EP2185614A1 - Polyuréthanes hyperramifiés, hydrophilisés - Google Patents

Polyuréthanes hyperramifiés, hydrophilisés

Info

Publication number
EP2185614A1
EP2185614A1 EP08804522A EP08804522A EP2185614A1 EP 2185614 A1 EP2185614 A1 EP 2185614A1 EP 08804522 A EP08804522 A EP 08804522A EP 08804522 A EP08804522 A EP 08804522A EP 2185614 A1 EP2185614 A1 EP 2185614A1
Authority
EP
European Patent Office
Prior art keywords
hydrophilized
hyperbranched
hyperbranched polyurethanes
polyurethanes according
diisocyanate
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Withdrawn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
EP08804522A
Other languages
German (de)
English (en)
Inventor
Pedro Cavaleiro
Sebastian Sonnhalter
Matthias Seiler
Stefan Bernhardt
Markus Schwarz
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.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
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 Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2185614A1 publication Critical patent/EP2185614A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules

Definitions

  • the invention relates to hydrophilicized, hyperbranched polyurethanes, their preparation and their use as dispersants, in particular for the dispersion of solids.
  • Hyperbranched polymers are already known.
  • EP 1 026 185 A1 discloses a process for the preparation of dendritic or highly branched polyurethanes by reacting diisocyanates and / or
  • Polyisocyanates with compounds having at least two isocyanate-reactive groups wherein at least one of the reactants having functional groups with respect to the other reactants of different reactivity and the reaction conditions are chosen so that in each reaction step only certain reactive groups react with each other.
  • Preferred isocyanates include u. a. aliphatic isocyanates, such as isophorone diisocyanate.
  • the compounds having at least two isocyanate-reactive groups are propylene glycol, glycerol, mercaptoethanol, ethanolamine, N-methylethanolamine, diethanolamine, ethanolpropanolamine, dipropanolamine, diisopropanolamine, 2-amino-1,3-propanediol, 2-amino-2-methyl -1, 3-propanediol and tris (hydroxymethyl) aminomethane mentioned by name.
  • polyurethanes obtainable by the process are intended as crosslinkers for polyurethanes or as building blocks for other polyaddition or polycondensation polymers, as
  • DE 100 30 869 A1 describes a process for the preparation of polyfunctional
  • Polyisocyanate polyaddition products comprising
  • an addition product (A) by reacting an a) isocyanate-reactive, at least trifunctional component (a1) or an isocyanate-reactive difunctional component (a2) or with a mixture of the components (a1) and (a2) with b ) Di- or polyisocyanate, wherein the reaction ratio is selected such that on average the addition product (A) contains an isocyanate group and more than one isocyanate-reactive group,
  • a preferred diisocyanate (b) is isophorone diisocyanate.
  • polyisocyanate polyaddition products obtainable by the process are proposed in particular for the production of paints, coatings, adhesives, sealants, cast elastomers and foams.
  • WO 2004/101624 discloses the preparation of dendritic or hyperbranched polyurethanes by
  • Isocyanate group and more than one hydroxyl group or a hydroxyl group and more than one isocyanate group 2) reaction of the addition product from step 1) to give a polyaddition product by intermolecular reaction of the hydroxyl groups with the isocyanate groups, it being possible initially to react with a compound containing at least two hydroxyl groups, mercapto groups, amino groups or isocyanate groups,
  • step 2) optionally reaction of the polyaddition product from step 2) with a compound containing at least two hydroxyl groups, mercapto groups, amino groups or isocyanate groups.
  • polyaminourethanes obtainable by the process are proposed as crosslinkers for polyurethane systems or as building blocks for other polyaddition or polycondensation polymers, as phase mediators, as rheology aids, as thixotropic agents, as nucleating agents or as active substance or catalyst carriers.
  • WO 02/068553 A2 describes a coating composition containing
  • a carbamate resin with a hyperbranched or star-shaped polyol core with a first chain piece based on a polycarboxylic acid or a polycarboxylic anhydride, with a second chain piece based on an epoxide and with carbamate groups on the core and / or the second chain piece and
  • the polyol core can be prepared by reacting a first compound containing more than 2 hydroxy groups, such as. 1, 2,6-hexanetriol, with a second compound containing a carboxyl and at least two hydroxy groups.
  • a first compound containing more than 2 hydroxy groups such as. 1, 2,6-hexanetriol
  • WO 97/02304 relates to highly functionalized polyurethanes which are composed of molecules with the functional groups A (B) n , where A is an NCO group or an NCO group-reactive group, B is an NCO group or one with an NCO group.
  • A is an NCO group or an NCO group-reactive group
