EP3601455A1 - Pâtes aqueuses de pigments à effet contenant un polymère et peintures de base produites à partir de ces pâtes - Google Patents

Pâtes aqueuses de pigments à effet contenant un polymère et peintures de base produites à partir de ces pâtes

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Publication number
EP3601455A1
EP3601455A1 EP18711380.8A EP18711380A EP3601455A1 EP 3601455 A1 EP3601455 A1 EP 3601455A1 EP 18711380 A EP18711380 A EP 18711380A EP 3601455 A1 EP3601455 A1 EP 3601455A1
Authority
EP
European Patent Office
Prior art keywords
effect pigment
mixture
polymer
weight
pigment paste
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Withdrawn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
EP18711380.8A
Other languages
German (de)
English (en)
Inventor
Patrick WILM
Dirk EIERHOFF
Jürgen Bauer
Carola Ulrike JAHN
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 Coatings GmbH
Original Assignee
BASF Coatings 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 BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP3601455A1 publication Critical patent/EP3601455A1/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Withdrawn legal-status Critical Current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
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/007—Metal oxide

Definitions

  • the present invention relates to an aqueous effect pigment paste comprising at least one effect pigment (a) and at least one polymer (b) which can be prepared by successive free-radical emulsion polymerization of three monomer mixtures (A), (B) and (C) of olefinically unsaturated monomers in water, an aqueous basecoat which can be prepared by admixing the effect pigment paste to at least one aqueous binder-containing component suitable for the preparation of the basecoat, a process for producing a multicoat system using this basecoat, and a use of the polymerizate (b) for dispersing effect pigments within an aqueous base effect pigment paste.
  • Pigment pastes and polymers used therein are known in the art. Through the use of pigment pastes, the technically complex process of pigment dispersion is substantially facilitated in the paint industry, since it ensures, for example, dust-free processing of pigments during the formulation of paints.
  • the pigments are optimally wetted by incorporation into the paste and very well dispersed, so that an improved distribution state is achieved in the resulting paint. This results in improved application-technological properties of the paint and the coating produced therefrom, for example, a particularly homogeneous color or color distribution of the paint.
  • Effect pigment-containing pigment pastes are prepared separately for the same reasons prior to incorporation into a coating such as a water-based paint as an intermediate, since a direct incorporation of these pigments in the paint causes the above problems, especially with regard to insufficient dispersion and wetting the pigments in the case of direct addition.
  • precisely matched polymers must be used as paste binders to obtain an optimally conditioned paste. Without an individual adaptation and accurate selection of the polymer, the respective pigment can usually not be optimally dispersed, so that the application-technological properties of the paint ultimately resulting therefrom are also not optimal.
  • the corresponding paste binder does not always correspond to the main binder of the coating composition, so that a further binder component is introduced into the coating agent by the paste.
  • the manufacturing process of the coating composition becomes more complex.
  • other coating components must in turn also be matched to this polymer.
  • there is less scope for the use of further additives and / or binder components in the coating since in particular the proportion of the primary binder of primary importance can be lowered too much.
  • a polymer which corresponds to the main binder in the resulting coating composition, must usually compromise on the choice of the main binder and thus the quality of the resulting coating composition and the received with multi-layer coating produced, but this is undesirable.
  • pigment pastes which are aqueous or have the lowest possible content of organic solvents.
  • DE 103 50 719 A1 discloses effect pigment pastes which contain, in addition to an effect pigment, a (meth) acrylate copolymer present in a primary dispersion.
  • these polymers described in DE 103 50 719 A1 have comparatively high glass transition temperatures, which may possibly lead to insufficient adhesion properties.
  • aqueous pigment pastes which, in addition to a pigment such as an effect pigment, contain a polyurethane-based copolymer which can be prepared by copolymerization of a mixture of olefinically unsaturated monomers in the presence of a polyurethane.
  • the pigment pastes disclosed in WO 2015/090811 A1 do not always lead to the desired pinhole robustness after incorporation into a coating agent such as a water-based paint.
  • effect pigment pastes containing polyester and comparatively high amounts of organic solvents, such as butyl glycol, are known in the prior art.
  • organic solvents such as butyl glycol
  • a disadvantage of these effect pigment pastes is their low storage stability and their comparatively high solvent and polyester content.
  • solvent-based effect pigment pastes are described, for example, in WO 92/15405 A1.
  • EP 1 534 792 B1 discloses aqueous metal pigment pastes which are free of binders, including friction resins, but which, inter alia, must necessarily contain a non-associative (meth) acrylic copolymer thickener. From EP 1 504 068 B1 corresponding aqueous micapigment pastes are known.
  • a disadvantage of these effect pigment pastes is that a thickening agent must necessarily be used for their preparation, which in the production of paints such as waterborne paints using these pastes a comparatively high amount of water is required to set a sufficient viscosity, which in turn leads to an undesirable reduction of Solid body of the resulting paint leads.
  • aqueous effect pigment paste which can be used to prepare a basecoat and which has advantages over the effect pigment pastes known from the prior art.
  • the aqueous basecoats thus prepared should optimally fulfill the required application-technological properties, in particular a good optical appearance, sufficient flop and good adhesion properties, if not improve them, but in no case worsen them.
  • the mixture (B) contains at least one polyunsaturated monomer and a polymer which is prepared from the mixture (B), a
  • a further subject matter of the present invention is an aqueous basecoat, wherein the basecoat is preparable by admixing at least one effect pigment paste according to the invention as component (1) to at least one aqueous component (2) suitable for the preparation of a basecoat which contains at least one polymer usable as a binder, wherein this polymer which can be used as a binder is the polymer (b) also present in the effect pigment paste and / or at least one polymer which is different therefrom.
  • the basecoats of the invention differ by this specific preparation of basecoats of the same composition, but on other Ways have been made in their properties such as the appearance of specks.
  • Another object of the present invention is a process for producing a multi-layer coating, in which
  • the substrate used in step (1a) preferably has an electrodeposition coating layer (ETL), more preferably an electrodeposition coating layer applied by cathodic deposition of an electrodeposition coating, and the basecoat used in step (1a) is applied directly to the ETL-coated substrate. wherein the electrodeposition coating layer (ETL) applied to the substrate is preferably cured when performing step (1a).
  • ETL electrodeposition coating layer
  • a further subject of the present invention is a use of the polymer (b) mentioned in connection with the first subject, ie a polymer having an average particle size in the range from 100 to 500 nm, preparable by successive free-radical emulsion polymerization of three monomer mixtures (A), ( B) and (C) of olefinically unsaturated monomers in water, wherein the mixture (A) contains at least 50% by weight of monomers having a solubility in water of less than 0.5 g / l at 25 ° C, and a polymer prepared from the mixture (A) has a glass transition temperature of from 10 to 65 ° C,
  • the mixture (B) contains at least one polyunsaturated monomer and a polymer which is prepared from the mixture (B), a
  • aqueous effect pigment paste according to the invention is distinguished by excellent storage stability and is therefore particularly suitable for use in automated production.
  • the polymer (b) present in the aqueous effect pigment paste of the invention can be used not only as the main binder in aqueous basecoats, but can also be used as a paste binder in an aqueous effect pigment paste.
  • improved formulation freedom is achieved since the other coating components of the basecoat do not have to be matched to a further paste binder other than the polymer (b) due to the now permitted use of the polymer (b) in the effect pigment paste.
  • the pigment paste according to the invention is an effect pigment paste.
  • pigment paste is known to the person skilled in the art and is defined, for example, in Rompp Lexikon, Paints and Printing Inks, Georg Thieme Verlag, 1998, 10th Edition, page 452:
  • Pigment pastes are preparations of pigment mixtures in support materials such as polymers in which the pigments are in a higher concentration present as it corresponds to the later application.
  • An effect pigment paste thus represents a pigment paste, which at least one Effect pigment - namely at least one effect pigment (a) - contains as a pigment.
  • the subsequent use of pigment pastes is usually in the production of coating materials such as basecoats.
  • a pigment paste is thus to be distinguished from a coating agent such as a basecoat in that it is merely a precursor for producing such a coating agent.
  • a pigment paste as such can therefore not be used as a basecoat itself.
  • the relative weight ratio of pigments to polymers is usually greater than in the coating compositions, for the production of which the paste is finally used.
  • the support materials such as polymers, which are also known as paste binders, and pigments
  • water and / or organic solvents are usually present in the pigment paste.
  • various additives such as wetting agents and / or thickeners can be used in a pigment paste.
  • the polymer (b) present in the effect pigment paste according to the invention is used as pigment paste binder (paste binder).
  • the effect pigment paste according to the invention represents an aqueous composition containing the components (a) and (b).
  • the effect pigment paste according to the invention is aqueous. It is preferably a system containing as solvent as the main component water, preferably in an amount of at least 20 wt .-%, and organic solvents in minor proportions, preferably in an amount of ⁇ 20 wt .-%, respectively based on the total weight of the effect pigment paste according to the invention.
  • the effect pigment paste according to the invention preferably contains at least 20% by weight, more preferably at least 25% by weight, most preferably at least 30% by weight, in particular at least 35% by weight, most preferably of water of at least 40 wt .-%, each based on the total weight of the effect pigment paste.
  • the effect pigment paste according to the invention preferably contains a proportion of water which is in a range from 20 to 75% by weight, more preferably in a range from 25 to 70% by weight, very particularly preferably in a range of 30 to 65% by weight or up to 60% by weight or up to 57.5% by weight, in each case based on the total weight of the effect pigment paste.
  • the effect pigment paste according to the invention preferably contains a proportion of organic solvents which is in a range of ⁇ 20% by weight, more preferably in a range of 0 to ⁇ 20% by weight, most preferably in a range of 0.5 to 20 Wt .-% or up to 17.5 wt .-% or up to 15 wt .-%, in each case based on the total weight of the effect pigment paste.
  • the addition of organic solvents is particularly suitable for effect pigment pastes containing aluminum effect pigments as effect pigment (a).
  • the effect pigment pastes according to the invention can also be completely or almost completely free of organic solvents, in particular if metal oxide-mica pigments (mica) are used as the effect pigment (a).
