Classifications

• • 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
  • C09B67/0022—Wet grinding of pigments
  • C09B67/0023—Wet grinding of pigments of phthalocyanines
• • 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
  • C09B67/006—Preparation of organic pigments
  • C09B67/0066—Aqueous dispersions of pigments containing only dispersing agents
  • C09B67/0067—Aqueous dispersions of phthalocyanine pigments containing only dispersing agents

Definitions

• the present invention relates to a process for the preparation of pigment preparations, characterized in that in an apparatus
• At least one emulsion copolymer having an average molecular weight Mw of at least 150,000 g / mol and containing at least one Ci-Cio-alkyl ester or at least one ⁇ -hydroxy-C2-C4-alkylene ester of at least one ethylenically unsaturated C 3 -Cio Contains carboxylic acid or at least one vinyl aromatic compound in copolymerized form, and
• the present invention furthermore relates to pigment preparations prepared by the process according to the invention and to the use of the pigment preparations according to the invention for coloring fibrous substrates. Furthermore, the present invention relates to fibrous substrates, colored using pigment preparations according to the invention.
• Colorant preparations which are to be used in modern methods of coloring fibrous substrates, such as, for example, textile substrates and / or cellulosic substrates, are subject to demanding requirements.
• Colored fibrous substrates should have a high brilliance of the colors, the coloring should be durable, i. have high fastness properties, such as rub fastness and light fastness.
• they should, when it comes to wood-containing cellulose-containing substrates, penetrate into the wood during incorporation in certain proportions and not merely remain on the surface. After incorporation, the colorants should no longer migrate.
• Colorant preparations generally contain as components at least one colorant, for example a pigment, and at least one dispersant, which is frequently selected from low molecular weight surface-active substances.
• a colorant for example a pigment
• dispersant which is frequently selected from low molecular weight surface-active substances.
• polymers as dispersants.
• colorant preparations may also contain polymeric binders, for example in the form of aqueous polymer dispersions. Depending on the application of the corresponding colorant preparation to the substrate, these ensure the stability of the coloration by ensuring indirect anchoring of the pigments on the respective substrate. With conventional dispersants, this anchoring is generally not achievable.
• US 2002/0132890 discloses a process in which polymers having a molecular weight M w of up to 100,000 g / mol are used, which inter alia contain at least one polyethylene glycol (meth) acrylate in copolymerized form.
• M w molecular weight of up to 100,000 g / mol
• the disadvantage is that the polymer synthesis described in US 2002/0132890 is very complicated.
• Emulsion copolymer (b) having an average molecular weight M w of at least 150,000 g / mol, the at least one Ci-Cio-alkyl ester or at least one ⁇ -hydroxy-C 2 -C 4 -alkylene ester of at least one ethylenically unsaturated C 3 -C 10 carboxylic acid or at least one polymerized vinylaromatic compound is also referred to below as emulsion copolymer (b).
• the shaking apparatus or the mill can be filled with grinding bodies, for example in the form of spheres or beads
• Beads may be, for example, glass, zirconia, or silica-aluminum-zirconium mixed oxide and have a mean diameter in the range of 0.3 to 3 mm.
• pigment is dispersed to a mean secondary particle diameter of 50 to 10,000 nm, preferably 100 to 1,000 nm, particularly preferably up to 500 nm.
• the distribution of secondary particle diameters can be set wide or narrow, as desired.
• the average particle diameter of emulsion copolymer (b) may also appear to increase due to agglomeration.
• the average particle diameter of emulsion copolymer (b) decreases by de-agglomeration.
• the average particle diameter of emulsion copolymer (b) remains essentially unchanged when carrying out the process according to the invention.
• pigments (a) are understood to mean virtually insoluble finely divided, inorganic or organic colorants as defined in DIN 55944.
• Pigment (a) can be selected from inorganic and preferably organic pigments.
• Exemplary selected inorganic pigments are white pigments, black pigments and colored pigments such as Zinc oxide, zinc sulfide, lithopone, lead white, lead sulfate, chalk, titanium dioxide (Cl
• Iron oxide brown (CI Pigment Brown 6 and 7), chrome iron brown, zinc iron brown,
• Iron oxide black iron manganese black, spinel black (CI Pigment Black 27),
• Carbon black CI Pigment Black 7
• orange-colored spinels and corundum CI Pigment Brown 29, 31, 33, 34, 35, 37, 39 and 40
• cadmium orange chrome orange, lead molybdate
• carbon blacks mention may be made in particular of those which have been prepared by the gas black process, the flame black process or the fumacic black process.
• the BET surface area of carbon black used in accordance with the invention can be, for example, in the range from 20 to 2000 m 2 / g, determined according to DIN 66131/2 or ISO 4652.
• Carbon black used according to the invention can be surface-modified, for example by oxidation.
• Carbon black used according to the invention can have acidic and / or basic groups, for example carboxyl groups, lactol groups, phenol groups, quinone groups, basic oxides with, for example, pyrone-like structures.
• pigment (a) is luster pigment, i. single-phase or multi-phase platelet-shaped pigment whose color play is characterized by the interplay of interference, reflection and absorption phenomena.
• luster pigment i. single-phase or multi-phase platelet-shaped pigment whose color play is characterized by the interplay of interference, reflection and absorption phenomena.
