EP1882526A1 - dispositif pour appliquer et essuyer un liquide - Google Patents

dispositif pour appliquer et essuyer un liquide Download PDF

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Publication number
EP1882526A1
EP1882526A1 EP20060117918 EP06117918A EP1882526A1 EP 1882526 A1 EP1882526 A1 EP 1882526A1 EP 20060117918 EP20060117918 EP 20060117918 EP 06117918 A EP06117918 A EP 06117918A EP 1882526 A1 EP1882526 A1 EP 1882526A1
Authority
EP
European Patent Office
Prior art keywords
container
liquid
applying
opening
wiping
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20060117918
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German (de)
English (en)
Inventor
Wolf-Rüdiger Huck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Priority to EP20060117918 priority Critical patent/EP1882526A1/fr
Priority to US12/309,318 priority patent/US20090305054A1/en
Priority to ES07802414T priority patent/ES2340735T3/es
Priority to DE200750003334 priority patent/DE502007003334D1/de
Priority to RU2009106682A priority patent/RU2409427C2/ru
Priority to AT07802414T priority patent/ATE462503T1/de
Priority to PCT/EP2007/057732 priority patent/WO2008012352A1/fr
Priority to EP20070802414 priority patent/EP2049271B1/fr
Publication of EP1882526A1 publication Critical patent/EP1882526A1/fr
Priority to US13/067,256 priority patent/US20110223326A1/en
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C17/00—Hand tools or apparatus using hand held tools, for applying liquids or other fluent materials to, for spreading applied liquids or other fluent materials on, or for partially removing applied liquids or other fluent materials from, surfaces
    • B05C17/002—Hand tools or apparatus using hand held tools, for applying liquids or other fluent materials to, for spreading applied liquids or other fluent materials on, or for partially removing applied liquids or other fluent materials from, surfaces with feed system for supplying material from an external source; Supply controls therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31989—Of wood

