EP1856172A1 - Pigments partiellement recouverts de polyurethanne, leur production et leur utilisation - Google Patents

Pigments partiellement recouverts de polyurethanne, leur production et leur utilisation

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Publication number
EP1856172A1
EP1856172A1 EP06708487A EP06708487A EP1856172A1 EP 1856172 A1 EP1856172 A1 EP 1856172A1 EP 06708487 A EP06708487 A EP 06708487A EP 06708487 A EP06708487 A EP 06708487A EP 1856172 A1 EP1856172 A1 EP 1856172A1
Authority
EP
European Patent Office
Prior art keywords
radiation
pigment
sub
compound
aqueous dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06708487A
Other languages
German (de)
English (en)
Inventor
Christian Krüger
Michael Kluge
Cedric Dieleman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE200510008930 external-priority patent/DE102005008930A1/de
Priority claimed from DE200510008932 external-priority patent/DE102005008932A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1856172A1 publication Critical patent/EP1856172A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • 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
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • 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

Definitions

  • At least partially coated with radiation-curable polyurethane pigments their preparation and use
  • the present invention relates to an aqueous dispersion containing an at least partially coated with at least one radiation-curable polyurethane (A) pigment (B), wherein at least one radiation-curable polyurethane (A) is obtainable by reacting
  • R 1, R 2 are identical or different and are independently selected from hydrogen and C 1 -C O -alkyl, X 1 is selected from oxygen and NR 3, A 1 is selected from C r C 2 -alkylene, unsubstituted or mono- or polysubstituted substituted with Ci-C 4 alkyl, phenyl or 0-C 1 -C 4 -AlkVl, where in CrC 2 o-alkyls one or more non-adjacent CH 2 groups may be replaced by oxygen; X 2 selected from hydroxyl and NH-R 3 , R 3 are identical or different and selected from hydrogen, C 1 -C 10 -AlkVl and phenyl.
  • the present invention relates to at least partially coated pigments prepared by dispersing at least one pigment (B) and at least one radiation-curable polyurethane (A), wherein radiation-curable polyurethane (A) is obtainable by reacting
  • the present invention relates to the preparation of at least partially coated pigments according to the invention and aqueous dispersions according to the invention and to their use.
  • inks used in the ink-jet process ink-jet printing processes such as thermal ink jet, piezo ink jet, continuous ink jet, valve jet, transfer printing process. They must have suitable viscosity and surface tension for printing, they must be storage stable, i.e., they should not coagulate or flocculate, and they must not cause clogging of the printer nozzle, which may be particularly problematic for inks containing inks, that is undissolved colorant particles.
  • the storage stability requirements of these recording fluids, and in particular inks means that dispersed colorant particles do not settle.
  • the inks must be stable to the addition of conductive salts and should show no tendency to flocculate when the ion content is increased.
  • the prints obtained must meet the coloristic requirements, i. high brilliance and color depth, and good fastnesses, e.g. Rub fastness, lightfastness, waterfastness and
  • prints can be fixed by so-called radiation curing.
  • radiation-curable inks s.
  • Radiation curable ink jet inks typically contain a material that can be cured by exposure to actinic radiation.
  • radiation-curable ink-jet inks can be accompanied by a photoinitiator.
  • the object was therefore the object to provide aqueous dispersions of pigments. It was a further object to provide inks for the ink-jet process, which can be cured particularly well by the action of actinic radiation. Another object was to provide processes for the production of inks for the ink-jet process. Finally, the object was to provide printed substrates and in particular printed textile substrates which have a particularly good feel and good fastness properties.
  • polyurethanes are understood to mean not only those polymers which are linked exclusively by urethane groups, but in a more general sense polymers which can be obtained by reacting di- or polyisocyanates with compounds containing active hydrogen atoms.
  • Polyurethanes within the meaning of the present invention may therefore contain, in addition to urethane groups, urea, biuret, carbodiimide, amide, ester, ether, uretonimine, uretdione, isocyanurate or oxazolidine groups.
  • An overview may be mentioned by way of example: Kunststoffhandbuch / Saechtling, 26th edition, Carl-Hanser-Verlag, Kunststoff 1995, page 491 ff.
  • radiation-curable polyurethane (A) is not hyperbranched polyurethane.
  • Hyperbranched polyurethanes are known as such and described, for example, in J.M.S. - Rev. Macromol. Chem. Phys. 1997, C37 (3), 555.
  • Aqueous dispersions of the invention contain at least one pigment (B) at least partially coated with at least one radiation-curable polyurethane (A).
  • pigment at least partially coated with at least one radiation-curable polyurethane is understood to mean pigment in particulate form whose outer surface is completely or partially covered by radiation-curable polyurethane, for example at least 10%, preferably at least at least 20%, more preferably at least 30%.
  • mixtures of polyurethane in particulate form in which a certain percentage of the pigment particles are not coated with radiation-curable polyurethane and in which the outer surface of the remaining pigment particles are completely or partially covered by radiation-curable pigment, fall within the definition of "at least partially with at least one radiation-curable polyurethane coated pigment ".
  • the degree of coating of pigment (B) can be determined for example by measuring the zeta potential, by microscopic methods such as light microscopy or electron microscopy methods (TEM, cryo-TEM, SEM) and especially by the freeze-fracture preparation technique, NMR spectroscopy or Determine photoelectron spectroscopy on dried at least partially coated pigment.
  • microscopic methods such as light microscopy or electron microscopy methods (TEM, cryo-TEM, SEM) and especially by the freeze-fracture preparation technique, NMR spectroscopy or Determine photoelectron spectroscopy on dried at least partially coated pigment.
  • At least partially enveloping pigments (B) are obtained by at least partial coating of water-insoluble finely divided organic or inorganic colorants as defined in DIN 55944. Preference is given to the preparation of aqueous dispersions of organic pigments according to the invention, wherein carbon black is included. The following are examples of particularly suitable pigments (B).
  • Anthanthrone pigments Cl. Pigment Red 168 (Cl. Vat Orange 3); Anthraquinone pigments: Cl. Pigment Yellow 147 and 177; Cl. Pigment Violet 31; Anthraquinone pigments: Cl. Pigment Yellow 147 and 177; Cl. Pigment Violet 31; Anthrapyrimidine pigments: Cl. Pigment Yellow 108 (CI Vat Yellow 20); - Quinacridone pigments: Cl. Pigment Red 122, 202 and 206; Cl. Pigment Violet 19;
  • Dioxazine pigments Cl. Pigment Violet 23 and 37; Flavanthrone pigments: Cl. Pigment Yellow 24 (CI Vat Yellow 1);
  • Isoindoline pigments Cl. Pigment Orange 69; Cl. Pigment Red 260; Cl. Pigment Yellow 139 and 185; - isoindolinone pigments: Cl. Pigment Orange 61; Cl. Pigment Red 257 and 260; Cl. Pigment Yellow 109, 110, 173 and 185;
  • Isoviolanthrone pigments Cl. Pigment Violet 31 (Cl. Vat Violet 1);
  • Tiiaryl carbonium pigments Cl. Pigment Blue 1, 61 and 62; Cl. Pigment Green 1; Cl. Pigment Red 81, 81: 1 and 169; Cl. Pigment Violet 1, 2, 3 and 27; Cl. Pigment Black 1 (aniline black); Cl. Pigment Yellow 101 (Aldazingelb); Cl. Pigment Brown 22.
