WO2007065839A2 - Procede de dispersion de preparations de pigments solides dans des liquides - Google Patents

Procede de dispersion de preparations de pigments solides dans des liquides Download PDF

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Publication number
WO2007065839A2
WO2007065839A2 PCT/EP2006/069100 EP2006069100W WO2007065839A2 WO 2007065839 A2 WO2007065839 A2 WO 2007065839A2 EP 2006069100 W EP2006069100 W EP 2006069100W WO 2007065839 A2 WO2007065839 A2 WO 2007065839A2
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WO
WIPO (PCT)
Prior art keywords
pigment
acid
pigments
pigment preparations
resins
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PCT/EP2006/069100
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German (de)
English (en)
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WO2007065839A3 (fr
Inventor
Georg Josef DÖRING
Hansulrich Reisacher
Uwe Mauthe
Uwe Fidorra
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Basf Aktiengesellschaft
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Publication of WO2007065839A2 publication Critical patent/WO2007065839A2/fr
Publication of WO2007065839A3 publication Critical patent/WO2007065839A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0002—Grinding; Milling with solid grinding or milling assistants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0003—Drying, e.g. sprax drying; Sublimation of the solvent

Definitions

  • the present invention relates to a process for dispersing solid pigment preparations in liquid media.
  • aqueous and / or solvent-containing pigment preparations are usually used, which are enhanced by a number of other auxiliaries, such as drying agents, agents for increasing the resistance to freezing, thickeners and anti-skin agents , must be stabilized. Due to their large volume, the liquid pigment preparations also require more effort in storage, packaging and transportation.
  • Solid pigment preparations whose color properties and dispersibility are comparable to liquid preparations, but which do not require the additives mentioned and, not least because of their smaller volume, are easier to handle, so-called "stir-in” pigments, are becoming increasingly popular in importance.
  • the high-speed mixer is preferably constructed as follows: It consists of a driven rotor that has two attachments with different diameters. A ring with narrow openings (stator) is inserted into the cylindrical mixing chamber so that it is located between the two rotor attachments.
  • the mixing room has at least one inlet, one outlet and a further closable opening.
  • a negative pressure vacuum
  • a negative pressure builds up, which can be used to advantage in order to transfer the pigment preparation, for example via a pipe, through the additional opening into the mixing room. port to disperse them finely distributed in the liquid medium in the gap between the rotor and stator using the shear forces.
  • the mixer preferably has only a small mixing space and is installed externally from the container containing the liquid medium and provided with a stirrer.
  • the liquid medium is transferred from this container to the mixer via the inlet and, after admixing the pigment preparation, is returned to the container via the outlet. This continuous process is continued until the entire pigment preparation is dispersed in the liquid medium.
  • the method according to the invention for dispersing solid pigment preparations in liquid media effectively avoids dust nuisance.
  • the finished product e.g. the paint
  • the finished product is homogenized significantly faster than when using a dissolver that is normally used for pigment dispersion.
  • the process according to the invention can be used to disperse solid pigment preparations in liquid media of all kinds.
  • These media can be purely aqueous media, mixtures of water and organic solvents, e.g. Alcohols, or only on organic solvents such as alcohols, glycol ethers, ketones, e.g. Methyl ethyl ketone, amides, e.g. N-methylpyrrolidone and dimethylformamide, esters, e.g. Ethyl and butyl acetate and methoxypropyl acetate, and aromatic or aliphatic hydrocarbons, e.g. XyIoI, mineral oil and petrol, are based.
  • the liquid media are water- or solvent-based binder systems which are based, for example, on paints, paints, printing inks and inks.
  • binder here means water-solvent-soluble, dispersible or emulsifiable, synthetic and natural or modified natural, generally film-forming compounds.
  • the organic binders can be synthetic (also modified natural) or natural binders.
  • the synthetic binders can basically be divided into polycondensation, polymerization and polyaddition resins.
  • the polycondensation resins are formed by a reaction between polyfunctional carboxylic acids and polyols or polyamino compounds.
  • suitable polycondensation resins are alkyd resins, aminoplasts, phenol resins, polyamide resins, polyester resins, epoxy resins and silicone resins.
  • the alkyd resins are polycondensation resins made from polyols, polyvalent carboxylic acids and fatty oils or free natural and / or synthetic fatty acids, at least one polyol having to be trifunctional or higher.
  • the alkyd resins can be modified by natural resins, phenolic resins, acrylic resins, styrene, epoxy resins, silicone resins, isocyanates, polyamides and aluminum alcoholates.
  • Examples of alkyd resins are linseed oil, soybean oil, safflower oil, castor oil and castor oil alkyd resins.
  • Aminoplasts are polycondensation products made from carbonyl compounds (especially formaldehyde, also higher aldehydes and ketones) and compounds containing NH groups, e.g. Urea (urea resins) or melamine (melamine resins).
  • the aminoplastics are often used in combination with alkyd resins, acrylates and epoxy resins (stove enamels).
  • Phenolic resins result from polycondensation products of phenols and aldehydes, especially formaldehyde. Phenol novolaks may be mentioned as an example.
  • Polyamide resins are polycondensation products made from diamines and dimerized fatty acid, which can be partially replaced by aliphatic or aromatic dicarboxylic acids.
