acids are, for example, the esters of vinyl alcohol with C1-C30 monocarboxylic acids such as acetic acid, propionic acid, n-butanoic acid, 2-methylpropanoic acid, n-pentanoic acid, 2,2-dimethylpropanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2,2,4,4-tetramethylpentanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, n-decanoic acid, n-undecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, stearic acid, lauric acid. Monomer C6)
The monomer composition M1) may additionally comprise at least one monomer C8) selected from esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-alkanediols and amides of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30 amino alcohols having a primary or secondary amino group.
Suitable esters of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-alkanediols are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate, etc.
Suitable amides of a,b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-amino alcohols having a primary or secondary amino group are 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, 2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide,
2-hydroxypropylmethacrylamide, 3-hydroxypropylacrylamide,
3-hydroxypropylmethacrylamide, 3-hydroxybutylacrylamide,
3-hydroxybutylmethacrylamide, 4-hydroxybutylacrylamide,
4-hydroxybutylmethacrylamide, 6-hydroxyhexylacrylamide, 6-hydroxyhexylmethacrylamide, 3-hydroxy-2-ethylhexylacrylamide and 3-hydroxy-2-ethylhexylmethacrylamide.
In a particular embodiment, the monomer composition M1) comprises acrylic acid and optionally at least one comonomer selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids other than acrylic acid, salts, anhydrides, esters and amides of such a,b-ethylenically unsaturated mono- and dicarboxylic acids other than acrylic acid, olefinically unsaturated sulfonic acids, salts of olefinically unsaturated sulfonic acids, nitrogen heterocycles having a free-radically polymerizable a,b-ethylenically unsaturated double bond, C2-C10 monoolefins, nonaromatic hydrocarbons having at least two conjugated double bonds, vinyl aromatics, N-vinyllactams and mixtures thereof.
In a specific embodiment, the monomer composition M1) comprises acrylic acid and optionally at least one comonomer selected from isobutene, diisobutene, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, maleic acid, maleic anhydride, itaconic acid, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, styrene and mixtures thereof. In a very specific embodiment, the monomer composition M1) comprises acrylic acid and optionally at least one comonomer selected from methacrylic acid, 2-acrylamido-2- methylpropanesulfonic acid and mixtures thereof.
More particularly, the monomer composition M1) consists to an extent of at least 80% by weight, preferably to an extent of at least 90% by weight and especially to an extent of at least 95% by weight, based on the total weight of the monomer composition M 1 ), of acrylic acid.
The monomer composition M1) may comprise each of the further monomers C1) to C6) preferably in an amount of 0% to 30% by weight, more preferably 0% to 20% by weight and especially 0% to 10% by weight, based on the total weight of the monomer composition M1). When the monomer composition M1) comprises at least one monomer selected from C1) to C6), it does so in each case preferably in an amount of 0.1 % to 30% by weight, more preferably 1 % to 20% by weight and especially 1.5% to 10% by weight, based on the total weight of the monomer composition M 1 ).
In a specific embodiment, the monomer composition M1) does not comprise any further comonomers except for the monomers A) and B).
Even more specifically, the monomer composition M1) does not comprise any further comonomers apart from acrylic acid.
The polymer composition P1) comprises essentially non-crosslinked polymers. The monomer composition M1) used for production of the polymer composition P1) of the invention thus especially does not comprise any added crosslinking monomers. In the context of the invention, crosslinking monomers are compounds having two or more than two polymerizable ethylenically unsaturated double bonds per molecule.
Preferably, the monomer composition M1), based on the total weight, comprises less than 0.1 % by weight, more preferably less than 0.05% by weight and especially less than 0.001 % by weight of crosslinking monomers having two or more than two free- radically polymerizable a,b-ethylenically unsaturated double bonds per molecule.
In a specific embodiment, the monomer composition M1) does not comprise any crosslinking monomers having two or more than two polymerizable a,b-ethylenically unsaturated double bonds per molecule. Polyether component PE)
Suitable polyether components PE) are polyetherols having a number-average molecular weight of at least 200 g/mol and the mono- and di(Ci-C6-alkyl) ethers thereof.
Suitable polyetherols and the mono- and di(Ci-C6-alkyl) ethers thereof may be linear or branched, preferably linear. Suitable polyetherols and the mono- and di(Ci-C6-alkyl) ethers thereof generally have a number-average molecular weight in the range from about 200 to 100000 g/mol, preferably 300 to 50000 g/mol and more preferably 500 to 40000 g/mol. Suitable polyetherols are, for example, water-soluble or water-dispersible nonionic polymers having repeat alkylene oxide units. Preferably, the proportion of repeat alkylene oxide units is at least 30% by weight, based on the total weight of the compound. Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers. Suitable alkylene oxides for preparation of alkylene oxide copolymers are, for example, ethylene oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide. Suitable examples are copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide. The alkylene oxide copolymers may comprise the copolymerized alkylene oxide units in randomly distributed form or in the form of blocks. Preferably, the proportion of repeat units derived from ethylene oxide in the ethylene oxide/propylene oxide copolymers is 40% to 99% by weight. Particularly preferred polyether components PE) are ethylene oxide homopolymers and ethylene oxide/propylene oxide copolymers.
Suitable polyether components PE) are additionally the mono- and di(Ci-C2-alkyl) ethers of the above-described polyetherols. Preference is given to polyalkylene glycol monomethyl ethers and polyalkylene glycol dimethyl ethers.
In a preferred embodiment the polyether component PE) comprises or consists of at least one polyetherol or a mono- or di-(Ci-C2-alkyl) ether thereof comprising exclusively ethylene oxide units incorporated as alkylene oxide units.
Suitable polyether components PE) are additionally surfactants containing polyether groups. In general, nonionic and ionic surfactants having at least one nonpolar group and at least one polar group and comprising a polyether group are suitable.
The surfactants PE) containing polyether groups are preferably selected from alkyl polyoxyalkylene ethers, aryl polyoxyalkylene ethers, alkylaryl polyoxyalkylene ethers, alkoxylated animal and/or vegetable fats and/or oils, fatty amine alkoxylates, fatty acid amide alkoxylates, fatty acid diethanolamide alkoxylates, polyoxyethylene sorbitan fatty acid esters, alkyl polyether sulfates, aryl polyether sulfates, alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl polyether sulfonates, alkylaryl polyether sulfonates, alkyl polyether phosphates, aryl polyether phosphates, alkylaryl polyether phosphates, glyceryl ether sulfonates, glyceryl ether sulfates, monoglyceride (ether) sulfates, fatty acid amide ether sulfates, polyoxyalkylene sorbitan fatty acid esters and mixtures thereof.
The preferred nonionic surfactants PE) containing polyether groups include, for example: alkyl polyoxyalkylene ethers which derive from low molecular weight C3-C6 alcohols or from C7-C30 fatty alcohols. The ether component here may be derived from ethylene oxide units, propylene oxide units, 1 ,2-butylene oxide units,
1 ,4-butylene oxide units and random copolymers and block copolymers thereof. Suitable nonionic surfactants comprise, inter alia, surfactants of the general formula (VI)
R10-O-(CH2CH2O)x-(CHR11CH2O)y-R12 (VI) in which R10 is a linear or branched alkyl radical having 6 to 22 carbon atoms,
R11 and R12 are each independently hydrogen or a linear or branched alkyl radical having 1 to 10 carbon atoms or H, where R12 is preferably methyl, and x and y are each independently 0 to 300. Preferably, x = 1 to 100 and y = 0 to 30.
These especially also include fatty alcohol alkoxylates and oxo alcohol alkoxylates, such as isotridecyl alcohol polyoxyethylene ethers and oleyl alcohol polyoxyethylene ethers. surfactants containing hydroxyl groups of the general formula (VII)
Figure imgf000027_0001
the sequence of the alkylene oxide units in the compounds of the formula (VII) is arbitrary, s, t, u and v are each independently an integer from 0 to 500, where the sum of s, t, u and v is > 0, R13 and R15 are each independently a straight-chain or branched saturated Ci-C4o-alkyl radical or a mono- or polyunsaturated C2-C4o-alkenyl radical, and
R14 is selected from methyl, ethyl, n-propyl, isopropyl and n-butyl.
In the compounds of the general formula (VII), the sum of s, t, u and v is preferably a value of 10 to 300, more preferably of 15 to 200 and especially of 20 to 150.
Preferably, t and u are each 0. In that case, the sum of s and v is preferably a value of 10 to 300, more preferably of 15 to 200 and especially of 20 to 150.
In the compounds of the general formula (VII), R13 and R15 are preferably independently a straight-chain or branched saturated C2-C3o-alkyl radical. At the same time, R13 and R15 may also be mixtures of different alkyl radicals.
In the compounds of the general formula (VII), R14 is preferably methyl or ethyl, especially methyl.
A preferred embodiment is surfactants containing hydroxyl groups of the general formula (VI 1.1)
R13-0-(CH2CH20)S-(CH2CH(CH3)0)V-CH2CH(0H)R15 (VII.1 ) where the sequence of the -(CH2CH20)- and the (CH2CH(CH3)0)- units is arbitrary, s and v are each independently an integer from 0 to 500, where the sum of s and v is > 0, and
R13 and R15 are independently a straight-chain saturated Ci-C3o-alkyl radical or a branched saturated C3-C3o-alkyl radical or a mono- or polyunsaturated C2-C30- alkenyl radical. In the compounds of the general formula (VI 1.1), the sum of s and v is preferably a value of 10 to 300, more preferably of 15 to 200 and especially of 20 to 150.
The group of these nonionic surfactants includes, for example, hydroxy mixed ethers of the general formula (C6-22-alkyl)-CH(OH)CH2O-(EO)20-i20-(C2-26-alkyl). alcohol polyoxyalkylene esters of the general formula (VIII) R16-0-(CH2CH20)p-(CH2CHR170)q-C(=0)R18 (VIII) where the sequence of the alkylene oxide units in the compounds of the formula (VIII) is arbitrary, p and q are each independently an integer from 0 to 500, where the sum of p and q is > 0,
R16 and R18 are each independently a straight-chain or branched saturated Ci-C4o-alkyl radical or a mono- or polyunsaturated C2-C4o-alkenyl radical, and
R17 is selected from methyl, ethyl, n-propyl, isopropyl and n-butyl.
In the compounds of the general formula (VIII), the sum of p and q is preferably a value of 10 to 300, more preferably of 15 to 200 and especially of 20 to 150.
In the compounds of the general formula (VIII), R16 and R18 are preferably each independently a straight-chain or branched saturated C4-C3o-alkyl radical. At the same time, R16 and R18 may also be mixtures of different alkyl radicals.
In the compounds of the general formula (VIII), R17 is preferably methyl or ethyl, especially methyl.
These include, for example, lauryl alcohol polyoxyethylene acetate. alkylaryl alcohol polyoxyethylene ethers, e.g. octylphenol polyoxyethylene ethers, alkoxylated animal and/or vegetable fats and/or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates, alkylphenol alkoxylates, for example ethoxylated isooctyl-, octyl- or nonylphenol, tributylphenol polyoxyethylene ether, fatty amine alkoxylates, fatty acid amide and fatty acid diethanolamide alkoxylates, especially ethoxylates thereof, polyoxyalkylene sorbitan fatty acid esters. One example of an alkyl polyether sulfate is sodium dodecyl poly(oxyethylene) sulfate (sodium lauryl ether sulfate, SLES). A preferred commercially available modified fatty alcohol polyglycol ether is a polyethylene oxide Cxhhx+i/Cyhhy+i-terminated at either end and having a free OH group and x, y = 6-14.
In a further embodiment the detergent formulation according to the invention may comprise at least one further substance selected from polymer compositions P2), which differs from the polymer composition P1), builder, bleach, additives different therefrom and mixtures thereof.
In another further embodiment the detergent formulation according to the invention comprising one or more separate domains comprising at least one further substance selected from polymer compositions P2), which differs from the polymer composition P1), builder, bleach, additives different therefrom and mixtures thereof.
In a preferred embodiment, the individual detergent formulations of the invention are water-soluble or water-dispersible. According to the field of use of the detergent formulation of the invention, it may be advantageous for the detergent formulation to constist of one single domain or more than one individual separate domains. The individual domains may differ in at least one physical and/or chemical property e.g. their content, their solubility in water etc. For example, it may be desirable for different domains to have different solubility in water. It may also be desirable, for example, for a domain on the outer surface to have a lesser degree of water solubility in order to prevent blocking and/or partial dissolution in the event of high air humidity and/or high contact moisture (e.g. hand moisture). Alternatively, it may also be desirable for an outer surface domain to have high water solubility in order to rapidly release an active ingredient present therein or ensheathed therewith on contact with water. Such a domain may then have water-insoluble outer packaging to prevent unwanted contact with water. According to the field of use of the detergent formulation of the invention, it may also be advantageous for the detergent formulations of the invention to have a temperature-dependent solubility in water. Alternatively, it may also be desirable to have different domains for active ingredients that are not completely compatible with each other, e.g. one domain containing an enzyme and another domain containing a bleach.
Polymer P2)
In a special embodiment, the detergent formulation of the invention comprises at least one polymer P2) different from polymers of the polymer composition P1). In one preferred embodiment the polymer P2) is in the same domain as the polymer composition P1). In another embodiment the polymer P2) may be in at least one separate domain.
The detergent formulation of the invention, preferably comprises at least one polymer P2) selected from natural and modified polysaccharides, homo- and copolymers comprising repeat units which derive from vinyl alcohol, vinyl esters, alkoxylated vinyl alcohols or mixtures thereof, homo- and copolymers comprising at least one copolymerized monomer selected from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine,
4-vinylpyridine, salts of the three latter monomers, vinylpyridine N-oxide,
N-carboxymethyl-4-vinylpyridium halides and mixtures thereof, homo- and copolymers of acrylic acid and/or methacrylic acid, especially copolymers comprising at least one copolymerized acrylic monomer selected from acrylic acid, acrylic salts and mixtures thereof, and at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof, copolymers comprising at least one copolymerized (meth)acrylic monomer selected from acrylic acid, methacrylic acid, salts thereof and mixtures thereof and at least one copolymerized hydrophobic monomer selected from Ci-Cs-alkyl esters of (meth)acrylic acid, C2-C10 olefins, styrene and a-methylstyrene, copolymers comprising at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof and at least one copolymerized C2-C8 olefin, homo- and copolymers of acrylamide and/or methacrylamide, polyamino acids, water-soluble or water-dispersible polyamides, polyalkylene glycols, mono- or diethers of polyalkylene glycols, and mixtures thereof.
The detergent formulation of the invention, preferably comprises at least one polymer P2) selected from cellulose ethers and cellulose esters, homo- and copolymers comprising repeat units which derive from vinyl alcohol, vinyl esters, alkoxylated vinyl alcohols or mixtures thereof, polymers selected from polyvinylpyrrolidone homopolymers, polyvinylimidazole homopolymers, copolymers comprising copolymerized vinylpyrrolidone and vinylimidazole, polyvinylpyridine N-oxide, poly-N-carboxymethyl-4-vinylpyridium halides, mixtures thereof.
The detergent formulation of the invention especially comprises at least one polymer P2) selected from cellulose derivatives, preferably carboxyalkyl celluloses and salts thereof, sulfoalkyl celluloses and salts thereof, acidic sulfuric ester salts of cellulose, alkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses and mixtures of two or more of these cellulose derivatives.
Polysaccharides suitable as polymers P2) are natural polysaccharides, for example cellulose, hemicellulose, xyloglucan, glycogen, starch (amylose and amylopectin), dextran, pectins, inulin, xanthan, chitin, callose, and thermally, hydrolytically or enzymatically degraded starch, e.g. maltodextrin etc.
Preferred modified polysaccharides are, for example, cellulose ethers, cellulose esters, cellulose amides, etc.
Cellulose ethers are derivatives of cellulose which arise through partial or complete substitution of the hydrogen atoms in the hydroxyl groups of the cellulose. Cellulose ethers from the reaction of cellulose with more than one etherifying agent are also referred to as cellulose mixed ethers.
Preferred cellulose ethers are selected from alkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses, carboxyalkyl celluloses and salts thereof, carboxyalkyl alkyl celluloses and salts thereof, carboxyalkyl hydroxyalkyl celluloses and salts thereof, carboxyalkyl hydroxyalkyl alkyl celluloses and salts, sulfoalkyl celluloses and salts thereof.
Preferred carboxyalkyl radicals are the carboxymethyl radical and the carboxyethyl radical. A particularly preferred carboxyalkyl radical is the carboxymethyl radical. Preferred sulfoalkyl radicals are the sulfomethyl radical and the sulfoethyl radical. A particularly preferred sulfoalkyl radical is the sulfomethyl radical. Preferred salts are the sodium, potassium, calcium and ammonium salts.
Particularly preferred cellulose ethers are selected from carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, ethyl cellulose, n-propyl cellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxybutyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl ethyl cellulose, carboxymethyl methyl cellulose, carboxymethyl ethyl cellulose, carboxymethyl hydroxyethyl cellulose, carboxymethyl hydroxyethyl methyl cellulose, carboxymethyl hydroxyethyl ethyl cellulose, sulfomethyl cellulose and sulfoethyl cellulose. The carboxyalkyl radicals and the sulfoalkyl radicals may also be in salt form.
Cellulose esters are derivatives of cellulose which form as a result of esterification of the hydroxyl groups with acids. Preference is given to the sulfuric esters of cellulose. In a specific embodiment, the sulfuric acid is subjected only to a partial esterification, such that the resulting sulfuric esters still have free acid groups or salts thereof. Particular preference is given to using acidic sulfuric ester salts of cellulose. These are notable for their graying-inhibiting effect.
Preferred modified polysaccharides are selected from methyl cellulose, ethyl cellulose, propyl cellulose, methyl/ethyl cellulose, ethyl/propyl cellulose, carboxymethyl cellulose, salts of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, etc.
In a further preferred embodiment, the polymers P2) are selected from homo- and copolymers comprising repeat units which derive from vinyl alcohol, vinyl esters, alkoxylated vinyl alcohols or mixtures thereof.
Suitable vinyl esters (vinyl acylates) are generally the esters of vinyl alcohol with C1-C15 carboxylic acids, preferably Ci-Cs carboxylic acids, more preferably C1-C4 carboxylic acids. Preferred vinyl acylates are vinyl acetate, vinyl n-propionate, vinyl n-butyrate, vinyl 2-ethylhexanoate, vinyl laurate, etc. Particular preference is given to vinyl acetate.
Partly or fully hydrolyzed polyvinyl acetates (PVAs) are generally referred to as "polyvinyl alcohol (PVOH)". Partly hydrolyzed polyvinyl acetates are obtained by incomplete hydrolysis of polyvinyl acetates, meaning that the partly hydrolyzed polymer has both ester groups and hydroxyl groups. The hydrolysis of the polyvinyl acetates can be effected in a manner known per se under alkaline or acidic conditions, i.e. with addition of acid or base.
The performance properties of polyvinyl alcohols are determined by factors including the polymerization level and the hydrolysis level (level of hydrolysis). With rising hydrolysis level, the water solubility decreases. Polyvinyl alcohols having hydrolysis levels up to about 90 mol% are generally soluble in cold water. Polyvinyl alcohols having hydrolysis levels of about 90 to about 99.9 mol% are generally no longer soluble in cold water but are soluble in hot water.
