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EP2101624A1 - Utilisation de mousses à cellules ouvertes dans les aspirateurs - Google Patents

Utilisation de mousses à cellules ouvertes dans les aspirateurs

Info

Publication number
EP2101624A1
EP2101624A1 EP07821696A EP07821696A EP2101624A1 EP 2101624 A1 EP2101624 A1 EP 2101624A1 EP 07821696 A EP07821696 A EP 07821696A EP 07821696 A EP07821696 A EP 07821696A EP 2101624 A1 EP2101624 A1 EP 2101624A1
Authority
EP
European Patent Office
Prior art keywords
dust
foams
open
range
vacuum cleaners
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Withdrawn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
EP07821696A
Other languages
German (de)
English (en)
Inventor
Ulf Baus
Stefan Frenzel
Bernhard Vath
Christof MÖCK
Stefan Tiekötter
Andre Bertram
Jörg KINNIUS
Cornelius Wolf
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP2101624A1 publication Critical patent/EP2101624A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • AHUMAN NECESSITIES
    • A47FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47LDOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L9/00Details or accessories of suction cleaners, e.g. mechanical means for controlling the suction or for effecting pulsating action; Storing devices specially adapted to suction cleaners or parts thereof; Carrying-vehicles specially adapted for suction cleaners
    • A47L9/10Filters; Dust separators; Dust removal; Automatic exchange of filters
    • AHUMAN NECESSITIES
    • A47FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47LDOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L9/00Details or accessories of suction cleaners, e.g. mechanical means for controlling the suction or for effecting pulsating action; Storing devices specially adapted to suction cleaners or parts thereof; Carrying-vehicles specially adapted for suction cleaners
    • A47L9/10Filters; Dust separators; Dust removal; Automatic exchange of filters
    • A47L9/12Dry filters
    • AHUMAN NECESSITIES
    • A47FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47LDOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L9/00Details or accessories of suction cleaners, e.g. mechanical means for controlling the suction or for effecting pulsating action; Storing devices specially adapted to suction cleaners or parts thereof; Carrying-vehicles specially adapted for suction cleaners
    • A47L9/10Filters; Dust separators; Dust removal; Automatic exchange of filters
    • A47L9/14Bags or the like; Rigid filtering receptacles; Attachment of, or closures for, bags or receptacles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids

