JP2001524572A - Pigment preparations comprising inorganic pigments - Google Patents

Abstract

  (57) [Summary] The invention relates to a) titanium, zinc, tin, tungsten, molybdenum, nickel, bismuth, cerium, indium, hafnium, iron oxides and / or silicon carbide, zinc sulfide, barium titanate, calcium titanate and / or silicon And / or from a group consisting of solid silicon compounds in which the silicon is present in stoichiometric excess, wherein the average diameter of the primary particles is <500 nm, and b) at least other than the compounds specified under a) A colorant. The present pigment preparations are characterized by the resistance of the substrates colored with the preparation to light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

【Technical field】

The present invention relates to inorganic pigments, in particular pigment preparations comprising silicon or silicon compounds, to a process for their preparation and to their use, in particular as printing inks for ink jet printing.

[0002]

[Background technology]

Aqueous preparations of colorants, such as those used for ink jet printing, comprise not only water-soluble dyes but also organic and inorganic pigments and carbon black as colorants. Organic dyes, when used, for example, in ink jet printing, generally provide highly glossy, strongly colored prints, but exhibit poor light fastness compared to color pigments. Organic pigments have the disadvantage of often inadequate lightfastness compared to inorganic pigments and are therefore often unsuitable for use in various applications, for example for outdoor applications.

[0003] Even with liquid colorant preparations, improving lightfastness has always been a part of many effort goals.

[0004]

DESCRIPTION OF THE INVENTION

The present invention provides colored pigment preparations that exhibit improved lightfastness with respect to a combination of high optical density and gloss, especially in ink jet printing.

Now, a) titanium, zinc, tin, tungsten, molybdenum, nickel, bismuth, cerium, indium, hafnium, iron oxides and / or silicon carbide, zinc sulfide, barium titanate, calcium titanate and / or Solid compounds from the group consisting of silicon and / or solid silicon compounds in which silicon is present in stoichiometric excess, in which the average diameter of the primary particles is <500 nm, preferably <150 nm, in particular <120 nm And b) at least one colorant other than the compound specified in a), c) an optional dispersant, and d) optional water.

The presence of the two components c) and d) is preferred.

The silicon and silicon compounds of component a) are described in unpublished German patent application DE-A-
It has already been disclosed in 19647294.

[0008] Elemental silicon comprises amorphous or crystalline silicon, preferably crystalline silicon. The size of the silicon particles is preferably 1-120 nm, particularly preferably 1-120 nm.
It is -70 nm, very particularly preferably 5-50 nm. These particles preferably have a particle size distribution with a half-width of 40 nm or less. Silicon particles having this average diameter are preferably produced in a gas phase reaction (CVR) by the method described in U.S. Pat. No. 5,472,477. Similarly, German Patent Application D
It can also be produced by the method specified in EA-19647294.

[0009] Further, a solid compound is a solid compound at room temperature, for example, a silicide, CaSi _Two And / or BaSi_TwoTo cover. "Silicon is present in stoichiometric excess
A "solid compound" preferably has the formula Si_xZ_1-xWhere x> 0.5, preferably x>
0.7 and Z = C, N, O, Ge, Ca, Ba and Sr. other
The presence of a substance shifts the energy position of the absorption edge within a certain range,
Let it change shape. The preferred solid compound here is Si_xC_1-xOr Si_xGe_1-xIn
You.

[0010] In one preferred embodiment of the present invention, the solid compound in which silicon is present in a stoichiometric excess has a core / shell structure. The average diameter of the primary particles is preferably at most 120 nm, particularly preferably at most 100 nm, very particularly preferably at most 50 nm. These particles preferably exhibit a particle size distribution with a half width of 40 nm or less. The particles preferably comprise a titanium nitride core and a silicon shell, the silicon volume fraction preferably being at least 30% per particle.

In another preferred embodiment of the invention, the silicon component a) comprises silicon and bluish green (
Red (600 nm <λ <7) over the 400 nm <λ <550 nm spectral range.
(00 nm) in the form of a solid compound comprising particles having a strong absorption in the spectral range.

The preparation of the silicon component a) is likewise described in German patent application DE-A-1 964 729.
No. 4 (Page 5 of the Priority Text, Section 1) and is the subject of this specification.

In one preferred embodiment, the primary particles of the silicon component a) are spherical. It may be in the form of aggregates or aggregates.

[0014] The primary particles of the silicon component a) may be surrounded by an oxide layer that prevents direct aggregation of the Si primary particles, thus preventing aggregation. The thickness of this oxide layer is preferably from 1 to 300 nm, particularly preferably from 10 to 100 nm. The oxide layer can be applied after the production of the particles, for example by metering oxygen into a CVR reactor. The oxide layer is preferably composed of SiO _2.

