CN101085899A - Coating compositions based on universal pigment preparations - Google Patents

Coating compositions based on universal pigment preparations Download PDF

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Publication number
CN101085899A
CN101085899A CNA2007101102661A CN200710110266A CN101085899A CN 101085899 A CN101085899 A CN 101085899A CN A2007101102661 A CNA2007101102661 A CN A2007101102661A CN 200710110266 A CN200710110266 A CN 200710110266A CN 101085899 A CN101085899 A CN 101085899A
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weight
component
coating composition
ketone
aforementioned
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A·温宁
D·洛斯特
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Evonik Operations GmbH
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Degussa GmbH
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D161/00Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/02Condensation polymers of aldehydes or ketones only
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D17/00Pigment pastes, e.g. for mixing in paints
    • C09D17/003Pigment pastes, e.g. for mixing in paints containing an organic pigment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D17/00Pigment pastes, e.g. for mixing in paints
    • C09D17/004Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/005Carbon black
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D201/00Coating compositions based on unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02Emulsion paints including aerosols
    • C09D5/024Emulsion paints including aerosols characterised by the additives
    • C09D5/028Pigments; Filters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02Polyalkylene oxides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to coating compositions comprising at least one solvent-containing binder, an aqueous universal pigment preparation and, if appropriate, auxiliaries and additives and their use as paints, varnishes, adhesives or printing inks.

Description

Coating composition based on universal pigment preparation
Technical field
The present invention relates to contain solvent cement, waterborne general pigment preparation by at least a, and the coating composition of auxiliary agent optionally and additive.
Background technology
Coating composition can be used as colorant (Farbe), paint vehicle (Lack), tackiness agent, printing ink or printing-ink, is used to apply the object that is for example prepared by metal or plastics.Described coating composition is applicable to all conventional applying methods that adopt in modern washing and plastic coat and the printing-ink industry, the printing of for example spraying, electrostatic spraying and the various printing processes of employing.
Typically by preparing pigment preparation earlier, then the mode with former lacquer (Stammlack) coating (auflacken) prepares Color paint.
In liquid medium, disperse filler and pigment during the preparation pigment preparation.This adopts dispersion agent to implement usually, thereby makes solid effectively disperse the mechanical shear stress of needs with reduction, realizes high as far as possible fill level simultaneously.Dispersion agent has promoted the decomposition of aggregate, and surface wetting as surface active cpd and/or that dispersed particle is treated in covering, makes these particle-stabilisedization to avoid disadvantageous reagglomeration.
In the production of colorant and paint vehicle, wetting agent and dispersion agent have promoted the introducing of pigment and filler, and it has determined the visual appearance and the physicochemical property of coating substantially as important recipe ingredient.For realizing its best applications, these solids must be dispersed in paint vehicle and the colorant on the one hand, in case dispersed obtains then must be stable on the other hand.In many cases, the function of stabilization component also can realize by binder ingredients.Because this class tackiness agent is to the contribution of faster drying and the increase of film former hardness, they also are the important component of coating.
For solvent-laden coating, serve as the solvent-laden pigment preparation of basis preparation with various wetting agents and dispersion agent usually, itself and the various former lacquer of solvent that contains apply.For water-borne coatings, serve as basis preparation aqueous pigment preparations also usually with various wetting agents and dispersion agent, it applies with the former lacquer of different water-baseds.
For fear of owing to preparing and storing expensive that a large amount of pigment preparations cause, obtain general pigment preparation and expect.
Comprise for the important parameter of in universal pigment preparation, using, at first, with the general consistency of other tackiness agent, for example with the consistency of important long oil alkyd, vegetables oil, hydrocarbon resin, acrylate resin and polymeric amide; Secondly, the general solvability in organic solvent, for example based on environmentalism and toxicology viewpoint adopt usually at petroleum solvent and pure aliphatic cpd.Have general consistency and deliquescent tackiness agent that this class can be used in the pigment preparation for example are recorded among the DE 4404809.
Dispersion agent as universal pigment preparation uses ethoxylated alkylphenol or alkoxy fatty alcohols especially, and it helps the spatial stability of the pigment dispersion phase that obtained.A large amount of criticisms of adopting ethoxylated alkylphenol to be subjected to the environmental toxicology aspect.Its application in washing composition and cleaning product is under an embargo in many countries.Paint and printing ink industry are estimated also similar ban can occur.Alkoxy fatty alcohols can not obtain and the same good pigment wettability of ethoxylated alkylphenol in many cases owing to lack adsorption group.The not absorbed portion of these product types has extra detrimental action for foam stabilization especially in aqueous pigment preparations.
The polyalkylene oxide of block copolymerization is no problem on toxicology, and has high absorbability, but has lower foam stabilizing action.It for example is recorded among the EP 1078946.Yet these products can not obtain foam inhibition completely.Therefore, must add active froth breaking material in hydrotropisms's pigment preparation at this.But these materials have other adverse side effect, for example unfavorable surface imperfection.Because its disadvantageous effect for water-resistant coating and light stability, many dispersing additives can not use.