Definitions

  • the present invention relates to the use of molded articles with dimensions of length-width-height each in the range of 1 mm to 3 cm as a dust binder in vacuum cleaners, wherein the molded article is or are made of chemically untreated open-cell foam having a density in the range of 5 to 500 kg / m 3 and a mean pore diameter in the range of 1 micron to 1 mm.
  • the present invention relates to vacuum cleaners comprising shaped articles characterized above.
  • Foams especially so-called open-cell foams, find applications in numerous applications.
  • open-cell foams of synthetic materials have proven to be versatile. Examples include seat cushions, filter materials, air conditioning systems and automotive parts, and cleaning materials.
  • vacuum cleaners in particular vacuum cleaners
  • dust retention systems are used, which are arranged between the air intake of a dust collecting chamber and the suction side of a fan and hold back the dust before it enters the fan.
  • a particularly well known variant is a bag-shaped filter that is internally pressurized, that is, the dust deposits inside the bag-shaped filter. Such filters must be replaced regularly.
  • vacuum cleaners especially in micro-vacuum cleaners, multi-purpose vacuum cleaners or commercial appliances, there are externally charged filters surrounding the blower.
  • bagless vacuum cleaners In addition to the vacuum cleaners described above, which have a bag or a bag, so-called “bagless vacuum cleaners” are used which work without dust bag. They usually contain a cyclone for dust separation or dust pre-separation and a downstream fine dust filter. Previously known bagless systems have the disadvantage that when emptying the cyclone - usually this is done via a flap at the bottom of the dust collector - a dust cloud is formed, which give this system an unhygienic aspect.
  • one or preferably at least two shaped bodies with dimensions of length-width height in the range of 1 mm to 3 cm are used as dust-binding agents in vacuum cleaners, the shaped bodies being made of chemically untreated open-cell foam having a density in the range from 5 to 500 kg / m 3 and a mean pore diameter in the range of 1 micron to 1 mm.
  • Moldings used according to the invention have dimensions of length-width height, in each case in the range from 1 mm to 3 cm, wherein at least one dimension, i. Length or width or height, greater than 5.5mm. At least two or all three dimensions may be greater than 5.5 mm.
  • moldings according to the invention are designed as cylinders, cylindrical disks, square columns, saddles, balls, flakes, granules, cuboids, cubes, preferably in the form of tablets or disks (pellets), but also as stars, letters , egg-shaped or hollow bodies containing moldings.
  • At least two shaped bodies are used, for example two to twenty, in particular two to five.
  • the moldings used according to the invention are approximately the same size, that is, the dimensions can vary by up to ⁇ 10%.
  • open-cell foams used according to the invention are those based on synthetic organic foam, for example foams based on polyurethane foams or aminoplast foams, for example urea-formaldehyde resins, and foams based on phenol-formaldehyde - Resins and in particular foams based on polyurethanes or aminoplast-formaldehyde resins, in particular melamine-formaldehyde resins, wherein foams based on polyurethanes in the context of the present invention also as polyurethane foams and foams based on melamine-formaldehyde resins as melamine Foams are referred to.
  • moldings used according to the invention are produced from open-celled foams which comprise synthetic organic materials, preferably polyurethane foams or aminoplast foams and in particular melamine foams.
  • the unmodified open-cell foams used for the production of moldings according to the invention are generally also referred to as unmodified foams in the context of the present invention.
  • the unmodified open-cell foams (a) used for carrying out the process according to the invention are described in more detail below.
  • the manufacturing method according to the invention is based on open-cell foam, in particular of foams in which at least 50% of all fins are open, preferably 60 to 100% and more preferably 65 to 99.9%, determined according to DIN ISO 4590.
  • Foams used as starting material are preferably hard foams, which in the sense of the present invention are foams which have a compressive strength of 1 kPa or more at a compression of 40%, determined in accordance with DIN 53577.
  • Foams used as starting material have a density in the range of 3 to 500 kg / m 3 , preferably 6 to 300 kg / m 3 and particularly preferably in the range of 7 to 300 kg / m 3 .
  • Open-celled foams used as starting material may have an average pore diameter in the range from 1 ⁇ m to 1 mm, preferably from 50 to 500 ⁇ m, determined by evaluating microscopic images of sections.
  • open-cell foams used as starting material may have a maximum of 20, preferably a maximum of 15, and particularly preferably a maximum of 10 pores per m 2 , which have a diameter in the range of up to 20 mm. The remaining pores usually have a smaller diameter.
  • open-cell foams used as starting material have a BET surface area in the range from 0.1 to 50 m 2 / g, preferably 0.5 to 20 m 2 / g, determined according to DIN 66131.
  • Foams made of synthetic organic material preferably of melamine foams.
  • Melamine foams which are particularly suitable as starting material for carrying out the preparation process according to the invention are known as such. They can be prepared, for example, by foaming i) a melamine-formaldehyde precondensate which, in addition to formaldehyde, may contain further carbonyl compounds such as aldehydes, ii) one or more blowing agents, iii) one or more emulsifiers, iv) one or more hardeners.
  • Melamine-formaldehyde precondensates i) may be unmodified, but may also be modified; for example, up to 20 mol% of the melamine may be replaced by other thermoset agents known per se, for example alkyl-substituted melamine, urea, urethane, carboxylic acid amides, dicyandiamide, guanidine , Sulfuryl amide, sulfonic acid amides, aliphatic amines, phenol and phenol derivatives.
