WO2020224962A1 - Films hydrosolubles à topographie tridimensionnelle - Google Patents

Films hydrosolubles à topographie tridimensionnelle Download PDF

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Publication number
WO2020224962A1
WO2020224962A1 PCT/EP2020/061211 EP2020061211W WO2020224962A1 WO 2020224962 A1 WO2020224962 A1 WO 2020224962A1 EP 2020061211 W EP2020061211 W EP 2020061211W WO 2020224962 A1 WO2020224962 A1 WO 2020224962A1
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WO
WIPO (PCT)
Prior art keywords
film
water
acid
salts
mixtures
Prior art date
Application number
PCT/EP2020/061211
Other languages
English (en)
Inventor
Benjamin SCHMIDT-HANSBERG
Andreas Schroeder
Matthias Arndt
Jürgen Detering
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of WO2020224962A1 publication Critical patent/WO2020224962A1/fr

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness

Definitions

  • the present invention relates to water-soluble multi-layered films having a three-dimensional topography on at least one, preferably only one side of the film, a process for preparing said water-soluble multi-layered film, an article comprising said water-soluble multi-layered film, the use of said water-soluble multi-layered film for dosing detergent into a laundry machine or a dishwashing machine and the use of said water-soluble multi-layered film for the production of water-soluble containers with a three-dimensional topography on the outer side.
  • the proportion of the polyvinyl alcohol film in the total weight of the washing or cleaning agent portion in the total weight of the single dose unit is between 2 and 20% by weight, depending on the application.
  • One objective in the art is to produce portion-wise packaging with three-dimensional topographies for aesthetic reasons but also for applying e.g. labels, instructions for use or hazard information.
  • the dissolution kinetics of the packaging is impaired due to different thicknesses of the different areas of the polyvinyl alcohol films.
  • the dissolution time of the portion-wise packaging is not too high in order to allow speedy release of the detergents and cleaners at the beginning of the washing and cleaning process.
  • child protection regulation requires that the dissolution time of said packaging must be at least 30 seconds.
  • the type and amount of three-dimensional topographies applied on the portion-wise packaging can significantly change the dissolution kinetics of said packaging compared to plain packaging.
  • portion-wise packaging of liquid, gel and solid detergents and cleaners show a high adherence to each other so that the packaging are literally glued together in their storage box.
  • the reason for the high adherence lies in the rather high static friction and coefficient of friction of the water-soluble films.
  • the present invention relates to a water-soluble multi-layered film comprising at least two film layers L1 and L2 in adherent contact to each other in any order,
  • At least one film layer L1 comprises a polymer composition P1 obtainable by radical polymerization of a monomer composition M1 in the presence of at least one polyether component PE,
  • M1 comprises at least one monomer A
  • A is selected from a,b-ethylenically unsaturated mono- or dicarbon acids, salts of a,b-ethylenically unsaturated mono- or dicarbon acids or mixtures thereof,
  • PE is selected from polyether alcohols with a number average molecular weight Mn of at least 200 g/mol, mono and di-(Ci to C 6 -alkyl)ethers of such polyether alcohols, polyether groups-containing tensides or mixtures thereof,
  • At least one film layer L1 comprises a mixture of
  • a polymer PT that comprises polymerized units of at least one monomer A’), selected from a,b-ethylenically unsaturated carboxylic acids, salts of a,b -ethylenically unsaturated carboxylic acids and mixtures thereof, and
  • polyether component PE selected from polyether alcohols with a number average molecular weight Mn of at least 200 g/mol, mono and di-(Ci to C 6 -alkyl)ethers of such polyether alcohols, polyether groups-containing tensides or mixtures thereof;
  • At least one film layer L2 comprises at least one polymer P2 which is different from polymer composition P1 and is selected from
  • homo-or copolymers comprising at least one monomer selected from N-vinylpyrrolidone, N- vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinyl-pyridine, salts of N- vinylimidazole, salts of 2-vinylpyridine, salts of 4-vinyl-pyridine, vinylpyridine-N-oxide, N- carboxymethyl-4-vinylpyridine halogenides or mixtures thereof;
  • acrylic acid monomer selected from acrylic acid, salts of acrylic acid or mixtures thereof and at least one maleic acid monomer selected from maleic acid, maleic acid anhydride, salts of maleic acid or mixtures thereof;
  • copolymer comprising at least a (meth)acrylic acid monomer selected from acrylic acid, methacrylic acid, salts of acrylic acid, salts of methacrylic acid or mixtures thereof and at least one hydrophobic monomer selected from Ci-Cs alkylesters of (meth) acrylic acid, C2- C10 olefins, styrene or a-methyl-styrene;
  • polyalkyleneoxide such as polyethyleneoxide
  • water-soluble multi-layered film has a three-dimensional topography on at least one, preferably only one side of the film resulting in locally thick and thin film areas,
  • the ratio of the thickness of the film in the locally thick film areas to the thickness of the film in the locally thin film areas is from 1.1 : 1.0 to 10.0 : 1.0.
  • the invention further relates to a process for preparing the water-soluble multi-layered film as defined above or below comprising the steps of
  • the present invention relates to an article comprising the water-soluble multi-layered film as defined above or below.
  • the present invention relates to the use of the water-soluble multi-layered film as defined above or below for dosing detergent into a laundry machine or a dishwashing machine.
  • the present invention relates to the use of the water-soluble multi-layered film as defined above or below for the production of water-soluble containers with a three-dimensional topography on the outer side.
  • the present invention related to the use of the water-soluble multi-layered film as defined above or below for reducing the adherence between two water-soluble multi-layered films.
  • the terms “detergent portion” and “cleaning agent portion” are understood to mean a quantity of a detergent or a cleaning agent which is sufficient for a washing or cleaning operation taking place in an aqueous phase.
  • This can be, for example, a laundry washing process, as is carried out with commercially available laundry machines or a dish washing process which is carried out with commercially available dish washing machines.
  • this term is also understood to mean an active ingredient portion for a handwash cycle or a manual cleaning process (as is carried out, for example, in a handwash basin or in a bowl).
  • the washing and cleaning-active multi-layered films according to the invention are preferably used for the production of active ingredient portions for mechanical washing or cleaning operations.
  • the term“polymer film” refers to a flat structure which has an essentially two-dimensional extension.
  • the thickness of the films according to the invention is preferably 0.5 pm to 20 mm, particularly preferably 1 pm to 10 mm.
  • the thickness of the polymer films of the invention is small in relation to the length and width.
  • the thickness of the polymer films is smaller by a factor of at least 2, more preferably of at least 5 and especially of at least 10 than the length of the greatest longitudinal axis.
  • the thickness of the polymer films is smaller by a factor of at least 20, more specifically at least 50, even more specifically at least 100 and very specifically at least 500 than the length of the greatest longitudinal axis.
  • the upper value for the greatest longitudinal extent of the polymer films of the invention is uncritical.
  • the polymer films of the invention can be produced, for example, in the form of film rolls, where the greatest length may even be in the region of 100 m or higher.
  • the polymer films of the invention are multi-layered films.
  • multi-layered film in connection with the present invention defines a self-supporting planar construction which comprises at least two film layers.
  • a multi-layered film according to the present invention is a film composite which comprises at least two films which are permanently connected with a substantial part of their surface over its entire surface. Thereby, it is understood that at least two films are permanently connected with at least 50% of their surface over its entire surface. If two films of different sizes are connected to each other, at least the film with the smaller surface is permanently connected over its entire surface to at least 50% of its surface.
  • the multi-layered films used in the process of the present invention differ from films used for the production of water-soluble container known in the art in which a single film or two or more films are connected by means of a seal seam. Those films known in the art are only connected over their entire surfaces to not more than 50% of their surfaces.
  • polymer film with a three-dimensional topography differs from the above defined essentially two-dimensional flat structure of the polymer film in defining a structure with a two- dimensional extension in x- and y-direction which on at least one surface, preferably only one surface, shows a structure of height differences in z-direction leading to locally thick and thin film areas.
  • the water-soluble film of the present invention is a multi-layered film.
  • the multi-layered film used in the process according to the present invention comprises at least two film layers L1 and L2 in any order, wherein at least one film layer L1 comprises a polymer composition P' ⁇ obtainable by radical polymerization of a monomer composition M 1 in the presence of at least one polyether component PE, whereby M1 comprises at least one monomer A, whereby A is selected from a,b-ethylenically unsaturated mono- or dicarbon acids, salts of a,b-ethylenically unsaturated mono- or dicarbon acids or mixtures thereof, and whereby PE is selected from polyether alcohols with a number average molecular weight Mn of at least 200 g/mol, mono and di-(Ci to C 6 -alkyl)ethers of such polyether alcohols, polyether groups- containing surfactants or mixtures thereof,
  • At least one film layer L1 comprises a mixture of
  • a polymer P1’ that comprises polymerized units of at least one monomer A’), selected from a,b-ethylenically unsaturated carboxylic acids, salts of a,b -ethylenically unsaturated carboxylic acids and mixtures thereof, and
  • polyether component PE selected from polyether alcohols with a number average molecular weight Mn of at least 200 g/mol, mono and di-(Ci to C 6 -alkyl)ethers of such polyether alcohols, polyether groups-containing tensides or mixtures thereof;
  • At least one film layer L2 comprises at least one polymer P2 which is different from polymer composition P1 and is selected from
  • homo-or copolymers comprising at least one monomer selected from N-vinylpyrrolidone, N- vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinyl-pyridine, salts of N- vinylimidazole, salts of 2-vinylpyridine, salts of 4-vinyl-pyridine, vinylpyridine-N-oxide, N- carboxymethyl-4-vinylpyridine halogenides or mixtures thereof;
  • acrylic acid monomer selected from acrylic acid, salts of acrylic acid or mixtures thereof and at least one maleic acid monomer selected from maleic acid, maleic acid anhydride, salts of maleic acid or mixtures thereof;
  • copolymer comprising at least a (meth)acrylic acid monomer selected from acrylic acid, methacrylic acid, salts of acrylic acid, salts of methacrylic acid or mixtures thereof and at least one hydrophobic monomer selected from C1-C8 alkylesters of (meth) acrylic acid, C2- C10 olefins, styrene or a-methyl-styrene;
  • polyalkyleneoxide such as polyethyleneoxide
  • At least one film layer L1 comprises a polymer composition P1 obtainable by radical polymerization of a monomer composition M1 in the presence of at least one polyether component PE.
  • the monomer composition M 1 consists only 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 abovementioned acids are, in particular, the sodium, potassium and ammonium salts and the salts with amines or aminoalcohols.
  • the monomers A can be used as such or as mixtures with one another. The stated proportions by weight are all based on the acid form.
  • the at least one a, b-ethylenically unsaturated carboxylic acid is preferably used in
  • the acid groups are preferably neutralized to at most 50 mol%, more preferably to at most 30 mol%.
  • the monomer A is particularly preferably selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, salts of the abovementioned carboxylic acids and mixtures thereof.
  • the monomer A is selected from acrylic acid, methacrylic acid, salts of acrylic acid, salts of methacrylic acid and mixtures thereof.
  • only acrylic acid is used as monomer A.
  • the monomer A is preferably used in an amount of 50 to 100 wt .-%, particularly preferably 60 to 100 wt .-%, based on the total weight of the monomer composition M 1.
  • the monomer composition M1 comprises at least 50% by weight, preferably at least 80% by weight, in particular at least 90% by weight, based on the total weight of the monomer composition M 1 , of acrylic acid and / or acrylic acid salts.
  • Monomer B is
  • the monomer composition M1 may comprise, in addition to the monomers A, at least one monomer B selected from unsaturated sulfonic acids, salts of unsaturated sulfonic acids, unsaturated phosphonic acid, salts of unsaturated phosphonic acids and mixtures thereof.
  • the monomer B is preferably selected from 2-acrylamido-2-methylpropane-sulfonic acid, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3- methacryloxypropylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, allylphosphonic acid, salts of the aforementioned acids and mixtures thereof.
  • Preferred monomer B is 2-acrylamido-2-methylpropanesulfonic acid.
  • Suitable salts of the abovementioned acids are in particular 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 are all based on the acid form.
  • the monomer composition M1 is then at least 50% by weight, particularly preferably at least 80% by weight, in particular at least 90% by weight, based on the total weight of the monomer composition M1 , of monomers A and B. If the monomer composition M1 comprises at least one monomer B, this is preferably used in an amount of 0.1 to 50% by weight, particularly preferably 1 to 25% by weight, based on the total weight of the monomer composition M1.
  • the monomer composition M 1) can thus have the following monomer compositions: A or A + B or A + C or A + B + C.
  • the monomer composition M1 additionally comprises at least one monomer C, selected from
  • x 0, 1 or 2
  • k and I independently of one another are an integer from 0 to 100, the sum of k and I being at least 2, preferably at least 5,
  • R 1 is hydrogen or Ci-Cs-alkyl
  • R 2 is hydrogen, C1-C30 alkyl, C2-C30 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
  • hydrocarbons having at least two conjugated double bonds having at least two conjugated double bonds
  • esters of a, b-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C3o-alkanols
  • C6 compounds having a radically polymerizable a, b-ethylenically unsaturated double bond and at least one cationogenic and/or cationic group per molecule
  • esters of vinyl alcohol or allyl alcohol with C1-C30 monocarboxylic acids
  • Preferred nitrogen heterocycles having a radically polymerizable a, b-ethylenically unsaturated double bond C1 are selected from 1-vinylimidazole (N-vinylimidazole), various vinyl- and allyl- substituted nitrogen heterocycles other than 1-vinylimidazole and mixtures thereof.
  • Suitable monomers C1 are also the compounds obtained by protonation or quaternization of 1- vinylimidazole and various vinyl- and allyl-substituted nitrogen heterocycles thereof.
  • suitable acids are e.g. 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. Protonation or
  • quaternization can generally be carried out both before and after the polymerization. Preferably, protonation or quaternization takes place after the polymerization.
  • charged monomers C1 are quaternized vinylimidazoles, in particular 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
  • 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.
  • the monomer composition M 1 comprises as comonomer C1 1-vinylimidazole.
  • the monomer composition M 1 may additionally comprise at least one monomer C2 selected from compounds of the general formulas (I. a) and (l.b) as defined above.
  • k is preferably an integer from 1 to 500, particularly preferably 2 to 400, in particular 3 to 250.