PCT/EP2006/050437 has described the pigment preparation based on the polyalkylene oxide that contains Styrene oxide 98min. of block copolymerization and ketone-urea formaldehyde combination, it has the extensive consistency with the tackiness agent that uses, with in organic solvent that uses and the solvability in the water, foamy forms and is suppressed in aqueous pigment preparations.Be very suitable for producing the solvent that contains coatings volatile organic compounds and use suitable for example ethylene glycol if this class contains the solvent pigment preparation, also be suitable for producing water-borne coatings.In addition, PCT/EP2006/050437 has described aqueous pigment preparations and has possessed application in the water-based coating of outstanding performance in production.
Summary of the invention
Therefore, one object of the present invention is to find coating composition, its can by use contain solvent painted or not the universal pigment preparation production allocated of chromogen lacquer and water-based.
Like this, can be by the known good technique performance using aqueous pigment preparations to make to contain solvent cement environmental friendliness more.
Astoundingly, the waterborne general pigment preparation of combination, pigment and water by using the polyalkylene oxide that contains Styrene oxide 98min. comprise block copolymerization basically and ketone-urea formaldehyde can be realized the purpose as basis of the present invention.
Astoundingly, have been found that the waterborne general pigment preparation of the combination, pigment and the water that in containing solvent, the painted or former lacquer of non-staining, use the polyalkylene oxide that contains Styrene oxide 98min. that comprises block copolymerization basically and ketone-urea formaldehyde, obtained stable coating system.
Theme of the present invention is a coating composition, and it comprises substantially:
A) at least a former lacquer of solvent that contains of 50 weight %-99 weight %, it comprises at least a tackiness agent, at least a solvent, optionally at least a tinting material, optionally at least a filler and auxiliary agent optionally and additive substantially,
B) the waterborne general pigment preparation of 1 weight %-50 weight %, it comprises the mix products of following component substantially:
I) polyalkylene oxide that contains Styrene oxide 98min. of at least a block copolymerization of 95 weight %-5 weight %,
With
Ii) not hydrogenation ketone-urea formaldehyde of 5 weight %-95 weight %,
And
The iii) at least a solvent of 0 weight %-80 weight %,
Component i wherein)-iii) weight part sum is 100 weight %,
With
Iv) tinting material
With
V) filler
With
Vi) auxiliary agent and the additive of 0 weight %-10 weight %,
Based on every kind of component iv) with component weight v) and, component i), component ii) with component iii) the amount of sum be 2 weight %-95 weight %, component amount v) also can be 0 weight % in pigment preparation,
C) auxiliary agent and the additive of 0 weight %-10 weight %.
The waterborne general pigment preparation with contain solvent painted or not chromogen lacquer be combined in not record among the PCT/EP2006/050437.
Since for example the organic solvent of aromatic substance can not with water compatible, therefore for a person skilled in the art, it is fully beyond expectation that this coating composition has satisfactory stability.
As component A) preferred drawing together to the former enamel-cover of wherein introducing pigment preparation of the present invention well known to a person skilled in the art that all contain solvent system.In a component (1K) or two components (2K) paint vehicle, these systems are physical dryness, oxidation drying or reactive dry with other approach for example.
Suitable tackiness agent comprises multiple physical dryness resin, example is nitrocotton, polyvinyl butyral acetal, VC multipolymer, acrylate, methacrylic ester, cellulose ester, ether of cellulose, hydrocarbon resin, resol, Gum Rosin, maleic acid resin, polystyrene resin, silicone resin, based on the varnish resin of rubber for example thermoprene, chlorinated rubber, chlorinatedpolyolefins or low polyhutadiene, polyolefine, polyvinylesters, polyvinyl alcohol, polyvinyl acetal, epoxide, aminoresin, acyl ammonia resin and vibrin.The example of oxidation drying coating comprises Synolac.1K coating is based on for example (methyl) acrylate resin, Resins, epoxy, polyvinyl acetate resins, vibrin or urethane resin.These resins can be undersaturated, promptly contain acrylate or methacrylic ester two key, for example (methyl) acrylate resin of (methyl) acroleic acid esterification, epoxy (methyl) acrylate resin, polyester (methyl) acrylate resin, polyethers (methyl) acrylate resin or urethane (methyl) acrylate resins.Suitable 1K coating also comprises based on having as those of the hydroxyl polyacrylate resin of the melamine resin of linking agent or block polyisocyanate or vibrin.The example of spendable 2K coating is for based on having polyepoxide system or the hydroxyl polyacrylate resin of non-block polyisocyanate as linking agent, or those of vibrin.