  • the proportion of organic solvents is preferably less than 10 wt .-%, in particular less than 5 wt .-%, each based on the total weight of the effect pigment paste.
  • the solids content of the effect pigment paste according to the invention is preferably in a range from 15 to 65% by weight, particularly preferably from 17.5 to 60% by weight, very particularly preferably from 20 to 55% by weight, in particular from 22.5 to 50% by weight, most preferably from 25 to 45% by weight, based in each case on the total weight of the effect pigment paste.
  • the determination of the solids content, ie the non-volatile content, is carried out according to the method described below.
  • the percentage sum of the solids of the effect pigment paste according to the invention and the proportion of water in the effect pigment paste according to the invention is preferably> 50% by weight, more preferably at least 55 or at least 60% by weight, very particularly preferably at least 65 or at least 70 wt .-%, in particular at least 75% by weight. Preferred among these are ranges of> 50 to 99 wt .-%, in particular 55 or 60 to 97.5 wt .-%.
  • an effect pigment paste according to the invention has a solids content of 30% by weight and a water content of 65% by weight, the percentage sum of the solid and the proportion of water defined above is 95% by weight.
  • the effect pigment paste according to the invention contains a proportion of polymer (b) in a range from 0 to 25 wt .-%, particularly preferably from 1, 5 to 20 wt .-%, most preferably from 2.0 to 17.5 wt .-%, in particular from 2.5 to 15 wt .-%, most preferably from 4.0 to 12.5 wt .-%, each based on the total weight of the effect pigment paste.
  • the determination or determination of the proportion of the polymer (b) on the effect pigment paste can be effected by determining the solids content (also called non-volatile content, solids content or solids content) of an aqueous dispersion containing the polymer (b), which is used to prepare the effect pigment paste becomes.
  • the effect pigment paste according to the invention contains a proportion of effect pigment (a) of at least 10% by weight, preferably of at least 11 or 12% by weight, more preferably of at least 13 or 14% by weight, in particular of at least 15 or 16 or 17 or 18 wt .-%, most preferably of at least 19 wt .-%, each based on the total weight of the effect pigment paste.
  • the effect pigment paste according to the invention preferably contains a proportion of effect pigment (a) in a range from 10 to 50% by weight, particularly preferably from 10 to 45% by weight, very particularly preferably from 10 to 40% by weight, in particular from 1 1 to 35 wt .-%, most preferably from 12 to 30 wt .-% or from 12 to 27.5 wt .-%, each based on the total weight of the effect pigment paste.
  • the relative weight ratio of the at least one effect pigment (a) to the polymer (b) in the effect pigment paste is at least 1: 1 or at least 1.2: 1 or at least 1.5: 1 or higher, more preferably at least 2.0: 1 or higher, most preferably at least 2.5: 1 or higher, especially at least 3.0: 1 or higher.
  • the relative weight ratio of the at least one effect pigment (a) to the polymer (b) in the effect pigment paste is in a range from 10: 1 to 1: 1 or from 8: 1 to 1: 1, more preferably in a range of 10: 1 to 1, 2: 1 or from 10: 1 to 1, 5: 1 or in a range from 8: 1 to 1, 2: 1 or from 8: 1 to 1, 5: 1.
  • the effect pigment paste according to the invention comprises at least one effect pigment as component (a), preferably in an amount of at least 10% by weight, based on the total weight of the effect pigment paste.
  • effect pigments are preferably pigments which are optically effecting or have a color and optical effect, in particular an optically effecting effect.
  • optically effecting and coloring pigment are therefore preferably interchangeable.
  • Preferred effect pigments are, for example, platelet-shaped metallic effect pigments, such as platelet-shaped aluminum pigments, gold bronzes, fire-colored bronzes and / or iron oxide-aluminum pigments, pearlescent pigments such as fish-silver, basic lead carbonate, bismuth oxychloride and / or metal oxide-mica pigments (mica) and / or other effect pigments, such as platelet-shaped graphite, platelet-shaped Iron oxide, multi-layer effect pigments from PVD films and / or liquid crystal polymer pigments.
  • platelet-shaped metallic effect pigments such as platelet-shaped aluminum pigments, gold bronzes, fire-colored bronzes and / or iron oxide-aluminum pigments
  • pearlescent pigments such as fish-silver, basic lead carbonate, bismuth oxychloride and / or metal oxide-mica pigments (mica)
  • / or other effect pigments such as platelet-shaped graphite, platelet-shaped Iron oxide, multi-layer effect pigment
  • the effect pigment paste according to the invention therefore preferably comprises as at least one effect pigment (a) at least one metallic effect pigment such as at least one preferably platelet-shaped aluminum effect pigment and / or at least one metal oxide-mica pigment.
  • the effect pigment paste according to the invention may optionally contain from the at least one effect pigment (a) various further pigments, in particular color pigments and / or fillers.
  • the effect pigment paste according to the invention preferably contains no such further pigment as a color pigment and also no filler.
  • the effect pigment paste according to the invention comprises at least one polymer (b) having an average particle size in the range from 100 to 500 nm, preparable by successive free radical emulsion polymerization of three monomer mixtures (A), (B) and (C) of olefinically unsaturated monomers in water, the Mixture (A) at least 50 wt .-% of monomers having a solubility in water of less than 0.5 g / l at 25 ° C and a polymer which is prepared from the mixture (A), a glass transition temperature of 10 to 65 Has ° C,
  • the mixture (B) contains at least one polyunsaturated monomer and a polymer which is prepared from the mixture (B), a
  • the polymers (b) are so-called seed-core-shell polymers (SCS polymers).
  • SCS polymers seed-core-shell polymers
  • Polymers (b) or aqueous dispersions containing such polymers are known, for example, from WO 2016/116299 A1.
  • the polymer (b) is a (meth) acrylic copolymer.
  • the polymer (b) present in the effect pigment paste according to the invention is used as pigment paste binder (paste binder).
  • binder in the sense of the present invention in accordance with DIN EN ISO 46 8 (German version, date: March 2007) preferably responsible for film formation non-volatile components of a composition such as the effect pigment paste of the invention or the basecoat
  • the non-volatile content may be determined according to the method described below
  • a base coat which comprises the polymer (b), a crosslinking agent such as a melamine resin and / or a free or blocked polyisocyanate and / or a polymeric ad contains additive.
  • the polymer (b) is preferably used in the form of an aqueous dispersion for the preparation of the effect pigment paste according to the invention.
  • the preparation of the polymer (b) comprises the successive free radical emulsion polymerization of three mixtures (A), (B) and (C) of olefinically unsaturated monomers, each in water. It is therefore a multi-stage radical emulsion polymerization, wherein i. first the mixture (A) is polymerized, then ii. in the presence of under i. polymer prepared, the mixture (B) is polymerized and further iii. in the presence of under ii. produced polymerizate the mixture (C) is polymerized. All three Thus, monomer mixtures are polymerized via a separately carried out free radical emulsion polymerization (that is to say stage or else polymerization stage), these stages taking place in succession.
  • the stages can - in terms of time - take place directly behind each other. It is also possible that after completion of a stage, the corresponding reaction solution stored for a certain period of time and / or transferred to another reaction vessel and only then the next stage is performed.
  • the preparation of the polymer (b) in addition to the polymerization of the monomer mixtures (A), (B) and (C) comprises no further polymerization.
  • radical emulsion polymerization is known to the person skilled in the art and will be explained in more detail below.
  • olefinically unsaturated monomers in an aqueous medium are preferably polymerized using at least one water-soluble initiator and in the presence of at least one emulsifier.
  • Corresponding water-soluble initiators are likewise known.
  • the at least one water-soluble initiator is preferably selected from the group consisting of potassium, sodium or ammonium peroxodisulfate, hydrogen peroxide, tert-butyl hydroperoxide, 2,2'-azobis (2-amidoisopropane) dihydrochloride, 2,2'-azobis (N , N'-dimethyleneisobutyr- amidine) dihydrochloride, 2,2'-azobis (4-cyanopentanoic) and mixtures of the aforementioned initiators, for example, hydrogen peroxide and sodium persulfate. Also belonging to the preferred group mentioned are the known redox initiator systems.
  • Redox initiator systems are in particular those initiators which comprise at least one peroxide-containing compound in combination with at least one redox coinitiator, for example reducing sulfur compounds such as bisulfites, sulfites, thiosulfates, dithionites or tetrathionates of alkali metals and ammonium compounds, sodium hydroxymethanesulfinate dihydrate and / or thiourea.
  • reducing sulfur compounds such as bisulfites, sulfites, thiosulfates, dithionites or tetrathionates of alkali metals and ammonium compounds, sodium hydroxymethanesulfinate dihydrate and / or thiourea.
  • peroxodisulfates with alkali metal or ammonium hydrogen sulfites for example ammonium peroxydisulfate and ammonium bisulfite.
  • the weight ratio of peroxide-containing compounds to the redox coinitiators is preferably
  • transition metal catalysts can be used in combination with the initiators, such as, for example, iron, nickel, cobalt, manganese, copper, vanadium or chromium salts, such as iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, copper-l-chloride, manganese-ll-acetate, vanadium-l-acetate, manganese-ll-chloride. Based on the total mass of the olefinically unsaturated monomers used in a polymerization, these transition metal salts are usually used in amounts of from 0.1 to 1000 ppm.
  • the initiators are preferably used in an amount of 0.05 to 20 wt .-%, preferably 0.05 to 10, particularly preferably from 0.1 to 5 wt .-%, based on the total weight of the monomers used in the particular polymerization, used.
  • An emulsion polymerization proceeds in a reaction medium containing water as a continuous medium and more preferably at least one emulsifier, preferably in the form of micelles.
  • the polymerization is started by decomposition of the water-soluble initiator in the water.
  • the growing polymer chain inserts into the emulsifier micelles and further polymerization then takes place in the micelles.
  • the reaction mixture therefore preferably consists mainly of water.
  • the components mentioned, that is to say monomers, water-soluble initiator, emulsifier and water, preferably account for at least 95% by weight of the reaction mixture.
  • the reaction mixture preferably consists of these components.
