Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
  • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
  • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F120/04—Acids; Metal salts or ammonium salts thereof
  • C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
  • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/04—Acids, Metal salts or ammonium salts thereof
  • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/12—Soft surfaces, e.g. textile
• • 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces

Definitions

• Incrustation inhibitor or dispersant There is the problem that polyethers and surfactants with polyacrylic acid in gel formulations are often not or only conditionally compatible, so that it comes to the phase separation or precipitation during mixing, what the possible uses of at least one of
• alkoxylates used are exclusively EO-PO block copolymers having a high PO content and polytetrahydrofuran. The described
• cycloaliphatic hydrocarbons acetone, cyclohexanone, THF and dioxane.
• WO 2008/139151 A1 describes a process in which polyethylene glycol is mixed with acrylic acid, isobornyl acrylate and further component and cured by UV exposure to give a solid gel. Due to the composition, it will be apparent to those skilled in the art that the gel is not water soluble. The gels serve as an indicator that a disk, z. As a computer-readable compact disc, not previously used.
• Glycerol monostearate and an alkyl-terminated polyethylene glycol methacrylate is polymerized.
• the latter is an associative monomer and not a polyether-containing surfactant in the context of the present invention.
• the process also requires the use of a large amount of organic solvents based on relatively little acrylic acid and surfactant.
• Lev Bromberg describes in the Journal of Physical Chemistry B (1998), 102, 11, 1956-1963, a material with thermoreversible gelation, the preparation of which acrylic acid is polymerized in the presence of a PEO-PPO-PEO block copolymer.
• the reaction is carried out in the absence of external solvents to achieve a high level of branching and crosslinking in the products obtained. These are neither water-soluble nor transparent. As possible uses for this
• the present invention is based on the object, a gel-like substance
• a first object of the invention is a process for the preparation of a gel-like polymer composition comprising: a) providing a monomer composition M) which
• the at least one is ⁇ , ⁇ -ethylenic
• the free-radical polymerization in step b) additionally takes place in the presence of a solvent LM) which is selected from water, C 1 -C 6 -alkanols, polyols other than PE, their mono- and dialkyl ethers, aprotic polar solvents and mixtures thereof.
• a solvent LM which is selected from water, C 1 -C 6 -alkanols, polyols other than PE, their mono- and dialkyl ethers, aprotic polar solvents and mixtures thereof.
• reaction mixture is subjected during the polymerization in step b) and that obtained in step b)
• Polymer composition is also in the form of a gel after condensation.
• Another object of the invention is a gelatinous polymer composition obtainable by a process as defined above and hereinafter.
• a polymer composition in the form of a transparent gel is obtained.
• the invention therefore provides a polymer composition as defined above and hereinafter in the form of a transparent gel.
• the gel composition according to the invention preferably contains
• Polymer compositions at least 10 wt .-%, preferably at least
• the solvent is preferably selected from the solvents LM) as before and within
• Polymer composition containing at least 10% by weight, preferably at least
• At least one solvent LM which is selected from water, Ci-C6-alkanols, non-PE) polyols, their mono- and Dialkyl ethers and mixtures thereof.
• the invention further provides a washing or cleaning agent comprising: at least one gel-like polymer composition according to the invention as defined above and below or obtainable by a process as defined above and below, at least one builder, optionally at least one enzyme, optionally at least a bleaching agent, e) optionally water, f) optionally at least one thickener, and g) optionally at least one further additive, preferably
• Corrosion inhibitors include defoamers, dyes, fragrances, fillers,
• Solubilizers organic solvents, electrolytes, pH adjusters, perfume carriers, fluorescers, hydrotropes, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents,
• Anti-crease agents color transfer inhibitors, antimicrobial agents, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, and Phobier-
• Impregnating agents, swelling and anti-slip agents and UV absorbers are Impregnating agents, swelling and anti-slip agents and UV absorbers.
• a further subject of the invention is a cleaning agent for the sanitary sector, which contains at least one gel-like polymer composition according to the invention as defined above and below or obtainable by a method as defined above and below, and at least one organic acid.
• Another object of the invention is an adhesive composition comprising or consisting of a polymer composition obtainable by a process as defined above and hereinafter.
• Adhesive composition is suitable for a variety of applications, e.g. for coated labels, especially plasticizer-free and / or self-adhesive and / or redetachable paper labels. DESCRIPTION OF THE INVENTION
• Polymer compositions have the following advantages:
• the process according to the invention is advantageously suitable for the production of
• compositions based on polymers of unsaturated carboxylic acids and polyethers It is now possible for the first time to provide gels and in particular clear, transparent gels based on polyacrylic acid and polyethers.
• the inventive method allows the substantial or complete abandonment of crosslinking monomers in the preparation of
• the process according to the invention is also suitable for the production of polymer compositions for adhesive compositions.
• Provision of these special polymer compositions is achieved by selecting a suitable glass transition temperature and / or polyether component PE), as explained in more detail below.
• Formulations which have a higher viscosity than a liquid and which in particular are self-supporting, d. H. which retain a form given to them without a form-stabilizing cladding.
• gel formulations are easily deformed by heating and / or shear forces or converted to a fluid form.
• the viscosity of the gel-form polymer compositions is preferably at 20 ° C in a range of greater than 600 to about 10,000,000 mPas, more preferably from 1,000 to 1,000,000 mPas, in particular from 2,000 to 500,000 mPas.
• Methacrylic acid may be derived in part by inserting the syllable "(meth)" into the compound derived from the acrylic acid.
• C 1 -C 6 -alkyl is a linear or branched alkyl radical having 1 to 5 carbon atoms. Examples of these are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and
• C 7 -C 30 -alkyl is a linear or branched alkyl radical having 6 to 30
• Carbon atoms include heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 2- Propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
• the preparation of the polymer compositions according to the invention is carried out by free-radical polymerization of the monomer composition M) in the presence of at least one polyether component PE), which generally has no copolymerizable double bond.
• PE polyether component
• special polymer compositions are obtained with advantageous properties. Without being bound by theory, this may for example be due to an effect of the polyether component PE) as a protective colloid or emulsifier. This can for example also result from an at least partial grafting to the polyether component as the graft base. However, mechanisms other than grafting are conceivable.
• the polymer compositions of the invention generally include the process products of radical polymerization, including, for. B.
• Graft polymers homopolymers and copolymers of the monomers present in the monomer mixture M), mixtures of graft polymers with ungrafted compounds of the polyether component PE) and any desired mixtures.
• reaction mixture and the polymer composition obtained in step b) are free from condensation to remove one
• the polymer composition according to the invention is not in the form of a solid. Solid compositions are subject to parallel
• the present invention further does not relate to the use of the gelatinous polymer composition in formulations for the mechanical
• TG glass transition temperature
• a glass transition temperature TG in the range of -100 to + 150 ° C, preferably from -20 to + 130 ° C used.
• the polymer compositions according to the invention for use in adhesive compositions preferably have a glass transition temperature T G in the range from -100 to + 10 ° C., preferably from -80 to 0 ° C.
• Polymer composition with desired glass transition temperature TG is within the skill of the art and can be checked by routine measurements.
• the glass transition temperatures (Tg) described in the context of this application can be determined by means of differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• the DSC measurement is expediently repeated once or twice on one and the same sample in order to obtain a defined thermal history of the polymer composition
• the polymer compositions of the invention are in the form of a transparent gel.
• the transparency of a material is determined by its absorption and scattering behavior, i. the amount of transmitted light and the appearance in the review.
• Total transmission is the ratio of transmitted light to incident light. As a measure of the light transmission is the
• Transmittance ⁇ used It is the quotient of the luminous flux ⁇ ⁇ behind and ⁇ ⁇ before the material to be tested and is given in percent. This value contains not only the absorption but also the scattering and reflection losses.
• the transmittance is generally determined in air and is given as a function of wavelength.
• the light transmittance (Ti_) is determined at a wavelength of 500 nm.
• the reference value for the maximum light transmittance (Ti_ value of 100%) is water.
• the polymer composition according to the invention in the form of a transparent gel preferably has a Ti.sub.n value measured at 500 nm, of at least 85%, particularly preferably of at least 90%, based on the light transmittance of water.
• Carboxylic acid monomer A) The ⁇ , ⁇ -ethylenically unsaturated carboxylic acid A) is preferably selected from acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid,
• the monomers A) also include the salts of the abovementioned acids, 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 proportions by weight are all based on the acid form.
• the at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid is preferably used in unneutralized form for the polymerization.
• the component A) is particularly preferably selected from acrylic acid, methacrylic acid and mixtures thereof. In particular, only acrylic acid is used as component A).
• the component 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).
• the monomer composition M) 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 monomers used, of acrylic acid.
• the polymer composition according to the invention contains substantially
• the monomer composition M) used to prepare the polymer composition according to the invention thus contains no or only small amounts of crosslinking monomers B).
• Crosslinkers in the context of the invention are compounds having two or more than two polymerizable ethylenically unsaturated double bonds per molecule.
• Crosslinkers B) are preferably used in an amount of 0 to 0.1% by weight, particularly preferably 0 to 0.05% by weight, based on the total weight of the monomer composition M).
• the Monomer composition M) no crosslinking monomers B) which have two or more than two polymerizable ⁇ , ⁇ -ethylenically unsaturated double bonds per molecule.
• Suitable crosslinkers B) are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the
• underlying alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.
• the underlying alcohols are dihydric alcohols such as
• Diethylene glycol triethylene glycol, tetraethylene glycol, dipropylene glycol,
• Tripropylene glycol Tripropylene glycol, tetrapropylene glycol, 3-thio-pentane-1, 5-diol, and
• propylene oxide groups incorporated.
• underlying alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose.
• the polyhydric alcohols can also be used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates.
• the polyhydric alcohols can also be first by reaction with epichlorohydrin in the
• crosslinkers B) are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C 3 -C 6 -carboxylic acids,
• acrylic acid methacrylic acid, itaconic acid, maleic acid or
• Fumaric acid examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octene-3-ol, 9-decene-1-ol, dicyclopentenyl alcohol, 10-undecene-1-ol, cinnamyl alcohol , Citronellol, crotyl alcohol or cis-9-octadecene-1-ol.
• crosslinkers B) are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
• crosslinker B) are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated in aliphatic hydrocarbons, eg. B.
• divinylbenzene divinyltoluene, 1, 7-octadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200 to 20,000 g / mol.
• crosslinkers B) are the acrylamides, methacrylamides and N-allylamines of at least divalent amines.
• Such amines are for example 1, 2-diaminoethane, 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, 1, 12-dodecanediamine, piperazine, diethylenetriamine or
• Isophoronediamine is also suitable.
• amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above.
• N-vinyl compounds of urea derivatives at least divalent amides, cyanurates or urethanes, for example of urea, ethyleneurea, propyleneurea or tartaramide, for.
• crosslinkers B) are divinyldioxane, tetraallylsilane or tetravinylsilane.
• the monomer composition M) may contain, instead of component A), at least one unsaturated sulfonic acid or phosphonic acid C).
• the monomer composition M) may additionally contain as component C) at least one unsaturated sulfonic acid or phosphonic acid.
• Component C) is preferably selected from 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate,
• component C) is 2-acrylamido-2-methylpropanesulfonic acid.
• the monomers C) also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts and the salts with amines.
• the monomers C) 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 M) preferably comprises at least 80% by weight, more preferably at least 90% by weight, in particular at least 95% by weight, based on the total weight of the monomer composition M), of monomers A) and C).
• the monomer composition M) contains at least one monomer C), it is preferably used in an amount of 0.1 to
• the monomer composition M) may additionally comprise at least one monomer D) selected from compounds of the general formulas (La) and (l.b)
• H 2 C C-C-X- (CH 2 -CH 2 -O) k (CH 2 -CH (CH 3 ) -O)
• H 2 C CH-CH 2 -O- (CH 2 -CH 2 -O) k (CH 2 -CH (CH 3 ) -O)
• sequence of the alkylene oxide units is arbitrary, k and I independently of one another are an integer from 0 to 1000, the sum of k and I being at least 2, preferably at least 5,
• R 1 is hydrogen or C 1 -C 8 -alkyl
• R 2 is hydrogen, C 1 -C 30 -alkyl, C 2 -C 3 o-alkenyl or C 5 -C 8 -cycloalkyl,
• Suitable polyether acrylates la) are z.