As B component) the waterborne general pigment preparation that uses comprises the polyalkylene oxide i that contains Styrene oxide 98min. as at least a block copolymerization of wetting agent and dispersion agent) and at least a ketone-urea formaldehyde is ii).The polyalkylene oxide that contains Styrene oxide 98min. of all block copolymerizations all is suitable for as component i in principle).
The polyalkylene oxide B that contains Styrene oxide 98min. of the block copolymerization that the present invention preferably uses) i) for example is recorded among the EP 1078946.It has general formula I:
R 1O(SO) a(EO) b(PO) c(BO) dR 2
R wherein 1Be straight chain or branching or alicyclic group with 8-13 carbon atom,
R 2Be hydrogen or aryl, alkyl or the hydroxy-acid group that all has 1-8 carbon atom,
The SO=Styrene oxide 98min.,
EO=oxyethane.
The PO=propylene oxide,
The BO=butylene oxide ring and
a=1-1.9,
b=3-50,
c=0-3,
d=0-3,
Wherein a, c or d are not 0, b>=a+c+d.
In principle all not hydrogenation ketone-urea formaldehyde all be suitable for as B component) ii).
As the preparation B component) ii) ketone can use all known ketone.Described ketone is the ketone with aliphatic series, alicyclic, aromatic hydrocarbyl, and wherein above-mentioned group can be identical or different and can and then be replaced and optionally also comprise phenol and/or urea or derivatives thereof by described alkyl on hydrocarbon chain.The example of spendable ketone comprise acetone, methyl phenyl ketone, methylethylketone, heptan-2-ketone, penta-3-ketone, methyl iso-butyl ketone (MIBK), pimelinketone, 4-tert-pentyl pimelinketone, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone, 3,3,5-trimethylcyclohexanone, cyclopentanone, 2,2,4-and 2,4, mixture, suberone, cyclooctanone and the cyclododecanone of 4-trimethylammonium cyclopentanone.
Preferably be recorded in the not hydrogenation ketone-urea formaldehyde B among the DE 4404809) ii) by alicyclic ketone, aldehyde and other monomer preparation optionally.
These not hydrogenation ketone-urea formaldehyde preferably comprise:
I. based on the ketone of all employings, at least a alkyl substituted cyclohexanone of 40-100mol% with alkyl of one or more 1-8 carbon atom,
II. based on the ketone of 1 mole of all employing, at least a aliphatic aldehyde of 0.8-2.0mol and
III. based on the ketone of all employings, having of 0-60mol% is aliphatic, alicyclic, other ketone of aromatic hydrocarbyl, and it can be identical or different, and can and then replace and optionally also comprise phenol and/or urea or derivatives thereof with above-mentioned alkyl on hydrocarbon chain.
Can mention 4-tert-pentyl pimelinketone, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone as the example of alkyl substituted cyclohexanone.Particularly preferred C1-C8 alkyl substituted cyclohexanone is 4-tertiary butyl pimelinketone and 3,3, the 5-trimethylcyclohexanone.
Straight or branched aldehyde is suitable as the aldehyde component usually and is particularly suitable as component I I in principle, for example is formaldehyde, acetaldehyde, butyraldehyde-n and/or isobutyric aldehyde, valeral and lauric aldehyde etc., use separately or with form of mixtures, but formaldehyde is preferred.Yet can use usually and be applicable to all aldehyde of ketone resin synthetic described in the document.
Preferred formaldehyde typically uses with the water or alcoholic solution (for example in methyl alcohol or the butanols) form of about 20%-40% weight concentration.Other type of service of formaldehyde also is feasible, for example uses as paraformaldehyde or three  alkane.For example the aromatic aldehyde of phenyl aldehyde also can be included in the mixture with formaldehyde.The water or the alcoholic solution of preferred formaldehyde.
What be suitable for the ketone component III is all ketone, be especially acetone, methyl phenyl ketone, methylethylketone, heptan-2-ketone, penta-3-ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, pimelinketone, cyclododecanone, 2,2,4-and 2,4, mixture, suberone and the cyclooctanone of 4-trimethylammonium cyclopentanone.Preferred methyl phenyl ketone and pimelinketone.
The polyalkylene oxide that contains Styrene oxide 98min. of block copolymerization used according to the invention and the ratio of mixture of ketone-urea formaldehyde are 95: 5-5: 95.If the ketone-urea formaldehyde that uses in this mixture surpasses 50 weight %, then owing to the viscosity reason must be used secondary solvent B) iii).
Owing to be the waterborne general pigment preparation, mainly make water as B component) iii).In addition, also can use a small amount of organic solvent.Organic solvent can be enumerated for example alcohol, ester, ketone, ether, glycol ether, aromatic hydrocarbon, hydrogenation aromatic hydrocarbon, halohydrocarbon, terpene hydrocarbon, aliphatic hydrocrbon, ester alcohol, dimethyl formamide or methyl-sulphoxide.