  • B is an NCO group or one with an NCO group.
  • Group reactive group, A is reactive with B and n is a natural number and at least equal to 2.
  • the preparation of the monomer A (B) n can be carried out, for example, starting from isophorone diisocyanate.
  • dispersants are generally used in order to achieve effective dispersion of the solids, to reduce the mechanical shear forces required for dispersion and, at the same time, to achieve the highest possible fill levels realize.
  • the dispersants assist in the breaking up of agglomerates, wet and / or occupy the surface of the particles to be dispersed as surface-active materials and stabilize them against undesired reagglomeration.
  • Dispersants in the manufacture of paints, lacquers, inks and other coating materials facilitate the incorporation of solids such as fillers and pigments which, as important formulation ingredients, substantially determine the visual appearance and physicochemical properties of such systems. For optimal utilization of these solids must be distributed evenly in the formulations on the one hand, on the other hand, the once reached distribution must be stabilized.
  • Fatty acids and their salts and alkylphenol ethoxylates, more complex high molecular structures are used as dispersants. Here it is specifically amino- and amido-functional systems that are widely used.
  • dispersing additives also negatively influences the water resistance or lightfastness of brushing materials, and additionally stabilizes the unwanted foam produced during production and processing. Also - due to lack of compatibility of the dispersing resins in many Auflackgütern - often undesirably affects the gloss.
  • dispersants for solids that exhibit further improved properties over the prior art. Described are dispersants that have the highest possible stabilizing effect on a variety of different solids.
  • the amount of high-priced pigments can be reduced without sacrificing color intensity.
  • the viscosity behavior of pastes, paints, coatings, printing inks and other Besch ichtungsstoffen containing dyes, solids, such as fillers and / or pigments significantly influenced by the dispersant used.
  • dispersants especially dispersants are required, which cause and maintain the lowest possible viscosity in the liquid paints and coatings, with a Newtonian viscosity behavior is preferred.
  • the invention relates to hydrophilicized, hyperbranched polyurethanes composed of
  • Z linear or branched hydrocarbon radical having 3 to 20 carbon atoms and wherein heteroatoms and / or functional groups may be present in the carbon chain,
  • T is a hydrogen radical and / or an optionally substituted, linear or branched aryl, arylalkyl, alkyl or alkenyl radical having 1 to 24 carbon atoms,
  • a, b, c are independently 0 to 100, with the proviso that the sum of a + b + c ⁇ 0, preferably 5-35, in particular 10-20, and provided that the sum of a + b + c + d> 0, d ⁇ 0, preferably 1 to 5.
  • n is equal to 4.
  • diisocyanates and polyisocyanates A) used according to the invention may be any desired aromatic, aliphatic, cycloaliphatic and / or (cyclo) aliphatic di- and / or polyisocyanates.
  • aromatic di- or polyisocyanates A in principle all known compounds are suitable. Particularly suitable are 1, 3 and 1, 4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, tolidine diisocyanate, 2,6-toluene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate ( 2,4'-MDI), 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates (MDI) and oligomeric diphenylmethane diisocyanates (polymer-MDI), xylylene diisocyanate, tetramethylxylylene diisocyanate and triisocyanatotoluene.
  • MDI monomeric diphenylmethane diisocyanates
  • polymer-MDI oligomeric diphenylmethane
  • Suitable aliphatic di- or polyisocyanates A) advantageously have 3 to 16 carbon atoms, preferably 4 to 12 carbon atoms, in the linear or branched alkylene radical and suitable cycloaliphatic or (cyclo) aliphatic diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical.
  • (cyclo) aliphatic diisocyanates the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z.
  • B. isophorone diisocyanate is the case.
  • TIN 4-isocyanatomethyl-1, 8-octane diisocyanate
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • H 12 MDI diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • mixtures of di- and polyisocyanates A) can be used.
  • oligo- or polyisocyanates are preferably used as component A), which consists of said di- or polyisocyanates or mixtures thereof by linking by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide , Uretonimine, oxadiazinetrione or iminooxadiazinedione structures.
  • Particularly suitable are isocyanurates, especially from IPDI and HDI.
  • triols B) are 1, 1, 1-trimethylolpropane, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, 1, 2,7-heptanetriol, 1, 2,8-octanetriol, 1, 2, 9-nonanetriol and 1,2,10-decanetriol, wherein 1, 2,6-hexanetriol and 1,1,1-trimethylolpropane is most preferred. It can also be used mixtures.