  • the at least one emulsifier is preferably in an amount of 0.1-10 wt .-%, particularly preferably 0.1-5 wt .-%, most preferably 0.1-3 wt .-%, each based on the Total weight of the monomers used in the respective polymerization stage used.
  • Emulsifiers are also known in principle. It is possible to use nonionic or ionic emulsifiers, including zwitterionic, if appropriate also mixtures of the abovementioned emulsifiers.
  • Preferred emulsifiers are optionally ethoxylated and / or propoxylated alkanols having 10 to 40 Carbon atoms.
  • ethoxylation or propoxylation for example, adducts modified with poly (oxy) ethylene and / or poly (oxy) propylene chains consisting of 5 to 50 molecular units.
  • sulfated, sulfonated or phosphated derivatives of the products mentioned are usually used in neutralized form.
  • Particularly preferred emulsifiers are neutralized Dialkylsulfosuccinic or Alkyldiphenyloxiddisulfonate suitable, for example, commercially available as EF-800 Fa. Cytec.
  • the emulsion polymerizations are advantageously carried out at a temperature of 0 to 160 ° C, preferably from 15 to 95 ° C, more preferably 60 to 95 ° C. In this case, it is preferable to operate with the exclusion of oxygen, preferably under an inert gas atmosphere.
  • the polymerization is carried out at atmospheric pressure, but also the use of lower pressures or higher pressures is possible. In particular, when polymerization temperatures are used which are above the boiling point of water at normal pressure, the monomers used and / or the organic solvents, higher pressures are generally selected.
  • the individual polymerization stages in the preparation of the polymer (b) can be carried out, for example, as so-called “starving polymerizations” (also known as “starve feed”, “starve fed” or “starved feed” polymerizations).
  • starving polymerization in the context of the present invention, an emulsion polymerization is considered in which the content of free olefinically unsaturated monomers in the reaction solution (also called reaction mixture) is minimized during the entire reaction time.
  • concentration ranges of the olefinically unsaturated monomers of 0.01 to 6.0 wt .-%, preferably 0.02 to 5.0 wt .-%, particularly preferably 0.03 to 4.0 wt .-%, in particular 0.05 to 3.5 wt .-%.
  • concentration ranges of the olefinically unsaturated monomers of 0.01 to 6.0 wt .-%, preferably 0.02 to 5.0 wt .-%, particularly preferably 0.03 to 4.0 wt .-%, in particular 0.05 to 3.5 wt .-%.
  • the highest one to be detected during the reaction Weight fraction at 0.5 wt .-%, 1, 0 wt .-%, 1, 5 wt .-%, 2.0 wt .-%, 2.5 wt .-% or 3.0 wt .-% are while all other detected values are then below the values specified here.
  • the total amount (also called total weight) of the monomers used in the respective polymerization stage corresponds to stage i. apparently the total amount of monomer mixture (A), for stage ii. the total amount of the monomer mixture (B) and for stage iii. the total amount of the monomer mixture (C).
  • the concentration of the monomers in the reaction solution can be determined, for example, by gas chromatography. In this case, a sample of the reaction solution is cooled immediately after sampling with liquid nitrogen and treated with 4-methoxyphenol as an inhibitor. In the next step, the sample is dissolved in tetrahydrofuran and then n-pentane is added to precipitate the polymer formed at the time the sample is taken.
  • the liquid phase (supernatant) is analyzed by gas chromatography using a polar and a nonpolar column to determine the monomers and a flame ionization detector is used.
  • Typical parameters for the gas chromatographic determination are the following: 25 m silica capillary column with 5% phenyl, 1% vinyl methyl polysiloxane phase or 30 m silica capillary column with 50% phenyl 50% methyl polysiloxane phase, carrier gas hydrogen, split injector 150 ° C, oven temperature 50 to 180 ° C, flame ionization detector, detector temperature 275 ° C, internal standard isobutyl acrylate.
  • the determination of the concentration of the monomers is carried out in the context of the present invention preferably by gas chromatography, in particular while maintaining the above-mentioned parameters.
  • the proportion of free monomers can be controlled in different ways.
  • One way to keep the proportion of free monomers low is to choose the dosing of the mixture of olefinically unsaturated monomers to the actual reaction solution in which the monomers come into contact with the initiator, very low. If the metered addition rate is so low that all monomers can react almost instantly when in the reaction solution, it can be ensured that the proportion of free monomers is minimized.
  • the metered addition rate is so low that all monomers can react almost instantly when in the reaction solution, it can be ensured that the proportion of free monomers is minimized.
  • the reaction conditions are preferably to be selected so that the initiator feed is started even before the beginning of the metering of the olefinically unsaturated monomers.
  • the dosage is started at least 5 minutes before, more preferably at least 10 minutes before.
  • at least 10% by weight of the initiator particularly preferably at least 20% by weight, very preferably at least 30% by weight of the initiator, in each case based on the total amount of initiator, is added before starting the metering of the olefinically unsaturated monomers. It is preferable to choose a temperature which allows a constant decomposition of the initiator.
  • the amount of initiator is also an important factor for the sufficient presence of radicals in the reaction solution. The amount of initiator should be chosen so that sufficient free radicals are available at all times so that the added monomers can react. If the amount of initiator is increased, even larger amounts of monomers can be reacted at the same time.
  • the control of the proportion of free monomers can be controlled by the interaction of amount of initiator, rate of initiator addition, rate of monomer addition, and choice of monomers. Both the slowing of the dosage, as well as the increase in the amount of initiator, as well as the early start with the addition of the initiator serve the goal of keeping the concentration of the free monomers below the limits mentioned above.
  • the concentration of the free monomers can be determined by gas chromatography as described above. Should this analysis determine a concentration of free monomers approaching the limit of starvation polymerization, for example due to low levels of highly reactive olefinically unsaturated monomers, the above parameters may be used to control the reaction.
  • the metering rate of the monomers can be reduced or the amount of initiator can be increased.
  • at least the polymerization stages ii. and iii. be carried out under starving conditions. This has the advantage of effectively minimizing the formation of new particulate matter in these two stages of polymerization. Instead, it succeeds, after stage i. existing particles (henceforth also referred to as seed) in stage ii. by the polymerization of Momomermischung B continue to grow (henceforth also called core). Likewise, it succeeds after stage ii. existing particles (hereinafter also called polymer comprising seed and core) in stage iii.
  • a polymer (b) comprising particles containing seed, core and shell results also referred to as SCS polymer.
  • SCS polymer a polymer comprising particles containing seed, core and shell results
  • the mixtures (A), (B) and (C) are mixtures of olefinically unsaturated monomers.
  • Suitable olefinically unsaturated monomers may be mono- or poly-olefinically unsaturated.
  • suitable and, if appropriate, preferred monomers which are generally usable and are suitable for all mixtures (A), (B) and (C) are described. Specific specific embodiments of the individual mixtures will be discussed below.
  • suitable monoolefinically unsaturated monomers include in particular (meth) acrylate-based monoolefinically unsaturated monomers, allyl-containing monoolefinically unsaturated monomers and further vinyl-group-containing monoolefinically unsaturated monomers such as, for example, vinylaromatic monomers.
  • the term (meth) acryl or (meth) acrylate in the context of the present invention comprises both methacrylates and acrylates. In any case, but not necessarily exclusively, (meth) acrylate-based monoolefinically unsaturated monomers are preferably used.
  • the (meth) acrylate-based, monoolefinically unsaturated monomers may be, for example, (meth) acrylic acid and esters, nitriles or amides of (Meth) acrylic acid act.
  • esters of (meth) acrylic acid, with a radical R, which is not olefinically unsaturated are preferred.
  • the radical R may be saturated aliphatic, aromatic or mixed saturated aliphatic-aromatic.
  • aliphatic is understood as meaning all organic radicals which are not aromatic.
  • the radical R is preferably aliphatic.
  • the saturated aliphatic radical may be a pure hydrocarbon radical or it may contain heteroatoms of bridging groups (for example oxygen from ether or ester groups) and / or be substituted by functional groups containing heteroatoms (for example alcohol groups). In the context of the present invention, therefore, a clear distinction is made between bridging groups containing heteroatoms and functional groups containing heteroatoms (ie terminal functional groups containing heteroatoms).
  • R is a pure hydrocarbon radical (alkyl radical), ie contains no heteroatoms from bridging groups (for example oxygen from ether groups) and also not with functional groups (for example alcohol groups ) is substituted.
  • R is an alkyl radical, it may be, for example, a linear, branched or cyclic alkyl radical. Of course, such an alkyl radical may also have linear and cyclic or branched and cyclic structural components.
  • the alkyl radical preferably has 1 to 20, more preferably 1 to 10 carbon atoms.
  • Particularly preferred monounsaturated esters of (meth) acrylic acid with an alkyl radical are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary Butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate, 3 ) 3,5-trimethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, cycloalkyl ( meth) acrylates such as cyclopentyl (meth) acrylate, isobornyl (meth) acrylate and cyclohexyl (meth) acrylate where
  • suitable radicals R are, for example, saturated aliphatic radicals which comprise functional groups containing heteroatoms (for example alcohol groups or phosphoric acid ester groups).
  • Suitable monounsaturated esters of (meth) acrylic acid with a saturated aliphatic radical substituted by one or more hydroxyl groups are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3
  • Suitable monounsaturated esters of (meth) acrylic acid with phosphoric acid ester groups are, for example, phosphoric acid esters of polypropylene glycol monomethacrylate, such as the commercially available Sipomer PAM 200 from Rhodia.
  • Possible further vinyl group-containing monoolefinically unsaturated monomers are monomers other than the above-described acrylate-based monomers with a radical R 'on the vinyl group which is not olefinically unsaturated:
  • the radical R ' may be saturated-aliphatic, aromatic or mixed-saturated aliphatic-aromatic, with aromatic and mixed saturated-aliphatic-aromatic radicals in which the aliphatic portions are alkyl groups, are preferred.