At component A) in and/or as B component iv), can use pigment and/or dyestuff as tinting material.For example can use organic or inorganic pigment and carbon black as pigment.
As exemplary titanium dioxide and the ferric oxide mentioned of mineral dye.
Admissible pigment dyestuff for example is azo pigment, metal complex pigment, anthraquinone pigment, phthalocyanine pigment, many ring pigment, particularly thioindigo, quinoline a word used for translation ketone, two  piperazines, pyrrolo-, naphthalene tetracarboxylic acid, perylene, Isoamidolin (on), flavanthrone, pyranthrone or isoviolanthrone series.
Spendable carbon black is channel black, flame black or furnace black.These carbon blacks can reoxidize extraly and/or become drip (verperln).
The dyestuff that dissolves in binder solution as using can adopt all natural or synthetic organic dyes.Has best transparency with its dyeing that obtains.Compare with pigment, its colour strength can all be utilized.
Natural dyestuff is an animal dyes, for example carminum, kermes, lac dye, purree, purple, sepia or cholelith; And vegetable dye, for example indigo, alizarine dyestuff, flavonol dyestuff, brazilin class dyestuff; Or colouring resin, for example dragon's blood or gamboge.
Synthetic dyestuff for example are basic dyestuff and color base, matching stain and water soluble metal complexes dyestuff, pure dissolubility and ester soluble dye and oil soluble and lipid-soluble dye.
Except that tinting material, also filler can be used in component A) in and/or as B component v).Described filler is mainly pulverous actual material that is insoluble to used medium.This filler mainly obtains by decomposing, make with extra care, grind the natural generation material that also is classified to particle fraction subsequently.Yet if relate to degree of cleaning (brightness) or degree particularly in small, broken bits, so for example the sintetics of vitriol or carbonate also can be used as filler.Be different from pigment, filler has low opaqueness usually.Except that increasing volume (reducing cost), it also plays very special effect in film, for example reflectivity, surface tissue, wearability or anti-rubble impact.Their use is decided by its particle size, particle size distribution, particle form, grain pattern, hardness, density, color, wettability, abradability, surface adsorption, specific refractory power, chemical constitution, purity, stability and price.Interaction in tackiness agent/filler zone is difficult to observation comprehensively.Yet the optimum quantity of determining filler is easy to those skilled in the art.Usually with based on tinting material, use the filler of 0 weight %-95 weight %.
Can be dispersed in water-based and/or contain filler example in the solvent paint vehicle for based on those of kaolin, talcum, mica, other silicate, quartz, cristobalite, wollastonite, perlite, diatomite, fibrous packing, aluminium hydroxide, barium sulfate or lime carbonate.
At component A) in and/or vi) can use as B component and well known to a person skilled in the art all auxiliary agents and the additive that is used for coating and pigment preparation.For example mention defoamer for this reason, air release agent, auxiliary rheological agents, tensio-active agent, it for example changes oilness, scuff resistance, resistance to blocking, flowability and gloss, base material wetting agent, siccative, stablizer or sterilant.
Theme of the present invention also is to prepare the method for coating composition, and this coating composition consists essentially of:
A) at least a former lacquer of solvent that contains of 50 weight %-99 weight %, it comprises at least a tackiness agent, at least a solvent, optionally at least a tinting material, optionally at least a filler and auxiliary agent optionally and additive substantially,
B) the waterborne general pigment preparation of 1 weight %-50 weight %, it comprises the mix products of following component substantially:
I) polyalkylene oxide that contains Styrene oxide 98min. of at least a block copolymerization of 95 weight %-5 weight %,
With
Ii) not hydrogenation ketone-urea formaldehyde of 5 weight %-95 weight %,
And
The iii) at least a solvent of 0 weight %-80 weight %,
Component i wherein)-iii) weight part sum is 100 weight %,
With
Iv) tinting material
With
V) filler
With
Vi) auxiliary agent and the additive of 0 weight %-10 weight %,
Based on every kind of component iv) with component weight v) and, component i), component ii) with component iii) the amount of sum be 2 weight %-95 weight %, component amount v) also can be 0 weight % in pigment preparation,
C) auxiliary agent and the additive of 0 weight %-10 weight %,
Wherein in suitable whipping appts, make B component in 20-80 ℃) with component A) and optionally component C) mixing mutually.
In in Dispermat, Scandex mixing machine, Red Devil, single roller mill, three-roll grinder, ball mill or other suitable device, preparing B component under the 20-80 ℃ of temperature).According to the present invention, the polyalkylene oxide i that contains Styrene oxide 98min. by block copolymerization) and the B component ii) formed of ketone-urea formaldehyde) can be pre-mixed with being used for dispersive dyestuff or pigment, perhaps add B component iv) before or directly be dissolved in water-based or the solvent-laden dispersion medium simultaneously.Then with B component) with component A) and optionally component C) mix in suitable whipping appts in 20-80 ℃, this whipping appts for example is dissolver (Disspolver) or Dispermat.
