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
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
• • 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
  • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment

Definitions

• the present invention is directed to pigment compositions containing besides an organic pigment at least two coloured compunds of opposing charge, and ink/paint compositions containing same.
• the ink/paint compositions show improved rheological (flow) performance and no loss or almost no loss in colour strength.
• diarylide pigments (1 ) water-soluble azo dyestuffs which have the same general chemical structure as the pigment but contain acidic groups and (2) fatty alcohols, fatty acids, fatty esters or fatty amines.
• One of the pair of agents (1) and (2) is not coloured and therefore does not contribute colour intensity to the pigment composition.
• the non-coloured portion can interfere with the performance of other pigment additives, and lithographic properties of resulting inks can be affected leading to printing problems.
• US-A-4'461 '647 describes so-called fucidized agents which are water-insoluble asymmetric dyestuffs substituted by long chain ammonium salts which are added to pigment dispersions in order to enhance their fluidity and flocculation resistance.
• Fluidizing agents are restricted to pigment derivatives and can suffer from colour strength loss, lithographic problems and interference with other pigment additives.
• pigment compositions comprising an organic pigment and a combination (complex) of at least two, normally water-soluble, coloured compounds (dyes) of opposing charge, e.g. of at least one anionic and one cationic dye, which dyes are readily available ones, as dispersants for the pigment, can largely overcome the mentioned problems of conventional pigment compositions. It is assumed that the dyes of opposing charge are complexed in such a way as to be retained within the pigment composition. Alternatively, the retention of both the dyes by separate desolubilisation mechanisms is also possible.
• the present invention provides in a first aspect, a pigment composition
• a pigment composition comprising (1) an organic pigment and (2) a combination of at least one anionic and at least one cationic coloured compound wherein the combination (2) comprises
• the present invention provides said pigment composition as a solid composition, preferably as a pigment powder or as pigment granules.
• the present invention provides a non-aqueous composition, preferably a non-aqueous pigment dispersion.
• the present invention provides methods for preparing said solid or non- aqueous pigment compositions.
• the present invention provides non-aqueous inks or paints (oil ink or paint compositions, based e.g. on petroleum distillates) containing said pigment dispersions, and methods for preparing them.
• the present invention provides the use of said non-aqueous inks or paints (ink or paint compositions) in printing and paint systems.
• the basis for the inventive pigment composition can be from the range of organic pigments such as, but not exclusively, monoazo, disazo, naphthol, dioxazone, azomethin, azocondensation, metal complex, nitro, perinone, quinoline, anthraquinone, benzimidozolone, isoindoline, isoindolinone, quinacridone, hydroxyanthraquinone, aminoanthraquinone, anthrapyrimidine, indanthrone, flavanthrone, pyranthrone, anthantrone, isoviolanthrone, diketopyrrolopyrrole, carbazole, perylene, indigo or thioindigo pigments.
• organic pigments such as, but not exclusively, monoazo, disazo, naphthol, dioxazone, azomethin, azocondensation, metal complex, nitro, perinone, quinoline, anthraquinone,
• the range of interesting organic pigments may comprise monoazo, disazo, naphthol, dioxazone, azomethin, azocondensation, metal complex, nitro, perinone, quinoline, anthraquinone, benzimidozolone, isoindoline, isoindolinone, quinacridone, hydroxyanthraquinone, aminoanthraquinone, anthrapyrimidine, indanthrone, flavanthrone, pyranthrone, anthantrone, isoviolanthrone, diketopyrrolopyrrole, carbazole, indigo or thioindigo pigments. Mixtures of the pigments may be used.
• Preferred pigments for the application of the present invention are mono- or disazo pigments, preferably mono- or diarylides, or metal complexes, preferably a copper phthalocyanine pigment, or naphthol pigments, preferably ⁇ -naphthol or a ⁇ -oxynaphthoic acid (BONA) pigments, or quinacridones or indanthrones.