  • Green 48 Cobalt green (CI Pigment Green 50); Ultramarine green; Cobalt blue (CI Pigment Blue 28 and 36); Ultramarine blue; Iron blue (CI Pigment Blue 27); Manganese blue; Ultramarine violet; Cobalt and manganese violet; Iron oxide red (CI Pigment Red 101); Cadmium sulphoselenide (CI Pigment Red 108); Molybdate red (Cl.
  • Iron oxide brown, mixed brown, spinel and corundum phases (CI Pigment Brown 24, 29 and 31), chrome orange;
  • Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53, CI Pigment Yellow 157 and 164); Chromium titanium yellow; Cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34), zinc yellow, alkaline earth dichromates; Naples yellow; Bismuth vanadate (CI Pigment Yellow 184);
  • Interference pigments metallic effect pigments based on coated metal flakes; Pearlescent pigments based on metal oxide-coated mica platelets; Liquid crystal pigments.
  • Preferred pigments (B) include monoazo pigments (in particular laked BONS pigments, naphthoic AS pigments), disazo pigments (especially diaryl yellow pigments, bisacetacetic acid acetanilide pigments, disazopyrazolone pigments), quinacridone pigments, quinophthalone pigments, perinone pigments, phthalocyanine pigments, triarylcarbonium pigments (alkali pigments) , rhodamine laked, dye salts with complex anions), isoindoline pigments and carbon blacks.
  • monoazo pigments in particular laked BONS pigments, naphthoic AS pigments
  • disazo pigments especially diaryl yellow pigments, bisacetacetic acid acetanilide pigments, disazopyrazolone pigments
  • quinacridone pigments quinophthalone pigments, perinone pigments, phthalocyanine pigments, triarylcarbonium pigments (alkali pigments) , rhodamine laked,
  • pigments (B) are: carbon black, Cl. Pigment Yellow 138, Cl. Pigment Red 122 and 146, Cl. Pigment Violet 19, Cl. Pigment Blue 15: 3 and 15: 4, Cl. Pigment Black 7, Cl. Pigment Orange 5, 38 and 43 and Cl. Pigment Green 7.
  • Radiation-curable polyurethanes (A) in the context of the present invention can be obtained by reacting
  • Diisocyanate (a) is selected, for example, from aliphatic, aromatic and cycloaliphatic diisocyanates.
  • aromatic diisocyanates are: 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) and so-called TDI mixtures (mixtures of 2,4-tolylene diisocyanate and 2, 6-tolylene diisocyanate).
  • aliphatic diisocyanates are: 1,4-butylene diisocyanate, 1,12-dodecamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate and especially hexamethylene diisocyanate (HDI).
  • 1,4-butylene diisocyanate 1,12-dodecamethylene diisocyanate
  • 1,10-decamethylene diisocyanate 1,10-decamethylene diisocyanate
  • 2-butyl-2-ethylpentamethylene diisocyanate 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • cycloaliphatic diisocyanates examples include isophorone diisocyanate (IPDI), 2-isocyanatopropylcyclohexyl isocyanate, 2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane-1,3-diisocyanate (H-TDI).
  • IPDI isophorone diisocyanate
  • 2,4'-methylenebis (cyclohexyl) diisocyanate 2,4'-methylenebis (cyclohexyl) diisocyanate
  • H-TDI 4-methylcyclohexane-1,3-diisocyanate
  • isocyanates having groups of different reactivity are 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine diisocyanate and 2,6-toluene diisocyanate.
  • diisocyanate (a) is reacted with at least one compound having at least two isocyanate-reactive groups (b), hereinafter also referred to as compound (b) for short.
  • Groups which are particularly well-suited for reaction with isocyanate are, for example, the SH group, the hydroxyl group, the NH 2 group and the NHR 3 group, in which R 3 is defined as mentioned above.
  • Compound (b) may be hydrophilic or hydrophobic. Preferably, at least one compound (b) is selected
  • 1,1,1-trimethylol-C 1 -C 4 -alkylcarboxylic acids for example 1,1,1-trimethylolacetic acid, 1,1,1-trimethylolpropanoic acid, 1,1,1-trimethylolbutyric acid, citric acid,
  • 1,1-dimethylol-C 1 -C 4 -alkylcarboxylic acids for example 1,1-dimethylolacetic acid, 1,1-dimethylolpropanoic acid, 1, 1-dimethylolbutyric acid, 1, 1-dimethylol-C 1 -C 4 -alkylsulfonic acids,
  • Poly-C 2 -C 3 -alkylene glycols having on average 3 to 300 alkylene oxide units per molecule, in particular polyethylene glycol having an average (number average) 3 to 300 ethylene oxide units per molecule and polyaddition products of ethylene oxide and propylene oxide with an average (number average) 3 to 300 Ethylene oxide units per molecule and a molar proportion of ethylene oxide which is higher than the proportion of propylene oxide;
  • M is selected in each case from alkali metal ions, in particular Na + , and ammonium ions,
  • Polyester diols which are produced by polycondensation of
  • At least one aliphatic or cycloaliphatic diol preferably ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, cis- and trans-1,4-cyclohexanediol, cis- and trans-1,4-dihydroxymethylcyclohexane (cyclohexanedimethanol), having at least one aliphatic, aromatic or cycloaliphatic dicarboxylic acid, for example succinic acid, glutaric acid, adipic acid, cyclohexane-1, 4-dicarboxylic acid, terephthalic acid, isophthalic acid.
  • succinic acid for example succinic acid, glutaric acid, adipic acid, cyclohexane-1, 4-dicarboxylic acid, terephthalic acid, isophthalic acid.
  • At least two dicarboxylic acids are used to prepare polyester diol, one aromatic and the other aliphatic, for example succinic and isophthalic, glutaric and isophthalic, adipic and isophthalic, succinic and terephthalic, glutaric and terephthalic acids , Adipic acid and terephthalic acid.
  • one aromatic and the other aliphatic for example succinic and isophthalic, glutaric and isophthalic, adipic and isophthalic, succinic and terephthalic, glutaric and terephthalic acids , Adipic acid and terephthalic acid.
  • a molar ratio in the range from 10: 1 to 1:10 is preferred, in particular a molar ratio in the range from 1.5: 1 to 1: 1.5.
  • polyester diols used as (c) have a hydroxyl number in the range from 20 to 200 mg KOH / g, preferably 50 to 180 very particularly preferably 100 to 160 mg KOH / g, determined according to DIN 53240.
  • polyester diols used as (b) have a molecular weight M w in the range from 500 to 100,000 g / mol, preferably 700 to 50,000 g / mol, particularly preferably up to 30,000 g / mol.
  • suitable compounds (b) are ethanolamine, diethanolamine, neopentylglycol, 1,4-butanediol, 1,6-hexanediol, 1,1-dimethylolpropane.