• Suitable polyetherols can easily be prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule, such as water or a short-chain alcohol R 2 -OH.
• the alkylene oxides can be used individually, alternately in succession or as a mixture.
• the polyether acrylates la) can be used alone or in
• the acid component used is preferably acrylic acid, methacrylic acid and mixtures thereof.
• Preferred monomers H) are N-methylaminoethyl (meth) acrylate
• N-ethylaminoethyl (meth) acrylate N- (n-propyl) aminoethyl (meth) acrylate
• component H) comprises as vinyl-substituted heteroaromatic compound at least one N-vinylimidazole compound.
• component H) is selected from N-vinylimidazole compounds and mixtures containing at least one N-vinylimidazole compound.
• N-vinylimidazole compounds of the general formula (IV) are also suitable.
• Suitable monomers H) are furthermore vinyl-and allyl-substituted nitrogen heterocycles, other than vinylimidazoles, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.
• Suitable esters of vinyl alcohol with Ci-C3o-monocarboxylic acids are, for. B.
• n-nonylvinyl esters n-decylvinyl esters, n-undecylvinyl esters, tridecylvinyl esters, myristyl vinyl esters, pentadecyl vinyl esters, palmityl vinyl esters, heptadecyl vinyl esters, octadecyl vinyl esters, nonadecyl vinyl esters, arrachinyl vinyl esters, behenyl vinyl esters,
• Lignocerenyl vinyl esters cerotinyl vinyl esters, melissinyl vinyl esters, palmitoleinyl vinyl esters, oleyl vinyl esters, linolyl vinyl esters, linolenyl vinyl esters, stearyl vinyl esters, lauryl vinyl esters and mixtures thereof.
• Suitable amide group-containing monomers K) are compounds of the general formula (V)
• the compounds of component K) are preferably selected from among primary amides of .alpha.,. Beta.-ethylenically unsaturated monocarboxylic acids and N-vinylamides Monocarboxylic acids, N-vinyllactams, N-alkyl and N, N-dialkylamides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and mixtures thereof.
• Preferred monomers K) are N-vinyl lactams and their derivatives, the z.
• one or more Ci-C6-alkyl substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. may have. These include z. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone,
• N-vinylpyrrolidone and / or N-vinylcaprolactam.
• Monocarboxylic acids are, for example, methyl (meth) acrylamide, methylethacrylamide, ethyl (meth) acrylamide, ethylethacrylamide, n-propyl (meth) acrylamide, isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide tert-butylethacrylamide, n-pentyl (meth) acrylamide, n-hexyl (meth) acrylamide, n-heptyl (meth) acrylamide, n-octyl (meth) acrylamide, 1,1,3,3-tetramethylbutyl (meth) acrylamide,
• Suitable open-chain N-vinylamide compounds as monomers K) are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide,
• Suitable esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-alkanediols are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
• Suitable amides of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-amino alcohols having a primary or secondary amino group are 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, 2-hydroxyethylethacrylamide,
• Suitable ⁇ , ⁇ -ethylenically unsaturated nitriles are acrylonitrile or methacrylonitrile.
• Suitable monomers O) with urea groups are N-vinylurea, N-allylurea or derivatives of imidazolidin-2-one. These include N-vinyl and
• a monomer composition M) which consists of acrylic acid and / or methacrylic acid.
• a monomer composition M) which consists of acrylic acid and / or methacrylic acid.
• Acrylic acid and / or methacrylic acid and - at least one ether group-containing monomer selected from
• step a) a
• step a) a
• Suitable polyether component PE are polyetherols having a number average molecular weight of at least 200 g / mol and their mono- and di- (C 1 -C 6 -alkyl ethers).
• Suitable polyetherols and their mono- and di- (C 1 -C 6 -alkyl ethers) may be linear or branched, preferably linear. Suitable polyetherols and their mono- and di- (C 1 -C 6 -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 contain alkylene oxide repeat units. The proportion of alkylene oxide repeating units is preferably 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, for. For example, ethylene oxide, propylene oxide, epichlorohydrin, 1, 2- and 2,3-butylene oxide.
• Suitable examples are copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide and copolymers of ethylene oxide, propylene oxide and at least one
• the alkylene oxide copolymers can randomly label the alkylene oxide units distributed or polymerized in the form of blocks.
• the proportion of repeating units derived from ethylene oxide is 40 to 99% by weight. Particularly preferred as
• Polyether component PE are ethylene oxide homopolymers
• polyether component PE Also suitable as polyether component PE are the mono- and di- (C 1 -C 2 -alkyl ethers) of the polyetherols described above. Preferred are
• Polyalkylene glycol monomethyl ether and polyalkylene glycol dimethyl ether are examples of polyalkylene glycol monomethyl ether and polyalkylene glycol dimethyl ether.
• Suitable as polyether component PE are also polyether-containing surfactants.
• suitable are nonionic and ionic surfactants which have at least one nonpolar and at least one polar group and which have one
• Polyether group include.
• the polyether-containing surfactants PE are preferably selected from alkylpolyoxyalkylene ethers, arylpolyoxyalkylene ethers, alkylarylpolyoxyalkylene ethers, alkoxylated animal and / or vegetable fats and / or oils, fatty amine alkoxylates, fatty acid amide alkoxylates, fatty acid diethanolamide alkoxylates,
• Polyoxyethylene sorbitan fatty acid esters alkyl polyether sulfates, aryl polyether sulfates, alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl polyether sulfonates,
• Alkylaryl polyether sulfonates alkyl polyether phosphate actives, aryl polyether phosphates, alkylaryl polyether phosphates, glycerol ether sulfonates, glycerol ether sulfates,
• the preferred nonionic surfactants polyether-containing surfactants PE include, for example: alkylpolyoxyalkylene ethers derived from low molecular weight C 3 -C 6 -alcohols or from C 7 -C 30 -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 0 is -O- (CH 2 CH 2 O) x - (CHR CH 2 O) y R 12 (VI), where R 10 is a linear or branched alkyl radical having 6 to 22 C atoms, R 11 and R 12 are independently hydrogen or a linear or branched Al kylrest having 1 to 10 carbon 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.
• Hydroxyl group-containing surfactants of the general formula (VII) -0- (CH2CH20) s- (CH2CH2CH20) t (CH2CH2CH2CH20) u (CH 2 CHR i4 0) v-CH 2 CH (OH) Ri5 (VII) wherein in the compounds of Formula (VII) the sequence of the alkylene oxide units is arbitrary, s, t, u and v independently of one another are 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 straight-chain or branched, saturated C 1 -C 40 -alkyl radical or a mono- or polyunsaturated C 2 -C 40 -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 independently of one another represent a straight-chain or branched, saturated C 2 -C 30 -alkyl group. In this case, R 13 and R 15 may also be kylreste for mixtures of various AI.
• R 14 is preferably methyl or ethyl, in particular methyl.
• a preferred embodiment are hydroxyl-containing surfactants of the general formula (VI 1.1)
• R 13 and R 15 independently of one another represent a straight-chain, saturated C 1 -C 30 -alkyl radical or a branched, saturated C 3 -C 30 -alkyl radical or a mono- or polyunsaturated C 2 -C 30 -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.
• non-ionic surfactants include, for example Hydroxymisch- ether of the general formula (C 6-22 alkyl) -CH (OH) CH 2 0- (EO) 2 oi 2 o- (C 22 6-alkyl).
• R 6 -O- (CH 2 CH 2 O) P - (CH 2 CHR 7 O) q -C ( O) R 18 (VIII) where in the compounds of the formula (VIII) the sequence of the alkylene oxide units is arbitrary, p and q independently 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 straight-chain or branched, saturated C 1 -C 4 -alkyl radical or a mono- or polyunsaturated C 2 -C 40 -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 straight-chain or branched, saturated C 4 -C 30 -alkyl radical.
• R 16 and R 18 can also be methyl radicals for mixtures of different AI.
• R 17 is preferably methyl or ethyl, in particular methyl.
• These include, for example, lauryl alcohol polyoxyethylene acetate.
• Alkylaryl alcohol polyoxyethylene ethers e.g. Octylphenol polyoxyethylene ethers, alkoxylated animal and / or vegetable fats and / or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fatty ethoxylates,
• Alkylphenol alkoxylates such as, for example, ethoxylated isooctyl, octyl or nonylphenol, tributylphenol polyoxyethylene ethers,
• alkylpolyethersulfate sodium dodecylpoly (oxyethylene) sulfate (sodium lauryl ether sulfate, SLES).
• Solvent LM solvent
• the radical polymerization in step b) can be carried out in the presence of a solvent LM), which is selected from water, C 1 -C 6 -alkanols, of PE)
• Suitable aprotic polar solvents are pyrrolidones and pyrrolidone derivatives. These include especially 2-pyrrolidone ( ⁇ -butyrolactam) and N-methylpyrrolidone.
• the free-radical polymerization in step b) preferably takes place in the presence of a solvent LM) which is selected from water, C 1 -C 6 -alkanols, polyols other than PE, their mono- and dialkyl ethers and mixtures thereof.
• a solvent LM which is selected from water, C 1 -C 6 -alkanols, polyols other than PE, their mono- and dialkyl ethers and mixtures thereof.
• Suitable polyols and their mono- and dialkyl ethers also include
• the solvent LM) is preferably selected from water, methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol mono (C 1 -C 4 -alkyl) ethers, ethylene glycol di (C 1 -C 4 -alkyl) ethers, 1, 2 Propylene glycol, 1,2-propylene glycol mono (C 1 -C 4 -alkyl) ethers, 1,2-propylene glycol di (C 1 -C 4 -alkyl) ethers, glycerol, polyglycerols, 2-pyrrolidone, N-methylpyrrolidone, oligoalkylene glycols having a number average mo
• Suitable oligoethylene glycols are among the CTFA designations PEG-6, PEG-8, PEG-12, PEG-6-32, PEG-20, PEG-150, PEG-7M, PEG-12M and PEG-1 15M
• Suitable alkylpolyalkylene glycols are the corresponding Pluriol A... E® brands of BASF SE. Preferred are the isomeric dipropylene glycols such as 1, 1'-oxydi-2-propanol, 2,2'-oxydi-1-propanol, 2 (2-hydroxypropoxy) -1-propanol and mixtures thereof.
• the solvent LM) is particularly preferably selected from water, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 2-dipropylene glycol and mixtures thereof.
• the solvent LM) used is water or a mixture of water and at least one solvent LM) other than water, selected from ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1, 2 Dipropylene glycol and mixtures thereof.
• the free-radical polymerization in step c) takes place in the presence of a solvent LM), which is at least 50 wt .-%, preferably at least 75 wt .-%, especially at least 90 wt .-%, based on the total weight the solvent LM), consists of water.
• the free-radical polymerization in step c) takes place in the presence of a solvent LM), which consists entirely of water.
• the gel-like polymer composition preferably contains at least 10% by weight, preferably at least 15% by weight, in particular at least 20% by weight, based on the total weight of the polymer composition, of at least one solvent LM).
• the gel-like polymer composition contains 10 to 90 wt .-%, preferably 15 to 80 wt .-%, in particular 20 to 70 wt .-%, based on the
• the preparation of the polymer compositions according to the invention comprises a free-radical polymerization of the monomer composition M) in the presence of at least one polyether component PE). It is preferably carried out in the feed process.
• at least the monomers are added in liquid form to the reaction mixture. Under the metering conditions, liquid monomers can be added to the reaction mixture without addition of a solvent LM), otherwise the monomers are used as a solution in a suitable
• the free-radical polymerization in step b) is carried out in feed mode, with feeds containing at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid containing no solvent LM).
• the metering rates of the monomer feed / the monomer feeds and any further feeds are preferably selected so that the
• Polymerization is maintained at the desired conversion rate.
• the addition of the individual feeds can be carried out continuously, periodically, with a constant or alternating metering rate, substantially simultaneously or with a time lag.
• the weight ratio of the monomer mixture M) to the component PE) is preferably in the range from 1:10 to 10: 1. If a solvent LM) is used to prepare the polymer composition, the weight ratio of the component PE) to the component LM) is preferably in the range from 0.3: 1 to 5: 1, particularly preferably 0.5: 1
• the free-radical polymerization in step b) preferably takes place at a temperature in the range from 20 to 90.degree. C., more preferably from 30 to 85.degree. C., in particular from 40 to 80.degree.
• 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 kept as constant as possible as a rule over the period of addition.