• mono- or disazo pigments preferably mono- or diarylides, or metal complexes, preferably a copper phthalocyanine pigment, or naphthol pigments, preferably ⁇ -naphthol or a ⁇ -oxynaphthoic acid (BONA) pigments, or quinacridones or indanthrones.
• organic pigments More preferably, the following organic pigments are used inventively:
• Mono- or diarylide yellow pigments selected from CI. Pigment Yellow 1 , 2, 10, 12, 13, 14,
• Monoarylide yellow pigments selected from CI. Pigment Yellow 1 , CI. Pigment Yellow 2, Ol.Pigment Yellow 65, Ol.Pigment Yellow 73, Ol.Pigment Yellow 74 and CI. Yellow 75.
• Diarylide yellow pigments selected from CI. Pigment Yellow 12, CI. Pigment Yellow 13, CI. Pigment Yellow 14, CI. Pigment Yellow 17 and CI. Pigment Yellow 83.
• Disazo orange pigments selected from CI. Pigment Orange 16 and CI. Pigment Orange 34.
• Naphthol red pigments selected from CI. Pigment Red 48:1, CI. Pigment Red 48:2, CI. Pigment Red 48:3, C.I. Pigment Red 48:4, CI. Pigment Red 48:5, CI. Pigment Red 49:1 , CI. Pigment Red 52:1 , CI. Pigment Red 52:2, CI. Pigment Red 52:3, CI Pigment Red 53:1 , CI. Pigment Red 53:2, CI. Pigment Red 53:3, CI. Pigment Red 57:1 , CI. Pigment Red 57:2, CI. Pigment Red 58:2, CI. Pigment Red 58:4, CI. Pigment Red 63:1 and CI. Pigment Red 64:1. Quinacridone red pigments such as CI. Pigment Red 202.
• Blue or green copper phthalocyanine pigments selected from CI. Pigment Blue 15:1 , CI. Pigment Blue 15:2, CI. Pigment Blue 15:3, CI. Pigment Blue 15:4, CI. Pigment Green 7 and CI. Pigment Green 36. Blue indanthrone pigments such as CI. Pigment Blue 60.
• the anionic dyes are typically, but not exclusively, commercially available dyes selected from acid dyes, direct dyes, reactive dyes and mordant dyes. As a rule, their chemical structure is different from that of the organic pigment.
• Acid dyes selected from CI Acid Black 1 , 24 and 48, CI.Acid Blue 1 , 7, 9, 25, 29, 40, 45, 74, 80, 83, 90, 92, 113, 120, 129 and 147, CI. Acid Green 1 ,3, 5, 25, 27, and 50, CI. Acid Orange 6, 7, 8, 10, 12, 51 , 52, 63 and 74, CI. Acid Red 1 , 4, 8, 14, 17, 18, 26, 27, 29, 37, 44, 50, 51 , 52, 66, 73, 88, 97, 103, 114, 150, 151 and 183, CI. Acid Violet 7 and 17, and CI. Acid Yellow 1 , 9, 11 , 17, 23, 25, 29, 34, 36, 42, 54, 76, 99 and 169.
• Direct dyes selected from CI. Direct Blue 1 , 14, 53 and 71 , CI. Direct Violet 51 , C.I. Direct Red 2, 23, 28, 75, 80 and 81 , and CI. Direct Yellow 4, 8, 9, 12, 27, 50, 62 and 172.
• Reactive dyes selected from CI. Reactive Black 5, CI. Reactive Blue 2, 4 and 15, CI. Reactive Orange 16, CI. Reactive Red 2 and 4, and CI. Reactive Yellow 2.
• Mordant dyes selected from CI. Mordant Black 17 and CI. Mordant Violet 5.
• anionic dyes can be used in the inventive pigment compositions.
• the anionic dyes may also be pigment derivatives bearing one or more anionic.i.e. acidic groups which impart to them a (certain) water solubility.
• anionic.i.e. acidic groups which impart to them a (certain) water solubility.
