Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0004—Coated particulate pigments or dyes
  • C09B67/0008—Coated particulate pigments or dyes with organic coatings
  • C09B67/0009—Coated particulate pigments or dyes with organic coatings containing organic acid derivatives
  • C09B67/001—Coated particulate pigments or dyes with organic coatings containing organic acid derivatives containing resinic acid derivatives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0004—Coated particulate pigments or dyes
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/10—Encapsulated ingredients
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B17/00—Azine dyes

Definitions

• the present invention relates to novel pigment compositions, to processes for the preparation thereof and to the use thereof for producing coloured engineering plastics (thermoplastics that maintain dimensional stability and most mechanical properties above 100°C or below 0°C), especially those based on polyamide.
• coloured engineering plastics thermoplastics that maintain dimensional stability and most mechanical properties above 100°C or below 0°C
• Mass-colouring of polymer processed at high temperatures, such as engineering plastics and in particular polyamides is usually carried out using so-called solvent dyes, which are soluble in the polyamide mass at high processing temperatures and which, besides having the requisite high heat resistance, also have adequate chemical stability with respect to, for example, the highly reductive medium of the polyamide melt.
• solvent dyes which are soluble in the polyamide mass at high processing temperatures and which, besides having the requisite high heat resistance, also have adequate chemical stability with respect to, for example, the highly reductive medium of the polyamide melt.
• soluble dyes generally have much poorer lightfastness, as compared with pigments.
• pigments in such polymers are restricted almost exclusively to inorganic pigments, most of which contain heavy metals, and to a very small selection of specific organic pigments, mainly from the phthalocyanine or quinacridone class.
• Inorganic pigments however, have generally low chroma and low colour strength.
• Organic pigments have disadvantages such as crystal phase and colour changes, migration, a frequent tendency of the coloured materials to fluoresce, and often a reactive interaction with the polymer, leading to degradation of the pigment and/or deterioration of the polymer's mechanical properties.
• EP 0046729 disclose azopyrimidine colourants.
• EP 0061 426 discloses diketopyrrolopyrrole pigments.
• WO 98/ 18866 discloses pteridine pigments.
• US 3,826,670 discloses encapsulated pigments with an intermediate ionically crosslinked polymeric salt and a skin consisting essentially of dense, amorphous, hydrated oxide or hydroxide of silicon, titanium or zirconium.
• EP 0744448 discloses pigments suitable for stencil inks, which are encapsulated in a polymeric matrix obtained from the reaction of polyisocyanates with polyols.
• WO 2006/089933 discloses aqueous dispersions comprising pigments that are at least partially sheathed in radiation-curable polyurethane, their production and use especially for inkjet printing.
• US 6,800,127 discloses pigment preparations comprising polyamide particles with an average size of below 50 ⁇ m and an average pigment size below 0.2 ⁇ m. However, especially the fastness properties are still not fully satisfactory.
• WO 06/ 111 493 is a patent application according to Art. 54(3) EPC and Rule 64.3 PCT, which is directed to pigments encapsulated by polymers which are not crosslinked.
• the present invention accordingly relates to a pigment composition
• a pigment composition comprising solid particles, which particles comprise from 20 to 75% by weight of an organic pigment and from 80 to 25% by weight of a crosslinked polymer, preferably from 25 to 60% by weight of an organic pigment and from 75 to 40% by weight of a crosslinked polymer, each based on the total weight of the solid particles, wherein the surface of the solid particles consists essentially of the crosslinked polymer and the crosslinked polymer is obtainable from a crosslinking agent and a prepolymer of average molecular weight M w from 2000 to 200000, preferably from 25000 to 150000, most preferred from 80000 to 125000, which prepolymer comprises (a)
• R 2 R 3 primary or secondary amino groups or (b2) unsaturated bonds, wherein Ri is H, Ci-C 4 alkyl, C 2 -C 4 alkenyl or COOR 5 , R 2 and R 3 are independently from one another H, OR 6 , NHR 6 , Ci-C 4 alkyl or C 2 -C 4 alkenyl, R 4 , R 5 and R 6 are independently from one another H, unsubstituted Ci-C 6 alkyl or C 2 -C 6 alkenyl, or C 2 -C 6 alkyl or C-2-C 6 alkenyl each substituted by one or more hydroxy and/or epoxy groups, and n is a number from 2 to 2000, preferably from 5 to 1500.
