阅读说明：本技术 水基颜料制剂、其制备和用途 (Water-based pigment preparations, their production and use ) 是由 B·舍恩哈特 D·贝克 D·伽柏 F·霍夫曼 R·卡泊菲儿 于 2020-01-20 设计创作，主要内容包括：本发明涉及水性颜料制剂,包含：(A)至少一种有机和/或无机颜料和/或填料(B)至少一种式(I)或(II)的分散剂,或式(I)和(II)的分散剂的混合物,其中:n是大于或等于1,优选1-5,更优选1-2的整数,z是大于或等于1,优选1-10,更优选1-4的整数,R1是含1-10个碳原子的脂族、线性或支化烃基或氢原子或结构单元-O-X或结构单元-CH-(2)-O-X,和结构单元X对应于式(III)。(The present invention relates to an aqueous pigment preparation comprising: (A) at least one organic and/or inorganic pigment and/or filler (B) at least one dispersant of the formula (I) or (II), or a mixture of dispersants of the formulae (I) and (II), wherein n is an integer of 1 or more, preferably 1 to 5, more preferably 1 to 2, z is an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, R1 is an aliphatic, linear or branched hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom or a structural unit-O-X or a structural unit-CH 2 -O-X, and the structural unit X corresponds to formula (III).)

1. An aqueous pigment preparation comprising:

(A) at least one organic and/or inorganic pigment and/or filler

(B) At least one dispersant of the formula (I) or (II), or a mixture of dispersants of the formulae (I) and (II),

wherein:

n is an integer greater than or equal to 1,

z is an integer greater than or equal to 1,

r1 is an aliphatic, linear or branched hydrocarbon radical having 1 to 10 carbon atoms, or a hydrogen atom, or the structural element-O-X or the structural element-CH₂-O-X，

And the structural unit X corresponds to formula (III):

wherein:

a is an integer of 1 to 10 and,

b is an integer of 0 to 10,

c is an integer of 1 to 50,

m is 1 or 2; and

r2 is an aliphatic, linear or branched hydrocarbon radical having from 1 to 10 carbon atoms,

and wherein 95% of the particles in component (a) have a particle size <1 μm.

2. Composition according to claim 1, characterized in that it further comprises:

(C) a wetting agent, a surfactant,

(D) and/or additional surfactants and/or dispersants,

(E) and/or one or more organic solvents and/or one or more hydrotropic substances and/or mixtures thereof,

(F) and/or further additives customary for the preparation of aqueous pigment dispersions, and

(G) optionally, water.

3. The pigment preparation according to claim 1 and/or 2, comprising from 5% to 80% by weight of component (a).

4. The pigment preparation according to at least one of the preceding claims, comprising from 0.1% to 30% by weight of component (B).

5. Pigment preparation according to at least one of the preceding claims, characterized in that the following composition of components (A) to (G):

(A)5 to 80 percent by weight of the total weight of the composition,

(B)0.1 to 30% by weight,

(C)0 to 10% by weight of a stabilizer,

(D)0 to 20% by weight of a water-soluble polymer,

(E)0 to 30% by weight of a water-soluble polymer,

(F)0 to 20% by weight of a water-soluble polymer,

(G) the rest of the water is the water,

based in each case on the total weight of the pigment preparation (100% by weight).

6. Pigment preparation according to at least one of the preceding claims, characterized in that the following composition of components (A) to (G):

(A)10 to 70% by weight of a surfactant,

(B)2 to 20 percent by weight of a surfactant,

(C)0.1 to 5% by weight,

(D)1 to 10% by weight of a surfactant,

(E)5 to 20 percent by weight of a surfactant,

(F)0.1 to 5% by weight,

(G) the rest of the water is the water,

based in each case on the total weight of the pigment preparation (100% by weight).

7. Pigment preparation according to at least one of the preceding claims, characterized in that the organic pigment in component (A) is a monoazo pigment, a disazo pigment, a laked azo pigment, a β -naphthol pigment, a naphthol AS pigment, a benzimidazolone pigment, a disazo condensation pigment, an azo metal complex pigment or a polycyclic pigment selected from phthalocyanine pigments, quinacridone pigments, perylene pigments, peryleneone pigments, thioindigo pigments, anthanthrone pigmentsAnthraquinone pigments, flavanthrone pigments, indanthrone pigments, isoviolanthrone pigments, pyranthrone pigments, dianthrone pigmentsOxazine pigments, quinophthalone pigments, isoindolinones, isoindoline pigments and diketopyrrolopyrrole pigments, or carbon black.

