EP1891154A2 - Compositions polymeres contenant des polyolefines et des copolymeres sequences amphiphiles ainsi qu'eventuellement d'autres polymeres et/ou des charges - Google Patents

Compositions polymeres contenant des polyolefines et des copolymeres sequences amphiphiles ainsi qu'eventuellement d'autres polymeres et/ou des charges

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Publication number
EP1891154A2
EP1891154A2 EP06763203A EP06763203A EP1891154A2 EP 1891154 A2 EP1891154 A2 EP 1891154A2 EP 06763203 A EP06763203 A EP 06763203A EP 06763203 A EP06763203 A EP 06763203A EP 1891154 A2 EP1891154 A2 EP 1891154A2
Authority
EP
European Patent Office
Prior art keywords
polymer composition
composition according
polyolefins
dye
block
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Withdrawn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
EP06763203A
Other languages
German (de)
English (en)
Inventor
Claudia Sierakowski
Ulrich Karl
Darijo Mijolovic
Karin Fischl
Michael Faber
Karl Siemensmeyer
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
Priority claimed from DE102005025018A external-priority patent/DE102005025018A1/de
Priority claimed from DE200510055078 external-priority patent/DE102005055078A1/de
Application filed by BASF SE filed Critical BASF SE
Priority to EP06763203A priority Critical patent/EP1891154A2/fr
Priority to EP09177763A priority patent/EP2159233A1/fr
Publication of EP1891154A2 publication Critical patent/EP1891154A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • 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
    • 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

Definitions

  • Polymer composition comprising polyolefins and amphiphilic block copolymers and optionally other polymers and / or fillers and methods for dyeing or printing such compositions
  • the present invention relates to polymer compositions comprising polyolefins, amphiphilic block copolymers of polyisobutene blocks and polyoxyalkylene blocks, and optionally other polymers and / or fillers. It further relates to a process for dyeing or printing such compositions and to the use of amphiphilic block copolymers as a coloring and printing aid of polyolefins.
  • Polyolefins especially polypropylene, are characterized by numerous excellent properties such as low specific gravity, high tear strength, good resistance to chemicals, low wettability by polar media, low water absorption capacity, good recyclability and a low price. They can be excellently processed into a variety of forms such as fibers, films and moldings.
  • WO 93/06177 discloses a process for dyeing fibers, in particular polyolefin fibers, in which the fiber is treated with a composition of a disperse dye and a swelling agent and heated to a temperature just below the melting point of the fiber, so that at least a part of the Disperse dye migiriert into the fiber. The remainder of the dye composition is then removed again from the surface of the fiber.
  • Melliand Textilberichte 77 (1996) 588-592 and 78 (1997) 604-605 disclose the dyeing of polypropylene fibers with special disperse dyes having Cs to Ci ⁇ -alkyl radicals, wherein preferably additionally surfactants are added to the dyeing liquor to obtain dyeings of high levelness and to increase the degree of fixation.
  • the problem with this is that the textile finisher would have to provide an additional range of dyes exclusively for the polyolefin dyeing available, which entails high costs.
  • No. 6,679,754 discloses the use of polyetheresteramides as an additive to polyolefins in order to improve their dyeability.
  • WO 04/35635 discloses the use of polyisobutene modified with terminal polar groups to improve the dyeability of polyolefins.
  • dyes there are mentioned, for example, anionic, cationic, mordant, direct-dispersion or vat dyes.
  • a polyisobutene-succinic anhydride (M n 550 g / mol) having a terminal group of a polyglycol ether (M n 300 g / mol) is used as an aid for coloring polypropylene with a cationic dye.
  • the dyeings are not always intense enough, especially when dyeing with disperse dyes or metal complex dyes. When dyeing with particulate vat dyes, it is difficult to obtain through-dyed and not just surface dyed fibers.
  • WO 04/72024 discloses the use of polyisobutenephosphonic acids to improve the dyeability of polypropylene.
  • WO 95/10648, EP-A 1 138 810 and WO 02/92891 disclose the use of various diesters of polyalkylene glycols with fatty acids having up to 21 carbon atoms for the hydrophilization of polypropylene. Preference is given to polyethylene glycols having a molecular weight of from 300 to 600 g / mol. The coloring of the modified polypropylenes is not disclosed.
  • DE-A 102004007501 aqueous polymer dispersions are disclosed which are stabilized by di-, tri- or multiblock copolymers of polyisobutene units and also polyoxyalkylene units. The use of these polymers to improve the dyeability of polyolefins is not disclosed.
  • the object of the invention was to provide polyolefins with improved inkability or printability as well as an improved process for the subsequent dyeing of polyolefins, in particular polypropylene with aqueous dyebaths. In this case, in particular homogeneous, no streaky dyeings should be obtained.
  • polymer compositions each comprising at least one polyolefin and at least one block copolymer comprising
  • hydrophobic block (A) which is composed essentially of isobutene units, as well as
  • hydrophilic block (B) which is composed essentially of oxyalkylene units, and whose mean molar mass M n is at least
  • compositions may be undyed polymer compositions or else colored compositions which additionally comprise at least one dye.
  • the polymer compositions may also optionally further comprise other polymers and / or fillers.
  • the invention in a second aspect, relates to a process for coloring polymers which comprises treating said undyed polymer composition with a formulation comprising at least water and a dye, the polymer composition being raised to a temperature during and / or after the treatment their glass transition temperature T 9 but heated smaller than their melting temperature.
  • the invention in a third aspect, relates to a process for printing substrates, comprising printing an unprinted substrate from a polymer composition with a suitable printing paste at least comprising rheology aids, solvents and a dye, wherein the polymer composition during and / or after printing at a temperature greater than its glass transition temperature T 9 but less than its melting temperature heated.
  • a suitable printing paste at least comprising rheology aids, solvents and a dye
  • the polymer composition during and / or after printing at a temperature greater than its glass transition temperature T 9 but less than its melting temperature heated.