• the addition of the feeds in step b2) takes place over a period of time which is advantageously chosen so that the heat of reaction formed in the exothermic polymerization reaction can be removed without major technical effort, for example without the use of a reflux condenser.
• the feeds are added over a period of 1 to 10 hours.
• the feeds are added over a period of 2 to 8 hours, more preferably over 3 to 5 hours.
• the optionally used solvent and / or any resulting condensation products are generally not removed. Ie.
• the polymerization can be carried out usually 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 is usually carried out at a constant temperature, but can also be varied as needed during the polymerization.
• the temperature is usually carried out at a constant temperature, but can also be varied as needed during the polymerization.
• Polymerization temperature usually in the range of 20 to 90 ° C.
• the polymerization temperature ranges from 30 to 85 ° C and
• the solvent or solvent mixture determines the maximum reaction temperature by the corresponding boiling temperatures.
• the polymerization can be carried out in the absence or in the presence of an inert gas. Usually, the polymerization is carried out in the presence of an inert gas. Under inert gas is usually understood to mean a gas which, under the given reaction conditions, does not react with the educts, reagents, solvents or the products formed.
• the polymerization is carried out in the presence of a solvent, this is selected from the solvents LM) described above.
• the monomers can be polymerized with the aid of radical-forming initiators, hereinafter also referred to as free-radical initiators or starters.
• Radical initiators (initiators) for radical polymerization are in principle all radical starters which are known in the art
• Reaction medium as it prevails at the time of their addition, are substantially soluble and have sufficient activity at the given reaction temperatures to start the polymerization.
• a single radical starter or a combination of at least two free radical initiators can be used.
• the peroxo and / or azo compounds customary for this purpose can be used, for example alkali metal or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate,
• initiator mixtures or redox initiator systems such as. B.
• Initiator system in the range of 0.01 to 10 wt .-%, preferably in the range of 0.1 to 5 wt .-%, particularly preferably in the range of 0.2 to 2 wt .-% and in particular in the range of 0.3 to 1, 5 wt .-%.
• the radical initiator is generally provided as a solution in a solvent which is at least one of the abovementioned
• Solvent LM Solvent LM
• the amount of regulator commonly employed in the process of the invention is from 1 to 40 pphm ("parts per hundred monomer", i.
• the amount of regulator used in the process according to the invention is preferably in the range from 3 to 30 pphm, more preferably in the range from 5 to 25 pphm.
• the regulator is added in step b2) completely via one of the feeds continuously to the polymerization mixture.
• the regulator it is also possible to add the regulator either completely to the template, ie before the actual polymerization, or only part of the regulator is initially introduced into the template and the remainder in step b2) is continuously fed to the polymerization mixture via one of the feeds added.
• the addition of the regulator can be carried out in each case without or with solvent LM).
• 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 reaction mixture
• the process according to the invention serves to prepare a clear gel composition.
• the amount of polyether component PE) in the initial charge (step b1)) is preferably 10 to 100% by weight, more preferably 25 to 100% by weight and in particular 30 to 100% by weight, based on the total weight of the polymerization used Polyether component PE).
• Polymer composition used polyether component PE) to the monomer composition used M) usually in the range of 1, 0: 10 to 10: 1.
• the content of solvent in the original is preferably from 10 to 90% by weight, based on the total weight of all starting materials present in the initial charge.
• the content of solvent in the initial charge is preferably from 15 to 85% by weight, in particular from 20 to 80% by weight, based on the total weight of all starting materials present in the initial charge.
• solvents LM Normally, solvents LM are used which have a boiling point
• the solvent LM in this first preferred embodiment is water, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol mono (C 1 -C 4 -alkyl) ethers,
• Ethylene glycol di (C 1 -C 4 -alkyl) ethers 1, 2-propylene glycol, 1, 2-propylene glycol mono (C 1 -C 4 -alkyl) ethers, 1, 2-propylene glycol di (C 1 -C 4 -alkyl) ethers, dipropylene glycols or
• the solvent LM used is water, ethanol, n-propanol, isopropanol, n-butanol or mixtures thereof.
• the polymer compositions obtained after completion of the polymerization (step b3)) are transferred to a suitable vessel and optionally cooled directly to ambient temperature (20 ° C).
• Polymer composition already a gel-like consistency. If desired, the rheological properties of the polymer composition
• the polymer composition used in the invention is preferably transparent, i. H. it has a light transmittance (Ti_ value) of at least 85%, in particular of at least 90%, based on the light transmittance of water.
• the polymer composition used in the invention preferably has a viscosity at 20 ° C in a range of greater than 600 to about 10,000,000 mPas, more preferably from 1,000 to 1,000,000 mPas, in particular from 2,000 to 500,000 mPas.
• the acid groups of the polymer composition according to the invention can not, partially or completely neutralized.
• the acid groups of the polymer composition of the invention are not or only partially neutralized.
• the acid groups of the polymer composition according to the invention are preferably present in unneutralized form.
• alkali metal bases such as caustic soda, potassium hydroxide, soda, sodium bicarbonate, potassium carbonate or potassium hydrogencarbonate, and alkaline earth metal bases such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate and ammonia or amines
• suitable Amines are z.
• Ci-C6-alkyl amines preferably n-propylamine and n-butylamine
• Dialkylamines preferably diethylpropylamine and dipropylmethylamine
• trialkylamines preferably triethylamine and triisopropylamine.
• amino alcohols for.
• trialkanolamines such as triethanolamine
• Alkyldialkanolamine such as methyl or
• Ethyldiethanolamin and dialkylalkanolamines such as dimethylethanolamine and 2-amino-2-methyl-1-propanol.
• the neutralization of the acid groups can also be carried out with the aid of mixtures of several bases.
• the base is particularly preferably selected from NaOH, KOH, 2-amino-2-methyl-1-propanol, triethylamine, diethylaminopropylamine, diethanolamine, triethanolamine, triisopropanolamine and mixtures thereof.
• the polymer composition according to the invention preferably has an acid group content of more than 1 mmol / g, more preferably more than
• a polymer composition in the form of a transparent gel preferably has an acid group content of from 1.5 mmol / g to 15 mmol / g, preferably from 4 mmol / g to 7 mmol / g.
• the acid groups of the polymer composition according to the invention are present in unneutralized form.
• the polymer composition has a solubility in water at 40 ° C and a pH of 8 of at least 5 g / L.
• Polymer composition as determined by gel permeation chromatography (GPC) using neutralized polyacrylic acid as the polymer standard is preferably 1,000 to 150,000 daltons.
• Polymer composition preferably have a total surfactant content of 0.1 to 75 wt .-%, particularly preferably from 0.5 to 60 wt .-%, in particular from 1 to 50 wt .-%, based on the total weight of the surfactant-containing
• Suitable additional surfactants are anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof.
• anionic surfactants are soaps, alkyl sulfonates,
• Alkyl oligoglucoside sulfates alkyl glucose carboxylates, protein fatty acid condensates and alkyl (ether) phosphates.
• Suitable soaps are z.
• alkali alkaline earth and ammonium salts of fatty acids, such as potassium stearate.
• R 15 and R 16 together have at least 6 and preferably 8 to 20, especially 10 to 16, carbon atoms.
• Alkaline earth ammonium, alkylammonium, alkanolammonium or
• Glucammonium salts are present.
• the olefin sulfonates are as
• the hydrolyzed alpha-olefin sulfonation product ie the alpha-olefin sulfonates, are composed of about 60% by weight of alkanesulfonates and about 40% by weight of hydroxyalkanesulfonates; Of these, about 80 to 85 wt .-% mono- and 15 to 20 wt .-% disulfonates.
• Preferred methyl ester sulfonates (MES) are obtained by sulfonation of
• Fatty acid methyl ester obtained from vegetable or animal fats or oils.
• Preferred alkyl sulfates are sulfates of fatty alcohols of the general formula R 17 -O-SO 3 Y, wherein R 17 is a linear or branched, saturated or unsaturated hydrocarbon radical having 6 to 22 carbon atoms and Y is an alkali metal, the monovalent charge equivalent of an alkaline earth metal, ammonium, mono -, di-, tri- or tetraalkylammonium, alkanolammonium or glucammonium.
• Suitable fatty alcohol sulfates will preferably be obtained by sulfation of native fatty alcohols or synthetic oxoalcohols and subsequent neutralization.
• Typical examples of fatty alcohol sulfates are the sulfation products of
• Caprolyl alcohol capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, behenyl alcohol and elaeostearyl alcohol, and the salts and mixtures thereof.
• Preferred salts of the fatty alcohol sulfates are the sodium and potassium salts, especially the sodium salts.
• Fatty alcohol sulfates are based on technical alcohol mixtures, the z. B. in the high pressure hydrogenation of technical methyl esters based on fats and oils or in the hydrogenation of aldehydes from the oxo process or in the
• Typical examples include technical alcohol sulfates based on vegetable raw materials.
• Preferred sarcosinates are sodium lauroyl sarcosinate or sodium stearoyl sarcosinate.
• Preferred protein fatty acid condensates are wheat based vegetable products.
• Preferred alkyl phosphates are mono- and Diphosphorklarealkylester.
• Suitable acylglutamates are compounds of the formula (I)
• COR 18 is a linear or branched acyl radical having 6 to 22
• acylglutamates Carbon atoms and 0, 1, 2 or 3 double bonds and X is hydrogen, an alkali metal, the monovalent charge equivalent of an alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
• the preparation of acylglutamates is carried out, for example, by Schotten-Baumann acylation of glutamic acid with fatty acids, fatty acid esters or fatty acid halides.
• Acylglutamates are commercially available, for example, from Clariant AG, Frankfurt / DE or Ajinomoto Co. Inc., Tokyo / JP. An overview of production and
• acylglutamates suitable as component b) are preferably derived from fatty acids having 6 to 22 and particularly preferably 12 to 18
• acylglutamate carbon atoms off.
• mono- or dialkali metal salts of acylglutamate are used. These include z. B. (tradenames from Ajinomoto, USA in parentheses): sodium cocoylglutamate (Amisoft CS-1 1), dinatnum cocoylglutamate (Amisoft ECS-22SB), triethanolammonium cocoylglutamate (Amisoft CT-12),
• Triethanolammonium lauroylglutamate (Amisoft LT-12), sodium myristoylglutamate (Amisoft MS-1 1), sodium stearoylglutamate (Amisoft HS-1 1P), and mixtures thereof.
• Additional nonionic surfactants include, for example:
• Glycerol esters such as glycerol monostearate
• Alkylpolyglycosides N-alkylgluconamides
• Alkyldimethylphosphine oxides such as, for example, tetradecyldimethylphosphine oxide.
• Suitable amphoteric surfactants are, for. Alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates
• cationic surfactants include, for example, quaternized
• Ammonium compounds in particular alkyltrimethylammonium and
• pyridine and imidazoline derivatives in particular alkylpyridinium halides.
• behenyl or cetyltrimethylammonium chloride can be used.
• the polymer composition according to the invention is advantageously suitable for use in detergents and cleaners.
• detergents are understood to mean those agents which are used for cleaning flexible materials with high absorbency, e.g. of materials with a textile character, while under
• Cleaning agents in the context of the present invention means such agents used to clean closed surface materials, i. with a surface which has no or only a few and small pores and consequently has no or only a low absorbency.
• flexible materials with high absorbency are those which contain or consist of natural, synthetic or semisynthetic fiber materials and which therefore generally have at least in part a textile character.
• the fibrous or fibrous materials may in principle be in any form found in use or in manufacture and processing.
• fibers may be disordered in the form of flake or debris ordered in the form of threads, yarns, threads, or in the form of
• the fibers may be raw fibers or fibers at any stage of processing. Examples are natural protein or cellulose fibers, such as wool, silk, cotton, sisal, hemp or
• Coconut fibers or synthetic fibers such as polyester, polyamide or polyacrylonitrile fibers.
• Examples of materials that have little or no pores and little or no absorbency are metal, glass, enamel or ceramic. Typical objects made of these materials are e.g. metal sinks,
• Wall cladding such as window frames, doors, plastic coverings such as floor coverings made of PVC or hard rubber, or hard or soft foams with largely closed surfaces.
• detergents containing the polymer composition of the present invention include detergents and cleaners, metal degreasers, glass cleaners, floor cleaners, general purpose cleaners, high pressure cleaners, neutral cleaners, alkaline cleaners, acid cleaners, spray degreasers, dairy cleaners, large kitchen cleaners, industrial equipment cleaners, particularly the chemical industry, Cleaner for car wash and also household all-purpose cleaner.
