EP1749129A1 - Method for the treatment of flexible substrates - Google Patents

Method for the treatment of flexible substrates

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Publication number
EP1749129A1
EP1749129A1 EP05745338A EP05745338A EP1749129A1 EP 1749129 A1 EP1749129 A1 EP 1749129A1 EP 05745338 A EP05745338 A EP 05745338A EP 05745338 A EP05745338 A EP 05745338A EP 1749129 A1 EP1749129 A1 EP 1749129A1
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EP
European Patent Office
Prior art keywords
pigment
weight
substrates
butyl
alkyl
Prior art date
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Granted
Application number
EP05745338A
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German (de)
French (fr)
Other versions
EP1749129B1 (en
Inventor
Dominik Winter
Tibor Duris
Holger SCHÖPKE
Andreas FECHTENKÖTTER
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BASF SE
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BASF SE
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Publication of EP1749129A1 publication Critical patent/EP1749129A1/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • D06P1/5257—(Meth)acrylic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79—Polyolefins

Definitions

  • the present invention relates to a method for treating flexible substrates, characterized in that
  • the method according to the invention is based on at least one substrate (A), with substrates preferably being understood to mean flexible substrates, i.e. Substrates that can be deformed manually at least once at room temperature without destruction, for example kinking, rolling up or unrolling, folding or bending.
  • substrates preferably being understood to mean flexible substrates, i.e. Substrates that can be deformed manually at least once at room temperature without destruction, for example kinking, rolling up or unrolling, folding or bending.
  • Preferred examples of flexible substrates are textiles, hereinafter also referred to as textile substrates, furthermore foils and manually deformable hollow bodies such as flax.
  • textile or textile substrates are to be understood as meaning textile fibers, textile semi-finished and finished products and finished products made therefrom which, in addition to textiles for the clothing industry, also include carpets and other home textiles, and textile structures serving technical purposes such as awnings ,
  • This also includes unshaped structures such as flakes, line-shaped structures such as twine, threads, yarns, linen, cords, ropes, threads, as well as body structures such as felts, fabrics, knitted fabrics, nonwovens, nonwovens and wadding.
  • Flexible substrates (A) are selected from substrates that
  • (A1) polyacrylic, polyester, silicone, polyamide, for example polycondensates of ⁇ , ⁇ -diamides with ⁇ , ⁇ -dicarboxylic acids or cyclic amides such as ⁇ -caprolactam, or preferred
  • -C-C ⁇ o-alkyl branched or unbranched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably dC 4 -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and very particularly preferably methyl,
  • CC 10 -alkyl can be branched or unbranched and are prepared as defined above.
  • Substrates made from one of the above polymers also include substrates which contain a certain proportion, for example at least 30% by weight, preferably at least 50% by weight, of at least one of the abovementioned polymers.
  • Mixed fabrics made of cotton / polyester or cotton / polyamide may be mentioned as examples.
  • polymers based on at least one monomer of the general formula I are not only homopolymers, but also copolymers which contain a substantial proportion, for example at least 50 mol%, of at least one monomer of the general formula I may contain polymerized.
  • ethylene-propylene copolymers are also suitable, which may contain at least 50 mol% of propylene in copolymerized form.
  • Polypropylene can be produced, for example, by Ziegler-Natta catalysis or by metallocene catalysis.
  • At least one flexible substrate is contacted with at least one aqueous formulation which contains at least one ethylene copolymer wax which
  • At least one ethylenically unsaturated carboxylic acid is preferably a carboxylic acid of the general formula II
  • R 2 selected from hydrogen, Crdo-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec .-Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably dC 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; COOH, COOCH 3 , COOC 2 H 5 .
  • R 3 selected from hydrogen, Crdo-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.
  • -Pentyl neo-pentyl, 1, 2-dimethylpropyI, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C t -C 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;
  • R 2 is very particularly preferably hydrogen and R 3 is hydrogen or methyl.
  • Ethylene copolymer waxes contained in aqueous formulations used according to the invention can contain up to 40% by weight, preferably up to 35% by weight, based in each case on the sum of ethylene and polymerized or polymerized ethylenically unsaturated carboxylic acid (s) of one or more further monomers contain in copolymerized form, for example vinyl acetate, one or more ethylenically unsaturated carboxylic acid esters, preferably of the formula III
  • R 4 selected from hydrogen, d-do-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl , sec.-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably dC 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
  • R 5 selected from hydrogen, CrCio-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec .-Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably dC 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; COOH, COOCH 3 , COOC 2 H 5
  • R 6 selected from -CC 10 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably CC 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.
  • CC 10 alkyl such as methyl, ethyl, n-
  • R 5 is very particularly preferably hydrogen and R 4 is hydrogen or methyl.
  • R 5 is very particularly preferably hydrogen and R 4 is hydrogen or methyl and R 6 is selected from methyl, ethyl, n-butyl and 2-ethylhexyl.
  • the ethylene copolymer waxes of ethylene and ethylenically unsaturated carboxylic acids described above can advantageously be prepared by radical-initiated copolymerization under high pressure conditions, for example in stirred high-pressure autoclaves or in high-pressure tube reactors.
  • the production in stirred high pressure autoclaves is preferred.
  • Stirred high-pressure autoclaves are known per se; a description can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, pp. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996 For them, the ratio length / diameter is predominantly in intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1.
  • Suitable pressure conditions for the polymerization are 500 to 4000 bar, preferably 1500 to 2500 bar.
  • the reaction temperatures are in the range from 170 to 300 ° C., preferably in the range from 200 to 280 ° C.
  • the polymerization can be carried out in the presence of a regulator.
  • the regulator used is, for example, hydrogen or an aliphatic aldehyde or an aliphatic ketone of the general formula IV
  • radicals R 7 and R 8 are the same or different and selected from
  • Ci-Ce-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo -Pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably dC -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- Butyl, sec-butyl and tert-butyl; C 3 -C 12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl
  • R 7 and R 8 are covalently bonded to one another to form a 4- to 13-membered ring.
  • R 7 and R 8 can be common: - (CH 2 ) -, - (CH 2 ) 5 -, - (CH 2 ) 6 , - (CH 2 ) 7 -, -CH (CH 3 ) -CH 2 -CH 2 -CH (CH 3 ) - or -CH (CH 3 ) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -.
  • Suitable regulators are alkyl aromatic compounds, for example toluene, ethylbenzene or one or more isomers of xylene. It is preferred not to use aldehydes and ketones of the general formula IV as regulators. Particularly preferably, no further regulators are metered in, with the exception of the so-called desensitizers, which can be added to organic peroxides for better handling and which can also function as a molecular weight regulator.
  • radical initiators such as organic peroxides, oxygen or azo compounds can be used as starters for radical polymerization. Mixtures of several radical initiators are also suitable. Suitable peroxides, selected from the commercially available substances, are
  • radicals R 9 to R 14 are the same or different and selected from
  • Ci-C ⁇ - alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, iso-butyl, tert.-butyl, n-pentyl, sec.-pentyl, iso-pentyl, n-hexyl, n-heptyl, n-octyl; preferably linear dC 6 -alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, particularly preferably linear CC 4 -alkyl such as methyl, ethyl, n-propyl or n-butyl, very particularly preferred is ethyl; C 6 -C 14 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-an
  • Peroxides of the general formulas V a to V c and processes for their preparation are known from EP-A 0 813 550.
  • Di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable as peroxides.
  • Azobisisobutyronitrile (“AIBN”) may be mentioned as an example as an azo compound.
  • Free radical initiators are metered in amounts customary for polymerizations.
  • desensitizers are added to numerous commercially available organic peroxides before they are sold in order to make them more manageable.
  • White oil or hydrocarbons such as isododecane in particular are suitable as desensitizers.
  • desensitizers Under the conditions of radical high-pressure polymerization, such desensitizers can have a regulating effect on molecular weight.
  • molecular weight regulators is understood to mean the additional use of further molecular weight regulators beyond the use of the desensitizers.
  • the quantitative ratio of the monomers ethylene and ethylenically unsaturated carboxylic acid (s) in the metering usually does not exactly correspond to the ratio of the units contained in the ethylene copolymer waxes used in the formulations according to the invention, because ethylenically unsaturated carboxylic acids are generally more easily incorporated into ethylene copolymer waxes than ethylene.
  • the monomers are usually metered in together or separately.
  • the monomers can be compressed to the polymerization pressure in a compressor.
  • the monomers are first brought to an increased pressure of, for example, 150 to 400 bar, preferably 200 to 300 bar and in particular 250 bar with the aid of a pump and then to the actual polymerization pressure using a compressor.
  • the polymerization can optionally be carried out in the absence and in the presence of solvents, mineral oils, white oil and other solvents which are present in the reactor during the polymerization and which were used for the desensitization of the radical initiator or radicals, are not considered solvents in the context of the present invention.
  • the polymerization is carried out in the absence of solvents.
  • ethylene copolymer wax by first copolymerizing ethylene with at least one ethylenically unsaturated carboxylic acid ester of the general formula III and then ester groups in a Saponifying ner polymer-analogous reaction, for example with potassium hydroxide solution or sodium hydroxide solution.
  • Aqueous formulations used according to the invention preferably contain 0.05 to 40% by weight, preferably 10 to 35% by weight, of one or more ethylene copolymer waxes, preferably in completely or partially neutralized form.
  • aqueous formulations used according to the invention usually contain one or more basic substances, for example hydroxides and / or carbonates and / or hydrogen carbonates of alkali metals, ammonia, organic amines such as, for example, triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine , Methylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, n-butyldiethanolamine, N, N-dimethylethanolamine.
  • basic substances for example hydroxides and / or carbonates and / or hydrogen carbonates of alkali metals, ammonia, organic amines such as, for example, triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine , Methylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, n-butyldiethanolamine, N, N-dimethylethanolamine.
  • Aqueous formulations used according to the invention preferably contain so much basic substance or substances that at least half, preferably at least three quarters of the carboxyl groups of the ethylene copolymer wax or waxes are neutralized.
  • Basic-acting substances can be added to formulations used according to the invention, for example during the dispersion of ethylene copolymer wax.
  • aqueous formulations used according to the invention contain so much basic substance or substances that the carboxyl groups of the ethylene copolymer wax or waxes are quantitatively neutralized.
  • Aqueous formulations used according to the invention usually have a basic pH, preferably from 7.5 to 14, particularly preferably from 8 or higher and very particularly preferably from 8.5 or higher.
  • Aqueous formulations used according to the invention preferably contain no protective colloids.
  • Aqueous formulations used according to the invention are stable even without such surface-active auxiliaries, ie at a shear stress of 100 cm -1 , the light transmittance does not change by more than 2%, measured in the case of a dispersion having a solids content of 0.1% by weight with pure water for reference.
  • the aqueous formulation used according to the invention contains at least one colorant selected from (C) at least one pigment and (D) at least one colorant.
  • pigments (C) are to be understood as meaning practically insoluble, dispersed, finely divided, organic or inorganic colorants as defined in DIN 55944. At least one organic pigment and / or metal pigment is preferably selected.
  • Organic pigments selected by way of example are:
  • Anthraquinone pigments Cl. Pigment Yellow 147 and 177; C.I. Pigment violet 31;
  • Indanthrone pigments Cl. Pigment Blue 60 (Cl. Vat Blue 4) and 64 (Cl. Vat Blue 6); - Isoindoline pigments: Cl. Pigment orange 69; Cl. Pigment Red 260; Cl. Pigment Yellow 139 and 185;
  • Isoindolinone pigments Cl. Pigment Orange 61; Cl. Pigment Red 257 and 260; Cl. Pigment Yellow 109, 110, 173 and 185;
  • Perinone Pigments Cl. Pigment Orange 43 (Cl. Vat Orange 7); Cl. Pigment Red 194 (Cl. Vat Red 15);
  • Perylene pigments Cl. Pigment black 31 and 32; Cl. Pigment Red 123, 149, 178, 179 (Cl. Vat Red 23), 190 (Cl. Vat Red 29) and 224; Cl. Pigment violet 29;
  • Triaryl carbonium pigments 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);
  • Pigment Yellow 101 Aldazine Yellow
  • Examples of particularly preferred pigments (C) 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.
  • Other suitable pigments (C) are metallic pigments such as gold bronze, silver bronze, iriodin pigments, glitter.
  • the average diameter of pigment (C) used in the process according to the invention is usually in the range from 20 nm to 1.5 ⁇ m, preferably in the range from 300 to 500 nm.
  • pigment (C) used in the process according to the invention is in spherical or approximately spherical particulate form, i.e. the ratio of longest diameter to smallest diameter is in the range from 1.0 to 2.0, preferably to 1.5.
  • pigment (C) used in the process according to the invention is in the form of needles or sticks.
  • Suitable dyes (D) are all textile dyes, for example vat dyes such as indigo and its derivatives, direct dyes, disperse dyes, acid dyes, metal complex dyes, naphthol dyes, sulfur dyes, reactive dyes and pigment dyes.
  • vat dyes such as indigo and its derivatives, direct dyes, disperse dyes, acid dyes, metal complex dyes, naphthol dyes, sulfur dyes, reactive dyes and pigment dyes.
  • the aqueous formulations used according to the invention can be prepared, for example, as described below.
  • the ethylene copolymer wax or waxes is heated to a temperature above its melting point. It is advantageously heated to a temperature which is at least 10 ° C., particularly advantageously to a temperature which is at least 30 ° C. above the melting point of the ethylene copolymer wax or waxes.
  • the mixture is heated to a temperature which is above the melting point of the ethylene copolymer wax which melts at the highest temperature.
  • it is advantageously heated to a temperature which is at least 10 ° C. above the melting point of the ethylene copolymer wax melting at the highest temperature.
  • it is particularly advantageously heated to a temperature which is at least 30 ° C. above the melting point of the ethylene copolymer wax melting at the highest temperature.
  • water and one or more basic substances and optionally further constituents such as ethylene glycol are added, the order of addition of water and the addition of basic or basic substances and other constituents is arbitrary. If the temperature is above 100 ° C, it is advantageous to work under increased pressure and to select the vessel accordingly.
  • the resulting emulsion is homogenized, for example by mechanical or pneumatic stirring or by shaking.
  • the aqueous formulation thus prepared can then be cooled.
  • At least one colorant can be added, selected from (C) at least one pigment and (D) at least one dye. Then water, ethylene copolymer wax (B) and colorant are mixed.
  • pigment (C) in the form of a so-called pigment preparation, i.e. in a form dispersed with water and optionally at least one surfactant.
  • the procedure is to contact at least one flexible substrate (A) with at least one aqueous formulation used according to the invention.
  • contact is made with (A) with an aqueous formulation at temperatures in the range from 20 to 100 ° C., preferably at room temperature.
  • contact is made at pressures in the range from 0.5 bar to 10 bar, in particular at atmospheric pressure.
  • (A) is contacted with an aqueous formulation at temperatures in the range from 70 to 180 ° C., preferably 90 ° C. to 120 ° C., and pressures above atmospheric pressure, for example up to 10 bar, are used for this purpose.
  • Contacting according to the invention can be carried out, for example, over a period of 0.1 seconds to 60 minutes, preferably 0.5 seconds to 30 minutes.
  • the contacting of substrate (A) with the aqueous formulation used according to the invention can be carried out, for example, by spraying, padding, coating, impregnation and printing, for example by the ink jet method.
  • the process according to the invention is preferably carried out by contacting flexible substrate with at least one aqueous formulation used according to the invention and then drying.
  • pre-dry the substrate treated according to the invention before the actual drying for example to a residual moisture in the range from 0.5 to 2% by weight.
  • Predrying or drying can be carried out on common equipment. For example, if you want to treat textile substrates, it can be carried out on all fixing and drying units that are common in the textile industry. Suitable drying or predrying temperatures are, for example, 50 to 300 ° C., preferably 70 to 180 ° C.
  • thermal treatment can be carried out over a period of, for example, 10 seconds to 60 minutes, preferably 0.5 minutes to 7 minutes, at temperatures in the range from 50 to 300 ° C., preferably 100 to 160 ° C., particularly preferably 110 to 130 ° C.
  • Polyamide, polyester, polyvinyl chloride, modified polyester, polyester blend, polyamide blend, polyacrylonitrile, polycarbonate are treated thermally advantageously at temperatures in the range from 130 to 250 ° C.
  • Polypropylene fabric preferably between 80 and 130 ° C., preferably 110 and 130 ° C. Temperature in general to understand the temperature of the medium surrounding the flexible substrate to be treated.
  • the aqueous formulation used according to the invention contains at least one further substance (E), which can be selected from thickeners, crosslinkers, fastness improvers, plasticizers, defoamers, wetting agents and leveling agents.
  • E further substance
  • Suitable crosslinkers are, for example, urea-formaldehyde and melamine-formaldehyde addition products, optionally in combination with inorganic salts such as, for example, MgCl 2 -6 H 2 O or NH 4 CI.
  • Other suitable crosslinkers are, for example, free or blocked isocyanates or polyisocyanates such as, for example, compounds of the general formula VI
  • Y 1 selected from NR 15 , oxygen and NH
  • Z 1 selected from hydrogen and CO-OR 15 ,
  • R 15 are the same or different and selected from Crdo-alkyl, particularly preferred are methyl and n-butyl.
  • crosslinkers are polyfunctional epoxides such as polyglycidyl ethers of polyols e.g. Pentaerythritol polyglycidyl ether and multi-functional aziridines such as trimethylolpropane tris (beta-aziridinyl propionate).