  • the use of the cited block copolymers was found to be an aid for coloring or printing polymer blends containing polyolefins or poly-olefins.
  • the mechanical properties of polyolefins are positively influenced by the addition of the block copolymers according to the invention.
  • the compositions are well suited for filling with inorganic or organic fillers.
  • the inventive use of the block copolymers instead of conventional auxiliaries makes it possible to markedly improve the impact strength and elongation at break of filled polyolefins.
  • the polymer composition according to the invention comprises at least one polyolefin and at least one block copolymer of at least one hydrophobic block (A) and at least one hydrophilic block (B).
  • the block copolymer serves as an aid for improving the properties, for example the dyeability of the polyolefin. If mixtures of different poly olefins are used, it also acts as an efficient compatibilizer.
  • the blocks (A) and (B) are interconnected by means of suitable linking groups. They can each be linear or also have branches.
  • Block copolymers of this type are known and their preparation can be carried out starting from starting compounds and methods which are known in principle from the person skilled in the art.
  • the hydrophobic blocks (A) are essentially composed of isobutene units. They are obtainable by polymerization of isobutene. However, the blocks may still have minor comonomers other than building blocks. Such building blocks They can be used to fine tune the properties of the block.
  • comonomers are, in addition to 1-butene and cis- or trans-2-butene, in particular isoolefins having 5 to 10 C atoms, such as 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl 1-hexene, 2-ethyl-1-pentene, 2-ethyl-1-hexene and 2-propyl-1-heptene or vinyl aromatics such as styrene and ⁇ -methylstyrene, C 1 -C 4 -alkylstyrenes such as 2, 3 and 4-methylstyrene and 4-tert-butylstyrene.
  • the proportion of such comonomers should not be too large.
  • the blocks may also contain the initiators used to start the polymerization. Starter molecules or fragments thereof.
  • the polyisobutenes thus prepared may be linear, branched or star-shaped. They can have functional groups only at one chain end or at two or more chain ends.
  • Functionalized polyisobutenes can be prepared starting from reactive polyisobutenes by providing them with functional groups in single-stage or multistage reactions which are known in principle to those skilled in the art.
  • reactive polyisobutene is understood by the person skilled in the art to mean polyisobutene which has a very high proportion of terminal ⁇ -olefin end groups.
  • the preparation of reactive polyisobutenes is also known and described for example in detail in the already cited documents WO 04/9654, pages 4 to 8, or in WO 04/35635, pages 6 to 10.
  • the molar mass of the hydrophobic blocks A is determined by the skilled person depending on the desired application.
  • the hydrophobic blocks (A) each have an average molar mass M n of from 200 to 10,000 g / mol.
  • M n is preferably from 300 to 8000 g / mol, particularly preferably from 400 to 6000 g / mol and very particularly preferably from 500 to 5000 g / mol.
  • the hydrophilic blocks (B) are composed essentially of oxyalkylene units.
  • Oxalkylene units are in a manner known in principle to units of the general formula -R 1 -O-.
  • a hydrophilic block may also comprise several different oxyalkylene units.
  • the hydrophilic blocks may also comprise further structural units, such as, for example, ester groups, carbonate groups or amino groups. They may furthermore also comprise the initiator or starter molecules or fragments thereof used for starting the polymerization. Examples include terminal groups R 2 -O-, wherein R 2 has the meaning defined above.
  • the hydrophilic blocks comprise as main components ethylene oxide units - (CH 2 ) zO- and / or propylene oxide units -CH 2 -CH (CH 3) -O, while higher alkylene oxide units, ie those having more than 3 carbon atoms, only in small amounts to Fine adjustment of the properties are present.
  • the blocks may be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide units.
  • the amount of higher alkylene oxide units should not exceed 10% by weight, preferably 5% by weight.
  • the hydrophilic blocks B are obtainable in a manner known in principle, for example by polymerization of alkylene oxides and / or cyclic ethers having at least 3 C atoms and optionally further components. They can also be prepared by polycondensation of di- and / or polyalcohols, suitable initiators and optionally further monomeric components.
  • alkylene oxides as monomers for the hydrophilic blocks B include ethylene oxide and propylene oxide, and furthermore 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide, 2,3-pentene oxide , 2-methyl-1, 2-butene oxide, 3-methyl-1, 2-butene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1, 2-pentenoxide, 2-ethyl-1 , 2-butene oxide, 3-methyl-1, 2-pentenoxide, decene oxide, 4-methyl-1, 2-pentenoxide, styrene oxide or be formed from a mixture of oxides of technically available raffinate streams.
  • cyclic ethers include tetrahydrofuran. Of course, mixtures of different alkylene oxides can be used. Depending on the desired properties of the block, the person skilled in the art makes a suitable choice among the monomers or further components.
  • the hydrophilic blocks B may also be branched or star-shaped. Such blocks are available by using starter molecules with at least 3 arms. Examples of suitable initiators include glycerol, trimethylolpropane, pentaerythritol or ethylenediamine.
  • suitable initiators include glycerol, trimethylolpropane, pentaerythritol or ethylenediamine.
  • the synthesis of alkylene oxide units is known to the person skilled in the art. Details are detailed in, for example, "Polyoxyalkylene" ⁇ x ⁇ Ullmann's Encyclopedia of Industrial Chemistry, 6 th Edition, Electronic Release.
  • the molar mass of the hydrophilic blocks B is at least 1000 g / mol and is determined by the skilled person depending on the desired application. At less than 1000 g / mol, the staining results are often unsatisfactory.
  • the hydrophilic blocks (B) each have an average molar mass M n of from 1000 to 20 000 g / mol.
  • M n is preferably from 1250 to 18000 g / mol, more preferably from 1500 to 15000 g / mol, and most preferably from 2500 to 8000 g / mol.