• the detergents and cleaners which comprise the polymer composition according to the invention are preferably gel-like, liquid or in portions at room temperature (20 ° C.).
• the polymer composition according to the invention is distinguished, in particular, by an outstanding action as co-builder, surfactant or soil release polymer.
• the constituents of the polymer composition further support the
• the washing and cleaning agent according to the invention preferably comprises the following constituents: a) at least one gel-like polymer composition according to the invention, b) at least one builder (also as sequestering agent, builder,
• Corrosion inhibitors defoamers, dyes, fragrances, fillers, solubilizers, organic solvents, electrolytes, pH adjusters, perfume carriers, fluorescers, hydrotropes, antiredeposition agents, optical brighteners, grayness inhibitors, inlet inhibitors,
• Anti-crease agents color transfer inhibitors, antimicrobial agents, antioxidants, corrosion inhibitors, antistatic agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.
• the detergents and cleaners according to the invention preferably comprise: a) from 0.1 to 90% by weight of at least one gel-like composition according to the invention
• a preferred embodiment are gel form detergents and cleaners. Gel-like detergents and cleaners are understood as meaning fluid agents which are included in the
• the gel-like detergents and cleaners according to the invention preferably have a viscosity of from 0.5 to 100 Pa.s, more preferably from 0.5 to 50 Pa.s and in particular from 1 to 30 Pa.s at 20 ° C.
• the gel-type detergents and cleaners preferably contain: a) 0.1 to 90% by weight of at least one gel-like composition according to the invention
• the washing and cleaning agent according to the invention particularly preferably comprises at least one enzyme.
• washing and cleaning agent according to the invention preferably comprises at least one bleaching agent.
• compositions are referred to the above statements.
• Component b) The detergents and cleaners according to the invention preferably contain at least one builder.
• Builders which are also sometimes referred to as sequestrants, builder, complexing agent, chelator, chelating or softening bind
• Alkaline earth metals and other water-soluble metal salts without precipitation help to break up dirt, disperse dirt particles, help to loosen dirt and sometimes have their own washing effect.
• Suitable builders can be both organic and inorganic in nature. Examples are aluminosilicates, carbonates, phosphates and polyphosphates,
• Polycarboxylic acids Polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, e.g. Hydroxyalkylphosphonklaren, phosphonates, aminopolycarboxylic acids and their salts and polymeric compounds containing carboxylic acid groups and their salts.
• Suitable inorganic builders are, for example, crystalline or amorphous
• Aluminosilicates with ion-exchanging properties such as zeolites.
• zeolites Various types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially reactive with other cations such as Li, K, Ca, Mg or ammonium is exchanged.
• Suitable zeolites are described, for example, in US-A-4604224.
• Crystalline silicates suitable as builders are, for example, disilicates or sheet silicates, for example 5-Na 2 Si 2 O or B-Na 2 Si 2 O 5 (SKS 6 or SKS 7).
• the silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates.
• Amorphous silicates such as sodium metasilicate having a polymeric structure or amorphous disilicate (Britesil® H 20 manufactured by Akzo) are also useful. Preferred among these is sodium disilicate.
• Suitable inorganic builders based on carbonate are carbonates and bicarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preferably, Na, Li and Mg carbonates or hydrogen carbonates, in particular sodium carbonate and / or
• Typical phosphates used as inorganic builders are alkali metal orthophosphates and / or polyphosphates, such as e.g. Pentasodium.
• Suitable organic builders are, for example, C4-C30-D1, tri- and tetracarboxylic acids, such as e.g. Succinic acid, propane tricarboxylic acid, butanetetracarboxylic acid,
• Cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acids having C 2 -C 20 -alkyl or -alkenyl radicals having C 2 -C 20 -alkyl or -alkenyl radicals.
• Suitable organic builders are furthermore hydroxycarboxylic acids and
• Polyhydroxycarboxylic acids include C4-C20 hydroxycarboxylic acids such as e.g. Malic acid, tartaric acid, gluconic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid and
• Sucrose mono-, di- and tricarboxylic acid Preferred among these are citric acid and its salts.
• Suitable organic builders are also phosphonic acids, e.g.
• Hydroxyalkylphosphonklaren aminophosphonic acids and the salts thereof. These include e.g. Phosphonobutane tricarboxylic acid, aminotris methylene phosphonic acid, ethylenediaminetetraethylene phosphonic acid,
• Suitable organic builders are also aminopolycarboxylic acids, such as
• NTA Nitrilotriacetic acid
• ⁇ -ADA ⁇ -alaninediacetic acid
• EDTA ethylenediaminetetraacetic acid
• Diethylenetriaminepentaacetic acid 1,3-propylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, N- (alkyl) ethylenediaminetriacetic acid, N- (hydroxyalkyl) ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cyclohexylene-1,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediamine disuccinic acid, serinediacetic acid, isoserinediacetic acid, Asparagine diacetic acid, L-glutamine diacetic acid, methyl glycine diacetic acid (MGDA) and the salts of
• aminopolycarboxylic acids Preferred among these are L-glutamic diacetic acid, methylglycine diacetic acid and their salts.
• Suitable organic builders are also polymeric compounds containing carboxylic acid groups, such as acrylic acid homopolymers. These preferably have a number average molecular weight in the range from 800 to 70,000 g / mol, particularly preferably from 900 to 50,000 g / mol, in particular from 1,000 to 20,000 g / mol, especially from 1,000 to 10,000 g / mol.
• the term 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.
• Suitable polymeric carboxylic acid group-containing compounds are also provided.
• Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated C 4 -C 8 -dicarboxylic acids, comonomers being monoethylenically unsaturated monomers from group (i) given below in amounts of up to 95% by weight, from group (ii) in amounts of up to 60% by weight and from group (iii) in amounts of up to 20% by weight.
• suitable unsaturated C 4 -C 8 -dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid.
• the group (i) comprises monoethylenically unsaturated Cs-Cs monocarboxylic acids such as acrylic acid,
• Methacrylic acid, crotonic acid and vinylacetic acid Preferably, from group (i), acrylic acid and methacrylic acid are used.
• Group (ii) comprises monoethylenically unsaturated C 2 -C 22 -olefins, vinyl-alkyl ethers having C 1 -C 8 -alkyl groups, styrene, vinyl esters of Ci-Cs-carboxylic acids, (meth) acrylamide and vinylpyrrolidone. From group (ii), preference is given to using C 2 -C 6 -olefins, vinylalkyl ethers having C 1 -C 4 -alkyl groups, vinyl acetate and vinyl propionate. If the polymers of group (ii) vinyl ester
• Group (iii) comprises (meth) acrylic esters of C 1 -C 8 -alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C 8 -amines, N-vinylformamide and N-vinylimidazole.
• Suitable polymeric carboxylic acid group-containing compounds are also provided.
• Homopolymers of monoethylenically unsaturated Cs-Cs monocarboxylic acids e.g. Acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, especially acrylic acid and methacrylic acid, copolymers of dicarboxylic acids, e.g.
• Suitable polymeric compounds containing carboxylic acid groups are furthermore
• Suitable weak ethylenically unsaturated carboxylic acids are, in particular, C 3 -C 6 monocarboxylic acids, such as acrylic acid and methacrylic acid.
• Suitable ethylenically unsaturated sulfonic acids are 2-acetylamidomethyl-1-propanesulfonic acid, 2-methacrylic acid amido-2-methyl-1-propanesulfonic acid, 2-methacrylamindo-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2- propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and salts of these acids.
• the copolymers can furthermore contain 0 to 30% by weight of ethylenically unsaturated C
• Monomers copolymerizable with the aforementioned monomers copolymerized is, for example, C1-C4 Alkyl esters of (meth) acrylic acid, C 1 -C 4 -hydroxyalkyl esters of (meth) acrylic acid, acrylamide, alkyl-substituted acrylamide, ⁇ , ⁇ -dialkyl-substituted acrylamide, vinylphosphonic acid, vinyl acetate, allyl alcohols, sulfonated allyl alcohols, styrene and other vinylaromatics, acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole or N-vinylpyridine.
• the weight-average molecular weight of these copolymers is in the range of 3,000 to 50,000 daltons.
• copolymers having about 77% by weight of at least one ethylenically unsaturated C 3 -C 6 monocarboxylic acid and about 23% by weight of at least one ethylenically unsaturated sulfonic acid.
• Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446, DE-A 4415623 and DE-A 4313909 are also suitable. Suitable unsaturated carboxylic acids are here
• acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and mixtures of acrylic acid and maleic acid grafted in amounts of 40 to 95 wt .-%, based on the component to be grafted.
• further monoethylenically unsaturated monomers may be present in copolymerized form.
• Monomers are the above-mentioned monomers of groups (ii) and (iii).
• Grafting base are degraded polysaccharides such as e.g. acidic or enzymatically degraded starches, inuline or cellulose, protein hydrolysates and reduced
• polyethylene glycols polyethylene glycols
• Ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyhydric Ci-C 2 2 alcohols See US-A-5756456).
• polyglyoxylic acids as described, for example, in EP-B-001004, US Pat. No. 5,399,286, DE-A-4106355 and EP-A-656914.
• the end groups of the polyglyoxylic acids can have different structures.
• polyamidocarboxylic acids and modified polyamidocarboxylic acids are suitable; these are known, for example, from EP-A-454126, EP-B-51 1037, WO-A94 / 01486 and EP-A-581452.
• polyaspartic acids or cocondensates of aspartic acid with other amino acids, C4-C25 mono- or dicarboxylic acids and / or C4-C25 mono- or - diamines can be used as polymeric compounds containing carboxylic acid groups become. Particular preference is given to using polyaspartic acids prepared in phosphorus-containing acids and modified with C 6 -C 22 -mono- or -dicarboxylic acids or with C 6 -C 22 -mono- or -diamines. Among the polymeric carboxylic acid group-containing compounds, polyacrylic acids are also preferred in partially or completely neutralized form.
• organic builders are iminodisuccinic acid,
• Oxydisuccinic acid aminopolycarboxylates, alkylpolyaminocarboxylates,
• Aminopolyalkylene phosphonates polyglutamates, hydrophobically modified citric acid, e.g. Agaricinic acid, poly (alpha) -hydroxyacrylic acid, N-acylethylenediamine triacetates such as lauroylethylenediamine triacetate, and alkylamides of ethylenediaminetetraacetic acid such as EDTA tallowamide.
• oxidized starches can also be used as organic builders.
• a mixture of different builders is used as component b).
• the mixture of various builders contains at least two of the following: at least one carbonate (e.g., sodium carbonate), at least one silicate (e.g., sodium disilicate), at least one polymeric carboxylic acid group-containing
• Compound or at least one polymeric carboxylic acid group-containing compound in which the carboxylic acid groups are partially or completely neutralized eg polyacrylic acid
• at least one (poly) hydroxycarboxylic acid or a salt thereof eg citric acid or a citrate
• at least one aminopolycarboxylic acid or a salt thereof eg methylglycinediacetic acid or a salt thereof, eg a sodium salt thereof
• at least one phosphonic acid eg 1-hydroxyethane 1- (1,1-diphosphonic acid
• the mixture particularly preferably contains at least one carbonate, at least one silicate and at least one polymeric optionally (partially) neutralized carboxylic acid group-containing compound and optionally at least one of the following constituents: at least one
• the mixture contains at least one carbonate, at least one silicate, at least one polymeric optionally (partially) neutralized carboxylic acid group-containing compound, at least one (poly) hydroxycarboxylic acid or a salt thereof and at least one phosphonic acid, and optionally at least one phosphate.
• the ingredients are preferably contained in the following amounts:
• carboxylic acid group-containing compound 5 to 20% by weight
• the percentages by weight are based on the total weight of the builder.
• the detergents and cleaners according to the invention preferably contain at least one enzyme.
• Suitable enzymes are those commonly used as industrial enzymes. These include both enzymes with optimal activity in the neutral to alkaline pH range, as well as enzymes with optimal activity in the acidic pH range.