  • Anti-fouling agents can be added, for example, to prevent the formation of deposits on rollers, for example foulards, during contacting.
  • Suitable anti-fouling agents are, for example, mixtures of polyalkoxylated alcohols, in particular polyethoxylated fatty alcohols.
  • Natural or synthetic thickeners can be used as thickeners (thickening agent!).
  • natural thickeners are alginate, guar, starch, core meal ether, cassia, tamarind cellulose ether, dextrins such as, for example, natural gums, galactomannan, xanthan, polysaccharide and mixtures of the aforementioned substances.
  • synthetic thickeners for example solutions of synthetic (co) polymers which are liquid at room temperature in, for example, white oil or as aqueous solutions or as water-in-oil emulsions, preferably with about 40% by weight (co-) Polymer.
  • thickeners are copolymers with 85 to 95% by weight of acrylic acid, 4 to 14% by weight of acrylamide and about 0.01 to 1% by weight of the (meth) acrylamide derivative of the formula VII
  • M w molecular weights in the range from 100,000 to 200,000 g / mol, in which R 16 is methyl or preferably hydrogen.
  • Formulations according to the invention can contain 30 to 70% by weight of white oil.
  • Aqueous thickeners usually contain a total of up to 25% by weight of (co) polymer, in some cases up to 50% by weight (so-called thickener dispersions), based on the total thickener. If it is desired to use aqueous formulations of a thickener, aqueous ammonia is generally added. The use too Granular, solid formulations of a thickener are conceivable, for example in order to be able to produce emission-free pigment prints.
  • Suitable fasteners are, for example, silicone oils and polysiloxanes that are liquid at room temperature.
  • the use of authenticity improvers can be dispensed with.
  • plasticizers are ester compounds selected from the groups of aliphatic or aromatic di- or polycarboxylic acids fully esterified with alkanols and phosphoric acid esterified at least once with alkanol.
  • alkanols are d-do alkanols.
  • Preferred examples of aromatic di- or polycarboxylic acids fully esterified with alkanol are phthalic acid, isophthalic acid and mellitic acid fully esterified with alkanol; examples of his: di-n-octyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate, di-n-octyl isophthalate, di-n-nonyl isophthalate, di-n-decyl isophthalate.
  • Preferred examples of aliphatic di- or polycarboxylic acids fully esterified with alkanol are, for example, dimethyl adipate, diethyl adipate, di-n-butyl adipate, diisobutyl adipate, dimethyl glutarate, dimethyl glutarate, glutarate, glutarate, di-bututate butyl ester of diisobutyl succinate and mixtures of the aforementioned compounds.
  • Preferred examples of phosphoric acid esterified at least once with alkanol are CrC 10 alkyl-di-C 6 -C 14 aryl phosphates such as isodecyl diphenyl phosphate.
  • plasticizers are aliphatic or aromatic di- or polyols which are at least monoesterified with dC 10 -alkyl carboxylic acid.
  • Preferred examples of aliphatic or aromatic di- or polyols esterified at least once with d-Cio-alkylcarboxylic acid is 2,2,4-trimethylpentane-1,3-diol-monoisobutyrate.
  • polyesters obtainable by polycondensation of aliphatic dicarboxylic acid and aliphatic diol, for example adipic acid or succinic acid and 1,2-propanediol, preferably with an M w of 200 g / mol, and polypropylene glycol alkylphenyl ether, preferably with an M w of 450 g / mol.
  • plasticizers are polypropylene glycols etherified with two different alcohols and having a molecular weight M w in the range from 400 to 800 g / mol, it being possible for one of the alcohols to be an alkanol, in particular a dC-ioalkanol, and the other alcohol preferably to be an aromatic alcohol , for example o-cresol, m-cresol, p-cresol and in particular phenol.
  • Suitable defoamers are, for example, silicone-containing defoamers such as those of the formula HO- (CH 2 ) 3 -Si [OSi (CH 3 ) 3 ] 2 .
  • Silicone-free defoamers are also suitable, such as polyalkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2 to 50-fold ethoxylated, preferably unbranched C 10 -C 20 -alkanols, unbranched C 0 -C 20 -alkanols and 2-ethylhexane 1-ol.
  • Suitable wetting agents are, for example, 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, alkyl polyglycosides, Alkylphosphonates, alkylphenylphosphonates, alkylphosphates, or alkylphenylphosphates.
  • 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, alky
  • Suitable leveling agents are, for example, block copolymers of ethylene oxide and propylene oxide with molecular weights M n in the range from 500 to 5000 g / mol, preferably 800 to 2000 g / mol.
  • Block copolymers of propylene oxide / ethylene oxide, for example of the formula EO 8 PO 7 EO 8 are very particularly preferred, EO being ethylene oxide and PO being propylene oxide.
  • the present invention furthermore relates to substrates treated by the process according to the invention.
  • Substrates according to the invention contain at least one ethylene copolymer wax in optionally crosslinked form.
  • Substrates according to the invention have good usage properties, for example good fastness properties, in particular wash fastnesses and rubbing fastnesses such as dry and wet rubbing fastness.
  • a special embodiment of the present invention is a method for producing printed flexible substrates and in particular printed textile by the method according to the invention, hereinafter also referred to as the textile printing method according to the invention.
  • Printing pastes according to the invention are advantageously prepared by mixing at least one aqueous formulation used according to the invention with auxiliaries common in the printing process and at least one pigment (C).
  • the depth of color is advantageously adjusted by coordinating the ratio of pigment (C) to the aqueous formulation used according to the invention.
  • Pigment is preferably added to the printing paste according to the invention in the form of pigment preparations.
  • Pigment preparations usually contain 20 to 60% by weight of pigment, furthermore water and one or more surface-active compounds, for example one or more emulsifiers, examples of which are multiply alkoxylated C 10 -C 30 -alkanols.
  • the ratio of pigment to aqueous formulation used according to the invention can be selected within wide limits. For example, it is possible to choose pigment and aqueous formulation used according to the invention in a weight ratio of 20: 1 to 1: 100. In a preferred embodiment of the present invention, the ratio of pigment to aqueous formulation used according to the invention is adjusted so that the weight ratio of pigment to solids content of aqueous formulation used according to the invention is in the range from 1: 1 to 1.30.
  • printing pastes according to the invention further contain grip improvers selected from silicones, in particular polydimethylsiloxanes, and fatty acid d-Cio-alkyl esters.
  • grip improvers selected from silicones, in particular polydimethylsiloxanes, and fatty acid d-Cio-alkyl esters. Examples of commercially available grip improvers which can be added to the printing pastes according to the invention are Acramin® plasticizer Sl (Bayer AG),
  • printing pastes according to the invention contain one or more emulsifiers as further additives, in particular if the printing pastes contain thickeners containing white oil 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).
  • a defoamer for example a silicone-based defoamer
  • adding at least one aqueous formulation used according to the invention with mixing, for example with stirring for example with stirring.
  • one or more emulsifiers and the pigment or pigments can be added.
  • one or more thickeners can be added and homogenized with further mixing, for example stirring.
  • a typical printing paste according to the invention contains, in each case per kilogram of printing paste according to the invention
  • print pastes according to the invention have a viscosity at 20 ° C. in the range from 0.3 to 4000 dPa-s, preferably 20 to 200 dPa-s and particularly preferably 60 to 100 dPa-s.
  • Viscosities can be determined using conventional methods, in particular, for example, using a rotary viscometer, for example the Viscotester VT02 or VT24 from Haake Mess-Technik GmbH u. Co., Düsseldorf.
  • Pigment printing using at least one printing paste according to the invention can be carried out by various methods which are known per se. As a rule, a stencil is used through which the printing paste according to the invention is pressed with a squeegee. This process is part of the screen printing process. Ren. Pigment printing processes according to the invention using at least one printing paste according to the invention deliver printed substrates with particularly high brilliance and depth of color of the prints with a good grip of the printed substrates at the same time. The present invention therefore relates to flexible substrates, printed by the printing process according to the invention using the printing pastes according to the invention.
  • Another embodiment of the present invention is a pigment coloring process using at least one formulation according to the invention, hereinafter also called pigment coloring process according to the invention.
  • the dyeing process according to the invention is preferably carried out by treating at least one flexible substrate, preferably a textile substrate, with at least one dye liquor which contains at least one formulation according to the invention.
  • Dyeing liquors which contain at least one formulation according to the invention are also called dyeing liquors according to the invention below.
  • Dyeing liquors according to the invention can contain wetting agents as an additive, preferably if the wetting agents are considered to be low-foaming, since the high turbulence in the dyeing process causes foaming to impair the quality of the dyeing due to the formation of irregularities.
  • deaerators is therefore advantageous for carrying out the pigment dyeing process according to the invention.
  • These are based, for example, on polyether siloxane copolymers. They can be contained in the dyeing liquors according to the invention in amounts of 0.01 to 2 g / l.
  • Dyeing liquors according to the invention can also contain anti-migration agents.
  • Suitable antimigration agents are, for example, block copolymers of ethylene oxide and propylene oxide with molecular weights M ⁇ in the range from 500 to 5000 g / mol, preferably 800 to 2000 g / mol.
  • one or more grip improvers can be added to the dyeing liquors according to the invention.
  • These are usually polysiloxanes or waxes.
  • Polysiloxanes have the advantage of permanence, while the waxes are slowly washed out during use.
  • the viscosities of the dye liquors according to the invention are preferably in the range of less than 100 mPa-s.
  • 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 are common.
  • a typical dye liquor according to the invention contains per liter
  • 0.5 to 400 g preferably 20 to 300 g ethylene copolymer wax (B), 0 to 100 g, preferably 0.1 to 10 g wetting agent, 0 to 100 g, preferably 0.1 to 10 g defoamer, 0 to 300 g, preferably 1 to 20 g of anti-fouling agent, 0 to 100 g, preferably 1 to 50 g of anti-migration agent, 0 to 100 g, preferably 1 to 50 g of leveling agent, 0.5 to 25 g, preferably 1 to 12 g of pigment (C).
  • B ethylene copolymer wax
  • C ethylene copolymer wax
  • Another aspect of the present invention is a method for producing dye liquors according to the invention.
  • the process according to the invention comprises mixing colorants, for example pigment (C), preferably in the form of pigment preparations which, in addition to pigment and water, contain one or more surface-active compounds, with additives listed above, such as further solvents, defoamers, grip improvers, emulsifiers and / or biocides and replenishing with water.
  • colorants for example pigment (C)
  • C preferably in the form of pigment preparations which, in addition to pigment and water, contain one or more surface-active compounds, with additives listed above, such as further solvents, defoamers, grip improvers, emulsifiers and / or biocides and replenishing with water.
  • additives listed above such as further solvents, defoamers, grip improvers, emulsifiers and / or biocides
  • the components of the dye liquors according to the invention are usually stirred in a mixing container, the size and shape of
  • Another aspect of the present invention is a method for dyeing flexible substrates using the inventive dye liquors described above, hereinafter also referred to as the dyeing method according to the invention, in particular as the pigment dyeing method according to the invention.
  • the dyeing process according to the invention can be carried out in common dyeing machines. Foulards are preferred which contain two rollers pressed together as an essential element, through which flexible substrate and in particular textile is guided.
  • Dyeing liquor according to the invention is filled in above the rollers and wets flexible substrate or the textile. The pressure of the rollers squeezes the flexible substrate or textile and ensures a constant application.
  • the actual dyeing step is usually followed by thermal drying and optionally fixation. Drying is preferably carried out at temperatures of 25 to 300 ° C. over a period of 10 seconds to 60 minutes, preferably 30 seconds to 10 minutes. If you want to fix, you fix at temperatures of 150 ° C to 190 ° C over a period of 30 seconds to 5 minutes.
  • a method for pigment coloring after the padding process is preferred.
  • Substrates printed and dyed according to the invention are distinguished by a particular brilliance of the colors with a good grip on the printed or dyed substrates.
  • Another aspect of the present invention is therefore substrates, colored by the process described above using the dye liquors according to the invention.
  • Another object of the present invention are colored flexible substrates obtainable by the pigment dyeing process according to the invention.
  • Dyed flexible substrates according to the invention are distinguished, for example, by good wash fastnesses, good dry and wet rubbing fastnesses and good fastness properties, in particular by low color depth losses in the brushing wash.
  • flexible substrates (A) and in particular foils or textile made of polypropylene with pigment-free aqueous formulation are contacted and then dried.
  • Evenly distributed, uncrosslinked ethylene copolymer wax acts on a flexible substrate as an adhesion promoter (primer) and allows bonding with any other materials.
  • the method according to the invention for printing on flexible substrates can be carried out as a transfer printing method.
  • a paper coated with wax for example with silicone wax
  • the dried paper is then dried at room temperature to 300 ° C., preferably at room temperature to 180 ° C.
  • the printed and dried paper is heated to a temperature together with the textile material Press or a hot calender at 70 to 300 ° C, preferably 10 to 100 s at 100 to 120 ° C, treated.
  • the printing paste is softened / melted and paper is transferred and fixed onto the 2 or 3-dimensional flexible substrate to be printed, for example a textile substrate or film.
  • the content of ethylene and acrylic acid or methacrylic acid in the ethylene copolymer wax was determined by NMR spectroscopy or by titration (acid number).
  • the acid number of the ethylene copolymer wax was determined titrimetrically in accordance with DIN 53402.
  • the KOH consumption corresponds to the acrylic acid or methacrylic acid content in the ethylene copolymer wax.
  • the MFI was determined according to DIN 53735 at 160 ° C and a load of 325 g.
  • the T reactor is the maximum internal temperature of the high-pressure autoclave.
  • “Content” is to be understood as the proportion of copolymerized ethylene or acrylic acid or methacrylic acid in the respective ethylene copolymer wax.
  • AS acrylic acid
  • MAS methacrylic acid
  • PA propionaldehyde
  • ID isodothecan
  • PO t-butyl hydroperoxide
  • ECW ethylene copolymer wax.
  • the viscosity was determined using a 5 mm beaker at 23 ° C. according to ISO 2431.
  • the “amount of NH 3 ” relates to the amount of 25% by weight aqueous ammonia solution.
  • the milling was continued until the pigment particles had an average diameter of 100 nm.
  • the ingredients according to Table 4 were stirred in a stirred vessel and the master pastes 3.1 to 3.4 were obtained by combining the ingredients with one another in the order shown in Table 4 and stirring. The mixture was then stirred for 15 minutes using an Ultra-Turrax high-speed stirrer at about 6000 revolutions. gen / min and then checked the pH. If the pH was below 8, the pH was adjusted to 8.5 by adding concentrated aqueous ammonia.
  • 2.1 or 2.2 is understood to mean the respective aqueous dispersion 2.1 or 2.2 from example 2.
  • the following were used as thickeners: dispersion of copolymer of acrylic acid (92% by weight), acrylamide (7.6% by weight), methylenebisacrylamide (0.4% by weight), quantitatively neutralized with ammonia (25% ig in water), molecular weight M w of approx. 150,000 g / mol as a water-in-mineral oil dispersion (volume ratio 2.6: 1) (bp of mineral oil: 190-230 ° C), solids content: 24% by weight %; stabilized with sorbitan monooleate (2.5% by weight, based on the total thickener).
  • Printing pastes according to the invention were prepared in accordance with Table 5 by mixing 970 g of base paste according to Table 4 with 30 g of blue pigment preparation from Example 3.1 each.
  • the printing parameters were: doctor blade 15 mm, stencil gauze ESTAL MONO E 55, magnetic draft level 6, simple printing, no pattern.
  • the substrates 5.1 and 5.2 according to the invention also called substrates 5.1 and 5.2 printed according to the invention, were obtained.
  • a comparative printing paste V4.5 which had been prepared analogously to printing paste 4.1 according to the invention, but ethylene copolymer wax dispersion 2.1 had been replaced by a dispersion (acrylate binder dispersion) of the following copolymer: n-butyl acrylate (66% by weight) %), Styrene (31% by weight), acrylic acid (1% by weight),
  • Methylolacrylamide (1% by weight), acrylamide (1% by weight), quantitatively neutralized with ammonia (25% by weight in water), with 2% by weight, based on the copolymer
  • Comparative substrate V5.5 was obtained.
  • the substrates according to the invention were tested for dry and wet rub fastness according to DIN EN ISO 105-X12 and wash fastness according to DIN EN ISO 105-C03. Best possible result: grade 5, worst possible result: grade 1.
  • Anti-migration agent With the anti-migration agent EO 8 PO 7 EO 8 used in the general recipe, EO always stands for ethylene oxide and PO for propylene oxide. It has the following properties: a cloud point in water of 40 ° C, a medium one molar mass M w of 1100 g / ml, solidification point ⁇ 5 C C, viscosity at 25 ° C: 175 mPa-s.
  • a textile substrate (polypropylene fabric) was dyed with a pad (manufacturer Mathis, type no. HVF12085), each with a liquor according to the invention produced according to 6.1.
  • the contact pressure of the rollers was 2.6 bar.
  • a fleet uptake of 55% resulted.
  • the application speed was 2 m / min.
  • the textile was then dried at 80 ° C. in a circulating air cabinet (manufacturer: Mathis, type no. LTF89534) for 60 s (circulating air 50%).
  • the final fixation was carried out for 5 minutes at 110 ° C. in circulating air (100%).