• the organic pigment is either directly embedded in the crosslinked polymer, or it is chemically or physically surface-modified or encapsulated, for example with a pigment derivative, a polymer or a layer of one or more transition metal oxides adsorbed on or bound to its surface.
• the pigment and any optional additional components should be fully surrounded by crosslinked polymer, as the surface of the solid particles should consist essentially of the crosslinked polymer, in order the desired properties to be obtained.
• the prepolymers are most suitably homo- or copolymers based on unsaturated monomers selected from the group consisting of acrylic acid, methacrylic acid, maleic acid and their derivatives, such as esters and amides thereof and maleic acid anhydride, which monomers may be copolymerized with less polar monomers such as vinyl chloride, vinyl alcohol or preferably styrene.
• the prepolymers comprise at least 30% by weight of repeating blocks of formula (I).
• prepolymers are crosslinked with any known crosslinking agent, for example reactive crosslinking agents such as polyisocyanates, polyhydrazides, poly- carboxylic acids, polyoxazolines, polyaziridines, polyepoxides, polysulfonazides, polyketimines, melamine-formaldehyde resins, urea-formaldehyde resins, or with crosslinking agents forming salts for example with carboxy groups of the prepolymer, such as polyamines or metal ions.
• Polyfunctional crosslinking agents comprise generally from 2 to 10, preferably 2, 3 or 4, especially 2 functional groups.
• a particularly preferred aspect of the invention is the use of self crosslinking prepolymers, which comprise both crosslinkable and crosslinking groups such as described above.
• the crosslinkable and crosslinking groups may be on the same backbone, optionally as blocks of a copolymer, or also on different backbones imbricated together.
• Suitable prepolymers are known and a large choice thereof is available commercially, too. Suitable prepolymers are for example disclosed in WO 01 /74735. Commercially available self crosslinking prepolymers are for example Acronal ® LR 8977, Acronal ® S 760 na (both BASF AG, Ludwigshafen/ DE) and Glascol ® C 44 (CIBA Specialty Chemicals Inc.).
• the amount of crosslinking agent is generally from 1 to 25% by weight, based on the amount of prepolymer.
• the crosslinking agent is separately added to the prepolymer, its amount is preferably from 2 to 20% by weight, most preferably from 3 to 10% by weight, based on the amount of prepolymer.
• the crosslinking agent is physically comprised in a self crosslinking prepolymer, its amount is preferably from 1 to 20% by weight, most preferably from 4 to 10% by weight, based on the amount of prepolymer.
• the amount of monomers comprising self crosslinking groups used to make the prepolymer is preferably from 1 to 20% by weight, most preferably from 4 to 10% by weight, based on the total amount of monomers used to make the prepolymer.
• the crosslinking reaction can take place simply at room temperature, such as in the case of aqueous acrylic prepolymer dispersions to which bishydrazides or aziridines are subsequently added, or at elevated temperature, such as from 50 to 300°C, especially from 130 to 200°C, optionally in the presence of a suitable catalyst, for example acids, metal compounds, amines, ammonium or hydroxy ions, such as hydrochloric acid, dibutyl tin laurate, triethylamine or tetrabutylammonium iodide.
• a suitable catalyst for example acids, metal compounds, amines, ammonium or hydroxy ions, such as hydrochloric acid, dibutyl tin laurate, triethylamine or tetrabutylammonium iodide.
• the instant pigment compositions generally comprise pigment particles having a size of from 0.01 to 10 ⁇ m, preferably up to 5 ⁇ m, most preferred from 0.05 to 2 ⁇ m, especially from 0.1 to 1 ⁇ m.
• the capsules comprising the pigment preferably have an average volume from 10 ⁇ 20 to 10 ⁇ 8 m 3 , especially from 10 ⁇ 18 to 10 ⁇ 10 m 3 .
• the instant pigment compositions comprise adequately from 0 to 20% by weight of other components, preferably from 0 to 3% by weight of volatile components, most preferred up to 2% by weight of volatile components, based on the total pigment composition.
• the volatile components preferably consist of organic solvents or water, most preferred water.