The preparations according to the invention are preferably based on the colorant of component b), preferably from 0.01 to 500
% By weight, in particular from 0.01 to 250% by weight, in particular from 0.01 to 20% by weight, of component a).

Examples of suitable colorants of component b) include organic and inorganic pigments other than component a),
Bonblack or a water-soluble and water-insoluble dye. Here, the dye also includes an optical brightener.

Suitable carbon blacks are, in particular, acidic or alkaline blacks from the group of furnaces or gas blacks, as well as chemically or physically modified or improved carbon blacks; Examples are zinc sulfide, ultramarine, iron oxide, cobalt blue and chromium oxide pigments, as well as oxides in finely divided oxide form, such as silicon dioxide, titanium dioxide, nickel oxide, chromium antimony titanium oxide, aluminum oxide, and more. Particulate metals such as copper, iron or aluminum; and examples of suitable organic color pigments are azo, diazo, polyazo,
Anthraquinone and thioindigo systems, and other polycyclic pigments such as those of phthalocyanine, quinacridone, dioxazine, isoindolinone, naphthalenetetracarboxylic acid and perylene and perylenetetracarboxylic acid, and perinone;
From the indigoid, thioindigoid and diketopyrrolopyrrole systems, furthermore metal complex pigments of azo, azomethine or methine dyes, or lake dyes, for example Ca, Mg, Al lakes containing sulfonic and / or carboxylic acid groups. It is a dye.

Examples of water-soluble organic dyes are acid and basic dyes, and examples of water-insoluble dyes are disperse dyes or whitening agents (optical brighteners). Examples of disperse dyes that may be mentioned are:
From the azo, diazo, anthraquinone, coumarin, isoindolenine, quinoline and methine series.

In one preferred embodiment, the preparations of the invention have a blue-green spectral range of 400
nm <λ <550 nm red spectral range from 600 nm <λ <700 nm
Metal oxides and / or nitrides having a strong absorption to the colorant.
This is especially the case when unique yellow or orange pigments are used. Suitable such additives are pigments comprising titanium nitride with an average diameter of 1-400 nm, preferably 10-120 nm, or aggregates thereof. It is, for example, the US patent US-
It can be produced according to A5472777. Similarly suitable colorants are, for example, Nubix® from Nubiola SA.
Ultramarine pigment available as a pigment. More preferred are iron (II
I) Hexacyanoferrate (II). Also, iridium oxide pigments doped with 5% by weight or more of tin are suitable.

The particle size of representatives of the other components a) is preferably 1-500 nm, particularly preferably 1
-120 nm. These can also be obtained, inter alia, by the method of US Pat. No. 5,472,477. Dispersants The dispersants preferably relate to molecules having a molar mass of from 1,000 to 500,000, preferably from 1,000 to 100,000, in particular from 1,000 to 10,000 g / mol. Dispersants can be non-ionic, anionic, cationic or amphoteric compounds.

Examples of nonionic dispersants are the following: alkoxylates, alkylamides, esters, amine oxides, and alkyl polyglycosides.

Further suitable nonionic dispersants are: compounds which can be alkylated with alkylene oxides, such as fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols. For example, styrene-
Reaction products with phenol condensates, carboxamides and resin acids. These dispersants include, for example, ethylene oxide, a) a saturated and / or unsaturated aliphatic alcohol having 6 to 20 carbon atoms, or b) an alkylphenol having 4 to 12 carbon atoms in the alkyl group, or A saturated and / or unsaturated aliphatic amine having 14-20 carbon atoms, or d) a saturated and / or unsaturated aliphatic acid having 14-20 carbon atoms, or e) a hydrogenated and / or non-hydrogenated resin acid. It is an ethylene oxide adduct from the type of reaction product.

Particularly suitable ethylene oxide adducts are 5-120, specified under a) -e)
, Preferably 5-60, especially 5-30 moles of ethylene oxide.

[0024] Nonionic polymer dispersants are particularly preferred.

Examples of polymeric dispersants are listed in the index “Water-Soluble Synthetic Polymers: Properties and Behavior” [Philip Molineux, CRC Publishing, Florida, 1983/84, Volume I + II]. Compound.

Further examples of suitable polymer dispersants are water-soluble and water-emulsifiable compounds, such as homopolymers, copolymers, graft polymers, graft copolymers, and random block copolymers. .