  • the synthesis of the block copolymers used according to the invention can preferably be carried out by first preparing the hydrophilic blocks B separately and reacting them in a polymer-analogous reaction with the functionalized polyisobutenes to form block copolymers.
  • the building blocks for the hydrophilic and hydrophobic blocks in this case have complementary functional groups, i. Groups that can react with each other to form linking groups.
  • the functional groups of the hydrophilic blocks are of course preferably OH groups, but they may also be, for example, primary or secondary amino groups. OH groups are particularly suitable as complementary groups for reaction with PIBSA.
  • the synthesis of the blocks B can also be carried out by reacting polar functional group-containing polyisobutenes (i.e., blocks A) directly with alkylene oxides to form blocks B.
  • the structure of the block copolymers used in the present invention can be influenced by selecting the kind and amount of the starting materials for the blocks A and B and the reaction conditions, particularly the order of addition.
  • the blocks A and / or B may be terminal, ie only connected to another block, or they may be connected to two or more other blocks.
  • the blocks A and B may be linearly linked together in an alternating arrangement. In principle, any number of blocks can be used. As a rule, however, there are no more than 8 blocks A or B in each case. This results in the simplest case a two-block copolymer of the general formula AB. Furthermore, they may be triblock copolymers of the general formula ABA or BAB. Of course, several Other blocks follow, for example ABAB, BABA, ABABA, BABAB or ABABAB.
  • it may be star-shaped and / or branched block copolymers or comb-like block copolymers, in which more than two blocks A are each bound to a block B or more than two blocks B to a block A.
  • they may be block copolymers of the general formula AB m or BA m , where m is a natural number> 3, preferably 3 to 6 and particularly preferably 3 or 4.
  • AB m is a natural number> 3, preferably 3 to 6 and particularly preferably 3 or 4.
  • the OH groups can be linked together in a manner known in principle with the succinic anhydride groups S to form ester groups.
  • the reaction can be carried out, for example, while heating in bulk. Suitable, for example, reaction temperatures of 80 to 150 ° C.
  • triblock copolymers A-B-A are readily prepared by reacting one equivalent of HO- [B] -OH with two equivalents of [A] -S. This is illustrated below by way of example with complete formulas.
  • An example is the reaction of PIBSA and a polyethylene glycol:
  • n and m stand independently of each other for natural numbers. They are selected by the person skilled in the art so that the initially defined molar masses result for the hydrophobic or hydrophilic blocks.
  • Star-shaped or branched block copolymers BA x can be obtained by reacting [B] - (OH) x with x equivalents [A] -S.
  • the resulting block copolymers may also have residues of starting materials, depending on the preparation conditions.
  • they can be mixtures of different products.
  • triblock copolymers of the formula ABA may also contain two-block copolymers AB as well as functionalized and unfunctionalized polyisobutene.
  • these products can be used without further purification for the application.
  • the products can also be cleaned. The person skilled in cleaning methods are known.
  • Preferred block copolymers for carrying out this invention are triblock copolymers of the general formula ABA, or their mixture with two-block copolymers AB and optionally by-products.
  • amphiphilic block copolymers are used according to the invention as an aid for improving the properties of polyolefins, for example for improving the coloration of polyolefins or for improving rheological properties.
  • polyolefins basically all known polyolefins are suitable.
  • they may be homopolymers or copolymers which are ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene or ⁇ -methylstyrene as monomers include.
  • Preference is given to polyolefins which comprise C 2 - to C 4 -olefins as the main constituent, more preferably to polypropylene or polyethylene homo- or copolymers.
  • Copolymers may be random copolymers or block copolymers.
  • Suitable comonomers in copolymers are preferably - depending on the polyolefin basic bodies - ethylene or other ⁇ -olefins, dienes such as hexadiene-1, 4, hexadiene-1, 5, heptadiene-1, 6, 2-methylpentadiene-1, 4, octadiene-1, 7, 6-methylheptadiene-1, 5, or polyenes such as octathene and dicyclopentadiene.
  • the proportion of the comonomers in the copolymer is generally not more than 40% by weight, preferably not more than 30% by weight, based on the sum of all constituents of a monomer, for example 20 to 30% by weight or 2 to 10% by weight, depending on the application.
  • the polyolefin is polyethylene, for example LDPE, HDPE or LLDPE.
  • the polyolefin is polypropylene.
  • These may be polypropylene homopolymers or copolymers. Suitable comonomers may in particular be ethylene and the abovementioned ⁇ -olefins, dienes and / or polyenes.
  • the choice of polypropylene is not limited. Particularly viscous polypropylenes can be processed with a high melt flow index. For example, it can be polypropylene having a melt flow index MFR (230 ° C., 2.16 kg) of less than 40 g / 10 min.
  • polystyrene resin may also be mixtures (blends) of different polyolefins, for example, polypropylene and polyethylene.
  • compositions according to the invention may also comprise chemically different polymers other than polyolefins.
  • other polymers may be polyamides or polyesters, in particular PET. With such additives, the properties of the polymeric compositions can be fine-tuned.
  • the amount of optional additional polymers will be determined by the skilled person depending on the desired properties of the polymeric composition. However, it should normally be 20% by weight, based on the total amount of polyolefins and the other polymers, i. the amount of all polymers except the amphiphilic block copolymers. If present, amounts of from 0.1 to 20% by weight, preferably from 1 to 15% by weight, more preferably from 2 to 10% by weight and very particularly preferably from 3 to 7% by weight, have proven useful.
  • the polyesters used may be conventional PET with a melting point of 255 to 265 ° C. It is particularly advantageous to use modified PET which has additional soft segments and accordingly has a lower degree of crystallization or melting point. Particularly advantageous for carrying out the invention, polyesters can be used which have a melting point of 50 to 250 ° C, preferably 60 to 200 ° C. The use of such polyester additives leads to particularly good dyeable fibers with particularly good light fastness and a very advantageous fleet extract. Furthermore, the fibers can be colored by admixtures of such polyester already at temperatures of 100 0 C.