• Examples of selected organic pigments which are also counted below vat dyes, are Monoazo pigments such as Cl. Pigment Brown 25, Cl. Pigment Orange 5,
• Disazo pigments such as Cl. Pigment Orange 16, 34, 44 and 72, Cl. Pigment Red 144, 166, 214 and 242, Cl. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106,
• disazo condensation pigments such as Cl. Pigment Yellow 93, 95 and 128,
• Anthanthrone pigments such as Cl. Pigment Red 168 and Cl. Vat Orange 3,
• Anthrachinonpigmente such as Cl. Pigment Yellow 147, 177 and 199, Cl. Pigment Violet 31,
• Anthrapyrimidine pigments such as Cl. Pigment Yellow 108, Cl. Vat Yellow
• Quinacridone pigments such as Cl. Pigment Red 122, 202, 206 and 209, Cl.
• Pigment Violet 19 Cl. Pigment Orange 48 and 49, quinophthalone pigments such as Cl. Pigment Yellow 138,
• Diketopyrrolopyrrolpigmente such as Cl. Pigment Orange 71, 73 and 81;
• Dioxazine pigments such as Cl. Pigment Violet 23 and 37, Cl. Pigment Blue
• Flavanthronpigmente such as Cl. Pigment Yellow 24, Cl. Vat Yellow 1,
• Indanthrone pigments such as Cl. Pigment Blue 60 and 64, Cl. Vat Blue 4 and 6,
• Isoindoline pigments such as Cl. Pigment Orange 61 and 69; Cl. pigment
• Isoviolanthrone pigments such as Cl. Pigment Violet 31 and CI. Vat Violet 1,
• Metal complex pigments such as Cl. Pigment Yellow 117, 129, 150, 153 and 177, Cl. Pigment Green 8, Cl. Pigment Red 257, perinone pigments such as Cl. Pigment Orange 43, Cl. Vat Orange 7, Cl.
• Perylene pigments such as Cl. Pigment Black 31 and 32, Cl. Pigment Red
• Pyrazoloquinazolone pigments such as Cl. Pigment Orange 67 and Pigment Red 251, thioindigo pigments such as Cl. Pigment Red 88 and 181, Cl. Vat Red 1; Cl. Pigment Violet 38 and Cl. Vat Violet 3;
• Triaryl carbonium pigments such as Cl. Pigment Blue 1, 61 and 62; Cl. Pigment Green 1, Cl. Pigment Red 81, 81: 1 and 169, Cl. Pigment Violet 1, 2, 3 and 27, Cl. Pigment Black 1 (aniline black), Cl. Pigment Yellow 101 (Aldazingelb); Cl. Pigment Brown 22.
• Examples of particularly preferred organic pigments are: Cl. Pigment Yellow 138, Cl. Pigment Red 122, Cl. Pigment Violet 19, Cl. Pigment Blue 15: 3 and 15: 4, Cl. Pigment Black 7, Cl. Pigment Orange 5, 38 and 43 and Cl. Pigment Green 7.
• mixtures of two or more different pigments (a) can also be used.
• pigment (a) which is in particulate form, i. in the form of particles.
• pigment (a) which is in particulate form, i. in the form of particles.
• crude pigments which are untreated pigments, as obtained after pigment synthesis.
• the particles may be regular or irregular in shape, for example, the particles may be in spherical or approximately spherical or needle shape.
• pre-milled pigment (a) is used.
• Pre-milled pigment may have an average particle diameter in the range from 0.1 to 5 ⁇ m, preferably to 3 ⁇ m and particularly preferably to 1 ⁇ m.
• pigment (a) which has been coated with at least one pigment derivative, for example a pigment sulfonic acid, a pigment amidosulfonic acid or a methyl enamine derivative of a pigment, for example during the premilling.
• pigment (a) can be coated with a pigment derivative derived from pigment (a).
• 10 minutes to 48 hours have been found to be a suitable period for dispersing, although a longer period is also conceivable.
• a dispersing time of from 15 minutes to 24 hours is preferred.
• Pressure and temperature conditions during dispersion are generally not critical, for example, normal pressure has proven to be suitable.
• pigment (a) is dispersed in the presence of (b) at least one emulsion copolymer having an average molecular weight Mw of at least 150,000 g / mol, for example up to 10,000,000 g / mol, preferably in the range from 200,000 to 2,000,000 g / mol preferably 500,000 to 1,000,000 g / mol, which at least one Ci-Cio-alkyl esters or at least one ⁇ -hydroxy-C2-C4 -alkylenester of at least one ethylenically unsaturated C 3 -C 0 - containing polymerized carboxylic acid or at least one vinylaromatic compound ,
• Ci-Ci alkyl ⁇ of at least one ethylenically unsaturated C 3 -C 0 carboxylic acid are methyl (meth) acrylate, ethyl (meth) acrylate, n-pro- pyl (meth) acrylate, isopropyl (meth) acrylate , n-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate
• Examples of particularly suitable ⁇ -hydroxy-C2-C4-alkylene ester of at least one ethylenically unsaturated C3-Ci ⁇ carboxylic acid are 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and in particular 2-hydroxyethyl (meth) acrylate.
• vinylaromatic compounds examples include ⁇ -methylstyrene, para-methylstyrene, 2,4-dimethylstyrene and in particular styrene.