Definitions

  • the invention relates to the field of application technology for applying and wiping a liquid onto a surface.
  • the invention relates to a means for applying and wiping a liquid comprising a container having a filling space and at least one opening for applying the liquid, characterized in that the container has on the outside at least one porous carrier material for wiping the liquid.
  • Hydrolyzable liquids such as primer compositions have long been used to improve adhesion, particularly those of adhesives and sealants.
  • silane and titanate compounds have long been known as such adhesion promoter compositions.
  • These primer compositions are used as primers or adhesion activators for the pretreatment of surfaces to be bonded or sealed.
  • the object of the present invention is therefore to provide a means which overcomes the disadvantages of the prior art and in particular enables to apply liquids to a predefined area of a surface and then to wipe them off again.
  • This means for applying and wiping a liquid is particularly suitable for adhesion promoter compositions which are used for improving the adhesion of adhesives and sealants.
  • an agent according to the invention allows a fast and reliable application process of a liquid, in particular a bonding agent composition, which leads to a faster and safer process during bonding and sealing and to lower material or processing costs.
  • the present invention relates to a means for applying and wiping at least one liquid to a substrate surface comprising a container having a filling space and at least one opening for applying the liquid, characterized in that the means at the Outside of the container, which does not contain the at least one opening, at least one porous carrier material for wiping the liquid.
  • the container may for example be a tube or a can.
  • the container comprises at least one opening for applying the liquid.
  • the at least one opening is arranged on one side of the container, preferably on the lid or on the tube head. If the container is a can, preferably the can lid comprises at least one, preferably a plurality of openings, preferably a plurality of small holes.
  • the container is made of a stable or easily deformable, preferably thin-walled material.
  • the material is a plastic, cardboard or a metal, for example aluminum, or a composite material, for example a plastic coated with aluminum.
  • a plastic is in particular polyolefin, preferably polypropylene or polyethylene or mixtures thereof, in question.
  • the container can be made of a material throughout, or it can be made of different materials.
  • the container preferably comprises a bottom, a lid and at least one wall, preferably a jacket.
  • the bottom, the lid and the at least one wall can be made of the same material or of different materials and be produced individually or in one piece, for example cast.
  • the lid may be made of a different material than the rest of the container, for example of a film which is einstechbar.
  • the container is preferably round, oval or angular, for example, three, four, five or polygonal, preferably hollow cylindrical, formed.
  • the container can contain indentations, protuberances or other deformations or form as ergonomic as possible, so that the user can hold the container well and the application and wiping is simplified.
  • the container may additionally contain support elements, for example clamp holders or screws or others. Such Retaining elements are particularly preferred when the container is being used by machine and the container will attach to a machine.
  • a filling space which can be filled with liquid.
  • the container which has at least one opening, can be closed so that the liquid does not escape unhindered. This is particularly preferred when the liquid is directly in the filling space of the container, without being additionally closed in a small container.
  • the at least one porous carrier material for wiping off the liquid is arranged on that outer side of the container which contains no opening.
  • the porous carrier material is arranged on the outside of the container opposite the opening, preferably at the bottom of the container.
  • the porous carrier material can also be arranged on more than one outer side of the container, for example on the bottom and on an outer wall of the container, or only on an outer wall.
  • porous is meant throughout the present text a material having gaps, in particular cavities, which can receive a liquid or which are permeable to a liquid.
  • a fiber material for example a fleece, felt or brush is also understood to be porous in the sense of the present invention.
  • the porous carrier material for wiping off the liquid preferably comprises or is a fibrous material or a sponge.
  • the fibers comprise or consist of organic or synthetic material.
  • it is cellulose, cotton fibers, protein fibers or synthetic fibers.
  • synthetic fibers are especially preferred fibers of polyester or of a homo- or copolymers of Ethylene and / or propylene or of viscose.
  • the fibers may here be short fibers or long fibers, spun, woven or non-woven fibers or filaments.
  • the fibers may be directional or stretched fibers.
  • the fiber material comprises cavities. These cavities are constructed by suitable manufacturing methods. It is preferred that the cavities are not completely closed, but that they communicate with the environment directly or via channels. This is intended to create a sponge-like structure which in particular enables a high absorption capacity of liquids.
  • the body constructed of fibers can be prepared by a variety of methods known to those skilled in the art.
  • bodies are used which are a fabric, scrim or knitted fabric.
  • the fiber material may be a looser material of staple fibers or filaments, the cohesion of which is generally given by the inherent adhesion of the fibers.
  • the individual fibers may have a preferred direction or be undirected.
  • the body made of fibers can be mechanically consolidated by needling, meshing or by swirling by means of sharp water jets.
  • a fiber material is a microfiber cloth, felt or fleece. But also wool or brush can be used.
  • a material which consists of foamed elastic material Both organic and synthetic material is suitable, in particular a plastic or natural sponge made using blowing agents.
  • the sponge comprises cavities or pores which are built up by suitable manufacturing methods or which are contained in the natural sponge. It is preferred that the cavities are not completely closed, but that they communicate with the environment directly or via channels. This should be a spongy structure can be created, which allows in particular a high absorption capacity of liquids.
  • the foamed plastic is made of polymers comprising or consisting of natural or synthetic elastic polymers, rubber of vulcanized rubber or thermoplastics.
  • a suitable as a sponge plastic is at service temperature, that is at temperatures between -20 to 50 ° C, preferably between 0 to 40 ° C, more preferably between 10 to 30 ° C, especially at 20 ° C, elastic.
  • suitable polymers are curing products of polymers which contain isocyanate groups, acrylate groups, epoxy groups and / or silane groups or mixtures thereof. Particularly suitable are polymers based on polyurethanes. Also suitable are melamine foams.
  • the fiber material in particular a cloth, felt or fleece, or the sponge may additionally be coated, in particular flocked, preferably with fibers of organic or synthetic material.
  • the fibrous material or sponge may first be coated with an adhesive and then flocked with fibers so that the fibers, such as natural hair, adhere to the adhesive and form a carpet or brush-like layer.
  • the adhesive must be a porous adhesive that is permeable to a liquid.
  • coated fiber materials or sponges are particularly suitable for the application agent which is used for applying the liquid to at least one substrate surface.
  • the outer side of the container having the at least one opening has an application means which simplifies the application of the liquid to a substrate surface.
  • the application agent for applying the liquid is preferably a sponge or a fibrous material. It is such a sponge or Fiber material suitable, as described above for the porous support material.
  • the application agent and the porous carrier material can consist of the same material in the composition for applying and wiping a liquid according to the invention or they can be made of different materials.
  • the porous carrier material and the application agent is one of a felt or melamine foam.
  • the application agent is preferably a fiber material, in particular a felt.
  • the application agent is preferably a sponge, in particular of melamine foam.
  • the application agent can always be made in the color red and the porous carrier material always in the color yellow, so that the consumer knows immediately that a liquid is applied with the red material and wiped off again with the yellow material.
  • the application agent and the porous carrier material are preferably attached to the container.
  • the attachment can be done, for example, chemically or mechanically, in particular by gluing, jamming, or nail, screw, barbs or rivets.
  • the application agent or the porous carrier material can first be attached to a molded part, which ensures a bond with the container in the edge region. This composite is preferably achieved via a screw connection via a thread.
  • the liquid is filled directly into the filling space of the container.
  • the container is preferably made of a stable material such as metal, a rigid plastic, or a composite material, such as a plastic coated with aluminum.
  • the lid is preferably made of a plastic or a foil, for example of an aluminum foil or a composite foil of aluminum and plastic, and may be either removed for application or at least partially opened, for example, pierced.
