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WO2000063318A1 - Composition fluorescente - Google Patents

Composition fluorescente Download PDF

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Publication number
WO2000063318A1
WO2000063318A1 PCT/EP2000/003165 EP0003165W WO0063318A1 WO 2000063318 A1 WO2000063318 A1 WO 2000063318A1 EP 0003165 W EP0003165 W EP 0003165W WO 0063318 A1 WO0063318 A1 WO 0063318A1
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WO
WIPO (PCT)
Prior art keywords
fluorescent
weight
polymer
mixture
acrylic acid
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.)
Ceased
Application number
PCT/EP2000/003165
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English (en)
Inventor
Johannes Leugs
Adrianus Hendrikus Van Rooijen
Volkhard Karl Wiese
Steffi Reinhardt
Volker Steinert
Michael Stephan
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 Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to AU2000243992A priority Critical patent/AU2000243992A1/en
Publication of WO2000063318A1 publication Critical patent/WO2000063318A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

Definitions

  • the invention on hand relates to a fluorescent composition consisting essentially of a fluorescent dyestuff and a polymer, wherein the polymer contains carboxylic acid and carboxylate groups.
  • fluorescent pigments are solid state solutions of common fluorescent dyes in polymeric resins or matrices.
  • matrices are used which are formed by melt condensation of melamine, formaldehyde, and toluenesulfon-amide, and polymers based on e.g. polymethyl methacrylate (“PMMA”), or polyamides.
  • PMMA polymethyl methacrylate
  • US 5,710,197 describes a process for the manufacture of a fluorescent pigment comprising a polymer matrix based on PMMA and a nonpolar fluorescent dye from the coumarin or perylene series.
  • the migration fastness was improved compared to products disclosed in DE-A 39 33 903, the migration fastness is still not satisfying for some applications.
  • only nonpolar dyes can be used, and the polymer matrix is crosslinked, i.e. a crosslinking monomer has to be added before or during the polymerization step thereby increasing costs and efforts for handling an additional component.
  • the object of this invention was to provide further fluorescent pigments with an improved migrations fastness.
  • the use of a crosslinking monomer should not be necessary, preferably it should be avoided, and it should be possible to use all fluorescent dyes and not only nonpolar dyes.
  • the migration fastness should not be improved at the expense of other properties such as light fastness, heat stability, or ecological reasons as well.
  • a polymer containing carboxylic acid and carboxylate groups is used.
  • Such as polymers which are obtainable by the polymerization of CH 2 C(H,Me)-(CH 2 ) n - COOH, wherein n is 0, 1, 2, 3, 4 or 5, and optional comonomers, which is treated after the polymerization step with a neutralising agent resulting in a polymer, wherein not all of the carboxylic acid groups are neutralized.
  • an acrylic acid and optional comonomers are used.
  • polymer shall include the term “copolymer” throughout the application.
  • the molecular weight of the polymer is chosen in the range of from 60,000 to 600,000, preferred from 75,000 to 500,000 g/mol.
  • hydroxides, carbonates and C 1 -C 4 alcoholates of alkali or alkaline-earth metals such as sodium oxide, potassium oxide, magnesium oxide, calcium oxide, lithium hydroxide, sodium hydroxide, or potassium hydroxide, magnesium carbonate, calcium carbonate, sodium methylate, sodium ethylate, magnesium hydroxide, or magnesium ethylate, or basic ammonium compounds such as ammonium hydroxide or salts having volatile anions such as carbonates or acetates, preferably ammonium carbonate, can be used.
  • alkali or alkaline-earth metals such as sodium oxide, potassium oxide, magnesium oxide, calcium oxide, lithium hydroxide, sodium hydroxide, or potassium hydroxide, magnesium carbonate, calcium carbonate, sodium methylate, sodium ethylate, magnesium hydroxide, or magnesium ethylate, or basic ammonium compounds such as ammonium hydroxide or salts having volatile anions such as carbonates or acetates, preferably ammonium carbonate, can be used.
  • a neutralising agent amides such as alkali metal amides like NaNH 2 ,or KNH 2 , or organic amines such as primary, secondary, tertiary or quaternary amines, preferably tetramethyl ammonium chloride.
  • the cation mentioned above may be a cation of the abovementioned alkali metals, alkaline-earth metals or unsubstituted or substituted ammonium.
  • a neutralising agent preferably with a hydroxide of an alkali metal, an alkaline-earth metal or ammonium, an alkali metal or alkaline-earth metal C C 4 alcoholate, an amide of an alkali metal, an amine, or a salt of an a alkali metal or alkaline-earth metal cation and a volatile anion, particularly preferred wherein the degree of neutralization ⁇ is in the range of from 0.05 to 1.00.
  • esters of methacrylic or acrylic acid such as 2-hydroxyethyl acrylate, acrylonitrile, methacrylonitrile, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, styrene and its derivatives, maleic acid, or maleic acid anhydride, or mixtures thereof, preferably methacrylic acid, may be used.