  • the polyester resins are polycondensation resins made from dihydric or polyhydric alcohols and dihydric or polyvalent organic acids or their anhydrides. Depending on the type and functionality of the starting materials, the polyester resins can be saturated or unsaturated, linear, branched or crosslinked and contain hydroxyl or carboxy groups as reactive end groups. The esterification of polyvalent alcohols with dicarboxylic acids and saturated or unsaturated fatty acids leads to alkyd resins.
  • Unsaturated polyester resins are polycondensation products made from unsaturated dicarboxylic acids, such as maleic or fumaric acid, and predominantly dihydric alcohols, such as ethylene glycol and 1,2-propanediol, and optionally saturated or aromatic dicarboxylic acids, such as adipic acid and phthalic acid, for modification. They can be copolymerized with ethylenically unsaturated monomers such as (methyl) styrene, (meth) acrylates and allyl ethers (hardening).
  • unsaturated dicarboxylic acids such as maleic or fumaric acid
  • dihydric alcohols such as ethylene glycol and 1,2-propanediol
  • aromatic dicarboxylic acids such as adipic acid and phthalic acid
  • polyester resins can be used in combination with aminoplasts (melamine, benzoguanamine and urea resins) (stoving lacquers).
  • Hydroxy-functional polyester resins are also part of polyurethane coatings and are crosslinked here with polyisocyanates (two-component polyurethane coatings) or with blocked diisocyanates (one-component polyurethane coatings).
  • Epoxy resins are polycondensation products made from aromatic dihydroxy compounds, especially bisphenol A, and epichlorohydrin. Since they have no film-forming properties by themselves, they are crosslinked with polyamines, polyaminoamides, ketimines, polyisocyanates, phenolic resins or aminoplasts (cold-curing two-component systems, air-drying systems, stoving enamels).
  • silicone resins are polymethylphenylsiloxanes, which are often combined with alkyd resins and polyester resins.
  • Combination silicone resins are the copolymers of low molecular weight, hydroxy-functional silicones with polyesters, alkyd resins and acrylic resins.
  • Suitable polymerization resins are vinyl ester polymers, acrylic resins, styrene-butadiene copolymers and chlorinated rubber.
  • Acrylic resins are the polymers of acrylic acid esters and methacrylic acid esters, mostly functional (meth) acrylic monomers and also non-acrylic monomers, such as styrene or vinyl esters, being used as comonomers. Accordingly, a distinction is made between pure acrylates and, for example, styrene acrylates.
  • the acrylate dispersions to be obtained by emulsion polymerization are also important here.
  • Acrylic resins which can be crosslinked thermally or in two components contain functional groups (hydroxyl, N-hydroxymethyl, carboxy, epoxy groups) for crosslinking reactions. They can be self-crosslinking (eg after the addition of aminoplasts, polyisocyanates (two-component polyurethane-acrylic), epoxy resins or polycarboxylic acids).
  • Styrene-butadiene copolymers are also preferably used as dispersions alone or in combination with alkyd resins.
  • Chlorinated rubbers are chlorination products from natural rubber or synthetic rubbers. They are used alone or in combination e.g. used with alkyd or acrylic resins.
  • Suitable polyaddition resins are in particular polyurethanes and polyureas.
  • polyurethanes is understood to mean polyaddition products comprising dihydric or higher-valent alcohols and isocyanates which have repeat units linked by urethane groups -NH-CO-O-.
  • Polyureas have the structural element -NH-CO-NH- and are obtained by reacting polyamines and isocyanates.
  • the polyurethanes are based on polyester diols and / or polyether diols as alcohol components and 2,4- or 2,6-toluenediisocyanate (TDI), 4,4'-methylenedi (phenyl isocyanate) (MDI), 4,4'-methylenedicyclohexyl isocyanate (H12MDI ), Isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI).
  • TDI 2,4- or 2,6-toluenediisocyanate
  • MDI 4,4'-methylenedi (phenyl isocyanate)
  • H12MDI 4,4'-methylenedicyclohexyl isocyanate
  • IPDI Isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • polyurethane lacquers which are based primarily on linear or branched saturated polyesters, alkyd resins or polyhydroxyacrylates as the polyol component, and also polyurethane dispersions which are prepared using so-called internal emulsifiers (for example 2 2-bis (hydroxymethyl) propionic acid or N-alkyldiethanolamine) are stabilized colloidally.
  • internal emulsifiers for example 2 2-bis (hydroxymethyl) propionic acid or N-alkyldiethanolamine
  • Natural binders are e.g. Natural resins, such as rosin and shellac, and natural oils, in particular oils which contain saturated or unsaturated fatty acids and, where appropriate, oxidative drying oils, such as linseed oil, castor oil, soybean oil and castor oil.
  • Modified natural binders have already been mentioned in part for synthetic binders. Important examples are: chemically modified natural resins such as rosin-maleinate resin; modified oils such as thick oils, isomerized oils, styrenized oils, cyclo oils, maleate oils, urethane oils and factorized oils; Cellulose derivatives such as cellulose nitrate, cellulose ethers and cellulose esters of organic acids; modified natural rubber, such as cyclo and chlorinated rubber. Finally, lime, white cement and silicate binders, such as potash water glass, may be mentioned as examples of inorganic binders.