  • the at least one liquid is filled into at least one separate small container, which can be introduced into the filling space of the container.
  • the at least one small container is preferably made of a material which is destructible by the application of pressure, in particular breaks, bursts or einreisst, for example of a brittle material, preferably made of glass or of a thin brittle plastic or a bag, in which by pressure the seam breaks.
  • a brittle material preferably made of glass or of a thin brittle plastic or a bag, in which by pressure the seam breaks.
  • Particularly suitable for this purpose are aluminum or glass or composite materials or other brittle materials, such as a thin brittle plastic.
  • the at least one small container can be an aluminum bag or a plastic bag coated with aluminum. This type of material has the advantage that the wall of the small container is completely separable, and therefore does not require accurate positioning of the bag.
  • the at least one small container breaks or it ruptures, and the liquid can escape into the filling space of the container.
  • the liquid is initially sealed in at least one small container and can only escape through the opening of the container after the small container has been broken. Since the small container is located inside the container, the container in this embodiment must be made of a material which is deformable so that the at least one small container can be broken through the container.
  • the container is made of a bendable plastic or cardboard, which, although deformable, is still sufficiently stable that it does not break when the at least one small container is broken.
  • a small container in the actual container has the advantage that the opening of the container does not necessarily have to be closed, and that if necessary, the required liquid very quickly can be made accessible and applied.
  • more than one small container may be used, for example two or three or more.
  • different liquids can be stored, which mix only after destroying the multiple small container and possibly react with each other. In this way, for example, two-component systems can be used.
  • a suitable two-component composition is, for example, a two-component adhesion promoter composition for surface pretreatment which comprises two components, the first component comprising at least one hydrolyzable adhesion promoter substance which is selected from the group comprising organosilicon compounds, organotitanium compounds, organozirconium compounds and mixtures thereof, as described below. Furthermore, the second component comprises at least one compound which reacts with the adhesion promoter substance or which triggers or catalyzes a condensation of the adhesion promoter substance, for example a catalyst as described below for the adhesion promoter composition, in particular an organotin compound or an acid.
  • the first component comprising at least one hydrolyzable adhesion promoter substance which is selected from the group comprising organosilicon compounds, organotitanium compounds, organozirconium compounds and mixtures thereof, as described below.
  • the second component comprises at least one compound which reacts with the adhesion promoter substance or which triggers or catalyzes a condensation of
  • the first and second components are in the unopened state in two separate chambers by at least one partition, for example, in two small containers and are mixed after opening the two small container in the filling of the container of the inventive composition before the mixed composition applied to at least one substrate surface becomes.
  • Mixing can be assisted by shaking.
  • the container may contain an element for mixing, for example one or more balls as a mixing aid, so that the at least two components are well mixed.
  • the ball may be provided with tips or edges as needed to facilitate tearing or destruction of the partition.
  • the thickness and type of the partition and the amount and surface shape of the balls used is to be chosen such that the destruction of the partition by simply shaking the package is possible, but not unintentionally, as with small shocks, such as occur during transport.
  • the thus prepared adhesion promoter composition is applied to a surface to be bonded or sealed.
  • a short time typically less than half an hour, between opening the at least two small containers and thus contacting the two components and the application on the substrate surface must be in order to achieve an optimal adhesion promoter effect.
  • the adhesion promoter composition is applied immediately.
  • liquid is meant throughout the present text a mass which flows, and which has a viscosity of less than 1000 mPa * s, preferably less than 500 mPa * s, even more preferably less than 100 mPa * s.
  • Particularly suitable according to the present invention are liquids which are low in viscosity and have a dynamic toughness of less than 100 mPa * s, preferably up to about 10 to 60 mPa * s.
  • solids-free liquids are particularly preferred.
  • liquids containing solid particles, such as soot are suitable.
  • the liquid is preferably a solution, an emulsion, a suspension or a dispersion, for example a paste.
  • stability is an important feature.
  • the stability can be controlled by a person skilled in the art, for example by varying solvents, concentrations, process parameters during production or by using suitable additives, in particular surfactants, emulsifiers, coemulsifiers or stabilizers.
  • the liquid can be for example a cleaning agent or a bonding agent.
  • adhesion promoter compositions in particular adhesion promoter compositions comprising at least one hydrolyzable adhesion promoter substance, in particular containing or consisting of a silane, titanate and / or zirconium compound.
  • the at least one hydrolyzable adhesion promoter substance can be an organosilicon compound.
  • organosilicon compounds known to the person skilled in the art, which are used as adhesion promoters, are suitable.
  • This organosilicon compound preferably carries at least one, in particular at least two, alkoxy groups which are or are bonded directly to a silicon atom via an oxygen-silicon bond.
  • the organosilicon compound carries at least one substituent which is bonded via a silicon-carbon bond to the silicon atom, and which optionally has a functional group which is selected from the group comprising oxirane, hydroxy, (meth) acryloxy, amino , Mercapto and vinyl groups.
  • organo-silicon compounds are organosilicon compounds of the formulas (I) or (II) or (III)
  • R 1 here represents a linear or branched, optionally cyclic, alkylene group having 1 to 20 C atoms, optionally with aromatic moieties, and optionally with one or more heteroatoms, in particular nitrogen atoms.
  • R 2 here stands for an alkyl group having 1 to 5 C atoms, in particular methyl or ethyl, or an acyl group.
  • R 3 here stands for an alkyl group having 1 to 8 C atoms, in particular methyl.
  • X here stands for an H, or a functional group which is selected from the group comprising oxirane, OH, (meth) acryloxy, amine, SH, acylthio and vinyl, preferably amine.
  • R 4 is alkyl, in particular having 1 to 20 carbon atoms, and the dashed line represents the bond to the substituent R 1 .
  • X 1 here stands for a functional group which is selected from the group comprising NH, S, S 2 and S 4 .
  • X 2 here stands for a functional group which is selected from the group comprising N and isocyanurate. a stands for one of the values 0, 1 or 2, preferably 0.
  • the substituent R 1 is in particular a methylene, propylene, methylpropylene, butylene or dimethylbutylene group. As is particularly preferred. As substituent R 1 is a propylene group.
  • Amino, mercapto or oxirane group-containing organosilicon compounds are also referred to as “aminosilanes”, “mercaptosilanes” or “epoxysilanes”.
  • Suitable organosilicon compounds of the formula (I) are, for example, the organosilicon compounds selected from the group comprising octyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, methyloctyldimethoxysilane; 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane; 3-methacryloxypropyltrialkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-amino-2-methylpropyltrimethoxysilane, N- (2-aminoethyl) -3-amin
  • organosilicon compounds cleave acetic acid in the hydrolysis.
  • organosilicon compounds are those which have an organic substituent bonded to the silicon atom, which additionally have a functional group, that is to say which is not an alkyl group, and a formula (I) in which X is not H. ,
  • Suitable organosilicon compounds of the formula (II) are, for example, the organosilicon compounds selected from the group comprising bis [3- (trimethoxysilyl) -propyl] -amine, bis- [3- (triethoxysilyl) -propyl] -amine, 4 , 4,15,15-tetraethoxy-3,16-dioxa-8,9,10,11-tetrathia-4-15-disilaoctadecane (bis (triethoxysilylpropyl) polysulfide or bis (triethoxysilylpropyl) tetrasulfane), bis (triethoxysilylpropyl) disulfide.
  • 3-aminopropyltrimethoxysilane N- (2-aminoethyl ) -3-aminopropyltrimethoxysilane, bis [3- (trimethoxysilyl) -propyl] -amine, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane and bis [3- (triethoxysilyl) -propyl] - amine and their mixtures with each other. It has been found that especially with aminosilanes
  • the at least one hydrolyzable adhesion promoter substance can furthermore be an organotitanium compound.
  • organotitanium compounds which are known to the person skilled in the art and which are used as adhesion promoters are suitable.
  • organotitanium compounds which carry at least one functional group selected from the group consisting of alkoxy group, sulfonate group, carboxylate group, dialkyl phosphate group, dialkyl pyrophosphate group and acetylacetonate group, or mixtures thereof, and which have an oxygen-titanium bond directly to a titanium atom is bound.