• examples of such groups are inorganic groups derived from mineral acids comprising sulfonic acid, sulfonate, sulfinic acid, sulfinate, phosphoric acid, phosphate groups, and organic groups derived from carboxylic acids/carboxylates (carboxylic acid salts).
• the anionic pigment derivative may be a derivative of organic pigment (1), on the one hand, but also need not to be of similar structure to organic pigment (1), on the other hand. As a rule, the anionic pigment derivatives give good results when associated with a non- derivative cationic dye.
• Preferred anionic pigment derivatives are those derived from the preferred pigments mentioned hereinbefore.
• the cationic dyes are typically, but not exclusively, also commercially available dyes which may be - according to their chemical characterization - azo, azomethin, methin, polymethin, azine, cyanine, oxazine, thiazine, thiazole, acridine, anthraquinone, triarylmethan, xanthene or ketone imine dyes.
• Their chemical structure is generally different from that of pigment (1).
• Cationic black dyes selected from CI. Basic Black 2 and CI. Basic Black 7.
• Cationic blue dyes selected from CI. Basic Blue 1 , 3, 6, 7, 9, 11 , 12, 16, 17, 24, 26, 40, 41 , 57, 66, 80, 123 and 159.
• Cationic green dyes selected from CI. Basic Green 1 , 4 and 5.
• Cationic orange dyes selected from CI. Basic Orange 2, 14, 21 and 54.
• Cationic red dyes selected from CI. Basic Red 1 , 2, 5, 9, 10, 13, 22, 29, 46 and 54.
• Cationic violet dyes selected from CI. Basic Violet 1 , 2, 3, 4, 10 and 35.
• Cationic yellow dyes selected from CI. Basic Yellow 1 , 2, 11 , 13, 17, 19, 21 , 24, 28, 40, 45, 53, 61 , 63 and 73.
• One or more cationic dyes can be used in the inventive pigment compositions.
• the cationic dye may also be a pigment derivative bearing one or more basic (basic means cationic) groups which impart to them a (certain) water solubility.
• Typical examples of cationic groups include ammonium groups (-NH 4 ) which may be primary, secondary, tertiary or quaternary substituted, further primary, secondary or tertiary amino groups, and also primary, secondary and tertiary carbon amido, sulfonamido, sulfinamido or phosphoramido.
• the cationic pigment derivative may be a derivative of organic pigment (1), on the one hand, but also need not to be of similar structure to organic pigment (1), on the other hand.
• Preferred cationic pigment derivatives are those derived from the preferred pigments mentioned hereinbefore.
• the cationic pigment derivatives can be combined with non-derivative anionic dyes to give good results, too.
• one of said pigment derivatives is not derived from organic pigment (1), i.e. this derivative has to show a different chemical structure from the base structure of organic pigment (1).
• Combination (2) of the inventive pigment compositions preferably comprises such pairs as:
• anionic/cationic coloured compound anionic/cationic dye or anionic/cationic pigment derivative
• anionic/cationic surfactant an anionic/cationic surfactant
• inventive pigment compositions with suff icient performance up to about 3/4 (0 to 75 mol%) of the anionic/cationic dye (anionic/cationic pigment derivative) can be replaced by an anionic/cationic surfactant, respectively.
• this replacement 0 to 50 mol% can be considered.
• Suitable surfactants are known to those skilled in the art. Preferably they comprise e.g. long chain (fatty, containing e.g. 8 to 22, preferably 8 to 18 carbon atoms) alcohols, acids, esters, amides or amines and their derivatives, such as alkoxylates (ethoxylates), which contain positively/negatively charged groups.