  • other thermoset agents known per se, for example alkyl-substituted melamine, urea, urethane, carboxylic acid amides, dicyandiamide, guanidine , Sulfuryl amide, sulfonic acid amides, aliphatic amines, phenol and phenol derivatives.
  • modified melamine-formaldehyde precondensates may comprise, for example, acetaldehyde, trimethylolacetaldehyde, acrolein, furfurol, glyoxal, phthalaldehyde and terephthalaldehyde.
  • Suitable blowing agents ii) are: water, inert gases, in particular carbon dioxide, and so-called physical blowing agents.
  • Physical blowing agents are compounds which are inert to the starting components and which are usually liquid at room temperature and evaporate under the conditions of the urethane reaction. The boiling point of these compounds is preferably below 110 ° C., in particular below 80 ° C.
  • the physical blowing agents also include inert gases which are introduced into or dissolved in the starting components i) and ii), for example carbon dioxide, nitrogen or noble gases.
  • Suitable liquid at room temperature compounds are usually selected from the group comprising alkanes and / or cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes having 1 to 8 carbon atoms, and tetraalkylsilanes having 1 to 3 carbon atoms in the alkyl chain, in particular tetramethylsilane.
  • Examples which may be mentioned are: propane, n-butane, iso- and cyclobutane, n-, iso- and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl tert-butyl ether, methyl formate, acetone and fluorinated alkanes which are in the troposphere and are therefore harmless to the ozone layer, such as trifluoromethane, difluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2
  • Tetrafluoroethane 1,1,1-trifluoro-2,2,2-trichloroethane, 1, 1, 2-trifluoro-1, 2,2-trichloroethane, Difluoroethane and heptafluoropropane.
  • the said physical blowing agents can be used alone or in any combination with each other.
  • emulsifiers iii) it is possible to use customary nonionic, anionic, cationic or betainic surfactants, in particular C 12 -C 30 -alkyl sulfonates, preferably C 12 -C 18 -alkyl sulfonates and polyethylenated C 10 -C 20 -alkyl alcohols, in particular of the formula R 1 -O (CH 2 -CH 2 -O) y -H, wherein R 1 is selected from C 10 -C 20 -alkyl and y may, for example, denote an integer in the range from 5 to 100.
  • Suitable hardeners iv) are, in particular, acidic compounds, such as, for example, inorganic Br ⁇ nsted acids, e.g. Sulfuric acid or phosphoric acid, organic Br ⁇ nsted acids such as acetic acid or formic acid, Lewis acids and so-called latent acids.
  • acidic compounds such as, for example, inorganic Br ⁇ nsted acids, e.g. Sulfuric acid or phosphoric acid, organic Br ⁇ nsted acids such as acetic acid or formic acid, Lewis acids and so-called latent acids.
  • Suitable melamine foams can be found in EP-A 0 017 672.
  • foams used as starting material may contain additives and additives common in foam chemistry, for example, antioxidants, flame retardants, fillers, colorants such as pigments or dyes, and biocides, for example
  • biocides are silver particles or monomeric or polymeric organic biocides such as, for example, phenoxyethanol, phenoxypropanol, glyoxal, thiadiazines, 2,4-dichlorobenzyl alcohols and preferably isothiazolone derivatives such as, for example, MIT (2-methyl-3 (2H) -isothiazolone ), CMIT (5-chloro-2-methyl-3 (2H) -isothiazolone), CIT (5-chloro-3 (2H) -isothiazolone), BIT (1,2-benzisothiazol-3 (2H) -one), Furthermore, copolymers of N, N-di-C 1 -C 10 -alkyl- ⁇ -amino-C 2 -C 4 -alkyl (meth) acrylate, in particular copolymers of ethylene with N, N-di-methyl-2-aminoethyl ( meth) acrylate,
  • fillers are:
  • Activated carbon Activated carbon, colorants such as dyes or pigments, fragrances such as perfume, and odor traps, such as cyclodextrins.
  • additives and / or additives it is possible to proceed, for example, by using at least one chemically unmodified foam in various operations or preferably simultaneously contacted with aqueous formulation of at least one additive. Then you can dry.
  • such an aqueous formulation contains one or more additives in proportions of 0 to a total of 50% by weight, based on foam, preferably 0.001 to 30% by weight, particularly preferably 0.01 to 25 Wt .-%, most preferably 0.1 to 20 wt .-%.
  • aqueous formulation of at least one additive on at least one additive for the production of moldings used according to the invention, it is furthermore possible, after the action of aqueous formulation of at least one additive on at least one additive, to chemically unmodified foam to be compressed one or more times mechanically.
  • the mechanical compression can be carried out batchwise or preferably continuously, batchwise, for example by pressing or plates, continuously, for example by means of rollers or calenders. If one wishes to calender, one can perform one or more calendering passes, for example one to twenty calendering passes, preferred are five to ten calendering passes.
  • calendering is performed prior to drying.
  • the procedure is followed by first drying at least one additive after contacting and applying aqueous formulation, then moistening it with water and then mechanically compressing it, for example by calendering.
  • thermally fix at temperatures of 120 ° C. to 250 ° C. over a period of 5 seconds to 5 minutes.
  • Suitable apparatuses are, for example, microwave ovens, plate pressing plants, drying ovens heated electrically or with gas flames, heated rolling mills or continuously operated drying devices using hot air blowers.
  • At least one shaping step is carried out. In this case, contacting with an aqueous formulation of additive or additive - if such a step is desired - and the shaping step in any order. It is preferable to first contact with aqueous formulation of additive or additive - if such a step is desired - and then perform the shaping step.
  • the shaping step is carried out mechanically, for example by grinding, shredding, granulating, preferably by tearing correspondingly larger parts, by punching or by cutting.