  • Particularly suitable compounds are those wherein all of the titanium-bonded substituents are selected from the group consisting of alkoxy group, sulfonate group, carboxylate group, dialkyl phosphate group, dialkyl pyrophosphate group and acetylacetonate group, wherein all substituents may be identical or different from each other.
  • Particularly suitable sulfonic acids are aromatic sulfonic acids whose aromatic groups have been substituted by an alkyl group.
  • Preferred sulfonic acids are radicals of the following formula (V)
  • carboxylates of fatty acids have proved particularly suitable as carboxylate groups.
  • Preferred carboxylates are decanoate.
  • Organo-titanium compounds are commercially available, for example from Kenrich Petrochemicals or DuPont.
  • suitable organotitanium compound compounds are, for example, Ken-React® KR TTS, KR 7, KR 9S, KR 12, KR 26S, KR 33DS, KR 38S, KR 39DS, KR44, KR 134S, KR 138S, KR 158FS, KR212, KR 238S, KR 262ES, KR 138D, KR 158D, KR238T, KR 238M, KR238A, KR238J, KR262A, LICA 38J, KR 55, LICA 01, LICA 09, LICA 12, LICA 38, LICA 44, LICA 97, LICA 99, KR OPPR, KR OPP2 from Kenrich Petrochemicals or Tyzor® ET, TPT, NPT, BTM, AA, AA-75, AA-95, AA-105, TE,
  • organotitanium compounds having substituents of the formulas (IV) and / or (V) bonded to the titanium atom via an oxygen-titanium bond.
  • the at least one hydrolyzable adhesion promoter substance can furthermore be an organozirconium compound.
  • organozirconium compounds known to the person skilled in the art, which are used as adhesion promoters, are suitable.
  • Particularly suitable are organozirconium compounds which carry at least one functional group which is selected from the group comprising alkoxy group, sulfonate group, carboxylate group, phosphate group or mixtures thereof, and which is bonded directly to a zirconium atom via an oxygen-zirconium bond.
  • alkoxy groups are, in particular, isopropoxy and so-called neoalkoxy substituents, in particular of the formula (IV) as described above, the dashed bond indicating the oxygen-zirconium bond in this case.
  • Particularly suitable sulfonic acids are aromatic sulfonic acids whose aromatic groups have been substituted by an alkyl group.
  • Preferred sulfonic acids are radicals of the following formula (V) as described above, where the dashed bond indicates the oxygen-zirconium bond.
  • carboxylates of fatty acids have proved particularly suitable as carboxylate groups.
  • Preferred carboxylates are stearates and isostearates.
  • Organozirconium compounds are commercially available, for example from Kenrich Petrochemicals.
  • suitable organozirconium compounds are, for example, Ken-React® NZ 38J, NZ TPPJ, KZ OPPR, KZ TPP, NZ 01, NZ 09, NZ 12, NZ38, NZ 44, NZ 97.
  • the adhesion promoter substance of the composition according to the invention may contain mixtures of at least one organosilicon compound with at least one organotitanium compound and / or with at least one organozirconium compound.
  • mixtures of at least one organotitanium compound with at least one organozirconium compound possible. Preference is given to mixtures of at least one organosilicon compound with at least one organotitanium compound.
  • adhesion promoter substances of the formulas (I) have proved particularly suitable as mixtures of organosilicon compounds, where at least one of these substituents carries H as substituent X and at least one of these substances has a functional group which is selected from the group comprising oxirane, (Meth ) acryloxy, amine, SH and vinyl, carries as substituents X.
  • These mixtures are preferably at least one alkyl trialkoxysilane with an aminoalkyltrialkoxysilane and / or mercaptoalkyltrialkoxysilane.
  • the adhesion promoter composition may comprise further constituents in addition to the described hydrolyzable adhesion promoter substances.
  • a further ingredient for example, at least one solvent in question.
  • mixtures of different solvents are advantageous. It has proven particularly suitable if mixtures of hydrocarbons with one another or mixtures of at least one hydrocarbon with at least one polar solvent which has at least one heteroatom in its structural formula are used.
  • the hydrocarbon may be saturated or olefinically or aromatically unsaturated.
  • the hydrocarbon is saturated.
  • O, N and S are particularly suitable.
  • the at least one heteroatom is an oxygen atom, which is particularly preferably in the form of hydroxyl, carbonyl, ether, carboxylic acid or carboxylic acid derivative groups, such as ester, amide or carboxylate group, in the structural formula of the polar solvent ,
  • Preferred polar solvents are water, alcohols and ketones.
  • Most preferred polar solvents are alcohols, in particular saturated, branched or linear or cyclic alcohols having 1 to 8 carbon atoms, preferably methanol, ethanol, propanol, isopropanol, butanol, higher alcohols such as ethylene glycol, glycerol, polyether polyols such as polyethylene glycols and ether alcohols such as butyl glycol, Methoxypropanol, and alkylpolyethylene glycols.
  • Aldehydes, esters, ethers, amides or ketones are also suitable, in particular acetone, methyl ethyl ketone, hydrocarbons, in particular methyl esters, ethyl esters, isopropyl esters, heptane, hexane, cyclohexane, xylene, toluene, octane, white spirit and mixtures thereof.
  • mixtures of water with alcohols having a water content of more than 50 wt .-%, preferably more than 65 wt .-%, in particular more than 80 wt .-%.
  • Solvent mixtures of an alcohol and of an aliphatic or cycloaliphatic hydrocarbon are particularly preferred.
  • the mixture of ethanol and heptane has been shown.
  • the content of solvent is preferably selected such that the content of organosilicon compound and / or organotitanium compound from 0.01 to 10 wt .-%, in particular between 0.5 to 10 wt .-%, having.
  • a reactive or non-reactive binder may be present.
  • Polyurethane prepolymers with isocyanate groups and / or silane groups are particularly suitable as reactive binders; or polyisocyanates may be present be, for example, tris (4-isocyanatophenyl) methane, tris (4-isocyanatophenyl) thiophosphate, the already mentioned monomeric MDI, TDI, HDI and IPDI, and oligo-, poly or copolymers of these monomers, such as polymeric HDI polymeric MDI, available commercially for example as Voranate ® M 229 (Dow), Desmodur ® VL R 20 (Bayer), or allophanates, biurets, uretdiones and isocyanurates of these monomers, in particular HDI biurets, such as commercially available as Desmodur ® N 100 (Bayer), Luxate ® HDB 9000 (Lyon
  • Binders based on epoxy resin or polyacrylate are particularly suitable as non-reactive binders.
  • Catalysts for the hydrolysis of, for example, silane groups for example in the form of organic carboxylic acids such as benzoic or salicylic acid, organic carboxylic anhydrides such as phthalic anhydride or hexahydrophthalic anhydride, silyl esters of organic carboxylic acids, organic sulfonic acids such as p-toluenesulfonic acid or Dodecylbenzenesulfonic acid, or other organic or inorganic acids, or mixtures of the aforementioned acids; and catalysts for the reaction of isocyanate groups, for example, tin compounds such as stannous octoate, monobutyltin trichloride, dibutyltin dichloride, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dicarboxylates, dioctylt
  • Zinc compounds such as zinc (II) octoate, and amino group-containing compounds such as 2,2'-dimorpholinodiethyl ether, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undo-7-ene; and other catalysts such as titanates and zirconates.
  • wetting agents fillers and additives can be used.
  • fillers and additives can be used.
  • examples of non-limiting nature of this are talc, soot, fumed silicas, chalks whose surfaces have been modified if necessary, organic and inorganic pigments, stabilizers, flow control agents, defoamers, surfactants, biocides, anti-settling agents, inhibitors, dyes, corrosion inhibitors, odors and chemical and physical drying agents.
  • UV absorbers and optical brighteners are also suitable as further constituents.
  • Such optical brighteners absorb UV light and emit visible, usually blue light.
  • a preferred optical brightener is Ciba Uvitex® OB from Ciba Specialty Chemicals.
  • Further suitable brighteners are, for example, in Kirk-Othmer, "Encyclopedia of Chemical Technology", 4th Ed., John Wiley & Sons, New York, Vol. 11, pp. 227-241 specified.
  • the UV absorbers may be, for example, organic in nature, such as those from the Tinuvin® product line of Ciba Specialty Chemicals, or they may be inorganic in nature, such as color pigments, especially carbon black or titanium dioxide.
  • a liquid which comprises or consists of a cleaning agent.
  • the cleaning agent preferably comprises a solvent.
  • solvents the same are suitable, as already described above for the adhesion promoter composition.
  • the solvent is water or alcohol, especially ethanol or heptane.
  • the cleaning agent preferably comprises a wetting agent.
  • wetting agents are anionic surfactants, in particular alkylbenzenesulfonates, or nonionic surfactants, especially ethoxylates.
  • Especially suitable wetting agents are ethoxylated polysiloxanes, ethoxylated fluorosurfactants, dodecylbenzenesulfonates or nonylphenol ethoxylates.
  • the cleaning agent may contain other fillers and additives.
  • these are adhesion promoters, talc, carbon black, fumed silicas, silicates, chalks, organic and inorganic pigments, stabilizers, flow control agents, defoamers, surfactants, biocides, anti-settling agents, inhibitors, dyes, corrosion inhibitors, odors and chemical and physical drying agents.
  • the cleaning agent comprises at least one silicic acid or at least one silicate or mixtures thereof.
  • those silicic acids or silicates are preferred which have a Mohs hardness of less than that of glass, preferably less than 7, preferably less than 6.6, more preferably less than 6, so that the glass or glass-ceramic surface will not be scratched.