• Preferred combinations (2) - when anionic/cationic surfactants are used - comprise: cationic dye/cationic surfactant + anionic dye, cationic dye/cationic surfactant + anionic pigment derivative, cationic pigment derivative/ cationic surfactant + anionic dye, cationic pigment derivative/ cationic surfactant + anionic pigment derivative (the two pigment derivatives must be structurally different), or anionic pigment derivative/anionic surfactant + cationic pigment derivative (the two pigment derivatives must be structurally different), and also anionic dye/anionic surfactant + cationic dye, anionic dye/anionic surfactant + cationic pigment derivative ,or anionic pigment derivative/anionic surfactant + cationic dye
• the molar ratio of the components - assuming that both are mono-anionic and monocationic - of combination (mixture) (2a)(anionic and cationic dye), (2b) (anionic and cationic pigment derivative), or (2c) can vary within a broad range. Possible ratios of about (0.1-10) : (10-0.1), or more preferred of (1-5) : (5-1) can be used.
• the inventive compositions of organic pigments or organic pigment compositions may contain usually from 50.1 to 99.8% by weight (b.w.), preferably from 80.0 to 99.0% (b.w.) of the pigment, usually from 0.1 to 49.8% (b.w.), preferably from 0.5 to 10.0% (b.w.) of at least one anionic coloured compound (dye), and usually from 0.1 to 49.8% (b.w.), preferably from 0.5 to 10% (b.w.) of at least one cationic coloured compound (dye).
• the combined amount of anionic/cationic coloured compounds in the pigment compositions is from 1 to 10% (b.w.).
• Aqueous preparations of these compositions have a solids content usually from about 0.5% to 20%, preferably from 5 to 18%.
• Aqueous based organic pigment dispersions can be prepared from dry pigments, by use of additional surfactants, at a level of at least 50% pigment by conventional techniques.
• pigment concentration normally is 8 to 20%.
• the (non-aqueous) pigment compositions may optionally contain further additives such as, but not exclusively, e.g. abietyl resins and abiety derivatives, surfactants, pigment derivatives, extenders, ink vehicle components, rheology modifiers, etc. Effective amounts should be used, e.g. from 0 to 50% (b.w.), based on the combined weight of the pigment and the dyes.
• the dyes may be used as a solution or dispersion in water or other suitable solvent.
• the dyes may also be used in press-cake, granule or dry powder form.
• the dye mixture (complex of anionic and cationic dye(s)) may also deliberatedly formed and isolated prior to use and utilised as a solution or dispersion in water or other suitable solvent.
• the dye mixture can be isolated as a filter (press) cake, redispersed into or for use in an aqueous pigment slurry, or mixed as filter cake with a filter cake of the pigment.
• the dye (mixture) complex may also be used in granule or dry powder form.
• the isolated and dried material (dye mixture) can then be added to an aqueous or solvent based slurry of the pigment or blended with a dry pigment.
• the anionic/cationic coloured compound (dye) may be incorporated independently or together into a preparation of pigment (1), preferably a water-based composition (dispersion), during or after its preparation by standard stirring/milling techniques (conditioning) or surface treating (coating)
• the dyes or dye complexes may be incorporated into the pigment during its synthesis, i.e. before or after coupling, but more preferably after completion of coupling, but before isolation, washing or drying.
• the method comprises e.g. heating an aqueous pigment slurry (as obtained by normal synthesis steps) containing the necessary additives, to induce flocculation, followed by optional cooling and isolation which comprises such steps as filtering and washing until salt free, and then drying and/or granulating the composition.
• the method can be started by a dispersion step for the pigment in an aqueous solution of the dyestuffs (at least one anionic and at least one cationic dye).
• Still another alternative comprises the co-flushing or co-drying of the pigment and the dye mixture.
• the preparation of flushed (pigment) compositions involves the addition of a flushing vehicle, such as an oil or a solution of resins and other additives, to the water-precipitated filter (press) cake or disperion (slurry) of the pigment/dye mixture composition.
• a flushing vehicle such as an oil or a solution of resins and other additives
• the direct transfer (flushing) of the pigment/dye mixture from the aqueous phase to the oil or non-polar phase is effected by kneading the filter cake and the vehicle together in a flusher or heavy- duty mixer under heat and vacuum.