Polyvinyl alcohols suitable as polymers P2) preferably have a hydrolysis level of 50 to 99.9 mol%, more preferably of 70 to 99 mol%, especially of 80 to 98 mol%. Polyvinyl alcohols suitable as polymers P2) preferably have a weight-average molecular weight of 10000 to 300000 g/mol, more preferably of 15000 to 250 000 g/mol.
Polyvinyl alcohols suitable as polymers P2) preferably have a viscosity of 2 to 120 mPa-s, more preferably of 7 to 70 mPa-s and especially of 15 to 60 mPa-s, measured to DIN 53015 on a 4% solution in water. In a further preferred embodiment, the polymers P2) are selected from homo- and copolymers comprising at least one copolymerized monomer selected from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, salts of the three latter monomers, vinylpyridine N-oxide, N-carboxymethyl-4-vinylpyridium halides and mixtures thereof.
N-Vinylimidazole, 2-vinylpyridine and 4-vinylpyridine can be converted to the corresponding salts by protonation or quaternization. Suitable acids are, for example, mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and carboxylic acids. Alkylating agents suitable for quaternization are Ci-C4-alkyl halides or Ci-C4-alkyl sulfates, such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.
Preference is given to polyvinylpyrrolidone homopolymers and copolymers comprising copolymerized N-vinylpyrrolidone and another different copolymerized ethylenically unsaturated monomer. Suitable N-vinylpyrrolidone copolymers are quite generally uncharged, anionic, cationic and amphoteric polymers.
Particularly preferred N-vinylpyrrolidone copolymers are selected from copolymers of N-vinylpyrrolidone and vinyl acetate, copolymers of N-vinylpyrrolidone and vinyl propionate, copolymers of N-vinylpyrrolidone, vinyl acetate and vinyl propionate, copolymers of N-vinylpyrrolidone and vinyl acrylate, copolymers of N-vinylpyrrolidone, ethyl methacrylate and methacrylic acid, copolymers of N-vinylpyrrolidone and N-vinylimidazole and the derivatives thereof obtained by protonation and/or quaternization, copolymers of N-vinylpyrrolidone and dimethylaminoethyl methacrylate and the derivatives thereof obtained by protonation and/or quaternization, copolymers of N-vinylpyrrolidone, N-vinylcaprolactam and N-vinylimidazole and the derivatives thereof obtained by protonation and/or quaternization. In a further preferred embodiment, the polymers P2) are selected from homo- and copolymers of acrylic acid and/or methacrylic acid.
In a first specific embodiment of the homo- and copolymers of acrylic acid and/or methacrylic acid, the polymer P2) used is an acrylic acid homopolymer. Acrylic acid homopolymers P2) preferably have a number-average molecular weight in the range from 800 to 70 000 g/mol, more preferably 900 to 50000 g/mol, particularly 1000 to 20000 g/mol and especially 1000 to 10 000 g/mol. In this context, the term "acrylic acid homopolymer" also encompasses polymers in which the carboxylic acid groups are in partly or fully neutralized form. These include acrylic acid homopolymers in which the carboxylic acid groups are present partly or completely in the form of alkali metal salts or ammonium salts. Preference is given to acrylic acid homopolymers in which the carboxylic acid groups are protonated or are partly or completely in the form of sodium salts. Homopolymers of acrylic acid particularly suitable as polymers P2) are the Sokalan ® PA brands from BASF SE.
In a second specific embodiment of the homo- and copolymers of acrylic acid and/or methacrylic acid, polymer P2) used is a copolymer comprising at least one copolymerized acrylic acid monomer selected from acrylic acid, acrylic salts and mixtures thereof and at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof. These preferably have a number-average molecular weight in the range from 2500 to 150000 g/mol, more preferably 2800 to 70000 g/mol, particularly 2900 to 50000 g/mol and especially 3000 to 30000 g/mol. Also included here are copolymers in which the carboxylic acid groups are in partly or fully neutralized form. For this purpose, it is either possible to use monomers in salt form for polymerization or for the resulting copolymer to be subjected to partial or complete neutralization. Preference is given to copolymers in which the carboxylic acid groups are protonated or are partly or completely in the form of alkali metal salts or ammonium salts. Preferred alkali metal salts are sodium or potassium salts, especially the sodium salts.
Preferred polymers P2) are copolymers of maleic acid (or maleic monomers) and acrylic acid (or acrylic monomers) in a weight ratio of 10:90 to 95:5, more preferably those in a weight ratio of 30:70 to 90:10.
Preferred polymers P2) are also terpolymers of maleic acid (or maleic monomers), acrylic acid (or acrylic monomers) and a vinyl ester of a C1-C3 carboxylic acid in a weight ratio of 10 (maleic acid):90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester). The weight ratio of acrylic acid to vinyl ester is preferably within a range from 30:70 to 70:30. Particularly suitable polymers P2) based on acrylic monomers and maleic monomers are the corresponding Sokalan ® CP brands from BASF SE.
In a third specific embodiment of the homo- and copolymers of acrylic acid and/or methacrylic acid, polymer P2) used is a copolymer comprising at least one
(meth)acrylic acid monomer selected from (meth)acrylic acid, (meth)acrylic salts and mixtures thereof and at least one hydrophobic monomer. The hydrophobic monomer is especially selected from Ci-Cs-alkyl esters of (meth)acrylic acid, for example the methyl, ethyl, n- and isopropyl, n-butyl and 2-ethylhexyl esters of (meth)acrylic acid and C2-C10 olefins, for example ethene, propene, 1,2-butene, isobutene, diisobutene, styrene and a-methylstyrene.
In a further preferred embodiment, the polymer P2) used is a copolymer of at least one maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof with at least one C2-C8 olefin. Also suitable are copolymers comprising at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof, at least one copolymerized C2-C8 olefin and at least one other different copolymerized comonomer. Particular preference is given to copolymers comprising at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof and at least one copolymerized C2-C8 olefin as the sole monomers. These preferably have a number-average molecular weight in the range from 3000 to 150 000 g/mol, more preferably 5000 to 70000 g/mol, particularly 8000 to 50000 g/mol and especially 10000 to 30000 g/mol. Also included here are copolymers in which the carboxylic acid groups are in partly or fully neutralized form. For this purpose, it is either possible to use maleic salts for polymerization or for the resulting copolymer to be subjected to partial or complete neutralization. Preference is given to copolymers in which the carboxylic acid groups are protonated or are partly or completely in the form of alkali metal salts or ammonium salts. Preferred alkali metal salts are sodium or potassium salts, especially the sodium salts.
A specific embodiment is copolymers of maleic acid with C2-C8 olefins in a molar ratio of 40:60 to 80:20, particular preference being given to copolymers of maleic acid with ethylene, propylene, isobutene, diisobutene or styrene. Particularly suitable compounds which contain carboxylic acid groups and are based on olefins and maleic acid are likewise the corresponding Sokalan ® CP brands from BASF SE.
A further preferred embodiment is that of copolymers comprising at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof, at least one copolymerized C2-C8 olefin and at least one copolymerized acrylic monomer selected from acrylic acid, acrylic salts and mixtures thereof.
A further preferred embodiment is that of copolymers comprising at least one copolymerized maleic monomer selected from maleic acid, maleic anhydride, maleic salts and mixtures thereof, at least one copolymerized C2-C8 olefin and at least one copolymerized ester of (meth)acrylic acid. In that case, the ester of (meth)acrylic acid is especially selected from Ci-Cs-alkyl esters of (meth)acrylic acid, for example the methyl, ethyl, n- and isopropyl, n-butyl and 2-ethylhexyl esters of (meth)acrylic acid.
In a further preferred embodiment, the polymers P2) are selected from homo- and copolymers comprising at least one copolymerized monomer selected from acrylamide, methacrylamide and mixtures thereof. These polymers P2) are preferably water-soluble or water-dispersible. These polymers P2) are especially water-soluble.
In a specific embodiment, the polymers P2) are selected from homopolymers of acrylamide or methacrylamide.
In a further specific embodiment, the polymers P2) are selected from copolymers of acrylamide and/or methacrylamide. These comprise at least one copolymerized comonomer selected from hydrophilic monomers (A1) other than acrylamide and methacrylamide, monoethylenically unsaturated amphiphilic monomers (A2) and further ethylenically unsaturated monomers (A3). Suitable hydrophilic monoethylenically unsaturated monomers (A1) are uncharged monomers such as N-methyl(meth)acrylamide, N,N'-dimethyl(meth)acrylamide or N-methylol(meth)acrylamide, monomers comprising hydroxyl and/or ether groups, for example hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether, hydroxyvinyl butyl ether, polyethylene glycol (meth)acrylate, N-vinylformamide, N-vinylacetamide, N-vinyl- pyrrolidone or N-vinylcaprolactam, and vinyl esters, for example vinyl formate or vinyl acetate. After polymerization, N-vinyl derivatives may be hydrolyzed to vinylamine units, and vinyl esters to vinyl alcohol units. Suitable hydrophilic monoethylenically unsaturated monomers (A1) are also monomers comprising at least one acidic group or salts thereof. These include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acryl- amidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid, 2-acrylamido- 2,4,4-trimethylpentanesulfonic acid, vinylphosphonic acid, allylphosphonic acid, N-(meth)acrylamidoalkylphosphonic acids, (meth)acryloyloxyalkylphosphonic acids and salts and mixtures thereof. The further monoethylenically unsaturated hydrophilic monomers may be hydrophilic cationic monomers. Suitable cationic monomers (A1c) especially include monomers having ammonium groups, especially ammonium derivatives of N-(m-aminoalkyl)(meth)acrylamides or w-aminoalkyl (meth)acrylates.
The amphiphilic monomers (A2) are monoethylenically unsaturated monomers having at least one hydrophilic group and at least one, preferably terminal, hydrophobic group.
The monomers (A3) may, for example, be monoethylenically unsaturated monomers which have a more hydrophobic character than the hydrophilic monomers (A1) and are accordingly water-soluble only to a minor degree. Examples of such monomers include N-alkyl- and N,N'-dialkyl(meth)acrylamides, where the number of carbon atoms in the alkyl radicals together is at least 3, preferably at least 4. Examples of such monomers include N-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide or N-benzyl(meth)acrylamide.
In a further preferred embodiment, the polymers P2) are selected from polyamino acids. Suitable polyamino acids are in principle compounds comprising at least one copolymerized amino acid such as aspartic acid, glutamic acid, lysine, glycine, etc. The polyamino acids also include the derivatives obtainable by polymer-analogous reaction, such as esterification, amidation, etc. Preferred polyamino acids are polyaspartic acid, polyaspartic acid derivatives, polyglutamic acid, polyglutamic acid derivatives and mixtures thereof.
Polyaspartic acid can be prepared, for example, by alkaline hydrolysis of polysuccinimide (PSI, anhydropolyaspartic acid). Polysuccinimide can be prepared by thermal condensation of aspartic acid or from ammonia and maleic acid. Polyaspartic acid can be used, for example, as a biodegradable complexing agent and cobuilder in washing and cleaning compositions.
Polyamino acids having surfactant properties can be obtained by at least partly converting the free carboxylic acid groups of polyaspartic acid or polyglutamic acid to N-alkylamides and/or to esters. Polyaspartamides can also be prepared by reaction of polysuccinimide with amines. For preparation of hydroxylethylaspartamides, the ring opening of polysuccinimide can be conducted with ethanolamine. DE 3700 128 A and EP 0458079 A describe the subsequent esterification of such hydroxyethyl derivatives with carboxylic acid derivatives. Copolymeric polyaspartic esters are obtainable as described in DE 19545678 A by condensation of monoalkyl esters of maleic or fumaric acid with addition of ammonia. DE 19545 678 A further states that copolymeric polyaspartic esters are obtainable by reaction of polysuccinimide with alcohols, optionally followed by hydrolysis. According to the esterification level and hydrophobicity of the alcohol component, polyaspartic esters, aside from their biodegradability, are notable for excellent properties as stabilizers for O/W and W/O emulsions, as a foam-stabilizing and foam-boosting cosurfactant in washing and cleaning compositions, and as a complexing agent for metal cations.
In a further preferred embodiment, the polymers P2) are selected from polyalkylene glycols and mono- or diethers of polyalkylene glycols. Preferred polyalkylene glycols have a number - average molecular weight in the range from 1000 to 4 000 000 g/mol, more preferably from 1500 to 1 000 000 g/mol.
Suitable polyalkylene glycols and the mono- and diethers thereof may be linear or branched, preferably linear. Suitable polyalkylene glycols are, for example, water- soluble or water-dispersible nonionic polymers having repeat alkylene oxide units. Preferably, the proportion of repeat alkylene oxide units is at least 30% by weight, preferably at least 50% by weight and especially at least 75% by weight, based on the total weight of the compound. Suitable polyalkylene glycols are polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers. Suitable alkylene oxides for preparation of alkylene oxide copolymers are, for example, ethylene oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide. Suitable examples are copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide. The alkylene oxide copolymers may comprise the copolymerized alkylene oxide units in randomly distributed form or in the form of blocks. Preferably, the proportion of repeat units derived from ethylene oxide in the ethylene oxide/propylene oxide copolymers is 40% to 99% by weight. Particular preference is given to ethylene oxide homopolymers and ethylene oxide/propylene oxide copolymers.
Suitable mono- and diethers of polyalkylene glycols are the mono-(Ci-Ci8-alkyl) ethers and di-(Ci-Ci8-alkyl) ethers. Preferred mono- and diethers of polyalkylene glycols are the mono-(Ci-C6-alkyl) ethers and di-(Ci-C6-alkyl) ethers. Especially preferred are the mono-(Ci-C2-alkyl) ethers and di-(Ci-C2-alkyl) ethers. Especially preferred are polyalkylene glycol monomethyl ethers and polyalkylene glycol dimethyl ethers.
Polymer mixtures are suitable, for example, for adjusting the mechanical properties and/or the dissolution properties of the multilayer films of the invention. The polymers used in the polymer mixture may differ in terms of their chemical composition and/or in terms of their physicochemical properties.
In a specific embodiment, the detergent formulation of the invention comprises at least one separate domain comprising a mixture of 2 or more polymers. Suitable mixtures may comprise 2 or more different polymer compositions P1) or at least one polymer composition P1) and at least one polymer P2) or 2 or more different polymers P2).
In a first embodiment, a polymer mixture comprising 2 or more polymers which differ in terms of their chemical composition is used. In a second embodiment, a polymer mixture comprising 2 or more polymers which differ in terms of their molecular weight is used. According to this second embodiment, for example, a polymer mixture comprising at least two polymers P2) comprising repeating units, which derive from vinyl alcohol, is used.
If the detergent formulation according to the invention consist of one single domain, this domain comprises the polymer composition P1) and at least one further component selected from polymers P2), builder, bleach, additives and mixtures thereof.
If the detergent formulation according to the invention consist of two or more domains, at least one domain comprises or consists of the polymer composition P1).
Furthermore, each domain may comprise components selected from the polymer composition P1), polymers P2), builder, bleach, additives and mixtures thereof.
The remaining further components, like builder, bleach and additives are defined below.
Characterization of the detergent formulation in form of a three dimensional body
The detergent formulation of the invention is in form of a three dimensional shaped body which has a clarity value of at least 70% according to ASTM D1003 and a haze value of less than 75% according to ASTM D 1003. If the three dimensional body has two or more domains, the clarity and haze values refer to those domains, which comprise or consist of the polymer composition P1).
As used herein, the term "haze" is defined as that percentage transmitted light which in passing through a specimen (plate) deviates from the incident light by more than 2.5° on the average. The haze is determined according to ASTM D 1003.
As used herein, the term "clarity" is defined as that percentage transmitted light which in passing through a specimen (plate) deviates from the incident light by less than 2.5° on the average. The specimen should have substantially plane-parallel surfaces free of dust, grease, scratches and blemishes, and shall be free of distinct internal voids and particles. The clarity is determined according to ASTM D 1003. The detergent formulation according to the invention is preferably characterized by a clarity value of 75 to 100%, more preferably 80 to 100%, especially 85 to 100%, in particular 90 to 99.9%, the clarity value being measured on plaques of 1.1 mm thickness and measured with the method according to ASTM D1003.
The detergent formulation according to the invention is preferably characterized by a haze value which is smaller than 75%; the haze value being measured at a plate of 1.1 mm thickness. The detergent formulation preferably is characterized by a haze of 1 to 75%, in particular 2 to 60% is preferred. The haze is determined according to ASTM D 1003.
The detergent formulation in form of a three dimensional shaped body is non-tacky. In the sense of the invention non-tackiness is characterized by low values of the static friction load and/or the sliding friction load. If the a plane surface of a three dimensional body that exhibit low static or sliding friction is in contact with a plane surface of another body the three dimensional body is non-tacky. Stiction or static friction is the friction that needs to be overcome to enable relative motion of stationary objects in contact. Kinetic friction, also known as dynamic friction or sliding friction, occurs when two objects are moving relative to each other and rub together. The static friction load is the force that needs to be overcome to achieve relative motion of two stationary objects in planar contact. The dynamic frictional load is the force that must be applied for the relative movement of two bodies in planar contact. The static friction load and/or the sliding friction load are measured with the method according to ISO EN 8295 and are given in Newton (N). Static friction load and static friction value have the same meaning. Likewise, dynamic friction load and dynamic friction value have the same meaning.
The detergent formulation according to the invention has a static friction value in the range of 0.5 N to 20.0 N, preferably in the range of 1.0 N to 17 N. The detergent formulation according to the invention has a sliding friction value in the range of 0.1 N to 5.0 N, preferably in the range of 0.2 N to 4.0 N value according to ISO EN 8295.
As mentioned before, the three dimensional shaped body is characterized in that it has dimensions of at least 1 mm, in particular at least 2 mm, more particularly at least 3 mm, especially at least 4 mm in all spatial directions. The largest dimension of the three dimensional body in a spatial direction is preferably at most 100 mm. Preferably, the largest dimension of the three dimensional shaped body in one spatial direction is in the range of 20 mm to 100 mm or in the range of 55 to 100 mm. The smallest dimension of the three dimensional shaped body in at least one spatial direction is preferably at least 2 mm, in particular at least 4 mm. Preferably, the dimensions of the three dimensional shaped body is chosen such that the body cannot be swallowed, e.g. by a child. The dimensions may be the same for all spatial directions, i.e. in case of a sphere. Typically the dimensions in some spatial directions are distinct from dimensions in other spatial directions. Preference given to bodies, wherein the aspect ratios of the largest dimension to the smallest dimension is in in the range from 1:1 to 20:1. In particular, the three dimensional shaped body in a first spatial direction has a dimension in the range of 20 to 100 mm, and dimensions in the range of 2 to 100 mm in spatial directions, which are orthogonal to the first direction and to each other and where the aspect ratio of the largeest dimension to the smallest dimesion is preferably in the range of 1 :1 to 20:1.