  • suitable silicas are amorphous or colloidal silicas, such as fumed silicas or silica gel. Particularly preferred is a fumed silica, e.g. commercially available as Aerosil® from Degussa.
  • the silicates include the salts and esters of orthosilicic acid.
  • silicates are the layered silicates, in particular the clay minerals belonging to the layered silicates, such as, for example, kaolinite, dickite, nacrite, smectites, glauconite, vermiculite or bentonite. Particularly preferred are bentonites.
  • a cleaning agent is preferably used for removing unwanted impurities, in particular silicone compounds or oils which are present as impurities on a wafer surface, in particular on a glass or glass ceramic surface.
  • the agent according to the invention can also be used to apply more than one liquid at the same time or a mixture of several liquids.
  • the container of the inventive composition may contain a plurality of chambers, for example a plurality of small containers.
  • the different chambers may contain the same or different liquids.
  • the Chambers are continuously separated by at least one partition, so that they may come into contact with each other or mixed after exiting the plurality of openings on the substrate surface, if necessary.
  • the container includes a plurality of small containers which may be destroyed so that the multiple liquids may still be mixed in the container before being applied to a substrate surface.
  • the agent according to the invention can be used in particular for applying and wiping a liquid, in particular a bonding agent composition.
  • the application and wiping of the liquid with the agent according to the invention can be carried out manually or mechanically, in particular by means of robots.
  • the substrate, on the surface of which the liquid is applied can be very different.
  • inorganic substrates such as glass, glass ceramic, concrete, mortar, brick, brick, plaster and natural stones such as granite or marble; Metals or alloys such as aluminum, steel, non-ferrous metals, galvanized metals; organic substrates such as wood, chipboards, plastics such as PVC, polycarbonates, PMMA, polyesters, epoxy resins; coated substrates such as powder-coated metals or alloys; and paints and varnishes, in particular automotive finishes.
  • the most preferred substrates are glass, especially with ceramic coated glass, painted surfaces, such as painted metal flanges, and plastics, in particular PVC.
  • the present invention can be used in particular in the pretreatment of substrate surfaces, which are then to be joined with an adhesive or sealant. Suitable applications are therefore, for example, the bonding of components in construction or civil engineering and in the manufacture or repair of industrial goods or consumer goods, especially windows, household machines or means of transport such as vehicles by sea or on land, preferably automobiles, buses, trucks, trains or Ships; the sealing of joints, seams or cavities in industrial production or repair, or in civil engineering.
  • the present invention is particularly suitable for applying a primer substance to a pane, preferably made of glass, where the pane is to be bonded, in particular glued, to at least one further substrate made of glass, wood, lacquer or plastic, in particular polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • the method according to the invention can preferably be used in vehicle construction, where glass is bonded to a body coated with paint, or in door or window construction, where glass is glued to a frame made of wood or plastic.
  • the invention relates to a method for bonding and / or sealing at least two substrate surfaces S1 and S2 comprising the steps: (a) applying and wiping off a primer composition by using a previously described agent on a substrate S1 and / or a substrate S2; (b) applying an adhesive or sealant to at least one substrate surface S1 and / or S2 or between the substrates S1 and S2; optionally (c) contacting the substrates S1 and S2 over the applied adhesive or sealant; and; (d) curing the applied adhesive or sealant; wherein the substrates S1 and S2 are the same or different from each other.
  • the composition When used as a sealant, the composition is applied between the substrates S1 and S2 and then the curing takes place. Usually, the sealant is pressed into a joint.
  • the application of the adhesive or sealant is preferably uniform.
  • the substrate S1 may be the same as or different from substrate S2 .
  • Suitable substrates S1 or S2 are, for example, inorganic substrates such as glass, glass-ceramic, concrete, mortar, brick, brick, gypsum and natural stones such as granite or marble; Metals or alloys such as aluminum, steel, non-ferrous metals, galvanized metals; organic substrates such as wood, plastics such as PVC, polycarbonates, PMMA, polyesters, epoxy resins; coated substrates such as powder-coated metals or alloys; and paints and varnishes, in particular automotive finishes.
  • inorganic substrates such as glass, glass-ceramic, concrete, mortar, brick, brick, gypsum and natural stones such as granite or marble
  • Metals or alloys such as aluminum, steel, non-ferrous metals, galvanized metals
  • organic substrates such as wood, plastics such as PVC, polycarbonates, PMMA, polyesters, epoxy resins
  • coated substrates such as powder-coated metals or alloys
  • paints and varnishes in particular automotive finishes.
  • one-component moisture-curing adhesives or two-component polyurethane adhesives are suitable as polyurethane adhesives.
  • Such adhesives contain polyisocyanates, especially in the form of isocyanate group-containing prepolymers.
  • Polyurethane adhesives such as those sold by Sika Nurse AG under the product lines Sikaflex®, SikaPower® and SikaForce®, are preferred.
  • (Meth) acrylate adhesives are to be understood as meaning two-component adhesives whose first component comprises acrylic acid and / or methacrylic acid and / or their esters, and whose second component comprises a free-radical initiator, in particular a peroxide.
  • Preferred such adhesives are commercially available from Sika Nurse AG under the SikaFast® product line.
  • Epoxy adhesives are adhesives which are formulated on the basis of glycidyl ethers, in particular diglycidyl ethers of bisphenol A and / or bisphenol F. Particularly suitable are two-component epoxy resin adhesives, one component of which is diglycidyl ether of Contain bisphenol-A and / or bisphenol-F and contain the second component polyamines and / or polymercaptans. Preference is given to two-component epoxy resin adhesives, such as those commercially available from Sika GmbH under the product line Sikadur®.
  • the two-component epoxy resin adhesives Sikadur®-Combiflex®, Sikadur®-31, Sikadur®-31DW and Sikadur®-33, preferably Sikadur®-Combiflex®, from Sika Buch AG have proven particularly suitable for bonding films.
  • Adhesives based on alkoxysilane-functional prepolymers are understood in particular to be adhesives based on MS polymers or SPUR (silane-terminated polyurethane) prepolymers.
  • the substrates can be pretreated prior to the application of the adhesive or sealant in addition to the application of an adhesion promoter composition.
  • a primer solution or a primer such pretreatments include in particular physical and / or chemical cleaning processes, for example sanding, sandblasting, brushing or the like, or treatment with cleaners or solvents.
  • a glued or sealed article is obtained.
  • Such an article may be a building, in particular a building of civil engineering, or a means of transport.
  • the article is preferably a means of transport, for example a vehicle by land or water, in particular an automobile, a bus, a truck, a train or a ship, or an attachment thereof.
  • the bonded or sealed article is a means of transport, in particular an automobile, or an attachment of a means of transport, in particular an automobile.
  • the agent according to the invention is particularly suitable for the simple application and wiping of a liquid on a substrate surface.
  • the inventive means simplifies the workflow and reduces the material consumption, since with a means the two steps can be carried out applying and wiping and it no additional cloth or no additional sponge is needed in a further step. For each step, both for the application as for wiping clean material is present and it must not be searched for a clean material for the application after wiping for wiping.
  • the agent according to the invention is particularly suitable for one-way applications, in particular for repair applications in the vehicle sector.
  • Fig. 1A shows a schematic representation of a longitudinal section through a container 2, which is suitable for the inventive means for applying and wiping a liquid.
  • a container 2 which comprises a cover 10, a bottom 11 and two side walls 12.
  • the two side walls 12 are part of a Sheath, such as a can or a tube.
  • the lid 10, the bottom 11 and the side walls 12 are shown in one piece. But they can also be made individually and be made of different materials.
  • the lid 10 includes at least one opening 4.
  • the lid 10 can also be attached as a separate part to the at least one opening 4 containing side of the container 2, so that the opening is closed and the liquid does not escape unintentionally.
  • the lid may be removed, for example, torn off or turned away. Through this at least one opening 4, the liquid can escape from the container 2 and applied to a substrate surface.
  • the outside 9 of the container is also shown.
  • Fig. 1A shows only one embodiment of a container 2 and not the inventive means for applying and wiping a liquid, which would additionally comprise a porous carrier material for wiping the liquid.
  • Figs. 1B, 1C and 1D show various outlines of a container 2. Here, a section along the line AA through the container 2 of Fig. 1A is shown.
  • the container 2 is formed in a hollow cylinder.
  • the filling space 3 is encased by the container 2, which has an outer side 9.
