WO2009106220A1 - Haftendes mittel zur applikation auf einem sanitärgegenstand - Google Patents
Haftendes mittel zur applikation auf einem sanitärgegenstand Download PDFInfo
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- WO2009106220A1 WO2009106220A1 PCT/EP2009/000873 EP2009000873W WO2009106220A1 WO 2009106220 A1 WO2009106220 A1 WO 2009106220A1 EP 2009000873 W EP2009000873 W EP 2009000873W WO 2009106220 A1 WO2009106220 A1 WO 2009106220A1
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- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- 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
- C09J147/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
- A61L9/04—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
- A61L9/05—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating specially adapted to be released by contact with a liquid, e.g. for toilets
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- 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
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- 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
- C09J151/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
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- 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
- C11D1/008—Polymeric surface-active agents
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- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0056—Lavatory cleansing blocks
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- 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
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- 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
- C11D3/3723—Polyamines or polyalkyleneimines
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- 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
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- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
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- 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
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- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
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- 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
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- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
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- 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
- C11D3/3788—Graft polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Definitions
- the present invention relates to an adhesive agent for the sanitary area, which is used in particular for application to a sanitary object such as a toilet sink.
- agents are viscous, generally pasty agents, e.g. be applied directly to the surface of the sanitary article from a corresponding container, adhere there and are rinsed only after a large number of rinses.
- adhesive sanitary agents which are used for cleaning and scenting and surfactants, water, fragrances and adhesion promoters include. After direct application to the sanitary object, these sanitary agents are rinsed off only after a larger number of rinsing cycles. A further development of these adhesive sanitary agents with smoother surfaces due to additions of polyhydric alcohols is disclosed in EP 1 325 103 Bl.
- the known adhesive sanitary agents can be applied in a simple and hygienic manner with a suitable device, they adhere to the surface of the sanitary object, retain their shape and are not washed down even when exposed to water as a whole, but only after a variety of rinses gradually dissolved completely.
- This adhesive sanitary means is that additional containers such as the so-called “toilet bowls", the use of which consumers perceive as unhygienic, especially when replacing the sanitary agent and when cleaning the toilet, be avoided.
- agents having an additional bleaching agent phase are described in WO 00/23558, agents having a detergent tablet phase and a gel phase in EP 1 418 225 A1 and detergent tablets having a phase comprising water-soluble salts and a water-insoluble salt in WO 00/58434.
- Such multi-phase agents can be achieved by dividing the various ones from a toilet cleansing and fragrancing agent Multi-phase features, such as a special intensive scent phase and a special cleaning-only phase, which better meet consumer demands.
- the present invention has for its object to provide a sanitary agent that can be applied in a simple and hygienic manner that is versatile and that meets the consumer's desires in terms of intensive fragrance and good cleaning.
- an agent having a viscosity of at least 30 Pa s as measured by a Haake viscometer, system plate / plate, plate diameter 10 mm, at a shear rate of 2.62 s -1 and 20 ° C. contains fillers and a coupling agent, wherein the coupling agent is selected from the group of polyalkylene derivatives, the hydrogenated polystyrene derivatives, the silicone systems, the copolymers of the group of monoalkyl esters of poly (methyl vinyl ethers / carboxylic anhydrides, the olefin homopolymers and the copolymers of two or more olefins, wherein the olefin homopolymers and copolymers may also be partially hydrogenated, partially oxidized or further functionalized via graft molecules and the polyalkyleneimines, also in alkoxylated form, of the polyetheramines (alkoxylated amines) and the polyglycerol polyetheral
- the special adhesion promoters cause the agent to adhere to the sanitary surface and that further materials such as piece-shaped agents, for example with cleansing or fragrant active substances, are attached to the surface. surface of the adhesive can be stuck.
- These adhesion promoters are also distinguished by the fact that the agents comprising these adhesion promoters can be rinsed off without residue and that the agents comprising these adhesion promoters are insensitive to fluctuations in the mixing ratio of adhesion promoter to filler.
- the viscosity and / or the rinsability of the agent can be adjusted and the desired scenting or coloring of the agent can be achieved.
- the composition can be used, on the one hand, as a water-soluble temporary adhesive for the attachment of piece-shaped cleaning agents, e.g. be used in the toilet bowl in the form of strangextru- d convinced moldings, so that no special holding devices are required for these detergents.
- the agent serves as a substitute for the consumer perceived as unhygienic toilet bowl.
- adhesive-containing bar-shaped agents with their own functionalities such as conventional Rimblocks with one or more phases, Rimblocks with fragrance phase, fragrance tablets, Rimblocks with bleach, etc. are attached, the adhesive hygienically replaced the toilet bowl and is gradually rinsed off the rinsing water stream together with the piece-shaped agent adhering thereto.
- tablets or active substances containing, water-soluble or water-insoluble plastics can be attached to the adhesive also from powders or granules.
- the agent has at least one of the adhesion promoters according to the invention and a thickener. Since the adhesion promoters of the invention are generally viscous liquids, it is necessary to add a thickener as a filler in order for the composition to have the desired high viscosity of at least 30 Pa s. After the adhesion promoters according to the invention are water-soluble, the addition of surfactants to increase the flushability is not required in this embodiment.