  • Such polyesters can be obtained by replacing some of the terephthalic acid units in the polyester with aliphatic dicarboxylic acid units, in particular with adipic acid units, to synthesize the polyesters.
  • aliphatic dicarboxylic acid units for example, it is possible to use a mixture of terephthalic acid and adipic acid in a molar ratio of 4: 1 to 1:20.
  • the ethylene glycol units can also be replaced by relatively long-chain diols, in particular C 3 -C 6 -alkanediols, such as, for example, 1,4-butanediol or 1,6-hexanediol.
  • amphiphilic block copolymers used according to the invention advantageously not only facilitate dyeability, but also act as efficient compatibilizers for blending various polymers.
  • Particularly noteworthy here are blends of various polyolefins, such as, for example, polypropylene and polyethylene or polypropylene with polyester or polyamide.
  • the polymer compositions according to the invention may optionally also comprise further typical additives and auxiliaries.
  • additives include antistatics, stabilizers or fillers.
  • Such additives are known in the art. For details, see, for example, "Polyolefins” in Ullmann's Encyclopedia of Technical Chemistry, & h Edition, 2000, Electronic Release.
  • Fillers for filling polyolefins are known in principle to the person skilled in the art. These are finely divided inorganic and / or organic solids, with which properties of the polyolefins, such as hardness, elongation, density, impact resistance, gas permeability or electrical conductivity can be influenced. Furthermore, fillers can also be used as flame retardants. It can be either more or less spherical fillers as well as platelets and / or needle-shaped or fiber-like fillers. Examples of suitable fillers include carbonates, hydroxides, oxides, mixed oxides, silicates or sulfates.
  • the fillers may be, for example, CaCCb. It may be CaCG "3 of natural origin, such as ground limestone, ground marble or ground chalk, or it may be precipitated CaCCh of industrial origin, other examples include dolomite CaMg (CO3) 2, natural or industrial Si02, such as Quartz, fumed SiO 2 or precipitated silica, BaSO 4 , CaSO 4 , ZnO, " I ⁇ O 2, MgO, Al 2 O 3, graphite, carbon black, phyllosilicates such as, for example, kaolin, montmorillonite, mica, talc or mica. Furthermore, fibers such as glass fibers, carbon fibers or aramid fibers can be used.
  • fillers which can serve as flame retardants include Al (OH) 3 or Mg (OH) 2.
  • the fillers can of course also be modified in a manner known in principle, for example be coated with suitable dispersants and / or water repellents.
  • the typical size of suitable fillers is generally 0.5 to 5 microns, preferably 1 to 3 microns. In the case of spherical or approximately spherical particles, this information refers to the diameter, otherwise to the length of the particles.
  • nanoparticles having a size of from 1 to 500 nm include, for example, nanoparticulate SiCb or ZnO.
  • nanoparticulate phyllosilicates in particular organically modified phyllosilicates, such as montmorillonite, hectorite, saponite, Glasgowl- lit or bentonite can be used. The preparation of such nanoparticles is described in WO 2004/11 1122 and corresponding products are commercially available.
  • Such nanoparticles may have a layer thickness of only about 1 nm, while their length and width may be in the range of 100 nm to 500 nm.
  • Preferred for carrying out the invention are CaCO 3, talc, glass fibers and phyllosilicates, in particular nanoparticulate phyllosilicates.
  • flame retardants may preferably be used, particularly preferably Al (OH) 3 and / or Mg (OH) 2 .
  • the amount of any fillers used is determined by the skilled person depending on the filler used and depending on the desired properties of the polymer. It is usually 1 to 100 wt.% Based on the sum of all components of the composition.
  • Fillers for improving mechanical properties can advantageously be used in an amount of 5 to 50% by weight, preferably 10 to 40% by weight and more preferably 15 to 35% by weight.
  • Fillers suitable as flame retardants for example Al (OH) 3 or Mg (OH) 2, can advantageously be used in amounts of 25 to 100% by weight, preferably 35 to 80% by weight and more preferably 40 to 60% by weight.
  • nanoparticles are used in amounts of not more than 10% by weight, for example 0.1 to 10% by weight, preferably 0.2 to 5% by weight.
  • amphiphilic block polymers are particularly effective in the case of filled polyolefins.
  • filling the polyolefins often decreases their elongation at break.
  • the amphiphilic block polymers By using the amphiphilic block polymers, the decrease in the elongation at break during filling is much lower. In other words, have polymer compositions at the same high degree of filling better mechanical-technological properties, or alternatively, the polymer can be filled with a larger amount of inexpensive filler.
  • the polymer compositions according to the invention can be present in any desired form, for example as any shaped bodies or films.
  • the polymer composition is in the form of fibers, yarns, fabrics, nonwovens, knits, knits and / or other textile materials.
  • Processes for producing fibers or yarns, fabrics, nonwovens and / or other textile materials from polymers or polymeric compositions produced therefrom are known to the person skilled in the art.
  • the materials may be, for example, clothing textiles, such as sportswear, underwear, outerwear, jackets, functional underwear, etc., or home textiles, such as curtains, tablecloths, bedding, upholstery fabrics, carpets or the like.
  • it may also be technical textiles, such as carpets or fleeces for automotive applications.
  • the preparation of the polymer compositions according to the invention can be carried out by various techniques.
  • the polyolefins can be prepared already in the presence of the block copolymers used in the invention.
  • the block copolymers with the polyolefins and optionally further components, in particular optionally present other polymers and / or fillers, after heating to the molten liquid by means of suitable equipment are intensively mixed together.
  • suitable equipment for example, kneaders, single-screw extruders, twin-screw extruders or other dispersing aggregates can be used.
  • the discharge of the molten polymer composition from the mixing units can take place in a manner known in principle via nozzles.