  • vinyl-containing monoolefinically unsaturated monomers are in particular vinyltoluene, alpha-methylstyrene and in particular styrene. Also possible are vinyl group-containing monounsaturated monomers in which the radical R 'has the following structure:
  • radicals R 1 and R 2 are alkyl radicals which, in each case or together, contain a total of 7 carbon atoms.
  • Such monomers are commercially available under the name VeoVa® 10 from Momentive.
  • olefinically unsaturated monomers such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, vinyl acetate, vinyl propionate, vinyl chloride, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylimidazole, N-vinyl-2-methylimidazoline and other unsaturated alpha-beta carboxylic acids.
  • Suitable multiply olefinically unsaturated monomers include esters of (meth) acrylic acid with an olefinically unsaturated radical R ".
  • the radical R" may be, for example, an allyl radical or a (meth) acrylic acid radical:
  • Preferred poly olefinically unsaturated monomers include ethylene glycol di (meth) acrylate, 1,2-propylene glycol, (meth) acrylate, 2,2-
  • preferred poly olefinic unsaturated compounds include acrylic and methacrylic acid esters of alcohols having more than two OH groups, such as trimethylolpropane tri (meth) acrylate or glycerol tri (meth) acrylate, but also trimethylolpropane di (meth) acrylate monoallyl ether, trimethylolpropane (meth) acrylate diallyl ether, pentaerythritol tri (meth) acrylate monoallyl ether, pentaerythritol di (meth) acrylate diallyl ether, pentaerythritol (meth) acrylate triallyl ether, triallyl sucrose, and pentaallylsucrose.
  • trimethylolpropane tri (meth) acrylate or glycerol tri (meth) acrylate but also trimethylolpropane di (meth) acrylate monoallyl ether, trimethylolpropane (
  • allyl ethers of mono- or polyhydric alcohols such as, for example, trimethylolpropane monoallyl ether. If used, hexanediol diacrylate and / or allyl (meth) acrylate are preferred as the polyunsaturated monomers.
  • the monomer mixtures (A), (B) and (C) used in the individual polymerization stages it is preferable to comply with special conditions set out below.
  • the mixtures (A), (B) and (C) are in any case different from each other. They thus each contain different monomers and / or different proportions of at least one particular monomer.
  • the mixture (A) contains at least 50 wt .-%, preferably at least 55 wt .-%, of olefinically unsaturated monomers having a water solubility of less than 0.5 g / l at 25 ° C.
  • a corresponding preferred monomer is styrene.
  • the solubility of the monomers in water is determined by the method described below.
  • the monomer mixture (A) preferably contains no hydroxy-functional monomers. Also preferably, the monomer mixture (A) contains no acid-functional monomers. Most preferably, the monomer mixture (A) contains no monomers having functional groups containing heteroatoms. This means that heteroatoms, if present, only in the form of verb groups are present. This is the case, for example, in the above-described (meth) acrylate-based, mono-olefinically unsaturated monomers which, as radical R, have an alkyl radical.
  • the monomer mixture (A) preferably contains only monoolefinically unsaturated monomers.
  • the monomer mixture (A) contains at least one monounsaturated ester of (meth) acrylic acid having an alkyl group and at least one vinyl group-containing mono-olefinically unsaturated monomer having a vinyl group-attached group which is aromatic or which is mixed-saturated aliphatic-aromatic in which case the aliphatic moieties of the residue are alkyl groups.
  • the monomers contained in the mixture (A) are selected so that a polymer prepared therefrom has a glass transition temperature of 10 to 65 ° C, preferably 30 to 50 ° C.
  • the glass transition temperature can be determined by the method described below.
  • Polymer prepared by the emulsion polymerization of the monomer mixture (A) is also referred to as seed.
  • the seed preferably has an average particle size of 20 to 125 nm (measured by dynamic light scattering as described below;
  • the mixture (B) contains at least one poly olefinically unsaturated monomer, preferably at least one double olefinically unsaturated monomer.
  • a corresponding preferred monomer is hexanediol diacrylate.
  • the monomer mixture (B) preferably contains no hydroxy-functional monomers. Also preferably, the monomer mixture (B) contains no acid-functional monomers. Most preferably, the monomer mixture (B) contains no monomers having functional groups containing heteroatoms. This means that heteroatoms, if present, are present only in the form of bridging groups. This is the case, for example, in the above-described (meth) acrylate-based, mono-olefinically unsaturated monomers which, as radical R, have an alkyl radical.
  • the monomer mixture (B) in addition to the at least one multi-olefinically unsaturated monomer, in any case, the following monomers: On the one hand at least one monounsaturated ester of (meth) acrylic acid with an alkyl radical and on the other hand, at least one vinyl group-containing mono-olefinically unsaturated monomer having a the radical group which is aromatic or which is mixed saturated aliphatic-aromatic, in which case the aliphatic moieties of the radical are alkyl groups.
  • the proportion of polyunsaturated monomers is preferably from 0.05 to 3 mol .-%, based on the total molar amount of monomers of the monomer mixture (B).
  • the monomers contained in the mixture (B) are selected so that a polymer prepared therefrom has a glass transition temperature of -35 to 15 ° C, preferably -25 to + 7 ° C.
  • the glass transition temperature can be determined by the method described below.
  • stage ii. The polymer prepared by the emulsion polymerization of the monomer mixture (B) in the presence of the seed is also referred to as the core. After stage ii. So results in a polymer comprising seed and core.
  • the polymer which after stage ii. preferably has an average particle size of 80 to 280 nm, preferably 120 to 250 nm (measured by dynamic light scattering as described below;
  • the monomers contained in the mixture (C) are selected so that a polymer prepared therefrom has a glass transition temperature of -50 to 15 ° C, preferably -20 to + 12 ° C.
  • the glass transition temperature can be determined by the method described below.
  • the olefinically unsaturated monomers of the mixture (C) are preferably selected so that the resulting polymer, comprising seed, core and shell, an acid number of 10 to 25 has. Accordingly, the mixture (C) preferably contains at least one alpha-beta unsaturated carboxylic acid, more preferably (meth) acrylic acid.
  • the olefinically unsaturated monomers of mixture (C) are additionally or alternatively preferably selected so that the resulting polymer, comprising seed, core and shell, has an OH number of 0 to 30, preferably 10 to 25. All of the abovementioned acid numbers and OH numbers are values calculated on the basis of the total monomer mixtures used.
  • the monomer mixture (C) contains at least one alpha-beta unsaturated carboxylic acid and at least one monounsaturated ester of (meth) acrylic acid having an alkyl group substituted with a hydroxyl group.
  • the monomer mixture (C) particularly preferably comprises at least one alpha-beta-unsaturated carboxylic acid, at least one monounsaturated ester of (meth) acrylic acid with an alkyl radical substituted by a hydroxyl group and at least one monounsaturated ester of (meth) acrylic acid with an alkyl radical. If, in the context of the present invention, an alkyl radical is mentioned without any further specification, this always means a pure alkyl radical without functional groups and heteroatoms.
  • polymer prepared by the emulsion polymerization of the monomer mixture (C) in the presence of seed and core is also referred to as a shell.
  • a polymer which comprises seed, core and shell, ie polymer (b) results.
  • the polymer (b) has an average particle size of from 00 to 500 nm, preferably from 125 to 400 nm, very particularly preferably from 130 to 300 nm (measured by dynamic light scattering as described below;
  • the proportions of the mixture (A) is from 0.1 to 10% by weight, the proportion of the mixture (B) from 60 to 80% by weight and the proportion of the mixture ( C) from 10 to 30 % By weight, in each case based on the sum of the individual amounts of the mixtures (A), (B) and (C).
  • the polymer (b) is preferably used in the form of an aqueous dispersion for the preparation of the effect pigment paste according to the invention.
  • This aqueous dispersion preferably has a pH of 5.0 to 9.0, more preferably 7.0 to 8.5, most preferably 7.5 to 8.5.
  • the pH can be kept constant even during the preparation, for example by the use of bases as mentioned below, or can also be adjusted specifically after the preparation of the polymer.
  • this aqueous dispersion has a pH of 5.0 to 9.0 and the at least one polymer (b) contained therein has a particle size of 100 to 500 nm. More preferred range combinations are: pH of 7.0 to 8.5 and a particle size of 125 to 400 nm, more preferably pH of 7.5 to 8.5 and a particle size of 130 to 300 nm.
  • the stages described i. to iii. without the addition of acids or bases known for adjusting the pH.
  • Be used in the preparation of the polymer (b) then, for example, carboxy-functional monomers, which in the context of stage iii. is preferred, then the pH of the dispersion after completion of stage iii. are at less than 7. Accordingly, then, addition of base may be necessary to adjust the pH to a higher value, such as a value in the preferred ranges. From the above, it follows that the pH in this case is preferably after the stage iii.
  • a base such as an organic, nitrogen-containing base such as ammonia, ammonia, trimethylamine, triethylamine, tributylamines, dimethylaniline, triphenylamine, N, N-dimethylethanolamine, methyldiethanolamine or triethanolamine, and by addition of sodium bicarbonate or borates and also mixtures of the aforementioned substances.
  • a base such as an organic, nitrogen-containing base such as ammonia, ammonia, trimethylamine, triethylamine, tributylamines, dimethylaniline, triphenylamine, N, N-dimethylethanolamine, methyldiethanolamine or triethanolamine, and by addition of sodium bicarbonate or borates and also mixtures of the aforementioned substances.
  • the pH value can also be adjusted before, during or after the emulsion polymerizations or between the individual emulsion polymerizations.
  • the adjustment of the pH to a desired value is not necessary.
  • the measurement of the pH is
  • the nonvolatile fraction is preferably in the range from 15 to 40% by weight, particularly preferably in the range from 20 to 30% by weight. in each case based on the total weight of the aqueous dispersion.
  • the non-volatile content is determined according to the method described below.
  • the aqueous dispersion used contains from 55 to 75 wt .-%, particularly preferably from 60 to 70 wt .-%, each based on the total weight of the dispersion, water.
  • the percentage sum of the solids of the dispersion and the proportion of water in the dispersion is at least 80% by weight, preferably at least 90% by weight. Preferred among these are ranges from 80 to 99% by weight, in particular from 90 to 97.5% by weight. Accordingly, the aqueous dispersion used largely consists of water and the polymer (b) and contains polluting components such as organic solvents in particular or only in small proportions.