  • fluorescent dyestuff all known fluorescent organic compounds can be used, preferably those which are soluble in the monomer or monomer mixture, most preferably are those which belong to the following families known as benzothioxanthene, benzoxanthene, xanthene, coumarin, naphthalimide, perylene, benz[4,5]imidazo[2,1-a]isoindol-11-one, particularly preferred as host compound in combination with quinacridones, perylenes, perinones, diketopyrrolopyrroles, rhodamines, coumarins, cyanins, phthalocyanines, porphyrins, styryl dyes as guest compounds, maleinimide, and acridine.
  • benzothioxanthene benzoxanthene, xanthene, coumarin, naphthalimide, perylene, benz[4,5]imidazo[2,1-a]isoindol-11-one
  • Basic Violet 10 rhodamine B, e.g. FLEXO RED 540® from BASF
  • Basic Violet 11 Basic Violet 16
  • Basic Yellow 40 such as MAXILON FLAVINE 10 GFF® from Ciba Specialty Chemicals
  • Basic Yellow 101 Basic Yellow 43, Solvent Yellow 44, Solvent Yellow131, and Solvent Yellow 135.
  • a further embodiment of the invention on hand concerns a fluorescent composition, wherein
  • the amount of the polymer containing carboxylic acid groups and carboxylate groups is chosen in the range of from 90 to 99.9, preferred from 97 to 99.5 % by weight, based on the fluorescent composition, and
  • the amount of fluorescent dyestuff is chosen in the range of from 10 to 0J , preferred from 3 to 0.5 % by weight, based on the fluorescent composition.
  • Another preferred embodiment concerns a fluorescent composition, wherein the polymer containing carboxylic acid groups and carboxylate groups is obtainable by (A) polymerizing a mixture consisting essentially of
  • a neutralising agent preferably with a hydroxide of an alkali metal, an alkaline-earth metal or ammonium, an alkali metal or alkaline-earth metal C r C 4 alcoholate, an amide of an alkali metal, an amine, or a salt of an a alkali metal or alkaline-earth metal cation and a volatile anion, particularly preferred wherein the degree of neutralization ⁇ is in the range of from 0.05 to 1.00.
  • the preparation of the polymers usually can be carried out by any known method in the art such as mass, suspension, emulsion, inverse emulsion or solution polymerization either batchwise or continuously, preferably a batchwise or continuous mass polymerization is chosen, particularly preferred is a continuous mass polymerization.
  • initiators are used for the present invention such as commonly used initiators for polymerisations e.g. peroxides, peresters, hydroperoxides and some azo compounds and also mixtures thereof.
  • Preferred initiators are selected from the group consisting of tert.-butyl peroxyneodecanoate (TBPND), tert.-butylperoxyethylhexylcarbonate (TBPEHC) tert.-amylperoxyneodecanoate (TAPND), tert.-amylperoxypivalate (TAPPI), tert.-butylperoxypivalate (TBPPI), 2,5-dimethyl- 2,5-di(2-ethylhexanoylperoxy)hexane (DHPEH), tert.-amylperoxy-2-ethylhexanoate (TAPEH), tert.-butylperoxy-2-ethylhexanoate (TBPEH), tert.-butylperoxy-3,5,5-trimethylhexanoate (TBPIN) and mixtures thereof.
  • TBPND tert.-butyl peroxyne
  • mixtures of tert.-butylperoxyneodecanoate and tert.-butylperoxy- ethylhexylcarbonate preferably chosen in the range of from 50 to 90% b.w. TBPND and 50 to 10% b.w. TBPEHC, the total sum being 100%, especially preferred is a weight ratio of in the range of from (70 to 80)/(30 to 20) (TBPND/TBPEHC).
  • the amount of initiator or mixture of initiators usually is chosen in the range of from 0J to 1.0 mol-%, preferably from 0.2 to 0.4 mol-%, based on the total quantity of monomers.
  • a further embodiment of this invention relates to a process for the preparation of the fluorescent composition comprising treating a mixture of (a) a polymer which contains carboxylic acid groups and (b) a fluorescent dyestuff with a neutralizing agent.
  • the abovementioned polymers as a rule are used.
  • the fluorescent dyestuff is incorporated before or during the polymerization step of the used polymer.
  • the treatment with the neutralizing agent usually is carried out in adding a neutralizing agent to the mixture of the polymer containing carboxylic acid groups and the fluorescent dyestuff.
  • the polymer is ground after the polymerization step, but before the neutralization step.
  • a particle size smaller than 100 ⁇ m is chosen.
  • the treatment with a neutralizing agent can be carried out in solution or in a melt of the polymer, preferably, the treatment with the neutralizing agent is carried out in a solvent.