Within the scope of the invention, an orthogonal coordinate system can be used to describe three dimensional bodies, whereby the largest longitudinal extension lies on one axis or of the coordinate system or parallel thereto, e.g. on the x-axis or parallel to the x-axis. In the case of bodies with a planar base surface, the base lies in the plane defined by the x-axis and the y-axis, also referred to as the x,y-plane. The z-axis orthogonal to x- and y-axes serves for the description of the material thickness. Typically the dimensions in the x-axis is in the range of 20 to 100 mm, while the dimensions in the y-axis and the z-axis are in the range of 2 to 100 mm. In particular the ratio of the dimension in direction of the x-axis to the dimension in the z-axis is in the range of 1 :1 to 20:1.
The shape of the three dimensional shaped body is not of particular importance for the purpose of the invention. It may be regular or irregular. The shape may be a geometrical or non-geometrical shape. Examples of geometrical shapes are polyhedrons, including Platonic bodies, Archimedean bodies, Catalan bodies (dual Archimedean bodies), Johnson bodies, including pyramids, and polygonal domes, further prisms, antiprisms, truncated pyramids, cuboids, round-shaped or spherical bodies including spheres, ellipsoids, cylinders, including circular cylinders, ellipsoidal cylinders, cylinders with spherical heads, cones and truncated cones, spherical domes, elliptic domes and ellipsoid domes, and mixed forms having polygonic and round shaped surfaces, including polyhedrons, such as cuboids or prisms, with rounded edges and the like. For aesthetic reasons, it is also possible to choose complex shapes, such as leaves, flowers, animals, etc.
The three dimensional shaped body may be hollow or massive.
The volume of the three dimensional shaped body is at least 0.001 cm3, in particular at least 0.01 cm3, more particularly at least 0.033 cm3 or at least 0.064 cm3 or at least 0.1 cm3 and especially at least 1 cm3. Frequently, the volume of the three dimensional shaped body is in the range of 0.01 to 50 cm3, in particular in the range of 0.033 to 25 cm3 or 0.064 to 25 cm3 or 0.1 to 25 cm3, especially in the range of 1 to 20 cm3. In case of hollow bodies, the volume refers to the massive parts of the body.
The detergent formulation according to the invention is flexible/elastic. In the context of the invention flexibility/elasticity is the property of a three dimensional body to be deformed (change the shape) under the action of force and to return to its original shape when the force is removed. The detergent formulation according to the invention, preferably has a flexibility/elasticity in the range of 15 to 55 N, more preferably in the range of 20 to 45 N, especially in the range of 25 to 40 N determined by TA.XTplus Texture Analyser.
Production of the detergent formulation in form of a three dimensional body
As mentioned above, the three dimensional body shaped bodies of the detergent composition are prepared by a process which comprises plastifying a detergent composition containing or consisting of the polymer composition P1), shaping the plastified detergent composition into the desired shape of a three dimensional shaped body and solidifying the plastified detergent composition by rapid cooling. In particular, the detergent formulation according to the invention can be obtained by mold casting, i.e. by pouring the liquified or plastified detergent composition containing or consisting of the polymer composition P1), e.g. a detergent solution or a molten detergend composition, into a mold with the shape of the respective body and allowing it to solidify.
As mentioned before, the process in particular comprises the following steps i) to iv) and optionally the drying step iv): i) providing a detergent composition comprising or consisting of the polymer composition P1 ) having a water content of at most 25% by weight, e.g. in the range of 1 to 25% by weight or in the range of 5 to 25% by weight, in particular in the range of 10 to 25% by weight, especially in the range of 10 to 20% by weight, based on the total weight of P1); ii) plastifying the detergent composition of step i) by heating the detergent composition to a temperature of at least 50°C, in particular at least 55°C, e.g. to a temperature in the range of 50 to 100°C, in particular in the range of 55 to 90°C or 55 to 85°C; iii) shaping the plastified detergent composition of step ii) into the desired shape of the three dimensional body; and iv) rapid cooling of the shaped detergent composition of step iii) to a temperature of at most -20°C, obtaining the detergent formulation in the shape of a three dimensional body, and v) optionally drying of the obtained detergent formulation.
Especially, the process for the prepartion of the detergent formulation in form of a three dimensional body as defined herein comprises the following steps: i) providing a polymer composition P1), having a water content at most of 25% by weight, e.g. in the range of 1 to 25% by weight or in the range of 5 to 25% by weight, in particular in the range of 10 to 25% by weight, especially in the range of 10 to 20% by weight, based on the total weight of P1 ); ii) plastifying the polymer composition P1) provided in step i) by heating to a temperature of at least 50°, in particular at least 55°C and/or at most 100°C, preferably at most 90°C, in particular at most 85°C, e.g. in the range of 50 to 100°C, in particular in the range of 55 to 90°C or 55 to 85°C; iii) shaping the plastified polymer composition P1) composition of step ii) into the desired shape of the three dimensional body, in particular by mold casting the plastified polymer composition P1) from step ii), iv) rapid cooling of the shaped, e.g. mold casted product from step iii) to a temperature at most -20°C, obtaining the detergent formulation in form of a three dimensional shaped body and v) optionally drying of the obtained detergent formulation.
Step i) providing a detergent composition comprising or consisting of the polymer composition P1)
The detergent composition used for producing the three dimensional shaped body can be prepared by analogy to the methods described in the prior art cited in the outset of the instant application. Typically it comprises the production by the polymer composition P1) by the process as described hereinafter, optionally followed by formulating the thus obtained polymer composition with further components, e. g. with components selected from the group consisting of the polymer P2) and conventional additives for detergent formulations which are described in section E of the instant application, including builders, Preferably, the detergent compositions used for producing the three dimensional shaped body comprises the polymer composition P1) or a mixture of the polymer composition P1 and the polymer P2) in an amount of at least 70% by weight, in particular at least 75% by weight, more particularly at least 80% by weight, based on the total weight of the detergent formulation. In particular, the detergent compositions comprises the polymer composition P1) or a mixture of the polymer composition P1 and the polymer P2) in an amount in the range of 70 to 99% by weight, more particular in the range of 75 to 99% by weight or in the range 75 to 95% by weight, in particular in the range of 75 to 90% by weight, especially in the range of 80 to 90% by weight, based on the total weight of the detergent formulation. In particular, the amount of the polymer composition P1 ) or the mixture of the polymer composition P1 ) and the polymer P2) in the detergent formulation is at least 90% by weight, especially at least 95% by weight, based on the total weight of the components in the detergent formulation, which are different from water, and may be up to 100% by weight, based on the total weight of the components in the detergent formulation, which are different from water.
Preferably, the detergent compositions used for producing the three dimensional shaped body comprises the polymer composition P1) or in an amount of at least 70% by weight, in particular at least 75% by weight, more particularly at least 80% by weight, based on the total weight of the detergent formulation. In particular, the detergent compositions comprises the polymer composition P1) in an amount in the range of 70 to 99% by weight, more particular in the range of 75 to 99% by weight or in the range 75 to 95% by weight, in particular in the range of 75 to 90% by weight, especially in the range of 80 to 90% by weight, based on the total weight of the detergent formulation. In particular, the amount of the polymer composition P1) in the detergent formulation is at least 90% by weight, especially at least 95% by weight, based on the total weight of the components in the detergent formulation, which are different from water, and may be up to 100% by weight, based on the total weight of the components in the detergent formulation, which are different from water.
Preferably, the polymer composition P1) is produced by
A) providing a monomer composition M1) comprising at least one monomer A) selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof,
B) subjecting the monomer composition M1) provided in step A) to a free-radical polymerization in the presence of at least one polyether component PE) selected from polyetherols having a number-average molecular weight of at least 200 g/mol, mono- and di(Ci-C6-alkyl) ethers thereof, surfactants containing polyether groups and mixtures thereof, optionally in the presence of at least one additive. With regard to the monomer composition provided in step A), reference is made in full to the aforementioned suitable and preferred monomers A) and the optional comonomers B) and C).
The free-radical polymerization of the monomer composition M1) in step B) is preferably conducted by the feed method. This generally involves metering at least the monomers in liquid form into the reaction mixture. Monomers which are liquid under the metering conditions can be fed into the reaction mixture without addition of a solvent S1); otherwise, the monomers are used as a solution in a suitable solvent S1). It is of course also possible to use monomers that are in solid form.
The free-radical polymerization for production of the polymer composition P1) can be effected in the presence of a solvent S1) selected from water, Ci-C6-alkanols, polyols other than PE) and the mono- and dialkyl ethers and mixtures thereof. Suitable polyols and the mono- and dialkyl ethers thereof also include alkylene glycol mono(Ci-C4-alkyl) ethers, alkylene glycol di(Ci-C4-alkyl) ethers, oligoalkylene glycols and mono(Ci-C4- alkyl) ethers and di(Ci-C4-alkyl) ethers thereof.
The solvent S1) is preferably selected from water, methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol mono(Ci-C4-alkyl) ethers, ethylene glycol di(Ci-C4-alkyl) ethers, 1,2-propylene glycol, 1,2-propylene glycol mono(Ci-C4-alkyl) ethers, 1,2-propylene glycol di(Ci-C4-alkyl) ethers, glycerol, polyglycerols, oligoalkylene glycols having a number-average molecular weight of less than 1000 g/mol and mixtures thereof. Suitable oligoethylene glycols are commercially available under the CTFA names
PEG-6, PEG-8, PEG-12, PEG-6-32, PEG-20, PEG-150, PEG-200, PEG-400, PEG-7M, PEG-12M and PEG-115M. These specifically include the Pluriol E® brands from BASF SE. Suitable alkyl polyalkylene glycols are the corresponding Pluriol A...E® brands from BASF SE.
The solvent S1) is more preferably selected from water, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
1 ,2-dipropylene glycol and mixtures thereof. In a specific embodiment, the solvent S1) used is selected from water and a mixture of water and at least one solvent S1) other than water, selected from ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
1 ,2-dipropylene glycol and mixtures thereof.
In a specific embodiment, the free-radical polymerization in step B) is effected in the presence of a solvent S1 ) consisting to an extent of at least 50% by weight, preferably to an extent of at least 75% by weight and especially to an extent of at least 90% by weight, based on the total weight of the solvent S1), of water. More particularly, the free-radical polymerization in step B) is effected in the presence of a solvent S1) consisting entirely of water.
Preferably, the free-radical polymerization in step B) is effected in feed mode, in which case feeds comprising at least one a,b-ethylenically unsaturated carboxylic acid do not comprise any solvent S1).
The metering rates of the monomer feed(s) and any further feeds (initiator, chain transfer agent, etc.) are preferably selected such that the polymerization is maintained with the desired conversion rate. The addition of the individual feeds here may be continuous, periodical, with constant or changing metering rate, essentially simultaneous or at different times. Preferably, the addition of all the feeds to the reaction mixture is continuous.
Preferably, for the free-radical polymerization, the monomer composition M1) and the polyether component PE) are used in a weight ratio of 0.5:1 to 5:1 , more preferably of 0.7:1 to 3:1.
If the polymer composition P1) is produced using a solvent S1), the weight ratio of the polyether component PE) to the component S1) is preferably in the range from 0.1 :1 to 5:1 , more preferably from 0.5:1 to 3:1.
Preferably, the free-radical polymerization in step B) is effected at a temperature in the range from 20 to 95°C, more preferably from 30 to 90°C, especially from 40 to 80°C.
The free-radical polymerization in step B) can be effected in the presence of at least one additive. Suitable additives are, for example, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, bitter substances, thickeners, solubilizers, organic solvents, electrolytes, antimicrobial active ingredients, antioxidants, UV absorbers and mixtures thereof.
Preferably, the free-radical polymerization in step B) of the process comprises B1) providing an initial charge comprising at least a portion of the polyether component PE), optionally at least a portion of the chain transfer agent CTA) and, if the polymerization is effected in the presence of a solvent S1), optionally at least a portion of S1 );
B2) adding the monomer composition M1) in one or more feed(s) and adding a feed comprising the free-radical initiator FRI), dissolved in a portion of at least one polyether component PE) and/or of the solvent S1), and optionally adding a feed comprising the amount of the chain transfer agent CTA) which is not used in the initial charge;
B3) optional post-polymerization of the reaction mixture obtained in step B2).
Typically, the initial charge is heated to the polymerization temperature before the feeds are added while stirring.
Preferably, the individual reactants are added simultaneously in separate feeds, the flow rates of the feeds generally being kept very substantially constant over the period of addition.
Preferably, the amount of polyether component PE) in the initial charge (step B1)) is 30% to 100% by weight, more preferably 65% to 100% by weight and especially 80% to 100% by weight, based on the total weight of the polyether component PE) used for polymerization.
Preferably, the content of solvent S1) in the initial charge is not more than 70% by weight, based on the total weight of the feedstocks in the initial charge. Preferably, the content of solvent in the initial charge is not more than 40% by weight, especially not more than 35% by weight, based on the total weight of the feedstocks in the initial charge. The amount of solvent generally changes only by a few percent by weight over the entire course of the process. Typically, solvents S1) having a boiling point at standard pressure (1 bar) of below 240°C are used.
In a further specific variant, the solvent is initially charged in its entirety.
In a further specific variant, the initial charge does not comprise any chain transfer agent. If a chain transfer agent is used, this is not added until step B2), via at least one of the feeds. The feeds are added in step B2) over a period of time which is advantageously selected such that the heat of reaction that arises in the course of the exothermic polymerization reaction can be removed without any great technical complexity, for example without the use of a reflux condenser. Typically, the feeds are added over a period of 1 to 10 hours. Preferably, the feeds are added over a period of 2 to 8 hours, more preferably over 2 to 6 hours.
In an alternative embodiment, the free-radical polymerization in step B) of the process is continuous. In that case, the monomer composition M1), the polyether component PE), at least one initiator, optionally at least one chain transfer agent CTA) and optionally at least one solvent S1) are added to the reactor in the form of one liquid stream or preferably at least two liquid streams. In general, the stream comprising the initiator generally does not comprise the chain transfer agent as well. If at least two liquid streams are used, these are typically mixed to obtain the reaction mixture. The polymerization can be effected in one stage or in two or more than two, i.e. in 2, 3, 4, 5 or more, stages. In a suitable embodiment, in the case of a multistage polymerization, at least one additional stream is mixed in between at least two of the polymerization stages. This may be a monomer-containing stream, initiator-containing stream, solvent- containing stream, chain transfer agent-containing stream, a mixture thereof and/or any other stream of matter.
During the free-radical polymerization, the optionally used solvent and/or any condensation products that form are generally not removed. In other words, during the polymerization, there is typically only very minor mass transfer with the surroundings, if any, within the scope of the technical options.
The polymerization can generally be effected at ambient pressure or reduced or elevated pressure. Preferably, the polymerization is conducted at ambient pressure.
The polymerization is generally effected at constant temperature, but it can also be varied during the polymerization if required. Preferably, the polymerization temperature is kept very substantially constant over the entire reaction period, i.e. steps B2) and B3). According to the feedstock which is used in the process of the invention, the polymerization temperature varies typically within the range from 20 to 95°C.
Preferably, the polymerization temperature varies within the range from 30 to 90°C and especially within the range from 40 to 80°C. If the polymerization is not conducted under elevated pressure and at least one optional solvent S1) has been added to the reaction mixture, the solvent or solvent mixture determines the maximum reaction temperature by virtue of the corresponding boiling temperatures.
The polymerization can be effected in the absence or presence of an inert gas. Typically, the polymerization is conducted in the presence of an inert gas. Inert gas is generally understood to mean a gas which, under the given reaction conditions, does not enter into any reaction with the reactants, reagents or solvents involved in the reaction or the products which form.
If the polymerization is conducted in the presence of a solvent, it is selected from the solvents S1) described above.
For preparation of the polymers, the monomers can be polymerized with the aid of free radical-forming initiators, also referred to hereinafter as free-radical initiators or initiators. Useful free-radical initiators for the free-radical polymerization are in principle all free-radical initiators which are essentially soluble in the reaction medium as exists at the time when they are added and have sufficient activity to initiate the polymerization at the given reaction temperatures. It is possible to introduce one individual free-radical initiator or a combination of at least two free-radical initiators into the process of the invention. In the latter case, the at least two free-radical initiators can be used in a mixture or preferably separately, simultaneously or successively, for example at different times in the course of the reaction.
Free-radical initiators which may be used for the free-radical polymerization are the peroxo and/or azo compounds customary for the purpose, for example hydrogen peroxide, alkali metal or ammonium peroxodisulfates (for example sodium peroxodisulfate), diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxymaleate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis(o-tolyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, tert-butyl peroctoate, dilauroyl peroxide, tert- butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride (= azobis(2-methylpropionamidine) dihydrochloride), azobis(2,4-dimethylvaleronitrile) or 2,2'-azobis(2-methylbutyronitrile).
Also suitable are initiator mixtures or redox initiator systems, for example ascorbic acid/iron(ll) sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodium disulfite, tert-butyl hydroperoxide/sodium hydroxymethanesulfinate,
H2O2/CU1.
In the process of the invention, the amount of initiator system (initiator) used varies within the range from 0.01 to 10 pphm, preferably within the range from 0.1 to 5 pphm, more preferably within the range from 0.2 to 2 pphm and especially within the range from 0.3 to 1.5 pphm (parts per hundred monomer = parts by weight per hundred parts by weight of monomer). In the process of the invention, the free-radical initiator is generally provided in the form of a solution in a solvent comprising at least one of the aforementioned solvents S1) and optionally additionally at least one polyether of polyether component PE).
The polymerization can be effected without using a chain transfer agent (polymerization chain transfer agent) or in the presence of at least one chain transfer agent. Chain transfer agents generally refer to compounds having high transfer constants which accelerate chain transfer reactions and hence bring about a reduction in the degree of polymerization of the resulting polymers. The chain transfer agents can be divided into mono-, bi- and polyfunctional chain transfer agents, according to the number of functional groups in the molecule that can lead to one or more chain transfer reactions. Suitable chain transfer agents are described in detail, for example, by K. C. Berger and G. Brandrup in J. Brandrup, E. H. Immergut, Polymer Handbook, 3rd edition, John Wiley & Sons, New York, 1989, pp. 11/81 - 11/141.
Suitable chain transfer agents are, for example, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde. Further usable chain transfer agents are formic acid and salts or esters thereof, such as ammonium formate, 2, 5-diphenyl-1 -hexene, hydroxyammonium sulfate and hydroxyammonium phosphate.
Further suitable chain transfer agents are allyl compounds, for example allyl alcohol, functionalized allyl ethers, such as allyl ethoxylates, alkyl allyl ethers, or glycerol monoallyl ether.
Chain transfer agents used are preferably compounds comprising sulfur in bound form. Compounds of this kind are, for example, inorganic hydrogensulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides and sulfones. These include di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide, dimethyl sulfoxide, dialkyl sulfide, dialkyl disulfide and/or diaryl sulfide. Also suitable as polymerization chain transfer agents are thiols (compounds which comprise sulfur in the form of SH groups, also referred to as mercaptans). Preferred chain transfer agents are mono-, bi- and polyfunctional mercaptans, mercaptoalcohols and/or mercaptocarboxylic acids. Examples of these compounds are allyl thioglycolates, ethyl thioglycolate, cysteine, 2-mercaptoethanol,
1 ,3-mercaptopropanol, 3-mercaptopropane-1 ,2-diol, 1 ,4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid, thiourea and alkyl mercaptans such as n-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan. Examples of bifunctional chain transfer agents which comprise two sulfur atoms in bonded form are bifunctional thiols, for example dimercaptopropanesulfonic acid (sodium salt), dimercaptosuccinic acid, dimercapto-1- propanol, dimercaptoethane, dimercaptopropane, dimercaptobutane, dimercaptopentane, dimercaptohexane, ethylene glycol bisthioglycolates and butanediol bisthioglycolate. Examples of polyfunctional chain transfer agents are compounds which comprise more than two sulfurs in bound form. Examples thereof are trifunctional and/or tetrafunctional mercaptans.