  • I is an integer from 0 to 100.
  • R 1 in the formula I. a) is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- butyl, tert-butyl, n-pentyl or n-hexyl, in particular hydrogen, methyl or ethyl.
  • R 2 in the formulas 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, arrachinyl, behenyl, lignocerenyl, cerotinyl, melissinyl, palmitoleinyl, oleyl, linolyl, linolenyl, stearyl, lauryl.
  • X in the formula l.a) is O or NH, in particular O.
  • the monomer composition M1 particularly preferably comprises at least one monomer C2 selected from compounds of the general formulas (I.a1 ) and (I.b1 )
  • H 2 C C— C— O— (CH2-CH 2 -0) k (CH2-CH(CH 3 )-0)
  • x 0, 1 or 2
  • k and I independently of one another are an integer from 0 to 100, the sum of k and I being at least 2, preferably at least 5,
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen, C1-C4-alkyl.
  • k is preferably an integer from 1 to 100, more preferably 2 to 50, in particular 3 to 30.
  • I is an integer from 0 to 50.
  • R 2 in the formulas 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 l.a) or I.a1) are e.g. the polycondensation products of the aforementioned a, b-ethylenically unsaturated mono- and/or dicarboxylic acids and their acid chlorides, amides and anhydrides with polyetherols.
  • Suitable polyetherols can be readily prepared by reacting ethylene oxide, 1 ,2-propylene 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 for the preparation of the polymers used according to the invention.
  • Suitable allyl alcohol alkoxylates l.b) or I.b1 are e.g. the etherification of allyl chloride with corresponding polyetherols.
  • Suitable polyetherols can be readily prepared by reacting ethylene oxide, 1 ,2-propylene oxide and/or epichlorohydrin with a starting 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 for the preparation of the polymers used according to the invention.
  • the monomer C2 used is methyl diglycol acrylate, methyl diglycol methacrylate, ethyl diglycol acrylate or ethyl diglycol methacrylate.
  • Preferred is ethyl diglycol acrylate.
  • the monomer composition M 1 may additionally comprise at least one monomer C3 selected from vinylaromatics.
  • Preferred vinylaromatics C3 are styrene, 2-methylstyrene, 4-methylstyrene, 2-(n-butyl)styrene, 4-(n-butyl)styrene, 4-(n-decyl)styrene and mixtures thereof. Particularly preferred are styrene and 2-methylstyrene, especially styrene.
  • the monomer composition M 1 may additionally comprise at least one unsaturated hydrocarbon C4 selected from C2-C10 monoolefins and non-aromatic hydrocarbons having at least two conjugated double bonds.
  • 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-methylbut-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 their position
  • Non-aromatic hydrocarbons having at least two conjugated double bonds denote 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 carbon-carbon double bonds predetermined by the ring size or those which, although they have the maximum number of conjugated carbon-carbon double bonds carbon atoms given by the ring size, do not conform to the Huckel rule; be it because they are homoaromatic, antiaromatic or a non-aromatic polyene.
  • Aliphatic hydrocarbons having at least two conjugated double bonds usually contain from 4 to 20 carbon atoms.
  • Examples of aliphatic hydrocarbons having at least two conjugated double bonds are 1 ,3-butadiene, 1 ,3-pentadiene, isoprene, 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 usually contain 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-cyclootadiene, 1 ,3,5-cyclootatriene, 1 ,3,5,7- cyclooctatetraene and the like.
  • Preferred monomers C4 are ethene, propene, butene, isobutene, diisobutene, isoprene, 1 ,3- butadiene and mixtures thereof.
  • the monomer composition M 1 may additionally comprise at least one monomer C5 selected from esters of a, b-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C3o-alkanols.
  • Suitable esters of a, b-ethylenically unsaturated mono- and dicarboxylic acids with C1-C30- alkanols are e.g. methyl(meth)acrylate, methyl(meth)acrylate, ethyl(meth)acrylate,
  • ethyl(eth)acrylate n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, tert- butyl(meth)acrylate tert-butyl(eth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, n- heptyl(meth)acrylate, n-octyl(meth)acrylate, 1 ,1 ,3,3-tetramethylbutyl(meth)acrylate,
  • ethylhexyl(meth)acrylate n-nonyl(meth)acrylate, n-decyl(meth)acrylate, n- undecyl(meth)acrylate, tridecyl(meth)acrylate, myristyl(meth)acrylate, pentadecyl(meth)acrylate, palmityl(meth)acrylate, heptadecyl(meth)acrylate, nonadecyl(meth)acrylate,
  • cerotinyl(meth)acrylate cerotinyl(meth)acrylate, melissinyl(meth)acrylate, palmitoleinyl(meth)acrylate,
  • the monomer composition M 1 may additionally comprise at least one monomer C6 selected from compounds having a 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 C6 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 generated from the amine nitrogens either by protonation or by quaternization with acids or alkylating agents. These include e.g. carboxylic acids such as lactic acid, or mineral acids such as phosphoric acid, sulfuric acid and
  • hydrochloric acid or as alkylating C1-C4 alkyl halides or sulfates such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.
  • Protonation or quaternization can generally be carried out both before and after the polymerization.
  • the monomers C6 are selected from esters of a, b-ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols which may be mono- or dialkylated on the amine nitrogen, amides of a, b-ethylenically unsaturated mono- and dicarboxylic acids with diamines which comprise at least one primary or secondary amino group, N, N-diallylamine, N, N-diallyl- N-alkylamines and their derivatives and mixtures thereof.
  • esters of a, b-ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols which may be mono- or dialkylated on the amine nitrogen, are preferably derived from C2 -C12 - aminoalcohols which are mono- or -dialkylated on the amino nitrogen C1 -C8 -monoalkyl.
  • the acid component of these esters are e.g. acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof.
  • Acrylic acid, methacrylic acid and mixtures thereof are preferably used as the acid component.
  • Preferred monomers C6 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 C6 are furthermore the amides of the abovementioned a, b-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group.
  • diamines having a tertiary and a primary or secondary amino group.
  • Preferred as monomers C6 are e.g. 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 M 1 may additionally comprise at least one monomer C7 selected from compounds of esters of vinyl alcohol or allyl alcohol with Ci-C30-monocarboxylic acids. Suitable esters of vinyl alcohol with C1-C30 monocarboxylic acids are e.g.
  • methyl vinylester ethyl vinylester, n-propyl vinylester, isopropyl vinylester, n-butyl vinylester, tert-butyl vinylester, n-pentyl vinylester, n-hexyl vinylester, n-heptyl vinylester, n-octyl vinylester, 1 , 1 ,3,3- tetramethylbutyl vinylester, ethylhexyl vinylester, n-nonyl vinylester, n-decyl vinylester, n- undecyl vinylester, tridecyl vinylester, myristyl vinylester, pentadecyl vinylester, palmityl vinylesters, heptadecyl vinylesters, octadecyl vinylesters, nonadecyl vinylesters, arrachinyl vinylesters, behenyl vinylesters,
  • the monomer composition M 1 may additionally comprise at least one monomer C8 selected from esters of a, b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30- alkanediols and amides of a, b-ethylenically unsaturated mono- and dicarboxylic acids with C 2 - C 30 -aminoalcohols with a primary or secondary amino group.
  • monomer C8 selected from esters of a, b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30- alkanediols and amides of a, b-ethylenically unsaturated mono- and dicarboxylic acids with C 2 - C 30 -aminoalcohols with a primary or secondary amino group.
  • Suitable esters of a, b-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30 alkanediols are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 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.
  • the monomer composition M 1 may additionally comprise at least one monomer C9 selected from amide group-containing monomers other than I. a), C6 and C8.
  • Suitable amide group-containing monomers C9 are compounds of the general formula (V)
  • R 6 and R 7 together with the amide group to which they are attached may also stand for a lactam having 5 to 8 ring atoms
  • R 7 and R 8 together with the nitrogen atom to which they are attached, may also stand for a five- to seven-membered heterocycle.
  • the monomers C9 are preferably selected from primary amides of a, b-ethylenically
  • unsaturated monocarboxyl ic acids N-vinylamides of saturated monocarboxylic acids, N- vinyllactams, N-alkyl and N, N-dialkylamides of a, b-ethylenically unsaturated monocarboxylic acids and mixtures thereof.
  • Preferred monomers C9 are N-vinyl lactams and their derivatives, which include e.g. one or more Ci-C 6 -alkyl substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert- butyl. These include e.g.
  • N-vinylpyrrolidone N-vinylpiperidone, N-vinylcaprolactam
  • N-vinyl-5- methyl-2-pyrrolidone N-vinyl-5-ethyl-2-pyrrolidone
  • N-vinyl-6-methyl-2-piperidone N-vinyl-6- ethyl-2-piperidone
  • N-vinyl-7-methyl-2-caprolactam N-vinyl-7-ethyl-2-caprolactam, etc.
  • N-vinylpyrrolidone and/or N-vinylcaprolactam are particularly preferred.
  • Suitable monomers C9 are furthermore acrylamide and methacrylamide.
  • Suitable N-alkyl and N, N-dialkylamides of a, b-ethylenically unsaturated monocarboxylic acids are e.g. methyl(meth)acrylamide, methylethacrylamide, ethyl(meth)acrylamide,
  • palmityl(meth)acrylamide palmityl(meth)acrylamide, heptadecyl(meth)acrylamide, nonadecyl(meth)acrylamide, arrachinyl(meth)acrylamide, behenyl(meth)acrylamide, lignocerenyl(meth)acrylamide, cerotinyl(meth)acrylamide, melissinyl(meth)acrylamide, palmitoleinyl(meth)acrylamide, oleyl(meth)acrylamide, linolyl(meth)acrylamide, linolenyl(meth)acrylamide,
  • stearyl(meth)acrylamide lauryl(meth)acrylamide, N-methyl-N-(n-octyl)(meth)acrylamide, N, N- di(n-octyl)(meth)acrylamide and mixtures thereof.
  • suitable open-chain N-vinylamide compounds as monomers C9 are N- vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N- vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl N-methylpropionamide, N-vinyl-butyramide and mixtures thereof.
  • N-vinylformamide is used.
  • the monomer composition M 1 may additionally comprise at least one monomer C10 selected from a, b-ethylenically unsaturated nitriles.
  • Suitable a, b-ethylenically unsaturated nitriles are acrylonitrile or methacrylonitrile.
  • the monomer composition M 1 may additionally comprise at least one monomer C1 1 selected from vinyl halides and vinylidene halides.
  • Suitable vinyl halides and vinylidene halides are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • the monomer composition M 1 may additionally comprise at least one monomer C12 selected from ethylenically unsaturated monomers having urea groups.
  • Suitable monomers C12 with urea groups are N-vinylurea, N-allylurea or derivatives of imidazolidin-2-one. These include N-vinyl and N-allylimidazolidin-2-one, N- vinyloxyethylimidazolidin-2-one, N-(2-(meth)acrylamidoethyl)imidazolidin-2-one, N-(2- (meth)acryloxyethyl)imidazolidine-2-one (i.e. 2-ureido(meth)acrylate), N-[2- ((meth)acryloxyacetamido)ethyl] imidazolidin-2-one, etc.
  • the monomer composition M1 comprises acrylic acid and optionally at least one comonomer selected from a, b-ethylenically unsaturated mono- (e.g. methacrylic acid) or dicarboxylic acids, salts, anhydrides, esters and amides other than acrylic acid a, b- ethylenically unsaturated mono- or dicarboxylic acids, olefinically unsaturated sulfonic acids (e.g.
  • 2-acrylamido-2-methylpropanesulfonic acid AMPS 2-acrylamido-2-methylpropanesulfonic acid AMPS
  • salts of olefinically unsaturated sulfonic acids C2 -C10-monoolefins, non-aromatic hydrocarbons having at least two conjugated double bonds, vinylaromatics, N-vinyllactams and mixtures thereof.
  • the monomer composition M1 comprises acrylic acid and optionally at least one comonomer selected from ethene, propene, isobutene, diisobutene, isoprene, 1 ,3- butadiene, methacrylic acid, 2-acrylamido-2-methylpropane-sulphonic acid, maleic acid, maleic anhydride, itaconic acid, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, styrene and mixtures thereof.
  • comonomer selected from ethene, propene, isobutene, diisobutene, isoprene, 1 ,3- butadiene, methacrylic acid, 2-acrylamido-2-methylpropane-sulphonic acid, maleic acid, maleic anhydride, itaconic acid, N-vinylpyrrolidone, N-vinylcaprolactam, N-viny
  • the monomer composition M1 comprises acrylic acid and optionally at least one comonomer selected from methacrylic acid, 2-acrylamido-2- methylpropanesulfonic acid mixtures thereof.
  • the monomer composition M1 consists of at least 80% by weight, preferably at least 90% by weight, in particular at least 95% by weight, based on the total weight of the monomer composition M 1 , of acrylic acid.
  • the monomer composition M 1 may preferably comprise the further monomers C1 to C12 in an amount of from 0 to 30% by weight, particularly preferably 0 to 20% by weight, in particular 0 to 10% by weight, based on the total weight the monomer composition M1. If the monomer composition M 1 comprises at least one monomer selected from C1 to C12, then in each case preferably in an amount of 0.1 to 30% by weight, particularly preferably 1 to 20% by weight, in particular 1.5 to 10 % by weight, based on the total weight of the monomer composition M 1.
  • the monomer composition M1 comprises no further comonomers apart from the monomers A and B. More specifically, the monomer composition comprises no further comonomers other than acrylic acid.
  • the polymer composition P1 substantially comprises uncrosslinked polymers.
  • the monomer composition M 1 used to prepare the polymer composition P1 thus comprises in particular no added crosslinking monomers.
  • Crosslinking monomers in the context of the invention are compounds having two or more than two polymerizable ethylenically unsaturated double bonds per molecule.
  • the monomer composition M1 based on the total weight less than 0.1 % by weight, more preferably less than 0.05 % by weight, in particular less than 0.001 % by weight of crosslinking monomers containing two or more than two radically have polymerizable a, b- ethylenically unsaturated double bonds per molecule.
  • the monomer composition M1 comprises no crosslinking monomers which have two or more than two polymerizable a, b-ethylenically unsaturated double bonds per molecule.
  • Suitable as polyether component PE are polyetherols having a number average molecular weight of at least 200 g/mol and their mono- and di-(Ci-C 6 -alkyl ethers).