  • the cross section is circular.
  • Fig. 1C the cross section through the container 2 is triangular, pentagonal in Fig. 1D.
  • Fig. 2A shows a schematic representation of a longitudinal section through an inventive means 1, which is suitable for applying and wiping a liquid 7.
  • Fig. 2A shows the porous substrate 5, which the outside 9 of the container 2 is mounted, which is on the, the at least one opening opposite side, ie at the bottom 11, is located.
  • the filling chamber 3 is filled with liquid 7 in this illustration.
  • the opening 4 by an application means 6, preferably covered by a sponge or felt.
  • the application agent 6 can either be attached to the opening during the production of the container 2, or the container 2 can be sold, for example, without application agent 6 and the application agent 6 can be attached to the opening 4 shortly before use, optionally after removal of a lid.
  • the liquid 7 soaks the felt or sponge 6 and can be applied by means of contact of the application agent 6 and a surface on a surface.
  • FIG. 2B and 2C show a section along the line BB through the side having the opening 4, here through the cover 10 of the container 2.
  • the lid 10 has a plurality of openings 4.
  • the lid 10 has an opening 4.
  • the opening may, for example, be a small hole or, for example, if a paste is used, a larger hole of a diameter of, for example, 0.1 mm to 10 mm.
  • Fig. 3A shows a schematic representation of a longitudinal section through a second embodiment of an inventive means 1.
  • the means shown in Fig. 3A comprises a porous substrate 5, which on the outside 9 of the container 2, which is located on the, the at least one opening adjacent side, ie on the side wall or on the jacket.
  • the bottom 11 has no porous carrier material 5 and at the opening 4 no application means 6 is attached.
  • the liquid 7 is not shown.
  • Fig. 3B shows a section along the line CC through the container 2 of Fig. 3A.
  • the container 2 preferably has an angular shape, which allows the holding of the container.
  • the container On the opposite side of the porous support material, the container has a bulge, for example, a pointed bulge, so that the container can be held and the liquid can be easily wiped off a surface.
  • the container comprises at least a portion of the length of a bulge for holding.
  • the bulge does not have to be on the entire length of the container.
  • the bulge may also serve to squeeze the liquid out of the opening. This can be done in particular if the container 2 is made of an elastic, deformable material.
  • a holder for example a clamping holder can also be attached to the container 2 in addition.
  • FIG. 4A shows a schematic representation of a longitudinal section through a third embodiment of a means 1 according to the invention.
  • the means shown in FIG. 4A has a tube shape which has a porous carrier material 5 at the bottom 11 .
  • the liquid 6 is in this embodiment, for example, a paste, which pressure action on the tube from the opening 4 can be pressed.
  • Fig. 4B shows a section along the line DD through the opening 4 of Fig. 4A.
  • the dashed line 9 represents the outside 9 of the tube, which lies in a deeper plane than the section DD.
  • FIG. 5A shows a preferred embodiment of a means 1 according to the invention.
  • the liquid 7 is located in a small container 8, which is located in the filling space 3 of the container 2.
  • the small container 8 is for example made of a fragile glass or plastic ampoule or a plastic or composite bag.
  • the small container 8 is preferably arranged in a tube arrangement or as shown in an ampoule arrangement.
  • This ampoule arrangement is embedded in a container 2 whose outer walls 9 are made of flexible plastic or cardboard.
  • this plastic container 2 has an opening 4, which is covered by an application means 6, in particular by a felt strip or a sponge.
  • the glass ampoules When activating the package, the glass ampoules are broken by bending the outer walls 9 or a blow on the outer walls 9 of the container 2 made of plastic or cardboard, so that the liquid 7 in the Container 2 flows.
  • the liquid 7 exits through the opening 4 and impregnates the felt or sponge 6 and can be applied by means of its contact with a surface.
  • the felt or sponge also helps to prevent any splinters that may result from the broken ampule from escaping from the container 2.
  • the means 1 in this embodiment has a porous carrier material 5 on the bottom 11, ie on the side opposite the opening 4.
  • This embodiment represents, in particular, a disposable package for the application and wiping of a liquid. It is especially well suited for small quantities.
  • this pack is suitable for the pretreatment of a vehicle window, in particular a car window.
  • FIG. 5B shows a further preferred embodiment of the means 1 according to the invention as already described in FIG. 5A.
  • the means 1 according to the invention shown in FIG. 5B comprises a container 2 with two small containers 8, which are arranged one behind the other.
  • the two small containers 8 contain two different liquids, preferably a first component 7 and a second component 7 '.
  • the partition walls 14 of the small containers 8 are broken by bending the outer walls 9 or striking the outer walls 9 of the container 2 made of plastic or cardboard, so that the two components 7, 7 'can mix and / or react with one another , Mixing can be assisted by shaking.
  • the container may contain an element for mixing, for example one or more balls 13 as a mixing aid, so that the at least two components 7, 7 'are well mixed.
  • the ball 13 may be provided with tips or edges as needed to facilitate tearing or destruction of the partition wall 14 of the small container 8.
  • the thickness and nature of the partition wall 14 of the small container 8 and the amount and surface shape of the balls used is to be chosen such that the destruction of the partition 14 by simply shaking the package is possible, but not unintentionally, as with small shocks, as in Transports occur.
  • FIG. 5C shows a further preferred embodiment of the means 1 according to the invention, as already described in FIGS. 5A and 5B, but with two small containers 8 which are arranged next to one another.
  • Fig. 5D shows a cross-section along the line EE through the container 2 of Fig. 5C.
  • the container 2 has in this embodiment an oval cross-section, which is particularly advantageous when the two small containers 8 are arranged side by side.
  • FIG. 5E shows a further preferred embodiment of the means 1 according to the invention as already described in FIGS. 5A and 5B, but with two small containers 8 which are arranged inside one another, that is to say for example in an ampoule-in-ampoule arrangement or in a bag-in Bag arrangement.
  • FIG. 6A shows a further embodiment of a means 1 according to the invention.
  • the filling space 3 of the container 2 contains two chambers 15, which are filled with two different liquids 7 and 7 '.
  • the two chambers are separated by a partition 14.
  • the partition wall 14 separates the filling space 3 of the container 2 in the longitudinal direction.
  • Each chamber 15 of the container 2 has an opening 4, which is preferably closed with a lid 10 before use of the inventive agent, so that the liquid does not escape unintentionally.
  • the cover 10 is removed or pierced, and an application means 6, in particular a felt strip or a sponge, is fastened to the side of the container 2 having the two openings 4.
  • the application agent 6 is attached from the beginning to the side of the container 2 having the two openings 4, and the cover 10, for example a tab, is pulled out can be, what you open the openings 4.
  • the means 1 in this embodiment has a porous carrier material 5 on the bottom 11, ie on the side opposite the opening 4.
  • This embodiment represents, in particular, a disposable package for the application and wiping of a liquid. It is especially well suited for small quantities. In particular, this pack is suitable for the pretreatment of a vehicle window, in particular a car window.
  • FIG. 6B shows a further embodiment of the device 1 according to the invention as already described in FIG. 6A.
  • the means 1 according to the invention shown in FIG. 6B comprises a container 2 with two chambers 15, which are separated from one another by a dividing wall 14, which is arranged transversely in the container 2.
  • the partition 14 break open or tear or burst, so that the two components 7, 7 'mix and / or can react with each other. Mixing can be assisted by shaking.
  • the container may contain an element for mixing, for example one or more balls 13 as a mixing aid, so that the at least two components 7, 7 'are well mixed.
  • the ball 13 may be provided with tips or edges as needed to facilitate tearing or destruction of the partition 14.
  • the thickness and nature of the partition 14 and the amount and surface shape of the balls used is to be chosen such that the destruction of the partition 14 by simply shaking the package is possible, but not unintentionally, as with small vibrations, such as occur during transport.
  • the substrate surface used was the air side of a float glass from the company Rocholl, Schönbrunn, Germany.
  • an agent according to the invention and a conventional process were used and the adhesion of the adhesive to the surface pretreated with the agent according to the invention was compared with the adhesion of the adhesive to the surface pretreated by conventional methods.
  • Sika® activator commercially available from Sika Buch AG
  • the adhesive was stored in a climate chamber ('KL') (23 ° C., 50% relative atmospheric humidity) and after a water storage of 7 days at 25 ° C. (WL ') and subsequent cataplasma storage ( , CP ') of 7 days at 70 ° C, 100% rel. Humidity, tested.
  • 'KL' 23 ° C., 50% relative atmospheric humidity
  • WL ' 25 ° C.
  • CP ' cataplasma storage