The chain transfer agent is more preferably selected from mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid, ethylhexyl thioglycolate and sodium hydrogensulfite.
Preferred chain transfer agents are also hypophosphorous acid (phosphinic acid) and salts of hypophosphorous acid. A preferred salt of hypophosphorous acid is the sodium salt.
If a chain transfer agent is used in the process of the invention, the amount is typically 1 to 40 pphm ("parts per hundred monomer", i.e. parts by weight based on one hundred parts by weight of monomer composition). Preferably, the amount of chain transfer agents used in the process of the invention is in the range from 3 to 30 pphm, more preferably in the range from 5 to 25 pphm. It is also possible to conduct the polymerization without adding a chain transfer agent.
Typically, the chain transfer agent is added continuously to the polymerization mixture in its entirety via one of the feeds in step B2). However, it is also possible to add the chain transfer agent either in its entirety to the initial charge, i.e. before the actual polymerization, or to include only some of the chain transfer agent in the initial charge and to add the remainder continuously to the polymerization mixture in step B2) via one of the feeds. The chain transfer agent can be added here in each case without or with solvent S1).
The amount of chain transfer agent and the way in which it is added to the reaction mixture have a major influence on the average molecular weight of the polymer composition P1). If no chain transfer agent or only a small amount of chain transfer agent is used and/or if the addition predominantly precedes the polymerization, this generally leads to higher average molecular weights of the polymer formed. If, by contrast, a relatively large amount of chain transfer agent is used and/or the chain transfer agent is added for the most part during the polymerization (step B2)), this generally leads to a smaller average molecular weight. In order to avoid or to reduce unwanted foam formation in the synthesis, in transport (for example in pumping) and in storage, and also in film production, defoamers and foam inhibitors may be used. In principle, all known foam inhibitors or defoamers are useful. Mention should be made here, for example, of (1) oil-based systems based on mineral oil or vegetable oil, which may additionally comprise waxes or silica particles, (2) water-based systems in which oil and waxes are dispersed, (3) silicone-based systems (polysiloxanes), for example in water-soluble form, as oil or water-based emulsion, (4) EO/PO-based polyalkoxylates, (5) alkyl polyacrylates, (6) fatty acids and fatty acid esters, especially mono- and diglycerides of fatty acids, (8) fatty alcohol alkoxylates, (9) defoamers from the class of the phosphoric esters and salts thereof, such as sodium (C6-C2o-alkyl)phosphates, e.g. sodium octylphosphate or tri(Ci-C2o- alkyl) phosphates, e.g. tributyl phosphate, and (10) metal soaps, such as aluminum stearate or calcium oleate. The polysiloxanes (polydimethylsiloxanes) can also be used in modified form, for example in alkyl group-modified or polyether group-modified form. These are used with preference.
Preferably, the polymer compositions P1) obtained when the polymerization has finished (step B3)) are transferred to a suitable vessel and optionally cooled directly to ambient temperature (20°C).
The polymer compositions P1) obtained in this way are advantageously suitable for production of detergent formulations in form of a three dimensional body, for example for use as a washing or cleaning composition. The production of three dimensional bodies thereon is described in detail hereinafter.
The weight-average molecular weight Mw of the polymer composition P1) of the invention was determined by means of gel permeation chromatography (GPC) in aqueous solution using neutralized polyacrylic acid as polymer standard. This type of molecular weight determination covers the components of the polymer composition P1) which comprise the monomers M1) in copolymerized form. The polymer composition P1) preferably has a weight-average molecular weight of 2000 to 100000 g/mol, preferably of 3000 to 80000 g/mol.
The polymer composition P1) has a sufficiently low glass transition temperature TG suitable for film formation. Preferably, the polymer compositions P1) have a glass transition temperature TG in the range from 0 to 80°C, more preferably from 0 to 60°C, especially from 0 to 30°C. In the process of the invention, the water content of the polymer composition P1 provided in step i) is at most 25% by weight based on the total weight of P1), e.g. in the range of 5 to 25% by weight, in particular in the range of 10 to 25% by weight, especially in the range of 10 to 20% by weight.
Preferably, the water content of the polymer composition P1 provided in step i) is in a range of 10 to 25% by weight based on the total weight of P1). In particular, the water content of the polymer composition P1 provided in step i) is in a range of 15 to 25% by weight based on the total weight of P1).
The water content of P1) can be adjusted by methods known by the skilled person.
Prior to use for detergent formulation in form as a three dimensional body production, the polymer composition P1) preferably has a content of acid groups of more than 1 mmol/g, more preferably of more than 1.3 mmol/g. Prior to use for detergent formulation in form as a three dimensional body production, the polymer composition P1) preferably has a content of acid groups of not more than 15 mmol/g. Prior to use for detergent formulation in form as a three dimensional body production, the polymer composition P1) especially has a content of acid groups of 1.5 mmol/g to 10 mmol/g.
In a preferred embodiment, the acid groups of the polymer composition P1) of the invention are in non-neutralized form.
In another preferred embodiment, the acid groups of the polymer composition P1) of the invention are partially neutralized. Particularly, 0 to 15% of the acid groups of the polymer composition P1) of the invention are neutralized. Especially, 5 to 10% of the acid groups of the polymer composition P1) of the invention are neutralized.
The thus obtained polymer composition P1) may be blended with the polymer P2) and/or with further additives to obtain the detergent composition. In particular, the polymer composition P1) or a mixture of the polymer composition P1) and the polymer P2) is used as the detergent composition for subsequent production steps of the three dimensional shaped body. Step ii)
As mentioned at the outset the production of the detergent formulation in form of a three dimensional body comprises plastifying the detergent composition obtained in step i), in particular the polymer composition P1) of step i). For the purposes of the present invention, the expressions "plastified detergent composition" "plastified polymer composition P1)" relates to polymer composition P1), which is heated to a temperature where its viscosity is sufficiently low that it gets flowable and can e.g. be transported in a pipe by applying pressure, e.g. by pumping, and can be casted in a mold or can be spread on a surface.
The detergent composition comprising or consisting of the polymer composition P1) can be plastified by heating it to a temperature of at least 50°C, in particular at least 55°C. Typically, the temperature will be at most 100°C. Preferably, the temperature of the detergent composition comprising or consisting of the polymer composition P1 ) is at most 90°C, in particular at 85°C. More particularly, the detergent composition comprising or consisting of the polymer composition P1) is heated to a temperature in the range from 50 to 100°C, especially in the range of 55 to 90°C or 55 to 85°C. Likewise, the polymer composition P1 ) can be plastified by heating it to a temperature of at least 50°C and preferably up to a temperature of at most 100°C in particular at most 90°C or at most 85°C. Preferably, the polymer composition P1) is heated to a temperature in the range from 50 to 100°C, in particular in the range of 50 to 90°C and especially in the range of 55 to 85°C.
Step iii) Shaping
The detergent composition comprising or consisting of the plastified polymer composition P1) from step ii) can be shaped into a three dimensional body by conventional molding techniques which include but are not limited to casting plastified detergent composition into a mold or by injection molding the detergent composition comprising or consisting of the plastified polymer composition P1).
In a special first embodiment, an injection molding process is employed for the production of a detergent formulation in form of a three dimensional body.
Multi-component injection molding may be used to produce injection molded parts consisting of two or more different polymer compositions. In the simplest case, the polymer compositions differ only in colour to achieve a specific design. However, different materials and thus different properties can also be combined in a targeted manner.
As with injection molding, there are also different techniques, e.g. composite injection molding or sandwich injection molding. Composite injection molding requires an injection molding machine with two or more injection units, but only one clamping unit. The parts can thus be produced cost-effectively with only one mold in a single operation. The injection units must work in harmony, but always be controllable independently of each other. The components can be injected through a single special nozzle or introduced into the mold at different points.
In injection molding, (embossed/functionalised) parts can be produced which consist of a polymeric carrier comprising or consisting of the polymer composition P1), and a covering material, such as a decorative material. There are various injection techniques, such as in-mold decorating (IMD), film insert molding (FIM), in-mold labeling (IML), in-mold coating (IMC) or in-mold painting (IMP). What they all have in common is that a pre-treated (embossed/functionalized) film is placed in an injection mold and injected and embossed with another plastic material to create a plastic part with functionality or film coating.
In particular, at least one of the following techniques is used for injection molding: In mold decoration (IMD), film insert molding (FIM), in-mold labeling (IML), in-mold coating (IMC) or in-mold painting (IMP).
The in-mold decoration process is a combination of hot pressing and film insert molding. It is used to emboss a functionality from a carrier foil, a special IMD foil, onto a substrate (polymer composition). The functionalized and/or embossed carrier film is placed in the injection mold. In the second step the polymer composition is injected. In the last step, the resulting molded part is removed from the mold and the carrier film is separated. The result is a plastic molding with an embossed functionality.
In the Film Insert Molding (FIM) process, the carrier film becomes part of the finished substrate. First, the carrier material, the stamping foil, can be functionalized (coated), preformed and cut. The foil, cut into shape, is placed in the injection mold and injected with a polymer composition. The exact sequence of the process steps is flexible.
Finally, the carrier foil may be removed or may form an integral part of the detergent formulation of the invention.
The in-mold coating is a combination of spraying and injection molding. First, a coating is applied to the injection mold by means of a spray gun. After the material has dried, the polymer composition is injected.
In the In-mold Painting process, the plastic material is sprayed in the first step, and the coating is sprayed on in the second step, i.e. the process steps are carried out in reverse order to the process steps of the IMC process.
Step iv) Cooling In order to solidify the shaped three dimensional body of the plastified shaped product obtained from step iii) is usually subjected to a deep cooling, in particular to a rapid cooling. Rapid cooling is also termed “shock frosting”. Deep cooling means that the shaped product obtained from step iii) to a temperature of at most -20°C, in particular at most -40°C, e.g. in the range of -20 to -200°C or -40 to -200°C. Rapid cooling and shock frosting, respectively, refer to a cooling, where the temperature of the shaped product obtained from step iii) is lowered with in at most 3 minutes, in particular at most 120 seconds to the desired temperature. Typically cooling rates of at least 0.5 K/s, especially at least 0.8 K/s, especially at least 1 K/s, e.g. in the range of 0.5 to 200 K/s or 0.8 to 150 K/s or 1 to 100 K/s are applied.
Rapid cooling can be achieved by contacting the shaped product from step iii) with a cooling agent, in particular a liquid or solid cooling agent having a temperature of at most -20°C, in particular at most -40°C, e.g. in the range of -20 to -200°C or -40 to - 200°C, whereby a the detergent formulation in form of a three dimensional body is obtained..
Suitable cooling mediums can be gasous, liquid or solid.
Preferred cooling agents are liquid nitrogen, solid carbon dioxide, liquid ethane, liquid propan, liquid perfluorinated alkanes. Suitable perfluorinated alkanes are e.g. perfluorohexane or perfluoro-(2-methyl-3-pentanone).
The cooling time required for rapid cooling depends on the size and mass of the detergent formulation according to the invention. Preferably, the cooling time is in the range of 5 to 120 seconds, in particular in the range of 10 seconds to 30 seconds. Preferably the shaped product from step iii) is kept at a temperature of at most -20°C, in particular at most -40°C for a period of at least minutes, e.g. for a period in the range of 5 to 60 minutes to complete solidification.
Step v) Drying
The detergent formulation obtained from step iv) may optionally be dried in order to remove volatile constituents of the detergent formulation, such as water. The detergent formulation obtained from step iv) can be dried by methods known by the skilled person. Typically drying is carried out at temperatures in the range of 0 to > 50°C, in particular in the range of 5 to 40°C.
Step vi) Including further additives The shaped detergent formulations obtained from the process of the present invention can be formulated with further additives.
A specific embodiment is a process for producing a detergent formulation of the invention comprising at least one additive. In this case, an individual separate domain or a plurality of domains but not all the domains or all the domains may each comprise one or more than one additive. Alternatively or additionally, it is possible that at least one additive is present in at least two domains. Additives may, as described above, already be added in the course of the free-radical polymerization in step B) or in the provision of the detergent formulation in form of a three dimensional body. Whether the addition is already effected in step B) or only in the provision of the detergent formulation according the invention depends on the nature and effect of the particular additive. The additives may be auxiliaries for adjustment of the properties of the detergent formulation in form of a three dimensional body or typical additives for the end use of the detergent formulation. Typical additives for the end use of the detergent formulation are especially selected from additives for washing compositions, cleaning compositions, dishwashing compositions, rinse aids, hygiene products, disinfectants, personal care compositions, crop protection compositions, bait traps, wetting agents, etc.
Preference is given to detergent formulations, which include at least one additive. Particular preference is given to detergent formulations, which include at least one further separate domain including an additive which is a constituent customary for washing and cleaning compositions.
In that case, the additive is preferably selected from nonionic, anionic, cationic and amphoteric surfactants, builders, complexing agents such as methylglycinediacetic acid, glutaminediacetic acid, glutamic acid diacetic acid and citric acid and the sodium and potassium salts thereof, bleaches, enzymes, enzyme stabilizers, bases, corrosion inhibitors, defoamers and foam inhibitors, wetting agents, dyes, pigments, fragrances, fillers, tableting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, bitter substances, fluorescers, hydrotropes, antiredeposition agents, optical brighteners, graying inhibitors, antishrink agents, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, anti-yellowing agents, corrosion inhibitors, antistats, ironing aids, hydrophobizing and impregnating agents, antiswell and antislip agents, plasticizers, scavengers, polymers other than the polymer compositions P1) and the polymers P2), agents for modification of gas permeability and water vapor permeability, antistats, glidants, slip agents, UV absorbers and mixtures thereof. In a preferred embodiment, the detergent formulation of the invention comprises, as additive, at least one enzyme and optionally at least one enzyme stabilizer. Suitable enzymes and enzyme stabilizers are those mentioned hereinafter as components E1).
Suitable bitter substances are those mentioned hereinafter as components E6).
Some additives and solvents, e. g. water, can fulfil more than one function, for example as solvent S1) and as plasticizer.
In order to make the detergent formulation of the invention more flexible, plasticizers can be added thereto in the course of production. For production of the detergent formulation, preferably 0.5% to 30% by weight, more preferably 2% to 20% by weight and especially 3% to 10% by weight of plasticizer is used, based on the total weight of the composition.
Suitable plasticizers are alkyleneamines, alkanolamines, polyols such as alkylene glycols and oligoalkylene glycols, e.g. 2-methylpropane-1,3-diol, 3-methylpentane-1 ,5- diol, hydroxypropylglycerol, neopentyl glycol, alkoxylated glycerol (for example Voranol® from Dow Chemicals), water-soluble polyesterpolyols (for example TriRez from Geo Specialty Chemicals) and mixtures thereof. Suitable plasticizers are also polyetherpolyols available under the Lupranol® name from BASF SE. The term "alkyleneamines" refers to condensation products of alkanolamines with ammonia or primary amines; for example, ethyleneamines are obtained by reaction of monoethanolamine with ammonia in the presence of a catalyst. This results in the following main components: ethylenediamine, piperazine, diethylenetriamine and aminoethylethanolamine.
Preferably, the plasticizers are selected from glycerol, diglycerol, propylene glycols having a weight-average molecular weight of up to 400, ethylene glycol, polyethylene glycols having a weight-average molecular weight of up to 400, diethylene glycol, triethylene glycol, tetraethylene glycol, sugar alcohols such as sorbitol, mannitol, xylitol, isomalt, lactitol, isopentyldiol, neopentyl glycol, trimethylolpropane, diethylenetriamine, triethylenepentamine, triethanolamine and mixtures thereof.
In order to make the detergent formulations of the invention more resistant to aggressive ingredients (for example chlorine-releasing compounds as used in the field of disinfection of water, etc.), it is possible to add what are called "scavengers" (capture molecules) to the composition. Suitable scavengers are polyamines, polymeric polyamines, such as polyethyleneimines, poly(amidoamines) and polyamides. In addition, it is also possible to use ammonium sulfate, primary and secondary amines having a low vapor pressure, such as ethanolamines, amino acid and salts thereof, and also polyamino acid and salts thereof, fatty amines, glucosamines and other aminated sugars. It is further possible to use reducing agents, such as sulfites, bisulfites, thiosulfites, thiosulfates, iodides, nitrites and antioxidants such as carbamates, ascorbates and mixtures thereof.
For production of the detergent formulations of the invention, it is possible to add further additives in the form of polymers to the polymer composition P1) and/or the polymers P2) before and/or during the production of the three dimensional body. Typically, 0.05% to 20% by weight, preferably 0.1 % to 15% by weight and more preferably 0.2% to 10% by weight of polymers (based on the total weight of the polymer composition P1), polymers P2) and additional polymers) are used. Such additives can simultaneously improve the washing properties of the detergent formulations, improve the mechanical properties of the detergent formulations, and increase the resistance of the detergent formulations to washing composition components. Suitable further polymers are, for example, oligosaccharides and polysaccharides, starch, degraded starches (maltodextrins), cellulose ethers, specifically hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, microcrystalline cellulose, inulin, carboxymethylcellulose, for example in the form of the sodium salts, alginic acid and alginates, pectin acid and pectins, polyethyleneimines, alkoxylated and especially ethoxylated polyethyleneimines, graft polymers of vinyl acetate onto polyalkylene glycols, especially onto polyethylene glycols, homopolymers of N-vinylpyrrolidone, copolymers of N-vinylpyrrolidone and N-vinylimidazole, copolymers of N-vinylpyrrolidone with vinyl acetate and with vinylcaprolactam, polyalkylene oxides, polyvinyl alcohol, polyvinyl alcohols with fractions of unhydrolyzed vinyl acetate, thickeners, for example xanthan gum, guar gum, gelatin, agar-agar and mixtures thereof. It is possible to subject the surface of the detergent formulations of the invention to at least a partial coating with at least one additive. It is also possible to subject the surface of at least one separate domain of the detergent formulations of the invention to at least partial coating with at least one additive. Such a treatment may serve, for example, to provide the surface with particular properties, such as nonstick action, antistatic action, hydrophilic or hydrophobic properties, etc. It is thus possible to provide the detergent formulations, for example, with better detachment properties from the carrier material used in the production, reduced tack, better compatibility with particular components ensheathed or coated therewith, etc. According to the nature and formulation of the additive, the application can be effected by standard methods, for example by spraying, dipping, powder application, etc. Suitable additives for coating of the surface of the detergent formulations of the invention are, for example, talc, surfactants such as silicone-containing surfactants, waxes, etc.
Printing or milling or engraving of the detergent formulations of the invention is also possible, in order to provide these, for example, with patterns, motifs, or inscriptions. The printing may follow the production of the detergent formulations or be effected in an intermediate step during the buildup of the layers. This printing step preferably follows directly inline after the film production, in a separate printing or converting process, or inline with the pod production. Suitable printing methods are inkjet printing, and also intaglio and planographic printing methods such as flexographic printing, gravure printing, offset printing or inkjet printing.