  • Suitable polyetherols and their mono- and di-(Ci-C 6 -alkyl ethers) may be linear or branched, preferably linear.
  • Suitable polyetherols and their mono- and di-(C1-C6-alkyl ethers) generally have a number-average molecular weight in the range from about 200 to 100,000, preferably from 300 to 50,000, particularly preferably from 500 to 40,000.
  • Suitable polyetherols are, for example, water-soluble or water-dispersible nonionic polymers which comprise alkylene oxide repeat units.
  • the proportion of alkylene oxide repeating 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 the preparation of alkylene oxide copolymers are e.g. ethylene oxide, propylene oxide, epichlorohydrine, 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 randomly distributed alkylene oxide units or in copolymerized form in the form of blocks.
  • the proportion of repeating units derived from ethylene oxide is 40 to 99% by weight.
  • Particularly preferred as the polyether component PE are ethylene oxide homopolymers and ethylene oxide / propylene oxide copolymers.
  • polyether component PE Also suitable as polyether component PE are the mono- and di-(Ci-C 6 -alkyl ethers) of the polyetherols described above. Preference is given to polyalkylene glycol monomethyl ether and polyalkylene glycol dimethyl ether. Also suitable as polyether component PE are polyether-containing surfactants. Generally suitable are nonionic and ionic surfactants which have at least one nonpolar and at least one polar group and which comprise a polyether group.
  • the polyether groups-containing surfactants PE are preferably selected from
  • alkylpolyoxyalkylenether arylpolyoxyalkylenether, alkylarylpolyoxyalkylenether, alkoxylated animal and/or vegetable fats and/or oils, fatty amine alkoxylates, fatty acid amide alkoxylates, fatty acid diethanolamide alkoxylates, polyoxyethylenesorbitan fatty acid esters,
  • alkylpolyethersulfates arylpolyethersulfates, alkylarylpolyethersulfates,
  • alkylpolyethersulfonates arylpolyethersulfonates, alkylarylpolyethersulfonates, alkylpolyether phosphateates, aryl polyether phosphates, alkylaryl polyether phosphates, glycerol ether sulfonates, glycerol ether sulfates, monoglyceride (ether) sulfates, fatty acid amide ether sulfates, polyoxyalkylene sorbitan fatty acid esters, and mixtures thereof.
  • ether monoglyceride
  • the preferred nonionic polyether group-containing surfactants PE include, for example:
  • Alkyl polyoxyalkylene ethers derived from C3-C6 low molecular weight alcohols or C7-C30 fatty alcohols.
  • the ether component 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 include, inter alia, surfactants of the general formula (VI)
  • R 10 is a linear or branched alkyl radical having 6 to 22 C atoms
  • R 11 and R 12 independently of one another are hydrogen or a linear or branched alkyl radical having 1 to 10 C atoms or H, wherein R 12 is preferably methyl, and
  • x and y are independently 0 to 300.
  • fatty alcohol alkoxylates and oxo alcohol alkoxylates such as iso- tridecyl alcohol and oleyl alcohol polyoxyethylene ethers.
  • the sequence of the alkylene oxide units is arbitrary, s, t, u and v independently represent an integer from 0 to 500, the sum of s, t, u and v being > 0, R 13 and R 15 independently of one another represent a linear or branched, saturated Ci-C4o-alkyl radical or a mono- or polyunsaturated C2-C4o-alkenyl radical, and
  • R 14 is selected from methyl, ethyl, n-propyl, isopropyl or n-butyl.
  • the sum of s, t, u and v is preferably from 10 to 300, particularly preferably from 15 to 200 and in particular from 20 to 150.
  • t and u are 0.
  • the sum of s and v is preferably from 10 to 300, particularly preferably from 15 to 200 and in particular from 20 to 150.
  • R 13 and R 15 are preferably, independently of one another, a linear or branched, saturated C2-C3o-alkyl radical.
  • R 13 and R 15 may also be mixtures of different alkyl radicals.
  • R 14 is preferably methyl or ethyl, in particular methyl.
  • a preferred embodiment are hydroxyl-containing surfactants of the general formula R 13 -0-(CH 2 CH 2 0) S -(CH 2 CH(CH 3 )0) V -CH 2 CH(0H)R 15
  • s and v are independently an integer from 0 to 500, the sum of s and v being > 0, and
  • R 13 and R 15 independently of one another represent a linear, saturated Ci-C3o-alkyl radical or a branched, saturated C3-C3o-alkyl radical or mono- or polyunsaturated C2-C3o-alkenyl radical.
  • the sum of s and v is preferably from 10 to 300, particularly preferably from 15 to 200 and in particular from 20 to 150.
  • nonionic surfactants include e.g. hydroxy mixed ethers of the general formula (C 6 -22-alkyl)-CH(OH)CH 2 O-(EO)20-i20-(C2-26-alkyl).
  • the sequence of the alkylene oxide units is arbitrary, p and q independently of one another represent an integer from 0 to 500, the sum of p and q being > 0, R 16 and R 18 independently of one another represent a linear or branched, saturated Ci-C4o-alkyl radical or a mono- or polyunsaturated C2-C4o-alkenyl radical, and
  • R 17 is selected from methyl, ethyl, n-propyl, isopropyl or n-butyl.
  • the sum of p and q is preferably from 10 to 300, particularly preferably from 15 to 200 and in particular from 20 to 150.
  • R 16 and R 18 independently of one another represent a linear or branched, saturated C4-C3o-alkyl radical.
  • R 16 and R 18 may also be mixtures of different alkyl radicals.
  • R 17 is preferably methyl or ethyl, in particular methyl.
  • lauryl alcohol polyoxyethylene acetate examples include e.g. lauryl alcohol polyoxyethylene acetate.
  • alkylarylalkoholpolyoxyethylenether e.g. Octylphenol polyoxyethylene ether
  • alkyl phenol alkoxylates such as ethoxylated isooctyl-, octyl- or nonylphenol, tributylphenol polyoxyethylene ethers,
  • alkylpolyethersulfate sodium dodecylpoly (oxyethylene) sulfate (sodium lauryl ether sulfate, SLES).
  • polymer composition P1 is prepared by
  • a monomer composition M 1 which comprises at least one monomer A which is selected from a, b-ethylenically unsaturated mono- and dicarboxylic acids, salts of a, b- ethylenically unsaturated mono- and dicarboxylic acids, anhydrides a, b-ethylenically unsaturated mono- and dicarboxylic acids and mixtures thereof,
  • step B) subjecting the monomer composition M 1 provided in step A) to a free radical polymerization in the presence of at least one polyether component PE which is selected from polyetherols having a number average molecular weight of at least 200 g/mol, mono- and di- (Ci-C 6 -alkyl) ethers such polyethers, polyether- groups containing surfactants and mixtures thereof, and optionally in the presence of at least one additive.
  • PE polyetherols having a number average molecular weight of at least 200 g/mol, mono- and di- (Ci-C 6 -alkyl) ethers such polyethers, polyether- groups containing surfactants and mixtures thereof, and optionally in the presence of at least one additive.
  • the radical polymerization of the monomer composition M1 in step B) is preferably carried out in the feed process.
  • at least the monomers in liquid form can be fed to the reaction batch.
  • Liquid monomers can be fed to the reaction mixture without the addition of a solvent LM1 , otherwise the monomers are used as a solution in a suitable solvent LM1. It is also possible to use monomers present in solid form.
  • the radical polymerization for the preparation of the polymer composition P1 can be carried out in the presence of a solvent LM1 which is selected from water, Ci-C 6 -alkanols, polyols other than PE, their mono- and dialkyl ethers and mixtures thereof.
  • a solvent LM1 which is selected from water, Ci-C 6 -alkanols, polyols other than PE, their mono- and dialkyl ethers and mixtures thereof.
  • Suitable polyols and their mono- and di-alkyl ethers also include alkylene glycol mono (Ci-C4-alkyl) ethers, alkylene glycol di (Ci- C4-alkyl) ethers, oligoalkylene glycols and their mono (Ci-C4-alkyl) ethers and di (Ci-C4-alkyl) ethers.
  • the solvent LM 1 is preferably selected from water, methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol mono (Ci-C4-alkyl) ethers, ethylene glycol di (C1-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 among the CTFA designations PEG-6, PEG-8, PEG-12, PEG-6-32, PEG-20, PEG-150, PEG-200, PEG-400, PEG-7M, PEG-12M and PEG-1 15M commercially available. These include in particular the Pluriol E ® brands of BASF SE. Suitable alkylpolyalkylene glycols are the corresponding Pluriol A... E® brands from BASF SE.
  • the solvent LM 1 is particularly 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.
  • the solvent used as LM1 is water or a mixture of water and at least one solvent LM1 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.
  • the radical polymerization in step B) is conducted in the presence of a solvent LM1 which comprises water in an amount of at least 50% by weight, preferably at least 75% by weight, especially at least 90% by weight, based on the total weight the solvent LM1.
  • a solvent LM1 which comprises water in an amount of at least 50% by weight, preferably at least 75% by weight, especially at least 90% by weight, based on the total weight the solvent LM1.
  • the radical polymerization in step B) takes place in the presence of a solvent LM1 , which consists of water.
  • the radical polymerization in step B) is conducted in feed mode, whereby feeds, which comprise at least one a, b-ethylenically unsaturated carboxylic acid, do not comprise a solvent LM1.
  • the feed rates of the monomer feed / the monomer feeds and any further feeds are preferably selected as such that the polymerization is maintained at the desired polymerization rate.
  • the addition of the individual feeds can be carried out continuously, periodically, with a constant or alternating feed rate, substantially simultaneously or with a time lag. Preferably, the addition of all feeds to the reaction mixture is carried out continuously.
  • the monomer composition M 1 and the polyether component PE are preferably used in the radical polymerization in a weight ratio of from 0.5:1 to 5:1 , particularly preferably from 0.7:1 to 3:1.
  • the weight ratio of the polyether component PE to the component LM 1 is preferably in the range from 0.1 :1 to 5:1 , particularly preferably from 0.5:1 to 3:1.
  • the radical polymerization in step B) preferably is conducted at a temperature in the range from 20 to 95°C, more preferably from 30 to 90°C, in particular from 40 to 80°C.
  • the radical polymerization in step B) can be carried out in the presence of at least one additive.
  • Suitable additives are e.g. corrosion inhibitors, defoamers, dyes, fragrances, thickeners, solubilizers, organic solvents, electrolytes, antimicrobial agents, antioxidants, UV absorbers and mixtures thereof.
  • the radical polymerization in step B) of the process preferably comprises the steps of
  • the template is heated to the polymerization temperature with stirring prior to adding the feeds.
  • the individual reactants are added simultaneously in separate feeds, wherein the flow rates of the feeds are usually kept as constant as possible over the period of addition.
  • the amount of polyether component PE in the initial charge (step B1) is preferably from 30 to 100% by weight, more preferably from 65 to 100% by weight and in particular from 80 to 100% by weight, based on the total weight of the polyether component PE used in the polymerization.
  • the amount of solvent LM1 in the template is not more than 70 % by weight, based on the total weight of the components of the template.
  • the amount of solvent in the template is not more than 40 % by weight, in particular not more than 35 % by weight, based on the total weight of the components of the template.
  • the amount of solvent changes over the entire course of the process usually only a few percent by weight.
  • solvents LM 1 are used which have a boiling point at atmospheric pressure (1 bar) of less than 240 °C.
  • the template contains no solvent. This is added only in step B2) via at least one of the feeds. In a very special variant, no solvent is introduced and no solvent is added over the entire course of the process.
  • the solvent is completely added in the template.
  • the template contains no regulator. If a regulator is used, it is added only in step B2) via at least one of the feeds.
  • step B2 The addition of the feeds in step B2) is conducted over a period of time which is advantageously chosen as such that the heat of reaction formed in the exothermic polymerization reaction can be withdrawn without major technical effort, e.g. 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 conducted continuously.
  • the monomer composition M1 , the polyether component PE, at least one initiator, optionally at least one regulator R and optionally at least one solvent LM 1 are added to the reactor in the form of a liquid stream or preferably at least two liquid streams.
  • the stream containing the initiator generally does not also include the regulator. If at least two liquid streams are used, they are mixed in a customary manner to obtain the reaction mixture.
  • the polymerization may be conducted 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 added between at least two of the polymerization stages. It may be a monomer-containing stream, initiator-containing stream, solvent-containing stream, regulator-containing stream, a mixture thereof and/or any other material stream.
  • the optional solvent and/or any resulting condensation products are generally not withdrawn. I.e. during the polymerization, there is usually no or only a very small, within the scope of the technical possibilities, mass transfer with the environment.
  • the polymerization can usually be carried out at ambient pressure or reduced or elevated pressure. Preferably, the polymerization is carried out at ambient pressure.
  • the polymerization is usually carried out at a constant temperature, but can also be varied as needed during the polymerization.
  • the polymerization temperature is kept as constant as possible over the entire reaction period, i.e. the steps B2) and B3).
  • the polymerization temperature usually ranges from 20 to 95°C.
  • the polymerization temperature is in the range of 30 to 90°C, and more preferably in the range of 40 to 80°C. If the polymerization is not carried out under elevated pressure and at least one optional solvent LM 1 was added to the reaction mixture, the solvent or solvent mixture determines the maximum reaction temperature by their corresponding boiling temperatures.
  • the polymerization can be carried out in the absence or in the presence of an inert gas.
  • an inert gas is usually understood to be a gas which, under the given reaction conditions, does not react with the educts, reagents, solvents or the resulting products involved in the reaction.
  • the solvent is selected from the solvents LM1 described above.
  • the monomers can be polymerized with the aid of radical-forming initiators, hereinafter also referred to as radical initiators or starters.
  • radical initiators hereinafter also referred to as radical initiators or starters.
  • Radical initiators (initiators) for radical polymerization are in principle all radical initiators which are substantially soluble in the reaction medium, as prevails at the time of their addition, and have sufficient activity at the given reaction temperatures to initiate the polymerization.
  • a single radical starter or a combination of at least two radical initiators can be used.
  • the at least two radical initiators can be added in a mixture or preferably separately, simultaneously or sequentially, e.g. at different times in the course of the reaction.