  • solvents inorganic polar solvents such as water, or organic polar solvents such as mentioned in Polymer Handbook, 3rd Edition, J.Brandrup, E.H.Immergut, John Wiley&Sons 1989, Cap. VIII, p.
  • 379 can be used, preferably alkanols having one, two or three hydroxy groups, esters like ethylacetate, ketones such as acetone, cyclic ethers such as dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, formamides such as dimethylformamide or mixtures thereof, more preferably a mixture of water and ethanol is used, preferably in a weight ration in the range of from 5:1 to 0.2:1 , particularly preferred from 2:1 to 0.5:1.
  • an amount of 50 to 200 kg of the desired solvent is used per 5 to 20 kg of the polymer.
  • the amount of chosen neutralizing agent depends primarily on the desired degree of neutralization and the chosen neutralizing agent. Therefore, it is preferred to calculate the amount of neutralizing agent if the desired degree of neutralization is defined.
  • Another preferred embodiment of this invention concerns a process for the preparation of the inventive fluorescent composition, wherein a compound selected from the group consisting of a hydroxide of an alkali metal, an alkaline-earth metal or ammonium, an alkali metal or alkaline-earth metal C 1 -C 4 alcoholate, an amide of an alkali metal, an amine, or a salt of an a alkali metal or alkaline-earth metal cation and a volatile anion, is chosen as neutralizing agent.
  • a compound selected from the group consisting of a hydroxide of an alkali metal, an alkaline-earth metal or ammonium, an alkali metal or alkaline-earth metal C 1 -C 4 alcoholate, an amide of an alkali metal, an amine, or a salt of an a alkali metal or alkaline-earth metal cation and a volatile anion is chosen as neutralizing agent.
  • Another preferred embodiment of the present invention relates to a process for the preparation of the inventive fluorescent composition, wherein the polymerization of the monomer or monomers in the presence of the fluorescent dyestuff is carried out in an extruder.
  • the neutralization is also carried out either in the same or in an additional extruder, or as described above.
  • this inventive process consists of the following steps: (A) introducing continuously into the extruder
  • (III) optionally from 0J to 1.0 mol-%, based on the amount of monomers (a) to (c), of an initiator,
  • a neutralizing agent preferably with a compound selected from the group consisting of a hydroxide of an alkali metal, an alkaline- earth metal or ammonium, an alkali metal or alkaline-earth metal C 1 -C 4 alcoholate, an amide of an alkali metal, an amine, or a salt of an a alkali metal or alkaline-earth metal cation and a volatile anion, particularly preferred wherein the degree of neutralization ⁇ is in the range of from 0.05 to 1.00.
  • the treating with a neutralising agent is carried out in a second extruder. And in a further preferred embodiment, the treating with a neutralising agent is carried out in the extruder after step (B), but before step (C).
  • the monomers are admixed with the initiator or mixture of initiators before it is introduced into the extruder.
  • the admixture can be carried out by known methods e.g. by mixing the components in usual vessels and agitators, static mixers etc. If the initiator or mixture of initiators is admixed with the monomers, it is preferred to cool the admixture after it is admixed, especially if it is desired to store it, usually at a temperature in the range of from -30 to 5°C, preferably from -20 to -5°C.
  • the usual additives and fillers such as rheology improvers usually in amounts ranging from 0.01 to 15% by weight, related to the total amount of reactants, dispersants usually in amounts in the range of from 0.01 to 30% by weight, related to the total amount of reactants, and stabilizers and antioxidants in effective amounts may be added.
  • the reaction temperature usually should be chosen sufficiently high to ensure that the polymerization reaction takes place in a reasonable time. In general, this depends of course from the chosen reactants, but can be figured out easily by a person skilled in the art, because the corresponding data are well-known in the art.
  • the reaction can be carried out at from 70 to 220°C, preferably from 90 to 200°C.
  • the reaction can be carried out at a temperature in the range of from 100 to 180°C.
  • the reaction time depends on the chosen reactants, the desired molecular weight of the polymer to be produced, the chosen reaction temperature, etc. Suitable reaction times can be found easily by a person skilled in the art, if necessary by a few pilot tests. As an example, in case a AA/MMA/BA mixture and Basic Violet 10 as dyestuff are chosen, the reaction time usually is within the range of 0J to 2 hours, if the reaction temperature is within the range of from 50 to 150°C.
  • any kind of extruder can be used, e.g. twin-screw extruders or kneading extruders, but co-rotating twin-screw extruders and especially co-rotating, closely intermeshing extruders are preferred.
  • a co-rotating twin-screw extruder is used with a UD (length/diameter) ratio in the range of from 30 to 60, particularly from 40 to 60.
  • UD length/diameter
  • the throughputs in the extruder depend on the different reactants and, of course, on the size of - 10 -
  • the throughput is preferably chosen in the range of from 0J to 10, more preferred from 1 to 8 kg/h.