• Emulsion copolymer (b) may, for example, at least one Ci-C ⁇ alkyl ester of at least one ethylenically unsaturated C3-Ci ⁇ carboxylic acid and at least one vinyl aromatic compound as copolymerized units.
• Emulsion copolymer (b) contains approximately form emulsion copolymer (b) at least one Ci-C ⁇ alkyl ester of at least one ethylenically unsaturated C 3 -C 0 - carboxylic acid and at least one ⁇ -hydroxy-C2-C4-alkylene ester of at least one ethylenically copolymerized unsaturated C3-Ci ⁇ carboxylic acid.
• emulsion copolymer (b) contains emulsion copolymer (b) at least one ⁇ -hydroxy-C2-C4-alkylene ester of at least one ethylenically unsaturated C3-Ci ⁇ carboxylic acid and at least one copolymerized vinyl aromatic compound.
• emulsion copolymer (b) at least one Ci-C ⁇ alkyl ester of at least one ethylenically unsaturated C3-Ci ⁇ contains carboxylic acid and at least one ⁇ -hydroxy-C 2 C 4 -alkylenester of at least one ethylenically unsaturated C Copolymerized 3 -Ci 0 carboxylic acid and at least one vinyl aromatic compound.
• emulsion copolymer (b) used in accordance with the invention may contain in copolymerized form at least one ethylenically unsaturated C 3 -C 10 -carboxylic acid, either as free acid or in partially or completely neutralized form.
• Suitable for neutralization are, for example, hydroxide and / or carbonate and / or bicarbonate of alkali metal, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium hydroxide, or preferably one or more amines such as ammonia and organic amines such as alkylamines , N-alkylethanolamines, alkanolamines and polyamines.
• alkylamines are: triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, piperidine, morpholine.
• Preferred amines are monoalkanolamines, N, N-dialkylalkanolamines, N-alkylalkanolamines, dialkanolamines, N-alkylalkanolamines and trialkanolamines having in each case 2 to 18 C atoms in the hydroxyalkyl radical and, if appropriate, in each case 1 to 6 C atoms in the alkyl radical, preferably 2 to 6 C Atoms in the alkanol radical and optionally 1 or 2 C atoms in the alkyl radical.
• Very particular preference is given to ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, n-butyldiethanolamine, N, N-dimethylethanolamine.
• At least one emulsion copolymer (b) is a cationic copolymer.
• Cationic copolymers for the purposes of the present invention are copolymers which comprise at least one ethylenically unsaturated compound in copolymerized form which contains at least one protonatable group, for example nitrogen atoms with a free electron pair, or cationic groups incorporated in the polymer chain, for example quaternary nitrogen atoms.
• cationic copolymer can be an amido-containing or amino-containing copolymer.
• Amido group-containing copolymers are, for example, those copolymers which are CO-NH 2 -piggers, CO-NH (C 1 -C 4 -alkyl) groups, CO-N (C 1 -C 4 -alkyl) 2 groups or groups of the formula I.
• t is an integer in the range of 2 to 5 and more preferably 2 or 3.
• Amino-containing copolymers are, for example, those copolymers which carry NH 2 groups, NH (C 1 -C 4 -alkyl) groups or N (C 1 -C 4 -alkyl) 2 groups or imidazole groups.
• cationic copolymer is present in acidic conditions, for example at pH values of 6 or less, in at least partially protonated form.
• cationic copolymers can be understood as meaning those copolymers which comprise as one of the comonomers one or more amides of at least one ethylenically unsaturated carboxylic acid, for example (meth) acrylamide in copolymerized form.
• cationic copolymer has a molecular weight M w in the range of 150,000 to 10,000,000 g / mol, preferably 200,000 to 2,000,000 g / mol, particularly preferably 300,000 to 1,000,000 g / mol.
• cationic copolymers are copolymers which are composed of at least one nonionic comonomer, for example at least one ⁇ -hydroxy-C 2 -C 4 -alkylene ester or at least one C 1 -C 10 -alkyl ester of at least one ethylenically unsaturated C 3 -Cio-carboxylic acid, and at least one comonomer having at least one protonatable or quaternized nitrogen atom per molecule.
• nonionic comonomer for example at least one ⁇ -hydroxy-C 2 -C 4 -alkylene ester or at least one C 1 -C 10 -alkyl ester of at least one ethylenically unsaturated C 3 -Cio-carboxylic acid
• Cationic copolymers for the purposes of the present invention may also contain one or more anionic comonomers, such as, for example, (meth) acrylic acid or croonic acid in copolymerized form. If cationic copolymers also contain at least one anionic monomer in copolymerized form, the molar fraction of cationic comonomers is always higher than the molar fraction of anionic comonomers, for example by 0.5 mol%, based on the total cationic copolymer, preferably at least 1 mol%, particularly preferably 1, 5 to 20 mol%.
• the cationic copolymer is preferably a synthetic cationic emulsion copolymer.
• pigment (a) is dispersed in the presence of (c) water, for example in proportions of from 0.01 to 10 parts by weight, preferably from 0.3 to 1 part by weight, more preferably from 0.5 to 0.95 parts by weight in each case to the sum of pigment (a) and emulsion copolymer (b).
• one or more organic solvents preferably one or more polar solvents, in particular one or more monohydric or polyhydric alcohols such as, for example, methanol, ethanol, isopropanol, n-propanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol or polyalkylene glycols, for example polyethylene glycols having a molecular weight M n in the range from 150 to 2,000 g / mol.