- ingredients such as dyes, fragrances, possibly surfactants, foamers, etc. may be added to this base recipe of adhesion promoters and thickeners.
- the agent in addition to the adhesion promoter and thickener and perfume, so that it can be used simultaneously for sticking and for scenting.
- the adhesive comprises the adhesion promoters according to the invention and as fillers surfactants, so that it can take over the cleaning function itself by the appropriate choice of the type and concentration of the surfactants and optionally further additives.
- the adhesive effect the attachment of other desired active agent agents in the toilet bowl, e.g. a fragrance, a bleach tablet, a descaling tablet, an advertising medium, etc. allows.
- the consumer may select a fragrance corresponding to his or her current preferences and apply the appropriate scent tablet to the applied cleaning adhesive so that it adheres to the adhesive, for example, to scent the toilet for the next 1 or 2 weeks.
- the adhesive according to the invention even makes it possible to use the adhesive together with a number of scent tablets or fragrances, bleach tablets, descaling tablets, intensive cleaning tablets. etc. offer in a common set and thus allow the user an individual placement of the adhesive.
- a bleach tablet is adhered to the surface of the adhesive.
- a cleaning tablet can also be glued onto the cleaning adhesive. Also, the construction of multi-layered agents consisting of the layers adhesive - functionality - adhesive - functionality is possible.
- the agent can also be used as a cold adhesive which can be rinsed off with water as a result of the added surfactants.
- the agent can be used as cold glue in the sanitary area, e.g. be used for attaching objects in urinals, urinals, but also to hand sinks or tiles in the shower or in kitchens, restaurants, slaughterhouses or other places where water is washed.
- agent according to the invention in washing systems for the cleaning of motor vehicles or for application to / in drains or gullies, for example, to scent them temporarily.
- the agent according to the invention can be used.
- a preferred class of water-insoluble adhesion promoters from the group of polyalkylene derivatives comprises polyalkylene chains having randomly distributed functional groups.
- the polyalkylene chains are preferably polybutadiene, polyisopropylene and polypropylene chains.
- the randomly distributed on the polyalkylene functional groups are preferably reactive groups, in particular from the group of anhydrides, thiols, epoxides or primary amines.
- polymers having randomly attached to the polybutadiene chain maleic anhydride groups Particular preference is given to polymers having randomly attached to the polybutadiene chain maleic anhydride groups.
- the particularly preferred maleic anhydride adduct on 1,4-cis-polybutadiene is available from Degussa under the name Polyvest.
- the adhesion promoters from the group of polystyrene derivatives are preferably crosslinked polystyrene derivatives dissolved in mineral oil, in particular alkylenestyrene copolymers, such as, for example, the hydrogenated butylene / ethylene / styrene copolymers and the hydrogenated ethylene / propylene / styrene copolymers, which are available, for example, from the company Pen- reco under the trade name Versagel M750 or Versagel M1600.
- non-water-soluble primer silicone systems can be used, for example, from the group of the acetic acid splitting Bausilikone (acetate system).
- Such organopolysiloxane mixtures which are also known as cold-vulcanizing, one-component silicone rubbers, usually crosslink at room temperature, with absorption of water from the surrounding atmosphere, to give rubber-elastic polymers.
- a chain extender and crosslinkers are used two- and preferably higher-functional Acetoxysi- lantagenen which split off by reaction with the polysiloxane or by hydrolysis of acetic acid and thus initiate the formation of a macromolecular network.
- the silicone systems based on amine / aminoxy systems, oxime systems, benzamide systems and alkoxy systems are also suitable as adhesion promoters, provided that they can be stabilized with the additional system components described hereinbelow to form homogeneous, stable mixtures.
- non-water-soluble olefin homopolymers and copolymers of two or more olefins as adhesion promoters.
- These compounds include e.g. the polybutadiene rubbers, the styrene-butadiene block u. copolymers and the polyisopropenes.
- random (block) polymers prepared by the 1,3-addition of butadiene or isoprene to styrene or alpha-methyl styrene, the homopolymers or copolymers of ethylene and propylene, such as the ethylene-propylene diene terpolymer, of US Pat Ethylene-ethylene oxide copolymers, the natural rubber and norbornene polymers such as polydicyclopentadiene.
- the compounds from the group of olefin homopolymers and copolymers can also be partially hydrogenated, partially oxidized or further functionalized via graft molecules.
- water-soluble adhesion promoters are copolymers from the group of the monoalkyl esters of poly (methyl vinyl ethers / carboxylic acid anhydrides, which are commercially available, for example, under the trade name Gantrez from ISP).
- polyalkyleneimines ie polymeric amines or polymers containing polymer groups.
- polyalkyleneimines are the polymeric spherical polyalkyleneimines which are based in particular on homopolymeric polyethylenes having a particular ratio of primary, secondary and tertiary amine functions. These polyethylenimines can quaternize with water or acids, i. Form polycations.
- polyalkyleneimines as alkylene group in addition to the ethylene group and methylene, propylene, butylene or higher alkylene groups include.
- Polyalkyleneimines are available, for example, from BASF under the trademark Lupasol with different molecular weights and degrees of crosslinking.
- polyalkyleneimines can also be derivatized and / or present as cationic polymers.
- Polyalkyleneimines are soluble in water and other polar solvents.