8. Pigment preparation according to at least one of the preceding claims, characterized in that the structural units (I) and (II) of component (B) are reaction products of alkoxylated trihydroxy or polyhydroxy polyols, preferably diglycerol, erythritol, glycerol, pentaerythritol, polyglycerol, sorbitol, trimethylolpropane or xylitol.

9. Pigment preparation according to at least one of the preceding claims, characterized in that it has a viscosity of less than 1.0Pa s.

10. Pigment preparation according to at least one of the preceding claims, characterized in that 95% of the pigment particles have a particle size of less than 500 nm.

11. Pigment preparation according to at least one of the preceding claims, characterized in that 99% of the pigment particles have a particle size of less than 500 nm.

12. Pigment preparation according to at least one of claims 1 to 11, characterized in that the average particle size is less than 200 nm.

13. Pigment preparation according to at least one of claims 1 to 12, characterized in that the average particle size is less than 150 nm.

14. A process for the preparation of a pigment preparation according to at least one of claims 1 to 13, characterized in that component (a) in the form of a powder, granules or an aqueous presscake is dispersed in the presence of water (G) and component (B) and optionally (C), (D), (E) and (F) and is then optionally admixed with water (G) and optionally with one or more of components (C), (D), (E) and (F) and the resulting aqueous pigment dispersion is optionally diluted with water (G).

15. A process for the preparation of a pigment preparation according to claim 14, characterized in that the dispersion is carried out using a stirred ball mill operating at a circumferential stirrer speed of more than 10 m/s.

16. A process for the preparation of a pigment preparation according to claim 14 and/or 15, characterized in that the dispersion is carried out under the action of non-metallic grinding media having a diameter of less than or equal to 1.2 mm.

17. Use of a pigment preparation according to one or more of claims 1 to 13 for pigmenting natural or synthetic materials.

18. Use according to claim 17 for pigmenting aqueous coating materials, coatings, emulsion/gloss paints, water-dilutable paints, glazes, varnishes and wood protection systems.

19. Use according to claim 17 for the preparation of inks for writing instruments, colored pencil leads, fiber-tip pens, needle pens, felt pens, gel-point pens, text markers and white board markers.

20. Use according to claim 17 for the preparation of inks, printing inks, inkjet inks, microemulsion inks, UV-curable inks, and for those inks which function according to the hot-melt process, color filters, electronic inks and electronic paper.

21. Use according to claim 17 for the preparation of electrophotographic toners and developers, one-or two-component powder toners, magnetic toners, liquid toners, latex toners, polymerization toners and specialty toners.

22. Use according to claim 17 for colouring natural and synthetic fibre materials, insulation materials, glass wool, casings, seeds, fertilizers, glass bottles, plaster, cement, wood dyes, waxes, paraffins, drawing inks, ballpoint pen pastes, chalk, washing and cleaning agents, shoe care agents, latex articles, abrasives, for spin dyeing viscose fibres, and for colouring plastics.

The aqueous pigment preparations described in the prior art generally have particle sizes and particle size distribution ranges which are too large for them to be used in the above-mentioned applications. Furthermore, at the desired pigment content, their rheological properties and storage stability are often inadequate. Their color strength and compatibility with the application systems also require significant further improvement.

To date, no aqueous pigment preparations have been described which satisfy all the conditions of the above-mentioned applications without having to accept disadvantages.

It is an object of the present invention to provide aqueous pigment preparations in which 95% of the particles are preferably less than 500nm in size. These should also be free of alkylphenol derivatives, tristyrylphenol derivatives, novolac derivatives and bisphenol a derivatives as well as primary and secondary amines, and should be readily dilutable with alcohols of different chain lengths without coagulation or flocculation. In addition, the formulations should have as high a transparency and color intensity as possible and a lowest possible tendency to foam. The aqueous formulation should be storage stable, i.e. the above properties should remain stable even during a prolonged period of storage. The formulations must also be shear stable, i.e. the colour properties or colour intensity must not change significantly under shear.

This object is surprisingly achieved by dispersing the pigments by using specific copolymers of a tri-or polyol, styrene oxide and alkylene oxide as defined below. By virtue of the at least ternary starting molecule, these polymers have a star-branched or dendrimer structure with a more hydrophobic core and a more hydrophilic periphery. The use of different copolymers based on different starter molecules and having a composition or block sequence different from those described provides aqueous pigment preparations which do not have all of the above-described performance characteristics, in particular with regard to the desired particle size distribution, color properties, compatibility, viscosity and stability.