As stated above, the detergent formulation of the invention may preferably consist of 1 to 10 domains, more preferably 1 to 8 domains, e.g. 1, 2, 3, 4, 5, 6, 7 or 8 domains. The design and arrangement of the domains of the invention is guided by the desired end use.
According to the invention, the detergent formulation of the invention comprise a polymer composition P1). In a specific embodiment, one or more separate domains of the detergent formulation of the invention consists of a polymer composition P1).
In a preferred embodiment, the detergent formulation of the invention comprise a homo- or copolymer P2) comprising repeat units which derive from vinyl alcohol, vinyl esters or mixtures thereof. Preferred polymers P2) are polyvinyl alcohols having a hydrolysis level of 50 to 99 mol%, more preferably of 70 to 98 mol%.
In a specific embodiment, the detergent formulation of the invention comprise a cold water-soluble polyvinyl alcohol P2) having a hydrolysis level of not more than 90 mol%. In a further preferred embodiment, the detergent formulation of the invention comprise at least one cellulose ether P2). Preferred cellulose ethers are selected from alkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses, carboxyalkyl celluloses and salts thereof, carboxyalkyl alkyl celluloses and salts thereof, carboxyalkyl hydroxyalkyl celluloses and salts thereof, carboxyalkyl hydroxyalkyl alkyl celluloses and salts, sulfoalkyl celluloses and salts thereof. Particularly preferred cellulose ethers are selected from carboxymethyl celluloses. The carboxyalkyl radicals may also be in salt form.
In a further preferred embodiment, the detergent formulation of the invention comprise at least one homo- or copolymer comprising at least one copolymerized monomer selected from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, salts of the three latter monomers, vinylpyridine N-oxide, N-carboxymethyl-4-vinylpyridium halides and mixtures thereof.
In a specific embodiment, the detergent formulation of the invention comprise a polyvinylpyrrolidone homopolymer.
In a further specific embodiment, the detergent formulation of the invention comprise a copolymer comprising copolymerized vinylpyrrolidone and vinylimidazole.
Washing, cleaning and dishwashing compositions
The detergent formulation according to the invention are suitable as such for use as a washing composition or as a cleaning composition or as a dishwashing composition. The term "dishwashing composition" here also covers rinse aids. Since the detergent formulation according to the invention comprise or consists of a polymer composition P1), they feature dispersing, film-inhibiting, emulsifying and/or surfactant properties, and so the polymer composition P1) also contributes to the washing and cleaning performance. The detergent formulation of the invention do not just improve the washing power, i.e. actively help to remove soil from the fabric or from hard surfaces such as ceramic, glass, plastic and metal, but also prevent redeposition of detached soil on concomitantly washed fabric or hard surfaces, meaning that they have a graying-inhibiting and deposition-inhibiting effect. Because of their washing and cleaning effect, they are especially suitable for formulation of laundry detergents and dishwashing compositions. In this embodiment too, the detergent formulation of the invention take the form of a three dimensional body, which may comprise one or more separate domains as defined above.
The minimum volume of the detergent formulations of the invention for use as a washing composition or as a cleaning composition or as a dishwashing composition is preferably chosen so that the body cannot be swallowed, e.g. by a child. In particular minimum volume of the detergent formulations of the invention for use as a washing composition or as a cleaning composition or as a dishwashing composition is at least 64 mm3, more preferably more than 100 mm3 and especially more than 200 mm3.
The detergent formulations dissolve at the start of the respective use (for example in the washing or rinse water), thus release the constituents of the washing and cleaning and dishwashing composition and, in dissolved form, because of their dispersing, film- inhibiting, emulsifying and surfactant properties, contribute considerably to the washing and cleaning performance. The detergent formulations of the invention do not just improve the washing power, i.e. actively help to remove soil from the fabric or from hard surfaces such as ceramic, glass, plastic and metal, but also prevent (re)deposition of detached soil and sparingly soluble salts of the water hardness ions on concomitantly washed fabric or hard surfaces, meaning that they have a graying- inhibiting and deposition-inhibiting effect. They especially prevent the redeposition of particulate soil, for example clay particles, soot particles and color pigments, and the deposition of sparingly soluble salts of the water hardness ions, such as the carbonates and silicates of calcium(ll) and magnesium (II) ions. Because of their washing effect, they are especially suitable for formulation of laundry detergents.
The washing or cleaning or dishwashing composition portions of the invention comprise, detergent formulations of the invention. They may comprise washing-active or cleaning-active components as additives. In addition, the washing or cleaning composition or dishwashing portions of the invention comprise measured amounts of at least one washing-active or cleaning-active composition within the detergent formulations. It is possible here that the washing composition or cleaning composition portions comprise just one individual washing- or cleaning-active composition. It is also possible that the washing composition or cleaning composition portions of the invention comprise two or more than two different washing- or cleaning-active compositions. The different compositions may differ with regard to the concentration of the individual components (in quantitative terms) and/or with regard to the nature of the individual components (in qualitative terms). It is more preferable that the components, in terms of type and concentration, are matched to the tasks that the active ingredient portion packages have to fulfil in the washing or cleaning operation or dishwashing operation.
The detergent formulations of the invention are also advantageously suitable for production of dosage forms that resemble a so-called multichamber systems known from the prior art. Those dosage forms have 2, 3, 4, 5 or more than 5 domains which each comprise a single component or a plurality of components of a washing or cleaning or dishwashing composition. This may in principle be a single washing- or cleaning-active ingredient, a single auxiliary or any desired mixture of two or more than two active ingredients and/or auxiliaries. The constituents of the individual domains are preferably in solid form. Those dosage forms are an option, for example, in order to separate components of a washing or cleaning or dishwashing composition that are incompatible or not very compatible from one another. For example one domain may comprise one or more enzyme(s) and another domain at least one bleach. Those dosage forms are also an option, for example, in order to facilitate controlled release of a particular component, for example at a certain time point in the washing or cleaning or dishwashing operation.
Where statements are made hereinafter regarding the qualitative and quantitative composition of washing and cleaning and dishwashing compositions, these shall always encompass the overall formulation composed of the detergent formulations and further components. In the case of formulation of this composition as a dosage form having more than one domain each domain may comprise an individual component or a plurality of components of the formulation, or the total amount of any component may be divided between two or more than two domains.
The washing composition or cleaning composition or dishwashing composition portions of the invention comprise at least one washing- or cleaning-active composition. These compositions may be any desired substances or substance mixtures that are of relevance in connection with a washing or cleaning or dishwashing operation. These are primarily the actual washing compositions or cleaning compositions or dishwashing compositions with their individual components explained in detail hereinafter.
In the context of the present invention, washing compositions are understood to mean those compositions which are used for cleaning of flexible materials having high absorptivity, for example of materials having a textile character, whereas cleaning compositions in the context of the present invention are understood to mean those compositions which are used for cleaning of materials having a closed surface, i.e. having a surface which has only few small pores, if any, and as a result has only low absorptivity, if any.
Examples of flexible materials having high absorptivity are those which comprise or consist of natural, synthetic or semisynthetic fiber materials and which accordingly generally have at least some textile character. The fibrous materials or those consisting of fibers may in principle be in any form that occurs in use or manufacture and processing. For example, fibers may be in unordered form in the form of staple or aggregate, in ordered form in the form of fibers, yarns, threads, or in the form of three dimensional structures such as nonwoven fabrics, lodens or felt, woven fabrics, knitted fabrics, in all conceivable binding types. The fibers may be raw fibers or fibers in any desired stages of processing. Examples are natural protein or cellulose fibers, such as wool, silk, cotton, sisal, hemp or coconut fibers, or synthetic fibers, for example polyester, polyamide or polyacrylonitrile fibers.
Examples of materials having only few and small pores, if any, and having zero or only low absorptivity are metal, glass, enamel or ceramic. Typical objects made of these materials are, for example, metallic sinks, cutlery, glass and porcelain dishware, bathtubs, washbasins, tiles, flags, cured synthetic resins, for example decorative melamine resin surfaces on kitchen furniture or painted metal surfaces, for example refrigerators and car bodies, printed circuit boards, microchips, sealed or painted woods, e.g. parquet or wall cladding, window frames, doors, plastics coverings such as floor coverings made of PVC or hard rubber, or rigid or flexible foams having substantially closed surfaces. Examples of cleaning compositions which may comprise the washing- and cleaning- active detergent formulation of the invention include washing and cleaning compositions, dishwashing compositions such as manual dishwashing compositions or machine dishwashing compositions (= dishwashing composition for the machine dishwasher), metal degreasers, glass cleaners, floor cleaners, all-purpose cleaners, high-pressure cleaners, neutral cleaners, alkaline cleaners, acidic cleaners, spray degreasers, dairy cleaners, commercial kitchen cleaners, machinery cleaners in industry, especially the chemical industry, cleaners for carwashing, and also domestic all-purpose cleaners.
Washing and cleaning and dishwashing compositions
The washing or cleaning composition of the invention in form of a three dimensional body preferably comprises the following constituents:
A) at least one polymer composition P1 ),
B) at least one surfactant,
C) optionally at least one builder,
D) optionally at least one bleach system,
E) optionally at least one further additive, preferably selected from enzymes, enzyme stabilizers, bases, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, fillers, tableting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, bitter substances, fluorescers, hydrotropes, antiredeposition agents, optical brighteners, graying inhibitors, antishrink agents, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, anti-yellowing agents, corrosion inhibitors, antistats, ironing aids, hydrophobizing and impregnating agents, antiswell and antislip agents and UV absorbers, and
F) optionally water.
In the context of the present invention, the builder C) also comprises compounds referred to as sequestrant, complexing agent, chelator, chelating agent or softener.
The bleach systems D) comprise, as well as bleaches, optionally also bleach activators, bleach catalysts and/or bleach stabilizers. More preferably, the washing and cleaning composition of the invention comprises at least one enzyme as additive E). A preferred embodiment relates to washing or cleaning compositions in form of a three dimensional body, comprising:
A) 25% to 98.8% by weight of at least one polymer composition P1 ), B) 1 % to 35% by weight of at least one surfactant,
C) 0.1 % to 50% by weight of at least one builder,
D) 0% to 20% by weight of a bleach system,
E) 0.1 % to 60% by weight of at least one further additive, preferably selected from enzymes, enzyme stabilizers, bases, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, fillers, tableting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, bitter substances, fluorescers, hydrotropes, antiredeposition agents, optical brighteners, graying inhibitors, antishrink agents, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, anti-yellowing agents, corrosion inhibitors, antistats, ironing aids, hydrophobizing and impregnating agents, antiswell and antislip agents and UV absorbers, and
F) 0% to 20% by weight of water.
The percent by weight data relate to the total weight of the washing and cleaning composition. The weight amounts of A) to F) add up to 100% by weight.
Preferably, the washing or cleaning compositions in three dimensional form comprise at the most 25% by weight of water, more preferably at the most 15% by weight of water, especially at the most 10% by weight of water. Component A)
With regard to suitable and preferred polymer compositions P1), reference is made to the details above.
Component B) The washing and cleaning compositions of the invention comprise at least one surfactant as component B). Suitable surfactants B) are nonionic, anionic, cationic or amphoteric surfactants.
Examples of surfactants B) which may be used in the context of the present invention include nonionic surfactants (NIS). Nonionic surfactants used are preferably alkoxylated alcohols. Preference is given to alkoxylated primary alcohols. Preferred alkoxylated alcohols are ethoxylated alcohols having preferably 8 to 18 carbon atoms in the alkyl radical and an average of 1 to 12 mol of ethylene oxide (EO) per mole of alcohol. The alcohol radical may be linear or preferably 2-methyl-branched or may comprise linear and methyl-branched radicals in a mixture, as typically present in oxo process alcohol radicals. Especially preferred are alcohol ethoxylates having linear or branched radicals from alcohols of native or petrochemical origin having 12 to 18 carbon atoms, for example from coconut alcohol, palm alcohol, tallow alcohol or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol.
The ethoxylated alcohols are preferably selected from:
Ci2Ci4-alcohols with 3 EO, 5 EO, 7 EO or 9 EO,
CgCu-alcohols with 7 EO,
C13-OXO process alcohols with 3 EO, 5 EO, 7 EO or 9 EO,
Ci3Ci5-alcohols with 3 EO, 5 EO, 7 EO or 9 EO,
Ci2Ci8-alcohols with 3 EO, 5 EO, 7 EO or 9 EO and mixtures thereof, 2-propylheptanol with 3 EO, 4 EO, 5 EO, 6 EO, 7 EO, 8 EO and 9 EO and mixtures of two or more than two of the aforementioned ethoxylated alcohols.
A preferred mixture of nonionic surfactants is a mixture of Ci2Ci4-alcohol (lauryl alcohol/myristyl alcohol) with 3 EO and C^Cis-alcohol (lauryl alcohol/myristyl alcohol/cetyl alcohol/stearyl alcohol) with 7 EO. Preference is also given to mixtures of short-chain alcohol ethoxylates (e.g. 2-propylheptanol with 7 EO) and long-chain alcohol ethoxylates (e.g. C16C18 with 7 EO).
The stated ethoxylation levels are statistical averages (number averages, Mn), which may be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples of these are tallow alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Also usable are nonionic surfactants comprising ethylene oxide (EO) and propylene oxide (PO) groups together in the molecule. It is possible here to use block copolymers with EO-PO block units or PO-EO block units, but also EO-PO-EO copolymers or PO-EO-PO copolymers. It is of course also possible to use mixedly alkoxylated nonionic surfactants in which EO and PO units are not in blocks but in random distribution. Such products are obtainable by simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.
Surfactants suitable as component B) are also polyetherols, preferably with a number- average molecular weight of at least 200 g/mol.
Suitable polyetherols may be linear or branched, preferably linear. Suitable polyetherols generally have a number-average molecular weight in the range from about 200 to 100000 g/mol, preferably 300 to 50000 g/mol, more preferably 500 to 40000 g/mol. Suitable polyetherols are, for example, water-soluble or water-dispersible nonionic polymers having repeat alkylene oxide units. Preferably, the proportion of repeat alkylene oxide units is at least 30% by weight, based on the total weight of the compound. Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers. Suitable alkylene oxides for preparation of alkylene oxide copolymers are, for example, ethylene oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide. Suitable examples are copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide. The alkylene oxide copolymers may comprise the copolymerized alkylene oxide units in randomly distributed form or in the form of blocks. Preferably, the proportion of repeat units derived from ethylene oxide in the ethylene oxide/propylene oxide copolymers is 40% to 99% by weight. Particular preference is given to ethylene oxide homopolymers and ethylene oxide/propylene oxide copolymers.
In addition, further nonionic surfactants which may be used are also alkyl glycosides of the general formula (IV)
R10O(G)i (IV) in which
R10 is a primary straight-chain or methyl-branched aliphatic radical having 8 to 22 carbon atoms,
G is a glycoside unit having 5 or 6 carbon atoms, and i is any number between 1 and 10.
In the compounds of the formula (IV), R10 is preferably a 2-methyl-branched aliphatic radical having 8 to 22 and preferably 12 to 18 carbon atoms. G is preferably glucose.
The oligomerization level i, which states the distribution of monoglycosides and oligoglycosides, is preferably within a range from 1.2 to 1.4.
A further class of nonionic surfactants which are used with preference in the context of the present invention and are used either as the sole nonionic surfactant or in combination with other nonionic surfactants is that of alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain. Especially preferred are fatty acid methyl esters as described, for example, in the Japanese patent application JP 58/217598, or those which are preferably prepared by the process described in the international patent application WO 90/13533.
Further suitable nonionic surfactants are amine oxides, for example N-cocoalkyl-N,N- dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides. These nonionic surfactants are preferably used as a mixture with alkoxylated alcohols. Preference is given to the mixture with ethoxylated fatty alcohols. The weight amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
Further suitable surfactants B) are polyhydroxy fatty acid amides of the formula (V)
Figure imgf000069_0001
in which the R11-C(=0) group is an aliphatic acyl radical having 6 to 22 carbon atoms, R12 is hydrogen, an alkyl radical having 1 to 4 carbon atoms or a hydroxyalkyl radical having 1 to 4 carbon atoms, and R13 is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can typically be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides includes in this connection also compounds of the formula (VI)
Figure imgf000070_0001
in which R14 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R15 is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene radical having 6 to 8 carbon atoms, and R16 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to Ci-C4-alkyl or phenyl radicals, and R17 is a linear polyhydroxyalkyl radical wherein the alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. R17 is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted to the desired polyhydroxy fatty acid amides, for example according to WO 95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
Suitable surfactants B) are also anionic surfactants. Typical examples of anionic surfactants are soaps, alkylsulfonates, alkylbenzenesulfonates, olefinsulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ethercarboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, for example acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, alkylglucose carboxylates, protein fatty acid condensates and alkyl (ether) phosphates. A first preferred embodiment is that of anionic surfactants of the sulfonate and sulfate types. Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzene sulfonates, olefinsulfonates, i.e. mixtures of alkene- and hydroxyalkanesulfonates, and disulfonates as obtained, for example, from Ci2-Ci8-monoolefins having a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from Ci2-Cis-alkanes, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis and/or neutralization. Also, likewise suitable are the esters of -sulfo fatty acids (estersulfonates), for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are understood to mean, inter alia, the mono-, di- and triesters, and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters here are the sulfation products of saturated fatty acids having 6 to 22 carbon atoms, for example of caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Preferred alk(en)yl sulfates are the alkali metal and especially the sodium salts of the sulfuric monoesters of Ci2-Cis-fatty alcohols, for example of coconut alcohol, tallow alcohol or lauryl, myristyl, cetyl or stearyl alcohol, or of the C10-C20-OXO process alcohols and the monoesters of secondary Cio-C2o-alcohols. Additionally, preferred are alk(en)yl sulfates comprising a synthetic petrochemical-based straight-chain C10-C20- alkyl radical. These have analogous degradation behavior to the equivalent compounds based on oleochemical raw materials. From the point of view of washing, preference is given to the Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates, and also Ci4-Ci5-alkyl sulfates. 2,3-Alkyl sulfates, which are prepared, for example, according to US patents 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the DAN® name, are also suitable anionic surfactants. Also suitable among other substances are the sulfuric monoesters of the straight-chain or branched C7-C21 alcohols which have been ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 to 4 EO. Owing to their high foaming level, they are conventionally used in cleaning compositions only in relatively small amounts, for example in amounts of 1 % to 5% by weight. Further suitable anionic surfactants in the context of the present invention are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and are the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates comprise Cs-Cis fatty alcohol radicals or mixtures of these. Particularly preferred sulfosuccinates comprise a fatty alcohol radical derived from ethoxylated fatty alcohols. Particular preference is given here in turn to sulfosuccinates wherein the fatty alcohol radicals are derived from ethoxylated fatty alcohols having a narrow homolog distribution. It is likewise also possible to use alk(en)ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.
Particularly preferred anionic surfactants are soaps. Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and especially soap mixtures derived from natural fatty acids, for example coconut fatty acids, palm kernel fatty acids, olive oil fatty acids or tallow fatty acids.
The anionic surfactants including the soaps may be present in the form of their sodium, potassium or ammonium salts, or as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.