- these polyimines can also be used in alkoxylated, in particular ethoxylated or propoxylated form.
- adhesion promoters are the so-called polyetheramines (alkoxylated amines), which are likewise water-soluble.
- alkyl or aryl radical can be branched so that (formally) di-, tri- or oligo- or poly (EO / PO) amines are formed.
- the alkoxylated polyamines undergo typical amine reactions with other functional groups (amide formation, urea analogues, imine formation with carbonyls, etc.).
- the alkoxylated polyamines are selected from the group of polyetheramines.
- the polyetheramines can tri, bi- and / or monofunctional primary amines and polyether groups include polyethylene oxide, mixed poly (ethylene oxide / propylene oxide) or polypropylene oxide groups, wherein the hydrophilicity of the polyetheramine decreases in this order.
- the alko- xylated amines may also have other polyether groups, such as polybutylene oxide groups.
- Polyether amines are available under the trademark Jeffamine ® T-5000, for example, at the company. Huntsman, USA.
- the molecular weights of the polyetheramines can vary over a wide range.
- polyetheramines having molecular weights between 500 and 5000 were used.
- viscosity-increasing substances such as, for example, pulverulent surfactants, polysaccharides (wood flour, starch, flour), lignin, etc.
- the ethoxylated polyimines according to the following formula, i. the systems obtainable by ethoxylation of the polyimines are used:
- R 1 alkyl or alkyl derivatives
- R 2 , R 3 (-CH 2 -CH 2 -O) n -R 4 or
- polyglycerol polyether alkylcarboxylic acids as water-soluble adhesion promoters.
- polyetheralkylcarboxylic acids esterified via glycerol such as polyethylene glycol 150 polyglyceryl 2-tristearate or PEG 150 diglyceryl tristearate or PEG 150 tetraglyceryl distearate, with PEG 150 polyglyceryl 2-tristearate being preferred.
- the polymer consists of a polyglyceryl backbone to which fatty acid residues are attached via flexible PEG chains.
- the thickening effect is probably based on associative interaction of the fatty acid residues of PEG-150 polyglyceryl-2 tristearates with the surfactant micelles in the formulation.
- a 3-dimensional network could be spanned, which leads to an increase in viscosity in the aqueous surfactant system (for example a rinsing process in the toilet).
- the structure of the polymer ie the polarity of the fatty acid ester (C chain length), the length of the flexible spacer (degree of ethoxylation of the PEG) and the structure of the backbone (number of glycerol units) have an influence on the thickening properties.
- adhesion promoters their reactivity must also be taken into account.
- no particularly reactive polymeric starting compounds such as, for example, reactive silicone compositions, should be used as adhesion promoters, since they continue to polymerize and thus become increasingly viscous.
- systems based on polyurethane or with epoxide-containing starting materials Compounds react too quickly and become viscoplastic when mixed. These systems stick only slightly or not at all anymore.
- the primer causes adhesion of the agent to the surface of the sanitary article.
- the compositions of the invention adhere to both dry and wet surfaces.
- the special adhesion promoters also cause the applied agent to be tacky on its surface so that other active agents can be adhered to the surface of the adhesive medium.
- the adhesion promoter also forms network-like structures which impart the required dimensional stability to the composition even under the strong action of rinse water.
- the concentration of the adhesion promoter to be used depends on the respective substance class and the network-forming capacity of the adhesion promoter and is generally between 2% by weight and 60% by weight, preferably between 7% by weight and 50% by weight and particularly preferably between 8% by weight. and 40% by weight.
- the agent according to the invention comprises fillers which may be selected from the group of surfactants, thickeners, fragrances, dyes, salts, foam stabilizers, foam boosters, foam generators and polymeric natural substances.
- surfactants it is possible in principle to use all known anionic and / or cationic and / or nonionic and / or amphoteric surfactants, powdery to highlypasteose being preferred.
- the proportion of surfactant in the composition should be between 0% by weight and 80% by weight, preferably 10% by weight to 60% by weight and more preferably 25% by weight to 45% by weight.
- the anionic surfactants take on several tasks in the present invention; on the one hand, they serve to soluble matrices to emulsify the polymeric matrix without completely destroying the adhesiveness. On the other hand, they contribute significantly to the plasticization of the starting polymer (adhesion promoter) by serving as a viscosity enhancer (thickener).
- the anionic surfactants should also be strongly foaming in order to visually show a cleaning effect, for example in a toilet bowl. Last but not least, a good cleaning action of the surfactants is desired, which is supported by the good wetting properties.
- anionic surfactants it is preferred to use one or more substances from the group of the salts of the carboxylic acids, the sulfuric monoesters and the sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids.
- the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
- Carboxylic acids (C6-C22) in the form of their metal salts (preferably alkali salts) and their natural or synthetic mixtures and alkali metal salts of sulfuric monoesters and long-chain alcohols can also be used as anionic surfactants.
- alkali metal salts of the alkyl ether sulfuric acids are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question.
- ethylene oxide propylene oxide can also be used. The subsequent sulfonation provides the relevant alkyl ether sulfuric acids.
- alkali metal salts of alkanesulfonic acids and olefinsulfonic acids can also be used as anionic surfactants in the context of the present invention.