The present invention therefore provides an aqueous pigment preparation comprising:

(A) at least one organic and/or inorganic pigment and/or filler,

(B) at least one dispersant of the formula (I) or (II), or a mixture of dispersants of the formulae (I) and (II),

wherein:

n is an integer greater than or equal to 1, preferably from 1 to 5, more preferably from 1 to 2,

z is an integer greater than or equal to 1, preferably from 1 to 10, more preferably from 1 to 4,

r1 is an aliphatic, linear or branched hydrocarbon radical having 1 to 10 carbon atoms, or a hydrogen atom or the structural element-O-X or the structural element-CH₂-O-X，

And the structural unit X corresponds to formula (III):

wherein:

a is an integer of 1 to 10 and,

b is an integer of 0 to 10,

c is an integer of 1 to 50,

m is 1 or 2; and

r2 is an aliphatic, linear or branched hydrocarbon radical having from 1 to 10 carbon atoms,

wherein 95% of the particles in component (A) have a particle size of less than 1 μm, preferably less than 500 nm.

In addition, the pigment preparations of the present invention may also comprise the following further additives:

(C) optionally, a wetting agent,

(D) optionally, additional surfactants and/or dispersants,

(E) optionally, one or more organic solvents and/or one or more hydrotropic substances and/or mixtures thereof,

(F) optionally further additives customary for the preparation of aqueous pigment dispersions, and

(G) and (3) water.

Preferred pigment preparations comprise from 5% to 80% by weight, preferably from 10% to 70% by weight, more preferably from 30% to 70% by weight, of component (a).

Preferred pigment preparations comprise from 0.1% to 30% by weight, preferably from 2% to 20% by weight, more preferably from 5% to 15% by weight, of component (B).

Particularly preferred pigment preparations comprise the components in the following amounts:

(A) from 5% by weight to 80% by weight, in particular from 10% by weight to 70% by weight,

(B) from 0.1% to 30% by weight, in particular from 2% to 20% by weight,

(C) from 0% by weight to 10% by weight, in particular from 0.1% by weight to 5% by weight,

(D) from 0% by weight to 20% by weight, in particular from 1% by weight to 10% by weight,

(E) from 0% by weight to 30% by weight, in particular from 5% by weight to 20% by weight,

(F) from 0% by weight to 20% by weight, in particular from 0.1% by weight to 5% by weight,

(G) the rest of the water is the water,

based in each case on the total weight of the pigment preparation (100% by weight).

When the pigment preparations of the present invention comprise one or more of components (C), (D), (E) and (F), the minimum concentrations of said components are, independently of one another, preferably at least 0.01% by weight, in particular at least 0.1% by weight, based on the total weight of the pigment preparation.

Component (A) of the pigment preparations of the present invention is a finely divided organic or inorganic pigment or filler or a mixture of different organic and/or inorganic pigments and/or fillers. Component (a) may also be a dye soluble in certain solvents and having pigmentary properties in other solvents. The pigments may be used in dry powder form or as water-wet press cakes.

Suitable organic pigments include monoazo pigments, disazo pigments, laked azo pigments (laked azo pigments), β -naphthol pigments, naphthol AS pigments, benzimidazolone pigments, disazo condensation pigments (disazo condensation pigments), azo metal complex pigments and polycyclic pigments, such AS phthalocyanine pigments (phthalocyanin pigments), quinacridone pigments (quinacridone pigments), perylene pigments (perylene pigments), perinone pigments (perinone pigments), thioindigo pigments (thioindigo pigments), anthanthrone pigments (anthraquinone pigments), anthraquinonoid pigments (anthraquinone pigments), flavanthrone pigments (flavanthrone pigments), indanthrone pigments (indanthrone pigments), isoanthraquinonyl violet pigments (isoquinonyl pigments), pyranthrone pigments (anthraquinonyl pigments), laked anthraquinone pigments (anthraquinonyl pigments), and perylene pigments (polycyclic pigments)Oxazine pigments (dioxazine pigments), quinophthalone pigments (quinophthalone pigments), isoindolinone pigments (isoindolinone pigments), isoindoline pigments (isoindolinone pigments), and diketopyrrolopyrrole pigments (diketopyrrolopyrrole pigments) or carbon black.