  • diisocyanate (a) is reacted with at least two compounds (b), one of which is selected from ethanolamine, diethanolamine, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,1-dimethylolpropane ,
  • diisocyanate (a) is reacted with at least one compound (b) and furthermore with at least one compound (c) of the general formula I
  • R 1 , R 2 are identical or different and are independently selected from C 1 -C 10 -alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2 Dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-buty
  • X 1 selected from oxygen and NR 3
  • a 1 selected from C r C 2 o-alkylene, preferably C 2 -C 10 -alkylene, for example -CH 2 -,
  • C 1 -C 4 -alkyl for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, preferably methyl, phenyl or -O-C 1 - C 4 -alkyl, for example -O-CH 3 , -O-C 2 H 5 , -O-nC 3 H 7 ,
  • -O-CH (CH 3 ) 2 -OnC 4 H 9 , -O-iso-C 4 H 9 , -O-sec-C 4 H g , -OC (CH 3 ) 3 , substituted C r C 20 Alkylene, for example, may be mentioned - CH (CH 3 ) -, -CH (C 2 H 5 ) -, -CH (C 6 H 5 ) -, - CH 2 -CH (CH 3 ) -, cis- and trans-CH (CH 3 ) -CH (CH 3 ) -, - (CHz) -C (CH 3 ) Z -CHz-, -CH 2 -CH (C 2 H 5 ) -, -CH 2 -CH (nC 3 H 7 ) -, -CH 2 -CH (JSO-C 3 H 7 ) -, where in unsubstituted or substituted CrC 20 alkylene one or more non-adjacent CH
  • X 2 selected from NH-R 3 and preferably oxygen
  • R 3 is different or preferably identical and selected from hydrogen, phenyl and C 1 -C 10 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
  • Very particularly preferred compounds (c) are 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate.
  • reaction of at least one diisocyanate (a), at least one compound (b) and compound (c) is preferably carried out in the presence of one or more catalysts.
  • Suitable catalysts are, for example, all catalysts customarily used in polyurethane chemistry.
  • Catalysts commonly used in polyurethane chemistry are preferably organic amines, especially tertiary aliphatic, cycloaliphatic or aromatic amines, and Lewis acidic organic metal compounds.
  • Tin compounds such as tin (II) salts of organic carboxylic acids, e.g. Tin (II) acetate, tin (II) octoate, tin (II) ethyl hexoate and tin (II) laurate and the dialkyltin (IV) derivatives of organic carboxylic acids, eg dimethyl tin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate and dioctyltin diacetate.
  • tin (II) salts of organic carboxylic acids e.g. Tin (II) acetate, tin (II) octoate, tin (II) ethyl hexoate
  • Metal complexes such as acetylacetonates of iron, titanium, aluminum, zirconium, manganese, nickel and cobalt are also possible.
  • Other Lewis acidic organic metal compounds are described by Blank et al. in Progress in Organic Coatings, 1999, 35, 19 et seq.
  • Preferred Lewis-acidic organic metal compounds are dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, diocytotin dilaurate, zirconium acetylacetonate and zirconium 2,2,6,6-tetramethyl-3, 5-heptanedionate.
  • Suitable cesium salts are those compounds in which the following anions are used: F “ , CP, CIO “ , CIO 3 “ , CIO 4 “ , Br “ , J “ , JO 3 “ , CN “ , OCN “ , NO 2 “ , NO 3 -, HCO 3 “ , CO 3 2 “ , S 2” , SH “ , HSO 3 “ SO 3 2 “ , HSO 4 - , SO 4 2” , S 2 O 2 2 “ , S 2 O 4 2 “ , S 2 O 5 2” , S 2 O 6 2 “ S 2 O 7 2” S 2 O 8 2 -, H 2 PO 2 “ , H 2 PO 4 -, HPO 4 2” PO 4 3 “ , P 2 O 7 4 “ , (OC n H 2n + I r, (C n H 2n - ! O 2 ) " , (C n H 2n - ! O 2 ) " , (C n H 2n -
  • Cesium carboxylates in which the anion is the formula are preferred (C n H 2n - I O 2 ) " as well as (C n + 1 H 2n _ 2 O 4 ) 2 ⁇ with n equal to 1 to 20.
  • Particularly preferred cesium salts have as anions monocarboxylates of the general formula (C n H 2n - I O 2 ) " , where n is the numbers 1 to 20.
  • customary organic amines are: triethylamine, 1,4-diazabicyclo [2,2,2] octane, tributylamine, dimethylbenzylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethylbutane-1, 4-diamine, N 1 N 1 N', N'-tetramethylhexane-1,6-diamine, dimethylcyclohexylamine, dimethyldodecylamine, pentamethyldipropylenetriamine, pentamethyldiethylenetriamine, 3-methyl-6-dimethylamino 3-azapentol, dimethylaminopropylamine, 1,3-bisdimethylaminobutane, bis (2-dimethylaminoethyl) ether, N-ethylmorpholine, N-methylmorpholine, N-cyclohexylmorpholine, 2-dimethyl
  • Preferred organic amines are trialkylamines having independently of one another two C 1 - to C 4 -alkyl radicals and one alkyl or cycloalkyl radical having 4 to 20 carbon atoms, for example dimethyl-C 4 -C 15 -alkylamine, such as dimethyldodecylamine or dimethyl-C 3 - C 8 - cycloalkylamine.
  • Also preferred organic amines are bicyclic amines, which may optionally contain another heteroatom such as oxygen or nitrogen, such as 1, 4-diazabicyclo [2.2.2] octane.
  • ammonium acetate or triethylamine and very particularly preferably N, N, N-trimethyl-N- (2-hydroxypropyl) ammonium 2-ethylhexanoate.
  • mixtures of two or more of the abovementioned compounds can also be used as catalysts.
  • Particular preference is given to choosing from the abovementioned compounds those which are soluble in organic solvents such as acetone, tetrahydrofuran (THF), N-methylpyrrolidone and / or N-ethylpyrrolidone.
  • organic solvents such as acetone, tetrahydrofuran (THF), N-methylpyrrolidone and / or N-ethylpyrrolidone.
  • Catalyst is preferably used in an amount of 0.0001 to 10 wt .-%, more preferably in an amount of 0.001 to 5 wt .-%, based on diisocyanate (a1).
  • Suitable solvents are water-immiscible solvents such as aromatic or aliphatic hydrocarbons such as toluene, ethyl acetate, hexane and cyclohexane and carboxylic acid esters such as ethyl acetate, further suitable solvents are acetone, THF and N-methylpyrrolidone and N-ethylpyrrolidone.
  • the one or more catalysts in solid or liquid form and most preferably dissolved in organic solvents such as acetone, tetrahydrofuran (THF), N-methylpyrrolidone or N-ethylpyrrolidone to.
  • organic solvents such as acetone, tetrahydrofuran (THF), N-methylpyrrolidone or N-ethylpyrrolidone to.
  • Diisocyanate (a) and compound (b) can be used in molar ratios of, for example, 10: 1 to 1: 5, preferably 5: 1 to 1: 3 and very particularly preferably 3: 1 to 1: 1, in each case based on the total amount Diisocyanate (a) and the total amount of compound (b).
  • Diisocyanate (a) and compound (c) can be used in molar ratios of, for example, 10: 1 to 1: 2, preferably 5: 1 to 1: 1 and very particularly preferably 4: 1 to 1: 1, in each case based on the total amount Diisocyanate (a) and the total amount of compound (c).