  • a temperature profile is applied to different zones of the used extruder depending on the chosen pigment and monomer.
  • Preferred e.g. is a temperature profile in which
  • the temperature in the third quarter of the extruder (0.5L ⁇ x ⁇ 0.75L) the temperature is in the range of 100 to 80% of the desired highest temperature, preferably the temperature is decreased at the end of this part of the extruder to 80 to 90% of the desired highest temperature,
  • the temperature in the last quarter of the extruder (0.75L ⁇ x ⁇ L) at the beginning of this part of the extruder the temperature preferably is chosen at about 80 to 90% of the desired highest temperature and then, in the following parts of the extruder, is increased to about 100 to 120% of the highest desired temperature chosen in the second part of the extruder (b).
  • the zone of the extruder with the desired highest temperature can be extended, preferably in combination with the overall length L of the extruder, and, of course, more detailed profiles can be chosen, usually depending on the chosen pigments, monomers, initiators, and chain transfer agents.
  • the reaction mixture is withdrawn continuously from the extruder by known methods, e.g. it is usually released into air and/or water at ambient temperature and atmospheric pressure. If desired, further work-up can be carried out such as granulating or pulverizing by known methods to yield granules, powders or pastes, if the powder is mixed with an organic solvent or water.
  • reaction mixture can be treated with a neutralizing agent in a solution as described above, or, in another preferred embodiment, in a second extruder.
  • the reaction mixture is treated with a neutralizing agent in a second extruder
  • the reaction mixture polymer comprising the fluorescent dyestuff
  • an extruder preferably a co-rotating twin screw extruder, with a L/D in the range of from 20 to 60, preferably 35 to 45, with throughput ratio in the range of from 1 to 20, preferably from 5 to 10 (throughput of copolymer in kg/h : throughput of aqueous neutralizing agent solution in kg/h).
  • the extruder barrel is divided in at least 10 zones, particularly 14 zones, usually all having the same length. As a rule the zones are connected into at least 5 heating zones, particularly 7 heating zones, wherein preferably each heating zone is heated individually.
  • the polymer melt is degassed at zone 11 at a pressure of about 200 mbar, then the extrudate is collected in a container and broken.
  • the degree of neutralization can be calculated from the concentration of carboxylic groups of the copolymer before and after neutralization by potentiometric titration with 1 N LiOH in water/acetone as solvent. Another preferred possibility is to use IR-analysis.
  • the inventive fluorescent compositions exhibit a particle size of below 10 ⁇ m, preferably from 1 to 5 ⁇ m.
  • inventive fluorescent compositions do not have a particle size below 10 ⁇ m
  • known methods can be applied to achieve the desired result, such as milling, e.g. in a ball mill, followed by e.g. fractionating by suspension sieving, preferably with a volatile non- solvent such as n-heptane using an ultrasonic disintegrator.
  • a volatile non- solvent such as n-heptane
  • ultrasonic disintegrator preferably with a volatile non- solvent such as n-heptane using an ultrasonic disintegrator.
  • Other possibilities such as using jet mills are known in the art.
  • Another preferred embodiment of this invention relates to an inventive fluorescent composition obtained according to the afore described inventive processes.
  • Another embodiment of the present invention is related to the use of the inventive fluorescent compositions for the preparation of coloring high molecular weight organic materials (having a molecular weight usually in the range of from 10 3 to 10 7 g/mol), e.g. biopolymers, plastic materials, including fibres, glasses, ceramic products, for formulations in decorative cosmetics, for the preparation of inks, printing inks, paint systems, in particular automotive lacquers, fluorescent whitening agents, photocell aggregates, color filters and dispersion colors and, furthermore, the inventive fluorescent compositions can be used in the biomedical field of application, e.g. for the preparation of diagnostic agents as well as in the fields of impact-printing and non-impact-printing and photo/repro in general.
  • inventive fluorescent compositions for the preparation of coloring high molecular weight organic materials (having a molecular weight usually in the range of from 10 3 to 10 7 g/mol), e.g. biopolymers, plastic materials, including fibres, glasses, ceramic products, for formulations in decorative cosmetic
  • suitable organic materials of high molecular weight which can be colored with the inventive fluorescent compositions of this invention are vinyl polymers, for example polystyrene, poly- ⁇ -methylstyrene, poly-p-methylstyrene, poly-p-hydroxystyrene, poly-p-hydroxyphenylstyrene, polymethyl methacrylate and polyacrylamide as well as the corresponding methacrylic compounds, polymethylmaleate, polyacrylonitrile, polymethacrylonitrile, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl acetate, polymethyl vinyl ether and polybutyl vinyl ether; polymers which are derived from maleinimide and/or maleic anhydride, such as copolymers of maleic anhydride with styrene; polyvinyl pyrrolidone; ABS; ASA; polyamides; polyimides; polyamidimides
  • cellulose, cellulose ethers and esters such as ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate, starch, chitin, chitosan, gelatin, zein; natural resins; synthetic resins such as alkyd resins, acrylic resins, phenolic resins, epoxide resins, aminoformaldehyde resins such as urea/formaldehyde resins and melamine/formaldehyde resin; vulcanized rubber; casein; silicone and silicone resins; rubber, chlorinated rubber; and also polymers which are used, for example, as binders in paint systems, such as novolaks which are derived from C,-C 6 -aldehydes such as formaldehyde and acetaldehyde and a binuclear or mononuclear, preferably mononuclear, phenol which, if desired, is substituted by one or two groups, one or two halogen atoms or
  • Particularly preferred high molecular weight organic materials are, for example, cellulose ethers and esters, e.g. ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate, natural resins or synthetic resins (polymerization or condensation resins) such as aminoplasts, in particular urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyester, ABS, ASA, polyphenylene oxides, vulcanized rubber, casein, silicone and silicone resins as well as their possible mixtures with one another.