Examples of particularly suitable polymer dispersants are AB, BAB and ABC block copolymers. In the AB or BAB copolymer, the A segment is a hydrophobic homopolymer or copolymer that secures affinity for the pigment, and the B block is a hydrophilic homopolymer or copolymer or a salt thereof, Ensure dispersion in aqueous medium. Polymer dispersants of this type and their synthesis are described, for example, in EP-A51
No. 8225 and EP-A 556 649.

Further examples of suitable polymeric dispersants are polyethylene oxide, polypropylene oxide, polyoxymethylene, polytrimethylene oxide, polyvinyl methyl ether, polyethylene imine, polyacrylic acid, polyarylamide, polymethacrylic acid , Polymethacrylamide, poly-N, N-dimethyl-acrylamide,
Poly-N-isopropylacrylamide, poly-N-acryloylglycinamide, poly-N-methacryloylglycinamide, polyvinyl alcohol, polyvinyl acetate, copolymer of polyvinyl alcohol and polyvinyl acetate, polyvinyl pyrrolidone, polyvinyl oxazolidone And polyvinyl methyl oxazolidone.

Also of interest are natural polymer dispersants such as cellulose, starch, gelatin or derivatives thereof as polymer dispersants. Particularly suitable polymers are those comprising amino acid units, such as polylysine, polyaspartic acid and the like.

Examples of anionic dispersants are: alkyl sulfates, ether sulfates, ether carboxylates, phosphate esters, sulfosuccinates, sulfosuccinate amides, Paraffin sulfonate, olefin sulfonate, sarcosine, isothionate, taurate and lignin type compounds.

[0031] Anionic polymer dispersants are particularly preferred.

Suitable anionic polymeric dispersants are, in particular, the condensation products of aromatic sulfonic acids with formaldehyde, for example of formaldehyde and alkylnaphthalenesulfonic acids or of formaldehyde and naphthalenesulfonic acids and / or benzenesulfonic acids, and optionally It is a condensation product of a substituted phenol with formaldehyde and sodium bisulfite.

The naphthol is further reacted with an alkanol and the product is subjected to an addition reaction with an alkylene oxide to convert at least some of the terminal hydroxyl groups to sulfo groups or monoesters of maleic acid, phthalic acid or succinic acid. The condensation products obtained by the conversion are also suitable.

Furthermore, dispersants from the group of the sulfosuccinates and the alkylbenzenesulfonates are suitable. Sulfated or alkoxylated fatty acid alcohols or salts thereof. Alkoxylated fatty alcohols are especially 5-120, preferably 5-60.
, In particular 5-30 granted saturated or unsaturated C ₆ -C ethylene oxide ₂₂ fatty acid alcohols, especially stearyl alcohol - a le. Particularly preferred is 8-1
Stearyl alcohol alkoxylated with 0 ethylene oxide units. The sulfated alkoxylated fatty acid alcohol is preferably in the form of a salt, especially an alkali metal or amine salt, preferably a diethylamine salt.

Further examples of anionic polymer dispersants are salts of polyacrylic acid, polyethylene sulfonic acid, polystyrene sulfonic acid, polymethacrylic acid, and polyphosphoric acid.

Further examples of anionic polymeric dispersants are copolymers of acrylic monomers, indicated by the following monomer combinations (ie, random, alternating or grafted): It is a copolymer: acrylamide, acrylic acid; acrylamide, acrylonitrile; acrylic acid, N-acryloylglycinamide; acrylic acid, ethyl acrylate; acrylic acid, methyl acrylate; acrylic acid, methylenebutyrolactam; N-acryloylglycine Amide, N-isopropylacrylamide; methacrylamide, methacrylic acid; methacrylic acid, benzyl methacrylate; methacrylic acid, diphenylmethyl methacrylate; methacrylic acid, methyl methacrylate; methacrylic acid, styrene.

Further anionic polymer dispersants are styrene-maleic anhydride copolymers, their copolymers with the acrylic monomers mentioned above, and polyurethane-based polymers, such as, among others, European Patent Application Publication No. It is based on the star-shaped oligourethanes of EP-A 331066 or EP-A400410.

Further, a graft polymer and a graft copolymer in which a nonionic and / or anionic vinyl monomer is grafted on a polymer backbone are also suitable. Synthetic or natural protective colloids can be used as the polymer backbone.