  • the comparison substrate was produced by dyeing with a comparison liquor which corresponded to the dye liquor F6.1 according to the invention, with the exception that instead of dispersion 2.1 an equal amount of acrylate binder dispersion was used, which was also used to prepare the comparison printing paste V4.5.
  • a paper coated with silicone wax was used with the printing pastes according to the invention, e.g. 8.1 and 8.2 printed and then dried at 100 ° C.
  • the printed and dried paper is treated together with textile on a hot press at 120 ° C for one minute. During this process, the printing paste softens / melts and paper is transferred and fixed onto the textile to be printed.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract

A method for the treatment of substrates, wherein (A) at least one substrate, which is selected from (A1) polyacryl, polyester, silicon, polyamide or (A2) one or several polymers based on a monomer having general formula (I), wherein R1 is selected from -Cl, C1-C10-alkyl, -CH=CH2, -C(Cl)=CH2, -C(CH3)=CH2 und -COOC1-C10-alkyl, is brought into contact with at least one aqueous formulation containing (B) at least one ethylene copolymer wax containing 60 - 95 per cent ethylene by weight and 5 - 40 per cent by weight of at least one ethylenically unsubstituted carboxylic acid in a polymerized manner, in addition to at least one colorant selected from (C) at least one pigment and (D) at least one dye.

Description

Verfahren zur Behandlung von flexiblen SubstratenProcess for the treatment of flexible substrates
Beschreibungdescription
Die vorliegende Erfindung betrifft ein Verfahren zur Behandlung von flexiblen Substraten, dadurch gekennzeichnet, dass manThe present invention relates to a method for treating flexible substrates, characterized in that
(A) mindestens ein flexibles Substrat, gewählt aus Substraten aus (A1) Polyacryl, Polyester, Silikon, Polyamid oder (A2) einem oder mehreren Polymeren auf Basis von einem Monomer der allgemeinen Formel I(A) at least one flexible substrate selected from substrates made of (A1) polyacrylic, polyester, silicone, polyamide or (A2) one or more polymers based on a monomer of the general formula I.
R1 in denen R1 gewählt wird aus Cl, C do-Alkyl, -CH=CH2, -C(CI)=CH2, -C(CH3)=CH2 und -COOC-rC^-Alkyl, mit mit mindestens einer wässrigen Formulierung kontaktiert, enthaltendR 1 in which R 1 is selected from Cl, C do-alkyl, -CH = CH 2 , -C (CI) = CH 2 , -C (CH 3 ) = CH 2 and -COOC-rC ^ alkyl, with contacted with at least one aqueous formulation containing
(B) mindestens ein Ethylencopolymerwachs, welches 60 bis 95 Gew.-% Ethylen und 5 bis 40 Gew.-% mindestens einer ethylenisch ungesättigten Carbonsäure einpo- lymerisiert enthält, weiterhin mindestens ein Farbmittel, gewählt aus (C) mindestens einem Pigment und (D) mindestens einem Farbstoff.(B) at least one ethylene copolymer wax which contains 60 to 95% by weight of ethylene and 5 to 40% by weight of at least one ethylenically unsaturated carboxylic acid copolymerized, furthermore at least one colorant selected from (C) at least one pigment and (D ) at least one dye.
Verfahren zum Beschichten, Färben und Bedrucken von flexiblen Substraten wie beispielsweise Folien oder faserigen Substraten wie beispielsweise Geweben, Gewirken oder Nonwovens stellen an die Formulierungen hohe Anforderungen. Eine besondere Herausforderung betreffen Formulierungen, die beispielsweise das Bedrucken von Polypropylen betreffen. Mit herkömmlichen Formulierungen bedruckte Substrate aus Polypropylen weisen in vielen Fällen ungenügende Echtheiten auf, was beispielsweise die Waschechtheit und die Nassreibechtheit betrifft. Auch bei anderen flexiblen Sub- strafen beispielsweise aus Polyvinylchlorid oder Silikon sind Behandlungsverfahren gefragt, die beispielsweise ein Bedrucken oder Färben mit guten Echtheiten gestatten.Processes for coating, dyeing and printing flexible substrates such as foils or fibrous substrates such as woven fabrics, knitted fabrics or nonwovens place high demands on the formulations. Formulations, for example the printing of polypropylene, pose a particular challenge. In many cases, substrates made of polypropylene printed with conventional formulations have insufficient fastness properties, for example in terms of wash fastness and wet rub fastness. Treatment methods are also required for other flexible substrates, for example made of polyvinyl chloride or silicone, which allow, for example, printing or dyeing with good fastness properties.
Weiterhin sind beispielsweise dem Verkleben von Polypropylen Grenzen gesetzt, wenn man beim Verkleben Temperaturen oberhalb des Schmelz- bzw. Erweichungspunkts von Polypropylen vermeiden will. Zwar kann man Polypropylen durch sogenannte Co- rona-Behandlung modifizieren, so dass anschließend ein Klebstoff hält. Corona-Be- handlungen sind jedoch üblicherweise teuer, verlaufen meist nur mit geringer Effizienz und weisen nur eine geringe Lagerstabilität der Modifizierung auf. Es bestand daher die Aufgabe, ein Verfahren bereit zu stellen, mit dem es gelingt, flexible Substrate zu behandeln und die aus dem Stand der Technik bekannten Nachteile zu vermeiden. Weiterhin bestand die Aufgabe, behandelte flexible Substrate bereit zu stellen. Weiterhin bestand die Aufgabe, Druckpasten und Färbeflotten bereit zustellen, unter deren Verwendung sich flexible Substrate behandeln lassen.Furthermore, there are limits to the bonding of polypropylene, for example, if you want to avoid temperatures above the melting or softening point of polypropylene when bonding. Polypropylene can be modified by so-called corona treatment so that an adhesive then holds. Corona treatments, however, are usually expensive, mostly run with little efficiency and have only a low storage stability of the modification. The object was therefore to provide a method which can be used to treat flexible substrates and to avoid the disadvantages known from the prior art. There was also the task of providing treated flexible substrates. Furthermore, there was the task of providing printing pastes and dyeing liquors which can be used to treat flexible substrates.
Dementsprechend wurde das eingangs definierte Verfahren gefunden.Accordingly, the method defined at the outset was found.
Das erfindungsgemäße Verfahren geht aus von mindestens einem Substrat (A), wobei unter Substraten vorzugsweise flexible Substrate verstanden werden, d.h. Substrate, die man bei Raumtemperatur mindestens einmal zerstörungsfrei manuell verformen kann, beispielsweise knicken, auf- oder abrollen, falten oder biegen. Bevorzugte Beispiele für flexible Substrate sind Textilien, im Folgenden auch textile Substrate genannt, weiterhin Folien und manuell verformbare Hohlkörper wie beispielsweise Fla- sehen.The method according to the invention is based on at least one substrate (A), with substrates preferably being understood to mean flexible substrates, i.e. Substrates that can be deformed manually at least once at room temperature without destruction, for example kinking, rolling up or unrolling, folding or bending. Preferred examples of flexible substrates are textiles, hereinafter also referred to as textile substrates, furthermore foils and manually deformable hollow bodies such as flax.
Unter Textil bzw. textilen Substraten sind im Rahmen der vorliegenden Erfindung Tex- tilfasem, textile Halb- und Fertigfabrikate und daraus hergestellte Fertigwaren zu verstehen, die neben Textilien für die Bekleidungsindustrie beispielsweise auch Teppiche und andere Heimtextilien sowie technischen Zwecken dienende textile Gebilde umfassen wie beispielsweise Markisen. Dazu gehören auch ungeformte Gebilde wie beispielsweise Flocken, linienförmige Gebilde wie Bindfäden, Fäden, Garne, Leinen, Schnüre, Seile, Zwirne sowie weiterhin Körpergebilde wie beispielsweise Filze, Gewebe, Gewirke, Nonwovens, Vliesstoffe und Watten.In the context of the present invention, textile or textile substrates are to be understood as meaning textile fibers, textile semi-finished and finished products and finished products made therefrom which, in addition to textiles for the clothing industry, also include carpets and other home textiles, and textile structures serving technical purposes such as awnings , This also includes unshaped structures such as flakes, line-shaped structures such as twine, threads, yarns, linen, cords, ropes, threads, as well as body structures such as felts, fabrics, knitted fabrics, nonwovens, nonwovens and wadding.
Flexible Substrate (A) wählt man aus Substraten, die ausFlexible substrates (A) are selected from substrates that
(A1) Polyacryl, Polyester, Silikonen, Polyamid, beispielsweise Polykondensaten von α,ω-Diamiden mit α,ω-Dicarbonsäuren oder cyclischen Amiden wie beispielsweise ε-Caprolactam, oder bevorzugt(A1) polyacrylic, polyester, silicone, polyamide, for example polycondensates of α, ω-diamides with α, ω-dicarboxylic acids or cyclic amides such as ε-caprolactam, or preferred
(A2) einem oder mehreren Polymeren auf Basis von einem Monomer der allgemeinen Formel I(A2) one or more polymers based on a monomer of the general formula I.
R1 in denen R1 gewählt wird ausR 1 in which R 1 is chosen from
Chlor,Chlorine,
Cι-Cιo-Alkyl, verzweigt oder unverzweigt, wie beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt d-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Bu- tyl und ganz besonders bevorzugt Methyl,-C-Cιo-alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably dC 4 -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and very particularly preferably methyl,
-CH=CH2, -C(Cl)=CH2, -C(CH3)=CH2 und -COOCrC-io-AIkyl, wobei C C10-Alkyl verzweigt oder unverzweigt sein kann und wie vorstehend definiert, hergestellt sind.-CH = CH 2 , -C (Cl) = CH 2 , -C (CH 3 ) = CH 2 and -COOCrC-io-alkyl, where CC 10 -alkyl can be branched or unbranched and are prepared as defined above.
Dabei sind unter Substraten aus einem der vorstehenden Polymeren auch solche Substrate umfasst, die einen gewissen Anteil, beispielsweise mindestens 30 Gew.-%, bevorzugt mindestens 50 Gew.-% an mindestens einem der vorstehend genannten Po- lymer enthalten. Beispielhaft seien Mischgewebe aus Baumwolle/Polyester oder Baumwolle/Polyamid genannt.Substrates made from one of the above polymers also include substrates which contain a certain proportion, for example at least 30% by weight, preferably at least 50% by weight, of at least one of the abovementioned polymers. Mixed fabrics made of cotton / polyester or cotton / polyamide may be mentioned as examples.
Unter Polymeren auf Basis von mindestens einem Monomer der allgemeinen Formel I sind dabei im Rahmen der vorliegenden Erfindung nicht nur Homopolymere zu verste- hen, sondern auch Copolymere, die einen wesentlichen Anteil, beispielsweise mindestens 50 mol-% von mindestens einem Monomer der allgemeinen Formel I einpolymeri- siert enthalten können. So sind beispielsweise auch Ethylen-Propylen-Copolymerisate geeignet, die mindestens 50 mol-% Propylen einpolymerisiert enthalten können.In the context of the present invention, polymers based on at least one monomer of the general formula I are not only homopolymers, but also copolymers which contain a substantial proportion, for example at least 50 mol%, of at least one monomer of the general formula I may contain polymerized. For example, ethylene-propylene copolymers are also suitable, which may contain at least 50 mol% of propylene in copolymerized form.
Ganz besonders bevorzugt sind Substrate aus Polyvinylchlorid (PVC) und Polypropylen (PP), die nach beliebigen Verfahren hergestellt sein können. Polypropylen kann beispielsweise durch Ziegler-Natta-Katalyse oder durch Metallocenkatalyse hergestellt sein.Substrates made of polyvinyl chloride (PVC) and polypropylene (PP), which can be produced by any process, are very particularly preferred. Polypropylene can be produced, for example, by Ziegler-Natta catalysis or by metallocene catalysis.
Erfindungsgemäß kontaktiert man mindestens ein flexibles Substrat mit mindestens einer wässrigen Formulierung, die mindestens ein Ethylencopolymerwachs enthält, welchesAccording to the invention, at least one flexible substrate is contacted with at least one aqueous formulation which contains at least one ethylene copolymer wax which
60 bis 95 Gew.-%, bevorzugt 65 bis 85 Gew.-% Ethylen und 5 bis 40 Gew.-%, bevorzugt 15 bis 35 Gew.-% mindestens einer ethylenisch ungesättigten Carbonsäure einpolymerisiert enthält, wobei Angaben in Gew.-% auf das gesamte Ethylencopolymerwachs bezogen sind. Bevorzugt handelt es sich bei mindestens einer ethylenisch ungesättigten Carbonsäure um eine Carbonsäure der allgemeinen Formel II60 to 95% by weight, preferably 65 to 85% by weight of ethylene and 5 to 40% by weight, preferably 15 to 35% by weight, of at least one ethylenically unsaturated carboxylic acid, in copolymerized form, details in% by weight all of the ethylene copolymer wax are covered. At least one ethylenically unsaturated carboxylic acid is preferably a carboxylic acid of the general formula II
Dabei sind in Formel II die Reste wie folgt definiert: In Formula II, the residues are defined as follows:
R2 gewählt aus Wasserstoff, Crdo-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt d-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl; COOH, COOCH3, COOC2H5.R 2 selected from hydrogen, Crdo-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec .-Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably dC 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; COOH, COOCH 3 , COOC 2 H 5 .
R3 gewählt aus Wasserstoff, Crdo-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-DimethylpropyI, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt Ct-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;R 3 selected from hydrogen, Crdo-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1, 2-dimethylpropyI, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C t -C 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;
Ganz besonders bevorzugt ist R2 Wasserstoff und R3 Wasserstoff oder Methyl.R 2 is very particularly preferably hydrogen and R 3 is hydrogen or methyl.
In erfindungsgemäß eingesetzten wässrigen Formulierungen enthaltene Ethylencopo- lymerwachse können bis zu 40 Gew.-%, bevorzugt bis zu 35 Gew.-%, bezogen jeweils auf die Summe aus Ethylen und einpolymerisierter bzw. einpolymerisierten ethylenisch ungesättigten Carbonsäure(n) eines oder mehrerer weiterer Monomere einpolymerisiert enthalten, beispielsweise Vinylacetat, - einen oder mehrere ethylenisch ungesättigte Carbonsäureester, bevorzugt der Formel IIIEthylene copolymer waxes contained in aqueous formulations used according to the invention can contain up to 40% by weight, preferably up to 35% by weight, based in each case on the sum of ethylene and polymerized or polymerized ethylenically unsaturated carboxylic acid (s) of one or more further monomers contain in copolymerized form, for example vinyl acetate, one or more ethylenically unsaturated carboxylic acid esters, preferably of the formula III
R4 gewählt aus Wasserstoff, d-do-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; be- sonders bevorzugt d-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl; R 4 selected from hydrogen, d-do-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl , sec.-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably dC 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
R5 gewählt aus Wasserstoff, CrCio-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt d-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl; COOH, COOCH3, COOC2H5,R 5 selected from hydrogen, CrCio-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec .-Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably dC 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; COOH, COOCH 3 , COOC 2 H 5 ,
R6 gewählt aus Cι-C10-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Di- methylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl.R 6 selected from -CC 10 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably CC 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.
Ganz besonders bevorzugt ist R5 Wasserstoff und R4 Wasserstoff oder Methyl.R 5 is very particularly preferably hydrogen and R 4 is hydrogen or methyl.
Ganz besonders bevorzugt ist R5 Wasserstoff und R4 Wasserstoff oder Methyl und R6 gewählt aus Methyl, Ethyl, n-Butyl und 2-Ethylhexyl.R 5 is very particularly preferably hydrogen and R 4 is hydrogen or methyl and R 6 is selected from methyl, ethyl, n-butyl and 2-ethylhexyl.
Vorstehend beschriebene Ethylencopolymerwachse von Ethylen und ethylenisch ungesättigten Carbonsäuren kann man vorteilhaft durch radikalisch initiierte Copolymeri- sation unter Hochdruckbedingungen herstellen, beispielsweise in gerührten Hoch- druckautoklaven oder in Hochdruckrohrreaktoren. Die Herstellung in gerührten Hochdruckautoklaven ist bevorzugt. Gerührte Hochdruckautoklaven sind an sich bekannt, eine Beschreibung findet man in Ullmann's Encyclopedia oflndustrial Chemistry, 5. Auflage, Stichworte: Waxes, Bd. A 28, S. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. Bei ihnen verhält sich überwiegend das Verhältnis Länge/Durchmesser in Intervallen von 5:1 bis 30:1, bevorzugt 10:1 bis 20:1. Die gleichfalls anwendbaren Hochdruckrohrreaktoren findet man ebenfalls in Ullmann's Encyclopedia oflndustrial Chemistry, 5. Auflage, Stichworte: Waxes, Bd. A 28, S. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996.The ethylene copolymer waxes of ethylene and ethylenically unsaturated carboxylic acids described above can advantageously be prepared by radical-initiated copolymerization under high pressure conditions, for example in stirred high-pressure autoclaves or in high-pressure tube reactors. The production in stirred high pressure autoclaves is preferred. Stirred high-pressure autoclaves are known per se; a description can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, pp. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996 For them, the ratio length / diameter is predominantly in intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1. The likewise applicable high-pressure tube reactors can also be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, pp. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996.