  • At least one nucleophilic alcohol or else is used for the preparation of radiation-curable polyisocyanate (A) Amine, which can also serve as a stopper and termed stopper (d).
  • suitable stoppers (d) are mono- and di-CVC- 4- alkylamines, in particular diethylamine. It is possible to use up to 10% by weight of stopper (d), based on radiation-curable polyurethane (A) to be synthesized.
  • diisocyanate (a), compound (b), compound (c) and optionally stopper (d) in solvent preferably in an organic solvent or a mixture of organic solvents such as toluene, acetone or tetrahydrofuran or React mixtures of the abovementioned solvents with one another.
  • solvent preferably in an organic solvent or a mixture of organic solvents such as toluene, acetone or tetrahydrofuran or React mixtures of the abovementioned solvents with one another.
  • the use of solvent is dispensed with in the reaction of diisocyanate (a) with compound (b), compound (c) and optionally stopper (d).
  • radiation-curable polyurethane (A) has no free NCO groups which, for example, could be detected by titration.
  • radiation-curable polyurethane (A) has a double bond density of 0.1 to 5 mol / kg (A), preferably 0.2 to 3 mol / kg (A), very particularly preferably 0.3 to 2 mol / kg (A), determinable for example by determination of the hydrogenation iodine number and by 1 H NMR spectroscopy.
  • the preparation of radiation-curable polyurethane (A) from diisocyanate (a), compound (b), compound (c) and optionally stopper (d) can be carried out in one stage or preferably in several stages.
  • diisocyanate (a) and compound (b) can be reacted in a first stage using, for example, a catalyst, stopping the reaction and thereafter adding diisocyanate (a) and compound (c) and optionally another compound (b).
  • radiation-curable polyurethane (A) After completion of the reaction of diisocyanate (a) with compound (b), compound (c) and optionally stopper (d), it is possible to isolate radiation-curable polyurethane (A), for example by separating unreacted starting materials such as diisocyanate (a) or compound ( c).
  • a suitable method of separating unreacted starting materials such as diisocyanate (a), compound (c) and optionally stopper (d) is distilling off, preferably at reduced pressure. Especially suitable are thin-film evaporators. Preference is given to the distilling off unreacted diisocyanate (a).
  • the molecular weight M w of the radiation-curable polyurethanes (A) to be used for the present invention can be, for example, 500 to at most 50,000 g / mol, preferably 1,000 to 30,000 g / mol, more preferably 2,000 to 25,000 g / mol, determined, for example, by gel permeation chromatography (GPC ).
  • radiation curable polyurethane (A) does not contain free NCO groups.
  • diisocyanate (a), compound (b), compound (c) and optionally stopper (d) it is possible to convert groups which have sufficiently acidic H atoms into the corresponding salts by treatment with bases.
  • bases are hydroxides and bicarbonates of alkali metals or alkaline earth metals or the carbonates of alkali metals.
  • Further suitable bases are volatile amines, ie amines having a boiling point up to 180 ° C at atmospheric pressure, such as ammonia, methylamine, dimethylamine, Tn-methylamine, ethylamine, diethylamine, triethylamine, ethanolamine or N-methyl-diethanolamine.
  • one or more pigments (B) and optionally water are added.
  • a solids content in the range of up to 3 to 40%, preferably up to 35%, particularly preferably 5 to 30%.
  • the weight ratio of radiation-curable polyurethane (A) to pigment (B) can be varied within wide limits.
  • the weight ratio of radiation-curable polyurethane (A) to pigment (B) is in the range from 5: 1 to 1: 3, preferably 3: 1 to 1: 2, more preferably 2: 1 to 2: 3 ,
  • radiation-curable polyurethane (A) and pigment (B) are dispersed.
  • the dispersion can be carried out in any suitable apparatus for dispersing.
  • shaking apparatuses such as e.g. called the company Skandex.
  • Radiation-curable polyurethane (A) and pigment (B) are preferably dispersed, for example, in ultrasound apparatus, high-pressure homogenizers, 2-, 3-, 4- or 5-
  • Roll mills mini mills, Henschel mixers, shaker mills, Angmühlen, tooth mills, bead mills, wet mills, sand mills, attritors, colloid mills, ultrasonic homogenizers, with Ultra-Turrax stirrer and in particular by grinding, for example in 2-, 3-, 4- or 5-roll mills Mini-mills, shaking mills, angmills, tooth mills, bead mills, wet mills, sand mills, colloid mills, ball mills, especially agitator ball mills.
  • aqueous dispersions according to the invention have a solids content in the range from 3 to 40%, preferably to 35%, particularly preferably 10 to 30%.
  • the average diameter of at least partially coated with radiation-curable polyurethane (A) pigment (B) is usually in the range of 20 nm to 1, 5 microns, preferably in the range of 60 to 500 nm, particularly preferably in the range of 60 to 350 after dispersion nm and in the context of the present invention generally designates the volume average.
  • Suitable measuring instruments for determining the mean particle diameter are, for example, Coulter Counter, e.g. Coulter LS 230.
  • the particle diameter refers to the mean diameter of the primary particles.
  • Novel aqueous dispersions do not contain a thermal initiator, ie, no compound which has a half-life at least at 6O 0 C for one hour and thereby decomposes into free radicals, such as peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds such as azobisisobutyronitrile (AIBN) or water-soluble AIBN derivatives, highly substituted, in particular hexa-substituted, ethane derivatives or redox catalysts.
  • a thermal initiator ie, no compound which has a half-life at least at 6O 0 C for one hour and thereby decomposes into free radicals, such as peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds such as azobisisobutyronitrile (AIBN) or water-soluble AIBN derivatives, highly substituted, in particular hexa-substituted, ethane derivative
  • aqueous dispersions according to the invention comprise at least one polyurethane (C).
  • Polyurethane (C) is obtainable, for example, by reacting diisocyanate (a) with compound (b).
  • pigment (B) is at least partially coated not only with radiation-curable polyurethane (A), but also with polyurethane (C).
  • aqueous dispersions according to the invention comprise radiation-curable polyurethane (A) and polyurethane (C) in the range from 10: 1 to 1: 2, preferably in the range from 8: 1 to 1: 1 (weight ratio).
  • aqueous dispersions according to the invention comprise at least one photoinitiator (D). Photoinitiator (D) can be added either before dispersing or after dispersing.
  • Suitable photoinitiators (D) may be, for example, photoinitiators known to those skilled in the art, e.g. those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K.K. Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P.K.T. Oldring (Eds), SITA Technology Ltd, London.
  • Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, vaIerophenone, hexanophenone, ⁇ -phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone , ⁇ -methylanthraquinone, tert-butylanthraquinone, anthraquinone-carboxylic acid ester, benzaldehyde, ⁇ -tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-in
  • non-yellowing or slightly yellowing photoinitiators of the phenylglyoxalic acid ester type, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
  • Preferred photoinitiators (D) are, for example, those photoinitiators which decompose upon activation, so-called ⁇ -decomposers such as, for example, benzaldialkyl ketal-type photoinitiators, such as, for example, Benzildimethylketal.