  • the effect pigment paste may additionally contain typical color pigments which are different from the effect pigment (a).
  • color pigment inorganic and / or organic pigments can be used.
  • the color pigment is an inorganic color pigment.
  • Particularly preferred color pigments are white pigments, colored pigments and / or Black pigments used. Examples of white pigments are titanium dioxide, zinc white, zinc sulfide and lithopone. Examples of black pigments are carbon black, iron manganese black and spinel black.
  • colored pigments are chromium oxide, chromium oxide hydrate green, cobalt green, ultramarine green, cobalt blue, ultramarine blue, manganese blue, ultramarine violet, cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red and ultramarine red, iron oxide brown, mixed brown, spinel and corundum phases and chromium orange, iron oxide yellow, nickel titanium yellow, chrome titanium yellow, Cadmium sulfide, cadmium zinc sulfide, chrome yellow and bismuth vanadate.
  • the proportion of the color pigments is preferably in the range from 1.0 to 40.0 wt.%, Preferably 2.0 to 35.0 wt.%, Particularly preferably 5.0 to 30.0 wt on the total weight of the aqueous effect pigment paste.
  • the effect pigment paste according to the invention preferably contains the at least one effect pigment (a) as sole pigment, ie it preferably contains no additional color pigments.
  • the effect pigment paste according to the invention preferably also contains no fillers.
  • the effect pigment paste may optionally contain at least one thickener (also referred to as thickener).
  • thickeners are inorganic thickeners, for example metal silicates such as sheet silicates, and organic thickeners, for example poly (meth) acrylic acid thickeners and / or (meth) acrylic acid (meth) acrylate copolymer thickeners, polyurethane thickeners and polymeric waxes.
  • the metal silicate is preferably selected from the group of smectites.
  • the smectites are particularly preferably selected from the group of montmorillonites and hectorites.
  • the montmorillonites and hectorites are selected from the group consisting of aluminum-magnesium silicates and sodium-magnesium and sodium-magnesium fluorine-lithium phyllosilicates. These inorganic phyllosilicates are marketed, for example, under the trademark Laponite®.
  • Thickeners based on poly (meth) acrylic acid and (meth) acrylic acid (meth) acrylate copolymer thickeners are optionally crosslinked and / or neutralized with a suitable base. Examples of such thickeners are "Alkali Swellable Emulsions" (ASE), and hydrophobically modified variants thereof, the “Hydrophically Modified Alkali Swellable Emulsions" (HASE).
  • these thickeners are anionic.
  • Corresponding products such as Rheovis® AS 1130 are commercially available.
  • Thickener on Base of polyurethanes eg, polyurethane associative thickeners
  • Corresponding products such as Rheovis® PU 1250 are commercially available.
  • suitable polymeric waxes are optionally modified polymeric waxes based on ethylene-vinyl acetate copolymers.
  • a corresponding product is commercially available, for example, under the name Aquatix® 842.
  • the at least one thickener in the effect pigment paste according to the invention is preferably present in an amount of at most 10% by weight, particularly preferably at most 7.5% by weight, very particularly preferably at most 5% by weight, in particular not more than 3% by weight. -%, most preferably of at most 2 wt .-%, each based on the total weight of the effect pigment paste, before.
  • the effect pigment paste according to the invention may contain one or more commonly used additives as further component (s).
  • the effect pigment paste may contain a specific proportion of at least one organic solvent.
  • the effect pigment paste may contain at least one additive selected from the group consisting of reactive diluents, fillers, light stabilizers, antioxidants, deaerating agents, emulsifiers, slip additives, polymerization inhibitors, radical polymerization initiators, adhesion promoters, leveling agents, film-forming aids, sag-control agents (SCAs), Flame retardants, corrosion inhibitors, siccatives, biocides and matting agents. They can be used in the known and customary proportions.
  • their content is from 0.01 to 20.0% by weight, more preferably from 0.05 to 15.0% by weight, particularly preferably from 0.1 to 10.0 % By weight, most preferably from 0.1 to 7.5% by weight, especially from 0.1 to 5.0% by weight and most preferably from 0.1 to 2.5% by weight ,
  • the production of the effect pigment paste according to the invention can be carried out using the mixing methods and mixing units which are customary and known for the preparation of pigment pastes.
  • the effect pigment paste according to the invention is suitable for the production of an aqueous basecoat material.
  • Another object of the present invention is therefore an aqueous basecoat, wherein the basecoat is prepared by admixing at least one effect pigment according to the invention as component (1) to at least one suitable for the preparation of a basecoat aqueous component (2) containing at least one usable as a binder polymer , wherein this polymer which can be used as a binder is the polymer (b) also present in the effect pigment paste and / or at least one polymer which is different therefrom.
  • the proportions in% by weight of all components (1), (2) and water present in the basecoat material according to the invention and further components optionally present in addition add up to 100% by weight, based on the total weight of the basecoat material.
  • the term of the basecoat is known in the art and, for example, defined in Römpp Lexikon, paints and printing inks, Georg Thieme Verlag, 1998, 10th edition, page 57. Under a basecoat is therefore in particular a used in automotive painting and general industrial paint coloring and / or to understand coloring and an optical effect giving intermediate coating material. This is generally applied to a pre-treated with filler or Grundier colller metal or plastic substrate, sometimes even applied directly to the plastic substrate. Even old paints, which may still have to be pretreated (for example, by grinding), can serve as substrates. Meanwhile, it is quite common to apply more than one basecoat. Accordingly, in one In this case, a first basecoat film is the substrate for a second. In order to protect a basecoat film, in particular against environmental influences, at least one additional clearcoat film is applied to it.
  • the component (2) used to prepare the basecoat material according to the invention contains at least one polymer which can be used as a binder, this polymer suitable as a binder being the polymer (b) also present in the effect pigment paste and / or at least one polymer other than this.
  • the polymer which can be used as a binder and contained in component (2) is preferably the polymer (b) also present in the effect pigment paste.
  • the basecoat contains at least one polymer (b) by the use of the effect pigment paste according to the invention for its production.
  • the at least one polymer (b) is preferably the main binder of the basecoat.
  • a binder component is preferably referred to when there is no other binder component in the coating agent such as the base paint, which is present in a higher proportion based on the total weight of the respective coating agent.
  • the term binder has already been defined above with reference to DIN EN ISO 4618 (German version, date: March 2007).
  • the basecoat according to the invention is aqueous. It is preferably a system containing as solvent mainly water, preferably in an amount of at least 20 wt .-%, and organic solvents in minor proportions, preferably in an amount of ⁇ 20 wt .-%, in each case based on the total weight of the basecoat according to the invention.
  • the basecoat material of the invention preferably contains at least 20% by weight, more preferably at least 25% by weight, very preferably at least 30% by weight, in particular at least 35% by weight, based in each case on water the total weight of the basecoat.
  • the basecoat material according to the invention preferably contains an amount of water which ranges from 20 to 65% by weight, more preferably from 25 to 60% by weight, most preferably from 30 to 55% by weight. %, in each case based on the total weight of the basecoat.
  • the basecoat material according to the invention preferably contains a proportion of organic solvents which is in a range of ⁇ 20% by weight, more preferably in a range of 0 to ⁇ 20% by weight, very particularly preferably in a range of 0.5 to ⁇ 20 wt .-% or to 15 wt .-%, in each case based on the total weight of the basecoat.
  • the solids content of the basecoat material according to the invention is preferably in a range from 10 to 45% by weight, more preferably from 1 to 42.5% by weight, very particularly preferably from 12 to 40% by weight, in particular from 13 to 37 , 5% by weight, in each case based on the total weight of the basecoat.
  • the determination of the solids content, ie the non-volatile content, is carried out according to the method described below.
  • the percentage sum of the solids of the basecoat of the invention and the proportion of water in the basecoat of the invention is preferably at least 40% by weight, preferably at least 50% by weight. Preferred among these are ranges from 40 to 95% by weight, in particular 45 or 50 to 90% by weight. Thus, for example, if a basecoat according to the invention has a solids content of 18% by weight and a water content of 25% by weight, the percentage sum of the solids and the proportion of water defined above is 43% by weight.
  • the basecoat material according to the invention preferably contains a proportion of polymer (b) in a range from 1.0 to 20% by weight, particularly preferably from 1.5 to 19% by weight, very particularly preferably from 2.0 to 18.0 Wt .-%, in particular from 2.5 to 17.5 wt .-%, most preferably from 3.0 to 15.0 wt .-%, each based on the total weight of the basecoat.
  • the determination or definition of the proportion of the polymer (b) in the basecoat can be determined by determining the solids content (also called nonvolatile content, Solids content or solids content) of an aqueous dispersion comprising the polymer (b), which is used for the preparation of both the effect pigment paste (component 1) and, if appropriate, for the preparation of component (2).
  • the solids content also called nonvolatile content, Solids content or solids content
  • the basecoat material according to the invention preferably contains a proportion of effect pigment (a) in a range from 1 to 20% by weight, particularly preferably from 1 to 5 to 18% by weight, very particularly preferably from 2 to 16% by weight, in particular from 2.5 to 15 wt .-%, most preferably from 3 to 12 wt .-% or from 3 to 10 wt .-%, each based on the total weight of the basecoat.
  • a proportion of effect pigment (a) in a range from 1 to 20% by weight, particularly preferably from 1 to 5 to 18% by weight, very particularly preferably from 2 to 16% by weight, in particular from 2.5 to 15 wt .-%, most preferably from 3 to 12 wt .-% or from 3 to 10 wt .-%, each based on the total weight of the basecoat.
  • the relative weight ratio of the at least one effect pigment (a) to the polymer (b) in the base coat ranges from 4: 1 to 1: 4, more preferably from 2: 1 to 1: 4, most preferably in a range from 2: 1 to 1: 3, in particular in a range from 1: 1 to 1: 3 or from 1: 1 to 1: 2.5.