  • Radical initiators which can be used for radical polymerization are the customary peroxo and/or azo compounds, for example hydrogen peroxide, alkali metal or ammonium peroxodisulfates (such as, 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 peroxymaleinate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis-(o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, tert-butyl peroctoate, dil
  • the radical initiator is generally provided as a solution in a solvent which comprises at least one of the abovementioned solvents LM1 and optionally additionally at least one polyether of the polyether component PE.
  • the polymerization can be carried out without the use of a regulator (polymerization regulator) or in the presence of at least one regulator.
  • Regulators generally refer to compounds having high transfer constants which accelerate chain transfer reactions and thus cause a reduction in the degree of polymerization of the resulting polymers. In the case of the regulators, one can distinguish between mono-, bi- or polyfunctional regulators depending on the number of functional groups in the molecule which can lead to one or more chain transfer reactions.
  • Suitable regulators are described in detail, for example, by K.C. Berger and G. Brandrup in J. Brandrup, E.H. Immergut, Polymer Handbook, 3rd ed., John Wiley & Sons, New York, 1989, p. 11 / 81 - II / 141.
  • Suitable regulators are, for example, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde.
  • regulators are formic acid, its salts or esters, such as ammonium formate, 2,5- diphenyl-1 -hexene, hydroxylammonium sulfate and hydroxylammonium phosphate.
  • Suitable regulators are allyl compounds, such as allyl alcohol, functionalized allyl ethers such as allyl ethoxylates, alkyl allyl ethers, or glycerol monoallyl ethers.
  • Compounds of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides and sulfones.
  • di-n-butylsulfide di-n- octylsulfide, diphenylsulfide, 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.
  • polymerization regulators are thiols (compounds which comprise sulfur in the form of SH groups, also referred to as mercaptans).
  • Preferred regulators 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 alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan.
  • Examples of bifunctional regulators containing two sulfur atoms in bonded form are bifunctional thiols, such as
  • dimercaptopropanesulfonic acid sodium salt
  • dimercaptosuccinic acid dimercapto-1 -propanol
  • dimercaptoethane dimercaptopropane
  • dimercaptobutane dimercaptopentane
  • dimercaptohexane ethylene glycol bis-thioglycolate and butanediol-bis-thioglycolate.
  • polyfunctional regulators are compounds containing more than two sulfur in bound form. Examples of these are trifunctional and/or tetrafunctional mercaptans.
  • the regulator is particularly preferably selected from mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid, ethylhexyl thioglycolate and sodium hydrogensulfite.
  • hypophosphorous acid phosphinic acid
  • salts of hypophosphorous acid are also preferred as regulators.
  • a preferred salt of the hypophosphorous acid is the sodium salt.
  • the amount is usually 1 to 40 pphm (parts per hundred monomer, i.e. parts by weight based on one hundred parts by weight of the monomer composition).
  • the amount of regulator used in the polymerization process is preferably in the range from 3 to 30 pphm, more preferably in the range from 5 to 25 pphm. It is also possible to carry out the polymerization without addition of a regulator.
  • the regulator is added continuously to the polymerization mixture in step B2) completely via one of the feeds.
  • the addition of the regulator can be carried out in each case without or with solvent LM1.
  • the amount of regulator and the way it is added to the reaction mixture have a strong influence on the average molecular weight of the polymer composition. If no regulator or only a small amount of regulator is used and/or if the addition is conducted predominantly before the polymerization, usually higher average molecular weights of the polymer are obtained. On the other hand, if larger amounts of regulators are used and/or if the addition of the regulator is conducted largely during the polymerization (step B2), usually a lower average molecular weight is obtained.
  • the polymer composition obtained after completion of the polymerization (step B3) is transferred to a suitable vessel and optionally cooled directly to ambient temperature (20°C).
  • the polymer compositions P1 obtained as such are advantageously suitable for the production of multi-layered films, e.g. for use as a coating of a liquid detergent or cleaning agent.
  • the weight-average molecular weight Mw of the polymer composition can be determined, for example, by means of gel permeation chromatography (GPC) in aqueous solution using neutralized polyacrylic acid as polymer standard, as is generally known to the person skilled in the art. In this type of molecular weight determination, the components of the polymer composition are detected, which comprise the monomers M1 in polymerized form.
  • the polymer composition P1 preferably has a weight-average molecular weight of from 2,000 to 100,000 g/mol, preferably from 3,000 to 80,000 g/mol.
  • the polymer composition P1 has a sufficiently low glass transition temperature Tg suitable for film formation.
  • the polymer compositions P1 preferably have a glass transition temperature Tg in the range from 0 to 80°C., more preferably from 0 to 60°C., in particular from 0 to 30°C.
  • the polymer composition P1 preferably has a content of acid groups of more than 1 mmol/g, particularly preferably more than 1.3 mmol/g, before it is used for film production (i.e. before it is dried).
  • the polymer composition P1 preferably has a content of acid groups of at most 15 mmol/g before it is used for film production.
  • the polymer composition P1 in particular has a content of acid groups of 1.5 mmol/g to 10 mmol/g before it is used for film production.
  • the acid groups of the polymer composition according to the invention are present in unneutralized form.
  • At least one film layer L1 comprises a mixture of a polymer PT) and a polyether component PE.
  • At least one polyether component PE and water are subjected to a blending operation by common methods known to a person skilled in the art. It is of critical importance that in the mixing step no a,b-ethylenically unsaturated monomers are subjected to a free-radical polymerization in the presence of the polyether component PE.
  • Physically mixing at least one polymer PT) and at least one polyether component PE on the one hand and polymerization of a,b-ethylenically unsaturated monomers capable of forming a polymer PT) in the presence of at least one polyether component PE as discussed above for the first embodiment of film layer L1 on the other hand are two alternatives for the formation of washing- and cleaning-active polymer compositions, each process having its own characteristic properties. For instance, compared to the free radical polymerization process mentioned above the process of physically mixing of at least one polymer PT) and at least one polyether component PE avoids any side reactions leading to undesirable by-products that might negatively affect the properties of the film.
  • the polymer PT) can be prepared by free-radical polymerization of a monomer composition M’) that comprises at least one monomer A’) which is selected from a,b-ethylenically unsaturated carboxylic acids, salts of a,b-ethylenically unsaturated carboxylic acids and mixtures thereof,
  • At least one monomer B’ which is selected from unsaturated sulfonic acids, salts of unsaturated sulfonic acids, unsaturated phosphonic acid, salts of unsaturated phosphonic acids and mixtures thereof, and
  • the monomer composition M’) used for producing the polymer PT) comprises at least one monomer A’) which is selected from a,b-ethylenically unsaturated carboxylic acids, salts of a,b -ethylenically unsaturated carboxylic acids and mixtures thereof.
  • the monomer composition M’) consists only 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, in particular, 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 weight fractions all refer to the acid form.
  • the at least one a,b-ethylenically unsaturated carboxylic acid is used for the polymerization in non-neutralized form. If the a,b-ethylenically unsaturated carboxylic acids are used for the polymerization in partially neutralized form, then the acid groups are neutralized preferably to at most 50 mol%, particularly preferably to at most 30 mol%.
  • the monomer A’ is selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, salts of the aforementioned carboxylic acids and mixtures thereof.
  • the monomer A’ is selected from acrylic acid, methacrylic acid, salts of acrylic acid, salts of methacrylic acid and mixtures thereof.
  • the monomer A’) is used preferably in an amount of from 50 to 100% by weight, particularly preferably 60 to 100% by weight, based on the total weight of the monomer composition M’).
  • the monomer composition M’) consists to at least 50% by weight, preferably to at least 80% by weight, in particular to at least 90% by weight, based on the total weight of the monomer composition M’), of acrylic acid and/or acrylic acid salts.
  • the monomer composition M’) can comprise, in addition to the monomers A’), at least one monomer B’) which is selected from unsaturated sulfonic acids, salts of unsaturated sulfonic acids, unsaturated phosphonic acid, salts of unsaturated phosphonic acids and mixtures thereof.
  • the 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-acryloxypropylsulfonic acid, 2-hydroxy-3- methacryloxypropylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, allylphosphonic acid, salts of the aforementioned acids, and mixtures thereof.
  • Suitable salts of the aforementioned acids are in particular 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 weight fractions all refer to the acid form.
  • the monomer composition M’) then consists to at least 50% by weight, particularly preferably to at least 80% by weight, in particular to at least 90% by weight, based on the total weight of the monomer composition M’), of monomers A’) and B’). If the monomer composition M’) comprises at least one monomer B’), then this is used preferably in an amount of from 0.1 to 50% by weight, particularly preferably 1 to 25% by weight, based on the total weight of the monomer composition M’).
  • the monomer composition M’) can additionally comprise at least one further monomer different from the monomers containing acid groups and salts thereof.
  • the monomer composition M’) additionally comprises at least one comonomer C’) selected from
  • x 0, 1 or 2
  • k and I independently of one another, are an integer from 0 to 100, where the sum of k and I is at least 2, preferably at least 5,
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen, C1-C4-alkyl
  • the monomer composition M’) can comprise the further monomers CT) to C3’) in each case preferably in an amount of from 0 to 30% by weight, particularly preferably 0 to 20% by weight, in particular 0 to 10% by weight, based on the total weight of the monomer composition M’). If the monomer composition M’) comprises at least one monomer selected from C1’) to C3’), then in each case preferably in an amount of from 0.1 to 30% by weight, particularly preferably 1 to 20% by weight, in particular 1.5 to 10% by weight, based on the total weight of the monomer composition M’). In a specific embodiment, the monomer composition M’) comprises no further comonomers apart from the monomers A’).
  • Preferred nitrogen heterocycles with a free-radically polymerizable a,b-ethylenically unsaturated double bond CT are selected from 1-vinylimidazole (N-vinylimidazole), vinyl- and allyl- substituted nitrogen heterocycles different from 1-vinylimidazole, and mixtures thereof.
  • Suitable monomers CT are also the compounds obtained by protonation or quaternization of 1- vinylimidazole and vinyl- and allyl-substituted nitrogen heterocycles different therefrom.
  • Acids suitable for the protonation are e.g. carboxylic acids, such as lactic acid, or mineral acids, such as phosphoric acid, sulfuric acid and hydrochloric acid.
  • Alkylating agents suitable for the 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 can generally take place either before or after the polymerization.
  • a protonation or quaternization takes place after the polymerization.
  • Examples of such charged monomers C1’) are quaternized vinylimidazoles, in particular 3-methyl-1 -vinylimidazolium chloride, methosulfate and ethosulfate.
  • Preferred monomers C1’) are furthermore vinyl- and allyl-substituted nitrogen heterocycles different from vinylimidazoles selected from 2-vinylpyridine, 4-vinylpyridine, 2-allylpyridine, 4- allylpyridine and the salts thereof obtained by protonation or by quaternization.
  • the monomer composition M’) 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.
  • the monomer composition M’) comprises 1 -vinylimidazole as comonomer C1’).
  • Suitable amide-group-containing monomers C2’ are compounds of the general formula (II)
  • R 3 and R 4 together with the amide group to which they are bonded, can also be a lactam having 5 to 8 ring atoms,
  • R 4 and R 5 together with the nitrogen atom to which they are bonded, can also be a five- to seven-membered heterocycle.
  • the monomers C2’) are selected from primary amides of a,b-ethylenically unsaturated monocarboxyl ic acids, N-vinylamides of saturated monocarboxylic acids,
  • N-vinyllactams N-alkyl- and N,N-dialkylamides, a,b-ethylenically unsaturated monocarboxylic acids and mixtures thereof.
  • Preferred monomers C2’ are N-vinyllactams and derivatives thereof, which can have, e.g., one or more C1 -C6-alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc.
  • N-vinylpyrrolidone N-vinylpiperidone, N-vinylcaprolactam
  • N-vinyl-5-methyl-2-pyrrolidone N-vinyl-5-ethyl-2-pyrrolidone
  • N-vinyl-6-methyl-2-piperidone N- vinyl-6-ethyl-2-piperidone
  • N-vinyl-7-methyl-2-caprolactam N-vinyl-7-ethyl-2-caprolactam.
  • N-vinylpyrrolidone and/or N-vinylcaprolactam are particularly preferred.
  • Suitable monomers C2’ are furthermore acrylamide and methacrylamide.
  • N-Alkyl- and N,N-dialkylamides of a,b-ethylenically unsaturated monocarboxylic acids suitable as monomers C2’) are, for example, methyl(meth)acrylamide, methylethacrylamide, ethyl(meth)acrylamide, ethylethacrylamide, n-propyl(meth)acrylamide,
  • Open-chain N-vinylamide compounds suitable as monomers C2’ are, for example,
  • N-vinylformamide N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide, N- vinylbutyramide and mixtures thereof. Preference is given to using N-vinylformamide.
  • the monomer composition M’) can additionally comprise at least one monomer C3’) selected from compounds of the general formulae (I. a) and (l.b), as defined above.
  • k is preferably an integer from 1 to 100, particularly preferably 2 to 50, in particular 3 to 30.
  • I is an integer from 0 to 50.
  • R 2 in the formulae I. a) and l.b) is hydrogen, methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl or tert-butyl.
  • x is preferably 1 or 2.
  • the polymer PT) comprises less than 15% by weight, preferably less than 10% by weight, polymerized units of monomers different from monomers A’).
  • the polymer PT) is essentially uncrosslinked.
  • the monomer composition M’) used for producing the polymer PT) thus comprises in particular no added crosslinking monomers.
  • crosslinking monomers are compounds with two or more than two polymerizable ethylenically unsaturated double bonds per molecule.
  • the monomer composition M’ comprises, based on the total weight, less than 0.5% by weight, even more specifically less than 0.1 % by weight, of crosslinking monomers which have two or more than two free-radically polymerizable a,b-ethylenically unsaturated double bonds per molecule.
  • the monomer composition M’ comprises no crosslinking monomers having two or more than two polymerizable a,b-ethylenically unsaturated double bonds per molecule.
  • the polymer PT) can be prepared by free-radical polymerization of a monomer composition M’). It is possible to work by any known free-radical polymerization process. In addition to polymerization in bulk, mention should be made especially of the processes of solution polymerization and emulsion polymerization, preference being given to solution polymerization.
  • the polymerization is preferably performed in water as a solvent. However, it can also be undertaken in alcoholic solvents, especially Ci-C4-alcohols, such as methanol, ethanol and isopropanol, or mixtures of these solvents with water.