  • ⁇ -decayers are derivatives of benzoin, isobutylbenzoin ethers, phosphine oxides, especially mono- and bisacylphosphine oxides, e.g. Benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ⁇ -hydroxyalkylacetophenones, e.g. 2-hydroxy-2-methylphenyl-propanone (D.1),
  • preferred photoinitiators (D) are hydrogen-abstracting photoinitiators, for example of the type of optionally substituted acetophenones, anthraquinones, thioxanthones, benzoic esters or the optionally substituted benzophenones.
  • Particularly preferred examples are isopropylthioxanthone, benzophenone, phenylbenzyl ketone, 4-methylbenzophenone, halomethylated benzophenones, anthrone, Michler's ketone (4,4'-bis-N, N-dimethylaminobenzophenone), A-chlorobenzophenone, 4,4'-dichlorobenzophenone, anthraquinone.
  • aqueous dispersions according to the invention are added so much photoinitiator (D) that the weight ratio of radiation-curable polyurethane (A) to photoinitiator (D) is in a range from 3: 1 to 10,000: 1, preferably 5: 1 to 5,000: 1, most preferably in a weight ratio of 10: 1 to 1000: 1.
  • the effectiveness of photoinitiators (D) in aqueous dispersions (A) according to the invention can, if desired, be increased by the addition of at least one synergist, for example of at least one amine, in particular of at least one tertiary amine.
  • Suitable amines are, for example, triethylamine, N, N-dimethylethanolamine, N-methylethanolamine, triethanolamine, aminoacrylates such as, for example, amine-modified polyether acrylates.
  • amines such as tertiary amines
  • a catalyst used tertiary amine can act as a synergist.
  • acidic groups such as COOH groups or SO 3 H groups
  • used tertiary amine act as a synergist. It is possible to add up to twice the molar amount of synergist, based on the photoinitiator (A) used.
  • UV absorbers convert UV radiation into heat energy.
  • Suitable UV absorbers are, for example, oxanilides, triazines and benzotriazole (the latter obtainable as Tinuvin® grades from Ciba specialty chemistry), benzophenones, hydroxybenzophenones, hydroquinone, hydroquinone monoalkyl ethers, such as, for example, hydroquinone monomethyl ether.
  • Radical scavengers bind intermediately formed radicals.
  • Suitable radical scavengers are, for example, sterically hindered amines, which are known as HALS (hindered amine light stabilizers). Examples for this are 2,2,6, 6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, for. Bis- (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate.
  • HALS hindered amine light stabilizers
  • polymerization inhibitor (E) can be added, more preferably up to 0.5% by weight.
  • Dispersions according to the invention can be added to one or more further compounds having C-C double bonds (F), hereinafter also referred to as unsaturated compounds (F).
  • unsaturated compounds (F) are, for example, compounds of the general formula I.
  • Further particularly suitable unsaturated compounds (F) are those of the general formula F.1.
  • R 1 , R 2 are identical or different and are independently selected from hydrogen and C 1 -C 10 -alkyl
  • n is an integer from 0 to 2, preferably 1;
  • R 8 selected from C 1 -C 4 -A ⁇ yI, such as nC 4 H 9 , nC 3 H 7 , iso-C 3 H 7 and preferably C 2 H 5 and CH 3 , or phenyl, A 3 , A 4 , A 5 the same or different and selected from
  • C r C 2 o-alkylene such as -CH 2 -, -CH (CH 3 ) -, -CH (C 2 H 5 ) -, -CH (C 6 H 5 ) -, - (CH 2 ) 2 -, - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 -, - ( CHz) 7 -, - (CHz) 8 -, - (CHZ) 9 -, - (CHz) 10 -, -CH (CH 3 HCH 2) Z-CH (CH 3) -; c / s- or frans-C 4 -C 0 cycloalkylene, such as c / s-1,3-cyclopentylidene, frans-1, 3-cyclopentylidene c / s-1, 4-cyclohexylidene, frans- 1, 4-
  • CrC 2 o-alkylene in which from one to seven non-adjacent C atoms in each case are replaced by oxygen, for example -CH 2 -O-CH 2 -, - (CHz) 2 -O-CH 2 -, - ( CHz) 2 -O- (CH 2 ) Z -, - [(CH 2 ) 2 -O] 2 - (CH 2 ) 2 -, - [(CH 2 ) 2 -O] 3 - (CH 2 ) 2 - ; C r C 20 alkylene substituted with up to 4 hydroxyl groups, wherein in C 1 -C 20 - alkylene from one to seven non-adjacent C atoms by
  • Substituted oxygen such as -CH 2 -O-CH 2 -CH (OH) -CH 2 -, -CH 2 -O- [CH 2 -CH (OH) -CH 2 1 2 -, -CH 2 -O - [CH 2 -CH (OH) -CH 2 ] S -; C 6 -C 4 -arylene, such as para-C 6 H 4 .
  • Particularly preferred examples of compounds of the general formula F.I are trimethylolpropane tri (meth) acrylate, tri (meth) acrylate of triethoxylated tetramethylolpropane, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate.
  • unsaturated compounds (F) are ethylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, dipropylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate.
  • unsaturated compounds (F) are partially or exhaustively (meth) acrylated polyols, such as, for example, partially or exhaustively dimerized trimethylolpropane (meth) acrylated, partially or exhaustively (meth) acrylated dimeric trimethylolethane, partially or exhaustively (meth) acrylated dimeric pentaerythritol.
  • acrylated polyols such as, for example, partially or exhaustively dimerized trimethylolpropane (meth) acrylated, partially or exhaustively (meth) acrylated dimeric trimethylolethane, partially or exhaustively (meth) acrylated dimeric pentaerythritol.
  • a total of up to 100% by weight, based on the sum of (A) and (B), of unsaturated compound (F) may be added, preferably up to 50% by weight and more preferably up to 25% by weight. %.
  • Aqueous dispersions according to the invention can be used well as or for the preparation of formulations for dyeing or printing substrates, for example for the production of dyeing liquors for pigment dyeing or for the production of printing pastes for pigment printing.
  • An object of the present invention fertil is therefore the use of aqueous dispersions of the invention as or for the preparation of formulations for dyeing or printing substrates.
  • a process for dyeing or printing substrates using at least one novel aqueous dispersion is provided by the present invention.
  • Suitable substrates are:
  • cellulosic materials such as paper, paperboard, cardboard, wood and wood-based materials, which may also be painted or otherwise coated, metallic materials such as foils, sheets or workpieces of aluminum, iron, copper, silver, gold, zinc or alloys of these metals which are lacquered or silicate materials such as glass, porcelain and ceramics which may be coated, polymeric materials of all types such as polystyrene, polyamides, polyesters, polyethylene, polypropylene, melamine resins, polyacrylates, polyacrylonitrile, polyurethanes, polycarbonates, polyvinyl chloride, polyvinyl alcohols, polyvinyl acetates, Polyvinylpyrrolidones and corresponding copolymers and block copolymers, biodegradable polymers and natural polymers such as gelatine, leather, both natural and artificial leather, as smooth, nappa or suede leather, foods and cosmetics, and in particular textile substrates such as fibers, yarns, threads, knits, Webware, non-woven
  • Aqueous dispersions according to the invention are particularly suitable as or for the production of inks for the ink-jet process, in particular of aqueous inks for the ink-jet process.