Particularly preferred choices of organic pigments which may be mentioned by way of example include carbon black pigments, such as gas or furnace carbon black; monoazo and disazo pigments, in particular the color index pigments pigment yellow 1, pigment yellow 3, pigment yellow 12, pigment yellow 13, pigment yellow 14, pigment yellow 16, pigment yellow 17, pigment yellow 73, pigment yellow 74, pigment yellow 81, pigment yellow 83, pigment yellow 87, pigment yellow 97, pigment yellow 111, pigment yellow 126, pigment yellow 127, pigment yellow 128, pigment yellow 155, pigment yellow 174, pigment yellow 176, pigment yellow 191, pigment yellow 213, pigment yellow 214, pigment yellow 219, pigment red 38, pigment red 144, pigment red 214, pigment yellow 38, pigment redRed 242, pigment red 262, pigment red 266, pigment red 269, pigment red 274, pigment orange 13, pigment orange 34 or pigment brown 41; beta-naphthol pigments and naphthol AS pigments, especially the color index pigment red 2, pigment red 3, pigment red 4, pigment red 5, pigment red 9, pigment red 12, pigment red 14, pigment red 53:1, pigment red 112, pigment red 146, pigment red 147, pigment red 170, pigment red 184, pigment red 187, pigment red 188, pigment red 210, pigment red 247, pigment red 253, pigment red 256, pigment orange 5, pigment orange 38 or pigment brown 1; laked azo pigments and metal complex pigments, especially color index pigments-pigment red 48:2, pigment red 48:3, pigment red 48:4, pigment red 57:1, pigment red 257, pigment orange 68 or pigment orange 70; benzimidazoline pigments, in particular the color index pigments pigment yellow 120, pigment yellow 151, pigment yellow 154, pigment yellow 175, pigment yellow 180, pigment yellow 181, pigment yellow 194, pigment red 175, pigment red 176, pigment red 185, pigment red 208, pigment violet 32, pigment orange 36, pigment orange 62, pigment orange 72 or pigment brown 25; isoindolinone pigments and isoindoline pigments, especially color index pigment-pigment yellow 139 or pigment yellow 173; phthalocyanine pigments, in particular color index pigment-pigment blue 15, pigment blue 15:1, pigment blue 15:2, pigment blue 15:3, pigment blue 15:4, pigment blue 15:6, pigment blue 16, pigment green 7 or pigment green 36; anthanthrone pigments, anthraquinone pigments, quinacridone pigments, peryleneOxazine pigments, indanthrone pigments, perylene pigments, peryleneketone pigments and thioindigo pigments, in particular the color index pigments pigment-pigment yellow 196, pigment red 122, pigment red 149, pigment red 168, pigment red 177, pigment red 179, pigment red 181, pigment red 207, pigment red 209, pigment red 263, pigment blue 60, pigment violet 19, pigment violet 23 or pigment orange 43; carbon of triaryl groupPigments, especially color index pigments-pigment red 169, pigment blue 56 or pigment blue 61; diketopyrrolopyrrole pigments, especially color index pigments pigment Red 254, pigment Red 255, pigmentsRed 264, pigment red 270, pigment red 272, pigment orange 71, pigment orange 73, pigment orange 81.

Also suitable are lake dyes, such as Ca, Mg and Al lakes of sulfonic acid and/or carboxylic acid group containing dyes.

Examples of suitable inorganic pigments are titanium dioxide, zinc sulfide, zinc oxide, iron oxide, magnetite, ferromanganese oxide, chromium oxide, ultramarine, nickel antimony titanium oxide or chromium antimony titanium oxide, manganese titanium rutile, cobalt oxide, mixed oxides of cobalt and aluminum, rutile mixed-phase pigments, sulfides of rare earths, spinels of cobalt with nickel and zinc, spinels based on iron and chromium with copper, zinc and manganese, bismuth vanadate and extender pigments. More specifically, the color index pigments pigment yellow 184, pigment yellow 53, pigment yellow 42, pigment yellow brown 24, pigment red 101, pigment blue 28, pigment blue 36, pigment green 50, pigment green 17, pigment black 11, pigment black 33, and pigment white 6 are used. It is also generally preferred to use mixtures of inorganic pigments. Mixtures of organic and inorganic pigments are also commonly used.