  • unmodified foam is produced as a shaped body having the dimensions defined at the outset; in particular, foaming can be carried out in molds, so that moldings of chemically unmodified foam are obtained, which are subsequently treated with aqueous formulation of aggregate or contact additive.
  • Shaped bodies described above can be used for example as dust in vacuum cleaners, in such a way that they are not firmly installed in the vacuum cleaner in question, but move when operating the vacuum cleaner in the vacuum cleaner in question within certain limits.
  • Moldings according to the invention can be used as dust binders, in particular in so-called bagless vacuum cleaners.
  • Dust binders for the purposes of the present invention are capable of binding coarse dust and preferably also the fine dust sucked into the vacuum cleaner, partially or preferably predominantly, for example more than 50% by weight.
  • the dust collecting vessel may be formed, for example, as a cyclone.
  • several moldings are metered directly into the dust collecting vessel.
  • one or more addition devices which may be integrated within the vacuum cleaner or in a suction attachment, or as an external apparatus with a dust collecting device. can be formed Sammelgefäß. So you need no more active elements in the vacuum cleaner.
  • the adding device or the adding devices can be designed, for example, as a flap, piston, screw or nozzle.
  • the addition of dust binder can be done directly or via a lock.
  • moldings according to the invention are added directly into the dust collecting vessel and the dust collecting vessel is placed in the vacuum cleaner together with the moldings.
  • molded articles are automatically metered into the dust collecting vessel.
  • certain proportions of dust binder are continuously metered in and corresponding amounts are metered in continuously.
  • Such automatic replenishment can also be carried out depending on the amount of dust.
  • Dust collectors can have any shape and any size depending on the type of vacuum cleaner.
  • dust collecting vessels in the sense of the present invention may be cube-shaped, cylindrical, conical or irregularly shaped.
  • suitable volumes are 0.1 dm 3 to 2 dm 3 , but also larger volumes up to 10 dm 3 are conceivable.
  • the dust collecting vessel may be formed, for example, as a bag or a bag, as a box or as a cyclone (centrifugal separator).
  • the filling level of the dust collecting vessel can be monitored, for example, electronically or mechanically, for example with sensors.
  • the dust collecting vessel may be formed as a box or as a cyclone.
  • the dust collecting vessel includes a device for mixing, for example, a mechanical device such as a stirrer, or a motor which sets the dust collecting vessel in motion, for example in oscillations or rotations.
  • a device for mixing for example, a mechanical device such as a stirrer, or a motor which sets the dust collecting vessel in motion, for example in oscillations or rotations.
  • the dust collection vessel does not include a mixing device.
  • the dust collecting vessel is filled to 10 to 60% by volume with moldings according to the invention, preferably from 25 to 50% by volume. In another embodiment of the present invention, at least one, for example two to twenty and in particular two to five of the above-described moldings are filled into a dust collecting vessel.
  • moldings according to the invention are capable of binding up to 3000% by weight of dust, based on their own weight, for example 500 to 3000% by weight.
  • the dust-binding capacity can be determined gravimetrically, for example.
  • Another object of the present invention are vacuum cleaners, in particular bagless vacuum cleaner, comprising at least one shaped body described above.
  • bagless vacuum cleaners comprising at least one, preferably two moldings described above, hereinafter also referred to as bagless vacuum cleaner according to the invention.
  • the molding or bodies of the invention work in this application practically as a dust binder (dust catcher), in particular for u. U. allergieauslösenden fine dust.
  • dust catcher dust binder
  • the dust particles adhere to moldings according to the invention and are therefore no longer freely movable, ie. H. they can no longer stir up as dust cloud when emptying the cyclone. Instead, they fall together with inventive molding on the floor.
  • essentially the surface properties (adsorption) of the shaped bodies according to the invention are used. Their advantageous filter properties are rather secondary in this case.
  • Another object of the present invention is a method for cleaning surfaces, in particular floors, using vacuum cleaners according to the invention, hereinafter also called cleaning process according to the invention.
  • vacuum cleaners according to the invention To carry out the purification process according to the invention, it is possible to proceed as known per se.
  • vacuum cleaners according to the invention very pure exhaust air is produced and only a small amount of fine dust is swirled.
  • a spray dried melamine / formaldehyde precondensate (molar ratio 1: 3, molecular weight about 500 g / mol) was added to an aqueous solution containing 3% by weight of formic acid and 1.5% of the sodium salt of a mixture of alkyl sulfonates of 12 to 18 C-atoms in the alkyl radical (emulsifier K 30 Fa. Bayer AG), wherein the percentages are based on the melamine / formaldehyde precondensate given.
  • concentration of the melamine / formaldehyde precondensate based on the total mixture of melamine / formaldehyde precondensate and water, was 74% by weight.
  • Compression hardness (40%) 1, 3 kPa determined according to DIN 53577, density 7.6 kg / m 3 determined according to EN ISO 845, average pore diameter 210 ⁇ m, determined by analysis of microscopic images on sections,
  • the weight of shaped bodies (F.1) was found to be about a factor
  • Shaped bodies (F.1) and (F.2) showed good dust-binding capacity.
  • Table 1 Particle diameter distribution of adsorbed mineral test dust on shaped bodies (F.2), rel. Weight gain of the sample: 9 times.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Filters For Electric Vacuum Cleaners (AREA)