- Alkanesulfonic acids may contain the sulfonic acid group terminally attached (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids).
- Typical representatives are alkylbenzenesulfonates, particularly preferably linear alkylbenzenesulfonates (LAS).
- anionic surfactants may be used in their neutralized form alone or in admixture with each other.
- the surfactant phase contains, based on its weight, preferably 10 to 90 and particularly preferably 40 to 85% by weight of lauryl sulfate.
- the anionic surfactants also serve as thickeners.
- nonionic surfactants alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol and on average from 2 to 8 EO per mole of alcohol.
- fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- alkyl glycosides of the general formula alkyl-O (G) can also be used as further nonionic surfactants, where alkyl is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol for a glycoside unit having 5 or 6 C atoms, preferably for glucose.
- nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide or alkanolamides may also be used.
- the proportion of the nonionic surfactant (s) in the entire surfactant phase can be up to 50%, preferably up to 30% and particularly preferably up to 25%.
- the surfactant phase may also be provided with cationic or amphoteric and zwitterionic surfactants.
- amphoteric surfactants are fatty acid amidopropyl betaines with C5-C21 fatty acid moieties, but also amphodiacetates.
- Cationic surfactants are preferably used in acidic formulations in combination with bactericidal substances.
- Zwitterionic surfactants can be described by way of example as quaternary ammonium, phosphonium or sulfonium components which are connected via an aliphatic bridge with another now anionic group such as carboxy, sulfonate, sulfate, phosphate or phosphonate.
- foaming agent olefin sulfonates, ether sulfates or acid methyl taurides can furthermore be added to the agent.
- strong foaming agents preferably 1 to 50, in particular 1 to 25% of the surfactant phase can be replaced by one or more foaming agents, for example from the group of betaines, the alkoxylated alkyl ether sulfates or lactobionic acid derivatives.
- foaming agents may be selected from fatty acid amidopropyl betaines having a C 5 -C 21 fatty acid moiety, such as cocoamido proplybetaine, the alkali metal or ammonium salts of the lauryl ether sulfates containing 1 to 5 EO, the lactobionococoylamide, the lactobionooleylamide, the lactobionotalgamide, etc., or mixtures thereof.
- These foaming agents work well in the Apply pressure-sensitive adhesive. Preference is given to using such cosurfactants which are present in solid, preferably pulverulent or highly viscous form.
- the adhesive may comprise other conventional ingredients, for example, salts, disinfectants (e.g., oxygen or chlorine releasers), preservatives such as isothiazolone derivatives, foam stabilizers such as e.g. Alkanolamides, water repellents such as e.g. Mineral oils or (partially) methylated siloxanes and silanes, calcium dispersants such as sodium salts of polycarboxylic acids or dyes.
- disinfectants e.g., oxygen or chlorine releasers
- preservatives such as isothiazolone derivatives
- foam stabilizers such as e.g. Alkanolamides
- water repellents such as e.g. Mineral oils or (partially) methylated siloxanes and silanes
- calcium dispersants such as sodium salts of polycarboxylic acids or dyes.
- the adhesive can also be used to scent the room air.
- fragrance compounds e.g. the synthetic products of aldehydes, alcohols, esters, ethers, ketones and hydrocarbons are used. Fragrance compounds of the ester type are known e.g. Benzyl acetate or benzyl formate.
- the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. Citronellal, to the ketones ⁇ -isomethylionone, to the alcohols citronellol, eugenol, geraniol and linalool.
- the hydrocarbons mainly include the terpenes such as limonene and pinene.
- mixtures of different fragrances are used, which together give the desired fragrance.
- perfume oils which contain natural fragrance mixtures such as are available from vegetable sources such as e.g. Pine, citrus, lavender, mint oil or oil from orange peel.
- the fragrances are incorporated directly into the batch in concentrations between 0.25% by weight and 20%, preferably between 3% by weight and 15% by weight and more preferably between 5% by weight and 10% by weight.
- salts may also be added to the formulation as, for example, sodium sulfate as fillers, for example to increase the dissolution rate.
- the salt content can be up to 90% by weight for a particularly inexpensive product. In general, the salt content is up to 10% by weight, preferably up to 5% by weight.
- Suitable salts are alkali salts of strong acids such as sodium sulfate, sodium chloride or sodium polyphosphates. Also usable are the alkali metal salts of mono-, di- and polycarboxylic acids, but also alkaline earth metal salts of strong acids such as calcium sulfate or salts of carbonic acid.
- Calcium salts can be used in particular to increase the service life of the composition, since they form for example with the maleic anhydrides of polybutadiene derivative-based polyols, which in turn hydrophobize and stabilize the entire system to form calcium soap networks on the surface and thus counteract rinsability.
- the rinse-off agent may include calcium soap dispersants such as e.g. Amphodipropionate (Lonza KL type) or maleic acid / acrylic acid copolymer Na salts (BASF Sokalan types such as Sokalan CP5 or CP45) can be added.
- calcium soap dispersants such as e.g. Amphodipropionate (Lonza KL type) or maleic acid / acrylic acid copolymer Na salts (BASF Sokalan types such as Sokalan CP5 or CP45) can be added.