  • alcoholic solvents especially Ci-C4-alcohols, such as methanol, ethanol and isopropanol, or mixtures of these solvents with water.
  • the free-radical polymerization of the monomer composition M’) is preferably carried out in the feed procedure.
  • at least the monomers are metered into the reaction mixture in liquid form.
  • Monomers that are liquid under the addition conditions can be introduced into the reaction mixture without adding a solvent. Otherwise the monomers are used as solution in a suitable solvent.
  • Suitable polymerization initiators are compounds which decompose thermally, by a redox mechanism or photochemically (photo initiators) to form free radicals.
  • thermal initiators having a decomposition temperature in the range from 20 to 180°C, especially from 50 to 90°C.
  • suitable thermal initiators are inorganic peroxo compounds such as peroxodisulfates (ammonium peroxodisulfate and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxo compounds such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, 5-dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, tert-butyl perneodecanoate, tert-butyl perbenzoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroc
  • initiators can be used in combination with reducing compounds as initiator/regulator systems.
  • reducing compounds include phosphorus compounds such as phosphorous acid, hypophosphites and phosphinates, sulfur compounds such as sodium hydrogensulfite, sodium sulfite and sodium formaldehyde sulfoxylate, and hydrazine.
  • redox initiator systems which consist of a peroxo compound, a metal salt and a reducing agent.
  • peroxo compounds are hydrogen peroxide, peroxodisulfate (as the ammonium, sodium or potassium salt), peroxosulfates, and organic peroxo compounds such as tert-butyl hydroperoxide, cumene hydroperoxide or dibenzoyl peroxide.
  • Suitable metal salts are in particular iron(ll) salts such as iron(ll) sulfate heptahydrate.
  • Suitable reducing agents are sodium sulfite, the disodium salt of 2-hydroxy-2-sulfinatoacetic acid, the disodium salt of 2-hydroxy-2-sulfonatoacetic acid, sodium hydroxymethanesulfinate, ascorbic acid, isoascorbic acid or mixtures thereof.
  • photoinitiators examples include benzophenone, acetophenone, benzyl dialkyl ketones and derivatives thereof.
  • thermal initiators preferably inorganic peroxo compounds, especially sodium peroxodisulfate.
  • the peroxo compounds are advantageously used in combination with sulfur-containing reducing agents, especially sodium hydrogensulfite, as the redox initiator system.
  • sulfur-containing reducing agents especially sodium hydrogensulfite
  • copolymers comprising sulfonate and/or sulfate as end groups are obtained, which are notable for exceptional cleaning power and scale inhibiting action.
  • phosphorus-containing regulator systems for example sodium hypophosphite and phosphinates.
  • initiator/regulator system should be matched to the substances used in each case. If, for example, the peroxodisulfate/ hydrogensulfite system is used, typically 1 to 7% by weight, preferably 2 to 6% by weight, of peroxodisulfate and generally 3 to 25% by weight, preferably 4 to 15% by weight, of hydrogensulfite are used, based in each case on monomer composition M’).
  • organic polymerization regulators are sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecyl mercaptan.
  • sulfur compounds such as mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid and dodecyl mercaptan.
  • the amount thereof is generally 0.1 to 25% by weight, preferably 0.5 to 20% by weight and more preferably 1.0 to 15% by weight, based in each case on monomer composition M’).
  • the polymerization temperature is generally 20 to 200°C, preferably 20 to 150°C and more preferably 20 to 120°C.
  • the polymerization can be performed under atmospheric pressure, but is preferably undertaken in a closed system under the autogenous pressure which evolves.
  • the polymerization can take place in the absence or in the presence of an inert gas.
  • the polymerization is carried out in the presence of an inert gas, e.g. nitrogen.
  • the weight-average molecular weight Mw of the polymer PT) can be determined by means of gel permeation chromatography (GPC) in aqueous solution using neutralized polyacrylic acid as polymer standard.
  • the polymer PT) preferably has a weight-average molecular weight of from 1000 to 100 000 g/mol, more preferably 1500 to 50 000 g/mol, in particular 2000 to 20 000 g /mol.
  • polymer P1’) has a polydispersity index (PDI) of from 1.2 to 6.0, more preferably 1.4 to 4.0, in particular 1.6 to 3.5.
  • the polymer PT) can be obtained in the acidic state, but it can also, if desired be partly neutralized by addition of bases.
  • bases are alkali metal hydroxides , like NaOH and KOH, alkaline earth metal hydroxides, like Ca(OH)2 and Mg(OH)2, ammonia and amine bases, like monoethanol amine.
  • bases are alkali metal hydroxides , like NaOH and KOH, alkaline earth metal hydroxides, like Ca(OH)2 and Mg(OH)2, ammonia and amine bases, like monoethanol amine.
  • sodium hydroxide is especially preferred. Neutralization can be performed as early as during the polymerization or after the polymerization has ended.
  • step i) for providing the aqueous composition Prior to its use in step i) for providing the aqueous composition, at the most 30 mol% of the carboxy groups of the polymer PT) are in the deprotonated form. Preferably, at the most 25 mol%, more preferably at the most 15 mol%, of the carboxy groups of the polymer PT) are in the deprotonated form. In a special embodiment, the acid groups of the polymer composition according to the invention are present in non-neutralized form.
  • the polymer PT) used in accordance with the invention can be used directly in the form of the aqueous solutions obtained in the course of preparation by means of solvent polymerization, or in dried form (obtained, for example, by spray drying, spray granulation such as fluid bed spray granulation or spouted bed spray granulation, roller drying or freeze drying).
  • Suitable polymers PT are commercially available or are intermediates of commercially available products.
  • a commercially available polyacrylic acid is employed that is not crosslinked and not neutralized or only to a low extend neutralized.
  • Suitable products are Sokalan ® CP 10 S, Sokalan ® CP 12 S, Sokalan ® CP 13 S, Sokalan ® PA 25 XS, Sokalan ® PA 80 S and Sokalan ® NR 2530 from BASF SE.
  • the polyether component PE of the mixture of polymer P1’) and polyether component PE is preferably defined as the polyether component PE used for the radical polymerization of polymer composition P1 as described above or below for the first embodiment of film layer L1.
  • the at least one film layer L1 of the second embodiment is preferably produced in a process comprising the steps of:
  • the weight ratio of the polymer PT) to the polyether component PE is in a range from 0.9 : 1 to 5 : 1 , and the aqueous composition has a water content of at least 10% by weight and at most 50% by weight, based on the total weight of the aqueous composition, and
  • the weight ratio of the polymer P1’) to the polyether component PE is in a range from 0.9 : 1 to 4 : 1 , more preferably 1 : 1 to 3 : 1.
  • the aqueous composition has a water content of at least 15% by weight, more preferably at least 20% by weight, based on the total weight of the aqueous composition.
  • the aqueous composition has a water content of at most 50% by weight, based on the total weight of the aqueous composition.
  • one or more mixers may be used to provide the aqueous composition. If more than one mixer is used, these may be mixers of identical or different design, which are used in any desired sequence, arrangement and combination, for example an arrangement of all mixers in series, a combination of a parallel and series arrangement or a parallel
  • Suitable mixers are in particular dynamic mixers whose mixing elements contain movable parts and static mixers, i.e. mixing elements without moving parts in the interior.
  • Mixers can be applied in a continuous manner as continuous mixers, whereby all components are continuously fed to the mixer and the obtained mixture or partial mixture is continuously discharged, in a discontinuous (batch wise) manner, whereby all components are added to the mixer in advance and the obtained mixture is discharged at least partially after the mixing operation is at least partially finished, or in a semibatch manner, whereby optionally at least one of the components is at least partially added in advance, while at least one of the components is at least partially dosed to the mixer and the obtained mixture is discharged at least partially, when the missing operation is at least partially finished.
  • Suitable mixers are in particular dispersing machines, stirred tanks, kneaders, extruders, dynamic mixers, static mixers, rotating mixers, and mills.
  • Suitable dispersing machines are machines of the rotor stator type, the rotating dispersion disc type, the dual asymmetric centrifuge type (Speedmixer), and all other common dispersing machines.
  • Suitable stirred tank reactors are equipped with at least one moving mixing element, such as a stirrer.
  • a stirrer such as a stirrer.
  • Common stirrer types comprise, for example, propeller stirrers, impeller stirrers, disk stirrers, paddle stirrers, anchor stirrers, oblique blade stirrers, crossbeam stirrers, helical ribbon impellers, screw-type stirrers, etc.
  • Kneaders are available in various designs.
  • the general shape of the kneader can preferably be conical or cylindrical or a combination of both geometries.
  • Common kneaders comprise single shaft and twin shaft designs, but also the utilization of three or more shafts is possible.
  • conveying elements or mixing elements, or preferably a combination of both are aligned along the shafts.
  • the shafts can be rotated continuously, oscillated or moved in a combination of rotation and oscillation. In case of multiple shafts, these can be aligned in parallel or in a defined angle. Kneaders for continuous service may comprise special zones for physical operations, such as cooling, heating, degassing, evaporation of volatiles etc.
  • Suitable rotating mixers are e.g. planetary mixers and double planetary mixers.
  • Mixers can next to mixing also be used to fulfill other purposes, such as cooling, heating, degassing, evaporation of water and optionally other components.
  • step i) the mixing is performed at temperature in the range from 0 to 100°C, more preferably 20 to 95°C, in particular 30 to 90°C.
  • step i) takes place over a period of 1 minutes to 48 hours, preferably 1 ,5 minutes to 24 hours.
  • mixing is performed batch-wise in a kettle as mixing apparatus.
  • the components to be mixed for providing the aqueous composition i.e. the polymer PT
  • the polyether component PE and water are initially completely fed to the kettle and then subjected to the mixing operation.
  • at least one of the components is added to the kettle in one or more than one portion to the mixing operation.
  • the initial feed comprises at least a part of the water used for providing the aqueous composition. More preferably, the initial feed comprises the complete amount of the water used for providing the aqueous composition.
  • mixing is performed batch-wise in a dual asymmetric centrifuge (HauschildTM Speedmixer).
  • the temperature is preferably in a range of from 0 to 100 °C, more preferably 20 to 70 °C, especially 40 to 75 °C.
  • the rotation speed is preferably in a range of from 100 to 3500 rpm, more preferably 1000 to 2500 rpm.
  • mixing takes place over a period of 0.2 to 10 minutes, more preferably 1 to 5 minutes.
  • mixing is performed batch-wise or semibatch-wise in a kneader.
  • a Duplex kneader is employed.
  • the rotation speed is preferably in a range of from 10 to 500 rpm, more preferably 20 to 100 rpm.
  • the temperature is preferably in a range of from 0 to 100 °C, more preferably 20 to 70 °C, especially 40 to 75 °C.
  • mixing takes place over a period of 2 min to 5 hours, more preferably 10 min to 120 min.
  • Suitable additives are those used for the formation of polymer films, like plasticizers, scavengers, agents for modification of gas permeability and water vapor permeability, antistats, glidants, slip agents, UV absorbers, etc. Suitable additives are also those mentioned in the following for the detergent and cleaner formulations.
  • at least one enzyme is used as additive.
  • Suitable enzymes are those as are customarily used as industrial enzymes. These include both enzymes with optimum activity in the neutral to alkaline pH range, as well as enzymes with optimum activity in the acidic pH range.
  • step ii) of the process according to the invention the aqueous composition obtained in step i) is converted to a polymer film.
  • the multilayer film comprises at least one film layer L1 comprising or consisting of a mixture of at least one polymer PT) and at least one polyether component PE.
  • the multi-layered film further comprises at least one other layer L2 which comprises at least one polymer P2 which is different from polymer composition P1 and is selected from
  • homo-or copolymers comprising at least one monomer selected from N-vinylpyrrolidone, N- vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinyl-pyridine, salts of N- vinylimidazole, salts of 2-vinylpyridine, salts of 4-vinyl-pyridine, vinylpyridine-N-oxide, N- carboxymethyl-4-vinylpyridine halogenides or mixtures thereof;
  • acrylic acid monomer selected from acrylic acid, salts of acrylic acid or mixtures thereof and at least one maleic acid monomer selected from maleic acid, maleic acid anhydride, salts of maleic acid or mixtures thereof;
  • copolymer comprising at least a (meth)acrylic acid monomer selected from acrylic acid, methacrylic acid, salts of acrylic acid, salts of methacrylic acid or mixtures thereof and at least one hydrophobic monomer selected from Ci-Cs alkylesters of (meth) acrylic acid, C2- C10 olefins, styrene or a-methyl-styrene;
  • polyalkyleneoxide such as polyethyleneoxide
  • the multi-layered film particularly preferably comprises at least one further layer which comprises at least one polymer P2 or consists of at least one polymer P2 which is selected from
  • copolymers compriseing copolymerized vinylpyrrolidone and vinylimidazole, polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium halides,
  • the multi-layered film comprises in particular at least one further layer which comprises at least one polymer P2 or consists of at least one polymer P2 selected from cellulose derivatives, preferably carboxyalkylcelluloses and salts thereof, sulfoalkylcelluloses and salts thereof, acidic sulfuric ester salts of cellulose, alkylcelluloses, hydroxyalkylcelluloses, (hydroxyalkyl) alkylcelluloses and mixtures of two or more of these cellulose derivatives.
  • cellulose derivatives preferably carboxyalkylcelluloses and salts thereof, sulfoalkylcelluloses and salts thereof, acidic sulfuric ester salts of cellulose, alkylcelluloses, hydroxyalkylcelluloses, (hydroxyalkyl) alkylcelluloses and mixtures of two or more of these cellulose derivatives.
  • Polysaccharides suitable as polymers P2 are natural polysaccharides, e.g. cellulose, hemicellulose, glycogen, starch (amylose and amylopectin), dextran, pectins, inulin, xanthan, chitin, callose, thermally, hydrolytically or enzymatically degraded starch, e.g. maltodextrin etc
  • Preferred modified polysaccharides are e.g. cellulose ethers, cellulose esters, cellulose amides, etc.
  • Cellulose ethers are derivatives of cellulose that result from partial or total substitution of the hydrogen atoms in the hydroxy 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 alkylcelluloses, hydroxyalkylcelluloses,
  • Preferred carboxyalkyl radicals are the carboxymethyl radical and the carboxyethyl radical. Particularly preferred as carboxyalkyl radical is the carboxymethyl radical.