Suitable surfactants B) are also cationic surfactants. Particularly preferred cationic surfactants are:
C7-C25-alkylamines;
N,N-dimethyl-N-(hydroxy-C7-C25-alkyl)ammonium salts; mono- and di(C7-C25-alkyl)dimethylammonium compounds quaternized with alkylating agents; ester quats, especially quaternary esterified mono-, di- and trialkanolamines esterified with C8-C22-carboxylic acids; imidazoline quats, especially 1-alkylimidazolinium salts of the formulae VII or VIII
Figure imgf000072_0001
where the variables are defined as follows: R18 is Ci-C25-alkyl or C2-C25-alkenyl,
R19 is Ci-C4-alkyl or hydroxy-Ci -Chalky I,
R20 is Ci-C4-alkyl, hydroxy-Ci-C4-alkyl or an R21-(CO)-R22-(CH2)r radical where R21 is H or Ci-C4-alkyl, R22 is -O- or -NH- and r is 2 or 3, where at least one R18 radical is a C7-C22-alkyl radical.
The surfactants B) may also be amphoteric surfactants. Suitable amphoteric surfactants are alkyl betaines, alkyl amidobetaines, alkyl sulfobetaines, aminopropionates, aminoglycinates and amphoteric imidazolium compounds. For example, it is possible to use cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine, sodium cocamphopropionate or tetradecyldimethylamine oxide.
The content of surfactants in detergent formulation of the invention is preferably 2% to 40% by weight and especially 5% to 35% by weight, based in each case on the overall formulation. Component C)
Builders, which are sometimes also referred to as sequestrant, complexing agent, chelator, chelating agent or softener, bind alkaline earth metals and other water-soluble metal salts without precipitation. They help to break up soil, disperse soil particles and help to detach soil, and sometimes themselves have a washing effect.
Suitable builders may either be organic or inorganic in nature. Examples are aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, e.g. hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and salts thereof and polymeric compounds containing carboxylic acid groups, and salts thereof. Suitable inorganic builders are, for example, crystalline or amorphous aluminosilicates having ion-exchanging properties, such as zeolites. Different types of zeolites are suitable, especially zeolites A, X, B, P, MAP and HS in their sodium form or in forms in which sodium has been partly exchanged for other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in US-A-4604224. Crystalline silicates suitable as builders are, for example, disilicates or sheet silicates, e.g. 5- Na2Si2C>5 or B-ls^ShOs (SKS 6 or SKS 7). The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as sodium, lithium and magnesium silicates. Likewise usable are amorphous silicates, for example sodium metasilicate having a polymeric structure, or amorphous disilicate (Britesil® H 20, manufacturer: Akzo). Among these, preference is given to sodium disilicate.
Suitable inorganic builder substances based on carbonate are carbonates and hydrogencarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to using sodium carbonates and hydrogencarbonates, lithium carbonates and hydrogencarbonates and magnesium carbonates and hydrogencarbonates, especially sodium carbonate and/or sodium hydrogencarbonate.
Customary phosphates used as inorganic builders are alkali metal orthophosphates and/or polyphosphates, for example pentasodium triphosphate.
Suitable organic builders are, for example, C4-C3o-di-, -tri- and -tetracarboxylic acids, for example succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acids having C2-C20- alkyl or -alkenyl radicals. Suitable organic builders are also hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include C4-C20-hydroxycarboxylic acids, for example malic acid, tartaric acid, gluconic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid, and sucrosemono-, -di- and - tricarboxylic acid. Among these, preference is given to citric acid and salts thereof.
Suitable organic builders are additionally phosphonic acids, for example hydroxy alkylphosphonic acids, aminophosphonic acids and the salts thereof. These include, for example, phosphonobutanetricarboxylic acid, aminotrismethylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, hexamethylenediaminetetramethylene phosphonic acid, diethylenetriaminepentamethylenephosphonic acid, morpholino methanediphosphonic acid, 1-hydroxy-Ci- to -Cio-alkyl-1 ,1-diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid. Among these, preference is given to 1-hydroxyethane-1,1-diphosphonic acid and salts thereof.
Suitable organic builders are also aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic dipropionic acid, nitrilotripropionic acid, b-alaninediacetic acid (b-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, propylene-1 ,3-diaminetetraacetic acid, propylene-1 ,2-diaminetetraacetic acid, N-(alkyl)ethylenediaminetriacetic acid, N-(hydroxyalkyl)-ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cyclohexylene-1 ,2-diaminetetraacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid, serinediacetic acid, isoserinediacetic acid, L-asparaginediacetic acid, L-glutamine diacetic acid, glutamic acid, diacetic acid, methylglycinediacetic acid (MGDA) and the salts of the aforementioned aminopolycarboxylic acids. Preference is given to methylglycinediacetic acid, glutamic acid diacetic acid and salts thereof. The salts of methylglycinediacetic acid may be in racemic form, meaning that D and L enantiomers are present in an equimolar mixture, or one enantiomer, e.g. the L enantiomer, may be present in excess.
Suitable organic builders are also polymeric compounds containing carboxylic acid groups, such as acrylic acid homopolymers. These preferably have a number-average molecular weight in the range from 800 to 70000 g/mol, more preferably from 900 to 50000 g/mol, particularly 1000 to 20 000 g/mol and especially 1000 to 10000 g/mol. In this context, the term "acrylic acid homopolymer" also encompasses polymers in which the carboxylic acid groups are in partly or fully neutralized form. These include acrylic acid homopolymers in which the carboxylic acid groups are present partly or completely in the form of alkali metal salts or ammonium salts. Preference is given to acrylic acid homopolymers in which the carboxylic acid groups are protonated or are partly or completely in the form of sodium salts. Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids, as described, for example, in EP-A 451 508 and EP-A 396 303.
Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated C4-C8 dicarboxylic acids, which may include copolymerized monoethylenically unsaturated monomers from the group (i) mentioned below in amounts of up to 95% by weight, from the group (ii) in amounts of up to 60% by weight and from the group (iii) in amounts of up to 20% by weight as comonomers. Suitable unsaturated C4-C8 dicarboxylic acids here are, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid. Group (i) encompasses monoethylenically unsaturated C3-C8 monocarboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid. Group (ii) encompasses monoethylenically unsaturated C2-C22 olefins, vinyl alkyl ethers having Ci-Cs-alkyl groups, styrene, vinyl esters of Ci-Cs carboxylic acids, (meth)acrylamide and vinylpyrrolidone. From group (ii), preference is given to using C2-C6 olefins, vinyl alkyl ethers having Ci-C4-alkyl groups, vinyl acetate and vinyl propionate. If the polymers of group (ii) comprise copolymerized vinyl esters, these may also be in partly or fully hydrolyzed form to give vinyl alcohol structural units. Suitable co- and terpolymers are known, for example, from US-A 3887806 and DE-A 4313909. Group (iii) encompasses (meth)acrylic esters of Ci-Cs alcohols, (meth)acrylonitrile, (meth)acrylamides of Ci-Cs amines, N-vinylformamide and N-vinylimidazole.
Suitable polymeric compounds containing carboxylic acid groups are also homopolymers of the monoethylenically unsaturated C3-C8 monocarboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, especially of acrylic acid and methacrylic acid, copolymers of dicarboxylic acids, for example copolymers of maleic acid or itaconic acid and acrylic acid in a weight ratio of 10:90 to 95:5, more preferably those in a weight ratio of 30:70 to 90:10 with molar masses of 1000 to 150000 g/mol; terpolymers of maleic acid, acrylic acid and a vinyl ester of a
C1-C3 carboxylic acid in a weight ratio of 10 (maleic acid):90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), where the weight ratio of acrylic acid to the vinyl ester may vary within the range from 30:70 to 70:30; copolymers of maleic acid with C2-C8 olefins in a molar ratio of 40:60 to 80:20, particular preference being given to copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50.
Suitable polymeric compounds containing carboxylic acid groups are also copolymers of 50% to 98% by weight of ethylenically unsaturated weak carboxylic acids with 2% to 50% by weight of ethylenically unsaturated sulfonic acids, as described, for example, in
EP-A-0877002. Suitable weak ethylenically unsaturated carboxylic acids are especially C3-C6 monocarboxyl ic acids, such as acrylic acid and methacrylic acid. Suitable ethylenically unsaturated sulfonic acids are 2-acetylamidomethyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-hydroxy propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1 -sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and salts of these acids. The copolymers may also comprise 0% to 30% by weight of copolymerized ethylenically unsaturated C4-C8 dicarboxylic acids, such as maleic acid, and 0% to 30% by weight of at least one monomer copolymerizable with the aforementioned monomers. The latter monomer comprises, for example, Ci-C4-alkyl esters of (meth)acrylic acid, Ci-C4-hydroxyalkyl esters of (meth)acrylic acid, acrylamide, alkyl-substituted acrylamide, N,N-dialkyl- substituted acrylamide, vinylphosphonic acid, vinyl acetate, allyl alcohols, sulfonated allyl alcohols, styrene and other vinylaromatics, acrylonitrile, N-vinylpyrrolidone, N-vinyl formamide, N-vinylimidazole or N-vinylpyridine. The weight-average molecular weight of these copolymers is in the range from 3000 to 50 000 daltons. Copolymers with about 77% by weight of at least one ethylenically unsaturated C3-C6 monocarboxylic acid and about 23% by weight of at least one ethylenically unsaturated sulfonic acid are particularly suitable.
Graft polymers of unsaturated carboxylic acids onto low molecular weight carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446, DE-A 4415623 and DE-A 4313909, are likewise suitable. Suitable unsaturated carboxylic acids here are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, and mixtures of acrylic acid and maleic acid, which are grafted on in amounts of 40% to 95% by weight, based on the component to be grafted. For the modification, it is additionally possible for up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers to be present in copolymerized form. Suitable modifying monomers are the aforementioned monomers of groups (ii) and (iii). Suitable graft bases are degraded polysaccharides, for example acidically or enzymatically degraded starches, inulins or cellulose, protein hydrolyzates and reduced (hydrogenated or reductively aminated) degraded polysaccharides, for example mannitol, sorbitol, aminosorbitol and N-alkylglucamine, and also polyalkylene glycols having molar masses with up to Mw = 5000, for example polyethylene glycols, ethylene oxide/propylene oxide or ethylene oxide/butylene oxide or ethylene oxide/propylene oxide/butylene oxide block copolymers and alkoxylated mono- or polyhydric C1-C22 alcohols (cf. US-A-5756456). Likewise suitable are polyglyoxylic acids as described, for example, in EP-B-001004, US-A-5399286, DE-A-4106355 and EP-A-656914. The end groups of the polyglyoxylic acids can have different structures. Also suitable are polyamidocarboxylic acids and modified polyamidocarboxylic acids; these are known, for example, from EP-A-454126, EP-B-511037, WO-A94/01486 and EP-A-581452.
It is also possible to use polyaspartic acids and the alkali metal salts thereof or cocondensates of aspartic acid with other amino acids, for example with glycine, glutamic acid or lysine, C4-C25 mono- or dicarboxylic acids and/or C4-C25 mono- or diamines as polymeric compounds containing carboxylic acid groups.
Among the polymeric compounds containing carboxylic acid groups, preference is given to polyacrylic acids, also in partly or fully neutralized form.
Suitable organic builders are also iminodisuccinic acid, oxydisuccinic acid, amino polycarboxylates, alkylpolyaminocarboxylates, aminopolyalkylenephosphonates, polyglutamates, hydrophobically modified citric acid, for example agaric acid, poly- [alpha]-hydroxyacrylic acid, N-acylethylenediamine triacetates such as lauroylethylene diamine triacetate, and alkylamides of ethylenediaminetetraacetic acid such as EDTA tallow amide.
In addition, it is also possible to use oxidized starches as organic builders.
Component D)
The bleach systems D) comprise at least one bleach and optionally at least one further component selected from bleach activators, bleach catalysts and bleach stabilizers.
Suitable bleaches are, for example, percarboxylic acids, e.g. diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or -terephthalic acid, salts of percarboxylic acids, e.g. sodium percarbonate, adducts of hydrogen peroxide onto inorganic salts, e.g. sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of hydrogen peroxide onto organic compounds, e.g. urea perhydrate, or of inorganic peroxo salts, e.g. alkali metal persulfates, or peroxodisulfates. Suitable bleach activators are, for example, polyacylated sugars, e.g. pentaacetylglucose; acyloxybenzenesulfonic acids and their alkali metal and alkaline earth metal salts, e.g. sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate; - N,N-diacylated and N,N,N',N'-tetraacylated amines, e.g. N,N,N',N'-tetraacetylmethylenediamine and -ethylenediamine (TAED), N,N-diacetylaniline, N,N-diacetyl-p-toluidine or 1 ,3-diacylated hydantoins such as 1 ,3-diacetyl-5,5-dimethylhydantoin; N-alkyl-N-sulfonylcarboxamides, e.g. N-methyl-N- mesylacetamide or N-methyl-N-mesylbenzamide; N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. monoacetylmaleic hydrazide; O,N,N-trisubstituted hydroxylamines, e.g. 0-benzoyl-N,N-succinylhydroxylamine, 0-acetyl-N,N-succinyl hydroxylamine or O,N,N-triacetylhydroxylamine; N,N'-diacylsulfurylamides, e.g. N,N'-dimethyl-N,N'-diacetylsulfurylamide or N,N'-diethyl-N,N'-dipropionylsulfurylamide; acylated lactams, for example acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonylbiscaprolactam; anthranil derivatives, for example 2-methylanthranil or 2-phenylanthranil; triacyl cyanurates, e.g. triacetyl cyanurate or tribenzoyl cyanurate; oxime esters and bisoxime esters, for example O-acetylacetone oxime or bisisopropyliminocarbonate; carboxylic anhydrides, e.g. acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride; enol esters, for example isopropenyl acetate; 1,3-diacyl-4,5-diacyloxyimidazolines, e.g. 1 ,3-diacetyl-
4.5-diacetoxyimidazoline; tetraacetylglycoluril and tetrapropionylglycoluril; diacylated
2.5-diketopiperazines, e.g. 1,4-diacetyl-2,5-diketopiperazine; ammonium-substituted nitriles, for example N-methylmorpholinioacetonitrile methylsulfate; acylation products of propylenediurea and 2,2-dimethylpropylenediurea, e.g. tetraacetylpropylenediurea; a-acyloxypolyacylmalonamides, e.g. a-acetoxy-N,N'-diacetylmalonamide; diacyldioxohexahydro-1 ,3,5-triazines, e.g. 1 ,5-diacetyl-2,4-dioxohexahydro-1 ,3,5- triazine; benz-(4H)-1,3-oxazin-4-ones with alkyl radicals, e.g. methyl, or aromatic radicals e.g. phenyl, in the 2 position.
A bleach system composed of bleaches and bleach activators may optionally also comprise bleach catalysts. Suitable bleach catalysts are, for example, quaternized imines and sulfonimines, which are described, for example, in US-A 5360569 and EP-A 453 003. Particularly effective bleach catalysts are manganese complexes, which are described, for example, in WO-A 94/21777. In the case of use thereof in the detergent formulation, such compounds are incorporated in maximum amounts of up to 1.5% by weight, especially up to 0.5% by weight, and in the case of very active manganese complexes in amounts of up to 0.1 % by weight. As well as the bleach system composed of bleaches, bleach activators and optionally bleach catalysts described, the use of systems with enzymatic peroxide release or of photoactivated bleach systems is also possible for the washing and cleaning compositions of the invention. Component E)
Suitable enzymes (= component E1) are those as customarily used as industrial enzymes. These include both enzymes with optimal activity in the neutral to alkaline pH range and enzymes with optimal activity in the acidic pH range. In a specific embodiment, component E1) additionally comprises at least one enzyme stabilizer. Suitable enzyme stabilizers E1) are those as customarily used.
The enzymes are preferably selected from aminopeptidases, amylases, arabinases, carbohydrases, carboxypeptidases, catalases, cellulases, chitinases, cutinases, cyclodextrin glycosyltransferases, deoxyribonucleases, esterases, galactanases, alpha-galactosidases, beta-galactosidases, glucanases, glucoamylases, alpha- glucosidases, beta-glucosidases, haloperoxidases, hydrolase invertases, isomerases, keratinases, laccases, lipases, mannanases, mannosidases, oxidases, pectinolytic enzymes, peptidoglutaminases, peroxidases, peroxygenases, phytases, polyphenol oxidases, proteolytic enzymes, ribonucleases, transglutaminases, transferases, xylanases and mixtures thereof.
The enzymes are specifically selected from hydrolases, such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannanases, other glycosyl hydrolases and mixtures of the aforementioned enzymes. All these hydrolases contribute to soil dissolution and removal of protein-, grease- or starch-containing soiling. Oxireductases can also be used for bleaching. Of particularly good suitability are enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens.
Preferred enzymes are described more particularly below:
Proteases:
Suitable proteolytic enzymes (proteases) may in principle be of animal, vegetable or microbial origin. Preference is given to proteolytic enzymes of microbial origin. These also include chemically or genetically modified mutants.
Lipases:
Suitable lipases may in principle originate from bacteria or fungi. These also include chemically or genetically modified mutants. Amylases: In principle, all a- and/or b-amylases are suitable. Suitable amylases may in principle originate from bacteria or fungi. These also include chemically or genetically modified mutants.
Cellulases:
In principle, all cellulases are suitable. Suitable cellulases may in principle originate from bacteria or fungi. These also include chemically or genetically modified mutants.
Peroxidases/oxidases:
Suitable peroxidases/oxidases may in principle originate from plants, bacteria or fungi. These also include chemically or genetically modified mutants.
Lyases:
In principle, all lyases are suitable. Suitable lyases may in principle originate from bacteria or fungi. These also include chemically or genetically modified mutants.
Compositions of the invention may comprise further enzymes which are referred to collectively by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectinylases (= pectinases), pectin esterases, xyloglucanases (= xylanases), pullulanases and b-glucanases.
Preferably, the washing or cleaning composition of the invention comprises at least one enzyme selected from proteases, amylases, mannanases, cellulases, lipases, pectin lyases and mixtures thereof.
Preferably, the washing or cleaning composition of the invention comprises at least one protease and/or amylase.
Preferably, the washing, cleaning or dishwashing composition of the invention comprises an enzyme mixture. For example, preference is given to enzyme mixtures comprising or consisting of the following enzymes: protease and amylase, protease and lipase (or lipolytic enzymes), protease and cellulase, amylase, cellulase and lipase (or lipolytic enzymes), protease, amylase and lipase (or lipolytic enzymes), protease, lipase (or lipolytic enzymes) and cellulase. The enzymes can be adsorbed onto carrier substances in order to protect them from premature decomposition. The washing or cleaning composition of the invention may optionally also comprise enzyme stabilizers E1). These include, for example, calcium propionate, sodium formate, boric acids, boronic acids and salts thereof, such as 4-formylphenylboronic acid, peptides and peptide derivatives, for example peptide aldehydes, polyols, such as propane-1 ,2-diol, and mixtures thereof.