• the enzymes are preferably selected from aminopeptidases, amylases, arabinases, carbohydrases, carboxypeptidases, catalases, cellulases, chitinases, cutinases, cyclodextrin glycosyltransferases, deoxyribonucleases, esterases, galactanases, alpha-galactosidases, beta-galactosidases, glucanases,
• Glucoamylases alpha-glucosidases, beta-glucosidases, haloperoxidases,
• Hydrolase invertases isomerases, keratinases, laccases, lipases, mannanases, mannosidases, oxidases, pectinolytic enzymes, peptidoglutaminases,
• Peroxidases Peroxygenases, phytases, polyphenol oxidase, proteolytic enzymes, and the like.
• Enzymes ribonucleases, transglutaminases, transferases, xylanases and
• the enzymes are specifically selected from hydrolases such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannanases, others
• Hydrolases contribute to the soil dissolution and removal of protein, fat or starchy soils.
• Oxireduktasen can be used for bleaching.
• Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents.
• proteolytic enzymes may in principle be of animal, vegetable or microbial origin. Preference is given to proteolytic enzymes of microbial origin. These include chemically or genetically modified mutants. Preferred proteases are serine proteases, metalloproteases or trypsin-like proteases. Preferably, an alkaline microbial protease is used.
• alkaline proteases are subtilisins, especially those derived from Bacillus, e.g. Subtilisin Novo, Subtilisin Carlsberg, Subtilisin 309, Subtilisin 147 and Subtilisin 168 (described in WO 89/06279).
• trypsin-like proteases are trypsin (e.g., from pig or bovine) and those described e.g. in WO 89/06270 Fusarium protease described.
• Preferred commercially available proteases include those below
• compositions according to the invention preferably comprise at least one protease in an amount of 0.00001% by weight to 30% by weight of enzyme protein, more preferably of 0.0001% by weight to 15% by weight of enzyme protein, in particular 0.001% by weight to 10% by weight % Of enzyme protein, more particularly 0.001% to 5% by weight of enzyme protein, based on the total weight of the invention
• Suitable lipases can in principle be derived from bacteria or fungi. These include chemically or genetically modified mutants.
• Suitable lipases are Humicola lanuginosa lipase, e.g. described in EP 258 068 and EP 305 216, Rhizomucor miehei lipase, such as e.g. described in EP 238 023, Candida lipase, such as C. antarctica lipase, e.g. the C. antarctica lipases A or B as described in EP 214 761, Pseudomonas lipase, such as P. alcaligenes and P. pseudoalcaligenes lipase, such as e.g. described in EP 218 272, P. cepacia lipase, e.g. described in EP 331 376, P.
• Humicola lanuginosa lipase e.g. described in EP 258 068 and EP 305 216
• Rhizomucor miehei lipase such as e.g. described in EP 238 023
• lipase such as e.g. in GB 1, 372,034, P. fluorescens lipase, Bacillus lipase, e.g. a B. subtilis lipase (Dartois et al., (1993), Biochemica et Biophysica acta 1 131, 253-260), B. stearo-thermophilus lipase (JP 64/744992) and B. pumilus lipase (WO 91/16422) ,
• cloned lipases including Penicillium camembertii lipase described by Yamaguchi et al., (1991), Gene 103, 61-67), Geotricum candidum lipase (Schimada, Y. et al., (1989) J. Biochem , 106, 383-388), and various Rhizopus lipases, such as R. delemar lipase (Hass, M.J. et al., (1991), Gene 109, 17-1 13), R. niveus lipase (Kugimiya et al., (1992) Biosci Biotech.
• lipolytic enzymes can be used, such as
• Cutinases e.g. a cutinase derived from Pseudomonas mendocina, e.g. described in WO 88/09367, or a cutinase derived from Fusarium solani pisi (as described for example in WO 90/09446).
• Especially suitable lipases are MI Lipase TM, Luma Fast TM and Lipo-max TM
• compositions according to the invention preferably comprise at least one lipase in an amount of 0.00001% by weight to 30% by weight of enzyme protein, more preferably of 0.0001% by weight to 15% by weight of enzyme protein, in particular 0.001% by weight to 10% by weight % Of enzyme protein, more particularly 0.001% to 5% by weight of enzyme protein, based on the total weight of the invention
• ⁇ and / or ⁇ -amylases are suitable.
• Suitable amylases can in principle be derived from bacteria or fungi. These include chemically or genetically modified mutants.
• amylases examples include ⁇ -amylases obtained from a specific strain of B. amyloliquefaciens or B. licheniformis, described in detail in GB 1, 296,839.
• Other suitable amylases include backbones, known as SP707 from Bacillus sp, AP1378, BSG B. stearothermophilus alpha-amylase, SP690, SP722, and AA560 from Bacillus sp.
• Suitable commercially available amylases include Stainzyme TM, Stainzyme Plus TM, Natalase TM, Duramyl TM, Termamyl TM, Fungamyl TM and BAN TM (available from Novozymes AS), and Rapidase TM, PREFERENCE TM S, EXCELLENZ TM S, and Maxamyl P TM (available from Genencor).
• compositions according to the invention preferably comprise at least one amylase in an amount of 0.00001% by weight to 30% by weight of enzyme protein, more preferably of 0.0001% by weight to 15% by weight of enzyme protein, in particular 0.001% by weight to 10% by weight % Of enzyme protein, more particularly 0.001% to 5% by weight of enzyme protein, based on the total weight of the invention
• Cellulases Basically all cellulases are suitable. Suitable cellulases can
• Suitable cellulases are described in US 4,435,307. These are fungal cellulases produced from Humicola insolens. Especially suitable
• Cellulases with color care properties are described in EP 0 495 257.
• Suitable commercially available cellulases include Celluzyme TM made from a strain of Humicola insolens, Carezyme TM, Celluclean TM, Endolase TM, Whitezyme TM (Novozymes A S), REVITALENZ TM (Dupont), Biotouch C TM (AB
• compositions of the invention preferably contain at least a cellulase in an amount of 0.00001% to 30% by weight of enzyme protein, more preferably from 0.0001% to 15% by weight of enzyme protein, especially 0.001% to 10% by weight of enzyme protein, more particularly 0.001 wt .-% to 5 wt .-% enzyme protein, based on the total weight of the inventive
• Suitable peroxidases / oxidases can in principle be derived from plants, bacteria or fungi. These include chemically or genetically modified mutants.
• Peroxidase enzymes are used in combination with hydrogen peroxide or a
• Hydrogen peroxide source e.g., a percarbonate, perborate, or persulfate.
• Oxidase enzymes are used in combination with oxygen. Both types of enzymes are used for "solution bleaching" to avoid dye transfer from one dyed fabric to another when washed together in a liquor. The use can preferably be carried out with effect enhancers, e.g. in WO 94/12621 and WO 95/01426.
• compositions according to the invention preferably comprise at least one peroxidase or oxidase in an amount of 0.00001% by weight to 30% by weight of enzyme protein, more preferably of 0.0001% by weight to 15% by weight of enzyme protein, in particular 0.001% by weight 10% by weight of enzyme protein, more particularly 0.001% by weight to 5% by weight of enzyme protein, based on the total weight of the polymer composition according to the invention.
• lyases are suitable. Suitable lyases can basically be derived from bacteria or fungi. These include chemically or genetically modified mutants.
• Suitable lyases are pectate lyases or pectin lyases.
• Suitable commercially available lyases include XPect TM (Novozymes A / S) and PREFERENCE TM F
• compositions according to the invention preferably contain at least one lyase in an amount of 0.00001% by weight to 30% by weight of enzyme protein, more preferably of 0.0001% by weight to 15% by weight of enzyme protein, in particular 0.001 wt .-% to 10 wt .-% enzyme protein, more particularly 0.001 wt .-% to 5 wt .-% enzyme protein, based on the total weight of the inventive
• compositions of the invention may contain other enzymes, which are summarized under the term hemicellulases. These include, for example
• compositions according to the invention preferably contain at least one hemicellulase in an amount of 0.00001% by weight to 30% by weight of enzyme protein, more preferably of 0.0001% by weight to 15% by weight of enzyme protein, in particular 0.001% by weight to 10% by weight % Of enzyme protein, more particularly 0.001% to 5% by weight of enzyme protein, based on the total weight of the invention
• the washing and cleaning agent according to the invention preferably comprises at least one enzyme which is selected from proteases, amylases, mannanases, cellulases, lipases, pectinylases and mixtures thereof.
• the washing and cleaning agent according to the invention preferably comprises at least one protease and / or amylase.
• the washing and cleaning agent according to the invention preferably contains an enzyme mixture.
• enzyme mixtures which contain or consist of the following enzymes are preferred:
• Amylase, cellulase and lipase or lipolytic enzymes
• proteease protease
• lipase or lipolytic enzymes
• cellulase The enzymes may be adsorbed to carriers to protect them against premature
• the washing and cleaning agent according to the invention may also contain enzyme stabilizers.
• enzyme stabilizers include, for example, calcium propionate, sodium formate, Boric acids, boronic acids and their salts, such as 4-formylphenylboronic acid, peptides and peptide derivatives, such as peptide aldehydes, polyols, such as 1, 2-propanediol, and mixtures thereof.
• the bleaching agents d) are preferably bleaching systems which, in addition to bleaching agents, optionally also contain bleach activators, bleach catalysts and / or bleach stabilizers.
• Suitable bleaching agents are, for example, percarboxylic acids, e.g. Diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or terephthalic acid, salts of percarboxylic acids, e.g. Sodium percarbonate, adducts of hydrogen peroxide with inorganic salts, e.g. Sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of hydrogen peroxide to organic compounds, e.g.
• percarboxylic acids e.g. Diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or terephthalic acid
• salts of percarboxylic acids e.g. Sodium percarbonate
• adducts of hydrogen peroxide with inorganic salts e.g
• Suitable bleach activators are, for example, polyacylated sugars, e.g.
• Alkaline earth metal salts e.g. Sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate;
• ⁇ -diacylated and ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacylated amines e.g. ⁇ , ⁇ , ⁇ ', ⁇ '- tetraacetylmethylenediamine and ethylenediamine (TAED), ⁇ , ⁇ -diacetylaniline, N, N-diacetyl-ptoluidin or 1, 3-diacylated hydantoins such as 1, 3-diacetyl-5,5-dimethylhydantoin ; N-alkyl-N-sulfonylcarbonamides, e.g.
• N-methyl-N-mesylacetamide or N-methylN-mesylbenzamide N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. monoacetylmaleic; ⁇ , ⁇ , ⁇ -trisubstituted
• Hydroxylamines e.g. 0-benzoyl-N, N-succinylhydroxylamine, O-acetyl- ⁇ , ⁇ -succinylhydroxylamine or ⁇ , ⁇ , ⁇ -triacetylhydroxylamine; ⁇ , ⁇ '-diacylsulfurylamide, e.g.
• Enol esters such as isopropenyl acetate; 1, 3-Diacyl-4,5-diacyloxy-imidazolines, eg 1, 3 Diacetyl-4,5-diacetoxy; Tetraacetylglycoluril and tetrapropionylglycoluril; diacylated 2,5-diketopiperazines, eg 1, 4-diacetyl-2,5-diketopiperazine;
• ammonium substituted nitriles e.g. N-Methylmorpholiniumacetonitrilmethylsulfat
• Acylation products of propylene diurea and 2,2-dimethyl-propylene diurea e.g. Tetraacetylpropylendihamstoff
• ⁇ -acyloxypolyacylmalonamides e.g. ⁇ -acetoxy- ⁇ , ⁇ '-diacetylmalonamide
• Diacyl-dioxohexahydro-1,3,5-triazines e.g.
• a bleaching system of bleaches and bleach activators may optionally also contain bleach catalysts.
• Suitable bleach catalysts are, for example, quaternized imines and sulfonimines, which are described, for example, in US Pat. No. 5,360,569 and EP-A 453,003. Particularly effective bleaching catalysts are
• Manganese complexes which are described for example in WO-A 94/21777. Such compounds, in the case of their use in detergents and cleaners, at most in amounts of up to 1, 5 wt .-%, in particular up to 0.5 wt .-%, in the case of very active manganese complexes in amounts up to 0.1 wt. -%, incorporated.
• bleaching system comprising bleaches, bleach activators and optionally bleach catalysts
• the use of systems with enzymatic peroxide release or of photoactivated bleach systems is also possible for the detergents and cleaners according to the invention.
• compositions used according to the invention are already suitable for modifying the rheological properties in the sense of thickening.
• At least one thickener f In order to impart the desired viscosity to the formulation according to the invention, it is additionally possible to use at least one thickener f).
• any known thickeners are suitable.
• Suitable thickeners may be both of natural origin and of synthetic nature.