Theme of the present invention also is the application of coating composition as colorant, paint vehicle, tackiness agent or printing-ink, and this coating composition comprises substantially:
A) at least a former lacquer of solvent that contains of 50 weight %-99 weight %, it comprises at least a tackiness agent, at least a solvent, optionally at least a tinting material, optionally at least a filler and auxiliary agent optionally and additive substantially,
B) the waterborne general pigment preparation of 1 weight %-50 weight %, it comprises the mix products of following component substantially:
I) polyalkylene oxide that contains Styrene oxide 98min. of at least a block copolymerization of 95 weight %-5 weight %
With
Ii) not hydrogenation ketone-urea formaldehyde of 5 weight %-95 weight %,
With
The iii) at least a solvent of 0 weight %-80 weight %,
Component i wherein)-iii) weight part sum is 100 weight %,
With
Iv) tinting material
With
V) filler
With
Vi) auxiliary agent and the additive of 0 weight %-10 weight %,
Based on every kind of component iv) with component weight v) and, component i), component ii) with component iii) the amount of sum be 2 weight %-95 weight %, component amount v) also can be 0 weight % in pigment preparation,
C) auxiliary agent and the additive of 0 weight %-10 weight %.
The characteristics of the present composition are remarkable high-caliber Environmental compatibility.In addition, because this aqueous pigment preparations that is generally used for water-borne coatings also can be used for containing coatings volatile organic compounds now, so it is economical.The coating composition storage-stable of the present invention that obtains.The technical feature of coating depends on the former lacquer of use.
Embodiment
Following examples are used for further explaining the present invention, limit its range of application and be not used in.
Embodiment
1) preparation contains the polyalkylene oxide (non-the present invention) of Styrene oxide 98min.
The pure and mild 16.3g of 336.4g (2.34mol) 3-methyl cyclohexanol (0.23mol) potassium methylate is added in the reactor.After the careful flushing of pure nitrogen gas, will initially feed and be heated to 110 ℃, and in 1 hour, add 308.2g (2.554mol) Styrene oxide 98min..After 2 hours, the addition reaction of Styrene oxide 98min. finishes again, and it is by proving less than the remaining oxidation styrene content of 0.1 weight % according to gas-chromatography.Be metered into 339.2g (7.71mol) oxyethane with special speed subsequently in reactor, this special speed is no more than 6 crust for making internal temperature be no more than 120 ℃ and pressure.After the oxyethane interpolation was finished, holding temperature was at 115 ℃, until the constant gauge pressure that shows that afterreaction finishes.At last, under 80-90 ℃ of decompression, remove the unreacted residual monomer.With the product that the phosphoric acid neutralization obtains, dephlegmate, and use filter aid by removing by filter the potassiumphosphate of formation.Suppose that functionality is 1, the molecular weight M=467g/mol that obtains by the mensuration of hydroxyl value.
2) preparation of ketone-urea formaldehyde (non-the present invention)
With 176.7g 4-tertiary butyl pimelinketone, 481.7g 3,3, the formalin solution of 5-trimethylcyclohexanone, 112.4g pimelinketone and 373.1g 30% weight concentration is introduced as initial charging, and is heated to 60 ℃.After this, in 15 minutes, drip the sodium hydroxide solution of 114.5g 50% weight concentration, and with this mixture heating up to 80 ℃.In 90 minutes, drip the 200.0g formalin solution, and keep this mixture to reflux 4 hours at 85 ℃.After adding Glacial acetic acid, wash formed resin with water to neutral.Distillation obtains having the light yellow brittle resin of 85 ℃ of softening temperatures.
3) has the preparation of compositions (non-the present invention) of bond properties and dispersing property
With 500g embodiment 1) the polyalkylene oxide that contains Styrene oxide 98min. and ketone-urea formaldehyde of 500g embodiment 2 under 80 ℃ of stirrings, be mixed with each other.Product is clarifying and 23 ℃ of viscosity with 88810mPas.
4) preparation of blue water-based universal pigment preparation (non-the present invention)
For this purpose, with 7.3g component 3) mix with 8.9g water, add 29.1gHeliogenblue L 7101 F blue pigmentss (BASF AG) subsequently.After adding the 2mm granulated glass sphere, under 25 ℃ and 2400 rev/mins, in Dispermat, implement to disperse 60 minutes.Use the mixture (1: 1 weight %) of dimethylaminoethanol and water aqueous pigment preparations to be adjusted to about 9 pH value.
Blue pigments preparation with 58mPa.s viscosity is easy to stir and is still.Surpassing 1 all rear stabilities 50 ℃ of storages does not still change.