  • the novel aqueous basecoat for the preparation of which the effect pigment paste according to the invention is used, preferably contains an aqueous dispersion of the polymer (b) which is introduced into the basecoat at least by admixing the effect pigment paste.
  • the polymer (b) has already been described above.
  • the aqueous basecoat according to the invention comprises at least at least at least one effect pigment, namely at least one effect pigment (a), at least at least by the use of the effect pigment paste according to the invention in its production.
  • Corresponding effect pigments (a) have already been described above.
  • the aqueous basecoat material according to the invention may contain other pigments which differ from the effect pigment (a), namely color pigments. Corresponding pigments have likewise already been described above.
  • these pigments are contained in the component (2) which is used for the preparation of the basecoat.
  • the total amount of all pigments in the basecoat is preferably in the range from 0.5 to 40.0% by weight, more preferably from 2.0 to 20.0% by weight, particularly preferably from 3.0 to 15.0% by weight. -%, in each case based on the total weight of the basecoat.
  • the novel aqueous basecoat preferably also contains at least one polymer other than the polymer (b) as binder, in particular at least one polymer selected from the group consisting of polyurethanes, polyureas, polyesters, poly (meth) acrylates and / or copolymers of said polymers, in particular Polyurethane-poly (meth) acrylates and / or polyurethane-polyureas.
  • this polymer other than the polymer (b) is contained in the component (2) used to prepare the base paint.
  • the component (2) contains no polymer (b), but instead at least one polymer selected from the group consisting of polyurethanes, polyureas, polyesters, poly (meth) acrylates and / or copolymers of said polymers, especially polyurethane Poly (meth) acrylates and / or polyurethane polyureas.
  • Preferred polyurethanes are described, for example, in German patent application DE 99 48 004 A1, page 4, line 19 to page 11, line 29 (polyurethane prepolymer B1), in European patent application EP 0 228 003 A1, page 3, line 24 to page 5, Line 40, European Patent Application EP 0 634 431 A1, page 3, line 38 to page 8, line 9, and international patent application WO 92/15405, page 2, line 35 to page 10, line 32.
  • Preferred polyesters are described, for example, in DE 4009858 A1 in column 6, line 53 to column 7, line 61 and column 10, line 24 to column 13, line 3 or WO 2014/033135 A2, page 2, line 24 to page 7, line 10 and page 28, line 13 to page 29, line 13 described.
  • Preferred polyurethane-poly (meth) acrylate copolymers ((meth) acrylated polyurethanes) and their preparation are described, for example, in WO 91/15528 A1, page 3, line 21 to page 20, line 33 and in DE 4437535 A1, page 2, line 27 to page 6, line 22 described.
  • Preferred polyurethane-polyurea copolymers are polyurethane-polyurea particles, preferably those having an average particle size of 40 to 2000 nm, wherein the polyurethane-polyurea particles, in each case in reacted form, containing at least one isocyanate group-containing polyurethane prepolymer anionic and / or anionic groups and at least one polyamine containing two primary amino groups and one or two secondary amino groups.
  • such copolymers are used in the form of an aqueous dispersion.
  • Such polymers can in principle be prepared by conventional polyaddition of, for example, polyisocyanates with polyols and polyamines. The average particle size of such polyurethane-polyurea particles is determined as described below (measured by dynamic light scattering as described below, see Determination Method 4).
  • the proportion of such polymer (b) of different polymers in the basecoat is preferably smaller than the proportion of the polymer (b) in the basecoat.
  • the polymers described are preferably hydroxy-functional and more preferably have an OH number in the range from 15 to 200 mg KOH / g, more preferably from 20 to 150 mg KOH / g.
  • the basecoats comprise at least one hydroxy-functional polyurethane-poly (meth) acrylate copolymer, more preferably at least one hydroxy-functional polyurethane-poly (meth) acrylate copolymer and at least one hydroxy-functional polyester and optionally a preferably hydroxy-functional polyurethane-polyurea copolymer.
  • the proportion of the further polymers as a binder can vary widely and is preferably in the range from 1.0 to 25.0% by weight, preferably 3.0 to 20.0% by weight, particularly preferably 5.0 to 15.0 Wt .-%, each based on the total weight of the basecoat.
  • the basecoat of the invention may contain at least one typical crosslinking agent known per se. If it contains a crosslinking agent, it is preferably at least one aminoplast resin and / or at least one blocked or free polyisocyanate, preferably an aminoplast resin. Among the aminoplast resins, melamine resins are particularly preferred. If the basecoat contains crosslinking agent, the proportion of these crosslinking agents, in particular aminoplast resins and / or blocked or free polyisocyanates, is particularly preferably aminoplast resins, among them preferably melamine resins, preferably in the range from 0.5 to 20.0 wt.%, preferably 1.0 to 15.0 wt.%, particularly preferably 1.5 to 10.0 wt. in each case based on the total weight of the basecoat. The proportion of crosslinking agent is preferably smaller than the proportion of the polymer (b) in the basecoat.
  • the basecoat according to the invention may contain further optional constituents or optional components. These are the same as mentioned above in connection with the effect pigment paste of the invention further constituents such as color pigments, fillers, thickeners, organic solvents and the abovementioned further additives.
  • the proportion of the color pigments is preferably in the range from 1.0 to 40.0 wt.%, Preferably 2.0 to 35.0 wt.%, Particularly preferably 5.0 to 30.0 wt on the total weight of the aqueous basecoat.
  • the at least one thickener in the basecoat material according to the invention is preferably present in an amount of at most 10% by weight, particularly preferably at most 7.5% by weight, very particularly preferably at most 5% by weight, in particular not more than 3% by weight. -%, most preferably of at most 2 wt .-%, each based on the total weight of the basecoat, before.
  • the content of the at least one further additive, based on the total weight of the basecoat material according to the invention, is preferably 0.01 to 20.0% by weight, more preferably 0.05 to 15.0% by weight, particularly preferably 0, From 1 to 10.0% by weight, very particularly preferably from 0.1 to 7.5% by weight, in particular from 0.1 to 5.0% by weight and most preferably from 0.1 to 2, 5% by weight.
  • the basecoat material according to the invention can be prepared using the mixing methods and mixing units customary and known for the production of basecoats, the effect pigment paste according to the invention being used as admixing component (component (1)).
  • component (1) admixing component
  • the polymer (b) is suitable for dispersing effect pigments within an aqueous effect pigment paste.
  • a further subject of the present invention is a use of the polymer (b) mentioned in connection with the first subject of the present invention for the dispersion of effect pigments within an aqueous effect pigment paste, preferably in an amount thereof of at least 10% by weight. contains, based on the total weight of the effect pigment paste.
  • Another object of the present invention is a process for producing a multi-layer coating (multi-layer coating), in which
  • the basecoat film (s) is cured together with the clearcoat film together, which is characterized in that the basecoat of the invention in step (1 a) or - if the method also comprises steps (1 b) and (2b) - in step (1 a) and / or (1 b), preferably in step (1 b) is used.
  • All of the abovementioned (preferred) statements with regard to the effect pigment paste according to the invention and the aqueous basecoat material according to the invention also apply to the process according to the invention. The process is used to produce effect and color and effect multicoat paint systems.
  • the substrate used in step (1a) preferably has an electrodeposition coating layer (ETL), more preferably an electrodeposition coating applied by cathodic deposition of an electrodeposition coating, and the basecoat used in step (1a) is applied directly to the ETL-coated preferably metallic substrate applied, wherein the applied on the substrate electrodeposition coating layer (ETL) in carrying out the step (1 a) is preferably already cured.
  • ETL electrodeposition coating layer
  • step (4) preferably the metallic substrate coated according to steps (1a) and (2a) on the preferably metallic substrate coated with a preferably cathodic cured electrodeposition coating layer, then the further base layers applied according to steps (1b) and (2b) Basecoat layer, and the in turn according to step (3) applied thereto clearcoat cured together.
  • the application of the aqueous basecoat of the invention is usually carried out on filler or Grundier sympater pretreated metal or plastic substrates.
  • said basecoat can also be applied directly to the plastic substrate.
  • the aqueous basecoat material according to the invention can preferably also be carried out without prior coating of the substrate, in particular a metal substrate, with a filler or primer filler.
  • the process according to the invention preferably contains stages (1b) and (2b), ie at least two basecoat films applied, wherein the basecoat according to the invention within the steps (1 a) and / or (1 b), more preferably only within the stage (1 b) is used.
  • the metal substrate used is preferably coated with a cured electrodeposition coating layer.
  • a metal substrate is to be coated, it is preferably coated with an electrodeposition coating prior to the application of the filler or primer filler or of the aqueous basecoat material according to the invention.
  • a plastic substrate is coated, it is preferably pretreated before the application of the filler or primer filler or of the aqueous basecoat material according to the invention.
  • the most commonly used methods are flaming, plasma treatment and corona discharge. Preferably, the flaming is used.
  • the application of the aqueous basecoat materials or basecoats according to the invention to a metal substrate can take place in the layer thicknesses customary in the automotive industry in the range of, for example, 5 to 100 micrometers, preferably 5 to 60 micrometers, particularly preferably 5 to 30 micrometers.
  • spray application methods are used, such as compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot air hot spraying.
  • aqueous basecoat or the aqueous basecoats After the application of the aqueous basecoat or the aqueous basecoats, this or these can be dried by known methods.
  • (1-component) basecoats which are preferred, may be flashed off at room temperature (23 ° C) for 1 to 60 minutes, and subsequently preferably dried at optionally slightly elevated temperatures of 30 to 90 ° C.
  • flash drying and drying is understood to mean evaporation of organic solvents and / or water, as a result of which the paint is drier but not yet cured, or a completely crosslinked paint film is not yet formed.
  • a commercially available clearcoat is also applied according to common methods, the layer thicknesses again being in the usual ranges, for example 5 to 00 micrometers.
  • the clearcoat After application of the clearcoat this can be flashed off at room temperature (23 ° C) for example, 1 to 60 minutes and optionally dried. Then the clearcoat is cured together with the applied basecoat. In this case, for example, crosslinking reactions take place, whereby an inventive effect and / or color and effect multilayer coating is prepared on a substrate.