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Paints Or Removers (AREA)
  • Automobile Manufacture Line, Endless Track Vehicle, Trailer (AREA)
  • Vehicle Cleaning, Maintenance, Repair, Refitting, And Outriggers (AREA)
  • Coating Apparatus (AREA)
EP20060117918 2006-07-26 2006-07-26 dispositif pour appliquer et essuyer un liquide Withdrawn EP1882526A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP20060117918 EP1882526A1 (fr) 2006-07-26 2006-07-26 dispositif pour appliquer et essuyer un liquide
US12/309,318 US20090305054A1 (en) 2006-07-26 2007-07-26 Means for applying and wiping away a liquid
ES07802414T ES2340735T3 (es) 2006-07-26 2007-07-26 Medio para aplicar y eliminar por secado un liquido.
DE200750003334 DE502007003334D1 (de) 2006-07-26 2007-07-26 Mittel zum auftragen und abwischen einer flüssigkeit
RU2009106682A RU2409427C2 (ru) 2006-07-26 2007-07-26 Устройство для нанесения и стирания жидкости
AT07802414T ATE462503T1 (de) 2006-07-26 2007-07-26 Mittel zum auftragen und abwischen einer flüssigkeit
PCT/EP2007/057732 WO2008012352A1 (fr) 2006-07-26 2007-07-26 Moyen pour appliquer et éponger un liquide
EP20070802414 EP2049271B1 (fr) 2006-07-26 2007-07-26 Moyen pour appliquer et éponger un liquide
US13/067,256 US20110223326A1 (en) 2006-07-26 2011-05-19 Means for applying and wiping away a liquid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20060117918 EP1882526A1 (fr) 2006-07-26 2006-07-26 dispositif pour appliquer et essuyer un liquide