Geeignete Druckbedingungen für die Polymerisation sind 500 bis 4000 bar, bevorzugt 1500 bis 2500 bar. Die Reaktionstemperaturen liegen im Bereich von 170 bis 300°C, bevorzugt im Bereich von 200 bis 280°C. Die Polymerisation kann man in Gegenwart eines Reglers durchführen. Als Regler verwendet man beispielsweise Wasserstoff oder einen aliphatischen Aldehyd oder ein aliphatisches Keton der allgemeinen Formel IVSuitable pressure conditions for the polymerization are 500 to 4000 bar, preferably 1500 to 2500 bar. The reaction temperatures are in the range from 170 to 300 ° C., preferably in the range from 200 to 280 ° C. The polymerization can be carried out in the presence of a regulator. The regulator used is, for example, hydrogen or an aliphatic aldehyde or an aliphatic ketone of the general formula IV
oder Mischungen derselben.or mixtures thereof.
Dabei sind die Reste R7 und R8 gleich oder verschieden und ausgewählt ausThe radicals R 7 and R 8 are the same or different and selected from
Wasserstoff; Ci-Ce-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt d-C -Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl; C3-C12-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cyclo- heptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl.Hydrogen; Ci-Ce-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo -Pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably dC -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- Butyl, sec-butyl and tert-butyl; C 3 -C 12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred.
In einer besonderen Ausführungsform sind die Reste R7 und R8 miteinander unter Bildung eines 4- bis 13-gliedrigen Rings kovalent verbunden. So können R7 und R8 beispielsweise gemeinsam sein: -(CH2) -, -(CH2)5-, -(CH2)6, -(CH2)7-, -CH(CH3)-CH2-CH2-CH(CH3)- oder -CH(CH3)-CH2-CH2-CH2-CH(CH3)-.In a particular embodiment, the radicals R 7 and R 8 are covalently bonded to one another to form a 4- to 13-membered ring. For example, R 7 and R 8 can be common: - (CH 2 ) -, - (CH 2 ) 5 -, - (CH 2 ) 6 , - (CH 2 ) 7 -, -CH (CH 3 ) -CH 2 -CH 2 -CH (CH 3 ) - or -CH (CH 3 ) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -.
Gut geeignete Regler sind alkylaromatische Verbindungen, beispielsweise Toluol, Ethylbenzol oder ein oder mehrere Isomere des Xylols. Bevorzugt verzichtet man auf den Einsatz von Aldehyden und Ketonen der allgemeinen Formel IV als Regler. Besonders bevorzugt dosiert man keine weiteren Regler mit Ausnahme der sogenannten Phlegmatisierer, die zur besseren Handhabbarkeit organischen Peroxiden beigefügt werden können und ebenfalls die Funktion eines Molekulargewichtsreglers haben können.Suitable regulators are alkyl aromatic compounds, for example toluene, ethylbenzene or one or more isomers of xylene. It is preferred not to use aldehydes and ketones of the general formula IV as regulators. Particularly preferably, no further regulators are metered in, with the exception of the so-called desensitizers, which can be added to organic peroxides for better handling and which can also function as a molecular weight regulator.
Als Starter für die radikalische Polymerisation können die üblichen Radikalstarter wie beispielsweise organische Peroxide, Sauerstoff oder Azoverbindungen eingesetzt wer- den. Auch Mischungen mehrerer Radikalstarter sind geeignet. Geeignete Peroxide, ausgewählt aus den kommerziell erhältlichen Substanzen, sindThe usual radical initiators such as organic peroxides, oxygen or azo compounds can be used as starters for radical polymerization. Mixtures of several radical initiators are also suitable. Suitable peroxides, selected from the commercially available substances, are
Didekanoylperoxid, 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexan, tert.-Amyl- peroxy-2-ethylhexanoat, Dibenzoylperoxid, tert.-Butylperoxy-2-ethylhexanoat, tert.-Butylperoxydiethylacetat, tert.-Butylperoxydiethylisobutyrat, 1 ,4-Di(tert.-butyI- peroxycarbonyI)-cyclohexan als Isomerengemisch, tert.-Butylperisononanoat 1 ,1-Di-(tert.-butylperoxy)-3,3,5-trimethylcyclohexan, 1 ,1-Di-(tert.-butylperoxy)-cy- clohexan, Methyl-isobutylketonperoxid, tert.-Butylperoxyisopropylcarbonat, 2,2-Di-tert.-butylperox)butan oder tert.-Butylperoxacetat; tert.-Butylperoxybenzoat, Di-tert.-amylperoxid, Dicumylperoxid, die isomeren Di-(tert.-butylperoxyisopropyl)benzole, 2,5-Dimethyl-2,5-di-tert.-butylperoxy- hexan, tert.-Butylcumylperoxid, 2,5-Dimethyl-2,5-di(tert.-butylperoxy)-hex-3-in, Di-tert.-butylperoxid, 1 ,3-Diisopropylbenzolmonqhydroperoxid, Cumolhydro- peroxid oder tert.-Butylhydroperoxid; oder dimere oder trimere Ketonperoxide der allgemeinen Formel V a bis V c.Didekanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert.-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert.-butylperoxy-2-ethylhexanoate, tert.-butylperoxydiethylacetate, tert.- Butyl peroxydiethyl isobutyrate, 1,4-di (tert-butyl peroxycarbonyl) cyclohexane as a mixture of isomers, tert-butyl perisononanoate 1,1-di (tert-butyl peroxy) -3,3,5-trimethylcyclohexane, 1,1-di - (tert-butylperoxy) -cyclohexane, methyl isobutyl ketone peroxide, tert-butyl peroxyisopropyl carbonate, 2,2-di-tert-butyl perox) butane or tert-butyl peroxacetate; tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, the isomeric di- (tert-butyl peroxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butyl peroxy-hexane, tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hex-3-yne, di-tert-butyl peroxide, 1,3-diisopropylbenzene monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide; or dimeric or trimeric ketone peroxides of the general formula V a to V c.
V a V b V c V a V b V c
Dabei sind die Reste R9 bis R14 gleich oder verschieden und ausgewählt ausThe radicals R 9 to R 14 are the same or different and selected from
Ci-Cδ-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, sec.-Butyl, iso-Butyl, tert.-Butyl, n-Pentyl, sec.-Pentyl, iso-Pentyl, n-Hexyl, n-Heptyl, n-Octyl; bevorzugt lineares d-C6-Alkyl wie Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, n-Hexyl, besonders bevorzugt lineares C C4-Alkyl wie Methyl, Ethyl, n-Propyl oder n-Butyl, ganz besonders bevorzugt ist Ethyl; C6-C14-Aryl wie Phenyl, 1-Naphthyl, 2-Naphthyl, 1-Anthryl, 2-Anthryl, 9-Anthryl, 1-Phenanthryl, 2-Phenanthryl, 3-Phenanthryl, 4-PhenanthryI und 9-Phenanthryl, bevorzugt Phenyl, 1-Naphthyl und 2-Naphthyl, besonders bevorzugt Phenyl.Ci-C δ- alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, iso-butyl, tert.-butyl, n-pentyl, sec.-pentyl, iso-pentyl, n-hexyl, n-heptyl, n-octyl; preferably linear dC 6 -alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, particularly preferably linear CC 4 -alkyl such as methyl, ethyl, n-propyl or n-butyl, very particularly preferred is ethyl; C 6 -C 14 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryI and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl.
Peroxide der allgemeinen Formeln V a bis V c sowie Verfahren zu ihrer Herstellung sind aus EP-A 0 813 550 bekannt. Als Peroxide sind Di-tert.-buty!peroxid, tert.-Butylperoxypivalat, tert.-Butylperoxyiso- nonanoat oder Dibenzoylperoxid oder Gemische derselben besonders geeignet. Als Azoverbindung sei Azobisisobutyronitril („AIBN") beispielhaft genannt. Radikalstarter werden in für Polymerisationen üblichen Mengen dosiert.Peroxides of the general formulas V a to V c and processes for their preparation are known from EP-A 0 813 550. Di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable as peroxides. Azobisisobutyronitrile (“AIBN”) may be mentioned as an example as an azo compound. Free radical initiators are metered in amounts customary for polymerizations.
Zahlreiche kommerziell erhältliche organische Peroxide werden mit sogenannten Phlegmatisierem versetzt, bevor sie verkauft werden, um sie besser handhabbar zu machen. Als Phlegmatisierer sind beispielsweise Weißöl oder Kohlenwasserstoffe wie insbesondere Isododekan geeignet. Unter den Bedingungen der radikalischen Hoch- druckpolymerisation können derartige Phlegmatisierer eine molekulargewichtsregelnde Wirkung haben. Im Sinne der vorliegenden Erfindung soll unter dem Einsatz von Molekulargewichtsreglern der zusätzliche Einsatz weiterer Molekulargewichtsregler über den Einsatz der Phlegmatisierer hinaus verstanden werden.So-called desensitizers are added to numerous commercially available organic peroxides before they are sold in order to make them more manageable. White oil or hydrocarbons such as isododecane in particular are suitable as desensitizers. Under the conditions of radical high-pressure polymerization, such desensitizers can have a regulating effect on molecular weight. For the purposes of the present invention, the use of molecular weight regulators is understood to mean the additional use of further molecular weight regulators beyond the use of the desensitizers.
Das Mengenverhältnis der Monomere Ethylen und ethylenisch ungesättigte Carbon- säure(n) bei der Dosierung entspricht üblicherweise nicht genau dem Verhältnis der Einheiten in den erfindungsgemäß verwendeten Formulierungen enthaltenen Ethylen- copolymerwachsen, weil ethylenisch ungesättigte Carbonsäuren im Allgemeinen leichter in Ethylencopolymerwachse eingebaut werden als Ethylen.The quantitative ratio of the monomers ethylene and ethylenically unsaturated carboxylic acid (s) in the metering usually does not exactly correspond to the ratio of the units contained in the ethylene copolymer waxes used in the formulations according to the invention, because ethylenically unsaturated carboxylic acids are generally more easily incorporated into ethylene copolymer waxes than ethylene.
Die Monomere werden üblicherweise gemeinsam oder getrennt dosiert.The monomers are usually metered in together or separately.
Die Monomeren können in einem Kompressor auf den Polymerisationsdruck komprimiert werden. In einer anderen Ausführungsform des erfindungsgemäßen Verfahrens werden die Monomeren zunächst mit Hilfe einer Pumpe auf einen erhöhten Druck von beispielsweise 150 bis 400 bar, bevorzugt 200 bis 300 bar und insbesondere 250 bar gebracht und danach mit einem Kompressor auf den eigentlichen Polymerisationsdruck.The monomers can be compressed to the polymerization pressure in a compressor. In another embodiment of the process according to the invention, the monomers are first brought to an increased pressure of, for example, 150 to 400 bar, preferably 200 to 300 bar and in particular 250 bar with the aid of a pump and then to the actual polymerization pressure using a compressor.
Die Polymerisation kann wahlweise in Abwesenheit und in Anwesenheit von Lösemitteln durchgeführt werden, wobei Mineralöle, Weißöl und andere Lösungsmittel, die während der Polymerisation im Reaktor zugegen sind und zum Phlegmatisieren des oder der Radikalstarter verwendet wurden, im Sinne der vorliegenden Erfindung nicht als Lösemittel gelten.The polymerization can optionally be carried out in the absence and in the presence of solvents, mineral oils, white oil and other solvents which are present in the reactor during the polymerization and which were used for the desensitization of the radical initiator or radicals, are not considered solvents in the context of the present invention.
In einer Ausführungsform wird die Polymerisation in Abwesenheit von Lösemitteln durchgeführt.In one embodiment, the polymerization is carried out in the absence of solvents.
Natürlich ist es auch möglich, Ethylencopolymerwachs so herzustellen, dass man zu- nächst Ethylen mit mindestens einem ethylenisch ungesättigten Carbonsäureester der allgemeinen Formel III zu copolymerisieren und anschließend die Estergruppen in ei- ner polymeranalogen Umsetzung zu verseifen, beispielsweise mit Kalilauge oder Natronlauge.Of course, it is also possible to produce ethylene copolymer wax by first copolymerizing ethylene with at least one ethylenically unsaturated carboxylic acid ester of the general formula III and then ester groups in a Saponifying ner polymer-analogous reaction, for example with potassium hydroxide solution or sodium hydroxide solution.
Erfindungsgemäß eingesetzte wässrige Formulierungen enthalten vorzugsweise 0,05 bis 40 Gew.-%, bevorzugt 10 bis 35 Gew.-% ein oder mehrere Ethylencopolymerwach- se, vorzugsweise in vollständig oder partiell neutralisierter Form.Aqueous formulations used according to the invention preferably contain 0.05 to 40% by weight, preferably 10 to 35% by weight, of one or more ethylene copolymer waxes, preferably in completely or partially neutralized form.
Zum Zwecke der partiellen oder vollständigen Neutralisation enthalten erfindungsgemäß eingesetzte wässrige Formulierungen üblicherweise eine oder mehrere basisch wirkende Substanzen, beispielsweise Hydroxide und/oder Carbonate und/oder Hydro- gencarbonate von Alkalimetallen, Ammoniak, organische Amine wie beispielsweise Triethylamin, Diethylamin, Ethylamin, Trimethylamin, Dimethylamin, Methylamin, Etha- nolamin, Diethanolamin, Triethanolamin, Methyldiethanolamin, n-Butyldiethanolamin, N,N-Dimethylethanolamin. Bevorzugt enthalten erfindungsgemäß eingesetzte wässrige Formulierungen so viel basisch wirkende Substanz bzw. basisch wirkende Substanzen, dass mindestens die Hälfte, bevorzugt mindestens drei Viertel der Carboxylgruppen des oder der Ethylencopolymerwachse neutralisiert ist. Basisch wirkende Substanzen kann man erfindungsgemäß eingesetzten Formulierungen beispielsweise während der Dispergierung von Ethylencopolymerwachs zusetzen.For the purpose of partial or complete neutralization, aqueous formulations used according to the invention usually contain one or more basic substances, for example hydroxides and / or carbonates and / or hydrogen carbonates of alkali metals, ammonia, organic amines such as, for example, triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine , Methylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, n-butyldiethanolamine, N, N-dimethylethanolamine. Aqueous formulations used according to the invention preferably contain so much basic substance or substances that at least half, preferably at least three quarters of the carboxyl groups of the ethylene copolymer wax or waxes are neutralized. Basic-acting substances can be added to formulations used according to the invention, for example during the dispersion of ethylene copolymer wax.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäß eingesetzte wässrige Formulierungen so viel basisch wirkende Substanz bzw. basisch wirkende Substanzen, dass die Carboxylgruppen des oder der Ethylencopolymerwachse quantitativ neutralisiert sind.In one embodiment of the present invention, aqueous formulations used according to the invention contain so much basic substance or substances that the carboxyl groups of the ethylene copolymer wax or waxes are quantitatively neutralized.
Erfindungsgemäß eingesetzte wässrige Formulierungen weisen üblicherweise einen basischen pH-Wert auf, bevorzugt sind pH-Werte von 7,5 bis 14, besonders bevorzugt von 8 oder höher und ganz besonders bevorzugt von 8,5 oder höher.Aqueous formulations used according to the invention usually have a basic pH, preferably from 7.5 to 14, particularly preferably from 8 or higher and very particularly preferably from 8.5 or higher.
Erfindungsgemäß eingesetzte wässrige Formulierungen enthalten vorzugsweise keine Schutzkolloide. Erfindungsgemäß eingesetzte wässrige Formulierungen sind auch ohne derartige oberflächenaktive Hilfsmittel stabil, d.h. bei einer Scherbelastung von 100 cm"1 ändert sich die Lichtdurchlässigkeit um nicht mehr als 2%, gemessen bei einer Dispersion mit einem Feststoffgehalt von 0,1 Gew.-% mit reinem Wasser als Refe- renz.Aqueous formulations used according to the invention preferably contain no protective colloids. Aqueous formulations used according to the invention are stable even without such surface-active auxiliaries, ie at a shear stress of 100 cm -1 , the light transmittance does not change by more than 2%, measured in the case of a dispersion having a solids content of 0.1% by weight with pure water for reference.
Erfindungsgemäß eingesetzte wässrige Formulierung enthält neben Ethylencopolymerwachs (B) mindestens ein Farbmittel, gewählt aus (C) mindestens einem Pigment und (D) mindestens einem Farbstoff. Unter Pigmenten (C) sind im Rahmen der vorliegenden Erfindung praktisch nicht lösliche, dispergierte feinteilige, organische oder anorganische Farbmittel gemäß der Definition in DIN 55944 zu verstehen. Bevorzugt wählt man mindestens organisches Pigment und/oder Metallpigment aus.In addition to ethylene copolymer wax (B), the aqueous formulation used according to the invention contains at least one colorant selected from (C) at least one pigment and (D) at least one colorant. In the context of the present invention, pigments (C) are to be understood as meaning practically insoluble, dispersed, finely divided, organic or inorganic colorants as defined in DIN 55944. At least one organic pigment and / or metal pigment is preferably selected.