  • the curing is preferably carried out thermally at temperatures of 60 to 200 ° C.
  • the coating of plastic substrates is basically analogous to that of metal substrates. However, it is generally cured at much lower temperatures of 30 to 90 ° C here. Preference is therefore given to the use of two-component clearcoats.
  • the said substrate of step (1a) may also be a multi-layer coating which has defects.
  • This multi-layer substrate coating which has defects, so it is an original finish, which is to be repaired or completely overpainted.
  • the inventive method is therefore suitable for repairing defects on multi-layer coatings.
  • Defects or film defects are generally termed disturbances on and in the coating, which are usually named according to their shape or appearance.
  • a variety of possible types of such film defects are known to those skilled in the art. These are described, for example, in Rompp-Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 235, "film defects". Positioning methods
  • the non-volatile content (of the solid) is determined according to DIN EN ISO 3251 (date: June 2008). In this case, 1 g of sample are weighed into a previously dried aluminum dish and dried for 60 minutes at 125 ° C in a drying oven, cooled in a desiccator, and then weighed back. The residue based on the total amount of the sample used corresponds to the non-volatile fraction.
  • the solubility of the monomers in water is determined by equilibrium with the gas space above the aqueous phase (analogous to the literature X.- S. Chai, QX Hou, FJ Schork, Journal of Applied Polymer Science Vol. 99, 1296-1301 (2006) ).
  • a 20 ml Gasraumprobenrschreibchen given to a defined volume of water such as 2 ml such a large mass of the respective monomer that this mass can not solve completely in any case in the selected volume of water.
  • an emulsifier (10 ppm, based on the total mass of the sample mixture) is added. In order to maintain the equilibrium concentration, the mixture is shaken constantly.
  • the supernatant gas phase is exchanged for inert gas, so that sets an equilibrium again.
  • the proportion of the substance to be detected is measured in the withdrawn gas phase (for example by means of gas chromatography).
  • the equilibrium concentration in water can be determined by graphically evaluating the proportion of monomer in the gas phase. The slope of the curve changes from a nearly constant value (S1) to a significantly negative slope (S2) as soon as the excess monomer content has been removed from the mixture.
  • the equilibrium concentration is reached at the intersection of the straight line with the slope S1 and the straight line with the slope S2.
  • the described determination is carried out at 25 ° C. 3. Determination of the glass transition temperatures of polymers obtainable in each case from monomers of the mixtures (A), (B) or (C)
  • the glass transition temperature T g is determined experimentally on the basis of DIN 51005 (Date: August 2005) "Thermal Analysis (TA) - Terms” and DIN 53765 “Thermal Analysis - Differential Scanning Calorimetry (DDK)” (date: March 1994). A sample of 15 mg is weighed into a sample pan and introduced into a DSC instrument.
  • the known Fox equation can be used for a purposeful estimation of the glass transition temperature expected during the measurement. Since the Fox equation is a good approximation, based on the glass transition temperatures of the homopolymers and their parts by weight without including the molecular weight, it can be used as a useful tool for those skilled in the synthesis, so that a desired glass transition temperature can be adjusted via a few targeted experiments ,
  • the mean particle size is determined by means of dynamic light scattering (photon correlation spectroscopy) (PCS) in accordance with DIN ISO 13321 (date: October 2004).
  • PCS dynamic light scattering
  • a "Malvern Nano S90" (Malvern Instruments) is used at 25 ⁇ 1 ° C.
  • the device covers a size range of 3 to 3000 nm and is equipped with a 4mW He-Ne laser at 633 nm respective samples are diluted with particle-free, deionized water as a dispersion medium and then measured in a 1 ml polystyrene cuvette with a suitable scattering intensity.
  • the evaluation was carried out by means of a digital correlator with the aid of the evaluation software Zetasizer Ver.
  • the average particle size means the arithmetic number average of the measured mean particle diameter (Z-average). The standard deviation of a 5-fold determination is ⁇ 4%.
  • the average particle size is understood to mean the arithmetic volume average of the average particle size of the individual preparations (V average). The maximum deviation of the volume average of five individual measurements is ⁇ 15%. The verification is carried out with polystyrene standards with certified particle sizes between 50 to 3000 nm.
  • the number-average molecular weight (M n ) is determined by means of a steam pressure osmometer type 10.00 in concentration series in toluene at 50 ° C. with benzophenone as calibration substance to determine the experimental calibration constant of the measuring device used according to E. Schröder, G Müller, K.-F. Arndt, "Guidelines of Polymer Characterization", Akademie-Verlag, Berlin, pp. 47-54, 1982.
  • the layer thicknesses are determined in accordance with DIN EN ISO 2808 (date: May 2007), method 12A using the measuring instrument MiniTest® 3100-4100 from ElektroPhysik.
  • the sample to be examined is applied to a filler coated steel sheet of dimensions 32 ⁇ 60 cm by means of a double electrostatic application, like a coating composition, in particular as a water-based lacquer applied, that a total layer thickness (dry film thickness) of 12-17 pm results.
  • a double electrostatic application like a coating composition, in particular as a water-based lacquer applied, that a total layer thickness (dry film thickness) of 12-17 pm results.
  • a further electrostatic application step is carried out, the resulting aqueous basecoat layer flashed for 10 minutes at room temperature and then dried in a convection oven for a further 10 minutes at 80 ° C.
  • a commercially available two-component clearcoat material (ProGloss® from BASF Coatings GmbH) having a dry film thickness of 40-45 ⁇ m is applied to the dried aqueous basecoat film.
  • the resulting clearcoat is flashed off for 10 minutes at room temperature. This is followed by curing in a convection oven at 40 ° C for a further 20 minutes.
  • the corresponding coated substrate is measured using a spectrophotometer from X-Rite (X-Rite MA68 Multi-Angle Spectrophotometer). The surface is illuminated with a light source. At different angles, a spectral detection is performed in the visible range.
  • Color values in the CIEL * a * b * color space can be calculated from the spectral measured values thus obtained, including the standard spectral values and the reflection spectrum of the light source used, where L * is the brightness, a * the red-green value and b * den Characterize yellow-blue value.
  • L * is the brightness
  • a * the red-green value
  • b * den Characterize yellow-blue value.
  • This process is described, for example, in ASTM E2194-12, in particular for coatings containing at least one effect pigment pigment.
  • the derived value often used for the quantification of the so-called metallic effect is the so-called flop index, which describes the dependence of the brightness on the observation angle (compare ABJ Rodriguez, JOCCA, 1992 (4), pp. 150-153). From the determined brightness values for the viewing angles 15 °, 45 ° and 110 °, the so-called flop index (FL) can be calculated according to the formula
  • multicoat paint systems are prepared according to the following general procedure:
  • the sample to be examined is applied as a water-based paint using a double pneumatic order, so that a total layer thickness (dry film thickness) of 22 -26 pm.
  • a 3-minute flash-off time takes place at room temperature (23 ° C) between the first and second pneumatic application.
  • the resulting aqueous basecoat film is then dried after renewed flash off at room temperature for 5 minutes in a convection oven for 10 minutes at 70 ° C.
  • a commercially available two-component clearcoat material (ProGloss from BASF Coatings GmbH) having a target layer thickness of 40-45 ⁇ m is applied to the dried aqueous basecoat.
  • the resulting clearcoat is flashed off for 10 minutes at room temperature. This is followed by curing in a circulating air oven at 140 ° C. for a further 20 minutes.
  • the structure to be obtained in this way is referred to below as the original finish (structure a).
  • the curing of the basecoat and clearcoat film at 20 minutes / 125 ° C hereinafter referred to as underbaked original paint, build b) or at 30 minutes / 160 ° C (hereinafter referred to as overburned original paint, build c) is performed.
  • Structure A is a refinish on Structure a, in which the second basecoat and clearcoat layer is cured at 140 ° C for 20 minutes.
  • Structure B refers to a refinish on build b in which the corresponding cure of the second basecoat and clearcoat layers is performed at 20 minutes / 125 ° C ,
  • the coated substrates are stored for a period of 10 days in a climate chamber according to test climate CH according to DIN EN ISO 6270-2 (date: September 2005). The coated substrates are then subjected to the appropriate tests 24 hours after removal from the climatic chamber.
  • KW2 clearly visible leaching of the existing damage in a lacquer layer
  • KW3 complete softening of a lacquer layer in the area of the jet plate
  • KW4 complete softening of a lacquer layer beyond the beam area
  • KW5 detachment of the complete lacquer layer to the substrate
  • the characteristic "distinctness of imgage" (DOI) is determined with the aid of the measuring device (the higher the value, the better the appearance.)
  • DOI characteristic "distinctness of imgage”
  • the corresponding tests were carried out on the unloaded samples
  • the coated substrates are stored for a period of 10 days in a climatic chamber according to test climate CH according to DIN EN ISO 6270-2 (date: September 2005), after which the coated substrates are removed from the climatic chamber 24 hours after removal the ripple is assessed and the samples are visually examined for swelling and blistering.
  • the number of bubbles is rated by a quantity of 1 to 5, with m1 very few and m5 very many bubbles are called.
  • the size of the bubbles is also rated by a size of 1 to 5, where with gl very small and g5 very large bubbles are called.
  • multicoat paint systems are produced in accordance with the following general specification based on DIN EN ISO 28199-1 (date: January 2010) and DIN EN ISO 28199-3 (date: January 2010):
  • the resulting layer is dried without previous flash-off in a convection oven for 5 minutes at 80 ° C.
  • the determination of the digester limit, i. the layer thickness above which the digesters occur is in accordance with DIN EN ISO 28199-3, point 5.
  • the storage stability 100 ml of the sample to be examined are filled into a measuring cup like an effect pigment-containing paste. After 2 weeks of storage at room temperature (23 ° C), the corresponding sample is visually evaluated for possible settling of the pigments and potential formation of supernatant serum. In the case of the presence of a serum phase, the volume of the serum is read and reported as a percentage of the total volume of the sample. The sample is filtered after the storage described above using a standard plastic sieve with a mesh size of 270 pm and the filter cake was examined for settling.