• organic solvents preferably one or more polar solvents, in particular one or more monohydric or polyhydric alcohols such as, for example, methanol, ethanol, isopropanol, n-propanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol or polyalkylene glycols, for example polyethylene glycols having a molecular weight M n in the range from
• the dispersion is carried out in the absence of non-polar organic solvents.
• non-polar organic solvents may be those organic solvents which do not completely mix with water at room temperature. Preference is given to working in the absence of non-polar solvents such as, for example, cyclohexane, toluene, ethylbenzene, n-heptane, n-hexane, xylene, for example ortho-xylene, meta-xylene and para-xylene.
• the content of nonpolar solvent is preferably less than 5% by weight, more preferably less than 1% by weight, based on the water used (c).
• none of the emulsion copolymers (b) used in copolymerized form comonomers obtained by simple esterification of alkylene glycol, dialkylene glycol, trialkylene glycol or polyalkylene glycol having molecular weights M w, for example in the range of 150 to 20,000 g / mol, in which alkylene in particular Ethylene or propylene and which are easily esterified with, for example, (meth) acrylic acid.
• none of the emulsion copolymers (b) employed comprises comonomers copolymerized by esterification of mono-C 1 -C 20 -alkylalkylene glycol, dialkylene glycol, trialkylene glycol or polyalkylene glycol having molecular weights M w in the range from 150 to 20,000 g, for example are available / mol, in which alkylene in particular ethylene or propylene and which are esterified with, for example, (meth) acrylic acid.
• Pigment preparations prepared by the method according to the invention described above.
• Pigment preparations according to the invention have a uniform distribution of pigment (a) and copolymer (b), in particular a good dispersion and separation of the particles of pigment (a) and in colorations a good fixation of the particles of pigment (a) on the corresponding substrates and are suitable Excellent for coloring fibrous substrates.
• Pigment preparations according to the invention may contain one or more additives (d) in one embodiment of the present invention.
• Suitable additives (d) are, for example, wetting agents, dispersants, defoamers, biocides, anti-settling agents, water retention agents and rheology modifiers.
• suitable wetting agents are nonionic, anionic or cationic surfactants, in particular ethoxylation and / or propoxylation products of fatty alcohols or propylene oxide-ethylene oxide block copolymers, ethoxylated or propoxylated fatty or oxo alcohols, furthermore ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulfates, alkylpolyglycosides , Alkylphosphonates, alkylphenylphosphonates, alkylphosphates, or alkylphenylphosphates.
• Suitable dispersants are aryl- or alkyl-substituted polyglycol ethers, furthermore substances which are described in US Pat. No. 4,218,218 and homologues with y (from the formulas from US Pat. No. 4,218,218) in the range from 10 to 37, furthermore arylsulfonic acid-formaldehyde condensation products , in particular naphthalenesulfonic acid-formaldehyde condensation products.
• Suitable defoamers are silicone-containing defoamers such as, for example, those of the formula HO- (CH 2 ) S-Si (CH 3 ) [OSi (CH 3 ) Sk or
• Silicone-free antifoams are also suitable, for example polyalkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2 to 50-times ethoxylated preferably unbranched C 10 -C 20 -alkanols, unbranched C 10 -C 20 -alkanols and 2-ethylhexan-1-ol.
• Suitable defoamers are fatty acid C 8 -C 20 -alkyl esters, preferably stearic acid C 10 -C 20 -alkyl esters, in which C 8 -C 20 -alkyl, preferably C 10 -C 20 -alkyl, can be unbranched or branched.
• BIT Benzisothiazolin-3-one
• MIT 2-methyl-2H-isothiazol-3
• CIT Chloro-2-methyl-2H-isothiazol-3-one
• Suitable anti-settling agents are silicates and silica gels, for example having an average particle diameter (in particular secondary particle diameter) in the range from 10 to 500 nm, in particular pyrogenic silica gels.
• Suitable pyrogenic silica gels are commercially available, for example, as Aerosil® grades.
• water retention agents examples include urea and polyhydric alcohols, e.g. Ethylene glycol, diethylene glycol, propylene glycol and 1,3-propanediol.
• Suitable rheology modifiers are cellulose derivatives, for example hydroxyethyl silicon. If it is desired to add one or more additives (d), the process according to the invention described above can be carried out in the presence of one or more additives (d).
• pigment preparations according to the invention contain
• Another object of the present invention is the use of inventive pigment preparations for coloring substrates, in particular fibrous substrates.
• Another object of the present invention are methods for coloring substrates, in particular fibrous substrates, using at least one pigment preparation according to the invention.
• Colorable substrates according to the invention can consist of any desired materials, for example polymer films. In particular, it may be fibrous substrates such as leather or imitation leather.
• cellulose-containing substrates are understood below to mean wood-containing and so-called wood-free papers, cardboard, cardboard, furthermore wood in any dimensions, for example wood blanks such as boards, rods, blocks, furthermore wood wool, wood-containing composite materials, wood blanks, plywood, chipboard, MDF boards (medium density fiberboard) Oriented Strand Board (OSB), based on woody annual plants, straw plates and fiber materials such as flax, linen, hemp, jute, cotton, bamboo fibers, paper mulberry fiber or wood pulp fibers.