  • cellulose ethers and esters e.g. ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate
  • natural resins or synthetic resins polymerization or condensation resins
  • aminoplasts in particular urea/formalde
  • organic materials in dissolved form as film formers, for example boiled linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and urea/formaldehyde resins as well as acrylic resins.
  • film formers for example boiled linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and urea/formaldehyde resins as well as acrylic resins.
  • Said high molecular weight organic compounds may be obtained singly or in admixture, for example in the form of granules, plastic materials, melts or in the form of solutions, in particular for the preparation of spinning solutions, paint systems, coating materials, inks or printing inks.
  • the inventive fluorescent compositions are used for the mass coloration of polyvinyl chloride, polyamides and, especially, polyolefins such as polyethylene and polypropylene as well as for the preparation of paint systems, including powder coatings, inks, printing inks, color filters and coating colors.
  • Illustrative examples of preferred binders for paint systems are alkyd/melamine resin paints, acryl/melamine resin paints, cellulose acetate/cellulose butyrate paints and two-pack system lacquers based on acrylic resins which are crosslinkable with polyisocyanate.
  • the inventive fluorescent compositions can be added in any desired amount to the material to be colored, depending on the end use requirements.
  • the fluorescent compositions prepared according to this invention can be used in an amount in the range from 0.01 to 40, preferably from 0J to 20% by weight, based on the total weight of the colored high molecular weight organic material.
  • composition comprising of
  • customary additives such as rheology improvers, dispersants, fillers, paint auxiliaries, siccatives, plasticizers, UV-stabilizers, and/or additional pigments or corresponding precursors in effective amounts, such as e.g. from 0 to 50% by weight, based on the total weight of (a) and (b).
  • the pigmenting of the high molecular weight organic materials with the inventive fluorescent compositions usually is effected by incorporating said inventive fluorescent compositions, if desired in the form of masterbatches, in the high molecular weight organic materials using customary apparatus suitable to this end, such as extruders, roll mills, mixing or milling apparatus.
  • the material thus treated is then normally brought into the desired final form by methods which are known per se, such as calandering, moulding, extrusion moulding, coating, casting, extruding, by injection moulding.
  • plasticizers can be added to the high molecular weight substances prior to moulding.
  • Plasticizers may be, for example, esters of phosphoric acid, phthalic acid and sebacic acid. Said plasticizers may be WO 00/63318 _ 1 5 _ PCT/EPOO/03165
  • inventive fluorescent compositions may advantageously be used in admixture with fillers, transparent and opaque white, colored and/or black pigments as well as customary luster pigments in the desired amount.
  • the corresponding high molecular weight organic substances such as binders, synthetic resin dispersions etc. and the inventive fluorescent compositions are usually dispersed or dissolved together, if desired 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 at once.
  • a further embodiment of the present invention relates to the use of the inventive fluorescent compositions for the preparation of dispersions and the corresponding dispersions, and paint systems, coating materials, color filters, inks and printing inks comprising the inventive fluorescent compositions.
  • a still further embodiment concerns a high molecular weight organic material comprising the inventive fluorescent composition.
  • the desired ink may contain up to 30 % by weight of the fluorescent composition, but will generally be in the range of 0J to 10, preferably from 0J to 8% by weight of the total ink composition for most thermal ink jet printing applications.
  • the inks usually contain polymeric dispersants such as random, block, branched or graft polymers or copolymers. Most preferred are polymeric dispersants made by the group transfer polymerization process, because in general these are free from higher molecular weight species that tend to plug pen nozzles.
  • the A segment usually is a hydrophobic homopolymer or copolymer which serves to link with the inventive fluorescent composition and the B block generally is a hydrophilic homopolymer or copolymer, or salts thereof and serves to disperse the pigment in the preferably chosen aqueous medium.
  • Such polymeric dispersants and the synthesis thereof are known from e.g. US 5,085,698.