  • strands can be formed and cut into granules.
  • the molten mass can also be shaped directly, for example by means of injection molding or blow molding, into desired shaped bodies or it can be shaped into fibers by means of suitable nozzles.
  • the block copolymer or the mixture of different block copolymers may preferably be added in bulk to the polyolefins, including any further components present, but it may also be added in solution.
  • the temperature for mixing is selected by the person skilled in the art and depends on the type of polyolefins used or, if appropriate, other polymers.
  • the polyolefins len soften on the one hand sufficiently, so that mixing is possible. On the other hand, they should not be too thin, because otherwise sufficient shear energy input can no longer take place and, under certain circumstances, thermal degradation is also to be feared.
  • temperatures of 120 to 300 0 C can be applied, without the invention being limited thereto. It proves to be particularly advantageous here that the block copolymers used according to the invention have high thermal stability.
  • the polymer compositions according to the invention generally contain from 35 to 99.95% by weight of the polyolefins, preferably from 50 to 99.9% by weight and more preferably from 60 to 99.85% by weight of the polyolefins and very particularly preferably from 70 to 99.8% by weight. %, in each case based on the sum of all components of the composition.
  • the amounts of polyolefins may be higher.
  • the compositions generally contain from 75 to 99.95% by weight of the polyolefins, preferably from 85 to 99.9% by weight, more preferably from 90 to 99.85% by weight and most preferably from 95 to 99.8% by weight. %, in each case based on the sum of all components of the composition.
  • the amount of block copolymer will be determined by those skilled in the art according to the desired properties of the composition. It is generally from 0.05 to 10% by weight, based on the sum of all components of the composition, preferably from 0.1 to 6% by weight, more preferably from 0.3 to 5% by weight and very particularly preferably from 0.5 to 3, 0% by weight.
  • the block copolymers can also be incorporated in a two-stage process.
  • at least one block copolymer is mixed with only a portion of the polyolefins and optionally other polymers with heating.
  • the already described techniques can be used for mixing.
  • Such a concentrate may contain 5 to 50% by weight, preferably 20 to 40% by weight, of the block copolymer.
  • the concentrate is then mixed in a second step with the rest of the polyolefins with heating and shaped according to the intended use. For example, threads can be made that can be further processed into yarns, fabrics, nonwovens or other textile materials.
  • the undyed polymer compositions prepared as described, in particular in the form of fibers, yarn fabrics, nonwovens and / or other textile materials, can be dyed in a simple manner by means of the process according to the invention.
  • the affinity of the polyolefins for dyes, in particular for dispersion dyes significantly increased.
  • dyed fabrics, fabrics or the like are obtained.
  • dyed clothing or home textiles can be obtained in this manner.
  • the entire tissue can be dyed.
  • initially only the fibers can be dyed and then the dyed fibers are processed into textile materials.
  • the undyed polymer composition is treated with a formulation comprising at least water and a dye.
  • a formulation comprising at least water and a dye.
  • An aqueous formulation for coloring textile materials is also referred to by the person skilled in the art as a "liquor".
  • the formulation comprises only water.
  • water-miscible organic solvents include monohydric or polyhydric alcohols, such as, for example, methanol, ethanol, n-propanol, i-propanol, ethylene glycol, propylene glycol or glycerol.
  • it may also be ether alcohols.
  • monoalkyl ethers of (poly) ethylene or (poly) propylene glycols such as ethylene glycol monobutyl ether.
  • the amount of such solvents other than water should, however, generally not exceed 20% by weight, preferably 10% by weight and more preferably 5% by weight, relative to the sum of all solvents of the formulation or liquor.
  • dyes such as, for example, cationic dyes, anionic dyes, mordant dyes, direct dyes, disperse dyes, development dyes, vat dyes, metal complex dyes, reactive dyes, sulfur dyes, acid dyes or substantive dyes, can be used as dyes in the formulation.
  • a disperse dye, a mixture of different disperse dyes or an acid dye or a mixture of different acid dyes is preferably used to carry out the invention.
  • Disperse dye is known to the person skilled in the art Disperse dyes are dyes with a low water solubility, which are used in disperse, colloidal form for dyeing, in particular for dyeing fibers and textile materials.
  • any disperse dyes can be used to carry out the invention. These can have different chromophores or mixtures of the chromophores. In particular, these may be azo dyes or anthraquinone dyes. Furthermore, they may be quinophthalone, naphthalimide, naphthoquinone or nitro dyes. Examples of disperse dyes take Cl. Disperse Yellow 3, Cl. Disperse Yellow 5, Cl. Disperse Yellow 64,
  • Disperse Red 60 Cl. Disperse Red 72, Cl. Disperse Red 82,
  • mixtures of different disperse dyes can be used. In this way, mixed colors can be obtained. Preference is given to those disperse dyes which have good fastness properties and in which trichromaticity is possible.
  • acid dye is known to the person skilled in the art and comprises one or more acid groups, for example a sulfonic acid group, or a salt thereof, which may contain various chromophores or mixtures of the chromophores such as Cl Acid Yellow 17, Cl Acid Blue 92, Cl Acid Red 88, Cl Acid Red 14 or Cl Acid Orange 67, disazo dyes such as Cl Acid Yellow 42, Cl Acid Blue 113 or Cl Acid Black 1 , Trisazo dyes such as Cl. Acid Black 210, Cl. Acid Black 234, metal complex dyes such as Cl. Acid Yellow 99, Cl. Acid Yellow 151 or Cl. Acid Blue 193 mordant dyes such as Cl. Mordant Blue 13 or Cl. Mordant Red 19 or acid dyes with various other structures such as Cl.
  • Acid Orange 3, Cl. Acid Blue 25 or Cl. Acid Brown 349 Further details on acid dyes and other examples are also given, for example, in “Industrial Dyes”, Edt. Klaus Hunger, Wiley-VCH, Weinheim 2003, pages 276-295 in detail. Of course, mixtures of different acid dyes can be used.