  • Very particularly good aqueous dispersions according to the invention can be used for the preparation of pigment-containing aqueous inks for the ink-jet process.
  • Another object of the present invention is thus the use of aqueous dispersions of the invention for the production of inks for the ink-jet process.
  • Another object of the present invention is a process for the preparation of inks for the ink-jet process using at least one aqueous dispersion according to the invention.
  • inks for the ink-jet process are also referred to as ink-jet inks or in short as inks.
  • inkjet inks according to the invention contain
  • aqueous dispersion according to the invention From 1 to 40% by weight, preferably from 2 to 35% by weight, of aqueous dispersion according to the invention, details in% by weight being based in each case on the total weight of the relevant ink according to the invention.
  • aqueous dispersions according to the invention directly as ink-jet inks.
  • Inks according to the invention for the ink-jet process may in another embodiment contain at least one additive (G).
  • ink-jet inks according to the invention are prepared by diluting the aqueous dispersion according to the invention with water and optionally mixing it with one or more additives (G).
  • the solids content of ink jet inks according to the invention is adjusted to be in the range from 3 to 40%, preferably up to 35%, particularly preferably 5 to 30%.
  • inks according to the invention for the ink-jet process may contain one or more organic solvents.
  • Low molecular weight polytetrahydrofuran (polyTHF) is a preferred additive (G), it may be used alone or preferably in admixture with one or more low volatility, water soluble or water miscible organic solvents.
  • Preferably used low molecular weight polytetrahydrofuran usually has an average molecular weight M w of 150 to 500 g / mol, preferably from 200 to 300 g / mol and particularly preferably about 250 g / mol (corresponding to a molecular weight distribution).
  • Polytetrahydrofuran can be prepared in a known manner via cationic polymerization of tetrahydrofuran. This produces linear polytetramethylene glycols.
  • Suitable solvents are polyhydric alcohols, preferably unbranched and branched polyhydric alcohols having 2 to 8, in particular 3 to 6, carbon atoms, such as ethylene glycol, 1,2- and 1,3-propylene glycol, glycerol, erythritol, pentaerythritol, pentitols such as arabitol, adonite and xylitol and hexitols such as sorbitol, mannitol and dulcitol.
  • polyhydric alcohols preferably unbranched and branched polyhydric alcohols having 2 to 8, in particular 3 to 6, carbon atoms, such as ethylene glycol, 1,2- and 1,3-propylene glycol, glycerol, erythritol, pentaerythritol, pentitols such as arabitol, adonite and xylitol and hexitols such as sorbitol,
  • polyethylene and polypropylene glycols which are to be understood as including the lower polymers (di-, tri- and tetramers), and their mono- (especially C r C 6 -, in particular C r C 4 -) alkyl ethers.
  • Examples are di-, tri- and tetraethylene glycol, diethylene glycol monomethyl, -ethyl, -n-, isopropyl-propyl and -n-butyl ether, triethylene glycol monomethyl, -ethyl, -n-propyl-, iso-propyl and n-butyl ethers, di-, tri- and tetra-1, 2- and -1, 3-propylene glycol and di-, tri- and tetra-1,2- and 1,3-propylene glycol monomethyl , -ethyl, -n-propyl, -iso-propyl and -n-butyl ether.
  • pyrrolidone and N-alkylpyrrolidones whose alkyl chain preferably contains 1 to 4, especially 1 to 2, carbon atoms.
  • suitable alkylpyrrolidones are N-methylpyrrolidone, N-ethylpyrrolidone and N- (2-hydroxyethyl) pyrrolidone.
  • solvents 1, 2 and 1, 3-propylene glycol, glycerol, sorbitol, diethylene glycol, polyethylene glycol (M w 300 to 500 g / mol), diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, pyrrolidone, N-methylpyrrolidone and N- ( 2-hydroxyethyl) pyrrolidone.
  • Polytetrahydrofuran can also be mixed with one or more (eg two, three or four) of the solvents listed above.
  • inks for the ink-jet process according to the invention may be 0.1 to 80% by weight, preferably 2 to 60% by weight, more preferably 5 to 50% by weight and most preferably 10 to 40 wt .-% non-aqueous solvent.
  • Non-aqueous solvents as additives (G), in particular also the abovementioned particularly preferred solvent combinations, can advantageously be supplemented by urea (generally from 0.5 to 3% by weight, based on the weight of the colorant preparation), which contains the water-retaining effect of the solvent mixture still reinforced.
  • urea generally from 0.5 to 3% by weight, based on the weight of the colorant preparation
  • Inventive inks for the ink-jet process may contain further additives (G), as are customary in particular for aqueous ink jet inks and in the printing and coating industry.
  • preservatives such as, for example, 1,2-benzisothiazolin-3-one (available commercially as Proxel brands from Avecia Lim.) And its alkali metal salts, glutaric dialdehyde and / or tetramethylolacetamide diurea, Protectole®, antioxidants, degasifier / Defoamers such as acetylenediols and ethoxylated acetylenediols, which usually contain 20 to 40 moles of ethylene oxide per mole of acetylenediol and at the same time can also have a dispersing effect, viscosity regulators, leveling agents, wetting agents (eg wetting surfactants based on ethoxylated or propoxylated fatty acid or ox), e
  • these agents are part of inks according to the invention for the ink-jet process, their total amount is generally 2% by weight, in particular 1% by weight, based on the weight the colorant preparations according to the invention and in particular the inks according to the invention for the ink-jet process.
  • AO represents identical or different alkylene oxide units, for example propylene oxide units, butylene oxide units and in particular ethylene oxide units,
  • R 4 , R 5 , R 6 , R 7 are each the same or different and selected from C 1 -C 20 -alkyl, unbranched or branched, such as methyl, ethyl, n-propyl, isobutyl,
  • b is the same or different and selected from integers in the range of 0 to 50, preferably 0 or 1 to 30 and particularly preferably 3 to 20.
  • R 5 or R 7 are methyl.
  • R 5 and R 7 are methyl, and R 4 and R 6 are isobutyl.
  • variable b is as defined above.
  • Inks according to the invention for the ink-jet process may furthermore contain a further photoinitiator which is not equal to the photoinitiator (D) which can be used in the preparation of aqueous dispersion according to the invention, but is chosen from the abovementioned photoinitiators.
  • D photoinitiator
  • inks for the ink-jet process according to the invention have a dynamic viscosity in the range from 2 to 80 mPa.s, preferably from 3 to 40 mPa.s, particularly preferably to 25 mPa.s, measured at 23 ° C. according to DIN 53018.
  • the surface tension of inks according to the invention for the ink-jet process is 24 to 70 mN / m, in particular 25 to 60 mN / m, measured at 25 ° C. according to DIN 53993.
  • the pH of inks according to the invention for the ink-jet process is from 5 to 10, preferably from 7 to 9.
  • Ink-jet inks according to the invention show advantageous overall application properties, in particular good write-on behavior and good continuous writing behavior (kogation), and, especially when using the particularly preferred solvent combination, good drying behavior, and result in high-quality printed images, i. high brilliance and color depth and high friction, light, water and wet rub fastness. They are particularly suitable for printing on coated and uncoated paper and textile.