  • radicals R and R " are hydrogen or an alkyl group having 1 to 4 carbon atoms and n is an integer greater than 0, more preferably in the range of 3 to 10.
  • the polyurethane I) preferably has a number average of at least 4 repeat units of the formula (Ib) per molecule
  • the polyurethane I) is obtainable by reacting a di- or polyisocyanate A) with a triol B) and at least one further diol C).
  • particularly favorable diols C) include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1, 2-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 3-butanediol, and / or 1,6-hexanediol.
  • the mixture of triol B) and diol C), based in each case on their total weight, preferably contains 50.0% by weight to ⁇ 100.0% by weight of triol B) and> 0.0% by weight to 50, 0% by weight of diol, more preferably 50.0% by weight to 75.0% by weight of triol and 25.0% by weight to 50.0% by weight of diol.
  • the hyperbranched polyurethane I) is further distinguished by the fact that it has on the number average at least 4, preferably at least 50, more preferably at least 200, most preferably at least 400 repeat units of the formula (I) per molecule.
  • the upper limit of repeating units of the formula (I) is conveniently 10,000, preferably 5,000 and in particular 2,500 repeating units, each based on the number average.
  • the hyperbranched polyurethane I) preferably has a weight average molecular weight Mw in the range of from 1,000 g / mol to 200,000 g / mol, favorably in the range of from 1,500 g / mol to 100,000 g / mol, preferably in the range of 2,000 g / mol to 75 000 g / mol, in particular in the range of 2 500 g / mol to 50 000 g / mol.
  • the degree of branching of the hyperbranched polyurethane I) is expediently in the range of> 10.0% to ⁇ 85.0%, preferably in the range of> 20.0% to 75.0%, in particular in the range of> 25.0% to 65 , 0%.
  • the molecular weight of hyperbranched polyurethane I) can be controlled by the relative proportion of monomers.
  • the use ratio of diisocyanates or polyisocyanates A) to triol B) and, where appropriate, C) is taken into consideration, taking into account any other substances present Comonomers preferably such that the ratio (in mol) of the reactive groups to one another, ie the ratio of the isocyanate groups to the hydroxyl groups as close as possible 1, preferably in the range of 5: 1 to 1: 5, preferably in the range of 4: 1 to 1: 4, more preferably in the range of 2: 1 to 1: 2, even more preferably in the range of 1, 5: 1 to 1: 1, 5 and in particular in the range of 1, 01: 1 to 1: 1, 01 is.
  • the polyethers II) are generally polyalkoxyalkylenes having terminal OH groups. They are obtained by addition of cyclic ethers such. For example, ethylene oxide or propylene oxide to mono- and / or bifunctional starter molecules. If the latter are mixed with trifunctional starters, branched reaction products can also be obtained.
  • starter molecules are generally monohydric and / or polyhydric alcohols such as methanol, ethanol, ethylene glycol, 1, 2-propanediol, trimethylolpropane, glycerol or sugar.
  • Preferred polyethers are reaction products of low molecular weight, mono and / or polyfunctional alcohols or water with alkylene oxides. Suitable polyethers preferably have 1 to 5, more preferably 2 to 3, OH groups per molecule. These can be either primary or secondary.
  • Preferred examples of the polyether building blocks of B radicals are alkylene oxides such as: ethylene oxide, propylene oxide, butylene oxide, styrene oxide, dodecene oxide, tetradecenoxide, 2,3-dimethyloxirane, cyclopentene oxide, 1,2-epoxy pentane, 2-isopropyloxirane, glycidyl methyl ester, glycidyl isopropyl ester, epichlorohydrin, 3 -Methoxy-2,2-dimethyloxirane, 8-oxabicyclo [5.1.0] octane, 2-pentyloxirane, 2-methyl-3-phenyloxirane, 2,3-epoxypropylbenzene, 2- (4-fluorophenyl) oxirane, tetrahydrofuran, and others thereof Enantiomeric pairs or enantiomeric mixtures.
  • alkylene oxides such as: ethylene oxide, propylene
  • the molar ratio of isocyanate groups of the hyperbranched polymer I) to OH groups of the polyether II) is between 1:50 and 1: 9, preferably between 1:20 and 1: 5 and particularly preferably between 1: 3 and 1: 1.
  • the invention also provides a process for the preparation of the hydrophilicized hyperbranched polyurethanes
  • hydrophilicized, hyperbranched polyurethanes according to the invention as dispersants of solids in liquid media and the hydrophilicized hyperbranched polyurethanes according to the invention dispersions such as pigment pastes, coating materials, printing inks and / or printing varnishes.
  • a solid in the sense of the present invention can in principle be any solid organic or inorganic material.
  • Such solids are pigments, fillers, dyes, optical brighteners, ceramic materials, magnetic materials, nanodisperse solids, metals, biocides, agrochemicals and pharmaceuticals which are used as dispersions.
  • Preferred solids are pigments, as described, for example, in the Color Index, Third Edition, Volume 3; The Society of Dyers and Colorists (1982) "and the following revised editions.