5) preparation of black water universal pigment preparation (non-the present invention)
For this purpose, with 13.4g component 3) mix with 16.4g water, add 26.9gSpecialschwarz 4 black pigments (Degussa AG) subsequently.After adding the 2mm granulated glass sphere, under 25 ℃ and 2400 rev/mins, in Dispermat, implement to disperse 80 minutes.Use the mixture (1: 1 weight %) of dimethylaminoethanol and water aqueous pigment preparations to be adjusted to about 9 pH value.
This black pigment preparation is easy to stir and is still.
6) contain the preparation (non-the present invention) of the former lacquer of solvent
With list in the table addition material 2400 rev/mins under 25 ℃ of bushing temperatures in DispermatCV, under the assistance of 2mm granulated glass sphere, stirred 20 minutes.At room temperature drying should white medium oil alkyd resin paint vehicle 24h then.Tackiness agent (solid) is 1: 0.8 with the ratio of white pigment.
Table 1: former coating compositions
Composition Consumption (weight %)
Alkydal F 49 (55% form) 61.92
Kronos?2310 27.24
Ca siccative (5%Ca) 0.77
Co siccative (10%Co) 0.53
Zr siccative (12%Zr) 0.18
Mn siccative (10%Mn) 0.10
Octa-Soligen?VP?033 0.26
Dimethylbenzene 4.5
Acetate methoxyl group propyl ester 2.1
Petroleum solvent 2.1
Borchinox?M2 0.3
Amount to 100.0
7) preparation of coating composition of the present invention
In order to prepare coating composition, with pigment preparation 4) and 5) introduce as initial charging, and in each case all by a part adding white former lacquer (6).Table 2 has shown this coating composition.
Table 2: coating composition
By 6) white that obtains paint 150.0 ?150.0 150.0 ?150.0 ?150.0
By 4) the blue pigments preparation that obtains 3.7 ?8.2 - ?- ?-
By 5) the black pigment preparation that obtains - ?- 4.6 ?9.1 ?-
Butyleneglycol 3.0 ?3.0 3.0 ?3.0 ?3.0
Hydropalat?535?N 2.3 ?2.3 2.3 ?2.3 ?-
The weight ratio of white pigment/blue pigments 27.5/2.5 ?25/5 - ?- ?-
Based on white pigment, the percentage ratio of black pigment (%) - ?- 3 ?6 ?-
Viscosity behind the 24h (mpa s) 604 ?693 622 ?672 ?1343
Coating technology performance on the standard steel
Film thickness (μ m) 25 ?25 25 ?25 ?25
K  nig pendulum hardness behind the 24h 24 ?27 28 ?27 ?28
K  nig pendulum hardness behind the 4d 45 ?43 45 ?43 ?50
K  nig pendulum hardness behind the 28d 59 ?57 65 ?63 ?80
Lattice are drawn test (Glitterschnitt) behind the 28d 0-1 ?0-1 0-1 ?0-1 ?0-1
Erichsen drawing test (mm) behind the 28d 7.0 ?6.5 6.5 ?6.5 ?7.0
20 °/60 ° glossiness behind the 28d 76/89 ?72/88 77/88 ?76/88 ?73/83
Mist degree behind the 28d (Glanzschleier) 64-72 ?31-105 45-49 ?50-52 ?28-36
Δ E rubs off (rub out) 0.84 ?1.10 1.02 ?1.08 ?-
Have good drying property, machinery and the color characteristics that high glossiness is become reconciled by what embodiment showed based on waterborne general pigment preparation and the coating composition of the present invention that contains solvent white Synolac paint vehicle.

Claims (27)

1. coating composition, it comprises substantially:
A) at least a former lacquer of solvent that contains of 50 weight %-99 weight %, it comprises at least a tackiness agent, at least a solvent, optionally at least a tinting material, optionally at least a filler and auxiliary agent optionally and additive substantially,
B) the waterborne general pigment preparation of 1 weight %-50 weight %, it comprises the mix products of following component substantially:
I) polyalkylene oxide that contains Styrene oxide 98min. of at least a block copolymerization of 95 weight %-5 weight %,
With
Ii) not hydrogenation ketone-urea formaldehyde of 5 weight %-95 weight %,
With
The iii) at least a solvent of 0 weight %-80 weight %,
Component i wherein)-iii) weight part sum is 100 weight %,
With
Iv) tinting material
With
V) filler
With
Vi) auxiliary agent and the additive of 0 weight %-10 weight %,
Based on every kind of component iv) with component weight v) and, component i), component ii) with component iii) the amount of sum be 2 weight %-95 weight %, component amount v) also can be 0 weight % in pigment preparation,
C) auxiliary agent and the additive of 0 weight %-10 weight %.
2. according to the coating composition of claim 1, be characterised in that in 1K or 2K paint vehicle, contain the former lacquer of solvent by physical dryness, oxidation drying or reactive dry with other approach.