• thickeners of natural origin are xanthan, locust bean gum, guar gum, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches such as hydroxyethyl starch, starch phosphate esters or starch acetates, dextrins, pectins and cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, Hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose and the like.
• Thickeners of natural origin are also inorganic thickeners, such as
• Polysilicic acids and clay minerals e.g. Phyllosilicates, as well as the silicates mentioned in the builders.
• synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partially) crosslinked homopolymers of acrylic acid, for example with an allyl ether of sucrose or pentaerythritol or homopolymers crosslinked with propylene
• Acrylic acid e.g. the Carbopol® grades from BF Goodridge (e.g., Carbopol® 676, 940, 941, 934 and the like) or the 3gel Sigma Polygel® grades (e.g., Polygel® DA), copolymers of ethylenically unsaturated mono- or dicarboxylic acids,
• terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl or ethyl acrylate and a (meth) acrylate derived from long chain ethoxylated alcohols such as the Acusol® brands from Rohm & Haas (eg Acusol® 820 or 1206A), copolymers of two or more monomers selected from acrylic acid, methacrylic acid and their Ci-C4-alkyl esters, eg Copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of
• Butyl acrylate and methyl methacrylate e.g. the Aculyn® and Acusol® brands from Rohm & Haas (eg Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular weight acrylic acid copolymers, for example with an allyl ether of sucrose or pentaerythritol cross-linked copolymers of C 30 -alkyl acrylates with one or more comonomers selected from acrylic acid,
• Methacrylic acid and their C 1 -C 4 -alkyl esters eg Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas.
• Maleic acid polymers with ethoxylated long-chain alcohols e.g. the Surfonic L series from Texaco Chemical Co. or Gantrez AN-1 19 from ISP; Polyethylene glycols, polyamides, polyimines and polycarboxylic acids.
• Preferred thickeners are xanthans and the above polyacrylic and
• Suitable additional surfactants g) other than component a) may be cationic, anionic, zwitterionic or nonionic. Suitable surfactants are those previously mentioned in the surfactant systems.
• Suitable organic solvents g) are selected from monohydric or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, they are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether,
• foam inhibitors or defoamers of component g) are soaps, paraffins or silicone oils, which may optionally be applied to support materials.
• Suitable bases of component g) are alkali metal hydroxides
• Alkaline earth metal bicarbonates ammonium bicarbonate and mixtures thereof. Preference is given to using Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate.
• the gel-like detergents or cleaning agents may contain further ingredients g) which further improve the performance and / or aesthetic properties of the gel-like detergent or cleaning agent.
• preferred agents comprise at least one further additive which is selected from electrolytes, pH adjusters, perfume carriers, fluorescers, hydrotropes, antiredeposition agents, optical brighteners, grayness inhibitors, inlet preventer,
• Anti-crease agents color transfer inhibitors, antimicrobial agents, antioxidants, corrosion inhibitors, antistatic agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.
• they can be dyed with suitable dyes.
• Preferred dyestuffs the choice of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity
• the polymer compositions according to the invention are particularly suitable for industrial and institutional cleaners (I & I cleaners).
• Industrial and institutional cleaners are typically detergents, all-purpose cleaners, foam cleaners,
• Gel cleaner for professional and usually automated cleaning processes, eg. As in large laundries, dairies, breweries, the food or beverage industry, the pharmaceutical industry or the galenics or sanitary cleaners.
• the cleaners can be strongly basic with a high electrolyte content and, if necessary, contain bleaches (such as hydrogen peroxide, sodium hypochlorite) or disinfectants as well as defoamers (eg in bottle cleaning).
• bleaches such as hydrogen peroxide, sodium hypochlorite
• disinfectants such as sodium hypochlorite
• defoamers eg in bottle cleaning
• the common enzymes mentioned above can also be contained in the industrial and institutional cleaners.
• cleaning baths stationary or moving
• spray cleaning ultrasonic, steam jet and
• High pressure cleaning mentioned optionally in combination with mechanical cleaning, eg. B. by rotating brushes.
• the mentioned formulations for cleaning include those for industry, transport, commerce and commerce and the private sector. Specific examples are: professional laundries, professional cleaning, metalworking industry, metal and metal working industry, automotive and automotive supply industry, electrical industry, electronics industry, photographic industry and industry, leisure industry and industry,
• Breweries retail outlets, such as bakeries, butchers and supermarkets; Hospitals, nursing homes, retirement homes, administration buildings, factory buildings, doctors'offices; motor vehicles (cars and trucks), buses, road tankers (inside and outside), rail tank cars, passenger and freight cars, and aircraft and ships; building façades, tiled or painted walls, wooden floors (parquet, planks) with screed or textile or plastic coverings, signaling and lighting equipment, furniture, railings, shields, signs, warning beacons, perimeter piles, kettles, dishes,
• the polymer composition according to the invention is furthermore advantageously suitable for the production of cleaners for the sanitary sector, which contain at least one organic acid.
• Acid sanitary cleaners are particularly suitable for toilet cleaning, for cleaning of washbasins, shower cabins, shower trays and
• the gel-form polymer composition according to the invention has a high compatibility with acidic surfactant compositions and is particularly advantageously suitable for use in acidic sanitary cleaners.
• a preferred acidic sanitary cleaner preferably comprises the following constituents: at least one gel-form polymer composition according to the invention, at least one organic acid, optionally water, optionally at least one thickener, and optionally at least one further additive,
• the acidic sanitary cleaner is preferably liquid or especially gel-like.
• Suitable organic acids are formic acid, acetic acid, citric acid or methanesulfonic acid. Particularly preferred are acetic acid or citric acid.
• the cleaner according to the invention preferably contains the organic acid in an amount from 1 to 40 wt .-%, in particular from 5 to 15 wt .-%, based on the
• the cleaner according to the invention preferably contains at least one surfactant in an amount of 0.5 to 50 wt .-%, in particular from 1 to 15 wt .-%, based on the total weight of the cleaner.
• Suitable thickeners are those mentioned above as component f), to which reference is made in its entirety.
• Suitable additives are those mentioned above as component g), to which reference is hereby made in their entirety. These include especially stabilizers, dyes and fragrances.
• the polymer composition of the present invention is suitable for the preparation of adhesive compositions which are adhesive, i. they are capable of bonding substrates without appreciably altering the substrates themselves, the cohesiveness of the bonded substrates being determined by adhesive forces (adhesive-to-substrate attractive forces) and cohesion (adhesive internal cohesiveness).
• Polymer compositions for preparing an adhesive composition are obtained by free radical polymerization of a monomer composition M) containing at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid A) as defined above.
• Preferred monomers A) are selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
• the acid groups may be present in protonated form or in the form of their salts.
• the monomer composition contains 0.5 to 15 wt .-%, particularly preferably 1 to
• acrylic acid e.g. (Meth) acrylic acid alkyl esters having a C 1 -C 10 -alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and ethylhexyl acrylate.
• (Meth) acrylic acid alkyl esters having a C 1 -C 10 -alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and ethylhexyl acrylate.
• mixtures of (meth) acrylic acid alkyl esters are also suitable.
• Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are e.g. Vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and vinyl acetate.
• Vinylaromatic compounds are vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
• nitriles are acrylonitrile and methacrylonitrile.
• the vinyl halides are with Chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
• Vinyl ethers include, for example, vinyl methyl ether or vinyl isobutyl ether. Preferred are vinyl ethers of alcohols containing 1 to 4 carbon atoms. Suitable hydrocarbons having 4 to 8 C atoms and two olefinic double bonds are, for example, butadiene, isoprene and chloroprene. Further
• Monomers are e.g. also hydroxyl-containing monomers, in particular Ci- Cio-hydroxyalkyl (meth) acrylates or (meth) acrylamide. Phenyloxyethyl glycol mono (meth) acrylate, glycidyl (meth) acrylate, aminoalkyl (meth) acrylates, e.g. Called 2-aminoethyl (meth) acrylate. Alkyl groups preferably have from 1 to 20 carbon atoms. Other monomers which may also be mentioned are crosslinking monomers.
• polyether component PE are the aforementioned polyetherols and especially polyethylene glycols.
• the type and amount of the monomers or the ratios of different comonomers to one another are such that the glass transition temperature is in the aforementioned range.
• the adhesive compositions of the invention may comprise at least one
• the solvent or dispersant of the adhesive composition can consist of only water, as well as of mixtures of water and liquids that can be mixed with it, such as methanol or ethanol. Preferably, only water is used.
• the pH of the adhesive composition is preferably adjusted to pH greater than 4.5, in particular to a pH of between 5 and 9.5.
• the adhesive compositions may be solely from the gel
• the adhesive composition may also contain other additives, e.g. Fillers, dyes, leveling agents,
• Thickeners preferably associative thickeners
• defoamers preferably associative thickeners
• pigments preferably associative thickeners
• wetting agents preferably associative thickeners
• tackifiers tackifying resins
• the adhesives wetting aids, z. Fatty alcohol ethoxylates,
• the amount of additives is generally 0.05 to 5 parts by weight, in particular 0.1 to 3 parts by weight per 100 parts by weight of polymer composition.
• the adhesive composition is substantially free of plasticizers.
• Plasticizers are additives that reduce the adhesive power.
• Substantially free of plasticizers means that the compositions are less as 1 wt .-%, preferably less than 0.5 wt.%, Based on the total composition of plasticizers, particularly preferably no plasticizer.
• the adhesive composition of the invention is preferably a pressure-sensitive adhesive.
• a pressure-sensitive adhesive is a viscoelastic adhesive whose ligated film contributes
• the adhesive composition according to the invention can be used for bonding at least two substrates or for producing self-adhesive articles.
• the substrates or self-adhesive articles to be joined are at least partially coated with the pressure-sensitive adhesive.
• the self-adhesive articles are removable after the bond.
• the self-adhesive articles may be e.g. to act on transparencies, tapes or labels.
• Suitable carrier materials are e.g.
• Bands may be unilaterally or bilaterally coated bands of the above substances.
• Self-adhesive labels according to the invention can be labels made of paper or a thermoplastic film.
• thermoplastic film comes e.g. Films of polyolefins (e.g., polyethylene, polypropylene), polyolefin copolymers, films of polyesters (e.g.
• thermoplastic polymer films are preferably corona treated.
• the labels are coated on one side with adhesive.
• Preferred substrates for the self-adhesive articles are paper and polymer films.
• Preferred self-adhesive articles are paper labels.
• the articles are at least partially coated on at least one surface with an adhesive composition according to the invention.
• the adhesive can be applied to the articles by conventional methods such as knife coating or brushing. The amount applied is preferably 0.1 to 20 g, more preferably 2 to 15 g
• the substrates which are joined together or to which the self-adhesive articles can be advantageously applied can be, for example, metal, wood, glass, paper or plastic.
• Self-adhesive articles are particularly suitable for bonding
• the self-adhesive articles of particular embodiments can be manually peeled off the articles without leaving an adhesive residue on the article.
• the adhesion to the objects is good, but the films, tapes and labels can be easily removed.
• the polymer compositions according to the invention are preferably suitable for formulation of cosmetic and pharmaceutical products, especially of aqueous cosmetic and pharmaceutical products.
• the invention further provides a cosmetic or pharmaceutical composition
• a cosmetic or pharmaceutical composition comprising a) at least one gel-like polymer composition according to the invention as defined above, b) at least one cosmetically or pharmaceutically acceptable active ingredient, and c) optionally at least one of the components a) and b)
• component c) comprises at least one cosmetically or
• the carrier component c) is selected from
• water-miscible organic solvents preferably C 2 -C 4 alkanols, in particular ethanol,
• cosmetically acceptable oil or fat components c) are described in Karl-Heinz Schmann, Fundamentals and formulations of cosmetics, 2nd edition, Verlag Wegig, Heidelberg, pp. 319-355, to which reference is hereby made.
• the cosmetic agents according to the invention may be skin-cosmetic, hair-cosmetic, dermatological, hygienic or pharmaceutical agents.
• the polymer composition according to the invention is especially suitable for the formulation of gels.
• the agents according to the invention are preferably in the form of a gel, foam, spray, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.
• the polymer composition according to the invention is especially suitable for the formulation of gels
• the cosmetic compositions according to the invention may additionally contain cosmetically and / or dermatologically active active substances and effect substances as well as auxiliaries.