Also suitable are lignin sulfonates, such as those obtained by the sulfite or kraft process. These are preferably partially hydrolyzed, oxidized,
Products which are propoxylated, sulfonated, sulfomethylated or disulfonated and fractionated by known methods, for example by molecular weight or by the degree of sulfonation. Mixtures of sulfite and kraft lignin sulfonate are also very effective. Particularly, a mixture of sulfite and kraft lignin sulfonate is very effective. Particularly suitable lignin sulfonates are 1,000-100,00
It has an average molecular weight of 0 or more, an active lignin sulfonate content of at least 80% and preferably a low polyvalent cation content. The extent of this sulfonation can vary widely.

Examples of cationic dispersants are as follows: quaternary alkyl ammonium compounds and imidazoles.

[0041] Cationic polymer dispersants are particularly preferred.

Examples of the cationic polymer dispersant include polyethyleneimine, polyvinylamine, poly (2-vinylpyridine), poly (4-vinylpyridine), poly (diallyldimethylammonium) chloride, poly (4-vinylbenzyl) Trimethylammonium) and poly (2-vinylpiperidine).

Examples of amphoteric dispersants are the following compounds: betaine, glycinate, propione
And imidazoline.

Anionic and cationic polymers can be summarized as polyelectrolytes and dissolve completely or partially in aqueous and / or organic layers.

The dispersants used are preferably, based on component a) and optionally b), 0.1-
It is used in an amount of 200% by weight, especially 0.5-100% by weight.

If water-insoluble dyes or pigments or carbon black are used as colorants, the amount of dispersant used is preferably based on the sum of components a) and b).

In addition to the dispersants used, the pigment preparations according to the invention may comprise further cationic, anionic, amphoteric and / or nonionic and / or surface-active compounds. Examples of these are the indexes “Surfactant Europa,
Directory of Surfactants Spread in Europe "[Gordon L. Hollis (H
ollis), Royal Society of Chemistry (Royal)
Society of Chemistry, Cambridge) (199)
5)].

If the dispersants used contain ionic groups, these auxiliaries can preferably be non-ionic or of the same ionic nature.

The pigment preparations used in particular as printing inks for ink-jet printing preferably contain an organic solvent as further component e).

Suitable organic solvents (e) are aliphatic C₁ -C_Four Alcohols, such as methanol,
Ethanol, isopropanol, n-propanol, n-butanol, isobutanol
Knol or tert-butanol, 1,5-pentadiol, aliphatic ketone,
For example, acetone, methyl ethyl ketone, methyl isobutyl ketone or diacetate
Alcohols, polyols such as ethylene glycol, propylene glycol
, Butylene glycol, diethylene glycol, triethylene glycol, triethylene glycol
Methylol propane, average molar mass 100-4000, preferably 400-15
00 g / mol polyethylene glycol or glycerol, monohydroxy
Ether, preferably monohydroxyalkyl ether, particularly preferably mono-C ₁ -C_FourAlkyl glycol ethers such as ethylene glycol monoalkyl,
Monomethyl, diethylene glycol monomethyl ether or diethylene glycol
Monoethyl ether, diethylene glycol monobutyl ether, dipropyl
Lenglycol monoethyl ether, thiodiglycol, triethyleneglycol
Monomethyl ether or monoethyl ether, and also 2-pyrrolidone, N
-Methyl-2-pyrrolidone, N-ethylpyrrolidone, N-vinyl-pyrrolidone,
1,3-dimethyl-imidazolidone, dimethylacetamide and dimethylform
Amides.

Mixtures of the abovementioned solvents are also suitable.

The amount of organic solvent is preferably 0-40, especially 2-20, based on the pigment preparation.
% By weight.

The amounts of water and organic solvent are preferably 20-99, in particular 30-97% by weight, based on the pigment preparation.

The pigment preparations can furthermore be used as agents for adjusting the viscosity of the ink, such as polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose and so long as they do not adversely affect the stability of the printing ink, the printing behavior and the drying on paper. Other reagents known to those skilled in the art may be included.

As further additives, mention may also be made of compounds from the group of the terpenes, terpenoids, fatty acids and fatty acid esters. The preferred compounds are ocimene, myrcene, geraniol, nerol, linalool, citronellol, geranial, citronellal, neral, limonene, menthol, such as (-) menthol, menthol. Or bicyclic monoterpenes, saturated and unsaturated fatty acids having 6-22 carbon atoms, such as stearic acid, oleic acid, linoleic acid and linolenic acid or mixtures thereof.

In essence, the present pigment preparations contain further additives, such as preservatives (biocides), further wetting or surfactants, spacers, leveling agents, stabilizers, further UV stabilizers. Agents, plasticizers, lubricants and optionally a pH regulator.

Examples of suitable biocides are isothiazolone and benzisothiazolone.