Beispielhaft ausgewählte organische Pigmente sindOrganic pigments selected by way of example are
- Monoazopigmente: Cl. Pigment Brown 25; Cl. Pigment Orange 5, 13, 36 und 67; Cl. Pigment Red 1 , 2, 3, 5, 8, 9, 12, 17, 22, 23, 31 , 48:1 , 48:2, 48:3, 48:4, 49, 49:1 , 52:1 , 52:2, 53, 53:1, 53:3, 57:1, 63, 112, 146, 170, 184, 210, 245 und 251; Cl. Pigment Yellow 1 , 3, 73, 74, 65, 97, 151 und 183;- Monoazo pigments: Cl. Pigment brown 25; Cl. Pigment Orange 5, 13, 36 and 67; Cl. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251; Cl. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183;
- Disazopigmente: Cl. Pigment Orange 16, 34 und 44; Cl. Pigment Red 144, 166, 214 und 242; Cl. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 und 188;- Disazo pigments: Cl. Pigment Orange 16, 34 and 44; Cl. Pigment Red 144, 166, 214 and 242; Cl. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;
- Anthanthronpigmente: Cl. Pigment Red 168 (Cl. Vat Orange 3);- Anthanthrone pigments: Cl. Pigment Red 168 (Cl. Vat Orange 3);
- Anthrachinonpigmente: Cl. Pigment Yellow 147 und 177; Cl. Pigment Violet 31 ;- Anthraquinone pigments: Cl. Pigment Yellow 147 and 177; Cl. Pigment violet 31;
- Anthrachinonpigmente: Cl. Pigment Yellow 147 und 177; C.I. Pigment Violet 31;- Anthraquinone pigments: Cl. Pigment Yellow 147 and 177; C.I. Pigment violet 31;
- Anthrapyrimidinpigmente: Cl. Pigment Yellow 108 (Cl. Vat Yellow 20);- Anthrapyrimidine pigments: Cl. Pigment Yellow 108 (Cl. Vat Yellow 20);
- Chinacridonpigmente: Cl. Pigment Red 122, 202 und 206; C.I. Pigment Violet 19;- Quinacridone pigments: Cl. Pigment Red 122, 202 and 206; C.I. Pigment violet 19;
Chinophthalonpigmente: Cl. Pigment Yellow 138;Quinophthalone Pigments: Cl. Pigment yellow 138;
- Dioxazinpigmente: Cl. Pigment Violet 23 und 37;- Dioxazine pigments: Cl. Pigment violet 23 and 37;
- Flavanthronpigmente: Cl. Pigment Yellow 24 (Cl. Vat Yellow 1);- Flavanthrone pigments: Cl. Pigment Yellow 24 (Cl. Vat Yellow 1);
- Indanthronpigmente: Cl. Pigment Blue 60 (Cl. Vat Blue 4) und 64 (Cl. Vat Blue 6); - Isoindolinpigmente: Cl. Pigment Orange 69; Cl. Pigment Red 260; Cl. Pigment Yellow 139 und 185;- Indanthrone pigments: Cl. Pigment Blue 60 (Cl. Vat Blue 4) and 64 (Cl. Vat Blue 6); - Isoindoline pigments: Cl. Pigment orange 69; Cl. Pigment Red 260; Cl. Pigment Yellow 139 and 185;
- Isoindolinonpigmente: Cl. Pigment Orange 61 ; Cl. Pigment Red 257 und 260; Cl. Pigment Yellow 109, 110, 173 und 185;- Isoindolinone pigments: Cl. Pigment Orange 61; Cl. Pigment Red 257 and 260; Cl. Pigment Yellow 109, 110, 173 and 185;
- Isoviolanthronpigmente: Cl. Pigment Violet 31 (Cl. Vat Violet 1);- Isoviolanthrone pigments: Cl. Pigment Violet 31 (Cl. Vat Violet 1);
- Metallkomplexpigmente: Cl. Pigment Yellow 117, 150 und 153; Cl. Pigment Green 8;- Metal complex pigments: Cl. Pigment Yellow 117, 150 and 153; Cl. Pigment green 8;
Perinonpigmente: Cl. Pigment Orange 43 (Cl. Vat Orange 7); Cl. Pigment Red 194 (Cl. Vat Red 15);Perinone Pigments: Cl. Pigment Orange 43 (Cl. Vat Orange 7); Cl. Pigment Red 194 (Cl. Vat Red 15);
Perylenpigmente: Cl. Pigment Black 31 und 32; Cl. Pigment Red 123, 149, 178, 179 (Cl. Vat Red 23), 190 (Cl. Vat Red 29) und 224; Cl. Pigment Violet 29;Perylene pigments: Cl. Pigment black 31 and 32; Cl. Pigment Red 123, 149, 178, 179 (Cl. Vat Red 23), 190 (Cl. Vat Red 29) and 224; Cl. Pigment violet 29;
- Phthalocyaninpigmente: Cl. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 und 16; Cl. Pigment Green 7 und 36;- Phthalocyanine pigments: Cl. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; Cl. Pigment green 7 and 36;
- Pyranthronpigmente: Cl. Pigment Orange 51; Cl. Pigment Red 216 (Cl. Vat Orange 4);- Pyranthrone pigments: Cl. Pigment Orange 51; Cl. Pigment Red 216 (Cl. Vat Orange 4);
- Thioindigopigmente: Cl. Pigment Red 88 und 181 (Cl. Vat Red 1); Cl. Pigment Violet 38 (Cl. Vat Violet 3);- Thioindigo pigments: Cl. Pigment Red 88 and 181 (Cl. Vat Red 1); Cl. Pigment Violet 38 (Cl. Vat Violet 3);
- Triarylcarboniumpigmente: Cl. Pigment Blue 1, 61 und 62; Cl. Pigment Green 1; Cl. Pigment Red 81 , 81 :1 und 169; Cl. Pigment Violet 1 , 2, 3 und 27; Cl. Pigment Black 1 (Anilinschwarz);- Triaryl carbonium pigments: 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 Yellow 101 (Aldazine Yellow);
- Cl. Pigment Brown 22.- Cl. Pigment Brown 22
Beispiele für besonders bevorzugte Pigmente (C) sind: Cl. Pigment Yellow 138, Cl. Pigment Red 122, Cl. Pigment Violet 19, Cl. Pigment Blue 15:3 und 15:4, Cl. Pigment Black 7, Cl. Pigment Orange 5, 38 und 43 und Cl. Pigment Green 7. Weitere geeignete Pigmente (C) sind metallische Pigmente wie beispielsweise Goldbronze, Silberbronze, Iriodinpigmente, Glitter.Examples of particularly preferred pigments (C) 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. Other suitable pigments (C) are metallic pigments such as gold bronze, silver bronze, iriodin pigments, glitter.
Der mittlere Durchmesser von im erfindungsgemäßen Verfahren eingesetztem Pigment (C) liegt üblicherweise im Bereich von 20 nm bis 1 ,5 μm, bevorzugt im Bereich von 300 bis 500 nm.The average diameter of pigment (C) used in the process according to the invention is usually in the range from 20 nm to 1.5 μm, preferably in the range from 300 to 500 nm.
In einer Ausführungsform der vorliegenden Erfindung liegt im erfindungsgemäßen Verfahren eingesetztes Pigment (C) in sphärischer oder annährend sphärischer partikulä- rer Form vor, d.h. das Verhältnis längster Durchmesser zu kleinster Durchmesser liegt im Bereich von 1 ,0 bis 2,0, bevorzugt bis 1 ,5.In one embodiment of the present invention, pigment (C) used in the process according to the invention is in spherical or approximately spherical particulate form, i.e. the ratio of longest diameter to smallest diameter is in the range from 1.0 to 2.0, preferably to 1.5.
In einer anderen Ausführungsform der vorliegenden Erfindung liegt im erfindungsgemäßen Verfahren eingesetztes Pigment (C) in Form von Nadeln oder Stiften vor.In another embodiment of the present invention, pigment (C) used in the process according to the invention is in the form of needles or sticks.
Geeignete Farbstoffe (D) sind alle Textilfarbstoffe, beispielsweise Küpenfarbstoffe wie beispielsweise Indigo und seine Derivate, Direktfarbstoffe, Dispersionsfarbstoffe, Säurefarbstoffe, Metallkomplexfarbstoffe, Naphtholfarbstoffe, Schwefelfarbstoffe, Reaktivfarbstoffe und Pigmentfarbstoffe.Suitable dyes (D) are all textile dyes, for example vat dyes such as indigo and its derivatives, direct dyes, disperse dyes, acid dyes, metal complex dyes, naphthol dyes, sulfur dyes, reactive dyes and pigment dyes.
Die Herstellung von erfindungsgemäß eingesetzten wässrigen Formulierungen kann man beispielsweise wie im Folgenden beschrieben durchführen. Man kann so vorgehen, dass man zunächst ein oder mehrere Ethylencopolymerwachse in Wasser disper- giert. Dazu kann man von einem oder mehreren der oben beschriebenen Ethylencopo- lymerwachse ausgehen. Dieses platziert man in einem Gefäß, beispielsweise einem Kolben, einem Autoklaven oder einem Kessel. In einer Variante erwärmt das oder die Ethylencopolymerwachse auf eine Temperatur über seinen Schmelzpunkt. Vorteilhaft erwärmt man auf eine Temperatur, die mindestens 10°C, besonders vorteilhaft auf eine Temperatur, die mindestens 30°C über dem Schmelzpunkt des oder der Ethylencopo- lymerwachse liegt. Setzt man mehrere verschiedene Ethylencopolymerwachse ein, so erwärmt man auf eine Temperatur, die über dem Schmelzpunkt des bei der höchsten Temperatur schmelzenden Ethylencopolymerwachses liegt. Vorteilhaft erwärmt man in dem Fall, dass man mehrere verschiedene Ethylencopolymerwachse einsetzt, auf eine Temperatur, die mindestens 10°C über dem Schmelzpunkt des bei der höchsten Tem- peratur schmelzenden Ethylencopolymerwachses liegt. Besonders vorteilhaft erwärmt man in dem Fall, dass man mehrere verschiedene Ethylencopolymerwachse einsetzt, auf eine Temperatur, die mindestens 30°C über dem Schmelzpunkt des bei der höchsten Temperatur schmelzenden Ethylencopolymerwachses liegt.The aqueous formulations used according to the invention can be prepared, for example, as described below. One can proceed by first dispersing one or more ethylene copolymer waxes in water. One can start from one or more of the ethylene copolymer waxes described above. This is placed in a vessel, for example a flask, an autoclave or a kettle. In one variant, the ethylene copolymer wax or waxes is heated to a temperature above its melting point. It is advantageously heated to a temperature which is at least 10 ° C., particularly advantageously to a temperature which is at least 30 ° C. above the melting point of the ethylene copolymer wax or waxes. If several different ethylene copolymer waxes are used, the mixture is heated to a temperature which is above the melting point of the ethylene copolymer wax which melts at the highest temperature. In the event that several different ethylene copolymer waxes are used, it is advantageously heated to a temperature which is at least 10 ° C. above the melting point of the ethylene copolymer wax melting at the highest temperature. In the event that several different ethylene copolymer waxes are used, it is particularly advantageously heated to a temperature which is at least 30 ° C. above the melting point of the ethylene copolymer wax melting at the highest temperature.
Anschließend gibt man Wasser und eine oder mehrere basisch wirkende Substanzen und gegebenenfalls weitere Bestandteile wie beispielsweise Ethylenglykol zu, wobei die Reihenfolge der Zugabe von Wasser und der Zugabe von basisch wirkender bzw. basisch wirkenden Substanzen sowie weiterer Bestandteile beliebig ist. Wenn die Temperatur über 100°C liegt, ist es vorteilhaft, unter erhöhtem Druck zu arbeiten und das Gefäß entsprechend zu wählen. Man homogenisiert die entstehende Emulsion, beispielsweise durch mechanisches oder pneumatisches Rühren oder durch Schütteln. Anschließend kann man die so hergestellte wässrige Formulierung abkühlen.Then water and one or more basic substances and optionally further constituents such as ethylene glycol are added, the order of addition of water and the addition of basic or basic substances and other constituents is arbitrary. If the temperature is above 100 ° C, it is advantageous to work under increased pressure and to select the vessel accordingly. The resulting emulsion is homogenized, for example by mechanical or pneumatic stirring or by shaking. The aqueous formulation thus prepared can then be cooled.
Danach kann man mindestens ein Farbmittel zugeben, gewählt aus (C) mindestens einem Pigment und (D) mindestens einem Farbstoff. Danach vermischt man Wasser, Ethylencopolymerwachs (B) und Farbmittel.Then at least one colorant can be added, selected from (C) at least one pigment and (D) at least one dye. Then water, ethylene copolymer wax (B) and colorant are mixed.
Wünscht man als Farbmittel mindestens ein Pigment (C) zuzugeben, so ist es bevorzugt, Pigment (C) in Form einer sogenannten Pigmentpräparation zuzugeben, d.h. in einer mit Wasser und gegebenenfalls mindestens einem oberflächenaktiven Stoff dispergierten Form.If it is desired to add at least one pigment (C) as the colorant, it is preferred to add pigment (C) in the form of a so-called pigment preparation, i.e. in a form dispersed with water and optionally at least one surfactant.
Zur Durchführung des erfindungsgemäßen Verfahrens zur Behandlung von flexiblen Substraten geht man so vor, dass man mindestens ein flexibles Substrat (A) mit mindestens einer erfindungsgemäß eingesetzten wässrigen Formulierung kontaktiert.To carry out the process according to the invention for the treatment of flexible substrates, the procedure is to contact at least one flexible substrate (A) with at least one aqueous formulation used according to the invention.
In einer Ausführungsform der vorliegenden Erfindung kontaktiert man (A) mit wässriger Formulierung bei Temperaturen im Bereich von 20 bis 100CC, bevorzugt bei Raumtemperatur.In one embodiment of the present invention, contact is made with (A) with an aqueous formulation at temperatures in the range from 20 to 100 ° C., preferably at room temperature.
In einer Ausführungsform der vorliegenden Erfindung kontaktiert man bei Drücken im Bereich von 0,5 bar bis 10 bar, insbesondere bei Atmosphärendruck.In one embodiment of the present invention, contact is made at pressures in the range from 0.5 bar to 10 bar, in particular at atmospheric pressure.
In einer Ausführungsform der vorliegenden Erfindung kontaktiert man (A) mit wässriger Formulierung bei Temperaturen im Bereich von 70 bis 180°C, bevorzugt 90°C bis 120°C, und wendet dazu Drücke oberhalb Atmosphärendruck an, beispielsweise bis 10 bar.In one embodiment of the present invention, (A) is contacted with an aqueous formulation at temperatures in the range from 70 to 180 ° C., preferably 90 ° C. to 120 ° C., and pressures above atmospheric pressure, for example up to 10 bar, are used for this purpose.
Erfindungsgemäßes Kontaktieren kann man beispielsweise über einen Zeitraum von 0,1 Sekunden bis 60 Minuten, bevorzugt 0,5 Sekunden bis 30 Minuten.Contacting according to the invention can be carried out, for example, over a period of 0.1 seconds to 60 minutes, preferably 0.5 seconds to 30 minutes.
Das Kontaktieren von Substrat (A) mit erfindungsgemäß eingesetzter wässriger Formulierung kann man beispielsweise durch Aufsprühen, Klotzen, Beschichten, Imprägnieren und Bedrucken, beispielsweise nach dem Ink-Jet-Verfahren, durchführen.The contacting of substrate (A) with the aqueous formulation used according to the invention can be carried out, for example, by spraying, padding, coating, impregnation and printing, for example by the ink jet method.
Man kann Substrat (A) einmal oder mehrmals in Folge mit erfindungsgemäß eingesetz- ter wässriger Formulierung kontaktieren. Zur Durchführung des erfindungsgemäßen Verfahrens geht man bevorzugt so vor, dass man flexibles Substrat mit mindestens einer erfindungsgemäß eingesetzten wässrigen Formulierung kontaktiert und im Anschluss daran trocknet.One can contact substrate (A) once or several times in succession with an aqueous formulation used according to the invention. The process according to the invention is preferably carried out by contacting flexible substrate with at least one aqueous formulation used according to the invention and then drying.
Besonders bevorzugt geht man so vor, dass man vor der eigentlichen Trocknung erfindungsgemäß behandeltes Substrat vortrocknet, beispielsweise auf eine Restfeuchte im Bereich von 0,5 bis 2 Gew.-%.It is particularly preferred to pre-dry the substrate treated according to the invention before the actual drying, for example to a residual moisture in the range from 0.5 to 2% by weight.
Die Vortrocknung bzw. Trocknung lässt sich auf gängigen Apparaturen durchführen. So ist sie beispielsweise, wenn man textile Substrate zu behandeln wünscht, auf allen in der Textilindustrie üblichen Fixier- und Trocknungsaggregaten durchführbar. Geeignete Trocknungs- bzw. Vortrocknungstemperaturen sind beispielsweise 50 bis 300°C, bevorzugt 70 bis 180°CPredrying or drying can be carried out on common equipment. For example, if you want to treat textile substrates, it can be carried out on all fixing and drying units that are common in the textile industry. Suitable drying or predrying temperatures are, for example, 50 to 300 ° C., preferably 70 to 180 ° C.