• Any organic pigment can be used, for example diketopyrrolopyrrole, quinacridone, azo, quinophthalone, phthalocyanine, indanthrone, flavanthrone, pyranthrone, anthraquinone, perylene, dioxazine, perinone, thioindigo, isoindolinone, isoindoline, pteridine and metal complex pigments.
• R 7 and Rs are each independently of the other a group of formula
• R 9 and Ri 0 are each independently of the other hydrogen, halogen, Ci-C 24 alkyl, trifluoromethyl, C 5 -C 6 cycloalkyl, Ci-Ci 8 alkoxy, Ci-Ci 8 alkylthio, Ci-Ci 8 alkylamino,
• R 11 and R 12 are each independently of the other hydrogen, halogen or Ci-C 6 alkyl
• Ri 4 and R 15 are each independently of the other hydrogen, halogen, Ci-C 6 alkyl, Ci-C 6 alkoxy or CN;
• Ri 6 , R17 and Ri 8 are independently from one another hydrogen; Ci-C 6 alkyl, C 3 -C 6 cycloalkyl, benzyl or phenyl each unsubstituted or substituted by halogen, OH, OR 26 , COR 26 , SR 26 , SO 2 R 26 , SO 3 R 26 , CN, COOH, COO " + Mi, COOR 26 , CONH 2 , CONHR 26 or CONR 26 R 27 , preferably Ri 6 , R17 or Ri 8 are hydrogen, most preferred Ri 6 , Ru and Ri 8 are all hydrogen;
• R 20 , R21, R22, R23 and R 24 are independently from one another hydrogen, halogen, SO 3 H, SO 3 " + Mi, SO 3 R 26 , SO 2 R 26 , SO 2 NH 2 , SO 2 NHR 26 , SO 2 NR 26 R 27 , COOH, COO " + Mi, COOR 26 , CONH 2 , CONHR 26 , CONR 26 R 27 , CN, NO 2 , OCOR 26 , NHCOR 27 , NR 26 COR 27 , R 26 , OH, OR 26 , SR 26 , NH 2 , NHR 26 or NR 26 R 27 ;
• R 20 and R 2 i or R 2i and R 22 are together as a pair NHCONH, CONHCO or butadienylen which is unsubstituted or substituted by R 26 and/or R 27 ;
• R 25 is H or R 26 ; or R 25 forms together with R 22 or R 24 a 5- or 6-membered saturated or unsaturated ring;
• R 26 and R 27 are Ci-C 6 alkyl, C 3 -C 6 cycloalkyl, benzyl or phenyl each unsubstituted or substituted by one or more halogen, OH, OCi-C 5 alkyl, COCi-C 5 alkyl, CN, NO 2 , COOCi-C 5 alkyl, COOH,
• M/ is Li + , Na + , K + , Y 2 Ca 2+ , Y 2 Sr 2+ , Y 2 Ba 2+ , Y 2 Co 2+ , Y 2 Cu 2+ , Y 2 Ni 2+ , Y 2 Mn 2+ , V 2 Mg 2+ , V 2 Zn 2+ , Vz Al 3+ , V 2 TiO 2+ , V 2 ZrO 2+ , or "NR 28 R 29 R 30 R 3 I, wherein R 28 to R 3 i are each independently of the others hydrogen; benzyl or Ci-C 24 alkenyl which are each unsubstituted or optionally substituted by hydroxy; [C 2 -C 4 alkylene-O] m H or [C 2 -C 4 alkylene-O] m R 26 , wherein m is a number from 1 to 8, or R 3 i is C 2 -Ci 2 alkylene linking two identical or different + N R 28 R 29 R 30 groups;
• Y 2 and Y 3 are independently from one another O or preferably NH, most preferred two or all three of Yi, Y 2 and Y 3 are NH;
• R 32 , R 33 , R 34 and R 35 are each independently of one another NH 2 , OH,
• Ci-C 4 alkyl NHR 36 , N(R 36 ) 2 or , or phenyl, biphenyl or naphthyl which are each unsubstituted or substituted by halogen, OH, NH 2 , Ci-C 4 alkyl or Ci-C 4 alkoxy, preferably NH 2 , OH, hydrogen, methyl, ethyl, NHCOR 37 , NHCOOR 37 , NHCONHR 37 , NHCONR 36 R 37 or phenyl which is unsubstituted or substituted by OH or NH 2 , most preferred NH 2 , OH, hydrogen, methyl, NHCOR 37 or phenyl which is unsubstituted or substituted by NH 2 , wherein
• R 36 is Ci-C 4 alkyl; phenyl which is unsubstituted or substituted by halogen, Ci-C 4 alkyl or Ci-C 4 -alkoxy, COR 37 , COOR 37 or CONHR 37 ; and