  • chemically modified natural resins such as rosin-maleinate resin
  • modified oils such as thick oils, isomerized oils, styrenized oils, cyclo oils, maleate oils, urethane oils and factorized oils
  • Cellulose derivatives such as cellulose nitrate, cellulose ethers and cellulose esters of organic acids
  • modified natural rubber such as cyclo and chlorin
  • the process according to the invention is particularly important for pigmenting paints, for example architectural paints, industrial paints, vehicle paints and radiation-curable paints, paints, both for exterior and interior of buildings, for example wood paints, lime paints, glue paints and emulsion paints, printing inks, for example offset printing inks, flexographic printing inks, toluene gravure inks , Textile printing inks and radiation-curable printing inks, as well as inks, including ink-jet inks.
  • paints for example architectural paints, industrial paints, vehicle paints and radiation-curable paints, paints, both for exterior and interior of buildings, for example wood paints, lime paints, glue paints and emulsion paints
  • printing inks for example offset printing inks, flexographic printing inks, toluene gravure inks , Textile printing inks and radiation-curable printing inks, as well as inks, including ink-jet inks
  • the solid pigment preparations to be dispersed can be in powder form or as coarse or fine-particle granules.
  • the solid pigment preparations contain as essential components one or more pigments and one or more surface-active additives and / or one or more binders.
  • they can contain one or more fillers not having their own color.
  • the pigment preparations can of course also contain other auxiliaries customary for pigment preparations, e.g. Thickeners, thixotropic agents, defoamers and / or stabilizers, such as antioxidants, in minor amounts.
  • An example of an important application of the method according to the invention is the dispersion of solid pigment preparations, which are essential components
  • the coloring component (A) of these pigment preparations is based on at least one pigment (A1), which can be present in combination with at least one filler (A2) that does not have its own color.
  • These pigment preparations can contain inorganic or organic pigments as pigment (A1).
  • the pigment preparations can of course also contain mixtures of different inorganic or different organic pigments or mixtures of inorganic and organic pigments.
  • the pigments are in finely divided form. Accordingly, the pigments usually have average particle sizes of 0.1 to 5 ⁇ m.
  • Colored, black and white pigments (color pigments) and gloss pigments can be used as inorganic pigments.
  • Typical organic pigments are colored and black pigments.
  • Suitable organic pigments include:
  • Anthraquinone pigments Cl. Pigment Yellow 147, 177 and 199;
  • Triaryl carbonium pigments Cl. Pigment Blue 1, 61 and 62;
  • Pigment Yellow 101 Aldazine Yellow
  • Pigment Brown 22 examples of suitable inorganic pigments are:
  • Green 48 Cobalt green (Cl. Pigment Green 50); Ultramarine green;
  • Cobalt blue (Cl. Pigment Blue 28 and 36; Cl. Pigment Blue 72);
  • Iron oxide red (Cl. Pigment Red 101); Cadmium sulfoselenide (CI. Pigment Red 108); Cerium sulfide (CI Pigment Red 265); Molybdate red (Cl. Pigment Red 104); Ultramarine red;
  • Iron oxide brown (Cl. Pigment Brown 6 and 7), mixed brown
  • Cerium sulfide (Cl. Pigment Orange 75); Iron oxide yellow (Cl. Pigment Yellow 42); Nickel Titanium Yellow (Cl.
  • Pigment yellow 53 Cl. Pigment Yellow 157, 158, 159, 160, 161, 162, 163, 164 and 189); Chrome titanium yellow; Spinel phases (Cl. Pigment Yellow 1 19); Cadmium sulfide and cadmium zinc sulfide (Cl. Pigment Yellow 37 and 35); Chrome yellow (Cl. Pigment
  • the luster pigments are platelet-shaped pigments composed of one or more phases, the play of colors of which is characterized by the interplay of interference, reflection and absorption phenomena.
  • These pigment preparations can contain the pigment (A1) in combination with a filler (A2), in particular inorganic filler, which does not have its own color.
  • These colorless or white fillers (A2) generally have a refractive index ⁇ 1.7.
  • the refractive index of chalk is 1, 55, of barite 1, 64, of kaolin 1, 56, of talc 1, 57, of mica 1, 58 and of silicates 1, 55.
  • the fillers (A2) are insoluble in the application medium and come in particular from the following chemical classes, examples of which include both products of natural origin and products of synthetic origin:
  • calcium and magnesium carbonates such as calcite, chalk, dolomite and magnesite
  • - sulfates natural: barium and calcium sulfates, such as barite and gypsum;
  • the fillers (A2) can have a wide variety of particle shapes. For example, it can be balls, cubes, platelets or fibers. Natural-based fillers usually have particle sizes in the range from about 1 to 300 ⁇ m. So commercial products based on natural chalk e.g. a dso value of usually 1 to 160 ⁇ m. Particle sizes below 1 ⁇ m are generally only available with fillers produced synthetically, in particular by precipitation processes.
  • Preferred fillers (A2) are carbonates and sulfates, natural and precipitated chalk and barium sulfate being particularly preferred. These products are commercially available, for example, under the names Omyacarb ® and Omyalite ® (from Omya) and Blanc fixe (from Sachtleben).
  • the coloring component (A) of these pigment preparations contains 5 to 100% by weight of pigment (A1) and 0 to 95% by weight of filler (A2). If fillers (A2) are part of the coloring component (A), their minimum content is generally 20% by weight, based on component (A).
  • these pigment preparations contain at least one water-soluble surface-active additive.
  • Nonionic and / or anionic water-soluble surface-active additives are particularly suitable here.
  • nonionic additives (B) are based on polyethers (additives (B1)).