Danach kann man über einen Zeitraum von beispielsweise 10 Sekunden bis 60 Minuten, bevorzugt 0,5 Minuten bis 7 Minuten bei Temperaturen im Bereich von 50 bis 300°C, bevorzugt 100 bis 160°C, besonders bevorzugt 110 bis 130°C thermisch behandeln. Polyamid, Polyester, Polyvinylchlorid, modifizierte Polyester, Polyestermischgewebe, Polyamidmischgewebe, Polyacryl nitril, Polycarbonat behandelt man thermisch vorteilhaft bei Temperaturen im Bereich von 130 bis 250°O Polypropylengewebe bevorzugt zwischen 80 und 130°C, bevorzugt 110 und 130°O Dabei ist unter der Temperatur im Allgemeinen die Temperatur des Mediums zu verstehen, welches das zu behandelnde flexible Substrat umgibt.Thereafter, thermal treatment can be carried out over a period of, for example, 10 seconds to 60 minutes, preferably 0.5 minutes to 7 minutes, at temperatures in the range from 50 to 300 ° C., preferably 100 to 160 ° C., particularly preferably 110 to 130 ° C. Polyamide, polyester, polyvinyl chloride, modified polyester, polyester blend, polyamide blend, polyacrylonitrile, polycarbonate are treated thermally advantageously at temperatures in the range from 130 to 250 ° C. Polypropylene fabric, preferably between 80 and 130 ° C., preferably 110 and 130 ° C. Temperature in general to understand the temperature of the medium surrounding the flexible substrate to be treated.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäß eingesetzte wässrige Formulierung mindestens einen weiteren Stoff (E), der ausgewählt sein kann aus Verdickern, Vernetzern, Echtheitsverbessern, Weichmachern, Entschäumern, Netzmitteln und Egalisiermitteln.In one embodiment of the present invention, the aqueous formulation used according to the invention contains at least one further substance (E), which can be selected from thickeners, crosslinkers, fastness improvers, plasticizers, defoamers, wetting agents and leveling agents.
Geeignete Vernetzer sind beispielsweise Harnstoff-Formaldehyd- und Melamin-Form- aldehyd-Additionsprodukte, gegebenenfalls in Kombination mit anorganischen Salzen wie beispielsweise MgCI2-6 H2O oder NH4CI. Andere geeignete Vernetzer sind beispielsweise freie oder blockierte Isocyanate bzw. Polyisocyanate wie beispielsweise Verbindungen der allgemeinen Formel VISuitable crosslinkers are, for example, urea-formaldehyde and melamine-formaldehyde addition products, optionally in combination with inorganic salts such as, for example, MgCl 2 -6 H 2 O or NH 4 CI. Other suitable crosslinkers are, for example, free or blocked isocyanates or polyisocyanates such as, for example, compounds of the general formula VI
wobei die Variablen wie folgt definiert sind: Y1 gewählt aus N-R15, Sauerstoff und N-H, Z1 gewählt aus Wasserstoff und CO-O-R15, where the variables are defined as follows: Y 1 selected from NR 15 , oxygen and NH, Z 1 selected from hydrogen and CO-OR 15 ,
R15 gleich oder verschieden und gewählt aus Crdo-Alkyl, besonders bevorzugt sind Methyl und n-Butyl.R 15 are the same or different and selected from Crdo-alkyl, particularly preferred are methyl and n-butyl.
Weitere geeignete Vernetzer sind mehrfach funktionelle Epoxide wie beispielsweise Polyglycidylether von Polyolen z.B. Pentaerythritpolyglycidylether sowie mehrfach funktioneile Aziridine wie beispielsweise Trimethylolpropan-tris(beta-aziridinylpropionat).Other suitable crosslinkers are polyfunctional epoxides such as polyglycidyl ethers of polyols e.g. Pentaerythritol polyglycidyl ether and multi-functional aziridines such as trimethylolpropane tris (beta-aziridinyl propionate).
Belagsverhinderer kann man beispielsweise zugeben, um während des Kontaktierens die Bildung von Belägen auf Walzen von beispielsweise Foulards zu verhindern. Geeignete Belagsverhinderer sind beispielsweise Mischungen von mehrfach alkoxylierten Alkoholen, insbesondere von mehrfach ethoxylierten Fettalkoholen.Anti-fouling agents can be added, for example, to prevent the formation of deposits on rollers, for example foulards, during contacting. Suitable anti-fouling agents are, for example, mixtures of polyalkoxylated alcohols, in particular polyethoxylated fatty alcohols.
Als Verdicker (Verdickungsmitte!) kann man natürliche oder synthetische Verdicker ein- gesetzen. Beispiele für natürliche Verdicker sind Alginat, Guar, Stärke, Kernmehlether, Cassia, Tamarinde Celluloseether, Dextrine wie beispielsweise natürliche Gummen, Galaktomannan, Xanthan, Polysaccharid und Mischungen der vorgenannten Stoffe. Bevorzugt ist der Einsatz von synthetischen Verdickern, beispielsweise von bei Raumtemperatur flüssigen Lösungen von synthetischen (Co-)Polymeren in beispielsweise Weißöl oder als wässrige Lösungen oder als Wasser-in-ÖI-Emulsionen, vorzugsweise mit etwa 40 Gew.-% (Co-)Polymer.Natural or synthetic thickeners can be used as thickeners (thickening agent!). Examples of natural thickeners are alginate, guar, starch, core meal ether, cassia, tamarind cellulose ether, dextrins such as, for example, natural gums, galactomannan, xanthan, polysaccharide and mixtures of the aforementioned substances. It is preferred to use synthetic thickeners, for example solutions of synthetic (co) polymers which are liquid at room temperature in, for example, white oil or as aqueous solutions or as water-in-oil emulsions, preferably with about 40% by weight (co-) Polymer.
Bevorzugte Beispiele für Verdicker sind Copolymere mit 85 bis 95 Gew.-% Acrylsäure, 4 bis 14 Gew.-% Acrylamid und etwa 0,01 bis 1 Gew.-% des (Meth)acrylamidderivats der Formel VIIPreferred examples of thickeners are copolymers with 85 to 95% by weight of acrylic acid, 4 to 14% by weight of acrylamide and about 0.01 to 1% by weight of the (meth) acrylamide derivative of the formula VII
mit Molekulargewichten Mw im Bereich von 100.000 bis 200.000 g/mol, in denen R16 für Methyl oder bevorzugt für Wasserstoff steht.with molecular weights M w in the range from 100,000 to 200,000 g / mol, in which R 16 is methyl or preferably hydrogen.
Erfindungsgemäße Formulierungen können 30 bis 70 Gew.-% Weißöl enthalten. Wäss- rige Verdicker enthalten üblicherweise insgesamt bis zu 25 Gew.-% (Co-)Polymer, in manchen Fällen bis zu 50 Gew.-% (sogenannte Verdickerdispersionen), bezogen auf den gesamten Verdicker. Wünscht man wässrige Formulierungen eines Verdickers einzusetzen, so setzt man im Allgemeinen wässriges Ammoniak zu. Auch der Einsatz granulärer, fester Formulierungen eines Verdickers sind denkbar, um beispielsweise Emissions-frei Pigmentdrucke herstellen zu können.Formulations according to the invention can contain 30 to 70% by weight of white oil. Aqueous thickeners usually contain a total of up to 25% by weight of (co) polymer, in some cases up to 50% by weight (so-called thickener dispersions), based on the total thickener. If it is desired to use aqueous formulations of a thickener, aqueous ammonia is generally added. The use too Granular, solid formulations of a thickener are conceivable, for example in order to be able to produce emission-free pigment prints.
Geeignete Echtheitsverbesserer sind beispielsweise bei Raumtemperatur flüssige Sili- konöle und Polysiloxane. In einer bevorzugten Variante der vorliegenden Erfindung kann man auf den Einsatz von Echtheitsverbesserern verzichten.Suitable fasteners are, for example, silicone oils and polysiloxanes that are liquid at room temperature. In a preferred variant of the present invention, the use of authenticity improvers can be dispensed with.
Beispiele für geeignete Weichmacher sind Esterverbindungen, gewählt aus den Gruppen der mit Alkanolen vollständig veresterten aliphatischen oder aromatischen Di- oder Polycarbonsäuren und der mindestens einfach mit Alkanol veresterten Phosphorsäure.Examples of suitable plasticizers are ester compounds selected from the groups of aliphatic or aromatic di- or polycarboxylic acids fully esterified with alkanols and phosphoric acid esterified at least once with alkanol.
In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Alkanolen um d-do-Alkanole.In one embodiment of the present invention, alkanols are d-do alkanols.
Bevorzugte Beispiele für mit Alkanol vollständig veresterte aromatische Di- oder Polycarbonsäuren sind mit Alkanol vollständig veresterte Phthalsäure, Isophthalsäure und Mellithsäure; beispielhaft seinen genannt: Di-n-octylphthalat, Di-n-nonylphthalat, Di-n- decylphthalat, Di-n-octylisophthalat, Di-n-nonylisophthalat, Di-n-decylisophthalat.Preferred examples of aromatic di- or polycarboxylic acids fully esterified with alkanol are phthalic acid, isophthalic acid and mellitic acid fully esterified with alkanol; examples of his: di-n-octyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate, di-n-octyl isophthalate, di-n-nonyl isophthalate, di-n-decyl isophthalate.
Bevorzugte Beispiele für mit Alkanol vollständig veresterte aliphatische Di- oder Polycarbonsäuren sind beispielsweise Adipinsäuredimethylester, Adipinsäurediethylester, Adipinsäuredi-n-butylester, Adipinsäurediisobutylester, Glutarsäuredimethylester, GIu- tarsäurediethylester, Glutarsäuredi-n-butylester, Glutarsäurediisobutylester, Bemstein- säuredimethylester, Bemsteinsäurediethylester, Bernsteinsäuredi-n-butylester Bern- steinsäurediisobutylester sowie Mischungen der vorstehend genannten Verbindungen.Preferred examples of aliphatic di- or polycarboxylic acids fully esterified with alkanol are, for example, dimethyl adipate, diethyl adipate, di-n-butyl adipate, diisobutyl adipate, dimethyl glutarate, dimethyl glutarate, glutarate, glutarate, di-bututate butyl ester of diisobutyl succinate and mixtures of the aforementioned compounds.
Bevorzugte Beispiele für mindestens einfach mit Alkanol veresterte Phosphorsäure sind CrC10-Alkyl-di-C6-C14-Aryl-Phosphate wie Isodecyldiphenylphosphat.Preferred examples of phosphoric acid esterified at least once with alkanol are CrC 10 alkyl-di-C 6 -C 14 aryl phosphates such as isodecyl diphenyl phosphate.
Weitere geeignete Beispiele für Weichmacher sind mindestens einfach mit d-C10-AI- kylcarbonsäure mindestens einfach veresterte aliphatische oder aromatische Di- oder Polyole.Further suitable examples of plasticizers are aliphatic or aromatic di- or polyols which are at least monoesterified with dC 10 -alkyl carboxylic acid.
Bevorzugte Beispiele für mindestens einfach mit d-Cio-Alkylcarbonsäure veresterte aliphatische oder aromatische Di- oder Polyole ist 2,2,4-Trimethylpentan-1 ,3-diol- monoisobutyrat.Preferred examples of aliphatic or aromatic di- or polyols esterified at least once with d-Cio-alkylcarboxylic acid is 2,2,4-trimethylpentane-1,3-diol-monoisobutyrate.
Weitere geeignete Weichmacher sind Polyester, erhältlich durch Polykondensation von aliphatischer Dicarbonsäure und aliphatischem Diol, beispielsweise Adipinsäure oder Bernsteinsäure und 1 ,2-Propandiol, vorzugsweise mit einem Mw von 200 g/mol, und Polypropylenglykolalkylphenylether, vorzugsweise mit einem Mw von 450 g/mol. Weitere geeignete Weichmacher sind mit zwei verschiedenen Alkoholen veretherte Polypropylenglykole mit einem Molekulargewicht Mw im Bereich von 400 bis 800 g/mol, wobei vorzugsweise einer der Alkohole ein Alkanol, insbesondere ein d-C-io-Alkanol sein kann und der andere Alkohol vorzugsweise ein aromatischer Alkohol, beispiels- weise o-Kresol, m-Kresol, p-Kresol und insbesondere Phenol sein kann.Other suitable plasticizers are polyesters obtainable by polycondensation of aliphatic dicarboxylic acid and aliphatic diol, for example adipic acid or succinic acid and 1,2-propanediol, preferably with an M w of 200 g / mol, and polypropylene glycol alkylphenyl ether, preferably with an M w of 450 g / mol. Further suitable plasticizers are polypropylene glycols etherified with two different alcohols and having a molecular weight M w in the range from 400 to 800 g / mol, it being possible for one of the alcohols to be an alkanol, in particular a dC-ioalkanol, and the other alcohol preferably to be an aromatic alcohol , for example o-cresol, m-cresol, p-cresol and in particular phenol.
Geeignete Entschäumer sind beispielsweise silikonhaltige Entschäumer wie beispielsweise solche der Formel HO-(CH2)3-Si[OSi(CH3)3]2. Auch Silikon-freie Entschäumer sind geeignet wie beispielsweise mehrfach alkoxylierte Alkohole, z.B. Fettalkoholalko- xylate, bevorzugt 2 bis 50-fach ethoxylierte vorzugsweise unverzweigte C10-C20-Alka- nole, unverzweigte Cι0-C20-Alkanole und 2-Ethylhexan-1-ol.Suitable defoamers are, for example, silicone-containing defoamers such as those of the formula HO- (CH 2 ) 3 -Si [OSi (CH 3 ) 3 ] 2 . Silicone-free defoamers are also suitable, such as polyalkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2 to 50-fold ethoxylated, preferably unbranched C 10 -C 20 -alkanols, unbranched C 0 -C 20 -alkanols and 2-ethylhexane 1-ol.
Geeignete Netzmittel sind beispielsweise nichtionische, anionische oder kationische Tenside, insbesondere Ethoxylierungs- und/oder Propoxylierungsprodukte von Fettal- koholen oder Propylenoxid-Ethylenoxid-Blockcopolymere, ethoxylierte oder propoxy- lierte Fett- oder Oxoalkohole, weiterhin Ethoxylate von Ölsäure oder Alkylphenolen, Alkylphenolethersulfate, Alkylpolyglycoside, Alkylphosphonate, Alkylphenylphosphona- te, Alkylphosphate, oder Alkylphenylphosphate.Suitable wetting agents are, for example, 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, alkyl polyglycosides, Alkylphosphonates, alkylphenylphosphonates, alkylphosphates, or alkylphenylphosphates.
Geeignete Egalisiermittel sind beispielsweise Blockcopolymerisate von Ethylenoxid und Propylenoxid mit Molekulargewichten Mn im Bereich von 500 bis 5000 g/mol, bevorzugt 800 bis 2000 g/mol. Ganz besonders besonders bevorzugt sind Blockcopolymerisate aus Propylenoxid/Ethylenoxid beispielsweise der Formel EO8PO7EO8, wobei EO für Ethylenoxid und PO für Propylenoxid steht.Suitable leveling agents are, for example, block copolymers of ethylene oxide and propylene oxide with molecular weights M n in the range from 500 to 5000 g / mol, preferably 800 to 2000 g / mol. Block copolymers of propylene oxide / ethylene oxide, for example of the formula EO 8 PO 7 EO 8 , are very particularly preferred, EO being ethylene oxide and PO being propylene oxide.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Substrate, behandelt nach dem erfindungsgemäßen Verfahren. Erfindungsgemäße Substrate enthalten mindestens ein Ethylencopolymerwachs in gegebenenfalls vernetzter Form. Erfindungsgemäße Substrate weisen gute Gebrauchseigenschaften auf, beispielsweise gute Echthei- ten, insbesondere Waschechtheiten und Reibechtheiten wie beispielsweise Trocken- und Nassreibechtheit.The present invention furthermore relates to substrates treated by the process according to the invention. Substrates according to the invention contain at least one ethylene copolymer wax in optionally crosslinked form. Substrates according to the invention have good usage properties, for example good fastness properties, in particular wash fastnesses and rubbing fastnesses such as dry and wet rubbing fastness.
Eine spezielle Ausführungsform der vorliegenden Erfindung ist ein Verfahren zur Herstellung von bedruckten flexiblen Substraten und insbesondere bedrucktem Textil nach dem erfindungsgemäßen Verfahren, im Folgenden auch erfindungsgemäßes Textildruckverfahren genannt.A special embodiment of the present invention is a method for producing printed flexible substrates and in particular printed textile by the method according to the invention, hereinafter also referred to as the textile printing method according to the invention.
Zur Durchführung des erfindungsgemäßen Textildruckverfahrens kann man beispielsweise so vorgehen, dass man mindestens eine erfindungsgemäße wässrige Formulie- rung zu einer Druckpaste, im Folgenden auch erfindungsgemäße Druckpaste genannt, verarbeitet und danach nach an sich bekannten Methoden textile Substrate bedruckt. Vorteilhaft stellt man erfindungsgemäße Druckpasten durch Mischen von mindestens einer erfindungsgemäß eingesetzten wässrigen Formulierung mit im Druckprozess gängigen Hilfsmitteln und mindestens einem Pigment (C) her. Die Farbtiefe stellt man vorteilhaft durch Abstimmen des Verhältnisses Pigment (C) zu erfindungsgemäß ein- gesetzter wässriger Formulierung ein.To carry out the textile printing process according to the invention, one can proceed, for example, by processing at least one aqueous formulation according to the invention into a printing paste, hereinafter also called printing paste according to the invention, and then printing textile substrates according to methods known per se. Printing pastes according to the invention are advantageously prepared by mixing at least one aqueous formulation used according to the invention with auxiliaries common in the printing process and at least one pigment (C). The depth of color is advantageously adjusted by coordinating the ratio of pigment (C) to the aqueous formulation used according to the invention.