• Cellulose-containing substrates in the context of the present invention may be designed, for example, flat or as a shaped body.
• precursors are to be understood as meaning in particular paper precursors, for example bleached and unbleached pulps and wood pulp, pulp and wood chips.
• textile substrates are textile fibers.
• textile fibers or textile substrates are textile fibers, semi-finished and semi-finished textile products and finished goods produced therefrom.
• carpets and other home textiles as well as technical textile textiles are included.
• These include unshaped structures such as flakes, linear structures such as twines, threads, yarns, lines, cords, ropes, threads and body structures such as felts, fabrics, knitted fabrics, nonwovens and wadding.
• the textiles may be of natural origin, for example cotton, wool or flax, or synthetic, for example polyamide, polyester, modified polyester, polyester blend, polyamide blend, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibers and glass fiber fabrics.
• the process according to the invention for coloring cellulosic substrates can be carried out by methods known per se. If, for example, one wishes to color paper, paperboard or cardboard, the process according to the invention can be carried out by contacting the pigment preparation according to the invention with paper, cardboard or cardboard, for example by brushing, spraying, dipping or impregnating.
• At least one pigment preparation according to the invention in particulate form is added to a paper precursor, for example the pulp.
• pulp may contain from 2 to 10% by weight of preferably bleached pulp and from 90 to 98% by weight of water, and preferably no further auxiliaries.
• pigment preparation according to the invention it is possible to add the pigment preparation according to the invention to the pulp, for example in amounts of from 0.001 to 1% by weight, based on the total pulp, and then process it into paper according to methods known per se.
• Examples of working with combinations of different pressure conditions are the alternating pressure method, the Rüping method and the boiler pressure suction method. If you want to work with combinations of increased pressure and reduced pressure, then you can work under oscillating conditions, including in connection with the present Invention understood multiple pressure changes from reduced pressure in the above-mentioned areas to increased pressure in the above-mentioned areas. The number of pressure changes is not critical per se, for example you can change the pressure conditions twice up to 500 times.
• the temperature for carrying out the method for coloring wood according to the invention for example 10 to 20 0 C and preferably room temperature are suitable.
• about 0.1 to 50 kg of treated pigment / m 3 , preferably up to 30 kg of treated pigment / m 3 of wood are applied. This embodiment is preferred if, for example, one would like to work according to printing methods.
• 0.01 to 20 g of treated pigment / m 2 of wood surface are applied. This embodiment is preferred if, for example, one would like to work by dipping.
• the pigment preparation according to the invention is applied together with one or more wood preservatives.
• Wood preservatives for example, as disclosed in EP-A 0 316602, are suitable. You can apply 200 to 600 g of wood preservative per m 2 wood surface on the surface, for example in the form of a dipping process. In the processes in which pressure is applied, as in the vacuum-pressure process, it is possible to use, for example, 1500 to 7000 kg of wood preservative per m 3 of wood.
• a period for the contact can be chosen for example 10 seconds to 48 hours, preferably 20 seconds to 24 hours.
• the method according to the invention for coloring textile substrates is a pigment dyeing process or a textile printing process, for example with a printing paste.
• a dyeing liquor for pigment dyeing or a printing paste for pigment printing, especially textile pigment printing is prepared by using at least one pigment preparation according to the invention.
• the present invention thus further provides a process for the production of dye liquors for pigment dyeing and for the production of printing pastes for the pigment. ment printing and the dyeing liquors and printing pastes according to the invention, hereinafter also called production process according to the invention.
• Dyeing liquors or printing pastes for pigment printing according to the invention may contain, in addition to at least one pigment preparation according to the invention, at least one compound (A) which is capable of crosslinking under the action of thermal energy or after addition of catalyst, for example one or more
• (A1) melamine derivatives which may optionally be alkoxylated, alkoxyalkylated or converted into semiaminals,
• melamine derivatives (A1) are, if appropriate, alkoxylated or alkoxyalkylated compounds or melamines reacted to semiaminals, in particular the general formula II
• R 2 , R 4 , R 6 are different or preferably identical and selected from CH 2 -OH,
• R 3 , R 5 , R 7 are identical or different selected from CH 2 -OH, CH 2 -OR 8 or hydrogen, wherein preferably at least one of the variables R 2 to R 7 is not hydrogen, R 8 are the same or different and selected from Ci-C4-alkyl, for example ethyl, n-propyl, n-butyl, iso-propyl and especially methyl, (CH 2 CH 2 O) m -H with m selected from integers in the range of 1 to 25.
• one selects those melamine derivatives of the general formula II in which three to five of the variants R 2 to R 7 are hydrogen and one to three of the variables R 2 to R 7 is selected from CH 2 OR 8 , where m is an integer in the range of 1 to 3.
• Melamine derivatives of the general formula II are known per se. Melamine derivatives of the formula II are generally not pure according to a defined formula. Usually, intermolecular rearrangements, ie, trans-acetalization reactions and re-aminalization reactions, and also, to a degree, condensation reactions and cleavage reactions are observed.
• the above formula II is to be understood in the sense that it defines the stoichiometric ratios of the variables of the radicals R 2 to R 7 and also includes intermolecular rearrangement products and condensation products.