Examples of suitable fillers are finely divided ores, minerals and slightly soluble or insoluble salts, such as carbonates, calcium carbonate, dolomite, silica, quartz, cristobalite, diatomaceous earth, silicates, aluminosilicates, silica, talc, kaolin, mica, feldspar and barium sulfate. It is also generally preferred to use mixtures of fillers. Mixtures of organic and/or inorganic pigments with fillers are likewise generally used. Formulations containing only one or more fillers are used, for example, in blending pigment formulations to adjust desired performance characteristics, such as pigment content, rheology, density, or compatibility.

The structural units (I) and (II) of component (B) are the reaction product of an oxyalkylatable trihydroxy or polyhydroxy polyol, preferably diglycerol, erythritol, glycerol, pentaerythritol, polyglycerol, sorbitol, trimethylolpropane or xylitol, more preferably glycerol and pentaerythritol.

In formula (III), the asterisk indicates the position of attachment of the group to the rest of the molecule (formula I or II). Starting from this bond, the structural unit having the stoichiometric index m must always be present before the structural unit having the stoichiometric index c, i.e. the polyol starter must always first react with styrene oxide and/or alkylene oxides other than ethylene oxide and then polymerize further with ethylene oxide. On the other hand, the blocks having stoichiometric indices a and b within the parentheses having the stoichiometric index m may be arranged in random or block.

As component (C) there are used, for example, cationic, anionic, amphoteric or nonionic compounds (wetting agents) which promote pigment wetting.

As component (D) of the pigment preparations of the present invention there are used conventional dispersants and surfactants which are suitable for preparing aqueous pigment dispersions, or mixtures of these substances. Anionic, cationic, amphoteric or nonionic surface-active compounds are generally used for this purpose. Of particular interest among them are dispersants having one or more medium or long chain hydrocarbon chains, including in some cases those having aromatic ring groups. Only a large number of compound options are listed here; however, the applicability of the formulations of the present invention is not limited to these examples. Examples are alkyl sulfates, such as lauryl, stearyl or stearyl sulfate, primary alkylsulfonates, such as dodecylsulfonate, and secondary alkylsulfonates, especially C₁₃-C₁₇Sodium alkane sulfonate salts, alkyl phosphate salts, alkyl benzene sulfonates such as dodecylbenzene sulfonic acid, and all salts of the compounds. Also suitable are soya phospholipids, or condensation products of fatty acids and taurine or hydroxyethanesulfonic acid, likewise castor oil rosin esters, fatty alcohols, fatty amines, alkoxylation products of fatty acids and fatty acid amides; these alkoxylation products may likewise have ionic end groups, for example in the form of sulfosuccinic acid monoesters or in the form of sulfonates, sulfates and phosphates, and also salts, sulfonates, sulfates or phosphates thereof. Nonionic or anionically modified copolymers prepared using macromonomers derived from polyethylene glycol/polypropylene glycol mono (meth) acrylates are also suitable, as are nonionic or anionically modified block copolymers, styrene oxide-containing polyoxyalkylenes.

Component (E) corresponds to an organic solvent or hydrotropic substance. They may be, for example, the following compounds or mixtures thereof: mono-or polyhydric alcohols, ethers and esters thereof, such as alkanols, especially those containing 1 to 4 carbon atoms, for example methanol, ethanol, propanol, isopropanol, butanol, isobutanol; dihydric or trihydric alcohols, especially those having from 2 to 5 carbon atoms, such as ethylene glycol, propylene glycol, propane-1, 3-diol, butane-1, 4-diol, pentane-1, 5-diol, hexane-1, 6-diol, hexane-1, 2, 6-triol, glycerol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol; lower alkyl ethers of polyhydric alcohols, such as ethylene glycol monomethyl, monoethyl or monobutyl ether, triethylene glycol monomethyl or monoethyl ether; ketones and ketoalcohols, such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol; copolymers of ethylene glycol and propylene glycol.