• R 37 is Ci-C 4 alkyl or phenyl which is unsubstituted or substituted by halogen, Ci-C 4 alkyl or Ci-C 4 -alkoxy, preferably Ci-C 4 alkyl or phenyl which is unsubstituted or substituted by chloro, methyl, ethyl, methoxy or ethoxy, most preferred methyl, ethyl or phenyl, with the proviso that at least two of the radicals R 32 , R 33 , R 34 and R 35 are NH 2 or OH, most preferred wherein R 32 and R 35 are identical, and R 33 and R 34 are identical and at least one of the pairs R 32 and R 35 or R 33 and R 34 is NH 2 or OH;
• R 3 s is a group ⁇ /
• R 39 is hydrogen, Ci-C 6 alkyl, benzyl or a group
• R 40 is hydrogen or R 3 S
• R 4 i, R 42 , R 43 and R 44 are each independently of the others hydrogen, Ci-C 6 alkyl, Ci-C 6 alkoxy, halogen or trifluoromethyl;
• R 45 and R 46 are each independently of the other hydrogen, halogen or Ci-C 6 alkyl
• one or more of R 20 , R21, R22, R23 and R 24 is COOH, COO + Mi, SO 3 H or SO3 ⁇ + Mi, particularly in combination with at least one of R16, R17 and Ris being hydrogen, thus forming a betaine or sulfobetaine salt, respectively.
• M/ is Li + , V 2 Ca 2+ , V 2 Sr 2+ , V 2 Ba 2+ , V 2 Mn 2+ , V 2 Mg 2+ or V 2 Zn 2+ .
• Halogen is typically fluoro, bromo or chloro, preferably bromo or especially chloro on aryl or heteroaryl, and fluoro on alkyl.
• Ci-Ci 2 Alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-octyl, 1 ,1 ,3,3- tetramethyl butyl, 2-ethylhexyl, nonyl, decyl or dodecyl.
• Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bomyl, 1-adamantyl or 2-adamantyl.
• C 2 -Ci 2 Alkenyl or C 3 -Ci 2 cycloalkenyl is respectively C 2 -Ci 2 alkyl or C 3 -Ci 2 cycloalkyl that is mono- or poly-unsaturated, wherein two or more double bonds may be isolated or conjugated, for example vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten- 1-yl, 1 ,3-butadien-2-yl, 2-cyclobuten-1-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl- 1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1 ,4-pentadien-3-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl,
• the pigments preferably have a specific surface area of from 10 to 150 m 2 /g. Special preference is given to opaque pigments having a specific surface area of from 12 to 50 m 2 /g and to transparent pigments having a specific surface area of from 50 to 100 m 2 /g.
• the instant pigment compositions are suitably prepared by dispersing the pigment and the prepolymer in an inert liquid medium, such as an organic solvent or preferably water, then crosslinking the prepolymer by addition of a crosslinking agent, addition of a crosslinking catalyst and/or heating.
• an inert liquid medium such as an organic solvent or preferably water
• the instant pigment compositions are then preferably isolated by filtration and dried.
• Crosslinking or optionally the final part of crosslinking, can also be effected upon final processing of the engineering plastic to be coloured.
• the pigment and the prepolymer can be dispersed together, or the pigment can be dispersed in a dispersion or solution of the prepolymer, or the prepolymer can be dispersed or dissolved in a dispersion of the pigment, or the prepolymer can be prepared by emulsion or suspension polymerisation in presence of the pigment, for example by adding the pigment to the polymerisable monomer or mixture of monomers before the subsequent polymerisation reaction.