  • ABC triblocks are also useful as dispersants.
  • the A block usually is a polymer compatible with water
  • the B block is a polymer capable of binding to the fluorescent composition
  • the C block is compatible with the organic solvent.
  • the A and C blocks are end blocks.
  • ABC triblocks and their synthesis are disclosed e.g. in EP-A 556,649. Suitable graft polymers are disclosed in US 5,231 ,131.
  • Representative compounds useful for this purpose include e.g. polymers of polyvinyl alcohol, cellulosics and ethylene oxide modified polymers, and dispersant compounds containing ionisable groups such as acrylic acid, maleic acid or sulfonic acid.
  • the polymeric dispersant is generally present in an amount in the range of from 0J to 30, preferably from 0,1 to 8% by weight of the total ink composition.
  • surfactants may be used as dispersants. These may be anionic, nonionic, or amphoteric surfactants. A detailed list of non-polymeric as well as some polymeric dispersants is disclosed in the section on dispersants of Manufacturing Confection Publishing Co., (1990) p. 110-129, McCutcheon's Functional Materials, North America Edition.
  • the ink contains an aqueous medium such as water or a mixture of water and at least one water-soluble organic solvent.
  • aqueous medium such as water or a mixture of water and at least one water-soluble organic solvent.
  • Water-soluble organic solvents are well known, representative examples of which are disclosed in e.g. US 5,085,698. Selection of a suitable WO 00/63318 greed _, PCT/EPOO/03165
  • mixture of water and water-soluble organic solvent depends on usually requirements of the specific application such as desired surface tension and viscosity, drying time of the ink, and the media substrate onto which the ink will be printed.
  • Particularly preferred is a mixture of a water-soluble solvent having at least two hydroxyl groups, e.g. diethylene glycol, and water, especially deionized water.
  • a water-soluble solvent having at least two hydroxyl groups e.g. diethylene glycol
  • water especially deionized water.
  • water usually would comprise from 30 to 95, preferably 60 to 95% by weight, based on the total weight of the aqueous medium.
  • the amount of aqueous medium generally is in the range of from 70 to 99.8, preferably from 84 to 99.8%, based on the total weight of the ink.
  • the ink may contain other ingredients well known to those skilled in the art such as surfactants to alter surface tension as well as to maximize penetration. However, because surfactants may destabilize dispersions, care should be taken to insure compatibility of the surfactant with the other ink components.
  • the surfactants may be present in amounts ranging from 0.01 to 5, preferably from 0.2 to 3% by weight, based on the total weight of the ink.
  • Biocides may be used in the ink compositions to inhibit growth of microorganisms. Sequestering agents such as EDTA may also be included to eliminate deleterious effects of heavy metal impurities. Other known additives, such as viscosity modifiers may also be added.
  • the inventive fluorescent compositions preferably are sufficiently small to permit free flow through an ink jet printing device, particularly at the ejecting nozzles that usually have a diameter of 10 to 50 ⁇ m.
  • a preferred range of the particle size of the inventive fluorescent compositions is chosen from 0.005 to 10 ⁇ m, preferably 0.01 to 2, and most preferably from 0.05 to 0.2 ⁇ m.
  • Spectrophotometrical measurements are carried out on a spectrophotometer SP68 from X- Rite using as software CGREC for windows 1.5. The measurements are performed at calibrated equipment with the observer at 10 degree, D65 as illuminant and gloss included. No special adaptations with respect to measurement of fluorescence have been made.
  • Cielab values which are based on the L ' aV-color space (1976) of the Commission Internationale de I'Eclairage (CIE; DIN 5033, part 3; DIN 6174).
  • L " indicates lightness
  • a " and b ' are the chromaticity coordinates.
  • the fluorescence is measured spectrophotometrically as that part of the reflection that is more than 100%.
  • a foil is put between two white PVC foils (100 parts SOLVIC 264 (from Solvay), 44 parts dioctyl-phthalate (“DOP"), 2 parts of a stabilizer (STANCLERE 3502) and 0.75 parts TiO 2 (2210, from Kronos) and stored under reduced pressure ( ⁇ 0J bar) at 80°C for 24 hours.
  • the discoloration of the white foil is measured spectrophotometrically against virgin white PVC foil and is expressed as ⁇ E according to the formula
  • Comparative example 1 A mixture of 5.446 g methyl methacrylate (MMA), 5.050 g 2-hydroxy ethyl methacrylate (HEMA), a solution of 0.113 g Basic Violet 10 (FLEXO®RED 540 from BASF) in 0.396 g HEMA, 71.1 mg tert.-butylperoxy neodecanoate (TBPND) and 71.8 mg tert.-butylperoxy ethyl hexyl carbonate (TBPEHC) is homogenized by ultrasonic bath for about 10 minutes. The homogenized mixture is then transferred into a heatable steel autoclave with a working volume of 200 ml. After closing the autoclave it is flushed with nitrogen 3 times. The mass polymerization is performed for 3 hours at 80 ⁇ C under a nitrogen pressure of 500 kPa (5 bar). Thereafter the mixture is transferred into an oven where it is ⁇
  • MMA methyl methacrylate
  • HEMA 2-hydroxy ethyl me
  • the product is ground in a ball mill for 90 minutes and is fractionated by suspension sieving with n-heptane using an ultrasonic disintegrator to particles smaller than 71 ⁇ m.