As component (F) are used, for example, thickeners, preservatives, viscosity stabilizers and grinding aids. Other conventional additives may be antisettling agents, light stabilizers, antioxidants, defoamers/deaerators, foam reducers, anti-caking agents and additives having a beneficial effect on viscosity and rheology. Suitable viscosity modifiers are, for example, polyvinyl alcohol and cellulose derivatives. Water soluble natural or synthetic resins and polymers may also be considered as film formers and binders to improve adhesive strength and abrasion resistance. The pH regulators used are organic or inorganic bases and acids. Preferred organic bases are amines, such as ethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, diisopropylamine, aminomethylpropanol or dimethylaminomethylpropanol. Preferred inorganic bases are sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia. Component (F) may also correspond to fats and oils of vegetable and animal origin, such as tallow, palm kernel fat, coconut fat, rapeseed oil, sunflower oil, linseed oil, palm oil, soya oil, peanut oil and whale oil, cottonseed oil, corn oil, olive oil, castor oil, rapeseed oil, safflower oil, soybean oil, thistle oil, sunflower oil, herring oil, sardine oil. Also commonly used additives are saturated and unsaturated higher fatty acids, such as palmitic acid, caprylic acid (cyprylic acid), capric acid, myristic acid, lauric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, caproic acid, caprylic acid, arachidic acid, behenic acid, palmitoleic acid, gadoleic acid, erucic acid and ricinoleic acid, and salts thereof.

The water used for preparing the pigment preparation component (G) is preferably used in the form of distilled or demineralized water. Drinking water (tap water) and/or water of natural origin may also be used.

The pigment preparations are characterized in that the particle size of component (A) is less than 1 μm, wherein preferably 95%, more preferably 99% of the pigment particles have a particle size of less than 1 μm, in particular less than 500 nm. The average particle size is less than 200nm, preferably less than 150 nm.

The pigment preparations have high transparency and color strength and have a low tendency to foam. They have a viscosity of less than 1.0 pas, preferably less than 0.7 pas, more preferably less than 0.5 pas. The pigment preparations are miscible with alcohols of different chain lengths, preferably ethanol, in any desired ratio without coagulation or flocculation of the pigment particles. The pigment preparations have good storage stability and good shear stability.

The pigment preparations of the present invention are also free of alkylphenol derivatives, tristyrylphenol derivatives, novolak derivatives and bisphenol a derivatives, as well as primary and secondary amines.

The invention also provides a process for the preparation of such pigment preparations, characterized in that component (A) in the form of a powder, granules or an aqueous presscake is dispersed in the presence of water (G) and component (B) and optionally (C), (D), (E) and (F) and then optionally admixed with water (G) and optionally one or more of components (C), (D), (E) and (F) and the resulting aqueous pigment dispersion is optionally diluted with water (G).

In this process, the pigment and the dispersant of the formula (I) or (II) or the mixture of dispersants of the formulae (I) and (II) are finely dispersed or finely divided in the presence of water using a dispersing unit or a combination of different dispersing units, preferably an agitated ball mill operating at a circumferential agitator speed of 10m/s or more and under the action of a non-metallic grinding medium having a diameter of less than or equal to 1.2mm, preferably less than or equal to 0.8 mm. The remaining additives may be present during the fine dispersion and/or added subsequently.

The present invention also provides for the use of the pigment preparations of the invention as colorants for the application of a wide variety of natural and synthetic materials, especially aqueous coating materials, paints, emulsion/gloss coatings (dispersion coatings), water-dilutable lacquers, glazes, varnishes and wood protection systems, printing inks, such as textile, flexographic, decorative or gravure printing inks, electrophotographic toners and developers, such as one-component or two-component powder toners (also known as one-component or two-component developers), magnetic toners, liquid toners, latex toners, polymerization toners, and specialty toners, inks, preferably inkjet inks, such as water-based or non-water-based ("solvent-based") inks, microemulsion inks, UV-curable inks, and also those which function according to the process, in hot-melt writing instruments, such as colored pencil leads, color pencils, and color pencils, Fiber-tipped pens, needle pens, felt pens, gel-coated rollers, inks for writing or whiteboard markers, and insulating materials, such as glass wool.

The pigment preparations of the present invention are also suitable for pigmenting a wide variety of polymeric materials, for example natural and synthetic fibre materials. Other applications are the colouring of sausage casings, seeds, fertilizers, glass, especially glass bottles, plaster, cement, wood colorants, waxes, paraffins (parafins), painting inks, ballpoint pen pastes, chalks, detergents and cleaners, shoe care agents, latex articles, abrasives, for spin-dyeing viscose (viscose), and for colouring a wide variety of plastics and high molecular weight materials. High molecular weight organic materials are for example: cellulose ethers/esters, for example ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, either alone or in mixtures, natural resins or synthetic resins, for example polymeric resins or condensation resins, such as aminoplasts, especially urea-and melamine-formaldehyde resins, alkyd resins, acrylic resins, phenolics, polycarbonates, polyolefins, for example polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylates, polyamides, polyurethanes or polyesters, rubbers, casein, latex, silicones, silicone resins.