• the dye mixture can also be used in surface treated (coated) form, i.e treated e.g. with abietyl resins or fatty acids, in any one of the methods decribed before
• inventive pigment compositions may be used in all customary industrial printing processes such as lithographic, flexographic, gravure, letterpress, screen, ink-jet, intaglio, aqueous or other printing inks, further in all customary industrial paint systems such as decorative, industrial, automotive or other paint systems, to provide improved rheology with no or at most minimalized reduction of colour strength.
• the method of preparation of the ink system is by methods of shear to induce dispersion into a varnish system.
• examples of the wide range of techniques are triple-roll-mill and bead mill.
• Varnish systems are also wide ranging and known by the artisan.
• Examples of the final application are off-set lithography and sheet fed.
• the dyes when preparing the printing inks or paint systems, may be incorporated independently or together (dye complexes) to a conventional ink or paint formulation before, during or after pigment addition.
• the inventive pigment compositions are usually dispersed or dissolved together, optionally together with customary additives, such as dispersants, fillers, paint auxiliaries, siccatives, plasticizers and/or additional pigments or pigment precursors, in a common solvent or mixture of solvents.
• customary additives such as dispersants, fillers, paint auxiliaries, siccatives, plasticizers and/or additional pigments or pigment precursors, in a common solvent or mixture of solvents. This can be achieved by dispersing or dissolving the individual components by themselves, or also several components together, and only then bringing all components together, or by adding everything together simultaneously.
• the desired effects and the other by-properties can be moderated by the appropriate selection of the relative ratio and total amount of the two dyes.
• the dyes should also be selected that undesirable effects on product shade do not occur.
• the pair of materials (dye complex) which are responsible for the improved rheological performance are both coloured, in general of the the same colour, almost no loss in colour strength is observed.
• Pigment Yellow 13 aqeous slurry containing 63 g of the pigment.an aqueous solution containing 2 g of 4,4'-bis[[1-[[(2,4-dimethylphenyl)amino]carbonyl]-2-oxypropyl]azo]-
• [1 ,1'-biphenyl]-2,2'disulphonic acid is added, followed by an aqueous solution containing 3.5 g of CI. Basic Yellow 40.
• an aqueous solution of Burez K50-505A potassium salt (potassium soap of disproportionated rosin, 50%, Eka-Nobel), containing the equivalent of 30 g resin acids, is added and the resulting slurry heated to roughly 95°C by direct steam injection.
• the slurry is acidified by dropwise addition of dilute hydrochloric acid, then cooled, filtered and washed until salt free.
• the resulting dye pair is thus formed in situ during pigment processing.
• Example 1 The Example 1 procedure is repeated with 64 g of CI. Pigment Yellow 13 plus 2.5 g of CI.
• Example 1 The Example 1 procedure is repeated with 63.8 g o CI. Pigment Yellow 13 plus 1.7 g of CI.
• Example 1 The Example 1 procedure is repeated with 64.1 g of CI. Pigment Yellow 13 plus 2.4 g of C
• Example 1 The Example 1 procedure is repeated with 64 g of CI. Pigment Yellow 13 plus 2.5 g of CI.
• Example 1 The Example 1 procedure is repeated with 66.5 g of CI. Pigment Yellow 13 and no added
• Example 1 The Example 1 procedure is repeated with 68.5 g of CI. Pigment Yellow 13 and no additions of either CI.
• Example 1 The Example 1 procedure is repeated with 65 g of CI. Pigment 13 but in absence of 4.4'- bis[[1 -[[(2,4-dimethylphenyl)amino]carbonyl]-2-oxypropyl]azo]-[1 ,1'-biphenyl]-2,2'- disulphonic acid.