  • the amount of dyes in the formulation will be determined by one skilled in the art according to the desired application.
  • the formulation may include other adjuvants beyond solvents and dyes.
  • suitable textile auxiliaries such as dispersing and leveling agents, acids, bases, buffer systems, surfactants, complexing agents, defoamers or UV-stabilizing stabilizers.
  • a UV absorber can be used as an aid.
  • a neutral or acidic formulation for example having a pH of from 3 to 7, preferably from 4 to 6.
  • the treatment with the polymer composition, in particular the fibers, yarns fabrics, nonwovens and / or other textile materials with the aqueous dye formulation can be carried out by conventional dyeing methods, for example by dipping into the formulation, spraying the formulation or applying the formulation by means of suitable equipment , It may be continuous or discontinuous.
  • Dyeing apparatuses are known to the person skilled in the art. The dyeing may, for example, be carried out batchwise with chaff skids, yarn dyeing apparatuses, unit beam dyeing apparatuses or jets or continuously by padding, padding, spraying or foam application methods with suitable drying and / or fixing equipment.
  • the ratio of polymer composition, in particular of the fibers, yarns, webs, nonwovens and / or other textile materials to the dyestuff formulation is determined by the person skilled in the art according to the desired application a ratio of polymer composition / dye formulation of 1: 5 to 1: 50, preferably 1: 10 to 1: 50, and a dye amount in the formulation of about 0.5 to 5 wt.%, Preferably 1 to 4 wt.% Related on the polymer composition, without the invention being set to this range.
  • the polymer composition is heated during and / or after the treatment to a temperature greater than its glass transition temperature T 9 but less than its melting temperature. This may preferably be carried out by heating the entire formulation to the relevant temperature and immersing the polymer composition in the formulation.
  • the temperature in the treatment depends naturally on the nature of the respective polyolefin and the dye used.
  • the glass transition temperatures and melting temperatures of polyolefins and other polymers are known in the art or can be easily determined in a known manner.
  • the treatment temperature is at least 60 ° C, in particular 60 to 140 0 C, preferably 80 to 14O 0 C.
  • For polypropylene homopolymers and copolymers are particularly temperatures of 95 to 140 0 C have proven.
  • the dye is incorporated into the polymer composition during the course of the thermal treatment to form a colored polymer composition. In the dyed polymer composition, the dye is preferably more or less evenly distributed, but the composition may also have concentration gradients.
  • the dye is preferably a dispersion or acid dye, more particularly a disperse dye.
  • the duration of the treatment is determined by one skilled in the art according to the nature of the polymer composition, the formulation and the dyeing conditions. It is also possible to change the temperature as a function of the duration of treatment. For example, can initially started at a lower temperature, for example, are then slowly increased at 70 to 100 ° C and the temperature at 120 to 14O 0 C. A heating phase of from 10 to 90 minutes, preferably from 20 to 60 minutes, and a subsequent high-temperature phase of from 10 to 90 minutes, preferably from 20 to 60 minutes, have proven useful. Alternatively, a short-term treatment, for example of about 0.5 to 5 minutes with steam or superheated steam is possible.
  • Dyeing may be followed by a customary aftertreatment, for example with detergents or oxidative or reductive clearing agents or fastness enhancers.
  • a customary aftertreatment for example with detergents or oxidative or reductive clearing agents or fastness enhancers.
  • Such post-treatments are known in principle to the person skilled in the art.
  • the uncolored or colored polymer compositions of the present invention can also be printed with excellent results.
  • substrates of the polymer compositions according to the invention are used.
  • the substrates may be any desired substrates, for example films of the polymer compositions according to the invention. They are preferably textile substrates. Examples of textile substrates include woven, knitted or nonwoven fabrics of the polymer compositions according to the invention.
  • printing pastes for textile printing can be used in a manner known in principle, which usually comprises at least one binder, a dye and a thickener, and optionally further additives, such as e.g. Wetting agents, rheology aids or UV stabilizers include.
  • colorants the dyes mentioned above can be used.
  • Dispersion or acid dyes are preferably used, particularly preferably disperse dyes.
  • Printing pastes for printing on textiles and their usual constituents are known to the person skilled in the art.
  • the printing method according to the invention can be carried out as a direct printing method, ie the printing paste is transferred directly to the substrate.
  • the skilled person can also make the printing by other methods, for example in direct printing with the ink-jet technology.
  • a thermal aftertreatment is also carried out according to the invention.
  • the substrate is heated from the polymer composition according to the invention during and / or preferably after printing to a temperature greater than its glass transition temperature T 9 but less than its melting temperature.
  • Preference is given to drying the printed substrate beforehand, for example at 50 to 90 ° C. over a period of 30 seconds to 3 minutes.
  • the temperature treatment is then preferably carried out at the temperatures already mentioned. A period of 30 seconds to 5 minutes has proven itself in devices known per se, for example drying cabinets, tenter frames or vacuum drying cabinets.
  • the dyeing or printing can be followed by a customary aftertreatment, as already described above.
  • dyed polymer compositions are obtainable which, in addition to the already described components, also contain dyes, in particular disperse dyes or acid dyes, particularly preferably disperse dyes.
  • the amount of dyes is preferably from 0.5 to 4% by weight, based on the amount of all components of the composition.
  • the colored polymer compositions may be, for example, clothing or home textiles.
  • inventively colored and / or printed polymer compositions are distinguished from prior art materials by more intensive and more uniform dyeings. They also have better rub fastness and very good wash fastness.
  • Block copolymer 1 is a block copolymer 1
  • 63.8 g of ethylhexanol are placed under an inert gas atmosphere ( N 2 protection). It is heated to 140 0 C before 99.4 g tetra are added dropwise ethylpentamin. After the addition is heated to 160 0 C and held for 3 h, the temperature. During the reaction partially volatile components distill over. For completeness, the pressure is lowered to 500 mbar for 30 minutes towards the end of the reaction. Thereafter, it is cooled to room temperature.