In addition, the pigment preparations of the present invention can also be used as colorants for color filters of flat panel displays (both for additive and subtractive color generation), also for photoresists, and also as colorants for electronic inks ("e-inks") or electronic paper ("e-paper").

Examples

Examples of dispersants for the pigment preparations of the present invention are the following compounds obtained by alkoxylation of the corresponding polyols.

Preparation of pigment preparations:

the pigments, in powder, granular form or as presscake, are slurried in deionized water with dispersants and other additives and then homogenized and predispersed using a dissolver (e.g., from VMA-Getzmann GmbH, model AE3-M1) or another suitable apparatus. Subsequent fine dispersion is carried out by means of a bead mill (e.g. AE3-M1 from VMA-Getzmann GmbH) or another suitable dispersing unit, milling with zirconium silicate beads or zirconium oxide beads having a size d of 0.4-0.6mm being carried out with cooling until the desired color strength, color properties, transparency and particle size distribution are achieved. The dispersion is then adjusted to the desired final pigment concentration with deionized water, the grinding media is removed, and the pigment preparation is isolated.

The pigment preparations described in the following examples were prepared by the above-described method, wherein the ingredients were used in the prescribed amounts to form 100 parts of each pigment preparation. In the examples that follow, parts are by weight.

Evaluation of pigment preparations:

color strength and hue were determined in accordance with DIN 55986. To determine compatibility by the rub-off test, an emulsion paint or enamel is applied to the paint card after mixing with the pigment dispersion. The lower portion of the paint card is then rubbed with a finger. If this subsequently rubbed area is more strongly coloured than the adjoining, non-subsequently treated area, there is intolerance (the rub-off test is described in DE 2638946). The transparency of the pigment preparations was determined in aqueous acrylate varnish by drawing on a paint card with a black contrast strip.

Using a cone and plate viscometer (MCR 72) from Anton Paar GmbH (titanium cone:1 ℃) at 20 ℃, wherein the viscosity is measured between 0 and 200s^-1The dependence of viscosity on shear rate was investigated in the range of (1). At 60s^-1The viscosity was evaluated at the shear rate of (1).

The particle size distribution was determined using a disk centrifuge from CPS Instruments (CPS disk centrifuge DC24000 UHR).

To check miscibility with ethanol, the pigment preparation was diluted with water to 1% by weight and then ethanol was added gradually in 5% increments to a maximum addition of 50% ethanol. To evaluate the stability, the homogeneity of the mixture was evaluated visually after 7 days.

To evaluate the storage stability of the dispersions, the viscosity was measured immediately after the preparation and after 28 days of storage at 50 ℃. Furthermore, the color intensity of the samples thus stored was determined for samples stored at room temperature. In addition, the uniformity and deposition distribution of the stored samples were evaluated by measuring the formed deposits and supernatant.

The pigment preparations described in the following examples were prepared by the above-described method, using the ingredients shown below in the prescribed amounts to form 100 parts of each pigment preparation. In the examples that follow, parts are by weight.

Example 1

45.0 parts of component (A), C.I. pigment Red 112

7.0 parts of component (B), dispersant according to sample 1

11.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <180nm and 95% of the particles are less than 350 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.34Pa · s. The formulation is shear stable and does not foam.

Example 2

30.0 parts of component (A), C.I. pigment Violet 023

8.0 parts of component (B), dispersant according to sample 1

10.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <100nm and 95% of the particles are less than 250 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.04Pa · s. The formulation is shear stable and does not foam.

Example 3

45.0 parts of component (A), C.I. pigment Red 112

7.0 parts of component (B), dispersant according to sample 2

11.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <180nm and 95% of the particles are less than 350 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.11Pa · s. The formulation is shear stable and does not foam.

Example 4

45.0 parts of component (A), C.I. pigment Red 112

7.0 parts of component (B), dispersant according to sample 3

11.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <180nm and 95% of the particles are less than 350 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.68Pa · s. The formulation is shear stable and does not foam.

Example 5

40.0 parts of component (A), C.I. pigment blue 015:3

8.0 parts of component (B), dispersant according to sample 3

10.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <100nm and 95% of the particles are less than 180 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.19Pa · s. The formulation is shear stable and does not foam.