  • Preferred as sulfoalkyl radical are the sulfomethyl radical and the sulfoethyl radical. Particularly preferred as sulfoalkyl radical is the sulfomethyl radical.
  • Preferred salts are the sodium, potassium, calcium and ammonium salts.
  • Particularly preferred cellulose ethers are selected from carboxymethylcellulose,
  • carboxyethylcellulose methylcellulose, ethylcellulose, n-propylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxybutylcellulose,
  • hydroxyethylmethylcellulose hydroxypropylmethylcellulose, hydroxyethylethylcellulose, hydroxypropylethylcellulose, carboxymethylmethylcellulose, carboxymethylethylcellulose, carboxymethylhydroxyethylcellulose, carboxymethylhydroxyethylmethylcellulose, carboxymethylhydroxyethylethylcellulose, sulfomethylcellulose and sulfoethylcellulose.
  • carboxyalkyl radicals and the sulfoalkyl radicals may also be present as salts.
  • Cellulose esters are derivatives of cellulose which are formed by esterification of the hydroxy groups with acids.
  • Preferred are the sulfuric acid esters of cellulose.
  • the sulfuric acid is only subjected to a partial esterification, so that the resulting sulfuric acid esters still have free acid groups or their salts.
  • Particular preferred are sulfuric ester salts of cellulose. These are distinguished by 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, hydroxyethylmethyl cellulose, hydroxyethylethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropylethyl cellulose, etc.
  • the polymers P2 are selected from homo- and copolymers comprising repeating units derived 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-C8-carboxylic acids, more preferably Ci-C4-carboxylic acids.
  • Preferred vinyl acylates are vinyl acetate, vinyl n-propionate, vinyl n-butyrate, vinyl 2- ethylhexanoate, vinyl laurate, etc. Particularly preferred is vinyl acetate.
  • Partially or completely saponified (hydrolyzed) polyvinyl acetates are generally referred to as "polyvinyl alcohol (PVOH)".
  • Partially hydrolysed polyvinyl acetates are obtained by incomplete hydrolysis of polyvinyl acetates, i.e. the partially hydrolyzed polymer has both ester groups and hydroxyl groups.
  • the saponification of the polyvinyl acetates can be carried out in a manner known per se in alkaline or acidic, i.e. with the addition of acid or base.
  • polyvinyl alcohols are determined inter alia by the degree of polymerization and the degree of hydrolysis (degree of saponification). As the degree of saponification increases, the solubility in water decreases. Polyvinyl alcohols with degrees of hydrolysis of up to about 90 mol% are generally soluble in cold water. Polyvinyl alcohols with degrees of hydrolysis 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 saponification degree of from 50 to 99.9 mol%, particularly preferably from 70 to 99 mol%, in particular from 80 to 98 mol%.
  • the properties of polyvinyl alcohols can further be modified by the incorporation of additional monomers such as the sodium salts of 2-acrylamido-2-methylpropane sulfonic acid, vinylsulfonic acid or allylsulfonic acid.
  • Polyvinyl alcohols suitable as polymers P2 preferably have a weight-average molecular weight of from 10,000 to 300,000 g/mol, more preferably from 15,000 to 250,000 g/mol.
  • Polyvinylalcohol that can typically be used as polymers P2 are known under the tradename PovalTM from Kuraray company. Non limited examples are PovalTM 8-88, PovalTM 18-88, PovalTM 26-88, PovalTM 30-92, PovalTM 10-98, PovalTM 20-98 or PovalTM 28-99.
  • blends comprising polyvinylalcohols of different molecular weight and degree of hydrolysis can be used.
  • Non limited examples are a blend of PovalTM 26-88 (three parts) and PovalTM 20-98 (one part) or a blend of PovalTM 30-92 (two parts) and PovalTM 10-98 (one part).
  • 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 in particular of 15 to 60 mPa s, measured according to DIN 53015 on a 4% solution in water.
  • the polymers P2 are selected from homopolymers and copolymers which comprise at least one monomer in copolymerized form, which is selected from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, salts thereof three latter monomers, vinylpyridine-N-oxide, N-carboxymethyl-4-vinylpyridium halides and mixtures thereof.
  • N-vinylimidazole, 2-vinylpyridine and 4-vinylpyridine can be converted by protonation or quaternization into the corresponding salts.
  • Suitable acids are e.g. mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and carboxylic acids.
  • Alkylating agents suitable for quaternization are C1-C4 alkyl halides or C1 -C4 alkyl sulfates such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.
  • N-vinylpyrrolidone copolymerized N-vinylpyrrolidone and another ethylenically unsaturated monomer different therefrom.
  • Suitable N-vinylpyrrolidone copolymers are generally neutral, anionic, cationic and amphoteric polymers.
  • N-vinylpyrrolidone copolymers are selected from
  • the polymers P2 are selected from homopolymers and copolymers of acrylic acid and/or methacrylic acid.
  • the polymer P2 used is an acrylic acid homopolymer.
  • homopolymers P2 preferably have a number-average molecular weight in the range from 800 to 70,000 g/mol, more preferably from 900 to 50,000 g/mol, in particular from 1000 to 20,000 g/mol, especially from 1000 to 10,000 g/mol.
  • acrylic acid homopolymer also encompasses polymers in which the carboxylic acid groups are partially or completely neutralized. These include acrylic acid homopolymers in which the carboxylic acid groups are present partially 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 in which the carboxylic acid groups are present partially or completely in the form of sodium salts.
  • Homopolymers of acrylic acid which are particularly suitable as polymers P2 are the Sokalan ® PA grades from BASF SE.
  • the polymer P2 used is a copolymer comprising at least one acrylic acid monomer selected from acrylic acid, acrylic acid salts and mixtures thereof and at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof, in copolymerized form.
  • acrylic acid monomer selected from acrylic acid, acrylic acid salts and mixtures thereof
  • maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof, in copolymerized form.
  • These preferably have a number-average molecular weight in the range from 2500 to 150,000 g/mol, more preferably from 2800 to 70,000 g/mol, in particular from 2900 to 50,000 g/mol, more particularly from 3000 to 30,000 g/mol.
  • Included here are also copolymers in which the carboxylic acid groups are partially or completely neutralized.
  • Preferred polymers P2 are copolymers of maleic acid (or maleic acid monomers) and acrylic acid (or acrylic acid monomers) in a weight ratio of 10:90 to 95: 5, particularly preferably in a weight ratio of 30:70 to 90:10.
  • Preferred polymers P2 are also terpolymers of maleic acid (or maleic acid monomers), acrylic acid (or acrylic acid 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 in a range of 30:70 to 70:30.
  • Particularly suitable polymers P2 based on acrylic acid monomers and maleic acid monomers are the corresponding Sokalan ® CP grades from BASF SE.
  • the polymer P2 is a copolymer, which comprises at least one (meth) acrylic acid monomer selected from (meth) acrylic acid, (meth) acrylic acid 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 such as e.g. the methyl, ethyl, n- and iso-propyl, n-butyl and 2-ethylhexyl esters of (meth) acrylic acid and C2-Cio-olefins, e.g. ethene, propene, 1 ,2-butene, isobutene, disobutene, styrene and a-methylstyrene.
  • the polymer P2 used is a copolymer of at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof with at least one C2-C8-olefin.
  • copolymers which comprise at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof, in copolymerized form at least one C2-Cs-olefin and at least one other comonomer which is different therefrom.
  • copolymers which comprise at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof and at least one C2-C8-olefin copolymerized as sole monomers. These preferably have a number average molecular weight in the range from 3000 to 150,000 g/mol, particularly preferably from 5000 to 70,000 g/mol, in particular from 8000 to 50,000 g/mol, more particularly from 10,000 to 30,000 g/mol. Included therein are also copolymers in which the carboxylic acid groups are partially or completely neutralized. For this purpose, either maleic acid salts can be used for the polymerization or the resulting copolymer is subjected to a partial or complete neutralization. Preferred are copolymers in which the carboxylic acid groups are protonated or partially or completely present in the form of alkali metal salts or ammonium salts. Preferred alkali metal salts are the sodium or potassium salts, especially the sodium salts.
  • a specific embodiment are copolymers of maleic acid with C2-C8 olefins in a molar ratio of 40:60 to 80:20, whereby copolymers of maleic acid with ethylene, propylene, isobutene, diisobutene or styrene are particularly preferred.
  • Particularly suitable polymeric carboxylic acid group- containing compounds based on olefins and maleic acid are likewise the corresponding
  • copolymers comprising at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof, at least one C2-C8 olefin and at least one acrylic acid monomer selected from acrylic acid, acrylic acid salts and mixtures thereof, in copolymerized form.
  • copolymers which comprise at least one maleic acid monomer selected from maleic acid, maleic anhydride, maleic acid salts and mixtures thereof, at least one C 2 -C 8 olefin and at least one ester of (meth) acrylic acid in copolymerized form.
  • the ester of (meth) acrylic acid is then in particular selected from C 2 -Cs-alkyl esters of (meth) acrylic acid, e.g. the methyl, ethyl, n- and iso-propyl, n-butyl and 2-ethylhexyl esters of (meth) acrylic acid.
  • the polymers P2 are selected from homopolymers and copolymers which comprise, in polymerized form, at least one monomer selected from acrylamide, methacrylamide and mixtures thereof. These polymers P2 are preferably water- soluble or water-dispersible. In particular, these polymers P2 are 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 comonomer in copolymerized form, which is selected from acrylamide and methacrylamide different hydrophilic monomers (A1 ), monoethylenically unsaturated, amphiphilic monomers (A2) and other ethylenically unsaturated monomers (A3).
  • Suitable hydrophilic, monoethylenically unsaturated monomers (A1 ) are neutral monomers, such as N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide or N-methylol (meth) acrylamide, monomers comprising hydroxyl and/or ether groups, such as e.g.
  • N-vinyl derivatives can be hydrolyzed after polymerization to vinylamine units, vinyl esters to vinyl alcohol units.
  • Suitable hydrophilic, monoethylenically unsaturated monomers (A1 ) are furthermore monomers which comprise 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- acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid, 2-acrylamido-2,4,4- trimethylpentanesulfonic acid, vinylphosphonic acid, allylphosphonic acid, N-(meth)
  • Suitable cationic monomers (A1 c) include, in particular, ammonium-group containing monomers, in particular ammonium derivatives of N-(w- aminoalkyl) (meth) acrylamides or w-aminoalkyl (meth) acrylic esters.
  • the amphiphilic monomers (A2) are preferably monoethylenically unsaturated monomers which have at least one hydrophilic group and at least one, preferably terminal, hydrophobic group.
  • the monomers (A3) may be e.g. monoethylenically unsaturated monomers which have a more hydrophobic character than the hydrophilic monomers (A1) and which accordingly are only slightly water-soluble.
  • Examples of such monomers include N-alkyl and N, N'-dialkyl (meth) acrylamides wherein the number of carbon atoms in the alkyl groups 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, which comprise at least one amino acid, such as aspartic acid, glutamic acid, lysine, glycine, etc. in copolymerized form.
  • 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 may e.g. 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 may e.g. be used as a biodegradable complexing agent and cobuilder in detergents and cleaners.
  • Polyamino acids having surfactant properties can be obtained by at least partially converting the free carboxylic acid groups of polyaspartic acid or polyglutamic acid into N-alkylamides and/or into esters.
  • Polyaspartic acid amides can also be prepared by reacting polysuccinimide with amines.
  • hydroxyethylaspartamides the ring opening of polysuccinimide can be carried out with ethanolamine.
  • DE 37 00 128 A and EP 0 458 079 A describe the subsequent esterification of such hydroxyethyl derivatives with carboxylic acid derivatives.
  • Copolymers of polyaspartic ester are, as described in DE 195 45 678 A, obtainable by condensation of monoalkyl esters of maleic or fumaric acid with addition of ammonia.
  • copolymeric polyaspartic esters are accessible by reaction of polysuccinimide with alcohols and optionally subsequent hydrolysis.
  • polyaspartic esters in addition to their biodegradability, are distinguished by excellent properties as stabilizers for O / W and W / O emulsions, foam-stabilizing and foam-enhancing cosurfactants in detergents and cleaners and as complexing agents 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, particularly preferably from 1 ,500 to 1 ,000,000 g/mol
  • Suitable polyalkylene glycols and their mono- or diethers may be linear or branched, preferably linear.
  • Suitable polyalkylene glycols are e.g. water-soluble or water-dispersible nonionic polymers, which comprise alkylene oxide repeat units. The proportion of alkylene oxide repeating units is preferably at least 30% by weight, preferably at least 50% by weight, in particular 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 the preparation of alkylene oxide copolymers are, for.
  • 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 randomly distributed alkylene oxide units or in copolymerized form in the form of blocks.
  • the proportion of repeating units derived from ethylene oxide is 40 to 99% by weight.
  • Particularly preferred are ethylene oxide homopolymers and ethylene oxide / propylene oxide copolymers.
  • Suitable mono- and diethers of polyalkylene glycols are the mono (C1-C18 alkyl ethers) and di (C1-C18 alkyl ethers).
  • Preferred mono- and diethers of polyalkylene glycols are the mono (C1-C6 alkyl ethers) and di (C1-C6 alkyl ethers).
  • Especially preferred are the mono (C1-C2 alkyl ethers) and di (C1-C2 alkyl ethers).
  • Particularly preferred are polyalkylene glycol monomethyl ether and polyalkylene glycol dimethyl ether.
  • the polymer P2 is selected from polyvinyl alcohols as defined above.
  • Polymer blends are suitable e.g. for adjusting the mechanical properties and/or the dissolution properties of the multi-layered films used in the present invention.
  • the polymers used in the polymer mixture may differ in terms of their chemical composition and/or in terms of their physico-chemical properties.
  • the multi-layered film used in the invention comprises at least one layer which comprises a mixture of two 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 which comprises 2 or more polymers which differ in their chemical composition.
  • a polymer mixture is used which comprises two or more polymers which differ in their molecular weight.
  • a polymer mixture is used which comprises at least two polymers P2 which comprise repeating units derived from vinyl alcohol.
  • the films to be produced according to the invention have at least one layer L1 which comprises a polymer composition P1 or consists of a polymer composition P1.