- all dyes can be incorporated into the agent as fillers, which have no pronounced substantivity to the surfaces to be treated with the dye-containing agents. If water-soluble dyes are used in the formulation and then come into contact with water as a finished product, for example, when rinsing with water in a toilet bowl, interesting color gradients can be achieved, which can also be correlated with marketing arguments. For example, a slow blue coloration (from light blue to deep blue) may indicate the slow activation of an agent to its maximum activity.
- the adhesive may also be acidified and include, for example, lime or urine stone-dissolving substances (acids) as fillers.
- co-thickeners may be added to the composition according to the invention in order to increase the plasticity of the composition.
- Bentonites, powder surfactants, xanthans, polybutadiene rubbers, polyisopropenes, block copolymers which comprise linked oligomers consisting of oligo- or polyethylene oxide and / or oligo- or propylene oxide and / or oligo- or polybutylene oxide and also arylethoxylates or alkyl can be used as (co) thickeners Aryl ethoxylates are used.
- the polymeric natural substances such as lignins or their alkali metal or alkaline earth metal salts can also be used as (co) thickeners.
- a preferred group of (co) thickeners are the hydrophilic xanthans. Through their use, a very hydrophilic compound is introduced into the agent, which immediately "absorbs” the water when the agent sticks to a moist surface.
- hydrophobicizers such as Aerosil, in particular methylated Aerosil (Carbot Carbon) can be added to the adhesive as fillers.
- tackifiers in particular from the class of hydrocarbon resins, natural resins such as tall resin or gum rosin or polyterpene resins, may also be added to the composition as fillers.
- the adhesive may further contain odoriferous agents (malodor counteractants), which are preferably added to the fragrances.
- odoriferous agents malodor counteractants
- Such odor binders are described, for example, in US Pat. No. 7,288,507 B2.
- the adhesive of the invention may be applied and renewed in a hygienic manner without touching any possibly contaminated devices connected to the toilet bowl.
- An essential advantage of the agent according to the invention is that it can be portioned according to the wishes of the consumer and / or can be offered in different portion packs.
- the adhesive may be applied, for example, by means of an application syringe or by application of pre-portioned quantities by means of suitable devices. These application devices may be, for example, "stapling systems", grippers or slides removable from films, dispenser systems having prestressed elements which apply a corresponding portion, for example to a ceramic surface.
- composition according to the invention can also be applied in a simple manner simultaneously to different parts of the sanitary object, for example, in order to adhere several active agent agents which would affect their effect in direct proximity, for example a fragrance tablet and a bleaching tablet.
- the adhesives according to the invention can only be rinsed off after a relatively large number of rinsing operations.
- the number of rinses depends of course on the composition of the respective agent, the amount applied and the geometry of the applied agent and is generally in an order with a thickness of 2 to 5 mm between 50 and 150, in particular more than 120 rinses.
- the shelf life is substantially defined by the rinsing time of the applied further body (bar means).
- a service life of 100 to 200, in some cases> 250 rinses can be achieved, whereby the pressure-sensitive adhesive is gradually removed together with the adhered material.
- the amount applied is 3 to 15 wt.%, In particular 5 to 10 wt.%, Of the mass of the adhered agent.
- the agent of the invention is white, ointment-like, pasty and / or creamy and dimensionally stable, so that it does not “run down” or "drips".
- the agent essentially shows intrinsic viscosity, ie the viscosity decreases with increasing shear forces. If the shear rates are low, however, a strong flow obstruction is observed; In addition, the viscosity curves show the occurrence of local maxima at a shear rate ramp between 2.5 s -1 and 30 s -1 . Obviously, there are different viscous areas or the agent changes its structure over the short measurement time (ramp time 100 sec).
- the viscosities of these agents to be determined on a Haake viscometer, system plate / plate, plate diameter 10 mm at a shear rate of 2.62 s -1 and 20 ° C. should be at least 30 Pas, preferably at least 45 and more preferably at least 100 Pas
- the viscosities should be between 150 and 300 and 6000 Pa s and more preferably between 200 and 1000 or between 1000 and 4000 Pa s.
- the compositions according to the invention which comprise surfactants, give a fine-bubble foam which can be adjusted in volume by means of suitable additives (foam boosters).
- the foam numbers of the agents according to the invention should be more than 40 ml of foam. Particularly preferred are agents with foam numbers> 60 ml, very particularly preferred are foam numbers of 140 ml or even more than 200 ml.
- the surface tension is a measure of the wetting of the surface. The smaller the surface tension, the better the surface is wetted. A good network effect is a prerequisite for a good cleaning performance of the considered means.
- the preparation of the agent according to the invention is carried out by stirring the components together at room temperature.
- Table 2 which is further attached to the end of the description, lists the reactants used in the preparation of the compositions according to the invention in Table 1.
- All of the adhesives according to the invention according to formulations V13 to V38 exhibit strong adhesion and are so sticky on the outside that conventional toilet cleaners having a mass of up to 50 g can be adhered to the compositions, depending on the quantities of adhesive applied.
- the ratio of glued mass of the piece-shaped agent to the adhesive mass is at a maximum of 100: 1, preferably at most 50: 1 and more preferably at a maximum of 10: 1.
- a better adhesion of the agent is achieved if the adhesive surface is larger.