  • polyethers (additives (B1)) are based on polyethers (additives (B1)).
  • additives (B1) are based on polyethers (additives (B1)).
  • C2-C4-alkylene oxides and phenyl-substituted C2-C4-alkylene oxides in particular polyethylene oxides, polypropylene oxides and poly (phenylethylene oxides), block copolymers, in particular polypropylene oxide and polyethylene oxide blocks or poly (phenylethylene oxide blocks) and poly (phenylene oxide) blocks, are here in particular having polymers, and also statistical copolymers of these alkylene oxides are suitable.
  • polyalkylene oxides can be prepared by polyaddition of the alkylene oxides to starter molecules, such as saturated or unsaturated aliphatic and aromatic alcohols, saturated or unsaturated aliphatic and aromatic amines, saturated or unsaturated aliphatic carboxylic acids and carboxamides. 1 to 300 mol, preferably 3 to 150 mol, of alkylene oxide are usually used per mol of starter molecule.
  • Suitable aliphatic alcohols generally contain 6 to 26 carbon atoms, preferably 8 to 18 carbon atoms, and can be unbranched, branched or cyclic.
  • Examples include octanol, nonanol, decanol, isodecanol, undecanol, dodecanol, 2-butyl octanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol (cetyl alcohol), 2-hexyl decanol, heptadecanol, octadecanol, 2-hearyl alcohol and stearyl alcohol , 2-octyldecanol, 2-nonyltridecanol, 2-decyltetradecanol, oleyl alcohol and 9-octadecenol and also mixtures of these alcohols, such as C ⁇ / Cio-, C13 / C15- and Ci ⁇ / Ci ⁇ -alcohols, and cyclopentanol and cyclohexanol.
  • these alcohols such as C ⁇
  • saturated and unsaturated fatty alcohols which are obtained from natural raw materials through fat splitting and reduction, and the synthetic fatty alcohols from oxo synthesis.
  • the alkylene oxide adducts with these alcohols usually have average molecular weights M n of 200 to 5,000.
  • Examples of the abovementioned aromatic alcohols in addition to unsubstituted phenol and ⁇ - and ⁇ -naphthol, are also the alkyl-substituted products, in particular those with C 1 -C 12 -alkyl, preferably C 4 -C 12 or C 1 -C 4 -alkyl, are substituted, such as hexylphenol, heptylphenol, octylphenol, nonylphenol, isononylphenol, undecylphenol, dodecylphenol, di- and tributylphenol and dinonylphenol, and bisphenol A and its reaction products with styrene, especially in the ortho positions to both OH groups by a total 4 Phenyl-1-ethyl radicals substituted bisphenol A, called.
  • Suitable aliphatic amines correspond to the aliphatic alcohols listed above.
  • the saturated and unsaturated fatty amines which preferably have 14 to 20 C atoms, are of particular importance.
  • Aniline and its derivatives may be mentioned as aromatic amines.
  • Suitable aliphatic carboxylic acids are in particular saturated and unsaturated fatty acids, which preferably contain 14 to 20 carbon atoms, and hydrogenated, partially hydrogenated and unhydrogenated resin acids and also polyvalent carboxylic acids, e.g. Dicarboxylic acids such as maleic acid.
  • Suitable carboxamides are derived from these carboxylic acids.
  • the alkylene oxide adducts with the monohydric amines and alcohols the alkylene oxide adducts with at least bifunctional amines and alcohols are of particular interest.
  • di- to pentavalent amines which in particular have the formula H 2 N- (R 1 -NR 2 ) n -H (R 1 : C 2 -C 6 -alkylene; R 2 : hydrogen or d- C ⁇ -alkyl; n: 1 to 5) correspond.
  • Examples include: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1, 3 propylenediamine, Dipropylenetriamine, 3-amino-1-ethyleneaminopropane, hexamethylenediamine, dihexamethylenetriamine, 1,6-bis- (3-aminopropylamino) hexane and N-methyldipropylenetriamine, with hexamethylenediamine and diethylenetriamine being particularly preferred and ethylenediamine being particularly preferred.
  • the amines are preferably first reacted with propylene oxide and then with ethylene oxide.
  • the ethylene oxide content of the block copolymers is usually about 10 to 90% by weight.
  • the block copolymers based on polyvalent amines generally have average molecular weights M n of 1,000 to 40,000, preferably 1,500 to 30,000.
  • Dihydric to pentavalent alcohols are preferred as at least bifunctional alcohols.
  • Examples include C2-C6-alkylene glycols and the corresponding di- and polyalkylene glycols, such as ethylene glycol, propylene glycol-1, 2 and -1, 3, butylene glycol-1, 2 and -1, 4, hexylene glycol-1, 6, dipropylene glycol and Polyethylene glycol, glycerol and pentaerythritol are mentioned, ethylene glycol and polyethylene glycol being particularly preferred and propylene glycol and dipropylene glycol being very particularly preferred.
  • Particularly preferred alkylene oxide adducts with at least bifunctional alcohols have a central polypropylene oxide block, that is, they start from a propylene glycol or polypropylene glycol, which is first reacted with further propylene oxide and then with ethylene oxide.
  • the ethylene oxide content of the block copolymers is usually from 10 to 90% by weight.
  • the block copolymers based on polyhydric alcohols generally have average molecular weights M n of 1,000 to 20,000, preferably 1,000 to 15,000.