  • the process for preparing the multi-layered film preferably comprises the steps of
  • aqueous solution of the polymer composition P1 as described above for the first embodiment of film layer L1 or an aqueous composition comprising a polymer PT) and a polyether component PE as described above for the second embodiment of film layer L1 wherein the aqueous solution or aqueous composition may, in addition to or instead of water, inter alia also include alcohol, such as 2-propanol,
  • the layer L2 comprises at least one polymer P2 or consists of at least one polymer P2 as described above
  • the layers L1 and/or L2 can be applied in a freely chosen order or also simultaneously and in each case optionally can be dried after each application of one or more layers.
  • said multi-layered film after drying the film after the application of L2 to the carrier material in step e), the layer L2 is combined with a second two-layered film in the sense of a lamination.
  • the second two-layered film can be produced simultaneously in steps (a) to (d) previously or in a parallel-connected installation. If the same composition was used for the contacting layers of the two films, the multilayer film produced in this way by lamination consists of three chemically different layers.
  • the two-layered film prepared in steps (a) to (d) is cut in the center in the machine direction; Subsequently, the two obtained film halves are laminated.
  • the advantage of the two abovementioned embodiments is a markedly accelerated drying due to the reduced layer thickness, which is directly related to an increased production speed.
  • the mass transfer of the solvent through the film at a constant diffusion coefficient is proportional to 1 / film thickness.
  • Additives can be added before or during the film formation in step b). Whether the addition takes place before or during step b) depends on the type and effect of the particular additive. For the film formation in step b) additives can be added to the aqueous composition before and/or during the film production.
  • an individual layer or a plurality of but not all the layers or all the layers may each comprise one or more than one additive.
  • at least one additive is present between at least two layers.
  • the additives may be auxiliaries for adjustment of the properties of the pourable compositions capable of film formation, typical additives of the washing and cleaning compositions or mixtures thereof.
  • a special embodiment is a multilayer film in which at least one of the layers includes an additive.
  • 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, bleach activators, bleach catalysts, enzymes, bases, corrosion inhibitors, foam inhibitors, defoamers, wetting agents, dyes, pigments, fragrances, bitter agents such as Bitrex ® , anti-yellowing agents, fillers, tableting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, bitter substances, fluorescers, hydrotropes, antiredeposition agents, optical brighten
  • Suitable enzymes are those as are customarily used as industrial enzymes. These include both enzymes with optimum activity in the neutral to alkaline pH range, as well as enzymes with optimum activity in the acidic pH range.
  • additives can fulfill several functions, e.g. as solvent S) and as plasticizer.
  • plasticizers can be added to them before or during production.
  • plasticizers preferably 0.5% to 30% by weight, more preferably 2% to 20% by weight and especially 3% to 15% 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-methyl-1 ,3-propanediol, 3-methyl-1 ,5-pentadiol,
  • Suitable plasticizers are also polyetherpolyols, which are available under the name Lupranol ® from BASF SE.
  • alkyleneamines refers to condensation products of alkanolamines with ammonia or primary amines, e.g. ethyleneamines are obtained by reaction of monoethanolamine with ammonia in the presence of a catalyst.
  • the plasticizers are selected from glycerol, diglycerol, propylene glycols with a weight-average molecular weight of up to 400, e.g. dipropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, sorbitol, isopentyldiol, polyethylene glycol, trimethylolpropane, diethylenetriamine, triethylenepentamine, triethanolamine and mixtures thereof.
  • glycerol diglycerol
  • propylene glycols with a weight-average molecular weight of up to 400, e.g. dipropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, sorbitol, isopentyldiol, polyethylene glycol, trimethylolpropane, diethylenetriamine, triethylenepentamine, triethanolamine and mixtures thereof.
  • scavengers capture molecules
  • Suitable scavengers are polyamines, polymeric polyamines, such as polyethyleneimines,
  • poly(amidoamines) and polyamides are also possible to use ammonium sulfate, primary and secondary amines with 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 can be used.
  • additives in the form of polymers to the polymer composition P1 or the aqueous composition comprising the polymer P1’) and the polyether component PE and/or to the polymers P2 before and/or during the film production.
  • 0.05 to 20% by weight, preferably 0.1 to 15% by weight, particularly preferably 0.2 to 10% by weight, of polymers (based on the total weight of the polymer compounds, i.e. if present the weight of polymer composition P1 or combined weight of polymers PT) and the polyether component PE, the weight of polymers P2 and additional polymers) are used.
  • Such additives can simultaneously improve the washing properties of the film, improve the mechanical properties of the film, and increase the resistance of the film to detergent components.
  • Suitable polymers are e.g. oligosaccharides and polysaccharides, starch, degraded starches (maltodextrins), cellulose ethers, specifically hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, hydroxypropylethylcellulose, microcrystalline cellulose, inulin, carboxymethylcellulose, e.g. in the form of the sodium salts, alginic acid and alginates, pectin acid and pectins,
  • polyethyleneimines alkoxylated, in particular ethoxylated polyethyleneimines, graft polymers of vinyl acetate on polyalkylene glycols, in particular on 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 nonhydrolyzed vinyl acetate, thickeners, such as, for example, xanthan gum, guar gum, gelatin, agar-agar and mixtures thereof.
  • thickeners such as, for example, xanthan gum, guar gum, gelatin, agar-agar and mixtures thereof.
  • At least one surface or both surfaces of the multilayer films of the invention may be subject to at least partial coating with at least one additive.
  • a treatment may serve, for example, to provide the surface with particular properties, such as nonstick action, antistatic action, hydrophilic or hydrophobic properties, etc.
  • the single and multilayer films for example, with better detachment properties from the carrier material used in the production, better roll-off properties, better glide properties, 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 multilayer films of the invention are, for example, talc, surfactants such as silicone-containing surfactants, waxes, etc.
  • the film production process is not subject to any particular restrictions and the person skilled in the art is able to apply any desired production process of which he is aware on account of his art knowledge.
  • Particularly suitable methods are coating bar methods, casting methods, roll application methods and extrusion methods.
  • the multilayer films of the invention are generally thermoplastic and can be subjected to a forming operation by thermoforming (i.e. hot forming, deep drawing or vacuum deep drawing).
  • thermoforming i.e. hot forming, deep drawing or vacuum deep drawing.
  • a process for producing water-soluble film packagings by a thermoforming process which comprises a hot forming or deep drawing step is described in WO 00/55044.
  • the multilayer film of the invention can be processed in a suitable manner, for example by cutting to a desired size and/or folding to form compartments.
  • edges can be sealed by standard sealing methods such as heat sealing, liquid sealing or pressure sealing.
  • the multilayer film of the invention may preferably consist of 2 to 20 layers, more preferably 2 to 15 layers and especially 2 to 10 layers. These specifically include multilayer films consisting of 2, 3, 4, 5, 6, 7 or 8 layers. The sequence of the layers of the multilayer films of the invention is guided by the desired end use.
  • the multi-layered film comprises at least two film layers L1 and L2 in any order.
  • the multi-layered film comprises at least one layer L1 and at least one layer L2 and that the multi-layered film comprises at least three layers.
  • the multi-layered film comprises at least three layers with the sequence of L2-L1-L2.
  • the multi-layered film consists of three layers with the sequence of L2-L1-L2.
  • the production process of the multi-layered film comprises a lamination step in which at least two parts of the multi-layered film are joined to form a multi-layered composite.
  • the each of two parts of the multi-layered film preferably comprises at least one layer L1 and/or L2.
  • the multi-layered film preferably has an overall thickness of at least 10 pm, more preferably of at least 25 pm, still more preferably of at least 50 pm and most preferably of at least 75 pm.
  • the upper limit of the thickness of the multi-layered film preferably does not exceed 500 pm, more preferably 400 pm, still more preferably 300 pm and most preferably 200 pm.
  • layer L1 preferably has a thickness of at least 5 pm, more preferably of at least 15 pm, still more preferably of at least 30 pm and most preferably of at least 50 pm.
  • the upper limit of the thickness of layer L1 preferably does not exceed 400 pm, more preferably 300 pm, still more preferably 200 pm and most preferably 100 pm.
  • Layer L2 preferably has a thickness of at least 1 pm, more preferably of at least 2.5 pm, still more preferably of at least 5 pm and most preferably of at least 7.5 pm.
  • the upper limit of the thickness of layer L2 preferably does not exceed 50 pm, more preferably 40 pm, still more preferably 30 pm and most preferably 25 pm.
  • the water-soluble film of the present invention has a three-dimensional topography on at least one side of the film resulting in locally thick and thin film areas.
  • the water-soluble film of the present invention has a three- dimensional topography on only one side of the film resulting in locally thick and thin film areas.
  • the ratio of the thickness of the film in the locally thick film areas to the thickness of the film in the locally thin film areas is from 1.1 : 1.0 to 10.0 : 1.0, preferably from 1.3 : 1.0 to 7.0 : 1.0, more preferably from 1.6 : 1.0 to 5.0 : 1.0 and most preferably from 2.0 : 1.0 to 4.5 : 1.0.
  • the thickness of the film in the locally thin film areas is preferably from 5 pm to 250 pm, more preferably from 10 pm to 200 pm, still more preferably from 20 pm to 100 pm and most preferably from 30 pm to 75 pm.
  • the thickness of the film in the locally thick film areas is preferably from 50 pm to 500 pm, more preferably from 75 pm to 400 pm, still more preferably from 90 pm to 300 pm and most preferably from 120 pm to 250 pm.
  • the three-dimensional topography is on the surface of the L2 layer of the water- soluble multi-layered film. It is thereby preferred that the L2 layer is one outer layer of the water- soluble multi-layered film with a three-dimensional topography.
  • the water-soluble multi-layered film with a three-dimensional topography comprises at least three layers with the sequence L2-L1-LX.
  • the L2 film layer is one outer surface layer of the water soluble multi-layered film as defined above and has the three-dimensional topography on the outer surface of the L2 film layer.
  • the LX film layer can have the same composition or a different composition as the L2 film layer without three-dimensional topography.
  • the LX layer preferably comprises the at least one polymer P2 as defined above.
  • the water-soluble multi-layered film with a three-dimensional topography comprises at least three layers with the sequence L2-L1-L2’.
  • the L2 film layer is one outer surface layer of the water-soluble multi-layered film as defined above and has the three-dimensional topography on the outer surface of the L2 film layer.
  • the L2’ film layer has the same composition as the L2 film layer without three-dimensional topography.
  • the water-soluble multi-layered film with the sequence L2-L1-L2’ has a three-dimensional topography on the outer surface of the L2 layer and a plain outer surface of the L2’ layer.
  • the three-dimensional topography can be any kind of topography suitable for being applied onto a water-soluble film.
  • the three-dimensional topography comprises design patterns, symbols, letters and GHS labelling.
  • the invention further relates to a process for preparing the water-soluble multi-layered film as defined above or below comprising the steps of
  • the three-dimensional topography is embossed on only one side of the film resulting in locally thick and thin film areas, preferably on layer L2.
  • Suitable processes for embossing waters-soluble films such as polyvinyl alcohol films are known in the art and are described e.g. in EP 1 842 647 A1 or EP 1 155 804 A1.
  • an emboss roll and a backup roll are used.
  • the film to be embossed is passed between the emboss roll and the backup roll.
  • the pattern applied to the emboss roll is embossed onto the outer surface of the film facing the emboss roll to apply the three-dimensional topography.
  • the backup roll has a plain surface only the surface of the film facing the emboss roll is embossed whereas the surface facing the backup roll maintains plain.
  • emboss roll a metal roll such as steel roll, a polymer coated metal roll such as polymer coated steel roll, a ceramic roll or a polymer coated ceramic roll can be used.
  • the polymer coating is preferably applied for reducing the water-soluble multi-layered film to stick onto the emboss roll. Suitable polymer coatings are e.g. PTFE coatings.
  • the surface of the emboss roll is suitably processed by applying a negative pattern of the three-dimensional topography to be embossed onto the surface of the water-soluble multi-layered film, preferably layer L2.
  • the negative pattern of the three dimensional topography is preferably applied in form or concave and convex shapes onto the surface of the emboss roll by means of engraving, lathing or the like.
  • the material of the backup roll is not particularly limited and can be selected from a metal roll, a ceramic roll, a polymer roll, a rubber roll, a cotton roll or a paper roll.
  • the water-soluble multi-layered film as defined above is preferably passed between the emboss roll and the backup roll with increased force.
  • the line force is preferably in the range of from 20 to 500 N/mm, more preferably from 50 to 400 N/mm, and most preferably from 100 to 300 N/mm. Thereby, the line force is defined as the pressing force of the pair of emboss and backup roll over the width of the water-soluble multi-layered film.
  • the line speed is preferably from 0.1 to 60 m/min, more preferably from 0.2 to 40 m/min and most preferably from 0.3 to 25 m/min.
  • the line speed can be up to 120 m/min, such as from 0.1 to 150 m/min, more preferably from 2.0 to 125 m/min, and most preferably from 10 to 110 m/min.
  • the water-soluble multi-layered film can be cooled before or after the embossing step to a temperature in the range of from -10°C to +20°C in order to fix the three-dimensional topography on the outer surface of the water-soluble multi-layered film.
  • the emboss roll is preferably maintained at a temperature of 10°C to 180°C.
  • the emboss roll is preferably heated to a temperature of 80°C to 180°C, more preferably of 100°C to 160°C and most preferably of 1 10°C to 140°C.
  • the emboss roll is not heated and is preferably maintained at a temperature of 10°C to 50°C, more preferably of 15°C to 40°C and most preferably of 20°C to 30°C.
  • the backup roll is preferably maintained at a temperature of 0°C to 120°C.
  • the emboss roll is preferably heated to a temperature of 60°C to 120°C, more preferably of 70°C to 1 10°C and most preferably of 80°C to 100°C.
  • the backup roll is actively cooled to temperature of 0°C to 50°C, more preferably of 5°C to 40°C and most preferably of 10°C to 30°C.
  • the thickness of the embossed outer surface layer of the waters-soluble multi-layered film, preferably layer L2, onto which the three-dimensional topography is applied is not affected by the embossing step as described above. This means that over the whole area of the film, including the thick areas and the thin areas of the three- dimensional topography, the thickness of embossed outer surface layer maintains the same. Instead the inner layer of the water-soluble multi-layered film, preferably layer L1 , is deformed from the embossing step as such that the thickness of the inner layer is lower in the thin areas and is higher in the thick areas of the three-dimensional topography.