  • reaction mixture is cooled to 60 ° C and the neutralization mixture (Table 1 .1, positions 20, 21 and 22) premixed in a separate vessel.
  • the neutralization mixture is added dropwise to the reactor within 40 minutes, the pH of the reaction solution being adjusted to a pH of 7.5 to 8.5. Subsequently, the reaction product is stirred for a further 30 min, cooled to 25 ° C and filtered.
  • Table 1 .2 Key data of the aqueous dispersion AD1 or of the polymer containing
  • the dissolution of diethylenetriaminediketimine in methyl isobutyl ketone was previously determined by azeotropic removal of water of reaction in the reaction of diethylenetriamine (BASF SE) with methyl isobutyl ketone in methyl isobutyl ketone at 110-1040 ° C. Dilution with methyl isobutyl ketone was adjusted to an amine equivalent mass (solution) of 124.0 g / eq. By means of IR spectroscopy, based on the residual absorption at 3310 cm-1, a blocking of the primary amino groups of 98.5% was determined. The solids content of the isocyanate group-containing polymer solution was determined to be 45.3%.
  • Solids content (130 ° C, 60 min, 1 g): 40.2% by weight
  • aqueous dispersion AD1 47.0 parts by weight of aqueous dispersion AD1, 41, 2 parts by weight of deionized water, 6 parts by weight of 2,4,7,9-tetramethyl-5-decynediol, 52% in butylglycol (available from BASF SE), 2.5 parts by weight of Dispex Ultra FA 4437 (available from BASF SE), 1, 5 parts by weight of Rheovis® AS 1 130 (available from BASF SE) and 1.8 parts by weight of 10% dimethylethanolamine in water are mixed together and the resulting mixture is subsequently homogenized.
  • the white paste is made from 33.4 parts by weight of titanium rutile Tayca MT500 HD (available from Tayca Corporation), 52.6 parts by weight of one made according to WO 91/15528 A1, p. 23, line 26 to page 24, reference 24 aqueous binder dispersion, 2.5 parts by weight of Disperbyk®-184 (available from BYK-Chemie GmbH), 2.7 parts by weight of 1-propoxy-2-propanol and 8.8 parts by weight of deionized water.
  • the red paste is prepared from 12 parts by weight of Sicotrans Red L 2818 (available from BASF SE), 49.7 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528 A1, p. 23, line 26 to page 24, line 24, 2 Parts by weight of butylglycol, 1 part by weight of 10% dimethylethanolamine in water, 2 parts by weight of Disperbyk®-184 (available from BYK-Chemie GmbH), 3 parts by weight of a commercial polyether (Pluriol® P900, available from BASF SE) and 30.3 parts by weight of deionized water ,
  • the black paste is composed of 58.9 parts by weight of a polyurethane dispersion prepared in accordance with WO 92/15405, page 14, line 13 to page 15, line 13, 10.1 parts by weight of carbon black (Color Black FW2 from Orion Engineered Carbons) Parts by weight of a polyester prepared according to Example D, column 16, Z. 37-59 of DE 40 09 858 A1, 7.8 parts by weight of a 10% aqueous dimethylethanolamine solution, 2.2 parts by weight of a commercially available polyether (Pluriol® P900 available BASF SE), 7.6 parts by weight of butyl diglycol and 8.4 parts by weight of deionized water. 5. Preparation of effect pigment pastes
  • the components listed in Tables 5.1 to 5.6 are combined in the order given and stirred for at least 20 minutes until a homogeneous mixture results.
  • the stirring is preferably carried out in such a way that a tone-like flow pattern is established, ie. a so-called donut effect (donut effect) is observed.
  • the effect pigment pastes are also referred to below as effect pigment blends.
  • aqueous phase in Table 6.1 are stirred together in the order given to form an aqueous mixture, and in the next step, a premix is prepared from the components listed under "Effect Pigment Premix”. This premix is added to the aqueous mixture.
  • aqueous phase in Table 6.2 are stirred together in the stated order to form an aqueous mixture, and in the next step, a premix is prepared from the components listed under "Effect Pigment Premix”. This premix is added to the aqueous mixture.
  • the mixture is then stirred for 10 minutes and brought to a pH of 8 and an injection viscosity of 85 ⁇ 5 mPa ⁇ s (WBL7 - WBL9) or 1 15 ⁇ 5 mPa ⁇ s (WBL10 - WBL12) using deionized water and dimethylethanolamine a shear load of 1000 s "1 , measured with a rotary viscometer (device Rheolab QC with tempering system C-LTD80 / QC Anton Paar) at 23 ° C, adjusted.
  • aqueous phase in Tables 6.3 to 6.6 are each stirred together in the stated sequence to form an aqueous mixture
  • a premix is prepared in each case from the components listed under "Effect pigment premix”.
  • the appropriate premix is added to the respective aqueous mixture.
  • the mixture is then stirred for 10 minutes and with the aid of deionized water and dimethylethanolamine to a pH value of 8 and a spray viscosity of 75 ⁇ 5 mPa-s at a shear stress of 1000 s "1 , measured with a rotary viscometer (Rheolab QC apparatus with Temperature control system C-LTD80 / QC Anton Paar) at 23 ° C, set.
  • Table 6.5 Preparation of waterborne basecoats WBL23 to WBL25 (not according to the invention) and WBL26 and WBL2 (according to the invention)
  • aqueous phase in Table 6.7 are stirred together in the order indicated to form an aqueous mixture,
  • a premix is added in each case from the components listed under "Effect Pigment Premix I” or "Effect Pigment Premix II”
  • These premixes are then each added to the aqueous mixture, which is stirred for 10 minutes and measured with the aid of deionized water and dimethylethanolamine to a pH of 8 and an injection viscosity of 80 ⁇ 5 mPa.s at a shear stress of 1000 s ' with a rotation s- viscometer (device Rheolab QC with tempering C-LTD80 / QC Anton Paar) at 23 ° C, adjusted.
  • WBL34a and WBL34b were carried out analogously to WBL34:
  • the components listed under "aqueous phase" in Table 6.8 are stirred together to give an aqueous mixture in the order indicated
  • Each premix is then added to the aqueous mixture, stirred for 10 minutes, and adjusted to pH 8 and injection viscosity of 80 ⁇ with the aid of deionized water and dimethylethanolamine 5 mPa-s at a shear stress of 1000 s measured with a rotary viscometer (Rheolab QC device with temperature control C-LTD80 / QC Anton Paar) at 23 ° C, adjusted.
  • Aqueous phase Aqueous phase:
  • Aqueous binder dispersion AD1 Aqueous binder dispersion AD1
  • the effect pigment masterbatches based on the ML5 and ML7 mixed paints according to the invention (which are used to prepare AS4-AS5, AS9-10, AS14-15) have excellent storage stability.
  • An effect pigment masterbatch by means of a polyester resin and butylglycol or by means of the non-inventive mixing lacquer ML1 (prepared in accordance with the patent EP 1 799 783 B1), on the other hand, exhibited partly drastic serum formation, depending on the pigment used.
  • iron oxide-coated aluminum pigments for example those available under the trade name Paliocrom® from BASF SE, can be processed to a stable premix with the aid of the ML6 blend according to the invention which, even after filtration, does not leave residues such as e.g. Pigment agglomerates as a result of insufficient stabilization.
  • Cooker limit 28 ⁇ 30 ⁇ 28 ⁇
  • inventive blending paint L3 in comparison to the prior art, i. in comparison to a premix of the pigments in a polyester resin in combination with butylglycol (WBL1 and WBL4) or with the mixing varnish L2, prepared in accordance with the patent EP 1 534 792 B1, column 11, line 1 -13 (WBL2 and WBL5 ), results in terms of the flop in each case to comparable results. Also, the cooker sensitivity is not adversely affected by the ML3 mica used to make WBL3 and WBL6.

Abstract

La présente invention concerne une pâte de pigment à effet aqueuse comprenant au moins un pigment à effet (a) et au moins un polymère (b) qui peut être produit par polymérisation en émulsion radicalaire successive de trois mélanges de monomères oléfiniquement insaturés (A), (B) et (C) dans l'eau. Elle concerne également une peinture de base aqueuse, qui peut être fabriquée par mélange de la pâte de pigment à effet avec au moins un composant aqueux contenant un liant, approprié pour la fabrication de la peinture de base, un procédé de réalisation d'une peinture multicouche au moyen de ladite peinture de base, ainsi qu'une utilisation du polymère (b) pour la dispersion de pigments à effet dans une pâte de pigment à effet aqueuse.
EP18711380.8A 2017-03-23 2018-03-22 Pâtes aqueuses de pigments à effet contenant un polymère et peintures de base produites à partir de ces pâtes Withdrawn EP3601455A1 (fr)

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EP17162526 2017-03-23
PCT/EP2018/057342 WO2018172475A1 (fr) 2017-03-23 2018-03-22 Pâtes aqueuses de pigments à effet contenant un polymère et peintures de base produites à partir de ces pâtes

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MX2019000828A (es) 2016-07-20 2019-05-23 Basf Coatings Gmbh Sistema de mezclado para producir composiciones de acabado acuoso, metodo para producirlas y composiciones de acabado acuoso producidas a partir de un sistema de mezclado.
EP3487702B1 (fr) 2016-07-20 2020-09-09 BASF Coatings GmbH Dispersions aqueuses contenant des produits de polymerisation multicouches contenant des polyurethanes et compositions d'agent de revetement les contenant
JP7143318B2 (ja) * 2017-03-23 2022-09-28 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング ポリマーを含む水性着色顔料ペースト、およびそれから製造されるベースコート
EP3914653B1 (fr) * 2019-01-23 2023-11-22 BASF Coatings GmbH Agent de revêtement aqueux contenant de l'acide polycarbonique à alignement amélioré des pigments à effet
WO2023117951A1 (fr) 2021-12-21 2023-06-29 Basf Se Appareil de génération d'un élément d'accès numérique

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CN110446762B (zh) 2023-05-26
CN110446762A (zh) 2019-11-12
WO2018172475A1 (fr) 2018-09-27
CA3053703A1 (fr) 2018-09-27
US20200102462A1 (en) 2020-04-02

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