- the usual adhesive surfaces are between 1000 mm 2 and 800 mm 2 (full-surface contact). But you can less than 400 mm 2 , when the adhesive is applied in the form of circulating beads.
- V20 is a recipe for an acid remedy.
- the lower purities of this agent are probably due to the fact that due to the low pH no lime soaps increasing the purge numbers are formed.
- the formulations V23a, V24, V29 and V30 comprise only one (anionic) surfactant and a coupling agent. These two-component compositions also show the desired adhesiveness, tack and purging numbers greater than 100%.
- the applied pure adhesion promoter Polyvest 800 S (1,4-cis butadiene maleic anhydride adduct), a low-viscosity product, immediately runs down the toilet bowl and shows no adhesion. Sticking a conventional toilet block of 50 g, 30 g, 10 g, 5 g is not possible on the pure adhesion promoter Polyvest. The piece-shaped agent falls off immediately; no sticky effects are observed.
- the pure adhesive Versagel M 1600 (hydrogenated butylene / ethylene / styrene copolymer) applied to the toilet bowl, on the other hand, sticks in the bowl and can not even be rinsed off after a large number of rinsing cycles. It is also possible to stick toilet blocks to this adhesion promoter, but the toilet blocks gradually move downwards with the sealant Versagel.
- the specimen was then glued directly into a ceramic toilet bowl.
- the specimens were glued with light pressure on the wet front inner surface of the toilet. Adhesives and specimens are ready for immediate use and can be rinsed directly.
- the starting substance in pure form is already a pressure-sensitive adhesive, which is permanently tacky over a long period of time (until the curing of the reactive groups).
- a pure adhesive without surface-active constituents
- the cohesive effect of the maleic anhydride function should e.g. in long-chain fatty alcohols or in long-chain PEG systems (e.g., Polyox WSR 303) incorporated into the formulation.
- the present formula may also play a role in the formation of poly-soaps from the calcium ions, which leads to a greater hydrophobization of the entire system and thus to a more severe solubility in water.
- Table 4 shows that the agents according to the invention differ significantly from the previously known agents of EP 1325103 Bl. The present agents are therefore much better foamer.
- the initial test is taken as the original value, all subsequent tests are compared with the original value (50/100/500 ms). If the deviation is greater than ⁇ 2 mN / m, replace the capillary with a new one.
- the surface tension was determined as a function of the age of the surface of a 0.1% solution (20 0 C). The surface tension after 100, 500, 1000 ms is considered.
- Table 5 shows various formulations of the adhesives according to the invention with polyalkyleneimines as adhesion promoters and in Table 6 with alkoxylated amines and polyglycerol polyetheralkylcarboxylic acids.
- the agent was applied to a toilet block, the applied amount was about 10% of the weight of the toilet block.
- the toilet block was then glued by the means on the sanitary surface.
- Tensopol USP 94 is a surfactant (C12-C16 lauryl sulfate) available from Manro.
- Marlinat 242 / 90T consists of C12-C14 alcohol polyethylene glycol and propylene ether (2 EO) sulfate, glycol triisopropanolammonium salt (Sasol).
- Orange Fun is a perfume available from Givaudan.
- Kelzan AS is a xanthan (thickener / koverdicker) available from Kelco.
- Genapol DAT is PEG-150 polyglyceryl-2-tristearate and PEG-6-caprylic / capric glyceride.
- Lupasol SK is a liquid polyethylenimine available from BASF with a molecular weight of about 2,000,000
- Lupasol P is a liquid polyethyleneimine available from BASF with a molecular weight of about 750,000.
- Emanon XLF is glycereth-7-caprylate / caprate, available from Kao Corporation, S.A.
- Jeffamine T 5000 is a polyetheramine available from Huntsman, U.S.A., having a molecular weight of about 5,000 (triamine made by reacting propylene oxide with a triol initiator, followed by amination of the terminal hydroxy groups).
- Jeffamine ST-404 is a derivative of polyetheramines of about 565 molecular weight, available from Huntsman, USA, (secondary amine version, secondary triamine, amine end groups are reacted with a ketone, e.g., acetone, and reduced.)
- Cab-Osil is fumed silica.
- Arboform water-soluble, is available from the company Tecnaro, Ilsfeld Germany and is a granulate which consists of the polymers lignin or ligand. Nin derivatives, biodegradable polyesters, lignocellulose or lignocellulosic fibers and natural resins, namely alliphatic and aromatic ketones, alcohols, carboxylic acids, lactones and polycycles in monomeric, oligomeric and polymeric form.
- Hydriol ® PGR is polyglycerolpolyricinoleate.
- All of the agents of the present invention have excellent adhesion / adhesion to both dry and wet surfaces.
- the initial test is taken as the original value, all subsequent tests are compared with the original value (50/100/500 ms). If the deviation is greater than ⁇ 2 mN / m, replace the capillary with a new one.
- the surface tension was determined as a function of the age of the surface of a 0.1% solution (20 0 C). The surface tension after 100, 500, 1000 ms is considered.
- the flushing numbers were measured with a flushing volume per flush of 8 l and a rinsing rhythm of 19 flushes per day according to a defined schedule.
- the rinse water temperature during the short rinse frequencies for example between the third and fifth rinse) 13 0 C to 14 0 C and during the long rest periods (for example, between the nineteenth and first rinse) 15 0 C to 16 0 C.