Publications (1)

Publication Number Publication Date
EP1882526A1 true EP1882526A1 (fr) 2008-01-30

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EP20060117918 Withdrawn EP1882526A1 (fr) 2006-07-26 2006-07-26 dispositif pour appliquer et essuyer un liquide
EP20070802414 Not-in-force EP2049271B1 (fr) 2006-07-26 2007-07-26 Moyen pour appliquer et éponger un liquide

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US (2) US20090305054A1 (fr)
EP (2) EP1882526A1 (fr)
AT (1) ATE462503T1 (fr)
DE (1) DE502007003334D1 (fr)
ES (1) ES2340735T3 (fr)
RU (1) RU2409427C2 (fr)
WO (1) WO2008012352A1 (fr)

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US8631941B2 (en) * 2010-04-22 2014-01-21 James Alexander Corporation Ampoule dispenser assembly and process
EP2760839B1 (fr) 2011-09-30 2015-11-25 Bristol-Myers Squibb Company Pyridinedione carboxamides convenant comme inhibiteurs de la lipase endothéliale
US10362848B1 (en) * 2017-10-03 2019-07-30 Elena Caruso Universal no-slip hairpin
JP7273390B2 (ja) * 2019-01-04 2023-05-15 株式会社ルミカ 物質収容器

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WO2003020358A1 (fr) * 2001-08-29 2003-03-13 Closure Medical Corporation Micro-applicateurs, systemes et procedes de distribution d'adhesifs et de produits d'etancheite

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EP1438097B1 (fr) 2001-09-04 2018-09-05 Covidien LP Catheter d'occlusion dote d'un ballon conforme pour une utilisation dans un systeme vasculaire complexe
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WO2000012411A2 (fr) * 1998-09-01 2000-03-09 Closure Medical Corporation Ensemble de conditionnement comportant un applicateur et un recipient de matieres adhesives
WO2003020358A1 (fr) * 2001-08-29 2003-03-13 Closure Medical Corporation Micro-applicateurs, systemes et procedes de distribution d'adhesifs et de produits d'etancheite

Also Published As

Publication number Publication date
EP2049271A1 (fr) 2009-04-22
DE502007003334D1 (de) 2010-05-12
US20090305054A1 (en) 2009-12-10
US20110223326A1 (en) 2011-09-15
ES2340735T3 (es) 2010-06-08
WO2008012352A1 (fr) 2008-01-31
RU2009106682A (ru) 2010-09-10
ATE462503T1 (de) 2010-04-15
EP2049271B1 (fr) 2010-03-31
RU2409427C2 (ru) 2011-01-20

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