The detergent formulation of the invention comprises the enzymes preferably in an amount of 0.1% to 5% by weight, more preferably 0.12% to 2.5% by weight, based on the total weight of the detergent formulation. Preferably, the detergent formulation comprises one or more separate domains comprising at least one enzyme. The enzyme in the separate domains is preferably in an amount of 0.1% to 5% by weight, more preferably 0.12% to 2.5% by weight, based on the total weight of the detergent formulation. Suitable organic solvents (= component E3) are selected from mono- or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, they are selected from ethanol, n- or isopropanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or -ethyl ether, diisopropylene glycol monomethyl or -ethyl ether, methoxy, ethoxy or butoxy triglycol, isobutoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, and mixtures of these solvents.
Useful foam inhibitors or defoamers (= component E4) are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
Suitable bases (= component E5) are alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, ammonium carbonate, alkali metal hydrogencarbonates, alkaline earth metal hydrogencarbonates, ammonium hydrogencarbonates and mixtures thereof. Preference is given to using sodium, lithium and magnesium carbonates or sodium, lithium and magnesium hydrogencarbonates, especially sodium carbonate and/or sodium hydrogencarbonate. In addition, the washing or cleaning compositions of the invention may comprise further additives E6) which further improve the performance and/or aesthetic properties. In general, preferred compositions comprise, in addition to the aforementioned components, at least one further additive selected from electrolytes, pH modifiers, perfume carriers, bitter substances, fluorescers, hydrotropes, antiredeposition agents, optical brighteners, graying inhibitors, antishrink agents, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, anti-yellowing agents, corrosion inhibitors, antistats, ironing aids, hydrophobizing and impregnating agents, antiswell and antislip agents, and UV absorbers.
Suitable dye transfer inhibitors are especially homo- or copolymers comprising at least one copolymerized monomer selected from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, salts of the three latter monomers, 4-vinylpyridine N-oxide, N-carboxymethyl-4-vinylpyridinium halides and mixtures thereof.
Suitable graying inhibitors and/or washing power boosters are especially: carboxymethylcellulose, graft polymers of vinyl acetate onto carbohydrates, for example onto degraded starch, graft polymers of vinyl acetate onto polyethylene glycol, alkoxylated oligo- and polyamines, e.g. ethoxylated hexamethylenediamine, which may additionally also be in quaternized and/or sulfated form, or alkoxylated polyethyleneimine with 16 to 24 EO per NH, copolymers based on styrene and maleic acid which may additionally also have been modified with end group-capped polyethylene glycol, copolymers based on styrene and acrylic acid.
In order to improve the aesthetic impression of the washing, cleaning or dishwashing compositions of the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which does not present any difficulty at all to the person skilled in the art, have high storage stability and insensitivity to the other constituents of the compositions and to light, and also no marked substantivity with respect to textile fibers, in order not to stain them.
The washing, cleaning or dishwashing compositions of the invention may comprise at least one bitter substance. Bitter substances are specially used in order to prevent inadvertent swallowing of the compositions, for example by infants. Suitable bitter substances are known to those skilled in the art. These include, for example, denatonium benzoate (benzyldiethyl-(2,6-xylylcarbamoyl)methylammonium benzoate), the bitterest-tasting substance known to date, which is commercially available under the Bitrex® name.
Dishwashing compositions
The above-described detergent formulations of the invention are also particularly advantageously suitable for dishwashing detergents, especially of dishwashing detergents for machine dishwashing processes (automatic dishwashing, ADW). The polymer composition P1) present in the detergent formulations exerts a dispersing, film-inhibiting, emulsifying and/or surfactant effect in dishwashing detergents. In addition, they ensure good rinse aid and/or drying performance. Examples of formulations of the invention for dishwashing include machine dishwashing compositions, rinse aids and machine dishwashing detergents with rinse aid function. Machine dishwashing processes in the domestic and commercial sector comprise a plurality of successive steps, the first comprising the mechanical removal of loosely adhering food residues and the second the actual cleaning operation with the aid of a machine dishwasher, and the third generally consisting of a rinsing step, which is followed by the drying of the cleaned dishware. These operations are conducted in more or less automated form, the central unit used being a machine dishwasher in which at least the cleaning step and generally also the subsequent rinsing step and/or the drying step are conducted.
In machine dishwashers for the domestic sector, the soiled dishware is generally cleaned in a single chamber, and the aforementioned treatment steps proceed successively in a controlled program. Fresh water passes through the softening unit to the pump well and is sprayed by means of moving spray arms over the ware to be rinsed. Water-insoluble substances rinsed off are filtered out in the pump well. In the second rinse cycle, a generally alkaline cleaning composition is added to the rinse water, heated to the set temperature and distributed over the ware to be rinsed. In the last rinse cycle, a rinse aid is added to the treatment liquid, which reduces the surface tension, as a result of which the treatment liquid runs more easily off the ware. After the last rinse cycle, the contents are dried. The components used in the rinse cycle, such as water treatment agents, cleaning compositions, rinse aids, etc., can be used either in the form of individual components or in multicomponent formulations. Multifunctional detergents of this kind comprise surfactants for rinsing and a polymer for water softening. In that case, it is unnecessary to separately dispense a rinse aid and a salt for water softening into the machine dishwasher. Commercial machine dishwashers consist basically of stationary bath tanks from which an essentially aqueous cleaning solution is jetted or sprayed onto the dishware, which moves past these baths on a conveyor belt, such that the used solution flows back into the bath tanks again. Water enters the last bath tank, flows via overflows in the manner of a cascade through all the other tanks and leaves the machine via the overflow of the first tank. The application of a generally highly alkaline cleaning solution generally takes place with the aid of nozzles provided therefor, or of a specific spraying system normally arranged in the middle region of the machine.
The detergent formulations of the invention are suitable for dishwashing compositions for machine dishwashing, which especially feature excellent film-inhibiting action. Preferred machine dishwashing composition formulations have inhibiting action with respect to both inorganic and organic film deposits. The inorganic film deposits are especially calcium and magnesium phosphate, calcium and magnesium carbonate, calcium and magnesium silicate and/or calcium and magnesium phosphonate, which arise from the calcium and magnesium salts present in the water and the builders present in standard dishwashing compositions. The organic film deposits are especially soil constituents from the rinse liquor, for example protein, starch and fat deposits. The formulations used in accordance with the invention for machine dishwashing are also effective against carry-over deposits, which originate from the residual water in the bottom of the machine dishwasher and comprise, inter alia, dishwashing composition residues and possibly also soil residues from the previous wash cycle of the machine dishwasher.
The dishwashing composition in form of a three-dimensonal body of the invention preferably comprises the following constituents:
Ga) at least one polymer composition P'\ ),
Gb) optionally at least one complexing agent,
Gc) at least one builder and/or cobuilder,
Gd) at least one nonionic surfactant,
Ge) optionally at least one component selected from bleaches, bleach activators and bleach catalysts,
Gf) optionally at least one enzyme,
Gg) optionally at least one further additive, preferably selected from anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, bitter substances, fillers, tablet disintegrants, organic solvents, tableting aids, disintegrants, thickeners and solubilizers,
Gh) optionally water. A preferred dishwashing composition in form of a three dimensional body of the invention comprises: Ga) 25% to 98.8% by weight of at least one polymer composition P1 ),
Gb) 0% to 50% by weight of at least one complexing agent,
Gc) 0.1 % to 70% by weight of at least one builder and/or cobuilder,
Gd) 0.1 % to 35% by weight of at least one nonionic surfactant,
Ge) 0% to 30% by weight of at least one component selected from bleaches, bleach activators and bleach catalysts,
Gf) 0% to 8% by weight of at least one enzyme,
Gg) 0% to 50% by weight of at least one further additive, preferably selected from anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, bitter substances, fillers, tablet disintegrants, organic solvents, tableting aids, disintegrants, thickeners and solubilizers, and Gh) 0% to 20% by weight of water, with the proviso that the weights of the components add up to 100% by weight.
With regard to suitable and preferred polymer composition Ga), reference is made to the general details relating to suitable and preferred polymer composition P1).
Complexing agents Gb) which may be used are, for example: nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid, aspartic acid diacetic acid, and also salts thereof in each case. Preferred complexing agents Gb) are methylglycinediacetic acid and glutamic acid diacetic acid and salts thereof. Particularly preferred complexing agents Gb) are methylglycinediacetic acid and salts thereof, especially the mono-, di- and trisodium, -potassium, -lithium and -ammonium salts. The salts of methylglycinediacetic acid may be in racemic form, meaning that D and L enantiomers are present in an equimolar mixture, or one enantiomer, e.g. the L enantiomer, may be present in excess. Preference is given in accordance with the invention to 3% to 50% by weight of complexing agent Gb).
Builders and/or co-builders Gc) used may especially be water-soluble or water- insoluble substances having the main task of binding calcium and magnesium ions. These may be low molecular weight carboxylic acids and also salts thereof such as alkali metal citrates, in particular anhydrous trisodium citrate or trisodium citrate dihydrate, alkali metal succinates, alkali metal malonates, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate and a-hydroxypropionic acid.
A further substance class with cobuilder properties which may be present in the dishwashing compositions of the invention is that of the phosphonates. These are in particular hydroxyalkanephosphonates or aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular significance as cobuilder. It is preferably used in the form of the sodium salt, the disodium salt giving a neutral reaction and the tetrasodium salt an alkaline reaction (pH 9). Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and the higher homologs thereof. They are preferably used in the form of the neutral sodium salts, for example as the hexasodium salt of EDTMP or as heptasodium and octasodium salts of DTPMP. The builder used in this case is from the class of the phosphonates, preferably HEDP. Aminoalkanephosphonates additionally have a pronounced heavy metal binding capacity. Accordingly, it may be preferable to use aminoalkanephosphonates, particularly DTPMP, or mixtures of the phosphonates mentioned, particularly if the compositions also comprise bleach.
Silicates may be used, inter alia, as builders. Crystalline sheet silicates having the general formula NaMSixC>2x+i yH20 may be present, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably 0 to 20. In addition, amorphous sodium silicates having an S1O2: Na20 ratio of 1 to 3.5, preferably 1.6 to 3 and in particular 2 to 2.8 may be used.
Furthermore, in the context of the dishwashing composition of the invention, builders and/or co-builders Gc) used may be carbonates and hydrogen carbonates, among which the alkali metal salts, particularly sodium salts, are preferred.
Furthermore, the cobuilders used may be homopolymers and copolymers of acrylic acid or methacrylic acid preferably having a weight-average molar mass of 2000 to 50000 g/mol. Suitable comonomers are in particular monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and also anhydrides thereof such as maleic anhydride. Also suitable are comonomers containing sulfonic acid groups such as 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid and methanesulfonic acid. Hydrophobic comonomers are also suitable, for example isobutene, diisobutene, styrene, alpha-olefins with 10 or more carbon atoms. Hydrophilic monomers having hydroxyl functions or alkylene oxide groups may also be used as comonomers. Examples include: allyl alcohol and isoprenol and also alkoxylates thereof and methoxypolyethylene glycol (meth)acrylate.
The dishwashing formulation of the invention preferably comprise builders and/or cobuilders Gc) in an amount of 5% to 80% by weight, more preferably 10% to 75% by weight, especially 15% to 70% by weight, more especially 15% to 65% by weight, based on the total weight of the dishwashing formulation.
Suitable nonionic surfactants Gd) are, for example, weakly foaming or low-foaming nonionic surfactants. The dishwashing formulation of the invention comprise nonionic surfactants preferably in an amount of 0.1 % to 20% by weight, more preferably of 0.1 % to 15% by weight, especially of 0.25% to 10% by weight, especially of 0.5% to 10% by weight, based on the total weight of the dishwashing formulation. Suitable nonionic surfactants include surfactants of the general formula (IX)
R31-0-(CH2CH20)a-(CHR32CH20)b-R33 (IX), in which R31 is a linear or branched alkyl radical having 8 to 22 carbon atoms,
R32 and R33 are each independently hydrogen or a linear or branched alkyl radical having 1 to 10 carbon atoms or H, where R32 is preferably methyl, and a and b are each independently 0 to 300. Preferably, a = 1 to 100 and b = 0 to 30.
Also suitable in the context of the present invention are surfactants of formula (X) R34-0-[CH2CH(CH3)0]c[CH2CH20]d[CH2CH(CH3)0]eCH2CH(0H)R35 (X), in which R34 is a linear or branched aliphatic hydrocarbyl radical having 4 to 22 carbon atoms or mixtures thereof,
R35 is a linear or branched hydrocarbyl radical having 2 to 26 carbon atoms or refers to mixtures thereof, c and e have values between 0 and 40, and d is a value of at least 15.
Also suitable in the context of the present invention are surfactants of formula (XI)
R360-(CH2CHR370)f(CH2CH20)g(CH2CHR380)h-C0-R39 (XI), in which
R36 is a branched or unbranched alkyl radical having 8 to 16 carbon atoms, R37, R38 are each independently H or a branched or unbranched alkyl radical having 1 to 5 carbon atoms, R39 is an unbranched alkyl radical having 5 to 17 carbon atoms, f, h are each independently a number from 1 to 5, and g is a number from 13 to 35.
The surfactants of the formulae (IX), (X) and (XI) may be either random copolymers or block copolymers; they are preferably block copolymers. Furthermore, in the context of the present invention, di- and multi-block copolymers constructed from ethylene oxide and propylene oxide can be used, which are commercially available, for example, under the name Pluronic® (BASF SE) or Tetronic® (BASF Corporation). Furthermore, reaction products of sorbitan esters with ethylene oxide and/or propylene oxide can be used. Amine oxides or alkyl glycosides are also suitable. An overview of suitable nonionic surfactants are disclosed in EP-A 851 023 and DE-A 198 19 187. Mixtures of two or more different nonionic surfactants may also be present. The dishwashing compositions of the invention may further comprise anionic or zwitterionic surfactants, preferably in a mixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are likewise specified in EP-A 851 023 and DE-A 198 19 187.
Bleaches and bleach activators Ge) used in connection with the dishwashing compositions of the invention may be representatives known to those skilled in the art. Bleaches are subdivided into oxygen bleaches and chlorine bleaches. Oxygen bleaches used are alkali metal perborates and hydrates thereof, and also alkali metal percarbonates. Preferred bleaches in this context are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate. Likewise useable as oxygen bleaches are persulfates and hydrogen peroxide. Typical oxygen bleaches are also organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1 ,12-diperoxydodecanedioic acid, 1 ,9-diperoxyazelaic acid, diperoxoisophthalic acid or2-decyldiperoxybutane-1 ,4-dioic acid. In addition, the following oxygen bleaches can also be used in the dishwashing composition: cationic peroxy acids, which are described in the patent applications US 5,422,028,
US 5,294,362 and US 5,292,447, and sulfonylperoxy acids, which are described in the patent application US 5,039,447. Oxygen bleaches can be used in amounts of generally 0.1 % to 30% by weight, preferably of 1 % to 20% by weight, more preferably of 3% to 15% by weight, based on the overall dishwashing formulation.
Chlorine bleaches and the combination of chlorine bleaches with peroxide bleaches can also be used in connection with the dishwashing compositions of the invention. Known chlorine bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N,N'-dichlorobenzoyl urea, p-toluenesulfonedichloroamide or trichloroethylamine. Preferred chlorine bleaches in this case are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate. Chlorine bleaches in this connection can be used in amounts of 0.1 % to 30% by weight, preferably of 0.1 % to 20% by weight, preferably of 0.2% to 10% by weight, more preferably of 0.3% to 8% by weight, based on the overall dishwashing formulation.
In addition, small amounts of bleach stabilizers, for example phosphonates, borates, metaborates, metasilicates or magnesium salts, may be added.
Bleach activators in the context of the present invention can be compounds which, under perhydrolysis conditions, give rise to aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or substituted perbenzoic acid. In this case, suitable compounds comprise, inter alia, one or more N- or O-acyl groups and/or optionally substituted benzoyl groups, for example substances from the class of the anhydrides, esters, imides, acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD),
N-acylimides such as N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates such as n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), pentaacetylglucose (PAG), 1 ,5-diacetyl-2,2-dioxohexahydro-1 ,3,5-triazine (DADHT) or isatoic anhydride (ISA). Also suitable as bleach activators are nitrile quats such as N-methylmorpholinium acetonitrile salts (MM A salts) or trimethylammonium acetonitrile salts (TMAQ salts). Preferred suitable bleach activators are from the group consisting of polyacylated alkylenediamines, more preferably TAED, N-acylimides, more preferably NOSI, acylated phenolsulfonates, more preferably n- or iso-NOBS, MM A, and TMAQ. Bleach activators in connection with the present invention can be used in amounts of 0.1 % to 30% by weight, preferably of 0.1 % to 10% by weight, preferably of 1 % to 9% by weight, more preferably of 1.5% to 8% by weight, based on the overall dishwashing formulation.
In addition to the conventional bleach activators or in place of them, so-called bleach catalysts may also be incorporated in rinse aid particles. These substances are bleach enhancing transition metal salts or transition metal complexes such as salen complexes or carbonyl complexes of manganese, iron, cobalt, ruthenium or molybdenum. Also usable as bleach catalysts are complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper with nitrogen- containing tripod ligands and also amine complexes of cobalt, iron, copper and ruthenium.
As component Gf), the dishwashing compositions of the invention may comprise 0% to 8% by weight of enzymes. If the dishwashing compositions comprise enzymes, they comprise them preferably in amounts of 0.1 % to 8% by weight. Enzymes may be added to the dishwashing composition in order to increase the cleaning performance or to ensure the same quality of cleaning performance under milder conditions (e.g. at low temperatures). The enzymes can be used in free form or a form chemically or physically immobilized on a support or in encapsulated form. The enzymes used most frequently in this context include lipases, amylases, cellulases and proteases. In addition, it is also possible, for example, to use esterases, pectinases, lactases and peroxidases. Preference is given in accordance with the invention to using amylases and proteases.
In connection with the dishwashing compositions of the invention, additives Gg) used may be, for example, anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tablet disintegrants, organic solvents, tableting aids, disintegrants, thickeners, solubilizers or water. The alkali carriers used may be, for example, in addition to the ammonium or alkali metal carbonates already mentioned as builder substances, ammonium or alkali metal hydrogencarbonates and ammonium or alkali metal sesquicarbonates, and also ammonium or alkali metal hydroxides, ammonium or alkali metal silicates and ammonium or alkali metal metasilicates and also mixtures of the aforementioned substances.
The corrosion inhibitors used may be, inter alia, silver anticorrosives from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes.
To prevent glass corrosion, which is noticeable as cloudiness, iridescence, streaks and lines on the glasses, preference is given to using glass corrosion inhibitors. Preferred glass corrosion inhibitors are, for example, magnesium, zinc and bismuth salts and complexes and polyethyleneimines.
Paraffin oils and silicone oils may optionally be used in accordance with the invention as defoamers and to protect plastics and metal surfaces. Defoamers are used preferably in proportions of 0.001% by weight to 5% by weight. In addition, dyes, for example patent blue, preservatives, for example Kathon CG, perfumes and other fragrances may be added to the cleaning formulation of the invention.
An example of a suitable filler in connection with the dishwashing compositions of the invention is sodium sulfate.