• Example 1 The Example 1 procedure is repeated with 66 g of CI. Pigment 13 but in absence of of 4.4'- bis[[1 -[[(2,4-dimethylphenyl)amino]carbonyl]-2-oxypropyl]azo]-[1 ,1 '-biphenyl]-2,2'- disulphonic acid. 2.5 g of CI. Basic Yellow is also used in place of CI. Basic Yellow 45.
• a stirred aqueous slurry containing CI. Pigment Blue 15:3 ( ⁇ -copper phthalocyanine) is heated to 90°O
• a slurry containing 2.5 g of copper phthalocyanine monosulfonic acid is added and stirring continued for 30 minutes.
• An aqueous solution containing the equivalent of 4 g of C.I. Basic Blue 9 (Methylene Blue) is then added and stirring continued for 30 minutes more.
• the resulting slurry is cooled, filtered and washed until salt free, then dried giving 58 g of pigment composition.
• This dry complex is added at a 3% level to a stirred aqueous slurry of CI. Pigment Blue 15:3 at 30°C and pH 1. After stirring for 1 hour the slurry is filtered, washed until salt free and dried.
• Example 6 The Example 6 procedure is repeated in the absence of CI. Basic Blue 9.
• Example 6 The Example 6 procedure is repeated in the absence of both CI. Basic Blue 9 and copper phthalocyanine monosulfonic acid.
• Example 8 The Example 8 procedure is repeated in the absence of both CI. Basic Blue 9 and copper phthalocyanine monosulfonic acid.
• aqueous dispersions containg 20% pigmentation which are tested into a commercial heatset varnish system on a Buhler SDY-200 three roll mill.
• the inks are then reduced to between 12 to 16% pigmentation (depending on the pigment type) by the addition of further varnish.
• Colouristic assessment is carried out on the prints produced from a Prufbau Printer and low shear flow assessed on a 45° angled plate after 2 or 24 hours, depending on the the pigment type (2 hours for yellow and red pigment commpositions, 24 hours for blue pigment compositions).
• This example relates to an isolated complex of a dyestuff pair as an ink additive.
• 2-oxypropyl]azo]-[1,1'-biphenyl]-2,2'-disulphonic acid is mixed thoroughly with an 80ml aqueous solution containing the equivalent of 1.5g cation weight of Basic Yellow 28.
• a 45ml aqueous solution of Burez K50-505A potassium salt, containing the equivalent of 1.6g resin acids is added resulting in increased alkalinity (pH 9.5).
• the mixture is heated to 60°C and the pH reduced to 5.0 by the addition of dilute hydrochloric acid.
• the resulting material was filtered, washed and dried giving a 90% yield.
• the dry product is ground and blended with a standard diarylide yellow composition (Pigment Yellow 174) at a weight ratio of 1 :19 respectively.
• a stirred aqueous based slurry containing 50 g pigmentary CI. Pigment Blue 60 is heated to 70°C. After stirring for 50 minutes the slurry is filtered, washed until salt free and dried. This material is used as a standard for comparison with examples 10 and 11.
• 120 g crystalline pigmentary Pigment Red 202 is prepared from size-reduced crude Pigment Red 202 in a traditional solvent conditioning treatment. The slurry is then isolated as a filter cake and washed thoroughly. This material is used as crystalline pigmentary Pigment Red 202 in examples 12 and 13. A portion is also dried and used as a comparative standard for examples 12, 13 and 14.

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• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Paints Or Removers (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)

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• 2003
  • 2003-04-24 CA CA002483836A patent/CA2483836A1/en not_active Abandoned
  • 2003-04-24 WO PCT/EP2003/004259 patent/WO2003093373A1/en not_active Ceased
  • 2003-04-24 EP EP03720522A patent/EP1499683A1/en not_active Withdrawn
  • 2003-04-24 BR BR0309630-0A patent/BR0309630A/pt not_active Application Discontinuation
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  • 2003-04-24 AU AU2003224122A patent/AU2003224122A1/en not_active Abandoned
  • 2003-04-24 CN CNB038095777A patent/CN100343342C/zh not_active Expired - Fee Related
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