Abstract

L'invention concerne l'utilisation de corps moulés dont les dimensions (longueur, largeur et hauteur) sont toutes situées dans la plage de 1 mm à 3 cm comme moyen de retenue de poussières dans les aspirateurs. Le ou les corps moulés sont fabriqués en mousse à cellules ouvertes non traitée chimiquement, d'une masse spécifique comprise dans la plage de 5 à 500 kg/m<SUP>3</SUP> et dont le diamètre moyen des pores est compris dans la plage de 1 µm à 1 mm.
EP07821696A 2006-10-27 2007-10-23 Utilisation de mousses à cellules ouvertes dans les aspirateurs Withdrawn EP2101624A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006051404A DE102006051404A1 (de) 2006-10-27 2006-10-27 Verwendung von offenzelligen Schaumstoffen in Staubsaugern
PCT/EP2007/061332 WO2008049831A1 (fr) 2006-10-27 2007-10-23 Utilisation de mousses à cellules ouvertes dans les aspirateurs

Publications (1)

Publication Number Publication Date
EP2101624A1 true EP2101624A1 (fr) 2009-09-23

Family

ID=38859028

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07821696A Withdrawn EP2101624A1 (fr) 2006-10-27 2007-10-23 Utilisation de mousses à cellules ouvertes dans les aspirateurs

Country Status (8)

Country Link
US (1) US20100313911A1 (fr)
EP (1) EP2101624A1 (fr)
JP (1) JP2010507423A (fr)
KR (1) KR20090087447A (fr)
CN (1) CN101528101A (fr)
CA (1) CA2666467A1 (fr)
DE (1) DE102006051404A1 (fr)
WO (1) WO2008049831A1 (fr)

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BRPI0709970A2 (pt) * 2006-04-18 2011-08-02 Basf Se processos para esterelizar vasos de trabalho, e para descontaminar material contaminado com microorganismos
JP5679664B2 (ja) * 2007-03-12 2015-03-04 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se 抗菌性を有するメラミン−ホルムアルデヒドフォーム
US8328894B2 (en) 2008-08-20 2012-12-11 S.C. Johnson & Son, Inc. Dust prevention and removal device
DE102009009324B4 (de) * 2009-02-17 2013-04-25 Miele & Cie. Kg Feinstaub-Filterkassette für Staubsauger
CN102309288A (zh) * 2011-09-08 2012-01-11 桐乡市健民过滤材料有限公司 一种加香无纺布集尘袋及其生产方法
US20140144319A1 (en) * 2012-11-27 2014-05-29 John J. Paoluccio Orbit filter magnets for cyclonic cleaners
JP2018140160A (ja) * 2017-02-28 2018-09-13 省吾 吉村 掃除機の集塵除去方法

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DE19911407A1 (de) * 1999-03-15 2000-09-21 Bsh Bosch Siemens Hausgeraete Verfahren zum Entleeren eines an oder in einem Staubsauger vorgesehenen, zumindest einen Teil des aus der Saugluft des Staubsaugers abgesonderten Schmutzes aufnehmenden Sammelbehältnisses
US6558453B2 (en) * 2000-01-14 2003-05-06 White Consolidated Industries, Inc. Bagless dustcup
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WO2006058675A2 (fr) * 2004-11-29 2006-06-08 Basf Aktiengesellschaft Mousses a cellules ouvertes modifiees et leur procede de production
BRPI0606431A2 (pt) * 2005-01-24 2017-06-27 Basf Ag processo para limpar superfícies, pedaço de espuma de aminoplasto, uso de pedaços de espuma de aminoplasto, compósito, processo para produzir compósitos, e, formulação de pedaço de espuma de aminoplasto

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Also Published As

Publication number Publication date
WO2008049831A1 (fr) 2008-05-02
CA2666467A1 (fr) 2008-05-02
US20100313911A1 (en) 2010-12-16
JP2010507423A (ja) 2010-03-11
CN101528101A (zh) 2009-09-09
DE102006051404A1 (de) 2008-05-08
KR20090087447A (ko) 2009-08-17

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