Further possible additives that should be mentioned in connection with the present invention include amphoteric and cationic polymers. In order to improve the aesthetic impression of the washing, cleaning or dishwashing compositions of the invention, they can be colored using suitable dyes. Preferred dyes, the selection of which presents no difficulty whatsoever to the person skilled in the art, have a high storage stability and insensitivity with respect to the other ingredients of the compositions and to light, and do not have any marked substantivity toward textile fibers, in order not to stain them. cleaners
The detergent formulations of the invention are also suitable for industrial and institutional cleaners (I & I cleaners). Industrial and institutional cleaners are typically washing compositions, all-purpose cleaners, foam cleaners, CIP (cleaning in place) cleaners for professional and generally automated cleaning operations, for example in industrial laundries, dairies, breweries, the food and drink industry, the pharmaceutical industry or pharmaceutical formulation, or sanitary cleaners.
The cleaners may be strongly basic with a high electrolyte content and, if required, comprise bleaches (such as hydrogen peroxide, sodium hypochlorite) or disinfectants and defoamers (for example in bottle cleaning). It is also possible for the standard aforementioned enzymes to be present in the industrial and institutional cleaners.
There is a great variety in terms of the types of cleaning for which the formulations of the invention are suitable. Examples include cleaning baths (stationary or mobile), spray cleaning, ultrasound cleaning, steam jet cleaning and high-pressure cleaning, optionally in combination with mechanical cleaning, for example by means of rotating brushes.
Said compositions for cleaning include those for industry, transport, commerce and industry, and for the private sector. Specific examples include: professional laundries, professional cleaning businesses, ore processing industry, metal and metalworking industry, automobile and automobile supply industry, electrical industry, electronics industry, photographic industry and businesses, leisure industry and businesses, construction material industry, brewing industry and businesses; foods industry (e.g. processing or production of meat, poultry, dairy and fish products), animal nutrition industry, cosmetics industry, pharmaceutical industry, agrochemical industry, gastronomy, the health sector, workshops, and public transport. Examples of objects to be cleaned are institutional laundry, hospital laundry, laundry from laundry collection, buildings containing living spaces, office spaces or commercial spaces of a wide variety of different kinds, and sanitary spaces, warehouses, breweries, small businesses such as bakeries, butcheries and supermarkets; hospitals, care homes, homes for the elderly, administration buildings, factory buildings, doctors' practices; and also motor vehicles (cars and trucks), buses, road tanker vehicles (interior and exterior), rail tanker wagons, passenger vehicles and goods vehicles, and aircraft and ships; and also building facades, tiled or painted walls, wooden floors (parquet, boards) with screed or textile or plastics coverings, signaling and lighting installations, furniture, railings, overhead signage, other signage, safety reflectors, delineating markers, tanks, dishware, glass panes, roads and paths, outside paving, road and railway tunnels.
Acidic sanitary cleaners The detergent formulations of the invention are also suitable for the sanitary sector comprising at least one organic acid. Acidic sanitary cleaners are especially suitable for WC cleaning, for cleaning of washbasins, shower cubicles, shower trays and swimming baths, and sinks in the kitchen sector. They are effective, for example, in the removal of limescale and urine scale deposits and in the removal of bacteria which typically form on the limescale and urine scale deposits. They ensure cleanliness and effectively prevent malodors. It has now been found that, surprisingly, the multilayer films of the invention have high compatibility with acidic surfactant compositions and are particularly advantageously suitable for use in acidic sanitary cleaners. A preferred acidic sanitary cleaner in form of a three dimensional body preferably comprises the following constituents: at least one polymer composition P1 ) as defined above, or obtainable by a process as defined above, at least one organic acid, optionally water, - optionally at least one thickener, and optionally at least one further additive.
The acidic sanitary cleaner is in solid form.
Suitable organic acids are formic acid, acetic acid, citric acid or methanesulfonic acid. Particular preference is given to acetic acid or citric acid. The cleaner of the invention comprises the organic acid preferably in an amount of 1 % to 40% by weight, especially of 5% to 15% by weight, based on the total weight of the cleaner. The cleaner of the invention preferably comprises at least one surfactant in an amount of 0.5% to 50% by weight, especially of 1 % to 15% by weight, based on the total weight of the cleaner.
Suitable thickeners in principle are any known thickeners (rheology modifiers), provided they do not have any adverse effect on the action of the washing and cleaning composition. Suitable thickeners may either be of natural origin or synthetic in nature.
Examples of thickeners of natural origin are xanthan, carob seed flour, guar flour, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches, such as hydroxyethyl starch, starch phosphate esters or starch acetates, dextrins, pectins and cellulose derivatives, such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose and the like.
Thickeners of natural origin are also inorganic thickeners, such as polysilicic acids and clay minerals, e.g. sheet silicates, and also the silicates specified under the builders.
Examples of synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partly) crosslinked homopolymers of acrylic acid, for example homopolymers, crosslinked with an allyl ether of sucrose or pentaerythritol or with propylene, of acrylic acid (carbomer), e.g. the Carbopol® brands from BF Goodridge (e.g. Carbopol® 676, 940, 941 , 934 or the like) or the Polygel® brands from 3V Sigma (e.g. Polygel® DA), copolymers of ethylenically unsaturated mono- or dicarboxylic acids, for example terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl or ethyl acrylate and a (meth)acrylate derived from long-chain ethoxylated alcohols, for example the Acusol® brands from Rohm & Haas (e.g. Acusol® 820 or 1206A), copolymers of two or more monomers selected from acrylic acid, methacrylic acid and their Ci-C4-alkyl esters, e.g. copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of butyl acrylate and methyl methacrylate, e.g. the Aculyn® and Acusol® brands from Rohm & Haas (e.g. Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular weight acrylic acid copolymers, for example copolymers, crosslinked with an allyl ether of sucrose or pentaerythritol, of Cio-C3o-alkyl acrylates with one or more comonomers selected from acrylic acid, methacrylic acid and their Ci-C4-alkyl esters (e.g. Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas).
Examples of synthetic thickeners are also reaction products of maleic acid polymers with ethoxylated long-chain alcohols, e.g. the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119 from ISP; polyethylene glycols, polyamides, polyimines and polycarboxylic acids. Also suitable are mixtures of the aforementioned thickeners.
Preferred thickeners are xanthans and the aforementioned polyacrylic and polymethacrylic compounds.
Suitable additives are those mentioned above as component E) for the washing and cleaning compositions of the invention, to which reference is made here in full. These especially include stabilizers, dyes and fragrances.
The invention is illustrated in detail by the examples described hereinafter. At the same time, the examples should not be regarded as a restriction of the invention.
EXAMPLES
Figure 1 shows the flexibility measurement of P1-1 , P1-2 and ADW tablet.
Figure 2 shows the flexibility measurement of an ADW tablet.
All the examples for production of a polymer composition P1) were created by the same general production method. The individually produced polymer compositions of the invention are referred to hereinafter as P1-1) to P1-2).
General production method for a polymer composition P1)
The initial charge was heated to 75°C while stirring at 100 rpm. Then feeds 1 , 2 and 3 were metered in within 4 h and the reaction mixture was polymerized for a further hour. The mixture was then allowed to cool down to room temperature. The polymer composition is obtained in the form of a transparent and viscous solution.
The weight-average molecular weight Mw of the polymer composition P1) obtained was determined by means of gel permeation chromatography (GPC) in aqueous solution using neutralized polyacrylic acid as polymer standard. In this type of molecular weight determination, the components of the polymer composition which comprise the aforementioned monomers M) in copolymerized form are ascertained.
• Standard: neutralized polyacrylic acid. The calibration was carried out with narrow distribution Na-PAA standards from PSS (Polymer Standards Service GmbH) with molecular weights of M = 1250 to M = 1 100 000 g/mol. In addition, PAA standards from the American Polymer Standards Corporation with molecular weight M = 1770 and M = 900 g/mol were used. The values outside of this elution range were extrapolated.
• Eluent: 0.01 mol/L phosphate buffer pH=7.4 in distilled water with 0.01 M Nalsh • Flow rate: 0.8 mL/min
• Amount injected: 100 mI_
• Concentration: 1.5 mg/ml_
• The sample solutions were filtered through Millipore IC Millex-LG filters (0.2 pm). · Column type: TSKgel GMPWXL
• Column set: 2 separation columns (length = each 30 cm), exclusion limit 1000- 8 000000 g/mol
Detector: DRI Agilent 1200 UV Agilent 1200 VWD [260nm] Production of polymer composition P1-1)
Figure imgf000095_0001
a) demineralized water b) 2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No. 2997-92-4)
The weight-average molecular weight Mw of the polymer composition P1-1) obtained was 10000 g/mol.
Production of polymer composition P1-2)
Figure imgf000095_0002
Figure imgf000096_0001
a) demineralized water b) 2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No. 2997-92-4)
The weight-average molecular weight Mw of the polymer composition P1-2) obtained was 12700 g/mol.
The polymer compositions P1-1 and P1-2 were plastified in an oven at 85-90°C. Subsequently, the plastified compositions were casted into silicone molds specificly designed for the friction measurement after DIN53375.
A) Rapid freezing of P1-1 and P1-2 (P1-1 A and P1-2A)
The plastified composition casted inside the silicon mold was allowed to cool to 30°C. Subsequently the mold was covered with a plastic bag to avoid water condensation ontop of the body and placed into solid carbon dioxide granules, where it rapidly cooled to about -80°C, and allowed to rest for 30-45 minutes at this temperature. The mold was taken from the solid carbon dioxide and allowed to warm to ambient temperature. The casted body of the polymer composition was removed from the mold and stored in a climate chamber at 25°C and 50% rel. humidity to avoid evaporation of water until the measurement was conducted.
B) Drying of P1-1 and P1-2 (P1-1 B and P1-2B)
The plastified composition casted inside the silicon mold was allowed to cool to ambient temperature. The body of the polymer composition was kept inside the silicon mold overnight. Subsequently the body was removed from the mold, dried for three days under ambient temperature and stored in a climate chamber at 25°C and 50% rel. humidity to avoid further evaporation of water until the measurement was conducted.
Friction measurement: The measurements are conducted according to the standard DIN EN ISO 8295:2004. The standard is used to measure the friction coefficient between two materials under specific conditions. A fixed normal load (1 ,96 N) is applied (controlled by the weight of a metallic block), a fixed contact surface (40 cm2) and the testing speed (100 mm/min) is also set. During this test, the static friction load (statischen Reibungskraft FS) (also called adhesive friction (Haftreibungskraft) in a predecessor standard to DIN EN ISO 8295:2004 (DIN 53375) which is not valid anymore since 11/1986) is measured as well as the dynamic friction load (dynamisch Reibungskraft FD) also called sliding friction (Gleitreibungskraft) in DIN 53375. The data a summarized in table 1.
Table 1:
Figure imgf000097_0001
*) after drying, body is deformed and has no flat contact surface Flexibility Measurements
The flexibility of the three dimensional embodiments was determined with a TA.XTplus Texture Analyzer by Stable Micro Systems. A 5 kg measurement cell was used and a spherical measurement probe with a diameter of 0.25 inch was applied for the penetration test. A spherical ring with a diameter of 70 mm and a wall thickness of 5 mm was used as a foundation for the three dimensional embodiment. The embodiment P1-1 or P 1-2 plastified as described above and the plastified embodiment was casted in a cylindrical mold in such a way that the resulting final three dimensional body had a diameter of 70 mm and a length in z-direction of 7 mm. The respective embodiment was allowed to cool and stored in a climate chamber at 25°C and 50% humidity for equilibration.
The flexibility of the embodiments was determined by the respective force necessary to deform the center of the embodiment by 12 mm with the spherical probe. The probe was moved 12 mm in z-direction with a speed of 0.2 mm/s to deform the embodiment. An exponential increase in the force up to the described maximum could be detected. Upon removal of the probe with the same speed of 0.2 mm/s, the deformation force declines in an exponential fashion, however with a higher slope.
As a comparative example, a common dishwashing detergent tablet (ADW tablet) with the dimension of 55 mm x 35 mm x 10 mm displays the following force-way curve (figure 2). As the tablet does not display the exponential increase and decay with a hysteresis-like behavior, it can be regarded as nonflexible. Furthermore, the maximum force applicable with this setup is already reached after a penetration distance of 0.6 mm, which is 5% of the total penetration distance applied to the dishwashing detergent tablet. The experimental data are summarized in table 2, figure 1 and figure 2.
Table 2
Figure imgf000098_0001
Haze and clarity measurements:
Specimens of the polymer compositions P1-1 and P1-2 were prepared by plastifying the polymer compositions P1-1 and P1-2, respecitively, by the procedure described above casting the plastified polymer composition in a cylindrical mold in such a way that the resulting final three dimensional body had a diameter of 70 mm and a length in z-direction of 4 mm. The respective product was allowed to cool and stored in a climate chamber at 25°C and 50% humidity for equilibration as described for protocol B above. For the purpose of comparison a sheet of polyvinyl alcohol (PVA) having a thickness of 1.5 mm was also analyzed. The measurements of haze and clarity were carried out as described in ASTM D1003. The results are summarized in the following table 3:
Figure imgf000098_0002
StD: Standard Deviation Application examples:
The washing effect of the detergent formulation according to the invention was determined as follows: Selected soiled fabrics were washed in the presence of ballast fabric made from cotton at 30°C with the addition of the detergent formulation P1-1A according to the invention in cylindrical shape with a diameter of 70 mm and height of 6 mm. After the wash cycle, the fabrics were rinsed, spun and dried. To determine the washing effect, the reflectance of the soiled fabric was measured before and after the washing using a photometer from Datacolor (Elrepho 2000) at 460 nm. The higher the reflectance value, the better the washing ability. Washing conditions:
Figure imgf000099_0001
Wash result (evaluation % reflectance), mean value of all 19 fabrics
Figure imgf000099_0002

Claims

Claims
1. A detergent formulation in form of a three dimensional shaped body having dimensions of at least 1 mm in all spatial directions further having a clarity value of at least 70% according to ASTM D1003 and having a haze value according to
ASTM D 1003, which is smaller than 75% where said a three dimensional shaped body comprises or consists of a polymer composition P1) obtainable by free-radical polymerization of a monomer composition M1) comprising at least one monomer A) selected from a,b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a,b-ethylenically unsaturated mono- and dicarboxylic acids, anhydrides of a,b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof, in the presence of at least one polyether component PE) selected from polyetherols having a number-average molecular weight of at least 200 g/mol and the mono- and di-(Ci-C6-alkyl ethers) thereof, surfactants containing polyether groups and mixtures thereof.
2. The detergent formulation according to claim 1 , where the aspect ratio of the largest dimension to the smallest dimension of the three dimensional shaped body is in the range from 1:1 to 1 :20.
3. The detergent formulation according to claim 1 or 2 having a static friction value in the range of 0.5 N to 20.0 N according to DIN EN ISO 8295 and/or a sliding friction value in the range of 0.1 N to 5.0 N according to DIN EN ISO 8295.
4. The detergent formulation according to any one of the preceding claims, wherein the three dimensional shaped body has a volume of at least 33 mm3, in particular at least 64 mm3.
5. The detergent formulation according to any one of the preceding claims, wherein the a,b-ethylenically unsaturated carboxylic acid consist of acrylic acid A) and optionally at least one further a,b-ethylenically unsaturated acid B), preferably B) is selected from carboxylic acids, sulfonic acids, phosphoric acids and mixtures thereof.
6. The detergent formulation according to any one of the preceding claims, wherein the polyether component PE) comprises or consists of at least one polyetherol having a number-average molecular weight in the range from about 200 to 100000 or a mono- or di-(Ci-C2-alkyl) ether thereof.
7. The detergent formulation according to any one of the preceding claims, wherein the polyether component PE) comprises or consists of at least one polyetherol or a mono- or di-(Ci-C2-alkyl) ether thereof comprising exclusively ethylene oxide units incorporated as alkylene oxide units.
8. The detergent formulation according to any one of the preceding claims, wherein the polyether component PE) comprises at least one surfactant containing polyether groups, selected from alkyl polyoxyalkylene ethers, aryl polyoxyalkylene ethers, alkylaryl polyoxyalkylene ethers, alkoxylated animal and/or vegetable fats and/or oils, fatty amine alkoxylates, fatty acid amide alkoxylates, fatty acid diethanolamide alkoxylates, polyoxyethylene sorbitan fatty acid esters, alkyl polyether sulfates, aryl polyether sulfates, alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl polyether sulfonates, alkylaryl polyether sulfonates, alkyl polyether phosphates, aryl polyether phosphates, alkylaryl polyether phosphates, glyceryl ether sulfonates, glyceryl ether sulfates, monoglyceride (ether) sulfates, fatty acid amide ether sulfates, polyoxyalkylene sorbitan fatty acid esters and mixtures thereof.
9. The detergent formulation according to any one of the preceding claims, where the amount of the polymer composition P1 ) in the detergent formulation is at least 75% by weight, based on the total weight of the detergent formulation.
10. The detergent formulation according to any one of the preceding claims, comprising at least 95% by weight of a) 75 to 95% by weight, based on the total weight of the detergent formulation, of the polymer composition P1) and b) 5 to 25% by weight of water, where the % by weight is based on the total weight of the detergent formulation.
11. The detergent formulation according to any one of the preceding claims, comprising one or more separate domains comprising at least one further component selected from polymer P2), which differ from the polymer composition P1), builder, bleach, additives and mixtures thereof.
12. The detergent formulation according to any one of claims 1 to 10, consisting of one single domain, comprising the polymer compostion P1) and optionally at least one further component selected from polymers P2), builder, bleach, additives and mixtures thereof.
13. A detergent formulation according to any one of the preceding claims which is obtainable by a process comprising the following steps i) providing a detergent composition comprising or consisting of the polymer composition P1 ) having a water content of at most 25% by weight, based on the total weight of P1 ); ii) plastifying the detergent composition of step i) by heating the detergent composition to a temperature of at least 50°C; iii) shaping the plastified detergent composition of step ii) into the desired shape of the three dimensional body; and iv) rapid cooling of the shaped detergent composition of step iii) to a temperature of at most -20°C, obtaining the detergent formulation in the shape of a three dimensional body.
14. A process for preparing a detergent formulation in form of a three dimensional body defined in claims 1 to 12 which comprises plastifying a detergent composition containing or consisting of the polymer composition P1), shaping the plastified detergent composition into the desired shape of a three dimensional shaped body and solidifying the plastified detergent composition by rapid cooling.
15. The process of claim 14 which comprises the steps: i) providing a detergent composition comprising or consisting of the polymer composition P1), having a water content of at the most 25% by weight, based on the total weight of P1), ii) plastifying the detergent composition of step i) by heating it to a temperature of at least 50°C, iii) shaping the plastified detergent composition from step ii) into the desired shape of the three dimensional shaped body and, iv) rapid cooling of the shaped, plastified detergent composition of step iii) to a temperature at most -20°C, obtaining the detergent formulation in the shape of a three dimensional shaped body.
16. A washing and cleaning composition comprising or consisting of the detergent formulation in form of a three dimensional shaped body defined in claims 1 to 12.
17. Use of the detergent formulation in form of a three dimensional shaped body defined in any one of claims 1 to 12 for self-dosing washing machines or dishwashing machines.
18. Kit of parts for washing mashines or dishwashing mashines comprising the detergent formulation in form of a three dimensional shaped body defined in any one of claims 1 to 12 and optionally further substance selected from builder, bleachadditives different therefrom and mixtures thereof, for a combined use.
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