Although the c.i. pigment blue 015: 3-based pigment preparations described in DE 102006002800 have a viscosity in the desired range of <1Pa · s, their pigment content is only 30% by weight. In contrast thereto, the pigment content in example 5 shown above is 40 wt%, which corresponds to an increase of > 33% of the pigment content, while maintaining good storage stability and viscosity.

Example 6

33.0 parts of component (A), C.I. pigment Black 007

13.0 parts of component (B), dispersant according to sample 3

1.0 part of component (C), a wetting agent

0.8 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <50nm and 95% of the particles are less than 100 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.25Pa · s. The formulation is shear stable and does not foam.

Although the c.i. pigment black 007-based pigment preparation described in DE 102006002800 has a viscosity in the desired range of <1Pa · s, its pigment content is only 25% by weight. In contrast thereto, the pigment content in example 6 shown above is 33% by weight, which corresponds to a 32% increase in pigment content, while maintaining good storage stability and viscosity.

Example 7

30.0 parts of component (A), C.I. pigment Violet 023

8.0 parts of component (B), dispersant according to sample 3

10.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <100nm and 95% of the particles are less than 250 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.03Pa · s. The formulation is shear stable and does not foam.

Example 8

45.0 parts of component (A), C.I. pigment Red 112

7.0 parts of component (B), dispersant according to sample 4

11.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <180nm and 95% of the particles are less than 350 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.29Pa · s. The formulation is shear stable and does not foam.

Example 9

40.0 parts of component (A), C.I. pigment blue 015:3

8.0 parts of component (B), dispersant according to sample 4

10.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <100nm and 95% of the particles are less than 180 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.28Pa · s. The formulation is shear stable and does not foam.

Although the c.i. pigment blue 015: 3-based pigment preparations described in DE 102006002800 have a viscosity in the desired range of <1Pa · s, their pigment content is only 30% by weight. In contrast thereto, the pigment content in example 9 shown above is 40 wt%, which corresponds to an increase of > 33% of the pigment content, while maintaining good storage stability and viscosity.

Example 10

33.0 parts of component (A), C.I. pigment Black 007

13.0 parts of component (B), dispersant according to sample 4

1.0 part of component (C), a wetting agent

0.8 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <50nm and 95% of the particles are less than 100 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.05Pa · s. The formulation is shear stable and does not foam.

Although the c.i. pigment black 007-based pigment preparation described in DE 102006002800 has a viscosity in the desired range of <1Pa · s, its pigment content is only 25% by weight. In contrast thereto, the pigment content in example 10 shown above is 33% by weight, which corresponds to a 32% increase in pigment content while maintaining good storage stability and viscosity.

Example 11

30.0 parts of component (A), C.I. pigment Violet 023

8.0 parts of component (B), dispersant according to sample 4

10.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a consistently high color strength and transparency. Average particle size <100nm and 95% of the particles are less than 250 nm. The rub-off test showed no difference in all cases compared to the area of subsequent rubbing. The formulation is miscible with ethanol and has been found to have good flowability and storage stability. The viscosity after preparation was 0.03Pa · s. The formulation is shear stable and does not foam.

Comparative example 1

40.0 parts of component (A), C.I. pigment blue 015:3

8.0 parts of component (B), dispersant according to comparative sample 1

10.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparation is neither flowable nor storage-stable, since it has solidified after standing for <1 day. This can be attributed to the dispersant used providing inadequate pigment wetting and particle stabilization.

Comparative example 2

33.0 parts of component (A), C.I. pigment Black 007

13.0 parts of component (B), dispersant according to comparative sample 1

1.0 part of component (C), a wetting agent

0.8 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have low color strength and transparency. The color intensity was only 60% in example 6. The rub-off test showed that the white dispersion was not tolerated because the subsequently rubbed areas had higher color intensity. The formulation was not storage stable as the viscosity rose from 0.03 pas to 2.5 pas after 28 days of storage at 50 ℃.

Comparative example 3

30.0 parts of component (A), C.I. pigment Violet 023

8.0 parts of component (B), dispersant according to comparative sample 1

10.0 parts of component (E), propylene glycol

0.6 part of component (F), a preservative

The remaining part of component (G), water

The pigment preparations have a very low color strength. The color intensity was only 90% of that in example 2. The miscibility of the pigment preparations with ethanol was poor, since clearly visible coagulation or flocculation occurred during the addition of ethanol, and the pigment was deposited visually after <1 day.