3. according to the coating composition of at least one of aforementioned claim, be characterised in that containing the former enamel-cover of solvent draws together nitrocotton as tackiness agent, polyvinyl butyral acetal, the VC multipolymer, acrylate, methacrylic ester, cellulose ester, ether of cellulose, hydrocarbon resin, resol, Gum Rosin, maleic acid resin, polystyrene resin, silicone resin, thermoprene, chlorinated rubber, chlorinatedpolyolefins, low polyhutadiene, polyolefine, polyvinylesters, polyvinyl alcohol, polyvinyl acetal, epoxy compounds, aminoresin, acyl ammonia resin, vibrin, Synolac, Resins, epoxy, polyvinyl acetate resins, urethane resin, (methyl) acrylate resin of (methyl) acrylated, epoxy (methyl) acrylate resin, polyester (methyl) acrylate resin, polyethers (methyl) acrylate resin, urethane (methyl) acrylate resin, the polyacrylic acid polyol resin, polyester polyol resin, melamine resin, polyisocyanate resin or block polyisocyanate resin are separately or with form of mixtures.
4. the coating composition any according to aforementioned claim is characterised in that B component) in the polyalkylene oxide i that contains Styrene oxide 98min. of contained block copolymerization) have a general formula I:
R 1O(SO) a(EO) b(PO) c(BO) dR 2
R wherein 1Be straight or branched or the alicyclic group that has 8-13 carbon atom in all cases,
R 2Be hydrogen or aryl, alkyl or hydroxy-acid group with 1-8 carbon atom,
The SO=Styrene oxide 98min.,
EO=oxyethane
The PO=propylene oxide
The BO=butylene oxide ring and
a=1-1.9,
b=3-50,
c=0-3,
d=0-3,
Wherein, a, c or d are not 0, and b>=a+c+d.
5. according to the coating composition of at least one of aforementioned claim, be characterised in that use have aliphatic series, ketone preparation alicyclic or aromatic hydrocarbyl is contained in B component) in ketone-urea formaldehyde ii).
6. according to the coating composition of at least one of aforementioned claim, be characterised in that use acetone, methyl phenyl ketone, methylethylketone, heptan-2-ketone, penta-3-ketone, methyl iso-butyl ketone (MIBK), pimelinketone, 4-tert-pentyl pimelinketone, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone, 3,3,5-trimethylcyclohexanone, cyclopentanone, 2,2,4-and 2,4, the mixture of 4-trimethylammonium cyclopentanone, suberone, cyclooctanone or cyclododecanone are contained in B component as being used for preparation) ketone-urea formaldehyde ketone ii).
7. according to the coating composition of at least one of aforementioned claim, be characterised in that and use phenol and/or the preparation of urea or derivatives thereof to be contained in B component) in ketone-urea formaldehyde ii).
8. the coating composition any according to aforementioned claim is characterised in that to be contained in B component) in not hydrogenation ketone-urea formaldehyde ii) comprise:
I. based on the ketone of all employings, at least a alkyl substituted cyclohexanone of 40-100mol% with alkyl of one or more 1-8 carbon atom,
II. based on the ketone of 1 mole of all employing, at least a aliphatic aldehyde of 0.8-2.0mol and
III. based on the ketone of all employings, having of 0-60mol% is aliphatic, alicyclic, other ketone of aromatic hydrocarbyl, and it can be identical or different, and can and then replace and optionally also comprise phenol and/or urea or derivatives thereof with above-mentioned alkyl on hydrocarbon chain.
9. according to the coating composition of at least one of aforementioned claim, be characterised in that and use 4-tert-pentyl pimelinketone, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone and 3,3, the 5-trimethylcyclohexanone is as pimelinketone I.
10. according to the coating composition of at least one of aforementioned claim, the aldehyde that is characterised in that common use straight chain or side chain is as the aldehyde component with as II, and described aldehyde for example is formaldehyde, acetaldehyde, butyraldehyde-n and/or isobutyric aldehyde, valeral and lauric aldehyde.
11., be characterised in that use formaldehyde according to the coating composition of claim 12.
12. coating composition according at least one of aforementioned claim, be characterised in that use acetone, methyl phenyl ketone, methylethylketone, heptan-2-ketone, penta-3-ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, pimelinketone, cyclododecanone, 2,2,4-and 2,4, mixture, suberone and the cyclooctanone of 4-trimethylammonium cyclopentanone are as the ketone component III.
13. the coating composition any according to aforementioned claim is characterised in that the polyalkylene oxide Bi that contains Styrene oxide 98min. of block copolymerization) with ketone-urea formaldehyde Bii) ratio of mixture be 95: 5-5: 95.
14. according to the coating composition of at least one of aforementioned claim, be characterised in that and contain water) as solvent Biii.
15. according to the coating composition of at least one of aforementioned claim, be characterised in that to contain organic solvent) as solvent Biii.