  • pigments examples include inorganic pigments such as carbon blacks, titanium dioxides, zinc oxides, Prussian blue, iron oxides, cadmium sulfides, chromium pigments such as chromates, molybdate and mixed chromates and lead sulfates, zinc, barium, calcium and mixtures thereof. Further examples of inorganic pigments are described in the book “H. Endriss, Current inorganic colored pigments, Vincentz Verlag, Hannover (1997) "called.
  • organic pigments examples include those from the group of azo, diazo, fused azo, naphthol, metal complex, thioindigo, indanthrone, isoindanthrone, anthanthrone, anthraquinone, isodibenzanthrone, triphendioxazine, quinacridone, perylene, Terrylen, Quaterrylen, Diketopyrrolopyrrol and Phtalocyaninpigmente. Further examples of organic pigments are described in the book "W. Herbst, K. Hunger, Industrial Organic Pigments, VCH, Weinheim (1993).
  • fillers such as talc, kaolin, silicas, barites and lime; ceramic materials such as aluminum oxides, silicates, zirconium oxides, titanium oxides, boron nitrides, silicon nitrides, boron carbides, mixed silicon aluminum nitrides and metal titanates; magnetic materials such as transition metal magnetic oxides such as iron oxides, cobalt-doped iron oxides and ferrites; Metals such as iron, nickel, cobalt and their alloys; and biocides, agrochemicals and pharmaceuticals, such as fungicides.
  • ceramic materials such as aluminum oxides, silicates, zirconium oxides, titanium oxides, boron nitrides, silicon nitrides, boron carbides, mixed silicon aluminum nitrides and metal titanates
  • magnetic materials such as transition metal magnetic oxides such as iron oxides, cobalt-doped iron oxides and ferrites
  • Metals such as iron, nickel, cobalt and their alloys
  • Pigment pastes, coating materials, printing inks and / or printing varnishes for the purposes of the present invention may be very different products.
  • They may be, for example, fillers, pigments and / or dyes containing systems.
  • liquid medium may contain organic solvents and / or water, as known in the art depending on the binders used.
  • liquid media and binder components such as polyols can be considered.
  • the coating materials, printing inks and / or printing varnishes do not necessarily have to contain a liquid phase, but may also be what are known as powder coatings.
  • the coating materials, printing inks and / or printing varnishes may comprise the customary state-of-the-art additives, for example wetting agents, leveling agents or defoamers, etc., and curing, crosslinking and / or drying according to different processes according to the state of the art.
  • coating materials in the context of the present invention are paints, lacquers, printing inks and other coating materials, such as solvent-borne lacquers and solvent-free lacquers, powder coatings, UV-curable lacquers, low solids, medium solids, high solids. Solids, automotive coatings, wood coatings, stoving enamels, 2-component paints, metal coating materials, toner compositions. Further examples of sweeteners are mentioned in “Bodo Müller, Ulrich Poth, Paint Formulation and Paint Formulation, Textbook for Training and Practice, Vincentz Verlag, Hannover (2003)” and “PG Garrat, Radiation Hardening, Vincent Verlag, Hannover (1996)”.
  • printing inks and / or printing varnishes in the context of the present invention are solvent-based printing inks, flexographic printing inks, gravure printing inks, letterpress or high-pressure inks, offset printing inks, litho printing inks, printing inks for packaging printing, screen printing inks, printing inks, such as printing inks for inkjet printers, inkjet inks, Printing varnishes, such as overprint varnishes.
  • the hydrophilicized, hyperbranched polyurethanes according to the invention can be used in pigment pastes, coating materials, printing inks and / or printing varnishes in a concentration of from 0.01 to 90.0% by weight, preferably from 0.5 to 35% by weight, and particularly preferably from 1 up to 25 wt .-% are used.
  • they may be used in admixture with wetting and dispersing agents of the prior art.
  • the diisocyanate is reacted with a triol to form the hyperbranched polyisocyanate.
  • a triol for this purpose, in a three-necked flask equipped with stirrer, internal thermometer, dropping funnel and gas inlet tube, the diisocyanate and 0.005% DBTL 100% (calculated on total amount) submitted under nitrogen blanketing. Thereafter, the corresponding triol, dissolved in N-methylpyrrolidone (NMP) at 25 0 C slowly added dropwise. After the addition, the temperature is raised to 60 0 C. The course of the reaction is monitored by decreasing the NCO number.
  • NMP N-methylpyrrolidone
  • TMP Trimethylolpropane
  • IPDI Isophorone diisocyanate
  • DBTL Dibutyltin dilaurate
  • TMP 1, 1, 1-trimethylolpropane
  • NMP Methyl-2-pyrrolidone
  • 2,6-hexanetriol CAS 106-69-4)
  • the NCO content is monitored by regular sampling and titration. At an NCO content ⁇ 0.1%, the reaction is complete. After removal of the solvent, the dispersing resin 1, a highly viscous brownish liquid, was formed.