• the cosmetic compositions of the invention contain at least one
• various constituents which are preferably selected from cosmetically active ingredients, emulsifiers, surfactants, preservatives, perfume oils, additional thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaches, gelling agents, conditioners, tinting agents, tanning agents,
• Dyes pigments, bodying agents, moisturizers, restoats, collagen, protein hydrolysates, lipids, antioxidants, defoamers, antistatic agents, emollients and emollients.
• the cosmetic agents may contain at least one conventional thickener.
• these include, for example, polysaccharides and organic sheet minerals such as xanthan gum ® (Kelzan ® from. Kelco), Rhodopol ® 23 (Rhone Poulenc) or Veegum ® (from RT Vanderbilt) or Attaclay ® (Engelhardt).
• Suitable thickening agents are also organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein) and inorganic thickening agents
• polysilicic acids clay mites such as montmorillonites, zeolites, silicas.
• Other thickeners are polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, e.g. B. propoxylated guar, and their
• polysaccharide thickeners are, for example, starches
• thickeners it is also possible to use phyllosilicates. These include, for example, available under the trade name Laponite ® magnesium or sodium magnesium phyllosilicates from Solvay Alkali and the magnesium silicates from Süd-Chemie.
• Suitable cosmetically and / or dermatologically active agents are, for. Skin and hair pigmentation agents, tanning agents, bleaching agents, keratin-hardening substances, antimicrobial agents, light filter agents, repellent agents, hyperemic substances, keratolytic and keratoplastic substances,
• Antidandruff agents antiphlogistics, keratinizing substances, antioxidants or radical scavengers active ingredients, skin moisturizing or moisturizing substances, moisturizing agents, deodorizing agents, sebostatic agents, plant extracts, antierythimatos or antiallergically active agents and mixtures thereof.
• Artificial skin tanning agents that are suitable for tanning the skin without natural or artificial irradiation with UV rays, z. B. dihydroxyacetone, alloxan and walnut shell extract. Suitable keratin-hardening substances are generally active ingredients, as used in antiperspirants, such as. B.
• Antimicrobial agents are used to destroy microorganisms or inhibit their growth and thus serve both as a preservative and as a deodorizing substance, which reduces the formation or intensity of body odor. These include z.
• preservatives such as p-hydroxybenzoic acid, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc.
• deodorizing substances are, for. Zinc ricinoleate, triclosan, undecylenic acid alkylolamides, triethyl citrate, chlorhexidine, etc.
• Suitable light-filtering agents are substances that absorb UV rays in the UV-B and / or UV-A range. Suitable UV filters are those mentioned above. Also suitable are p-aminobenzoic acid esters, cinnamic acid esters, benzophenones, camphor derivatives and UV-radiation-stopping pigments, such as titanium dioxide, talc and zinc oxide. Suitable repellent agents are compounds capable of preventing or repelling certain animals, particularly insects, from humans. This includes z. B. 2-ethyl-1, 3-hexanediol, N, N-diethyl-m-toluamide, etc.
• Suitable hyperemic substances which stimulate the circulation of the skin are, for. Essential oils, such as mountain pine, lavender, rosemary,
• Suitable keratolytic and keratoplastic substances are, for. Salicylic acid, Calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc. Suitable
• Antidandruff agents are for. Sulfur,
• Zinkpyrithion Zinkpyrithion, Aluminiumpyrithion, etc. Suitable anti-inflammatory drugs that counteract skin irritation, z. Allantoin, bisabolol, dragosantol, chamomile extract,
• the cosmetic agents according to the invention may contain as cosmetic active ingredient (as well as optionally as adjuvant) at least one cosmetically or pharmaceutically acceptable polymer.
• cosmetically or pharmaceutically acceptable polymer include, in general, anionic, cationic, amphoteric and neutral polymers.
• anionic polymers are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes, eg. B. Luviset PUR® Fa. BASF, and polyureas.
• Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (eg Luvimer® 100P), copolymers of ethyl acrylate and methacrylic acid (eg Luvimer® MAE), copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold® 8, strong), copolymers of vinyl acetate, crotonic acid and optionally further vinyl esters (eg Luviset® grades),
• Maleic anhydride copolymers optionally reacted with alcohol, anionic polysiloxanes, e.g. Carboxy-functional, t-butyl acrylate, methacrylic acid (e.g., Luviskol® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, e.g. B. C4-C3o-alkyl esters of (meth) acrylic acid, C4-C3o-alkyl vinyl ester, C4-C30-alkyl vinyl ether and hyaluronic acid.
• anionic polysiloxanes e.g. Carboxy-functional, t-butyl acrylate
• methacrylic acid e.g., Luviskol® VBM
• hydrophobic monomers e.g. B.
• anionic polymer is furthermore the methyl methacrylate / methacrylic acid / acrylic acid / urethane acrylate copolymer available under the name Luviset® Shape (INCI name: Polyacrylate-22).
• anionic polymers are furthermore vinyl acetate / crotonic acid copolymers, for example those sold under the names Resyn® (National Starch) and Gafset® (GAF), and vinylpyrrolidone / vinyl acrylate copolymers, available, for example, under the trademark Luviflex® (BASF) , Other suitable
• Polymers are the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF) and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyesters. Furthermore suitable
• Stepan be marketed under the names Stepanhold-Extra and -R1 and the Carboset® brands of the company. BF Goodrich.
• Suitable cationic polymers are, for. As cationic polymers called Polyquaternium INCI, z. B. Copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviset Clear®, Luviquat Supreme®, Luviquat® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold);
• cationic cellulose derivatives Polyquaternium-4 and -10
• acrylamidocopolymers Polyquaternium-7)
• chitosan Suitable cationic (quaternized) polymers are also Merquat® (dimethyldiallylammonium chloride-based polymer), Gafquat® (quaternary polymers formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxyethylcellulose with cationic groups), and plant-based cationic polymers, z. B.
• Guarpolymere such as the Jaguar® brands of the company Rhodia.
• Especially suitable polymers are neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate,
• Polysiloxanes polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, polyaspartic acid salts and derivatives.
• polyethyleneimines and their salts polyethyleneimines and their salts
• polyvinylamines and their salts cellulose derivatives
• polyaspartic acid salts and derivatives include, for example, Luviflex® Swing (partially saponified copolymer of polyvinyl acetate and polyethylene glycol, BASF).
• Suitable polymers are also nonionic, water-soluble or
• water dispersible polymers or oligomers such as polyvinyl caprolactam, e.g. B.
• Luviskol® Plus BASF SE
• polyvinylpyrrolidone and their copolymers in particular with vinyl esters, such as vinyl acetate, for. Luviskol® VA 37, VA 55, VA 64, VA 73 (BASF SE); Polyamides, z. B. based on itaconic acid and aliphatic diamines, as z. B. in DE-A-43 33 238 are described.
• Suitable polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer® (National Starch) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate 2-hydroxypropyl methacrylate copolymers and zwitterionic polymers, as described for example in the German
• Patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 are disclosed.
• zwitterionic polymers are Methacroylethylbetain / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL), and copolymers
• Suitable polymers are also nonionic, siloxane-containing, water-soluble
• polyether siloxanes such as Tegopren® (Fa.
• compositions of the invention contain at least one polymer which acts as a thickener.
• suitable polymeric thickeners are optionally modified polymeric natural substances (carboxymethylcellulose and other cellulose ethers,
• Polycarboxylic acids polyethers, polyimines, polyamides). These include the polyacrylic and polymethacrylic compounds, some of which have already been mentioned above, for example the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name: Carbomer).
• polyacrylic acids are u. a. available from BF Goodrich under the trade name Carbopol®, e.g. Carbopol 940
• acrylic acid copolymers which are obtainable, for example, from Rohm & Haas under the trade names Aculyn® and Acusol®, eg. The anionic non-associative polymers Aculyn 22, Aculyne 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37-3).
• associative thickeners e.g. based on modified polyurethanes (HEUR) or hydrophobically modified acrylic or methacrylic acid copolymers (HASE thickener, High Alkali Swellable Emulsion).
• the agents according to the invention are a skin cleanser.
• Preferred skin cleansers are soaps of liquid to gelatinous consistency, such as transparent soaps, luxury soaps, de-icing soaps, cream soaps, baby soaps,
• agents according to the invention to cosmetic agents for the care and protection of the skin, nail care products or preparations for decorative cosmetics.
• Suitable skin cosmetic agents are, for.
• face lotions face masks, deodorants, and other cosmetic lotions.
• Means for use in decorative cosmetics include, for example, masking pens, theatrical paints, mascara and eye shadows, lipsticks, kohl pencils, eyeliner, rouges, powders and
• the polymer compositions according to the invention can be used in nasal strips for pore cleansing, in anti-acne agents, repellents,
• Shaving preparations, depilatories, personal care products, foot care products and baby care are Shaving preparations, depilatories, personal care products, foot care products and baby care.
• the skin care compositions according to the invention are in particular W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, skin lotions and moisturizing lotions.
• Skin cosmetic and dermatological compositions based on the polymer compositions according to the invention described above show advantageous effects.
• the polymers can contribute to moisturizing and conditioning the skin and to improving the feel on the skin.
• By adding the polymers of the invention can be achieved in certain formulations, a significant improvement in skin compatibility.
• Skin cosmetic and dermatological compositions preferably comprise at least one polymer composition according to the invention in a proportion of about 0.001 to 30 wt .-%, preferably 0.01 to 20 wt .-%, most preferably 0.1 to 12 wt .-%, based on the Total weight of the agent.
• compositions of the invention in a form suitable for skin care such. B. as cream, foam, gel, pen, mousse, milk, spray (pump spray or propellant spray) or lotion can be applied.
• the skin cosmetic preparations can in addition to the inventive
• Skin cosmetics customary active ingredients and excipients, as described above, included. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaching agents, suntanning agents, collagen,
• Protein hydrolysates stabilizers, pH regulators, dyes, salts, thickeners, gel formers, bodying agents, silicones, humectants, moisturizers and other common additives.
• Preferred oil and fat components of the skin cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as. B.
• Carbon atoms, animal and vegetable oils such as.
• sunflower oil coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as.
• Excipients such as pigments
• the skin cosmetic and dermatological preparations can also conditioning substances based on
• Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
• the preparation of the cosmetic or dermatological preparations is carried out by customary methods known to the person skilled in the art.
• the cosmetic and dermatological agents are in the form of
• Emulsions especially as water-in-oil (W / O) or oil-in-water (0 / W)
• Emulsions are also possible to choose other types of formulations, for example hydrodispersions, gels, oils, oleogels, multiple emulsions, for example in the form of W / O / W or O / W / O emulsions, anhydrous ointments or ointment bases, etc.
• hydrodispersions for example hydrodispersions, gels, oils, oleogels, multiple emulsions, for example in the form of W / O / W or O / W / O emulsions, anhydrous ointments or ointment bases, etc.
• Emulsions are prepared by known methods.
• the emulsions generally contain conventional constituents, such as fatty alcohols, fatty acid esters and especially fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
• conventional constituents such as fatty alcohols, fatty acid esters and especially fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
• a suitable emulsion for.
• a skin cream, etc. generally contains an aqueous phase which is emulsified by means of a suitable emulsifier in an oil or fat phase.
• Preferred fat components which may be included in the fat phase of the emulsions are: hydrocarbon oils such as paraffin oil, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in these oils; animal or vegetable oils, such as Sweet almond oil, avocado oil, calophilum oil, lanolin and derivatives thereof, castor oil, sesame oil, olive oil, jojoba oil, karite oil, hoplostethus oil; Mineral oils whose beginning of distillation under atmospheric pressure at about 250 ° C and their
• Distillation end point at 410 ° C such.
• Vaseline oil Esters of saturated or unsaturated fatty acids, such as alkyl myristates, e.g. For example, i-propyl, butyl or cetyl myristate, hexadecyl stearate, ethyl or i-propyl palmitate, octanoic or Decanklandretriglyceride and Cetylricinoleat.
• the fat phase may also contain other oil-soluble silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
• oil-soluble silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
• waxes are used, such as. Carnauba wax,
• an emulsion of the invention may be present as O / W emulsion.
• Such an emulsion usually contains an oil phase, emulsifiers that stabilize the oil phase in the water phase, and an aqueous phase that is usually thickened.
• emulsifiers are preferably O / W emulsifiers, such as
• compositions according to the invention to a shower gel, a shampoo formulation or a bathing preparation.