• hydrophilized isocyanurates are one to three equivalents of polyalkylene oxides such as, for example, polypropylene oxide or, preferably, polyethylene oxide, optionally simply etherified with C 1 -C 4 -alkanol, reacted isocyanurates, for example of the formula III
• variables R 9 are different or preferably identical and for example stand for (ChfeVNCO, where h is an integer in the range from 2 to 20, preferably 4 to 12, very particularly preferably all variables R 9 are the same and h is 6 ,
• hydrophilized diisocyanates and polyisocyanates and capped isocyanates are, for example, those described in EP-A 0 358 979, EP-A 1 227 116, EP-A 1 024 184, EP-A 1 110 987, EP-A 0 728 786 mentioned compounds.
• polyglycidyl ethers (A3) having 2 to 5 glycidyl groups per molecule, preferably 2 to 4 glycidyl groups per molecule are, for example, pentaerythritol triglycidyl ethers and glycerol 1, 3-diglycidyl ethers and mixtures of the abovementioned compounds.
• Examples of carbodiimides (A4) include dicyclohexylcarbodiimide and the systems described in the patent applications EP-A 1 002 001, DE-A 199 54 500 and DE-A 100 00 656.
• Examples which may be mentioned of examples of urea or urea derivatives (A5) which may be reacted to give aminals or aminals are optionally: polyunsaturated, in particular mono- to tetraalkylated, in particular methylolated and alkoxyalkylolated, in particular methoxymethylolated urea compounds and their di- , Tri- and tetramers or oligomeric or polymeric, linear, branched or cyclic precondensates.
• alkylolated urea compounds as di- / tri-tetrameric or oligomeric or polymeric, linear or branched or cyclic addition / condensation products of urea and polyfunctional alkyl aldehydes, in particular glyoxal and their alkoxylated, especially methoxylated compounds.
• Inventive dyeing liquors or printing pastes for pigment printing may further contain one or more catalysts.
• Suitable catalysts are, for example: ammonium chloride, ZnCb, Zn (NO 3) 2, in each case also in the form of their hydrazides, NH 4 Cl, and very particularly preferably MgCb, for example in the form of its hexahydrate. It is possible, for example, to use from 0.001 to 1% by weight of catalyst, based on co-opting agents such as, for example, dyeing liquor for textile dyeing, ink for the ink-jet process or printing paste for pigment printing.
• dyeing liquors according to the invention have a weakly acidic pH, preferably in the range from 4 to 6.5.
• the dynamic viscosity of the dyeing liquors according to the invention is in the range of less than 100 mPa.s, measured at 20 ° C.
• the surface tensions of the dyeing liquors according to the invention are to be adjusted so that wetting of the goods is possible. Surface tensions of less than 50 mN / m, measured at 20 ° C., are suitable.
• inventive dyeing liquors may contain additives or auxiliaries.
• Preferred additives are organic solvents in concentrations from 0 to
• Suitable solvents are, for example, polyethylene glycols and monohydric alkylene glycol or monohydric polyethylene glycols such as, for example, diethylene glycol mono-n-butyl ether.
• inventive dyeing liquors can be one or more auxiliary agents
• wetting agents preferably low-foaming wetting agents, since foaming may affect the quality of the dyeing by forming unegalities.
• wetting agents used are: ethoxylation and / or propoxylation products of fatty alcohols or propylene oxide / ethylene oxide block copolymers, ethoxylated or propoxylated fatty or oxo alcohols, furthermore ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulfates, alkylpolyglycosides, alkylphosphonates, alkylphenyl phosphonates, alkyl phosphates, or alkylphenyl phosphates.
• Dry textile fabrics or knits such as those used in continuous pigment dyeing, contain a large amount of air. If it is desired to dye dry textile fabrics, the use of deaerators is advantageous in the dyeing process according to the invention. These are based, for example, on polyethersiloxane copolymers or on phosphoric acid esters. They may be present in quantities of from 0.01 to 2 g / l in the dyeing liquors of the invention.
• handle improvers are usually polysiloxanes or waxes based on polyethylene or polyethylene glycol. Polysiloxanes have the advantage of permanence, while some waxes can be washed out slowly during use. However, in one embodiment of the present invention, one can dispense with the addition of handle improvers.
• antimigration agents are copolymers of acrylic acid with acrylic acid amide.
• the molar proportion of acrylic acid can be between 20 and 80%; the acylic acid amide portion is then complementary to 100.
• suitable anti-migration agents are, for example, random copolymers or block copolymers of ethylene oxide with propylene oxide.
• the molar fraction of ethylene oxide may be between 20 and 80%; the proportion of propylene oxide is then complementary to 100.
• a further aspect of the present invention is a process for producing the inventive dyeing liquors, also called production process according to the invention.
• the production process according to the invention usually comprises mixing at least one pigment treated according to the invention in particulate form with one or more additives and / or auxiliaries listed above, such as solvents, defoamers, handle improvers, emulsifiers and / or biocides and filling with water.
• the production method according to the invention usually comprises stirring the components in a mixing container, wherein the size and shape of the mixing container are not critical. Preferably, the stirring is followed by a clarification filtration.
• the preparation process according to the invention can be carried out, for example, by reacting at least one pigment preparation according to the invention and optionally a compound (A) and, if appropriate, a catalyst with a dye for the dyeing process. Mixing required printing aids and adjusting the colorant content by dilution with water.
• the water used to practice the production process of the invention need not be completely desalted. The rule is that partially desalinated water or very soft water is used. If not sufficiently soft water is available, one can use complexing agent (water softener), in order to reduce the water hardness.