  • 250 mg of the obtained fluorescent pigment are mixed with 5.0 g of pulverized polyvinylchloride ("PVC", 100 parts SOLVIC 264 (from Solvay), 44 parts dioctyl-phthalate (“DOP”), 2 parts of a stabilizer (STANCLERE 3502) in a mortar. Then 45.0 g of the same PVC is molten on a two roll mill at 170°C and the PVC/fluorescent pigment mixture is incorporated into the PVC-melt for 5 minutes. The PVC-melt is taken from the two roll mill and about 20 g is pressed into a transparent foil at 190°C.
  • PVC pulverized polyvinylchloride
  • DOP dioctyl-phthalate
  • STANCLERE 3502 stabilizer
  • Example 1 A test tube is charged with 4.356 g MMA, 5.839 g acrylic acid (AA), a solution of 0.11 g FLEXO®RED 540 in 0.44 g AA, 47.9 mg TBPND and 48.3 mg TBPEHC.
  • the polymerization procedure is carried out according to comp. example 1. After the polymerization the product is ground. Then 9.257 g of the product is dissolved in 100 g of a water/ethanol mixture (1:1 w/w-%). Afterwards 1.816 g of a solution of sodium methylate in methanol (30% by weight) are added. For isolating the product, the solvent is removed in a rotary evaporator and the product is dried to constant weight. The product is ground in a ball mill and is fractionated to particles smaller than 5 micron by suspension sieving with n- heptane using an ultrasonic disintegrator. The product is filtered and dried to constant weight.
  • a transparent foil and an opaque foil are made of the fluorescent pigment according to the procedure described in comp. example 1.
  • Example 2 Example 1 is repeated, except that the test tube is charged with 3.267 g MMA, 0.545 g butyl acrylate (BA), 6.384 g AA, a solution of 0.110 g FLEXO®RED 540 in 0.440 g AA, 48.3 mg TBPND and 48.7 mg TBPEHC, and that the neutralization is carried out with the following amounts: 10.012 g of the product is dissolved in about 100 g of a water/ethanol - 20 -
  • Example 3 Example 1 is repeated, except that the test tube is charged with 3.267 g MMA, 1.089 g BA, 5.712 g AA, a solution of 0.110 g FLEXO®RED 540 in 0.440 g AA, 46.4 mg TBPND and 46.8 mg TBPEHC, and that the neutralization is carried out with the following amounts: 8.886 g of the product are dissolved in about 100 g of a water/ethanol mixture (1:1 w/w-%), and 2.643 g of a solution of sodium methylate in methanol (30 % b.w.) are added.
  • Example 4 Example 1 is repeated, except that the test tube is charged with 2J78 g MMA, 1.634 g BA, 6.129 g AA, a solution of 0.110 g FLEXO®RED 540 in 0.440 g AA, 46J mg TBPND and 46.5 mg TBPEHC, and that the neutralization is carried out with the following amounts: 8.432 g of the product are dissolved in about 100 g of a water/ethanol mixture (1:1 w/w-%), and 3.388 g of a solution of sodium methylate in methanol (30 % b.w.) are added.
  • Example 5 Example 1 is repeated, except that the test tube is charged with 2J78 g MMA, 0.545 g BA, 7.644 g AA, a solution of 0.110 g FLEXO®RED 540 in 0.440 g AA, 50.7 mg TBPND and 51.1 mg TBPEHC, and that the neutralization is carried out with the following amounts: 9.577 g of the product are dissolved in about 100 g of a water/ethanol mixture (1:1 w/w-%), and 0.5206 g lithium hydroxide monohydrate (LiOH H 2 O) solubilised in 30 g water are added.
  • LiOH H 2 O lithium hydroxide monohydrate
  • Example 6 Example 1 is repeated, except that the test tube is charged with 3.267 g MMA, 0.545 g BA, 6.565 g AA, a solution of 0.110 g FLEXO®RED 540 in 0.440 g AA, 49.2 mg TBPND and 49.6 mg TBPEHC, and that the neutralization is carried out with the following amounts: 10.431 g of the product are dissolved in about 100 g of a water/ethanol mixture (1:1 w/w-%), and 0.361 g magnesium ethylate suspended in 30 g methanol are added.