• Such formulations contain at least one inventive
• Other suitable active ingredients and / or adjuvants are generally selected from lipids,
• Humectants preferably contain from 2 to 50 wt .-%, preferably 5 to 40 wt .-%, particularly preferably 8 to 30 wt .-% of surfactants, based on the
• shower gel / shampoo formulations additional thickeners, such.
• sodium chloride PEG-55, propylene glycol oleate, PEG-120-methylglucose dioleate and others, and preservatives, other active ingredients and excipients and water.
• Hair treatment agents according to the invention preferably comprise at least one polymer composition according to the invention in an amount in the range from about 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the composition.
• the hair treatment compositions according to the invention are in the form of a mousse, hair mousse, hair gel, shampoos, hair sprays, hair mousse, top fluids, leveling agent or "hot oil” treatments.
• the hair cosmetic preparations as
• Hair foams include both aerosol foams and pump foams without propellant gas. Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or
• the compounds used in the hair sprays and hair foams according to the invention are water-dispersible, they can be used in the form of aqueous microdispersions having particle diameters of usually from 1 to 350 nm, preferably from 1 to 250 nm.
• Solid contents of these preparations are usually in a range of about 0.5 to 20 wt .-%.
• these microdispersions do not require emulsifiers or surfactants for their stabilization.
• the hair cosmetic formulations according to the invention comprise a) from 0.05 to 5% by weight, preferably from 0.1 to 3% by weight, at least
• % at least one of a) to e) and g) different water-soluble or water-dispersible polymer, g) 0 to 45 wt .-%, preferably 0.05 to 25 wt .-%, further constituents, wherein the components a) to g) add to 100 wt .-%.
• alcohol all alcohols customary in cosmetics are to be understood, for.
• ethanol isopropanol, n-propanol.
• Other constituents are understood to include the additives customary in cosmetics, for example propellants, defoamers, surface-active compounds, d.
• propellants for example propellants, defoamers, surface-active compounds, d.
• H. Surfactants, emulsifiers, foaming agents and solubilizers.
• the surface-active compounds used can be anionic, cationic, amphoteric or neutral. Other common ingredients may also be z.
• Preservatives perfume oils, opacifiers, active ingredients, UV filters, care ingredients such as panthenol, collagen, vitamins, protein hydrolysates, alpha and beta hydroxycarboxylic acids, stabilizers, pH regulators, dyes,
• Viscosity regulators for gelling agents, salts, humectants, refatting agents, complexing agents and other conventional additives.
• Conditioner polymers which can be used in combination with the polymers according to the invention, if very special properties are to be set.
• Suitable conventional hair cosmetic polymers include, for example, the abovementioned cationic, anionic, neutral, nonionic and amphoteric polymers, to which reference is hereby made.
• the preparations may additionally contain conditioning substances based on silicone compounds.
• Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes,
• the polymer compositions according to the invention are particularly suitable as thickeners in hairstyling preparations, in particular hair foams and hair gels.
• hair foams and hair gels As emulsifiers, all commonly used in hair foams
• Emulsifiers are used. Suitable emulsifiers may be nonionic, cationic or anionic or amphoteric.
• the polymer compositions according to the invention are also suitable for styling gels.
• additional gelling agents it is possible to use all gel formers customary in cosmetics. For this purpose, reference is made to the aforementioned conventional thickener.
• polymer compositions according to the invention are also suitable for the polymer compositions according to the invention.
• customary conditioning agents can be used in combination with the inventive compositions to achieve certain effects
• Polymer compositions are used. These include, for example, the aforementioned cationic polymers with the name Polyquaternium according to INCI, in particular copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives
• polyquaternium-4 and -10 acrylamide copolymers
• protein hydrolysates can be used, as well as conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes,
• Polyarylalkylsiloxanes, polyethersiloxanes or silicone resins are suitable silicone compounds.
• suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).
• CTFA dimethicone copolyols
• CTFA amino-functional silicone compounds
• cationic guar derivatives such as guar hydroxypropyltrimonium chloride (INCI) can be used.
• polymer compositions according to the invention are also suitable for use in pharmaceutical preparations of any kind and in the coating of such pharmaceutical preparations.
• Another object of the invention is the use of a compound of formula (I) or formula (1.1), as defined above, as an adjuvant in pharmacy.
• Typical pharmaceutical compositions comprise A) at least one polymer composition according to the invention, as defined above,
• compositions C) are the excipients known to be useful in the pharmaceutical, food technology and related fields, in particular those listed in relevant pharmacopoeias (eg DAB, Ph. Eur., BP, NF) and other excipients whose properties are physiological application.
• Suitable excipients C) may be: lubricants, wetting agents, emulsifying and suspending agents, preservatives, antioxidants, anti-irritants,
• Chelating agents emulsion stabilizers, film formers, gel formers,
• Odor masking agents resins, hydrocolloids, solvents, solubilizers, neutralizing agents, permeation enhancers, pigments, quaternary
• Ammonium compounds lipid and superfatting agents, ointment, cream or oil bases, silicone derivatives, stabilizers, sterilants, propellants,
• a related embodiment is based on expert knowledge, as shown for example in Fiedler, H. P. Lexicon of excipients for pharmacy, cosmetics and related fields, 4th ed., Aulendorf: ECV Editio Kantor Verlag, 1996.
• the active ingredients may be mixed or diluted with a suitable excipient.
• Excipients may be solid, semi-solid or liquid materials which may serve as a vehicle, carrier or medium for the active ingredient. If desired, the admixing of further auxiliaries takes place in the manner known to the person skilled in the art.
• these are aqueous solutions or solubilisates for oral or parenteral administration.
• Copolymers to be used according to the invention also for use in oral
• Dosage forms such as tablets, capsules, powders, solutions. Here they can provide the poorly soluble drug with increased bioavailability.
• emulsions for example fat emulsions, can be used in addition to solubilisates.
• compositions of the above type can be obtained by processing the pharmaceutical composition of the present invention with pharmaceutical agents by conventional methods and using known and new drugs.
• all pharmaceutical active ingredients and prodrugs are suitable for the production of the pharmaceutical agents according to the invention.
• These include benzodiazepines, antihypertensives, vitamins, cytostatic drugs - especially taxol, anesthetics,
• Neuroleptics antidepressants, antibiotics, antifungals, fungicides, chemotherapeutics, urologics, platelet aggregation inhibitors, sulfonamides, spasmolytics, hormones, immunoglobulins, serums, thyroid medicines, psychotropic drugs, antiparkinson drugs and other antihyperkinetics, ophthalmics, neuropathy preparations,
• Calcium metabolism regulators muscle relaxants, anesthetics, lipid lowering agents, liver therapeutics, coronary agents, cardiac drugs, immunotherapeutics, regulatory
• Fibrinolytics Fibrinolytics, enzyme preparations and transport proteins, enzyme inhibitors, emetics, circulation-promoting agents, diuretics, diagnostics, corticoids, cholinergics, biliary tract therapeutics, antiasthmatics, broncholytics, beta-blockers, calcium antagonists, ACE inhibitors, arteriosclerotic agents, antiphlogistics,
• Anticoagulants antihypotonics, antihypoglycemics, antihypertensives, antifibrinolytics, antiepileptics, antiemetics, antidotes, antidiabetics, antiarrhythmics, antianemics, antiallergic drugs, anthelmintics, analgesics, analeptics, aldosterone antagonists,
• Suitable active pharmaceutical ingredients are in particular the active substances mentioned in paragraphs 0105 to 0131 of US 2003/0157170.
• the polymer compositions according to the invention are also suitable in the food industry.
• Food preparations are in the context of the present invention, dietary supplements such. As food-containing preparations and dietary foods to understand. In addition, the own
• Polymer compositions according to the invention also for feed additives for animal nutrition.
• polymer compositions according to the invention are suitable for the preparation of preparations of dietary supplements such as water-insoluble vitamins and provitamins such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives such as tocopherol acetate and vitamin K.
• dietary supplements such as water-insoluble vitamins and provitamins such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives such as tocopherol acetate and vitamin K.
• the polymer composition according to the invention is furthermore advantageously suitable for the production of crop protection agents. Surprisingly, it was found that the gel-form polymer composition of the present invention has high compatibility with a variety of crop protection agents and adjuvants.
• a preferred crop protection agent preferably comprises the following constituents: at least one gel-form polymer composition according to the invention, at least one active ingredient, optionally at least one adjuvant, optionally water, optionally at least one thickener, and optionally at least one further additive,
• Crop protection agents are, for example, those belonging to the group of herbicides, fungicides, insecticides, growth regulators, safeners, acaricides, molluscicides and nematicides.
• adjuvants for example of oils, special solvents, surfactants or surfactant mixtures is advantageous.
• adjuvants are in the
• Crop protection Auxiliary agents that control the activity of an active substance here:
• Plant protection products and / or its selectivity with respect to the desired effect (for example fungicides, insecticides, herbicides, bactericides, nematicides,
• adjuvants are based in many cases on their interfacial activity, which improves the contact of the form of administration of the active ingredient with the plant surface and, by reducing the surface tension, the penetration of the plant
• the at least one active ingredient is present in the gel phase, it is in phase in a total amount of preferably 2 to 60% by weight, particularly preferably 5 to 50% by weight and in particular 10 to 40% by weight. , based on the total weight of the phase.
• the at least one adjuvant is present in the gel phase, it is in the phase in a total amount of preferably 2 to 50 wt .-%, particularly preferably from 5 to 40 wt .-% and in particular from 10 to 30 wt .-% , based on the total weight of the phase.
• the active ingredient and / or the adjuvant may be present in significantly greater amounts in the gel formulation according to the invention than is possible in conventional liquid formulations.
• the plant protection agent according to the invention may additionally contain at least one thickener.
• Suitable thickeners are those previously mentioned as component f), which is hereby incorporated by reference in its entirety.
• Plant protection agent contains thickeners preferably in an amount of 0.002 to 10 wt .-%, particularly preferably from 0.02 to 10 wt .-%, more preferably from 0.04 to 2 wt .-%, in particular from 0.1 to 1 wt .-% and especially from 0.1 to
• the crop protection agent according to the invention may comprise further components.
• Suitable dispersants or surfactants are preferably nonionic. In principle, they may be of a similar nature to the adjuvants described above, differing from them by a generally higher one
• Tristyrylphenol ethoxylate such as Rhodia soprophor 3D33
• Rhodia soprophor 3D33 Rhodia soprophor 3D33
• comb polymers e.g., Atlox 4913 from Croda
• Suitable preservative is, for example, dichlorophen.
• Suitable biocides are, for example, isothiazolinones, such as benzylisothiazolinone and methylisothiazolinone.
• Suitable antifreeze agents are, for example, glycerol, ethylene glycol and propylene glycol.
• veterinary dosage forms in particular Rumen-stable forms, as well as dosage forms with vitamins, carotenoids, trace elements, Nutraceuticals, amino acids and
• Another object of the invention is the use of a polymer composition according to the invention, as defined above, for membrane production, in cosmetics, in crop protection, for seed coating, in food, in pet food, as adhesive raw materials, papermaking, as binders or auxiliaries for leather and textile , as a microbicidal surface coating, in the nonwoven area, in washing and
• PET polyethylene terephthalate
• pphm Parts by weight per 100 parts by weight of monomer (parts per hundred monomer).
• FIG. 1 shows the viscosity of a sample of the polymer composition from Example 19 of Table 1 as a function of the angular frequency.
• Figure 2 shows the loss and storage modulus of a sample of
• Measuring instrument Rotary rheometer DHR-1 from TA-Instruments with Peltier system Measuring geometry: Plate-plate, 0 40 mm, h -1, 0 mm
• the polyether component (PE) and solvent (LM) were charged in an amount as shown in Table 1, purged with nitrogen for a few minutes, and heated to 75 ° C.
• the feeds 1 to 3 were then simultaneously at 75 ° C and with stirring at 100 revolutions / minute within 4 hours
• Feed 1 contained monomer (M)
• feed 2 contained a starter (S) dissolved in a small amount of solvent (LM)
• feed 3 contained the regulator (R) and optionally further solvent.
• Inventive polymer compositions of Examples 1 to 19 were prepared according to this general preparation procedure.
• PE4 polyethylene glycol, molecular weight of 400 g / mol
• PE5 polypropylene glycol, molecular weight of 400 g / mol
• PE6 alkyl polyglucoside R1 2-mercaptoethanol
• R2 sodium hypophosphite, 55% aqueous solution

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