  • the inner layer L1 has a higher fluidity as the outer layer L2, so that during the embossing step the fluidity of the polymer composition P1 of layer L1 is more increased as the fluidity of the polymer P2, and the polymer composition P1 is squeezed out of the thin areas and flows into the thick areas of the three-dimensional topography, before the fluidity of the polymer P2 of layer L2 is affected.
  • polyvinyl alcohol films which are commercially used for e.g. single-use packaging of detergents or cleaners, are affected by the embossing step as discussed above as such that the film thickness in the thin areas of the three-dimensional topography is thinner than in the thick areas.
  • the dissolution kinetics of the water-soluble multi layered film is defined by the dissolution of the outer surface layer, preferably layer L2.
  • the dissolution time of the embossed water-soluble multi-layered film with the three-dimensional topography is surprisingly the same as that of the plain film as the surface thickness of the outer layer maintains the same, whereas for polyvinyl alcohol films the dissolution time of the embossed film with the three-dimensional topography is lower than that of the plain film due to the differences in thickness of the polyvinyl alcohol layer.
  • the water-soluble multi-layered film with three-dimensional topography according to the present invention has a dissolution time in a disintegration test carried out according to MSTM-205 at 10° C water temperature of not more than 270 s, more preferably of not more than 210 s and most preferably of not more than 180 s.
  • the water-soluble multi-layered film with three-dimensional topography according to the present invention has to have a dissolution time in a disintegration test carried out according to MSTM-205 at 10° C water temperature of at least 30 s.
  • the water-soluble multi-layered film with three-dimensional topography according to the present invention preferably has a dissolution time in a disintegration test carried out according to MSTM-205 at 10° C water temperature of at least 45 s, more preferably at least 60 s and most preferably at least 90 s.
  • the static friction of a water-soluble multi-layered film with three-dimensional topography in adherent contact with a plain water-soluble multi-layered film is not more than 7.5 N, more preferably not more than 6.5 N, even more preferably not more than 5.5 N and most preferably not more than 4.0 N.
  • the lower limit of the static friction of a water-soluble multi-layered film with three-dimensional topography in adherent contact with a plain water-soluble multi-layered film is usually at least 2.5 N, more preferably at least 3.0 N.
  • the static friction of two water-soluble multi-layered films with three-dimensional topography in adherent contact with each other is not more than 5.0 N, more preferably not more than 4.0 N, even more preferably not more than 3.0 N and most preferably not more than 2.0 N.
  • the lower limit of the static friction of two water-soluble multi-layered films with three- dimensional topography in adherent contact with each other is usually at least 0.5 N, more preferably at least 1.0 N.
  • the coefficient of friction of a water-soluble multi-layered film with three-dimensional topography in adherent contact with a plain water-soluble multi-layered film is not more than 4.0, more preferably not more than 3.5, even more preferably not more than 3.0 and most preferably not more than 2.5.
  • the lower limit of the coefficient of friction of a water-soluble multi-layered film with three- dimensional topography in adherent contact with a plain water-soluble multi-layered film is usually at least 0.5, more preferably at least 1.0.
  • the coefficient of friction of two water-soluble multi-layered films with three- dimensional topography in adherent contact with each other is not more than 3.0, more preferably not more than 2.5, even more preferably not more than 2.0 and most preferably not more than 1.5.
  • the lower limit of the coefficient of friction of a water-soluble multi-layered film with three- dimensional topography in adherent contact with a plain water-soluble multi-layered film is usually at least 0.1 , more preferably at least 0.2.
  • the relative reduction of the coefficient of friction of two water-soluble multi-layered films with three-dimensional topography in adherent contact with each other compared to two plain water- soluble multi-layered films in adherent contact with each other is preferably at least 50%, more preferably at least 60%, still more preferably at least 70% and most preferably at least 75%.
  • the present invention further relates to an article comprising the water-soluble multi-layered film as defined above or below.
  • the water-soluble multi-layered film according to the invention is preferably situated as such that the three-dimensional topography of the water-soluble multi-layered film is situated on at least the outer surface of the article.
  • the article is a water-soluble container.
  • Said water-soluble container preferably encapsulates liquid and/or solid compositions with cleaning properties.
  • the composition with cleaning properties preferably is a cleaning or washing composition, more preferably a laundry or dishwashing composition, including fabric care compositions, pre treatment or soaking compositions and rinse additive compositions.
  • the composition preferably comprises at least one active cleaning ingredient such as chelating agents, builders, bases, enzymes, perfumes, bleaches, bleach activators, bleach catalysts, fabric softeners, fabric conditioners, surfactants, polymeric dispersants, fabric care agents, soil release polymers, soil repellant polymers, dye transfer inhibitors, thickeners, rheology modifier, anti-corrosion agents, antibacterial agents, effervescence sources, brighteners, photo-bleaches or mixtures thereof.
  • Laundry compositions and especially fabric care compositions preferably comprise at least one or more softening agents such as quaternary ammonium compounds and/or softening clays, and preferably additional agents such as anti-wrinkling aids, perfumes and chelating agents.
  • the water-soluble container comprises one compartment which is filled with one composition.
  • the composition suitably is solid, liquid, gel-like or any combination thereof.
  • the water-soluble container comprises two or more compartments, which can be filled with only one composition but preferably are filled with different
  • compositions suitable for the composition or compositions.
  • the composition or compositions suitably is solid, liquid, gel-like or any combination thereof.
  • the two or more compartments are filled with different compositions it is preferred that one composition is filled in one compartment.
  • the composition preferably is a cleaning or washing composition as described above or below.
  • the water-soluble container can have any kind of dimensions and shapes.
  • the water-soluble container has a maximum dimension in each direction of not more than 13 cm.
  • the water-soluble container is suitable for any kind of cleaning or washing application.
  • the water-soluble container is a detergent pod or dishwashing pod.
  • Such water-soluble containers can be prepared by deep drawing as disclosed e.g. in EP 18 177 730.
  • the present invention further relates to the use of the water-soluble multi-layered film as defined above or below for dosing detergent into a laundry machine or a dishwashing machine.
  • the present invention relates to the use of the water-soluble multi-layered film as defined above or below for the production of water-soluble containers with a three-dimensional topography on the outer side.
  • the present invention related to the use of the water-soluble multi-layered film as defined above or below for reducing the adherence between two water-soluble multi-layered films.
  • At least one, most preferably both of the two water-soluble multi-layered films shows a three-dimensional topography as defined above or below.
  • At least one, most preferably both the two water-soluble multi-layered films is a film as defined above or below.
  • Poval 30-92 polyvinyl alcohol having a viscosity of 28.0-32.0 mPas and a degree of hydrolysis of 91.5-93.3 mol%, commercially available from Kuraray Europe GmbH,
  • Poval 10-98 polyvinyl alcohol having a viscosity of 9.0-11.0 mPas and a degree of hydrolysis of 98.0-98.8 mol%, commercially available from Kuraray Europe GmbH,
  • Lutensol A07 C13C15-OXO alcohol with 7 EO commercially available from BASF SE
  • Oxo alcohol and water were initially charged and the initial charge was heated to 75 ° C with stirring at 100 rpm.
  • the feeds 1 , 2 and 3 were then added in 4 hours and the reaction mixture was polymerized for an additional hour. Then the mixture was allowed to cool to room
  • the polymer composition was obtained in the form of a transparent and viscous solution.
  • the concentration of the polymer composition was diluted to 65% wt% with deionized water.
  • the application solution was well mixed and tempered at 80°C until the stirred-in air had completely escaped.
  • an automatic film-applicator and a universal applicator from Zehntner were used.
  • the PVOH application solution was applied at room temperature to the surface of a galvanized steel sheet metal carrier previously degreased with ethanol.
  • the gap width of the doctor blade was chosen so that the layer after drying at 40°C has a thickness of 10 pm.
  • the application solution of the wash active polymer solution was applied at room temperature.
  • the gap width of the doctor blade was adjusted so that after drying at 40°C, the total layer thickness of the film is 90 pm. Subsequently, the PVOH application solution was applied again such that the total thickness of the film is 120 pm.
  • the above described three-layer film was embossed on one side with a hexagonal ordered dot pattern of 1120 pm dot diameter and a pitch (center-to-center distance) of 1680 pm.
  • the embossing tool was facing on the 10 pm L2 interface. Embossing was carried out at room temperature with a line force of 206N/mm and 0.5m/min using a calender from Saueressig resulting in minimum thickness of 48-59 pm and maximum thickness of 190-201 pm and a ratio of 3.2-4.2 between thickest and thinnest area.
  • top film is fixed on a slide.
  • the friction table is covered with a fixed large film as counter part of the friction pair.
  • the slide carrying the top sample film is placed on the friction table carrying the bottom film and measurement (and camera) started.
  • the time between placing the slide and starting the measurement is between 5 to 10 seconds.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne un film multicouche hydrosoluble présentant une topographie tridimensionnelle sur au moins un, de préférence seulement sur un côté du film, se traduisant par des zones de film localement épaisses et minces, le rapport entre l'épaisseur du film dans les zones de film localement épaisses et l'épaisseur du film dans les zones de film localement minces étant de 1,1 : 1,0 à 10,0 : 1,0 ; l'invention concerne également un procédé de préparation dudit film ; un article comprenant ledit film, l'utilisation dudit film pour doser un détergent dans un lave-linge ou un lave-vaisselle et l'utilisation dudit film pour la production de contenants hydrosolubles présentant une topographie tridimensionnelle sur le côté extérieur.
PCT/EP2020/061211 2019-05-03 2020-04-22 Films hydrosolubles à topographie tridimensionnelle WO2020224962A1 (fr)

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EP19172639 2019-05-03

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3700128A1 (de) 1987-01-03 1988-07-14 Hoechst Ag Biologisch abbaubare poly- (hydroxyalkyl)- aminodicarbonsaeure-derivate, verfahren zu ihrer herstellung und verwendung derselben fuer depotzubereitungen mit kontrollierter wirkstoffabgabe
EP0458079A2 (fr) 1990-04-26 1991-11-27 Hoechst Aktiengesellschaft Agent de contraste ultrasonique, sa préparation et application comme diagnostic ou thérapeutique
DE19545678A1 (de) 1995-12-07 1997-06-12 Goldschmidt Ag Th Copolymere Polyaminosäureester
WO2000055044A1 (fr) 1999-03-17 2000-09-21 Unilever Plc Procede de production d'emballage hydrosoluble
EP1155804A1 (fr) 2000-05-19 2001-11-21 The Nippon Synthetic Chemical Industry Co., Ltd. Procédé de préparation d'un film d'alcool polyvinylique grainé
WO2007057653A1 (fr) * 2005-11-16 2007-05-24 Reckitt Benckiser (Uk) Limited Procede de moulage par injection et compression d'un polymere soluble dans l'eau et recipient realise en polymere soluble dans l'eau
EP1842647A1 (fr) 2006-04-03 2007-10-10 Kuraray Europe GmbH Laminé multicouche avec des feuilles gaufrées sur une face à base de l'alcool polyvinylique partiellement acétalisé
WO2015054100A2 (fr) * 2013-10-07 2015-04-16 Monosol, Llc Capsules hydrosolubles à libération retardée, procédés et articles associés
EP2955219A1 (fr) * 2014-06-12 2015-12-16 The Procter and Gamble Company Sachet soluble dans l'eau comprenant une zone en relief
WO2016061025A1 (fr) * 2014-10-13 2016-04-21 Monosol, Llc Film hydrosoluble à base d'un mélange de résines alcool polyvinylique, procédés associés, et articles associés
EP3348608A1 (fr) * 2015-09-11 2018-07-18 The Nippon Synthetic Chemical Industry Co., Ltd. Film soluble dans l'eau, emballage pharmaceutique, et procédé de production d'un film soluble dans l'eau
WO2019048474A1 (fr) * 2017-09-06 2019-03-14 Basf Se Films polymères actifs de lavage et de nettoyage, leur procédé de production et leur utilisation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3700128A1 (de) 1987-01-03 1988-07-14 Hoechst Ag Biologisch abbaubare poly- (hydroxyalkyl)- aminodicarbonsaeure-derivate, verfahren zu ihrer herstellung und verwendung derselben fuer depotzubereitungen mit kontrollierter wirkstoffabgabe
EP0458079A2 (fr) 1990-04-26 1991-11-27 Hoechst Aktiengesellschaft Agent de contraste ultrasonique, sa préparation et application comme diagnostic ou thérapeutique
DE19545678A1 (de) 1995-12-07 1997-06-12 Goldschmidt Ag Th Copolymere Polyaminosäureester
WO2000055044A1 (fr) 1999-03-17 2000-09-21 Unilever Plc Procede de production d'emballage hydrosoluble
EP1155804A1 (fr) 2000-05-19 2001-11-21 The Nippon Synthetic Chemical Industry Co., Ltd. Procédé de préparation d'un film d'alcool polyvinylique grainé
WO2007057653A1 (fr) * 2005-11-16 2007-05-24 Reckitt Benckiser (Uk) Limited Procede de moulage par injection et compression d'un polymere soluble dans l'eau et recipient realise en polymere soluble dans l'eau
EP1842647A1 (fr) 2006-04-03 2007-10-10 Kuraray Europe GmbH Laminé multicouche avec des feuilles gaufrées sur une face à base de l'alcool polyvinylique partiellement acétalisé
WO2015054100A2 (fr) * 2013-10-07 2015-04-16 Monosol, Llc Capsules hydrosolubles à libération retardée, procédés et articles associés
EP2955219A1 (fr) * 2014-06-12 2015-12-16 The Procter and Gamble Company Sachet soluble dans l'eau comprenant une zone en relief
WO2016061025A1 (fr) * 2014-10-13 2016-04-21 Monosol, Llc Film hydrosoluble à base d'un mélange de résines alcool polyvinylique, procédés associés, et articles associés
EP3348608A1 (fr) * 2015-09-11 2018-07-18 The Nippon Synthetic Chemical Industry Co., Ltd. Film soluble dans l'eau, emballage pharmaceutique, et procédé de production d'un film soluble dans l'eau
WO2019048474A1 (fr) * 2017-09-06 2019-03-14 Basf Se Films polymères actifs de lavage et de nettoyage, leur procédé de production et leur utilisation

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Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 2997-92-4
K.C. BERGERG. BRANDRUP: "J. Brandrup, E.H. Immergut, Polymer Handbook", 1989, JOHN WILEY & SONS, pages: ll,81 - ll,141

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