Pigment fügt man der erfindungsgemäßen Druckpaste vorzugsweise in Form von Pigmentzubereitungen zu. Pigmentzubereitungen enthalten üblicherweise 20 bis 60 Gew.-% Pigment, weiterhin Wasser und eine oder mehrere oberflächenaktive Ver- bindungen, beispielsweise einen oder mehrere Emulgatoren, beispielhaft seien mehrfach alkoxylierte C10-C30-Alkanole genannt.Pigment is preferably added to the printing paste according to the invention in the form of pigment preparations. Pigment preparations usually contain 20 to 60% by weight of pigment, furthermore water and one or more surface-active compounds, for example one or more emulsifiers, examples of which are multiply alkoxylated C 10 -C 30 -alkanols.
Das Verhältnis Pigment zu erfindungsgemäß eingesetzter wässriger Formulierung kann man in weiten Grenzen wählen. So ist es beispielsweise möglich, Pigment und erfindungsgemäß eingesetzte wässrige Formulierung in einem Gewichtsverhältnis von 20 : 1 bis 1 : 100 zu wählen. In einer bevorzugten Ausführungsform der vorliegenden Erfindung stellt man das Verhältnis Pigment zu erfindungsgemäß eingesetzter wässriger Formulierung so ein, dass das Gewichtsverhältnis von Pigment zu Feststoffanteile von erfindungsgemäß eingesetzter wässriger Formulierung im Bereich von 1 : 1 bis 1 : 30 liegt.The ratio of pigment to aqueous formulation used according to the invention can be selected within wide limits. For example, it is possible to choose pigment and aqueous formulation used according to the invention in a weight ratio of 20: 1 to 1: 100. In a preferred embodiment of the present invention, the ratio of pigment to aqueous formulation used according to the invention is adjusted so that the weight ratio of pigment to solids content of aqueous formulation used according to the invention is in the range from 1: 1 to 1.30.
Natürlich ist es auch möglich, zunächst Pigment und erfindungsgemäß eingesetzte wässrige Formulierung in einem Gewichtsverhältnis im Bereich von 20 : 1 bis 10 : 1 vorzumischen und erst unmittelbar vor dem Druck weitere erfindungsgemäß eingesetz- te wässrige Formulierung oder ein konventionelles Acrylatbindemittel zuzumischen.Of course, it is also possible first to premix the pigment and the aqueous formulation used according to the invention in a weight ratio in the range from 20: 1 to 10: 1 and to add further aqueous formulation used according to the invention or a conventional acrylate binder only immediately before printing.
Weitere gängige Hilfsmittel für Druckpasten im Textildruck sind aus Ullmann, Handbuch der technischen Chemie und Verfahrenstechnik bekannt, vergleiche beispielsweise Ullmann's Enyclopedia oflndustrial Chemistry, 5. Auflage, Stichwort: Textile Auxiliaries, Bd. A26, S. 286 ff. und 296 ff., Verlag Chemie, Weinheim, Deerfield/Florida, Basel; 1996, und aus dem Textil-Hilfsmittel-Katalog, Konradin Verlag Robert Kohlhammer GmbH, D-70771 Leinfelden-Echterdingen. Als gängige Hilfsmittel seien Verdicker, Fixierer, Griffverbesserer, Entschäumer, Rheologieverbesserer, Säurespender und Emulgatoren beispielhaft genannt:Other common tools for printing pastes in textile printing are known from Ullmann, Handbook of Technical Chemistry and Process Engineering, compare for example Ullmann's Enyclopedia of Industrial Chemistry, 5th edition, keyword: Textile Auxiliaries, Vol. A26, pp. 286 ff. And 296 ff., Publisher Chemistry, Weinheim, Deerfield / Florida, Basel; 1996, and from the Textile Aids Catalog, Konradin Verlag Robert Kohlhammer GmbH, D-70771 Leinfelden-Echterdingen. Examples of common auxiliaries are thickeners, fixers, grip improvers, defoamers, rheology improvers, acid donors and emulsifiers:
In einer bevorzugten Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Druckpasten weiterhin Griffverbesserer, ausgewählt aus Silikonen, insbesondere Polydimethylsiloxanen, und Fettsäure-d-Cio-Alkylestem. Beispiele für kommerziell erhältliche Griffverbesserer, die den erfindungsgemäßen Druckpasten zugesetzt werden können, sind Acramin® Weichmacher Sl (Bayer AG),In a preferred embodiment of the present invention, printing pastes according to the invention further contain grip improvers selected from silicones, in particular polydimethylsiloxanes, and fatty acid d-Cio-alkyl esters. Examples of commercially available grip improvers which can be added to the printing pastes according to the invention are Acramin® plasticizer Sl (Bayer AG),
Luprimol SIG®, Luprimol TX 4732 und Luprimol CW® (BASF Aktiengesellschaft). In einer bevorzugten Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Druckpasten als weitere Zusätze einen oder mehrere Emulgatoren, insbesondere dann, wenn die Druckpasten Weißöl-haltige Verdicker enthalten und als Öl- in-Wasser-Emulsion anfallen. Beispiele für geeignete Emulgatoren sind aryl- oder al- kylsubstituierte Polyglykolether. Kommerziell erhältliche Beispiele für geeignete Emulgatoren sind Emulgator W® (Bayer), Luprintol PE New® und Luprintol MP® (BASF Aktiengesellschaft).Luprimol SIG®, Luprimol TX 4732 and Luprimol CW® (BASF Aktiengesellschaft). In a preferred embodiment of the present invention, printing pastes according to the invention contain one or more emulsifiers as further additives, in particular if the printing pastes contain thickeners containing white oil and are obtained as an oil-in-water emulsion. Examples of 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).
Zur Herstellung von erfindungsgemäßen Druckpasten kann man beispielsweise so vorgehen, dass man Wasser, gegebenenfalls einen Entschäumer, beispielsweise einen Entschäumer auf Silikonbasis verrührt und unter Mischen, beispielsweise unter Rühren, mindestens eine erfindungsgemäß eingesetzte wässrige Formulierung zufügt. Danach kann man einen oder mehrere Emulgatoren und das oder die Pigmente zugeben.For the preparation of printing pastes according to the invention, one can proceed, for example, by stirring water, if appropriate a defoamer, for example a silicone-based defoamer, and adding at least one aqueous formulation used according to the invention with mixing, for example with stirring. Then one or more emulsifiers and the pigment or pigments can be added.
Als nächstes kann man einen oder mehrere Griffverbesserer zugeben, beispielsweise eine oder mehrere Silikonemulsionen.Next one can add one or more grip improvers, for example one or more silicone emulsions.
Anschließend kann man ein oder mehrere Verdickungsmittel hinzufügen und unter weiterem Vermischen, beispielsweise Rühren, homogenisieren.Then one or more thickeners can be added and homogenized with further mixing, for example stirring.
Eine typische erfindungsgemäße Druckpaste enthält, jeweils pro Kilogramm erfindungsgemäßer DruckpasteA typical printing paste according to the invention contains, in each case per kilogram of printing paste according to the invention
0,5 bis 400 g, bevorzugt 10 bis 250 g Ethylencopolymerwachs (B),0.5 to 400 g, preferably 10 to 250 g of ethylene copolymer wax (B),
0 bis 100 g, bevorzugt 1 bis 5 g Emulgator,0 to 100 g, preferably 1 to 5 g of emulsifier,
1 bis 500 g, bevorzugt 3 bis 100 g Verdicker,1 to 500 g, preferably 3 to 100 g thickener,
0 bis 500 g, bevorzugt 0,1 bis 250 g, bevorzugt 0,5 bis 120 g Pigment (C), gegebenenfalls weitere Hilfsmittel; der Rest ist bevorzugt Wasser.0 to 500 g, preferably 0.1 to 250 g, preferably 0.5 to 120 g pigment (C), optionally further auxiliaries; the rest is preferably water.
In einer Ausführungsform der vorliegenden Erfindung haben erfindungsgemäße Druckpasten bei 20°C eine Viskosität im Bereich von 0,3 bis 4000 dPa-s, bevorzugt 20 bis 200 dPa-s und besonders bevorzugt 60 bis 100 dPa-s. Viskositäten lassen sich nach gängigen Methoden bestimmen, insbesondere beispielsweise mit einem Rotations- viskosimeter, beispielsweise dem Viscotester VT02 oder VT24 der Fa. Haake Mess- Technik GmbH u. Co., Karlsruhe.In one embodiment of the present invention, print pastes according to the invention have a viscosity at 20 ° C. in the range from 0.3 to 4000 dPa-s, preferably 20 to 200 dPa-s and particularly preferably 60 to 100 dPa-s. Viscosities can be determined using conventional methods, in particular, for example, using a rotary viscometer, for example the Viscotester VT02 or VT24 from Haake Mess-Technik GmbH u. Co., Karlsruhe.
Pigmentdruck unter Verwendung mindestens einer erfindungsgemäßen Druckpaste kann nach verschiedenen Verfahren durchgeführt werden, die an sich bekannt sind. In der Regel verwendet man eine Schablone, durch die man die erfindungsgemäße Druckpaste mit einer Rakel presst. Dieses Verfahren gehört zu den Siebdruckverfah- ren. Erfindungsgemäße Pigmentdruckverfahren unter Verwendung mindestens einer erfindungsgemäßen Druckpaste liefern bedruckte Substrate mit besonders hoher Brillanz und Farbtiefe der Drucke bei gleichzeitig gutem Griff der bedruckten Substrate. Gegenstand der vorliegenden Erfindung sind daher flexible Substrate, bedruckt nach dem erfindungsgemäßen Druckverfahren unter Verwendung der erfindungsgemäßen Druckpasten.Pigment printing using at least one printing paste according to the invention can be carried out by various methods which are known per se. As a rule, a stencil is used through which the printing paste according to the invention is pressed with a squeegee. This process is part of the screen printing process. Ren. Pigment printing processes according to the invention using at least one printing paste according to the invention deliver printed substrates with particularly high brilliance and depth of color of the prints with a good grip of the printed substrates at the same time. The present invention therefore relates to flexible substrates, printed by the printing process according to the invention using the printing pastes according to the invention.
Eine andere Ausführungsform der vorliegenden Erfindung ist ein Pigmentfärbeverfahren unter Verwendung von mindestens einer erfindungsgemäßen Formulierung, im Folgenden auch erfindungsgemäßes Pigmentfärbeverfahren genannt. Das erfindungsgemäße Färbeverfahren führt man vorzugsweise so aus, dass man mindestens ein flexibles Substrat, vorzugsweise ein textiles Substrat, mit mindestens einer Färbeflotte behandelt, die mindestens eine erfindungsgemäße Formulierung enthält. Färbeflotten, die mindestens eine erfindungsgemäße Formulierung enthalten, werden im Folgenden auch erfindungsgemäße Färbeflotten genannt.Another embodiment of the present invention is a pigment coloring process using at least one formulation according to the invention, hereinafter also called pigment coloring process according to the invention. The dyeing process according to the invention is preferably carried out by treating at least one flexible substrate, preferably a textile substrate, with at least one dye liquor which contains at least one formulation according to the invention. Dyeing liquors which contain at least one formulation according to the invention are also called dyeing liquors according to the invention below.
Erfindungsgemäße Färbeflotten können als Zusatz Netzmittel enthalten, bevorzugt wenn die Netzmittel als schaumarm gelten, da bei den hohen Turbulenzen im Färbe- prozess Schaumbildung die Qualität der Färbung durch Bildung von Unegalitäten be- einträchtigt wird.Dyeing liquors according to the invention can contain wetting agents as an additive, preferably if the wetting agents are considered to be low-foaming, since the high turbulence in the dyeing process causes foaming to impair the quality of the dyeing due to the formation of irregularities.
Trockene textile Gewebe, Gewirke oder Vlies, wie sie in der kontinuierlichen Pigmentfärbung eingesetzt werden, enthalten eine große Menge von Luft. Zur Durchführung des erfindungsgemäßen Pigmentfärbeverfahrens ist daher der Einsatz von Entlüftern vorteilhaft. Diese basieren beispielsweise auf Polyethersiloxan-Copolymeren. Sie können in Mengen von 0,01 bis 2 g/l in den erfindungsgemäßen Färbeflotten enthalten sein.Dry textile fabrics, knitted fabrics or fleece, such as those used in continuous pigment dyeing, contain a large amount of air. The use of deaerators is therefore advantageous for carrying out the pigment dyeing process according to the invention. These are based, for example, on polyether siloxane copolymers. They can be contained in the dyeing liquors according to the invention in amounts of 0.01 to 2 g / l.
Weiterhin können erfindungsgemäße Färbeflotten Antimigrationsmittel enthalten. Ge- eignete Antimigrationsmittel sind beispielsweise Blockcopolymerisate von Ethylenoxid und Propylenoxid mit Molekulargewichten Mπ im Bereich von 500 bis 5000 g/mol, bevorzugt 800 bis 2000 g/mol.Dyeing liquors according to the invention can also contain anti-migration agents. Suitable antimigration agents are, for example, block copolymers of ethylene oxide and propylene oxide with molecular weights M π in the range from 500 to 5000 g / mol, preferably 800 to 2000 g / mol.
Weiterhin kann man den erfindungsgemäßen Färbeflotten als Zusatz einen oder meh- rere Griffverbesserer zusetzen. Hierbei handelt es sich in der Regel um Polysiloxane oder um Wachse. Polysiloxane haben hierbei den Vorteil der Permanenz, während die Wachse langsam während des Gebrauchs ausgewaschen werden.Furthermore, one or more grip improvers can be added to the dyeing liquors according to the invention. These are usually polysiloxanes or waxes. Polysiloxanes have the advantage of permanence, while the waxes are slowly washed out during use.
Die Viskositäten der erfindungsgemäßen Färbeflotten liegen bevorzugt im Bereich von unter 100 mPa-s. Die Oberflächenspannungen der erfindungsgemäßen Färbeflotten sind so einzustellen, dass ein Benetzen der Ware möglich ist. Gängig sind Oberflächenspannungen von kleiner 50 mN/m. In einer Ausführungsform der vorliegenden Erfindung enthält eine typische erfindungsgemäße Färbeflotte pro LiterThe viscosities of the dye liquors according to the invention are preferably in the range of less than 100 mPa-s. 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 are common. In one embodiment of the present invention, a typical dye liquor according to the invention contains per liter
0,5 bis 400 g, bevorzugt 20 bis 300 g Ethylencopolymerwachs (B), 0 bis 100 g, bevorzugt 0,1 bis 10 g Netzmittel, 0 bis 100 g, bevorzugt 0,1 bis 10 g Entschäumer, 0 bis 300 g, bevorzugt 1 bis 20 g Antibelagsmittel, 0 bis 100 g, bevorzugt 1 bis 50 g Antimigrationsmittel, 0 bis 100 g, bevorzugt 1 bis 50 g Egalisiermittel, 0,5 bis 25 g, bevorzugt 1 bis 12 g Pigment (C).0.5 to 400 g, preferably 20 to 300 g ethylene copolymer wax (B), 0 to 100 g, preferably 0.1 to 10 g wetting agent, 0 to 100 g, preferably 0.1 to 10 g defoamer, 0 to 300 g, preferably 1 to 20 g of anti-fouling agent, 0 to 100 g, preferably 1 to 50 g of anti-migration agent, 0 to 100 g, preferably 1 to 50 g of leveling agent, 0.5 to 25 g, preferably 1 to 12 g of pigment (C).
Ein weiterer Aspekt der vorliegenden Erfindung ist ein Verfahren zur Herstellung erfindungsgemäßer Färbeflotten. Das erfindungsgemäße Verfahren umfasst das Vermischen von Farbmittel, beispielsweise Pigment (C), vorzugsweise in Form von Pigment- Zubereitungen, die neben Pigment und Wasser ein oder mehrere oberflächenaktive Verbindungen enthalten, mit oben aufgeführten Zusätzen wie weiteren Lösemitteln, Entschäumern, Griffverbesserern, Emulgatoren und/oder Bioziden und Auffüllen mit Wasser. Zur Ausübung des Verfahrens zur Herstellung von erfindungsgemäßen Färbeflotten verrührt man üblicherweise die Komponenten der erfindungsgemäßen Färbeflot- ten in einem Mischbehälter, wobei Größe und Form des Mischbehälters unkritisch sind. Bevorzugt schließt sich an das Verrühren eine Klärfiltration an.Another aspect of the present invention is a method for producing dye liquors according to the invention. The process according to the invention comprises mixing colorants, for example pigment (C), preferably in the form of pigment preparations which, in addition to pigment and water, contain one or more surface-active compounds, with additives listed above, such as further solvents, defoamers, grip improvers, emulsifiers and / or biocides and replenishing with water. To carry out the process for producing dye liquors according to the invention, the components of the dye liquors according to the invention are usually stirred in a mixing container, the size and shape of the mixing container being uncritical. Clarification is preferably followed by stirring.