- the temperature of the rinse water was checked and noted every working day.
- the V2-Ste ⁇ n consisted of 32 wt.% Anionic surfactant, 6 wt.% Nat ⁇ umcumolsulfonat, 43 wt.% Filler, 10.5 wt.% Calcium sulfate, 0.5 wt.% Polyox WSR 303 Resin (Union Carbide), 2 wt % Polyethylene glycol
- Descaling tablet and is therefore bubbled off the surface.
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Abstract
Description
Claims
Priority Applications (22)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009801070598A CN101970630B (zh) | 2008-02-29 | 2009-02-09 | 用于施用在卫浴用品上的粘附剂 |
DK09714305.1T DK2250245T3 (da) | 2008-02-29 | 2009-02-09 | Klæbemiddel til påføring på en sanitær genstand |
MX2010009477A MX2010009477A (es) | 2008-02-29 | 2009-02-09 | Agente adhesivo para la aplicacion sobre un objeto sanitario. |
CA2715142A CA2715142C (en) | 2008-02-29 | 2009-02-09 | Adhesive agent for application on a sanitary object |
BRPI0907965A BRPI0907965B1 (pt) | 2008-02-29 | 2009-02-09 | produto para instalações sanitárias, seus usos e conjunto de limpeza para vaso sanitário compreendendo o mesmo |
AU2009218816A AU2009218816B2 (en) | 2008-02-29 | 2009-02-09 | Adhesive agent for application on a sanitary object |
US12/735,987 US8461093B2 (en) | 2008-02-29 | 2009-02-09 | Adhesive agent for application on a sanitary object |
NZ587145A NZ587145A (en) | 2008-02-29 | 2009-02-09 | Adhesive agent for application on a sanitary object |
EP09714305A EP2250245B1 (de) | 2008-02-29 | 2009-02-09 | Haftendes mittel zur applikation auf einem sanitärgegenstand |
BRPI0923668-6A BRPI0923668B1 (pt) | 2008-02-29 | 2009-02-09 | Produto para instalações sanitárias, seus usos e conjunto de limpeza para vaso sanitário compreendendo o mesmo |
JP2010547986A JP5524086B2 (ja) | 2008-02-29 | 2009-02-09 | サニタリー物品上に塗布するための接着剤 |
PL09714305T PL2250245T3 (pl) | 2008-02-29 | 2009-02-09 | Środek adhezyjny do stosowania w urządzeniu sanitarnym |
AT09714305T ATE526388T1 (de) | 2008-02-29 | 2009-02-09 | Haftendes mittel zur applikation auf einem sanitärgegenstand |
ES09714305T ES2373886T3 (es) | 2008-02-29 | 2009-02-09 | Agente adhesivo para la aplicación sobre un objeto sanitario. |
ZA2010/07508A ZA201007508B (en) | 2008-02-29 | 2010-10-21 | Adhesive agent for application on a sanitary object |
US12/925,887 US8444771B2 (en) | 2008-02-29 | 2010-11-02 | Method for cleaning and/or deodorizing toilet bowl or urinal using an adhesive agent |
US12/925,943 US8835371B2 (en) | 2008-02-29 | 2010-11-02 | Adhesive agent for application on a sanitary object |
AU2011200084A AU2011200084B2 (en) | 2008-02-29 | 2011-01-10 | Adhesive agent for application on a sanitary object |
HK11104029.4A HK1149776A1 (en) | 2008-02-29 | 2011-04-20 | Adhesive agent for application on a sanitary object |
HR20110950T HRP20110950T1 (hr) | 2008-02-29 | 2011-12-19 | Adhezivno sredstvo za primjenu na sanitarni objekt |
US13/914,203 US20140037569A1 (en) | 2008-02-29 | 2013-06-10 | Adhesive agent for application on a sanitary object |
US14/301,029 US9783711B2 (en) | 2008-02-29 | 2014-06-10 | Adhesive agent for application on a sanitary object |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008012092.8 | 2008-02-29 | ||
DE102008012092A DE102008012092A1 (de) | 2008-02-29 | 2008-02-29 | Haftendes Mittel zur Applikation auf einem Sanitärgegenstand |
DE102008051173.0 | 2008-10-14 | ||
DE200810051173 DE102008051173A1 (de) | 2008-10-14 | 2008-10-14 | Haftendes Mittel zur Applikation auf einem Sanitärgegenstand |
Related Child Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/735,987 A-371-Of-International US8461093B2 (en) | 2008-02-29 | 2009-02-09 | Adhesive agent for application on a sanitary object |
US12/925,943 Continuation-In-Part US8835371B2 (en) | 2008-02-29 | 2010-11-02 | Adhesive agent for application on a sanitary object |
US12/925,887 Continuation-In-Part US8444771B2 (en) | 2008-02-29 | 2010-11-02 | Method for cleaning and/or deodorizing toilet bowl or urinal using an adhesive agent |
US13/914,203 Continuation US20140037569A1 (en) | 2008-02-29 | 2013-06-10 | Adhesive agent for application on a sanitary object |
Publications (1)
Publication Number | Publication Date |