Suitable spacers and leveling agents have, in particular, an average particle diameter in the range from 0.2 to 30 μm and are described, for example, in DE 33 33 542. The spacer is preferably insoluble in water and resistant to the addition of solvents used in the ink. Examples of suitable spacers or leveling agents are polymethyl methacrylate, polystyrene, styrene-divinylbenzene copolymer, cross-linked polymethyl methacrylate,
And cross-linked or non-cross-linked polyvinyl toluene.

Suitable stabilizers are o-, m- and p-dihydroxybenzene, hydroxychroman, 5-hydroxycoumarane, spirochroman, spiroindane, p-alkoxyphenol, sterically hindered phenols, gallic acid derivatives, Methylenedioxybenzene, aminophenol, aminoaniline, sterically hindered amine, esterified or etherified derivative having a phenolic hydroxyl group, and acylated or alkylated derivative having an aromatic amino group, metal complex It is.

Particularly suitable stabilizers are compounds based on sterically hindered amines, preferably 2,2,6,6-tetraalkylpiperidines, particularly preferably at least one covalently bound 2,2,6,6 Service 2, 2, tetraalkylpiperidine fragment
It is a compound based on 6,6-tetraalkylpiperidine.

In many cases, it has been found to be particularly effective to use certain color image stabilizer combinations.

[0062] Suitable UV absorbers are described, for example, in DE 19503885.

The plasticizers and lubricants used are, for example, core-shell latexes having a soft core and hard shell, latexes consisting of a soft core and a shell of cross-linked gelatin, and those having a soft interlayer.

Examples of pH adjusters include NaOH, ammonia or aminomethylpropanol,
N, N-dimethylaminoethanol.

Examples of preservatives are methyl and chloromethylisothiazolin-3-one, benzisothiazolin-3-one or mixtures thereof.

As a further special aspect of the invention, in addition to components a) and b) and optionally c) and d), further sterically hindered amines, preferably 2,2,6,6-tetraalkylpiperidines And particularly preferably at least one covalently bound 2,2
There is a pigment preparation of the present invention comprising a compound based on a 2,2,6,6-tetraalkylpiperidine, including a 2,6,6-tetraalkylpiperidine fragment.

The pigment preparations according to the invention preferably comprise 0.01 to 500% by weight, preferably 0.01 to 500% by weight, based on the colorant of component b).
250% by weight, in particular 0.01-20% by weight, of component a), 1-99.95% by weight, based on the preparation, preferably 1-65% by weight of component b
A), optionally 0.1 to 200% by weight, in particular 0.5 to 100% by weight, based on the sum of components a) and optionally components a) and b), of dispersants of component c) and pigment preparations. 0-98% by weight, in particular 0.2-98% by weight, particularly preferably 10-98% by weight, very particularly preferably 30-98% by weight, based on water.

The invention furthermore relates to the pigments and colorants b) of component a), especially if they are organic or inorganic pigments or water-insoluble dyes or whitening agents, dispersants c) and optionally The invention relates to a process for the preparation of pigment preparations as printing inks for ink-jet printing, characterized in that at least a part of the further additives is homogenized and the homogenized mixture is optionally subjected to wet grinding.

According to the present invention, the preparation of the pigment preparation is for converting the “crude pigment” obtained from the preparation of the pigment into the desired finely divided state and for breaking up their agglomerates and / or aggregates To this end, it also involves optionally modifying the surface of the pigment of component a) in water and / or a polar organic solvent. A method for this purpose is described, for example, in European Patent Application Publication No. EP
No. 0650945A2.

Another possibility of breaking up the pigment agglomerates of component a) is to pretreat the pigment powder with a dilute ammonia solution.

According to the present invention, a pigment preparation comprising component a) and a pigment preparation further comprising only the pigment of component b) or only water-insoluble pigments are first prepared separately, To obtain the pigment preparation of the present invention.

If a water-insoluble colorant of component b) is used, the pigment of component a) is optionally combined with the colorant of component b) in powder form or water-moist presscake form, optionally after surface modification. Firstly, optionally with a dispersant and at least some water, preferably deionized water, it is generally subjected to an optional pre-milling step prior to homogenous milling, for example by using a stirred vat, solubilizer and similar equipment. Beating (ie introducing and homogenizing) the suspension
I do.

The milled suspension may contain a low-boiling (boiling point <150 ° C.) solvent fraction which can be removed by evaporation in the course of further milling. However, it may also contain a fraction of the high-boiling solvent or further additives as described above, for example grinding aids, defoamers or wetting agents.