  • alkylene oxide are known and commercially available for example under the name Tetronic ®, Pluronic ® and Pluriol® ® (BASF), and Atlas ® (Uniqema) available.
  • water-soluble anionic surface-active agents particularly suitable as component (B) are additives based on polymers of ethylenically unsaturated carboxylic acids (B2), additives based on polyurethanes (B3) and additives based on acidic phosphoric acid, phosphonic acid, Sulfuric acid and / or sulfonic acid esters of the above-mentioned polyethers (B4).
  • Suitable anionic water-soluble surface-active additives based on polymers of unsaturated carboxylic acids (B2) are, in particular, additives from the group of homo- and copolymers of ethylenically unsaturated monocarboxylic acids and / or ethylenically unsaturated dicarboxylic acids, which may also contain, in copolymerized form, vinyl monomers containing no acid function. the alkoxylation products of these homo- and copolymers and the salts of these homo- and copolymers and their alkoxylation products.
  • Vinyl aromatics such as styrene, methyl styrene and vinyl toluene; Ethylene, propylene, isobutene, diisobutene and butadiene; Vinyl ethers such as polyethylene glycol monovinyl ether;
  • Vinyl esters of linear or branched monocarboxylic acids such as vinyl acetate and vinyl propionate; Alkyl esters and aryl esters of ethylenically unsaturated monocarboxylic acids, in particular acrylic and methacrylic esters, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-ethylhexyl, nonyl, lauryl and hydroxyethyl
  • Dialkyl esters of ethylenically unsaturated dicarboxylic acids such as dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, dipentyl, dihexyl, di-2-ethylhexyl, dinonyl, dilauryl and di-2-hydroxyethyl maleate and - fumarate;
  • Vinyl pyrrolidone Acrylonitrile and methacrylonitrile, styrene, isobutene, diisobutene, acrylic acid ester and polyethylene glycol monovinyl ether being preferred.
  • Examples of preferred homopolymers of these monomers include polyacrylic acids.
  • copolymers of the monomers mentioned can be composed of two or more, in particular three, different monomers.
  • Statistical copolymers, alternating copolymers, block copolymers and graft copolymers can be present.
  • Preferred copolymers are styrene / acrylic acid, acrylic acid / - maleic acid, acrylic acid / methacrylic acid, butadiene / acrylic acid, isobutene / maleic acid, diisobutene / maleic acid and styrene / maleic acid copolymers, each may contain acrylic acid esters and / or maleic acid esters as additional monomer components.
  • the carboxyl groups of the nonalkoxylated homo- and copolymers are preferably at least partially in salt form in order to ensure water solubility.
  • the alkali metal salts such as sodium and potassium salts, and the ammonium salts are suitable.
  • the non-alkoxylated polymeric additives (B2) usually have average molecular weights M w of 900 to 250,000.
  • the molecular weight ranges particularly suitable for the individual polymers naturally depend on their composition. In the following, molecular weights are given by way of example for various polymers: polyacrylic acids: M w from 900 to 250,000; Styrene / acrylic acid copolymers: M w from 1,000 to 50,000; Acrylic acid / methacrylic acid copolymers: M w from 1,000 to 250,000; Acrylic acid / maleic acid copolymers: M w from 2,000 to 70,000.
  • Alkoxylation products as additives (B2) of particular interest are Alkoxylation products as additives (B2) of particular interest.
  • polyether alcohols themselves, preferably polyethylene glycols and polypropylene glycols, and also their derivatives which are end group-capped, especially the corresponding monoethers, such as monoaryl ethers, for example monophenyl ether, and in particular mono-C 1 -C 26 -alkyl ethers, for example with fatty alcohols etherified ethylene and propylene glycols, and the polyetheramines, which can be prepared, for example, by converting a terminal OH group of the corresponding polyether alcohols or by polyaddition of alkylene oxides to preferably primary aliphatic amines. Polyethylene glycols, polyethylene glycol monoethers and polyetheramines are preferred.
  • the surface-active properties of the additives (B2) can be set in a targeted manner by controlling the ratio of polar to non-polar groups.
  • anionic surface-active additives are also known and commercially available for example under the name Sokalan ® (BASF), Joncryl ® (Johnson Polymer), Alcosperse ® (Alco), Geropon ® (Rhodia), Good-Rite ® (Goodrich), Neoresin ® (Avecia), Orotan ® and Morez ® (Rohm & Haas), Disperbyk ® (Byk) and Tegospers ® (Goldschmidt). These pigment preparations can also contain additives based on polyurethane (B3) as anionic surface-active additives.
  • polyurethane includes not only the pure reaction products of polyvalent isocyanates (B3a) with isocyanate-reactive hydroxyl-containing organic compounds (B3b), but also those reaction products which are obtained by adding further isocyanate-reactive compounds, e.g. of primary or secondary amino groups carrying carboxylic acids are additionally functionalized. These additives are distinguished from other surface-active additives by their low ionic conductivity and their neutral pH.
  • Diisocyanates are particularly suitable as polyvalent isocyanates (B3a) for the preparation of the additives (B3), but it is also possible to use compounds having three or four isocyanate groups. Both aromatic and aliphatic isocyanates can be used.