  • Example 2 Analogously to Example 1, the hydrophilicized, hyperbranched polyurethanes 2 to 11 were prepared using the educts listed in Table 3.
  • hydrophilized, hyperbranched polyurethanes and solids were compared in the following formulations for coatings, printing inks and / or printing varnishes:
  • the ratio of the amount of pigment to the amount of the hydrophilicized, hyperbranched polyurethane according to the invention (dispersing additive) was kept constant in a pigment-dependent manner in all experiments.
  • the ratio of hydrophilized, hyperbranched polyurethanes to pigment in the case of carbon black pigments was 17.8% of hydrophilized, hyperbranched polyurethanes (additive) on pigment and 15% of hydrophilicized, hyperbranched polyurethanes (additive) on pigment in the case of organic colored pigments.
  • the ingredients of the recipe are weighed into 250 ml screw-cap jars in accordance with the above recipes and mixed with glass beads (100 g of glass beads per 100 g of ground material). The sealed jars are then mixed in a Skandex mixer
  • Tinted UV-curable flexographic ink Tinted UV-curable flexographic ink
  • the UV-curable flexographic ink was mixed with the white tinting lacquer.
  • the blends were carried out in the ratio 20: 1 (41, 67g white pigment to 1g org. Colored pigment and 35.71g white pigment to 1g carbon black pigment).
  • the mixture is then homogenized for 1 min in a universal shaker (Hausschild Engineering, DAC 150 Dual Asymmetry Centrifuge).
  • the tinted UV-curable flexographic inks were knife-coated with a spiral doctor blade (24 ⁇ m) on white cardboard (Leneta). The drying was carried out with the aid of a 120 W / cm medium pressure mercury vapor lamp (Beltron GmbH, Beltron UV lamps). The speed of the conveyor belt was 8m / min.
  • the determination of the rheological behavior of the UV-curable flexographic ink thus prepared is carried out with the aid of a rotational viscometer.
  • a plate / cone system has been selected (Euro Physics, Rheo 2000 RC20, 45 microns, angle 1 °; 25 0 C measured temperature).
  • the color measurement of the white blend (24 ⁇ m layer thickness on Leneta cardboard) was carried out with a device from X-Rite (type: X-Rite SP 60).
  • X-Rite type: X-Rite SP 60
  • CIE Lab system is useful as a three-dimensional system for the quantitative description of the color loci.
  • the colors green (negative a-values) and red (positive a * -values) are plotted on one axis and the colors blue (negative b * values) and yellow (positive b * values) on the axis arranged at right angles to them. Values).
  • the two axes intersect at the achromatic point.
  • CIE-Lab system not only color loci but also color gaps can be described by specifying the three coordinates.
  • the hydrophilized, hyperbranched polyurethanes 1 to 11 were tested in UV-curable flexographic ink with the carbon black pigment Spezialschwarz® 250 as described above.
  • the results are shown in Table 6 and show that the hydrophilicized, hyperbranched polyurethanes according to the invention had lower L * values than the blank sample or the comparative examples (the dispersion resin-free flexographic ink).
  • the desire here is for low L * values (brightness value).
  • the values given in the result tables are mean values from three measurements.
  • Comparative Example V 1 Solsperse® 24000 (Lubrizol Corp.) Comparative Example V 2: Solsperse® 32000 (Lubrizol Corp.) Comparative Example V 3: Solsperse® 39000 (Lubrizol Corp.) Comparative Example V 4: Tego Dispers® 681 UV ( Tego Chemie Service GmbH)
  • Example 23 Tego Dispers® 681 UV ( Tego Chemie Service GmbH)
  • Desired are low L * (brightness values), and a low viscosity at low shear loads. It has been found that the hydrophilicized hyperbranched polyurethanes used according to the invention as dispersing resins show lower L * values and a lower viscosity at a given shear gradient compared with the blank sample or the comparative examples.
  • the positive properties of the hydrophilicized, hyperbranched polyurethanes used according to the invention are not limited to black pigments, but also extend to the other solids commonly used in the prior art. It is known to the person skilled in the art that, in particular, yellow pigments and violet pigments are difficult to disperse. Therefore, below is an example of the universal applicability of the hydrophilized, hyperbranched polyurethanes used as dispersing resins the yellow pigment Irgalite® Yellow BAW (Ciba) and Hostaperm® Violet P-RL (Clariant International Ltd.).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des polyuréthanes hyperramifiés, hydrophilisés, leur production et leur utilisation comme agents de dispersion, notamment pour la dispersion de solides.
EP08804522A 2007-10-15 2008-09-22 Polyuréthanes hyperramifiés, hydrophilisés Withdrawn EP2185614A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007049587A DE102007049587A1 (de) 2007-10-15 2007-10-15 Hydrophilierte, hyperverzweigte Polyurethane
PCT/EP2008/062595 WO2009049992A1 (fr) 2007-10-15 2008-09-22 Polyuréthanes hyperramifiés, hydrophilisés