  • Comparative example 2 A test tube is charged with 5.446 g methyl methacrylate (MMA), 5.050 g 2-hydroxy ethyl methacrylate (HEMA), a solution of 0.113 g MAXILON®Yellow 10GFF (Ciba Specialty Chemicals) in 0.396 g HEMA, 71.1 mg tert.-butylperoxy neodecanoate (TBPND) and 71.8 mg tert.-butylperoxy ethyl hexyl carbonate (TBPEHC). The mixture is homogenized by ultrasonic for about 10 minutes. Mass polymerization is carried out in a steel autoclave with a working volume of 200 ml.
  • MMA methyl methacrylate
  • HEMA 2-hydroxy ethyl methacrylate
  • MAXILON®Yellow 10GFF Ciba Specialty Chemicals
  • the following table contains the compositions of the inventive fluorescent compositions according to the examples 1-9 and the two comp. examples as well as the degree of neutralization, ⁇ , wherein MMA, BA etc. means the corresponding MMA-, BA-units etc. within the polymer :
  • CORONA®MAGENTA S21 (containing 4% Basic Violet 10, from DayGlo Corp.) is used for the preparation of a transparent foil and an opaque foil according to the procedure described in comp. example 1.
  • the polymer melt is degassed at zone 12 at a pressure of about 5 kPa (50 mbar).
  • the extrudate is collected in a container and broken.
  • the polymer melt is degassed at zone 11 at a pressure of about 20 kPa (200 mbar).
  • the extrudate is collected in a container and broken.
  • the degree of neutralization is calculated from the concentration of carboxylic groups of the copolymer before and after neutralization by potentiometric titration with 1 N LiOH in water/acetone as solvent.
  • MMA etc. means MMA-units etc. in the polymer chain (this composition does not correspond to the starting composition of example 7 due to loss of AA because of its conversion into Na-AA).
  • Table 4 Results of tests of example 8

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition fluorescente qui est principalement formée d'une matière colorante fluorescente et d'un polymère, ledit polymère contenant de l'acide carboxylique et des groupes carboxylate. On décrit également un procédé de préparation et d'utilisation de cette composition fluorescente.
PCT/EP2000/003165 1999-04-19 2000-04-10 Composition fluorescente Ceased WO2000063318A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2000243992A AU2000243992A1 (en) 1999-04-19 2000-04-10 Fluorescent composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP99810322 1999-04-19
EP99810322.0 1999-04-19

Publications (1)

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WO2000063318A1 true WO2000063318A1 (fr) 2000-10-26

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WO (1) WO2000063318A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1256609A3 (fr) * 2001-05-09 2003-10-22 BASF Drucksysteme GmbH Encre luminescente pour l'impression flexographique des marques de contrôle

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0198392A1 (fr) * 1985-04-10 1986-10-22 E.I. Du Pont De Nemours And Company Neutralisation partielle d'une photoréserve développable à l'eau
US4911451A (en) * 1989-03-29 1990-03-27 Sullivan Michael J Golf ball cover of neutralized poly(ethylene-acrylic acid) copolymer
EP0518225A1 (fr) * 1991-06-13 1992-12-16 E.I. Du Pont De Nemours And Company Encres aqueuses pigmentées pour des imprimantes à jet d'encre
EP0691390A2 (fr) * 1994-07-06 1996-01-10 Basf Aktiengesellschaft Dispersions aqueuses contenant une matière fluorescente
DE19636077A1 (de) * 1996-09-05 1998-03-12 Basf Ag Verwendung wäßriger Polymerisatdispersionen für den Korrosionsschutz metallischer Oberflächen
US5821283A (en) * 1995-10-06 1998-10-13 Rohm And Haas Company Ink composition and method for preparing

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0198392A1 (fr) * 1985-04-10 1986-10-22 E.I. Du Pont De Nemours And Company Neutralisation partielle d'une photoréserve développable à l'eau
US4911451A (en) * 1989-03-29 1990-03-27 Sullivan Michael J Golf ball cover of neutralized poly(ethylene-acrylic acid) copolymer
EP0518225A1 (fr) * 1991-06-13 1992-12-16 E.I. Du Pont De Nemours And Company Encres aqueuses pigmentées pour des imprimantes à jet d'encre
EP0691390A2 (fr) * 1994-07-06 1996-01-10 Basf Aktiengesellschaft Dispersions aqueuses contenant une matière fluorescente
US5821283A (en) * 1995-10-06 1998-10-13 Rohm And Haas Company Ink composition and method for preparing
DE19636077A1 (de) * 1996-09-05 1998-03-12 Basf Ag Verwendung wäßriger Polymerisatdispersionen für den Korrosionsschutz metallischer Oberflächen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1256609A3 (fr) * 2001-05-09 2003-10-22 BASF Drucksysteme GmbH Encre luminescente pour l'impression flexographique des marques de contrôle
US6852157B2 (en) 2001-05-09 2005-02-08 Basf Aktiengesellschaft Flexographic printing ink for printing control marks

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