  • di- and triisocyanates examples include: 2,4-tolylene diisocyanate (2,4-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), para-xylylene diisocyanate, 1,4-diisocyanatobenzene , Tetramethylxylylene diisocyanate (TMXDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI) and triisocyanatotoluene as well as isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate Bis (4-isocyanatocyclohexyl) propane, trimethylhexane diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,
  • Mixtures of isocyanates can of course also be used. Examples include: Mixtures of structural isomers of 2,4-toluenediisocyanate and triisocyanatotoluene, e.g. Mixtures of 80 mol% 2,4-tolylene diisocyanate and 20 mol% 2,6-tolylene diisocyanate; Mixtures of ice and trans-cyclohexane-1,4-diisocyanate; Mixtures of 2,4- or 2,6-tolylene diisocyanate with aliphatic diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate.
  • Suitable isocyanate-reactive organic compounds (B3b) are preferably compounds with at least two isocyanate-reactive hydroxyl groups per molecule. Suitable However, compounds (B3b) which are net are also compounds which have only one isocyanate-reactive hydroxyl group per molecule. These monofunctionalized compounds can partially or completely replace the compounds containing at least two isocyanate-reactive hydroxyl groups per molecule in the reaction with the polyisocyanate (B3a).
  • polyether diols polyether diols
  • polyester diols lactone-based polyester diols
  • diols and triols with up to 12 carbon atoms
  • dihydroxycarboxylic acids dihydroxysulfonic acids
  • dihydroxyphosphonic acids polycarbonate diols
  • polyhydroxyolefins polysiloxanes with an average of at least two hydroxyl groups per molecule.
  • Suitable polyether diols (B3b) are, for example, homopolymers and copolymers of C2-C4-alkylene oxides, such as ethylene oxide, propylene oxide and butylene oxide, tetrahydrofuran, styrene oxide and / or epichlorohydrin, which in the presence of a suitable catalyst, e.g. Boron trifluoride are available.
  • a suitable catalyst e.g. Boron trifluoride
  • Further suitable polyether diols can be obtained by (co) polymerizing these compounds in the presence of a starter with at least two acidic hydrogen atoms, e.g.
  • polyether diols (B3b) are polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetrahydrofuran and copolymers thereof.
  • the molecular weight M n of the polyether diols is preferably 250 to 5000, particularly preferably 500 to 2500.
  • Polyester diols (hydroxypolyesters) suitable as isocyanate-reactive compound (B3b) are generally known.
  • Preferred polyester diols (B3b) are the reaction products of diols with dicarboxylic acids or their reactive derivatives, e.g. Anhydrides or dimethyl esters.
  • Suitable dicarboxylic acids are saturated and unsaturated aliphatic and aromatic dicarboxylic acids, which can carry additional substituents, such as halogen.
  • Preferred aliphatic dicarboxylic acids are saturated unbranched ⁇ , ⁇ -dicarboxylic acids which contain 3 to 22, especially 4 to 12, C atoms.
  • dicarboxylic acids examples include: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1, 12-dodecanedioic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, Endomethylentetrahydrophthal Acid Oxy - drid, terephthalic acid, dimethyl terephthalate and dimethyl isophthalate.
  • Saturated and unsaturated aliphatic and cycloaliphatic diols are particularly suitable as diols.
  • the particularly preferred aliphatic ⁇ , ⁇ -diols are unbranched and have 2 to 12, in particular 2 to 8, especially 2 to 4, carbon atoms.
  • Preferred cycloaliphatic diols are derived from cyclohexane.
  • diols examples include: ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 2-methylpropane-1, 3-diol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1 , 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, ice and trans-but-2-ene-1, 4-diol, 2-butyne-1, 4-diol and ice and trans-1 , 4-Di (hydroxymethyl) cyclohexane.
  • the molecular weight M n of the polyester diols is preferably 300 to 5,000.
  • Polyester diols based on lactone which are suitable as isocyanate-reactive compound (B3b) are based in particular on aliphatic saturated unbranched ⁇ -hydroxycarboxylic acids having 4 to 22, preferably 4 to 8, carbon atoms. Branched ⁇ -hydroxycarboxylic acids in which one or more —Chb groups in the alkylene chain are replaced by —CH (C 1 -C 4 -alkyl) - are also suitable.
  • Examples of preferred ⁇ -hydroxycarboxylic acids are ⁇ -hydroxybutyric acid and ⁇ -hydroxyvaleric acid.
  • diols are also suitable as isoeyanate-reactive compounds (B3b), the same preferences as above apply.
  • isoeyanate-reactive compounds B3b are triols which have in particular 3 to 12, especially 3 to 8, carbon atoms.
  • Trimethylolpropane is an example of a particularly suitable triol.
  • Dihydroxycarboxylic acids suitable as isocyanate-reactive compounds (B3b) are, in particular, particularly suitable aliphatic saturated dihydroxycarboxylic acids, which preferably contain 4 to 14 carbon atoms. Dihydroxycarboxylic acids of the formula are very particularly suitable R
  • COOH in A 1 and A 2 mean identical or different Ci-C4-alkylene radicals and R represents hydrogen or Ci-C4-alkyl.
  • DMPA dimethylolpropionic acid
  • dihydroxysulfonic acids and dihydroxyphosphonic acids are also suitable as isocyanate-reactive compounds (B3b).
  • dihydroxycarboxylic acid is also intended to include compounds which contain more than one carboxyl function (or anhydride or ester function). Such compounds can be obtained by reacting dihydroxy compounds with tetracarboxylic acid dianhydrides, such as pyromellitic dianhydride or cyclopentantetracarboxylic acid dianhydride, in a molar ratio of 2: 1 to 1.05: 1 in a polyaddition reaction and preferably have an average molecular weight M n of 500 to 10,000 .