  • Another aspect of the present invention is a process for the preparation of inks for the ink-jet process according to the invention.
  • the process according to the invention for the production of inks for the ink-jet process is characterized in that at least one aqueous dispersion according to the invention, water and optionally at least one aggregate (G) are mixed with one another, for example in one or more steps.
  • Mixturing and intensive shaking, for example, and dispersing, for example in ball mills or stirred ball mills, may be mentioned as suitable mixing techniques.
  • inventive aqueous dispersion water, optionally (C), optionally (D), optionally (E), optionally (F) and optionally (G) is not critical per se.
  • At least one radiation-curable polyurethane (A) and at least one polyurethane (C) are synthesized, then dispersed with (B), diluted with water and mixed with one or more of the desired additives (D) , (E), (F) and / or (G).
  • At least one radiation-curable polyurethane (A) is synthesized and then dispersed with pigment (B) and at least one of the desired additives (C), (D), (E), (F) and (G).
  • At least one radiation-curable polyurethane (A) and at least one polyurethane (C) are synthesized and then dispersed with pigment (B) and at least one of the desired additives (D), (E), (F) and ( G).
  • a further aspect of the present invention is a process for printing flat or three-dimensional substrates by the ink-jet process using at least one ink according to the invention for the ink-jet process, also referred to below as the printing process according to the invention.
  • at least one ink-jet ink according to the invention is printed onto a substrate.
  • at least one inkjet ink according to the invention is printed on a substrate and subsequently treated with actinic radiation.
  • the usually aqueous inks are sprayed in small droplets directly onto the substrate.
  • the inks according to the invention for the bubble jet process and for the process by means of a piezoelectric crystal.
  • Water-soluble radiation-curable products (A) according to the invention can be cured by actinic radiation; for example, actinic radiation having a wavelength range from 200 nm to 450 nm is suitable. For example, actinic radiation having an energy in the range from 70 mJ / cm 2 to 2000 mJ / cm 2 is suitable. Actinic radiation can be useful to introduce, for example, continuously or in the form of lightning.
  • Suitable are for example temperatures in the range of 30 to 12O 0 C for a period ranging from 10 seconds to 24 hours, preferably up to 30 min, more preferably up to 5 min.
  • IR radiation in a wavelength range above 800 nm is suitable as IR radiation.
  • Suitable devices for intermediate drying are, for example, drying ovens or vacuum drying ovens for intermediate thermal drying, furthermore IR lamps.
  • the heat developed by the action of actinic radiation can also have an inter-drying effect.
  • a further embodiment of the present invention are substrates, in particular textile substrates, which have been printed according to one of the abovementioned printing processes according to the invention and are characterized by particularly sharply printed images or Distinguish drawings as well as excellent grip.
  • printed substrates according to the invention have few "soft spots”.
  • Another object of the present invention are at least partially coated pigments prepared by dispersing at least one pigment (B) and at least one radiation-curable polyurethane (A), wherein radiation-curable polyurethane (A) is obtainable by reacting
  • R 1 , R 2 are identical or different and are independently selected from hydrogen and C 1 -C 10 -alkyl
  • X 1 selected from oxygen and NR 3 ,
  • a 1 is selected from C 1 -C 20 -alkylene, unsubstituted or mono- or polysubstituted by C 1 -C 4 -alkyl, phenyl or O-CrC 4 alkyl, in which C r C 20 alkylene, one or more non- adjacent CH 2 groups may be replaced by oxygen;
  • X 2 is selected from hydroxyl and NH-R 3, R 3 are identical or different and are selected from hydrogen, C 1 -C 0 -alkyl and phenyl.
  • At least partially coated pigments according to the invention are particularly suitable for the production of inks for the ink-jet process.
  • a process for the preparation of at least partially coated pigments according to the invention is described above and also the subject of the present invention.
  • At least partially coated pigments according to the invention can be obtained from aqueous dispersions according to the invention by removal of the water, for example by drying, freeze-drying, filtration or a combination of the abovementioned measures.
  • the NCO content was monitored in each case according to DIN 53185 by titration.
  • the degree of coating of pigments according to the invention was determined by transmission electron microscopy using a freeze-fracture technique.
  • Tetrahydrofuran (THF) was dried by distillation over Na / benzophenone before use.
  • Solids content The percentages in the context of the present invention always refer to% by weight. Solids contents are within the scope of the present inventions fertil always by drying for 30 minutes at 150 0 C determined.
  • polyester diol (b.1.1) having a molecular weight M w of 2400 g / mol and an OH number of 140 mg KOH / g, prepared by polycondensation of isophthalic acid, adipic acid and 1, 4-dihydroxymethylcyclohexane (isomer mixture ) in a molar ratio of 1: 1: 2, were heated to 130 0 C.
  • the resulting melt was filled into a 2-liter reactor equipped with stirrer, reflux condenser, gas inlet tube and dropping funnel, filled and stirred at 130 ° C. under nitrogen.
  • polyester diol (b.1.1) was present as a clear melt, the mixture was cooled to 80 ° C. with stirring.
  • neopentyl glycol (b.1.2) and 120.7 g of 1, 1-dimethylolpropionic acid (b.1.3) were added and then cooled to 60 ° C. Thereafter, 750 g of tetrahydrofuran (THF), 308.2 g of diisocyanate (a.1) and 308.2 g of hexamethylene diisocyanate (HDI) (a.1) were added. Subsequently, 1000 ppm of di-n-butyltin dilaurate were added (based on HDI) and the mixture was stirred at 60 ° C.
  • THF tetrahydrofuran
  • a.1 diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • THF tetrahydrofuran
  • 22.1 g of 2-hydroxyethyl acrylate (d.1) in 66.2 g of THF were added.
  • the mixture was stirred at 50 ° C. until the titrimetrically determined NCO content had dropped to 3.1% by weight, based on the reaction mixture, and then admixed with 495.0 g of polyurethane of 1.1 and a further 0.2% by weight.
  • Di-n-butyltin dilaurate based on the reaction mixture.
  • IPDI isophorone diisocyanate
  • Aqueous dispersions of the invention were prepared on a shaking apparatus (Skandex) with 60 g of glass beads (diameter 0.25-0.5 mm). The formulations are summarized in Table 1. After weighing the ingredients and the Glass balls in Skandex, the resulting mixture was shaken for a time according to Table 1. Thereafter, a sample was taken and the mean diameter of dispersed pigment was determined (Coulter Counter LS230). The pH was measured and, if necessary, adjusted to 7.5 with triethanolamine. The aqueous dispersions WD.4.1 to WD.4.3 according to the invention were obtained.
  • Table 1 Ingredients and recipe parameters for aqueous dispersions WD.4.1 to WD.4.3 according to the invention
  • Biocide 1 20 wt .-% solution of 1,2-benzisothiazolin-3-one in propylene glycol (A.4) is calculated on the solids content.
  • aqueous dispersions of the invention were obtained by proceeding as described above, but in each case replaced (A.4) by (A.1), (A.2) and (A.3).
  • the following aqueous dispersions according to the invention were obtained:
  • Ink T4.1.1 of the invention had a pH of 7.6 and a dynamic viscosity of 4.2 mPa.s at 25 ° C.