The wet milling of component a) or of component b) or of a) + b) serves both premilling and milling. In this case, the pigment concentration of the suspension is preferably above the concentration desired for the final pigment preparation or for printing. The desired final pigment concentration is preferably adjusted after wet milling. After pre-milling, the milling is performed to the desired finely divided state of the particles. Milling equipment suitable for this milling step include, for example, kneaders, roll mills, kneader screws, ball mills, rotor-stator mills, solubilizers, corundum disk mills, vibratory mills, and the like. In particular, it comprises a high-speed, continuous or discontinuous charged stirred ball mill containing a grinding medium of diameter 0.1-5 mm. The grinding media can be glass, ceramic or metal, for example steel. The milling temperature is preferably in the range from 0 to 250 ° C., but is generally at room temperature, in particular below the cloud point of the dispersant of component c) used and of the optional surfactant.

In a likewise preferred manner, the grinding is partly or wholly carried out in a high-pressure homogenizer or a so-called jet disperser (known from DE-A 195 36 845).
Can be performed. With these devices, fragments of grinding media in suspension and / or elution of soluble substances from grinding media (ie ions from glass media)
Can be reduced to a minimum or completely avoided.

In the dilution step, the pigment preparation obtained is mixed in a manner known per se, optionally with the remaining amount of dispersant and optionally further additives, into water, homogenized and the preparation or printing ink To the desired final pigment concentration or color strength. In this case, it is also possible to add additional dispersants as needed, for example to prevent reaggregation of the fine pigment particles in the diluent.

In the milling step for producing pigment concentrates, a method for producing pigment preparations in which sufficient dispersant is present for stabilization is particularly advantageous. Subsequently or after dilution with water, the excess surfactant and / or dispersant present in the solution and not adsorbed on the pigment is preferably removed, and then the remaining fraction of the pigment preparation is added. To standardize the desired pigment preparation.

A method for removing the dispersant present in the solution is, for example, stretching of the suspension and subsequent tilting of the supernatant. Membrane filtration or microfiltration techniques are also suitable.

It is also possible to optionally add other additives, for example polyurethane or acrylic polymers, to further improve the water fastness. These polymers may be water-soluble or essentially water-emulsifiable and may be soluble in the one present in b).

In a preferred method, the pigment preparation is mixed and homogenized using a jet disperser or a high-pressure homogenizer in order to suppress foam formation and prevent possible re-agglomeration.

Standardization of the desired pigment preparation is to standardize for the desired viscosity, color strength, hue, density and surface tension of the ink.

Prior to using the pigment preparation as a printing ink, the ink may optionally be added, for example, from 0.5-5
Filtered through a μm membrane filter or glass filter.

In general, the physical properties of the ink are standardized for use in conventional ink jet printing. Its surface tension is preferably 20-70 mN / m and its viscosity is preferably not more than 20 mPas, especially 0.5-10 mPas.

The printing ink of the present invention and the printing ink used in the present invention, when used as a printing ink for ink jet printing, give printed matter having excellent light fastness and high optical density, and further have the following advantages. Has: outstanding dispersion and storage stability over a wide temperature range, no clogging of the print head (known as kogation or clogging), various substrates of the printed matter, for example mechanical Paper, intermediate paper, size and coating paper, polymer film,
High water and migration fastness on OHP sheets, no bleeding when used with dye or other pigment inks, even in multicolor printing.

The pigment preparations described above are preferably used as printing inks for ink jet printing.

Ink jet printing is known per se and is generally carried out in such a way that the printing ink fills the acceptor container of the ink jet print head and is sprayed in droplets onto a substrate. The jetting of the ink in droplet form is preferably by means of a piezoelectric crystal, a heated cannula (bubble jet or hot jet method), in which pressure is applied to the ink system and the ink droplets are jetted accordingly, or by mechanical This is done by a static pressure increase. The droplets are deposited on a substrate, such as paper, wood, textile, plastic, or metal,
Fired along the target from one or more small nozzles (fire
d). Under electronic control, individual droplets together on a substrate form a structural symbol or graphic.

A method is also possible in which a very small volume in the form of droplets is provided on a substrate from one ink jet by electrostatic deflection.

The invention furthermore relates to the use of the pigment preparations as printing inks for ink jet printing and for pigmenting natural or synthetic materials, in particular plastics, leather and paper, in whole or only on the surface.

In particular, the pigment preparations are used in automotive paints, emulsion paints, dispersion coating materials, printing inks, water-dilutable coating systems, aqueous flexographic and gravure inks, wallpaper colorants, aqueous wood preservatives For producing preservative and wood stains, primers, and also for the cores of color pencils, fiber tip pens, ink jet inks, Indian inks, pastes for ball pens, chalks, laundry detergents and cleaning products. It is also suitable for coloring pigments in shoes, nonwoven fabrics, colorants for paper raw materials, colored paper coating slips, printing inks for cardboard packaging, colorants for latex products, abrasives, spin dyeings and films.