  • tetracarboxylic acid dianhydrides such as pyromellitic dianhydride or cyclopentantetracarboxylic acid dianhydride
  • polycarbonate diols examples include the reaction products of phosgene with an excess of diols, in particular unbranched saturated aliphatic ⁇ , ⁇ -diols having 2 to 12, in particular 2 to 8, especially 2 to 4, carbon atoms.
  • Polyhydroxyolefins suitable as isocyanate-reactive compound (B3b) are, above all, ⁇ , ⁇ -dihydroxyolefins, with ⁇ , ⁇ -dihydroxybutadienes being preferred.
  • polysiloxanes which are also suitable as isocyanate-reactive compound (B3b) contain on average at least two hydroxyl groups per molecule.
  • Particularly suitable polysiloxanes have an average of 5 to 200 Si atoms (number average) and are mainly substituted with Ci-Ci2-alkyl groups, especially methyl groups.
  • isocyanate-reactive compounds (B3b) which have only one isocyanate-reactive hydroxyl group include, in particular, aliphatic, cycloaliphatic, araliphatic or aromatic monohydroxycarboxylic acids and sulfonic acids.
  • the polyurethane-based additives (B3) are prepared by reacting the compounds (B3a) and (B3b), the molar ratio of (B3a) to (B3b) generally being 2: 1 to 1: 1, preferably 1: 2: 1 to 1: 1, 2.
  • isocyanate-reactive compounds (B3b) it is possible to add further compounds with isocyanate-reactive groups, for example dithiols, thioalcohols, such as thioethanol, aminoalcohols, such as ethanolamine and N-methylethanolamine, or diamines, such as ethylenediamine, and thereby polyurethanes which, in addition to the urethane groups, also carry isocyanurate groups, allophanate groups, urea groups, biuret groups, uretdione groups or carbodiimide groups.
  • isocyanate-reactive compounds are aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which carry at least two primary and / or secondary amino groups.
  • the carboxyl groups of the reaction products (B3) are preferably at least partially in salt form in order to ensure solubility in water.
  • alkali metal salts such as sodium and potassium salts and ammonium salts are suitable.
  • the additives (B3) usually have average molecular weights M w of 500 to 250,000.
  • the surface-active properties of the additives (B3) can be set in a targeted manner by controlling the ratio of polar to nonpolar groups.
  • Such anionic surface-active additives are known and commercially available eg under the name Borchi® ® GEN SN95 (Borchers).
  • Water-soluble anionic surface-active additives based on acidic phosphoric acid, phosphonic acid, sulfuric acid and / or sulfonic acid esters of polyesters (B4) are based in particular on the reaction products of the above-mentioned polyethers (B1) with phosphoric acid, phosphorus pentoxide and phosphonic acid or Sulfuric acid and sulfonic acid.
  • the polyethers are converted into the corresponding phosphoric acid monoesters or diesters and phosphonic acid esters or the sulfuric acid monoesters and sulfonic acid esters.
  • acidic esters are preferably in the form of water-soluble salts, especially as alkali metal salts, especially sodium salts, and ammonium salts, but they can also be used in the form of the free acids.
  • Preferred phosphates and phosphonates are derived primarily from alkoxylated, especially ethoxylated, fatty and oxo alcohols, alkylphenols, fatty amines, fatty acids and resin acids
  • preferred sulfates and sulfonates are based in particular on alk- oxylated, especially ethoxylated, fatty alcohols, alkylphenols and amines, also polyvalent amines, such as hexamethylene diamine.
  • anionic surface active additives are known and commercially available for example under the name Nekal ® (BASF), Tamol ® (BASF), Crodafos ® (Croda), Rhodafac ® (Rhodia), Maphos ® (BASF), Texapon ® (Cognis), Empicol ® (Albright & Wilson), Matexil ® (ICI), Soprophor ® (Rhodia) and Lutensit ® (BASF).
  • Nekal ® BASF
  • Tamol ® BASF
  • Crodafos ® Crodafos ® (Croda)
  • Rhodafac ® Rhodia
  • Maphos ® BASF
  • Texapon ® Cognis
  • Empicol ® Albright & Wilson
  • Matexil ® ICI
  • Soprophor ® Rosit ®
  • Lutensit ® BASF
  • the preferred pigment preparations contain 45 to 90% by weight, preferably 55 to 90% by weight, of the coloring component (A) and 5 to 50% by weight, preferably 10 to 45% by weight, of water-soluble surface-active additive as a component (B).
  • these pigment preparations can also contain an antioxidant as additional component (C).
  • Component (C) is advantageously a constituent of those pigment preparations which contain at least 5% by weight of an additive (B) containing alkylene oxide groups in combination with inorganic pigments based on iron oxides, and stabilizes the pigment preparations for the drying step involved in their preparation.
  • antioxidants (C) are the known classes of sterically hindered phenols, aromatic amines, thiosynergists, phosphites and phosphonites and sterically hindered amines.
  • the antioxidants based on sterically hindered phenols contain as essential building block a phenol substituted by at least one tert-butyl group in the ortho position, in particular by tert-butyl groups in both ortho positions, to the OH group.
  • Most of the known products contain several of these building blocks, which are connected to each other via different bridge links.