Publications (1)

Publication Number Publication Date
EP2185614A1 true EP2185614A1 (fr) 2010-05-19

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US (1) US20100216943A1 (fr)
EP (1) EP2185614A1 (fr)
CN (1) CN101412799A (fr)
DE (1) DE102007049587A1 (fr)
WO (1) WO2009049992A1 (fr)

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DE102011088787A1 (de) 2011-12-16 2013-06-20 Evonik Industries Ag Siloxannitrone und deren Anwendung
CN105037677B (zh) * 2015-09-07 2019-01-18 东莞市吉鑫高分子科技有限公司 一种高支化热塑性聚氨酯弹性体及其制备方法
CN108948851B (zh) * 2018-03-06 2022-04-08 英德侗富贵科技材料有限公司 一种超支化分散剂及其制备方法
CN109880038B (zh) * 2019-03-05 2021-09-28 广州浦利姆环保科技有限公司 水性聚氨酯及其制备方法、水性色浆
CN110746568A (zh) * 2019-11-07 2020-02-04 合肥工业大学 一种超支化水溶性聚氨酯及其制备方法
CN112778488A (zh) * 2020-12-29 2021-05-11 江南大学 一种反应性支化聚氨酯高分子分散剂的制备方法
CN113663539B (zh) * 2021-09-16 2022-11-01 西安热工研究院有限公司 一种超支化抗菌型聚氨酯反渗透膜及其制备方法
CN114716871B (zh) * 2022-04-15 2023-09-29 中国科学院理化技术研究所 一种改性颜料、其制备方法及应用
CN117736606B (zh) * 2023-12-18 2024-05-17 江苏众立生包装科技有限公司 含有改性聚脲的水性油墨的制备方法

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DE102007049587A1 (de) 2009-04-16
CN101412799A (zh) 2009-04-22
US20100216943A1 (en) 2010-08-26
WO2009049992A1 (fr) 2009-04-23

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