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WO2009106220A1 true WO2009106220A1 (de) | 2009-09-03 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2009/000873 WO2009106220A1 (de) | 2008-02-29 | 2009-02-09 | Haftendes mittel zur applikation auf einem sanitärgegenstand |
Country Status (19)
Country | Link |
---|---|
US (3) | US8461093B2 (de) |
EP (2) | EP2275524B1 (de) |
JP (2) | JP5524086B2 (de) |
KR (2) | KR101622943B1 (de) |
CN (2) | CN102167960B (de) |
AT (2) | ATE528382T1 (de) |
AU (2) | AU2009218816B2 (de) |
BR (2) | BRPI0907965B1 (de) |
CA (2) | CA2715142C (de) |
DK (2) | DK2250245T3 (de) |
ES (2) | ES2375023T3 (de) |
HK (2) | HK1149776A1 (de) |
HR (2) | HRP20110950T1 (de) |
MX (1) | MX2010009477A (de) |
NZ (2) | NZ590378A (de) |
PL (2) | PL2250245T3 (de) |
PT (2) | PT2275524E (de) |
WO (1) | WO2009106220A1 (de) |
ZA (1) | ZA201007508B (de) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009039675A1 (de) | 2009-09-02 | 2011-03-10 | Buck- Chemie Gmbh | Applikator für ein stückförmiges Mittel für den Sanitärbereich und Verpackungseinheit |
US7919447B1 (en) * | 2010-03-12 | 2011-04-05 | S.C. Johnson, Inc | Array of self-adhesive cleaning products |
WO2011112256A2 (en) | 2010-03-12 | 2011-09-15 | S. C. Johnson & Son, Inc. | Array of self-adhering articles and merchandise display system for identifying product types to users |
DE102010032417A1 (de) | 2010-07-27 | 2012-02-02 | Buck- Chemie Gmbh | Haftendes saures Sanitärreinigungs- und Beduftungsmittel |
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DE102012106742A1 (de) | 2012-07-25 | 2014-01-30 | Geting Solutions Gmbh | Stückförmiges Mittel zur Applikation auf einem Sanitärgegenstand |
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DE102012109397A1 (de) | 2012-10-02 | 2014-04-03 | Geting Solutions Gmbh | Applikator für stückförmige Mittel für den Sanitärbereich |
EP2716572A1 (de) | 2012-10-02 | 2014-04-09 | GETing solutions GmbH | Applikator für stückförmige Mittel für den Sanitärbereich |
US10047322B2 (en) | 2013-06-18 | 2018-08-14 | Buck Service Gmbh | Agent for removing stains and deposits comprising an alkylene styrene copolymer |
WO2014202651A1 (de) * | 2013-06-18 | 2014-12-24 | Geting Solutions Gmbh | Mittel zur entfernung von flecken und ablagerungen |
DE102013107665A1 (de) | 2013-07-18 | 2015-01-22 | Geting Solutions Gmbh | Material zum Abdecken von klebenden Flächen |
DE102013107874A1 (de) | 2013-07-23 | 2015-02-19 | Buck-Chemie Gmbh | Spülrandloser Sanitärgegenstand, insbesondere Toilette oder Urinal |
EP2924184A1 (de) | 2013-07-23 | 2015-09-30 | Buck-Chemie GmbH | Sanitärgegenstand, insbesondere toilette oder urinal, und reinigungsverfahren |
WO2015010830A1 (de) * | 2013-07-26 | 2015-01-29 | Buck-Chemie Gmbh | Haftendes mittel zur applikation auf einem sanitärgegenstand |
EP2851416A1 (de) * | 2013-09-19 | 2015-03-25 | Bolton Manitoba SpA | Klebende Reinigungs- und/oder Parfum- und/oder Desinfektionszusammensetzung |
ITMI20131545A1 (it) * | 2013-09-19 | 2015-03-20 | Bolton Manitoba S P A | Composizione adesiva detergente e/o profumante e/o igienizzante |
EP2985329B2 (de) † | 2014-08-14 | 2019-11-27 | Buck Service GmbH | Material zum abdecken von klebenden flächen |
DE102014111629A1 (de) | 2014-08-14 | 2016-02-18 | Geting Solutions Gmbh | Material zum Abdecken von klebenden Flächen |
EP2985329B1 (de) | 2014-08-14 | 2017-05-17 | Buck Service GmbH | Material zum abdecken von klebenden flächen |
EP2985329A1 (de) | 2014-08-14 | 2016-02-17 | GETing solutions GmbH | Material zum abdecken von klebenden flächen |
DE102015110123A1 (de) | 2015-06-24 | 2016-12-29 | Buck Service Gmbh | Vorrichtung zur Aufnahme eines Toilettenreinigungsmittels |
EP3109367A1 (de) | 2015-06-24 | 2016-12-28 | Buck Service GmbH | Vorrichtung zur aufnahme eines toilettenreinigungsmittels |
WO2018046308A2 (de) | 2016-09-07 | 2018-03-15 | Buck-Chemie Gmbh | Set für die toilettenunterhaltsreinigung |
DE102016116697A1 (de) | 2016-09-07 | 2018-03-08 | Buck-Chemie Gmbh | Set für die Toilettenunterhaltsreinigung |
DE102017105339A1 (de) | 2017-03-14 | 2018-09-20 | Buck Group AG | Duftzusatz für Wäsche |
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