Particularly preferably, the pigment preparations are used as printing inks for ink jet printing.

[0091]

【Example】

 Example 1 Production and Use of Zinc Oxide as a Light Stabilizer in Ink Jet Inks

[0092]

Embedded image

The raw material solution (A) (raw ink) of a sodium salt type magenta dye having an E1 / 1 value of 12 was prepared without using the salt of the above-described magenta dye having an E1 / 1 value of 53 (salt-free).
e) Aqueous solution (pure dye content approx. 10.4% by weight) 22.8 g 1, prepared by homogeneous mixing of 1,5-pentadiol 6.2 g 2-pyrrolidone 6.2 g and water 64.8 g. (E1 / 1 value: absorbance value of the longest wavelength absorption band of the light spectrum obtained by measuring a 1% solution of the dye in a measurement cell having a path length of 1 cm) Further, 1,5-pentanediole 8.0 g 2-pyrrolidone A solvent mixture (B) consisting of 8.0 g of 84.0 g of water was also prepared.

Subsequently, 5 g of the raw material solution (A), 4.4 g of the solvent mixture (B), had a primary particle diameter of 10 to 30 nm as measured by a transmission electron microscope (TEM), and was measured by ultracentrifugation. mass distribution, 43 nm less than (d ₅₀ of 43 nm) particles 50 wt% 65 nm less than (65 nm of d ₅₀₎ particle 90 wt% 25 nm less than (25 nm of d ₅₀₎ particle 10 mass% of oxide having an aggregate particle size A printing ink is manufactured by homogeneously mixing 0.6 g of an aqueous zinc oxide dispersion containing 30% by weight of zinc, 2% by weight or less of polyacrylic acid and water, and the ink thus manufactured is originally contained in a black cartridge HP51626A. By filling it as an alternative to the ink that was previously used, HP DeskJet 500C (Hutet Packard (H
The printing was performed using a thermal ink jet printer (manufactured by Ewlett Packard). The inks of the present invention printed perfectly and had very good storage stability.

Standard paper (Agfa-701, Agfa-Gebert (Agfa-Ge
vaert)) and special ink-jet paper (HOMOGENTISATE PHYTYLT)
(RANSFERASE Premium), Hewlett-Packard), and the prints were then exposed to xenon light of 750 W / m ² intensity for 12 hours, filtering out UV light below 290 μm wavelength. The residual color difference D was then determined according to the Cielab system, which was compared with the unexposed printed material.
Lightfastness was evaluated based on E * and hue angle difference Hab *. Table 1 shows the results. The smaller the value of the residual color difference, the better the light fastness.

Example 2 As described in Example 1, a printing ink was prepared comprising 5 g of the raw material solution (A), 2.5 g of the solvent mixture (B), and 2.5 g of the same zinc oxide dispersion as in Example 1. And printed and tested as in Example 1. Comparative Example As described in Example 1, a printing ink consisting of 5 g of the raw solution (A) and 5 g of the solvent mixture without light stabilizer (B) was prepared and printed as in Example 1, Tested.

[0097]

[Table 1]

It can be seen that the dye inks prepared and printed according to Examples 1 and 2 show a significantly improved lightfastness.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 11/00 C09D 11/00 201/00 201/00 D06P 1/44 D06P 1/44 E (81) Designation Country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG) , CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, D , DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT , UA, UG, US, UZ, VN, YU, ZW (72) Inventor Nitzsen, Peter-Rozier Germany Day 41542 Dolmagane Magnolien Jutrase 6 (72) Inventor Hausier, Bernd Germany Republic Day-51373 Reefel Kusen-Mühlenbeek 90 (72) Inventor Kutzkert, Eberhard Germany Day-51375 Reefel Kusen Amsielf Embrandt 67 F-term (reference) 4H057 AA02 B A15 CA29 CA38 CB35 CB37 CB39 CB40 CB41 CB43 CB49 CB54 CC02 DA01 DA21 GA06 4J002 AA001 DA037 DE096 DE106 DE116 DE136 DE186 DG016 DJ006 EU118 FD096 FD097 FD098 4J037 AA08 AA11 AA15 AE22 AA22 DD22 CE052 CF022 CG032 CG142 CG172 CH032 CK032 CQ012 DF012 DJ012 HA036 HA216 HA326 HA436 JB01 KA06 KA08 KA09 LA06 LA07 MA08 MA10 NA03 PC08 PC09 PC10 4J039 AE07 BA01 BA04 BA13 BA18 BA20 BA30 BA31 BA33 BC35 BC36 BC33 BC38 BC BC54 BE01 BE06 BE07 BE08 BE12 BE22 CA06 EA33 EA35 GA24