16. coating composition according at least one of aforementioned claim, be characterised in that as solvent Biii) contain alcohol, ester, ketone, ether, glycol ether, aromatic hydrocarbon, hydrogenation aromatic hydrocarbon, halohydrocarbon, terpene hydrocarbon, aliphatic hydrocrbon, ester alcohol, dimethyl formamide or methyl-sulphoxide, separately or with form of mixtures.
17., be characterised in that at component A according to the coating composition of at least one of aforementioned claim) in and/or iv) contain pigment and/or dyestuff as B component as tinting material, separately or with form of mixtures.
18., be characterised in that to comprise organic and/or mineral dye and/or carbon black as pigment according to the coating composition of at least one of aforementioned claim.
19. according to the coating composition of at least one of aforementioned claim, be characterised in that as mineral dye to comprise titanium dioxide or ferric oxide, separately or with form of mixtures.
20. coating composition according at least one of aforementioned claim, be characterised in that as pigment dyestuff and comprise azo pigment, metal complex pigment, anthraquinone pigment, phthalocyanine pigment, many ring pigment, particularly thioindigo, quinoline a word used for translation ketone, two  piperazines, pyrrolo-, naphthalene tetracarboxylic acid, perylene, Isoamidolin (on), flavanthrone, pyranthrone or isoviolanthrone serial pigment are separately or with form of mixtures.
21. according to the coating composition of at least one of aforementioned claim, be characterised in that as carbon black to comprise channel black, flame black or furnace black, separately or with form of mixtures.
22. according to the coating composition of at least one of aforementioned claim, be characterised in that to comprise natural or synthetic dyestuff, separately or with form of mixtures as dyestuff.
23. according to the coating composition of at least one of aforementioned claim, be characterised in that as natural dyestuff to comprise animal dyes or vegetable dye, separately or with form of mixtures.
24. coating composition according at least one of aforementioned claim, be characterised in that as natural dyestuff to comprise carminum, kermes, lac dye, purree, purple, sepia, cholelith, indigo, alizarine dyestuff, flavonol dyestuff, brazilin class dyestuff, dragon's blood or gamboge, separately or with form of mixtures.
25. coating composition according at least one of aforementioned claim, be characterised in that as synthetic dyestuff to comprise basic dyestuff and color base matching stain and water soluble metal complexes dyestuff, pure dissolubility and ester soluble dye, or oil soluble and lipid-soluble dye, separately or with form of mixtures.
26. a method for preparing coating composition, this coating composition consists essentially of:
A) at least a former lacquer of solvent that contains of 50 weight %-99 weight %, it comprises at least a tackiness agent, at least a solvent, optionally at least a tinting material, optionally at least a filler and auxiliary agent optionally and additive substantially,
B) the waterborne general pigment preparation of 1 weight %-50 weight %, it comprises the mix products of following component substantially:
I) polyalkylene oxide that contains Styrene oxide 98min. of at least a block copolymerization of 95 weight %-5 weight %
With
Ii) not hydrogenation ketone-urea formaldehyde of 5 weight %-95 weight %,
With
The iii) at least a solvent of 0 weight %-80 weight %,
Component i wherein)-iii) weight part sum is 100 weight %,
With
Iv) tinting material
With
V) filler
With
Vi) auxiliary agent and the additive of 0 weight %-10 weight %,
Based on every kind of component iv) with component weight v) and, component i), component ii) with component iii) the amount of sum be 2 weight %-95 weight %, component amount v) also can be 0 weight % in pigment preparation,
C) auxiliary agent and the additive of 0 weight %-10 weight %,
Wherein in suitable whipping appts, make B component in 20-80 ℃) with component A) and optionally component C) mixing mutually.
27. coating composition is as the application of colorant, paint vehicle, tackiness agent or printing-ink, this coating composition comprises substantially:
A) at least a former lacquer of solvent that contains of 50 weight %-99 weight %, it comprises at least a tackiness agent, at least a solvent, optionally at least a tinting material, optionally at least a filler and auxiliary agent optionally and additive substantially,
B) the waterborne general pigment preparation of 1 weight %-50 weight %, it comprises the mix products of following component substantially:
I) polyalkylene oxide that contains Styrene oxide 98min. of at least a block copolymerization of 95 weight %-5 weight %
With
Ii) not hydrogenation ketone-urea formaldehyde of 5 weight %-95 weight %,
With
The iii) at least a solvent of 0 weight %-80 weight %,
Component i wherein)-iii) weight part sum is 100 weight %,
With
Iv) tinting material
With
V) filler
With
Vi) auxiliary agent and the additive of 0 weight %-10 weight %,
Based on every kind of component iv) with component weight v) and, component i), component ii) with component iii) the amount of sum be 2 weight %-95 weight %, component amount v) also can be 0 weight % in pigment preparation,
C) auxiliary agent and the additive of 0 weight %-10 weight %.
CNA2007101102661A 2006-06-09 2007-06-08 Coating compositions based on universal pigment preparations Pending CN101085899A (en)

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