  • the anti-oxidants based on aromatic amines are mainly diarylamines, amine / ketone condensation products, e.g. Aniline / acetone condensates and substituted p-phenylenediamines.
  • thiosynergists are the metal salts of dialkyldithiocarbamic acids, zinc dialkyldithiophosphates and esters (particularly dilauryl, dimyristyl and distearyl esters) of thiodipropionic acid.
  • the antioxidants based on phosphites and phosphonites are usually the esters of the corresponding phosphoric acids with alkyl-substituted, in particular tert-butyl-substituted, phenols.
  • the antioxidants based on sterically hindered amines contain, as an essential building block, a 2,6-dialkyl-substituted, in particular a -dimethyl-substituted, piperidine, which is linked in the 4-position to a wide range of bridging elements with other piperidine units.
  • HALS sterically hindered amines
  • Antioxidants are well known and available, for example under the name Irganox ®, Irgaphos® ®, Chimassorb ® and Irgastab ® (Ciba), topanol ® (ICI), Hostanox ® (Clariant) and Goodrite ® (Goodyear).
  • an antioxidant (C) is contained in the pigment preparations to be dispersed, its content is generally 0.1 to 5% by weight, in particular 0.1 to 2% by weight.
  • the pigment preparations are typically prepared by first subjecting the pigment (A1) to an aqueous suspension, in aqueous suspension containing at least part of the additive (B) and optionally the antioxidant (C), if desired a filler (A2) before or after the wet reduction of the Pigments (A1) is added to the suspension and the suspension is then dried, optionally after adding the remaining amount of additive (B).
  • the pigment (A1) can be used as a dry powder or in the form of a press cake.
  • the pigment (A1) used is preferably a finished product, i.e. the primary grain size of the pigment is already set to the value desired for the application. This pigment finish is particularly recommended for organic pigments, since the raw material obtained during pigment synthesis is generally not suitable for the application.
  • the primary grain size can also be set in the pigment synthesis, so that the pigment suspensions obtained can be used directly in the process according to the invention.
  • the finished pigment (A1) usually reaglomerates again on drying or on the filter unit, it is subjected to wet grinding, e.g. subjected to grinding in a stirred ball mill.
  • the additive (B) contained in the finished pigment preparation should be present, preferably the entire amount of additive (B) is added before the wet comminution.
  • the antioxidant (C) which may also form part of the pigment preparations, it is expedient to add it before the wet comminution.
  • a filler (A2) is used, it can be added before or after wet grinding. If it already has the desired particle size distribution, it is preferably only dispersed in the pigment suspension after the wet comminution of the pigment (A1). This applies in particular to fillers with a low hardness, such as chalk, which would be undesirably comminuted when the pigment was ground. Conversely, the comminution of a filler which is too coarse can advantageously be combined with the comminution of the pigment.
  • Finely divided granules with average grain sizes of 50 to 5,000 ⁇ m, in particular 100 to 1,000 ⁇ m, can be obtained.
  • Spray drying usually gives granules with average grain sizes ⁇ 20 ⁇ m.
  • Finely divided preparations can be obtained by drying in a paddle dryer and by evaporation with subsequent grinding.
  • the spray granulation is preferably carried out in a spray tower with a single-component nozzle.
  • the suspension is sprayed here in the form of larger drops, the water evaporating.
  • the additives melt at the drying temperatures and thus lead to the formation of largely spherical granules with a particularly smooth surface (BET values of generally ⁇ 15 m 2 / g, in particular ⁇ 10 m 2 / g).
  • the gas inlet temperature in the spray tower is generally 180 to 300 ° C, preferably 150 to 300 ° C.
  • the gas outlet temperature is usually 70 to 150 ° C, preferably 70 to 130 ° C.
  • the residual moisture of the pigment granules obtained is preferably ⁇ 5% by weight.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Mixers Of The Rotary Stirring Type (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

L'invention concerne un procédé de dispersion de préparations de pigments solides dans des liquides caractérisé en ce qu'il fait intervenir un mélangeur à grande vitesse fonctionnant selon le principe du rotor/stator.
PCT/EP2006/069100 2005-12-07 2006-11-30 Procede de dispersion de preparations de pigments solides dans des liquides WO2007065839A2 (fr)

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DE102005058633.3 2005-12-07
DE102005058633A DE102005058633A1 (de) 2005-12-07 2005-12-07 Verfahren zur Dispergierung von festen Pigmentzubereitungen in flüssigen Medien

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB818489A (en) * 1957-01-16 1959-08-19 Columbium Carbon Company Improvements in process and apparatus for effecting particulate dispersions
FR2789687A1 (fr) * 1999-02-12 2000-08-18 Lcw Les Colorants Wackherr Materiau pigmentaire dispersable en milieu aqueux
US20040206275A1 (en) * 2003-04-16 2004-10-21 Shakhnovich Alex I. Modified organic colorants and dispersions, and methods for their preparation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB818489A (en) * 1957-01-16 1959-08-19 Columbium Carbon Company Improvements in process and apparatus for effecting particulate dispersions
FR2789687A1 (fr) * 1999-02-12 2000-08-18 Lcw Les Colorants Wackherr Materiau pigmentaire dispersable en milieu aqueux
US20040206275A1 (en) * 2003-04-16 2004-10-21 Shakhnovich Alex I. Modified organic colorants and dispersions, and methods for their preparation

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