Claims (12)

[Claims] 1. a) titanium, zinc, tin, tungsten, molybdenum, nickel, bismuth, cerium, indium, hafnium, oxides of iron and / or silicon carbide, zinc sulfide, barium titanate, calcium titanate and / or From the group consisting of silicon and / or solid silicon compounds in which silicon is present in stoichiometric excess, solid compounds in which the average diameter of the primary particles is <500 nm, and b) less than the compounds specified in a) A pigment preparation, comprising: at least one colorant. 2. A) silicon and / or a solid silicon compound in which the silicon is present in a stoichiometric excess, wherein the average diameter of the primary particles is <120 nm, and b) at least one colorant. A pigment preparation according to claim 1. 3. Titanium, zinc, tin, having an average primary particle size of <120 nm,
Including as component a) a solid compound from the group consisting of oxides of tungsten, molybdenum, nickel, bismuth, cerium, indium, hafnium, iron and / or silicon carbide, zinc sulfide, barium titanate and / or calcium titanate. A pigment preparation according to claim 1, wherein the pigment preparation comprises: 4. The pigment preparation according to claim 1, which comprises, in addition to components a) and b), at least one dispersant c) and water d). 5. The solid compound in which silicon is present in a stoichiometric excess is of the formula Si _x Z_1-xWhere x> 0.5, preferably x> 0.7 and Z = C, N, O, Ge, C
The pigment preparation according to claim 1, which is a compound of a, Ba and Sr. 6. The pigment according to claim 1, wherein the colorant of component b) used is an organic or inorganic pigment, carbon black or a water-soluble or water-insoluble dye or an optical brightener. Preparation. 7. The following group: aliphatic C ₁ -C ₄ alcohols, such as methanol,
Ethanol, isopropanol, n-propanol, n-butanol, isobutanol or tert-butanol, 1,5-pentaneddiol, aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or di Acetone alcohol, polyol such as ethylene glycol, propylene glycol
, Butylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane, average molar mass of 100-4000, preferably 400-1.
500 g / mol of polyethylene glycol or glycerol, monohydroxy ether, preferably monohydroxyalkyl ether, particularly preferably mono-hydroxyalkyl ether.
C ₁ -C ₄ alkyl glycol d - ether, for example ethylene glycol - monoalkyl, monomethyl, diethylene glycol monomethyl ether or diethylene glycol - monoethyl - ether, diethylene glycol - monobutyl - ether, dipropylene glyco - monoethyl - ether, Chiojiguriko - Le, triethylene Glycol monomethyl ether or monoethyl ether, and also 2-pyrrolidone,
2. The composition of claim 1, further comprising an organic solvent from N-methyl-2-pyrrolidone, N-ethylpyrrolidone, N-vinyl-pyrrolidone, 1,3-dimethyl-imidazolidone, dimethylacetamide and dimethylformamide or mixtures thereof. A pigment preparation as described. 8. 0.01-500% by weight, preferably 0%, based on component b).
. 01-250% by weight, in particular 0.01-20% by weight, of component a), 1-99.95% by weight, based on the preparation, preferably 1-65% by weight of component b
0) to 200% by weight, in particular 0% by weight, based on the total of components a) and optionally components a) and b)
Pigment preparation according to claim 1, comprising -100% by weight of a dispersant of component c) and 0-98% by weight, based on the pigment preparation, in particular 0.2-98% by weight of water. . 9. A further sterically hindered amine, preferably an amine based on a 2,2,6,6-tetraalkylpiperidine, particularly preferably at least one covalently bound 2,2,6,6-tetraalkylpiperidine. 2,2,6,6- including skeleton
2. A pigment preparation according to claim 1, comprising one based on a tetraalkylpiperidine. 10. Use of the pigment preparation according to claim 1 as a printing ink for ink jet printing. 11. Pigmentation and coloring of natural or synthetic materials, in particular emulsified paints, printing inks, water-dilutable coating systems and automotive paints, and also plastics, leather and paper, entirely and only on surfaces. Use of the pigment preparations according to claim 1 for pigmenting and coloring, in particular, colored paper coating slips. 12. Use of the pigment preparation according to claim 1 for producing a printing ink for ink jet printing.