  • Ink T4.1.2 of the invention had a pH of 7.6 and a dynamic viscosity of 4.2 mPa.s at 25 ° C.
  • the ink T4.1.1 or T4.1.2 according to the invention was in each case filled into a cartridge and printed on paper with an Epson Mimaki TX2 720 printer at 720 dpi.
  • the rubbing fastness tests gave good values.
  • the ink according to the invention T4.1.1 or T4.1.2 was printed on cotton with a printer Mimaki TX 2 720X at 720 dpi.
  • variant 1 was a thermal drying with subsequent exposure
  • variant 2 was an exposure to actinic radiation with subsequent thermal drying
  • variant 3 was an exposure to actinic radiation without thermal drying.
  • a UV irradiation device from the company IST was used with two different UV emitters: Eta Plus M-400-U2H, Eta Plus M-400-U2HC. It was exposed for 10 seconds and entered an energy of 1000 mJ / cm 2 .
  • the printed substrates S4.1.1 to S4.3.1 according to the invention (ink T4.1.1) and S4.1.2 to S4.3.2 (ink T4.1.2) according to Table 2 were obtained and certain rub fastnesses according to ISO-105-D02: 1993 and US Pat Wash fastness according to ISO 105-C06: 1994.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Ink Jet (AREA)

Abstract

L'invention concerne une dispersion aqueuse, contenant un pigment (B) recouvert au moins partiellement d'un polyuréthanne (A) durcissable aux rayonnements, ledit polyuréthanne (A) étant obtenu par transformation des composés suivants : (a) au moins un diisocyanate, comprenant (b) un composé présentant au moins deux groupes destinés à entrer en réaction avec l'isocyanate et (c) au moins un composé de formule (I). Dans cette formule, les variables sont définies ci-après : R<SUP>1</SUP>, R<SUP>2</SUP> sont identiques ou différents et, indépendamment l'un de l'autre, représentent hydrogène ou alykle C<SUB>1</SUB>-C<SUB>10</SUB>, X<SUP>1</SUP> représente oxygène et N-R<SUP>3</SUP>, A<SUP>1</SUP> représente alkylène C<SUB>1</SUB> -C<SUB>20</SUB>, non substitué ou substitué une ou plusieurs fois par alykle C<SUB>1</SUB>-C<SUB>4</SUB>, phényle, ou alkyle O-C<SUB>1</SUB> -C<SUB>4</SUB>, un ou plusieurs groupes CH<SUB>2</SUB> non adjacents pouvant être remplacés par oxygène dans l'alkylène C<SUB>1</SUB>-C<SUB>20</SUB>, X<SUP>2</SUP> représente hydroxyle et NH-R<SUP>3</SUP>, R<SUP>3</SUP> est identique ou différent et représente hydrogène, alkyle C<SUB>1</SUB>-C<SUB>10</SUB> et phényle.
EP06708487A 2005-02-24 2006-02-23 Pigments partiellement recouverts de polyurethanne, leur production et leur utilisation Withdrawn EP1856172A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE200510008930 DE102005008930A1 (de) 2005-02-24 2005-02-24 Mit strahlungshärtbarem Polyurethan zumindest partiell umhüllte Pigmente, ihre Herstellung und Verwendung
DE200510008932 DE102005008932A1 (de) 2005-02-24 2005-02-24 Strahlungshärtbare wässrige Polyurethandispersionen
PCT/EP2006/060233 WO2006089934A1 (fr) 2005-02-24 2006-02-23 Pigments partiellement recouverts de polyurethanne, leur production et leur utilisation

Publications (1)

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EP1856172A1 true EP1856172A1 (fr) 2007-11-21

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US (1) US20080146691A1 (fr)
EP (1) EP1856172A1 (fr)
JP (1) JP2008531779A (fr)
CA (1) CA2598970A1 (fr)
WO (1) WO2006089934A1 (fr)

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DE102007040376A1 (de) 2007-08-20 2009-02-26 Karl Wörwag Lack- Und Farbenfabrik Gmbh & Co. Kg Lack, flexibler Schichtverbund mit einem Träger und einer darauf aufgebrachten Lackschicht sowie deren Verwendung
EP2143748A1 (fr) * 2008-07-10 2010-01-13 Cytec Surface Specialties, S.A. Compositions aqueuses de polyuréthanes durcissables par irradiation
DE102009037323A1 (de) * 2009-08-14 2011-02-17 Eckart Gmbh Tintenstrahldrucktinte enthaltend Effektpigmente mit hohem Glanz
JP5585957B2 (ja) 2010-08-12 2014-09-10 東海カーボン株式会社 ポリウレタン樹脂付加顔料、ポリウレタン樹脂付加顔料の製造方法、顔料分散組成物およびインクジェットインク組成物
EP2721085A1 (fr) * 2011-06-14 2014-04-23 Basf Se Dispersions de poluyrethanne aqueuses durcissables par rayonnement
EP2703458B1 (fr) * 2012-08-31 2015-07-08 Hewlett-Packard Industrial Printing Ltd. Composition d'encre photo-durcissable
EP2845885B1 (fr) 2012-08-31 2018-01-31 HP Scitex Ltd Composition d'encre photodurcissable
WO2016018876A1 (fr) * 2014-07-31 2016-02-04 E. I. Du Pont De Nemours And Company Encres aqueuses pour jet d'encre contenant du polyuréthane amphotère comme liant
CN109312185A (zh) 2016-07-20 2019-02-05 惠普发展公司，有限责任合伙企业 具有预处理固定液的喷墨墨水组
EP3433325B1 (fr) 2016-07-20 2021-09-22 Hewlett-Packard Development Company, L.P. Ensemble d'encres pour jet d'encre
US10759192B2 (en) 2016-07-20 2020-09-01 Hewlett-Packard Development Company, L.P. Pre-treatment fixing fluid
EP3414293A1 (fr) 2016-07-20 2018-12-19 Hewlett-Packard Development Company, L.P. Encre pour impression par jet d'encre
US11098212B2 (en) 2017-02-27 2021-08-24 Hewlett-Packard Development Company, L.P. Polyurethane-based binder dispersion
CN110198965B (zh) 2017-02-27 2022-04-01 惠普发展公司，有限责任合伙企业 基于聚氨酯的粘合剂分散体
TW202400124A (zh) 2022-06-15 2024-01-01 拓華生技股份有限公司 牙齒亮白組成物、套組及其使用方法

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DE4434554A1 (de) * 1994-09-28 1996-04-04 Basf Ag Strahlungshärtbare wäßrige Polyurethandispersionen
JPH08311384A (ja) * 1995-05-22 1996-11-26 Dainippon Ink & Chem Inc 孔版インキ用ポリマー微粒子
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DE10360043A1 (de) * 2003-12-18 2005-07-21 Basf Ag Mit Polyadditionsprodukten umhüllte Pigmente, Verfahren zu ihrer Herstellung und ihre Verwendung

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US20080146691A1 (en) 2008-06-19
WO2006089934A1 (fr) 2006-08-31
CA2598970A1 (fr) 2006-08-31
JP2008531779A (ja) 2008-08-14

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