• water softener complexing agent
• Particularly suitable water softeners are, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriamine-pentacetic acid, hydroxyethylethylenediaminetriacetic acid or methylglycinediacetic acid.
• the amount of water added for the preparation of the dyeing liquor according to the invention depends on the color depth to be achieved on the textile on one side and the amount of dyeing liquor to be applied by means of suitable equipment, for example by means of padding on textile on the other side.
• a further aspect of the present invention is a process for dyeing textile substrates using the dyeing liquors according to the invention described above.
• the process can be carried out in common machines.
• Preferred are foulards, which contain as an essential element two superimposed rollers through which the textile is guided. Above the rollers, the liquid is filled in and wets the textile. The pressure squeezes off the textile and ensures a constant application.
• the textile is guided over a deflection roller through a trough with the dyeing liquor. Subsequently, surplus liquor is pressed off via a pair of rollers, which are mounted above the liquor, thus ensuring a constant application.
• the actual dyeing step is usually followed by a thermal drying and fixing, preferably drying at temperatures of 70 to 120 0 C over a period of 30 seconds to 3 minutes and then fixed at temperatures of 150 0 C to 200 0 C. a period of 30 seconds to 5 minutes.
• Colored, in particular printed and / or colored, substrates colored in accordance with the invention are distinguished by particular brilliance of the colors combined with outstanding grip of the printed or dyed substrates.
• Another aspect of the present invention are therefore substrates colored according to the method described above using the dyeing liquors according to the invention.
• the invention it is possible according to the invention to incorporate at least one pigment preparation according to the invention into a printing paste.
• the printing paste according to the invention for the pigment printing from at least one pigment preparation according to the invention by mixing with commonly used in the printing process aids and subsequent adjustment of the colorant content by dilution with water ago.
• thickener natural or synthetic thickeners can be used. Preference is given to the use of synthetic thickeners, for example of generally liquid solutions of synthetic polymers in, for example, white oil or as aqueous solutions.
• the synthetic polymers contain acid groups that are completely or partially neutralized with ammonia. Ammonia is released during the fixation process, which lowers the pH and starts the fixation process.
• the lowering of the pH required for the fixation may alternatively be achieved by the addition of non-volatile acids, e.g. Citric acid, succinic acid, glutaric acid or malic acid take place.
• Printing pastes according to the invention may contain from 30 to 70% by weight of white oil.
• Aqueous thickeners usually contain up to 25% by weight of polymer. If it is desired to use aqueous formulations of a thickener, aqueous ammonia is generally added. The use of granular, solid formulations of a thickener are also conceivable in order to be able to produce emission-free pigment prints.
• Printing pastes according to the invention may further comprise handle improvers, which are usually selected from silicones, in particular polydimethylsiloxanes, and fatty acid esters.
• handle improvers which are usually selected from silicones, in particular polydimethylsiloxanes, and fatty acid esters. Examples of commercially available handle improvers which can be added to the printing pastes according to the invention are Acramin® Weichma- rather Sl (Bayer AG), Luprimol SIG® and Luprimol CW® (BASF Aktiengesellschaft).
• One or more emulsifiers may be added as further additives according to the invention, especially when the pastes contain white oil-containing thickeners and are obtained as an oil-in-water emulsion.
• suitable emulsifiers are aryl- or alkyl-substituted polyglycol ethers.
• Commercially available examples of suitable emulsifiers are Emulsifier W® (Bayer), Luprintol PE New® and Luprintol MP® (BASF Aktiengesellschaft).
• Bronsted acids can be added as further additives, the use of which is particularly preferred for pastes on a non-aqueous basis.
• Pigment printing using at least one printing paste according to the invention or at least one pigment preparation according to the invention can be carried out by various processes which are known per se. Usually a stencil is used to press the print paste with a squeegee. This process belongs to the screen printing process. Subsequently, thermal energy is allowed to act or at least one catalyst is added.
• the pigment printing method according to the invention using the printing pastes according to the invention provides printed substrates with particularly high brilliance and depth of color of the prints with at the same time excellent grip of the printed substrates.
• the present invention therefore substrates printed by the method according to the invention using the printing pastes according to the invention.
• Suitable apparatuses are, for example, microwave ovens, Plattenpresswer- ke, with hot air blowers, heated electrically or with gas flame drying cabinets, heated rolling mills or continuously operated drying equipment.
• substrates to be colored are cellulosic substrates.
• Cellulosic substrates are understood below to mean wood-containing and so-called wood-free papers, cardboard, cardboard, furthermore wood in any dimensions, for example wood blanks such as boards, rods, blocks, furthermore wood wool, wood-containing composite materials, wood blanks, plywood, chipboard, MDF boards (medium density fiberboard) Oriented Strand Board (OSB), based on woody annual plants, straw plates and fiber materials such as flax, linen, hemp, jute, cotton, bamboo fibers, paper mulberry fibers or hull pulp.
• Cellulose-containing substrates in the context of the present invention may be designed, for example, flat or as a shaped body.
• the process according to the invention for coloring cellulosic substrates can be carried out by methods known per se. If, for example, one wishes to color paper, cardboard or cardboard, the process according to the invention can be carried out by contacting a pigment preparation according to the invention with paper, cardboard or cardboard, for example by brushing, spraying, dipping or impregnating.