  • vibrations of the PIB framework 2953, 1465, 1396, 1365 and 1238 cm 1 .
  • Moplen HP 561 S (Basell).
  • Moplen HP 561 S is a homo-polypropylene (metallocene catalysis) with very narrow molecular weight distribution. It is especially suitable for spinning continuous filaments and nonwovens.
  • the throughput is 5 kg / h
  • the block copolymer or the comparative polymer is melted at 8O 0 C and added at a rate of 250 g / h.
  • the dosing pump runs at 100-200 g / h.
  • the draw is 1: 3 and the titer 17 dtex.
  • the spinning is carried out at a temperature between 200 0 C and 230 0 C.
  • the dyeings were carried out by using the knitting pieces prepared as described with the addition of the specified dyes in the indicated amounts in deionized water at pH 4.5 in an AHIBA dyeing machine from initially 9O 0 C within 40 minutes to 130 0 C. heated at a heating rate of 1 ° C / min and left at 130 ° C for a further 60 minutes.
  • the stains were removed, rinsed cold and dried at 100 ° C.
  • Liquor ratio 1: 50 (Note: The long liquor ratios given here were used because of the small amounts of substrate and are not related to the substances used according to the invention.) In the technical, i.e. production scale, the very short liquor ratios usual today can be used.)
  • Disperse Yellow 1 14 Disperse Red 60, Disperse Red 82 and Disperse Blue 56 were used in each case. An amount of 2% by weight, based on the weight of the textile to be dyed, was used. Dyeing with acid dyes:
  • the dyeings were carried out as described for disperse dyes, but the maximum temperature of the dyebath was maintained at 105 ° C.
  • the assessment was based on the following parameters:
  • Streaking is understood by the person skilled in the art to mean that individual fibers or fiber bundles of a textile are dyed to different intensities, resulting in a striped pattern.
  • wash fastness To determine the wash fastness of the dyeings obtained was a quick wash with 2g / l mild detergent, liquor ratio 1: 200, 5 minutes at 60 0 C was judged whether the PP dye lightened during the wash, ie whether dye bleed, and whether uncolored accompanying tissue was soiled.
  • the dyed textiles obtained with the block copolymers 1 and 2 used according to the invention had a high color depth both when using disperse dyes and when using acid dyes.
  • the handle of the knits was not hardened.
  • the fabrics did not show any streaks (see Figure 1).
  • polypropylene was further additized with the above-mentioned comparative polymer (terminal, polar terminal group of tetraethylene-pentamine terminated polymer) in the same manner.
  • Dyeing tests were carried out with commercial blue and red vat dyes.
  • the textile showed a lower color depth than when using the block copolymers used according to the invention, but above all a very strong streakiness (FIG. 2).
  • the rubbing fastness was only small.
  • An electron micrograph showed that the fibers were only superficially colored (see Figure 4).
  • Figure 1 shows a dyed according to the invention with a blue disperse dye textile.
  • Figure 2 shows a textile additized with the comparative polymer and dyed with a vat dye.
  • FIG. 3 shows a section through polypropylene fibers colored according to the invention with a red dye.
  • FIG. 4 shows a section through polypropylene fibers additized with the comparison polymer and colored with a red vat dye.
  • Printing pastes used in the invention were prepared according to the following procedure.
  • X g of dye dispersion are homogenized with 100-x g of the stock thickening with intensive stirring. Type and amount of the dyes used are given below.
  • the knitted fabric to be printed is fixed on the printing table by commercially available printing table adhesive.
  • a screen printing stencil (gauze E 55) with a stripe pattern of 4 cm width is then applied to this knitted fabric, in which the printing paste is applied at the edge.
  • a circular doctor blade with a diameter of 15 mm is then placed on the edge of the template and moved over the area to be printed by means of magnetic tension (thickness adjustment 6).
  • the mixture is then dried at 8O 0 C in a drying oven and then fixed for 10 min at 13O 0 C or 140 0 C in hot steam.
  • Applied textile substrates For the compression tests, polypropylene knitted fabrics made from additized polypropylene fibers were used. The preparation has already been described above.
  • Knitted fabric 1 without additive (for comparison purposes)
  • Knitted fabric 2 3.5% by weight Block copolymer 2 (1000-6000-1000)
  • Knitted fabric 3 5 wt.% Block copolymer 1 (550-1500-550)
  • Knitted fabric 4 Mixture of 1 wt.% Block copolymer 2 (1000-6000-1000) with 3% PET
  • Disperse Yellow 54 (Dianix Yellow S-3G, Dystar Co.) Cl.
  • Dispers Red 91 (Dianix Red S-BEL, Dystar Co.) Cl.
  • Dispers Blue 60 (Dianix Turquoise S-BG, Dystar Co.) Commercially available black dye (Dianix Black S-2B, Dystar)
  • the quality of the prints was tested for their rubfastness and washfastness at 60 ° C.
  • the washfastness was tested in analogy to DIN ISO EN 105 C 03.
  • the knitted fabric is washed after dyeing or printing under standardized conditions.
  • test strips made from other materials are also washed. These stripes should remain white, i. no dye should be transferred to the other washed-in textiles.
  • Grades from 1 to 5 are given. Grade 5 is pure white, grade 1 is strongly colored.
  • Table 4-2 Test parameters and results when printing on PET knit
  • the printing tests show that very wash- and rubbed-on prints are obtained when printing with the knitted fabrics of the polymer composition according to the invention. In addition, the obtained shades are very brilliant and color deep.
  • Samples of polypropylene were each processed into a filled polypropylene in the melt extruder as described above with a commercial CaCO 3 filler having a particle size of 2 ⁇ m.
  • the samples each contained 20% by weight of CaCCb with respect to all components of the composition.