• the present invention also relates to a method of producing a coloured engineering plastic, wherein an engineering plastic and a tinctorially effective amount of at least one pigment composition according to the invention are processed together at a temperature of 200°C or above, preferably from 220 to 350°C, most preferred from 240 to 330 0 C.
• the amount of instant pigment composition will be from 0.001 to 70% by weight, based on the total weight of the engineering plastic and instant pigment composition. Preferred are in the case of coloured items from 0.01 to 10% by weight, and in the case of masterbatches from 30 to 60% by weight, each based on the total weight of the engineering plastic and instant pigment composition.
• the engineering plastics to be colored with the instant pigment compositions are generally polymers having a molecular weight in the range of from 10 4 to 10 8 g/mol. Colouring the engineering plastics with the pigment composition according to the invention is carried out, for example, by mixing such a pigment composition into the substrates using roll mills or mixing or grinding apparatuses, as a result of which the pigment composition is finely distributed in the engineering plastic.
• the high engineering plastic comprising the admixed pigment composition is then processed by methods known perse, such as calendering, compression moulding, extrusion, spread-coating, melt-spinning, casting or by injection moulding, whereby the coloured material acquires its final shape.
• Admixture of the pigment composition can also be effected immediately prior to the actual processing step, for example by continuously feeding a solid, for example pulverulent, pigment composition and, at the same time, a granulated or powdered engineering plastic, and optionally also additional ingredients such as, for example, additives, directly into the intake zone of the processing equipment, where mixing takes place immediately before processing.
• Crosslinking may also be effected or completed at this stage.
• the instant pigment compositions largely retain their structure upon processing, so that the instant crosslinked polymer remains around the pigments, thus preventing a direct contact between the pigment and the engineering plastic.
• the instant pigment compositions also have an excellent compatibility with engineering plastics.
• plasticisers In order to produce non-rigid mouldings or to reduce their brittleness, it is possible to incorporate so-called plasticisers into the engineering plastics prior to shaping.
• plasticisers for example, esters of phosphoric acid, phthalic acid or sebacic acid.
• the plasticisers may be incorporated into the polymers before or after incorporation of the colorant.
• further pigments or other colorants in any desired amounts, optionally together with further additional ingredients such as, for example, fillers or siccatives (drying agents).
• Preferred engineering plastics suitable for colouring in accordance with the invention are very generally polymers having a dielectric constant >2.5 at 20°C, preferably polyester (e.g. PET), polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene/acrylonitrile (SAN) or acrylonitrile/butadiene/styrene (ABS).
• polyester e.g. PET
• PC polycarbonate
• PS polystyrene
• PMMA polymethyl methacrylate
• polyamide polyethylene
• polypropylene styrene/acrylonitrile
• ABS acrylonitrile/butadiene/styrene
• polyester Special preference is given to polyester and very special preference is given to polyamide, for example polyamide 6, polyamide 6.6, polyamide 12 and aramid.
• the pigment compositions according to the invention are well dispersible in the afore-mentioned materials, especially polyamides, and provide them with strongly coloured, level hues and in-use fastness properties, especially thermal stability, lightfastness, migration fastness and washing fastness, without fluorescence and deterioration of the mechanical properties.
• Example 1 28.5 g of a 35.2% wet press cake of the pigment of formula
• Example 2 18.2 g of a 55% wet press cake of the pigment of formula are dispersed into 250 ml of water containing 20 g of
• Acronal ® LR 8977 (50 ⁇ 1% solids, BASF). The polymer is then precipitated by the addition of HCI, and the solids are filtered and dried at 60° C / 10 4 Pa.
• Example 3 23.7 g of a 42.2% wet press cake of the pigment of formula
• Examples 4-6 Test plates made of polyamide 6 (Ultramid ® B3K, BASF) containing 0.2% of the encapsulated pigments according to examples 1-3 are prepared by injection molding from a pre-concentrate compounded in a twin-screw extruder. The processing temperatures are between 240 and 300 0 C. So produced test plates show excellent temperature and light stability, as well as excellent wash stability, no migration of the colorants and no fluorescence.
• polyamide 6 Ultramid ® B3K, BASF

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Paints Or Removers (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Coloring (AREA)

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• 2007
  • 2007-10-15 WO PCT/EP2007/060944 patent/WO2008049749A1/en not_active Ceased
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