• At least one pigment preparation according to the invention is added to a paper precursor, for example the pulp.
• pulp may contain from 2 to 10% by weight of preferably bleached pulp and from 90 to 98% by weight of water, and preferably no further auxiliaries.
• pigment preparation according to the invention it is possible to add the pigment preparation according to the invention to the pulp, for example in amounts of from 0.001 to 1% by weight, based on the total pulp, and then process it into paper according to methods known per se.
• Examples of working with combinations of different pressure conditions are the alternating pressure method, the Rüping method and the boiler pressure suction method. If you want to work in combinations of increased pressure and reduced pressure, so you can work under oscillating conditions, including in the context of the present invention, multiple pressure changes from reduced pressure in the above-mentioned areas to increased pressure in the above-mentioned areas , The number of pressure changes is not critical per se, for example you can change the pressure conditions twice up to 500 times.
• the temperature for carrying out the method for coloring wood according to the invention for example 10 to 20 0 C and preferably room temperature are suitable.
• the present invention in one embodiment of the present invention, about 0.1 to 50 kg of pigment preparation according to the invention / m 3 , preferably up to 30 kg of pigment preparation according to the invention / m 3 of wood, is applied. This embodiment is preferred if, for example, one would like to work according to printing methods.
• the present invention brings 0.01 to 20 g pigment preparation according to the invention / m 2 wood surface. This embodiment is preferred if, for example, one would like to work by dipping.
• the pigment preparation according to the invention is applied together with one or more wood preservatives.
• Suitable wood preservatives are, for example, as disclosed in EP-A 0 316602. you can apply 200 to 600 g of wood preservative per m 2 wood surface on the surface, for example in the form of a dipping process. In the processes in which pressure is applied, as in the vacuum-pressure process, it is possible to use, for example, 1500 to 7000 kg of wood preservative per m 3 of wood.
• a period for the contact can be chosen for example 10 seconds to 48 hours, preferably 20 seconds to 24 hours.
• Another object of the present invention are fibrous substrates, preferably cellulosic substrates, colored by the method according to the invention. They are characterized by particular brilliance of the colors, low tendency to bleed and in the case of colored wood according to the invention by good light fastness and weather resistance.
• a solution was prepared by mixing 500 ml of demineralized water, 2.8 g of compound 11.1, dissolved in a further 4.2 g of water, in a 5 l kettle with anchor stirrer, nitrogen inlet and three metering devices.
• DMAPMAM N, N-dimethylaminopropylmethacrylamide
• mixture 1.1.1 and mixture 1.1.2 were started simultaneously. Mixture 1.1.1 was added within 2 hours, mixture 1.1.2 within 2 hours 15 minutes. During the addition, the temperature was maintained at 80 ° C.
• the mixture was stirred for 30 minutes at 80 0 C and then for deodorization simultaneously a solution of 4.76 g of tert-butyl hydroperoxide (70 wt .-% in water), diluted with 40 ml of distilled water, and a solution of 4.4 g of HO-CH 2 -SO 2 Na in 40 ml of distilled water over a period of 90 minutes added.
• the laboratory mill used was a Dispermat CA-40-C from Getzmann, equipped with a grinding vessel type APS 1000 ml, a double grinding disk 70 mm made of polyamide and glass beads (diameter 0.6-0.8 mm).
• the pigment preparation according to the invention which was thus obtainable was finally forced through the grinding vessel outlet screen with compressed air and thereby separated from the glass beads.
• a dyeing liquor according to the invention was prepared. To this was added 500 ml of water and added one by one with stirring:
• pigment preparation according to the invention from Example 1.2, 30 g of a PO / EO block copolymer (42 units of propylene / 29 units of ethylene per mole),
• the dyeing liquor according to the invention thus prepared is padded by means of a padder (manufacturer Mathis, No. HVF12085) on cotton pretreated with a ready-to-dye finish.
• the liquor intake was about 70%.
• the mixture was then dried at 110 0 C then fixed in a Mathis dryer damper type DHE-36582 50 s and on a Mathis dryer fixer LTF8958 45 s at 180 0 C. A deep blue level color was obtained.
• a textile sample (10 g of dyed cotton according to the invention) was treated in a wash liquor prepared from 300 ml of water and 2 g of Marseille soap at 95 ° C. for 30 minutes. The textile sample was then removed from the wash liquor and placed on a metal surface using staples fixed at the edges. 50 ml of the hot wash liquor was added to the fabric sample. This fabric sample was then rubbed fifty times with a hand brush and then dried. The dried fabric sample was then evaluated by the gray scale. The rating gave a score of 4-5.
• a mixture of 70 wt .-% bleached Kiefemsulfatzellstoff and 30 wt .-% bleached birch sulphate pulp was ground in a laboratory refiner to a freeness of 22 ° after Schopper-Riegler. This gave a ground pulp mixture with a solids content of 10.3 wt .-%, determined by oven drying.
• Inventive colored paper was characterized by brilliance, high bleeding fastness and high light fastness.

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• 2005
  • 2005-08-11 DE DE200510038358 patent/DE102005038358A1/de not_active Withdrawn
• 2006
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  • 2006-08-02 WO PCT/EP2006/064992 patent/WO2007017451A1/de active Application Filing
  • 2006-08-02 CN CNA2006800295143A patent/CN101243141A/zh active Pending
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