  • the clean, unoccupied CaCCh was once used with PIBSA1000 and in another trial with stearic acid, which is commonly used as a tool to incorporate CaCCh fillers. In each case 20% by weight of the fillers so incorporated was incorporated in the polypropylene.
  • the melt flow index (according to ISO 1133), impact strength (according to ISO 180/1 A) and the elongation at break (according to ISO 527-2) were determined from the samples. The results are summarized in Table 5.
  • Texturing transforms smooth, continuous man-made fibers into more voluminous, more or less elastic yarns by heat treatment. By texturing but the elasticity of the yarns should not or not be reduced if possible.
  • the texturing tests were carried out with a false-twist texturing machine type AFK-2 (Barmag, Remscheid). Tests were carried out at various texturing speeds of 400 m / s to 1000 m / s. The temperature of the heater was linearly increased from 200 to 220 0 C at 400 m / s to 250 to 27O 0 C at 1000 m / s.
  • a polypropylene without additive and once polypropylene with 5 wt.% Of the block copolymer 2 was used.
  • the compositions were prepared by melt extrusion at 2500 m / min as described above and spun into a fiber (POY) which was used for the texturing experiments.
  • the target fiber titer of the DTY was 82.7 dtex at 34 filaments.
  • Table 6 Elongation of the textured yarn as a function of the texturing rate without and with 5% of the block copolymer 2.
  • a second reaction step were 720.8 g of the polyester obtained from adipic acid and butanediol were heated to 180 0 C with 454.4 g of dimethyl terephthalate, 680 g of 1, 4-butanediol and 2 g of tetrabutyl under nitrogen and with slow stirring. Formed methanol was distilled off. Thereafter, the mixture was heated to 230 ° C. in the course of 2 hours and 13.08 g of pyromellitic dianhydride were added and, after a further h, 0.8 g of an aqueous solution of phosphorous acid (50% by weight). Thereafter, excess butanediol was distilled off under reduced pressure.
  • a polyester having a melting point of 94 ° C., an OH number of 16 mg KOH / g and an acid number of less than 1 mg KOH / g was obtained.
  • a composition of 95% by weight of polypropylene, 3.75% by weight of the described polyester and 1.25% by weight of the block copolymer 2 was prepared by melt extrusion as above, spun into a fiber at 230 ° C. and made from the fibers as described above Textiles made. DTY titers were spun between 35 dtex / 32 filaments and 260 dtex / 12 filaments. The additive was metered from a concentrate with an addition of 10%.
  • Dyeing tests were carried out with the textiles. The dyeing tests were carried out as described above.
  • the fleet extract is better, i. the fiber absorbs more dye. Accordingly, the dyeing process is cheaper and the wastewater is less polluted with dye.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

L'invention concerne des compositions polymères contenant des polyoléfines, des copolymères séquencés amphiphiles comprenant des séquences polyisobutène et des séquences polyoxyalkylène ainsi qu'éventuellement d'autres polymères et/ou des charges. L'invention concerne également des procédés pour colorer de telles compositions ou réaliser une impression sur ces dernières ainsi que l'utilisation de copolymères séquencés amphiphiles comme auxiliaires pour colorer des polyoléfines et réaliser une impression sur ces dernières.
EP06763203A 2005-05-30 2006-05-19 Compositions polymeres contenant des polyolefines et des copolymeres sequences amphiphiles ainsi qu'eventuellement d'autres polymeres et/ou des charges Withdrawn EP1891154A2 (fr)

Priority Applications (2)

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EP06763203A EP1891154A2 (fr) 2005-05-30 2006-05-19 Compositions polymeres contenant des polyolefines et des copolymeres sequences amphiphiles ainsi qu'eventuellement d'autres polymeres et/ou des charges
EP09177763A EP2159233A1 (fr) 2005-05-30 2006-05-19 Procédé pour la coloration des compositions polymériques comprenant les polyoléfines.

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DE102005025018A DE102005025018A1 (de) 2005-05-30 2005-05-30 Polymerzusammensetzung umfassend Polyolefine und amphiphile Blockcopolymere sowie Verfahren zum Einfärben derartiger Zusammensetzungen
DE200510055078 DE102005055078A1 (de) 2005-11-16 2005-11-16 Polymerzusammensetzung umfassend Polyolefine und amphiphile Blockcopolymere sowie Verfahren zum Einfärben oder Bedrucken derartiger Zusammensetzungen
EP06111891 2006-03-29
PCT/EP2006/062469 WO2006128796A2 (fr) 2005-05-30 2006-05-19 Compositions polymeres contenant des polyolefines et des copolymeres sequences amphiphiles ainsi qu'eventuellement d'autres polymeres et/ou des charges et procedes pour colorer de telles compositions ou realiser une impression sur ces dernieres
EP06763203A EP1891154A2 (fr) 2005-05-30 2006-05-19 Compositions polymeres contenant des polyolefines et des copolymeres sequences amphiphiles ainsi qu'eventuellement d'autres polymeres et/ou des charges

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JP2009517516A (ja) * 2005-12-02 2009-04-30 ビーエーエスエフ ソシエタス・ヨーロピア 高分子材料中の、ポリイソブテン誘導体と染料との錯化により色移りの低下した染料
CN101506314A (zh) * 2006-08-25 2009-08-12 巴斯夫欧洲公司 包含聚异丁烯衍生物和非离子表面活性添加剂的颜料制剂
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AU2006254249A1 (en) 2006-12-07
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BRPI0610488A2 (pt) 2016-11-16
TW200712121A (en) 2007-04-01
EP2159233A1 (fr) 2010-03-03
WO2006128796A2 (fr) 2006-12-07
CA2609408A1 (fr) 2006-12-07
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US20090039543A1 (en) 2009-02-12
MX2007014194A (es) 2008-02-07
US20100107345A1 (en) 2010-05-06

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