Ein weiterer Aspekt der vorliegenden Erfindung ist ein Verfahren zum Färben von flexiblen Substraten unter Verwendung der oben beschriebenen erfindungsgemäßen Färbeflotten, im Folgenden auch als erfindungsgemäßes Färbeverfahren, insbesondere als erfindungsgemäßes Pigmentfärbeverfahren bezeichnet. Das erfindungsgemäße Färbeverfahren kann in gängigen Färbemaschinen durchgeführt werden. Bevorzugt sind Foulards, die als wesentliches Element zwei aufeinandergepresste Rollen enthalten, durch die flexibles Substrat und insbesondere Textil geführt wird. Oberhalb der Rollen ist erfindungsgemäße Färbeflotte eingefüllt und benetzt flexibles Substrat bzw. das Textil. Durch den Druck der Rollen wird das flexible Substrat bzw. das Textil abgequetscht und ein konstanter Auftrag gewährleistet.Another aspect of the present invention is a method for dyeing flexible substrates using the inventive dye liquors described above, hereinafter also referred to as the dyeing method according to the invention, in particular as the pigment dyeing method according to the invention. The dyeing process according to the invention can be carried out in common dyeing machines. Foulards are preferred which contain two rollers pressed together as an essential element, through which flexible substrate and in particular textile is guided. Dyeing liquor according to the invention is filled in above the rollers and wets flexible substrate or the textile. The pressure of the rollers squeezes the flexible substrate or textile and ensures a constant application.
An den eigentlichen Färbeschritt schließt sich üblicherweise eine thermische Trock- nung und optional eine Fixierung an. Bevorzugt trocknet man bei Temperaturen von 25 bis 300°C über einen Zeitraum von 10 Sekunden bis 60 Minuten, bevorzugt 30 Sekunden bis 10 Minuten. Wenn man zu fixieren wünscht, so fixiert man bei Temperaturen von 150°C bis 190°C über einen Zeitraum von 30 Sekunden bis 5 Minuten.The actual dyeing step is usually followed by thermal drying and optionally fixation. Drying is preferably carried out at temperatures of 25 to 300 ° C. over a period of 10 seconds to 60 minutes, preferably 30 seconds to 10 minutes. If you want to fix, you fix at temperatures of 150 ° C to 190 ° C over a period of 30 seconds to 5 minutes.
Bevorzugt ist ein Verfahren zur Pigmentfärbung nach dem Klotzprozess. Erfindungsgemäß bedruckte und gefärbte Substrate zeichnen sich durch besondere Brillanz der Farben bei gleichzeitig gutem Griff der bedruckten bzw. gefärbten Substrate aus. Ein weiterer Aspekt der vorliegenden Erfindung sind daher Substrate, gefärbt nach dem oben beschriebenen Verfahren unter Verwendung der erfindungsgemäßen Färbeflotten .A method for pigment coloring after the padding process is preferred. Substrates printed and dyed according to the invention are distinguished by a particular brilliance of the colors with a good grip on the printed or dyed substrates. Another aspect of the present invention is therefore substrates, colored by the process described above using the dye liquors according to the invention.
Ein weiterer Gegenstand der vorliegenden Erfindung sind gefärbte flexible Substrate, erhältlich nach dem erfindungsgemäßen Pigmentfärbeverfahren. Erfindungsgemäße gefärbte flexible Substrate zeichnen sich beispielsweise durch gute Waschechtheiten, gute Trocken- und Nassreibechtheiten sowie gute Echtheiten, insbesondere durch geringe Farbtiefeverluste bei der Kochbürstwäsche aus.Another object of the present invention are colored flexible substrates obtainable by the pigment dyeing process according to the invention. Dyed flexible substrates according to the invention are distinguished, for example, by good wash fastnesses, good dry and wet rubbing fastnesses and good fastness properties, in particular by low color depth losses in the brushing wash.
In einer anderen Ausführungsform der vorliegenden Erfindung kontaktiert man flexible Substrate (A) und insbesondere Folien oder Textil aus Polypropylen mit pigmentfreier wässriger Formulierung und trocknet im Anschluss danach. Auf flexiblem Substrat gleichmäßig verteiltes unvernetztes Ethylencopolymerwachs wirkt als Haftvermittler (Primer) und erlaubt das Verkleben mit beliebigen anderen Materialien.In another embodiment of the present invention, flexible substrates (A) and in particular foils or textile made of polypropylene with pigment-free aqueous formulation are contacted and then dried. Evenly distributed, uncrosslinked ethylene copolymer wax acts on a flexible substrate as an adhesion promoter (primer) and allows bonding with any other materials.
In einer anderen Ausführungsform der vorliegenden Erfindung kann man das erfin- dungsgemäße Verfahren zum Bedrucken von flexiblen Substraten als Transferdruckverfahren durchführen. Dazu bedruckt man ein mit Wachs, beispielsweise mit Silikonwachs beschichtetes Papier mit mindestens einer erfindungsgemäßen Druckpaste und trocknet danach das bedruckte Papier bei Raumtemperatur bis 300 °C, bevorzugt bei Raumtemperatur bis 180 °C Das bedruckte und getrocknete Papier wird zusammen mit dem Textilmaterial auf einer heißen Presse oder einem heißen Kalander bei 70 bis 300 °C, bevorzugt 10 bis 100 s bei 100 bis 120 °C, behandelt. Während dieses Prozesses kommt es zum Erweichen/Schmelzen der Druckpaste und Übertragung und Fixierung von Papier auf das zu bedruckende 2- oder 3-dimensionale flexible Substrat, beispielsweise textiles Substrat oder Folie.In another embodiment of the present invention, the method according to the invention for printing on flexible substrates can be carried out as a transfer printing method. For this purpose, a paper coated with wax, for example with silicone wax, is printed with at least one printing paste according to the invention and the dried paper is then dried at room temperature to 300 ° C., preferably at room temperature to 180 ° C. The printed and dried paper is heated to a temperature together with the textile material Press or a hot calender at 70 to 300 ° C, preferably 10 to 100 s at 100 to 120 ° C, treated. During this process, the printing paste is softened / melted and paper is transferred and fixed onto the 2 or 3-dimensional flexible substrate to be printed, for example a textile substrate or film.
Die Erfindung wird durch Arbeitsbeispiele erläutert.The invention is illustrated by working examples.
Arbeitsbeispieleworking examples
1. Herstellung von Ethylencopolymerwachs1. Production of ethylene copolymer wax
In einem Hochdruckautoklaven, wie er in der Literatur beschrieben ist (M. Buback et al., Chem. Ing. Tech. 1994, 66, 510), wurden Ethylen und Acrylsäure bzw. Methacryl- säure gemäß Tabelle 1 copolymerisiert. Dazu wurde Ethylen (12,0 kg/h) unter dem Reaktionsdruck von 1700 bar in den Autoklaven eingespeist. Getrennt davon wurden die in Tabelle 1 angegebene Menge Acrylsäure bzw. Methacrylsäure zunächst auf einen Zwischendruck von 260 bar verdichtet und anschließend unter dem Reaktions- druck von 1700 bar eingespeist. Getrennt davon wurde Initiatorlösung, bestehend aus tert.-Butylperoxypivalat in Isododekan (Menge und Konzentration s. Tabelle 1 ), unter dem Reaktionsdruck von 1700 bar in den Autoklaven eingespeist. Getrennt davon wurde die in Tabelle 1 angegebene Menge Regler, bestehend aus Propionaldehyd in Isododekan, Konzentration s. Tabelle 1, zunächst auf einen Zwischendruck von 260 bar verdichtet und anschließend mit Hilfe eines weiteren Kompressors in den Hochdruckautoklaven eingespeist. Die Reaktionstemperatur betrug 220CC Man erhielt Ethylencopolymerwachse gemäß Tabelle 1 mit den aus der Tabelle 2 ersichtlichen analytischen Daten.In a high-pressure autoclave, as described in the literature (M. Buback et al., Chem. Ing. Tech. 1994, 66, 510), ethylene and acrylic acid or methacrylic acid were copolymerized according to Table 1. For this purpose, ethylene (12.0 kg / h) was fed into the autoclave under the reaction pressure of 1700 bar. Separately, the amount of acrylic acid or methacrylic acid given in Table 1 was first compressed to an intermediate pressure of 260 bar and then under the reaction pressure of 1700 bar fed. Separately, initiator solution, consisting of tert-butyl peroxypivalate in isododecane (quantity and concentration, see Table 1), was fed into the autoclave under the reaction pressure of 1700 bar. Separately, the amount of regulator stated in Table 1, consisting of propionaldehyde in isododecane, concentration s. Table 1, initially compressed to an intermediate pressure of 260 bar and then fed into the high-pressure autoclave with the aid of another compressor. The reaction temperature was 220 ° C. Ethylene copolymer waxes according to Table 1 were obtained with the analytical data shown in Table 2.
Der Gehalt an Ethylen und Acrylsäure bzw. Methacrylsäure im Ethylencopolymerwachs wurde NMR-spektroskopisch bzw. durch Titration (Säurezahl) bestimmt. Die Säurezahl des Ethylencopolymerwachses wurde titrimetrisch nach DIN 53402 bestimmt. Der KOH-Verbrauch korrespondiert mit dem Acrylsäure- bzw. Methacrylsäure-Gehalt im Ethylencopolymerwachs. Der MFI wurde nach DIN 53735 bei 160°C und einer Belastung von 325 g bestimmt.The content of ethylene and acrylic acid or methacrylic acid in the ethylene copolymer wax was determined by NMR spectroscopy or by titration (acid number). The acid number of the ethylene copolymer wax was determined titrimetrically in accordance with DIN 53402. The KOH consumption corresponds to the acrylic acid or methacrylic acid content in the ethylene copolymer wax. The MFI was determined according to DIN 53735 at 160 ° C and a load of 325 g.
Tabelle 1 : Herstellung von EthylencopolymerwachsenTable 1: Preparation of ethylene copolymer waxes
Unter TReaktor ist die maximale Innentemperatur des Hochdruckautoklaven zu verstehen. The T reactor is the maximum internal temperature of the high-pressure autoclave.
Tabelle 2: Analytische Daten von EthylencopolymerwachsenTable 2: Analytical data of ethylene copolymer waxes
Unter „Gehalt" ist der Anteil an einpolymerisiertem Ethylen bzw. Acrylsäure bzw. Methacrylsäure im jeweiligen Ethylencopolymerwachs zu verstehen. Abkürzungen: AS : Acrylsäure, MAS : Methacrylsäure, PA : Propionaldehyd, ID : Isodothekan, PO : t-Butylhydroperoxid, ECW : Ethylencopolymerwachs. 2. Herstellung von wässrigen Dispersionen von Ethylencopolymerwachsen “Content” is to be understood as the proportion of copolymerized ethylene or acrylic acid or methacrylic acid in the respective ethylene copolymer wax. Abbreviations: AS: acrylic acid, MAS: methacrylic acid, PA: propionaldehyde, ID: isodothecan, PO: t-butyl hydroperoxide, ECW: ethylene copolymer wax. 2. Preparation of aqueous dispersions of ethylene copolymer waxes
In einem 2-Liter-Autoklaven mit Ankerrührer wurde die in Tabelle 3 angegebene Menge Ethylencopolymerwachs nach Beispiel 1 vorgelegt. Es wurden die in Tabelle 3 angegebenen Mengen deionisiertes Wasser sowie Ammoniak zugesetzt und unter Rühren auf 120°C erhitzt. Nach 30 Minuten bei 120° wurde innerhalb von 15 Minuten auf Raumtemperatur abgekühlt. Man erhielt die Dispersionen 2.1 bzw. 2.2. Tabelle 3: Herstellung von wässrigen Dispersionen von EthylencopolymerwachsThe amount of ethylene copolymer wax according to Example 1 given in Table 3 was placed in a 2 liter autoclave with anchor stirrer. The amounts of deionized water and ammonia given in Table 3 were added and the mixture was heated to 120 ° C. with stirring. After 30 minutes at 120 °, the mixture was cooled to room temperature within 15 minutes. Dispersions 2.1 and 2.2 were obtained. Table 3: Preparation of aqueous dispersions of ethylene copolymer wax
Die Viskosität wurde mit einem 5 mm Becher bei 23CC nach ISO 2431 bestimmt Die „Menge NH3" bezieht sich auf die Menge an 25 Gew.-% wässriger Ammoniaklö- sung.The viscosity was determined using a 5 mm beaker at 23 ° C. according to ISO 2431. The “amount of NH 3 ” relates to the amount of 25% by weight aqueous ammonia solution.
3. Herstellung von erfindungsgemäßen Druckpasten 3.1 Herstellung einer blauen Pigmentpräparation In einer Rührwerkskugelmühle des Typs Drais Superflow DCP SF 12 wurden miteinander vermählen:3. Production of Printing Pastes According to the Invention 3.1 Production of a Blue Pigment Preparation In a stirred ball mill of the Drais Superflow DCP SF 12 type, the following were milled:
2640 g Pigment Blau 15:32640 g pigment blue 15: 3
460 g n-C18H37O(CH2CH2O)25H460 g nC 18 H 37 O (CH 2 CH 2 O) 25 H
600 g Glycerin600 g glycerin
2300 g destilliertes Wasser2300 g of distilled water
Das Vermählen wurde fortgesetzt, bis die Pigmentpartikel einen mittleren Durchmesser von 100 nm aufwiesen.The milling was continued until the pigment particles had an average diameter of 100 nm.
3.2. Herstellung von Stammpasten3.2. Manufacture of master pastes
Man verrührte in einem Rührgefäß die Ingredienzien gemäß Tabelle 4 und erhielt die Stammpasten 3.1 bis 3.4, indem man die Ingredienzien in der in der Tabelle 4 aufge- führten Reihenfolge miteinander vereinigte und verrührte. Man verrührte danach 15 Minuten mit einem Schnellrührer des Typs Ultra-Turrax mit etwa 6000 Umdrehun- gen/min und prüfte danach den pH-Wert. Wenn der pH-Wert unter 8 lag, stellte man einen pH-Wert von 8,5 durch Zugabe von konzentriertem wässrigen Ammoniak ein.The ingredients according to Table 4 were stirred in a stirred vessel and the master pastes 3.1 to 3.4 were obtained by combining the ingredients with one another in the order shown in Table 4 and stirring. The mixture was then stirred for 15 minutes using an Ultra-Turrax high-speed stirrer at about 6000 revolutions. gen / min and then checked the pH. If the pH was below 8, the pH was adjusted to 8.5 by adding concentrated aqueous ammonia.
Tabelle 4: Herstellung von Stammpasten 3.1 bis 3.4Table 4: Production of stock pastes 3.1 to 3.4
Unter 2.1 bzw. 2.2 wird die jeweilige wässrige Dispersion 2.1 bzw. 2.2 aus Beispiel 2 verstanden. Als Verdicker wurde jeweils eingesetzt: Dispersion von Copolymer aus Acrylsäure (92 Gew.-%), Acrylamid (7,6 Gew.-%), Methylenbisacryl- amid (0,4 Gew.-%), quantitativ neutralisiert mit Ammoniak (25%ig in Wasser), Molekulargewicht Mw von ca. 150.000g/mol als Wasser-in-Mineralöl-Dispersion (Volumenverhältnis 2,6 : 1 ) (Sdp. des Mineralöls: 190-230°C), Feststoffgehalt: 24 Gew.-%; stabilisiert mit Sorbitanmonooleat (2,5 Gew.-%, bezogen auf gesamten Verdicker). 2.1 or 2.2 is understood to mean the respective aqueous dispersion 2.1 or 2.2 from example 2. The following were used as thickeners: dispersion of copolymer of acrylic acid (92% by weight), acrylamide (7.6% by weight), methylenebisacrylamide (0.4% by weight), quantitatively neutralized with ammonia (25% ig in water), molecular weight M w of approx. 150,000 g / mol as a water-in-mineral oil dispersion (volume ratio 2.6: 1) (bp of mineral oil: 190-230 ° C), solids content: 24% by weight %; stabilized with sorbitan monooleate (2.5% by weight, based on the total thickener).
3.3. Vermischen von Stammpasten mit blauer Pigmentpräparation aus Beispiel 3.2.3.3. Mixing stock pastes with blue pigment preparation from Example 3.2.
Durch Vermischen von je 970 g Stammpaste gemäß Tabelle 4 mit jeweils 30 g blauer Pigmentpräparation aus Beispiel 3.1 wurden erfindungsgemäße Druckpasten gemäß Tabelle 5 hergestellt. Printing pastes according to the invention were prepared in accordance with Table 5 by mixing 970 g of base paste according to Table 4 with 30 g of blue pigment preparation from Example 3.1 each.
Man erhielt erfindungsgemäße Druckpasten 4.1 bis 4.4 gemäß Tabelle 5.Printing pastes 4.1 to 4.4 according to the invention according to Table 5 were obtained.
Tabelle 5: Herstellung von erfindungsgemäßen DruckpastenTable 5: Production of printing pastes according to the invention
4. Druckexperimente, Tests der Drucke 4. Printing experiments, printing tests
Man bedruckte nach dem Siebdruckverfahren Substrate aus Polypropylengewebe, Flächengewicht 170 g/m2.Substrates made of polypropylene fabric, basis weight 170 g / m 2, were printed using the screen printing process.
Die Druckparameter waren: Rakel 15 mm, Schablonengaze ESTAL MONO E 55, Magnetzugstufe 6, einfacher Druck, kein Muster.The printing parameters were: doctor blade 15 mm, stencil gauze ESTAL MONO E 55, magnetic draft level 6, simple printing, no pattern.
Man trocknete im Trockenschrank bei 80°C und fixierte anschließend auf einem Fixier- schrank durch fünfminütiges Erhitzen mit Heißluft bei 110°OIt was dried in a drying cabinet at 80 ° C. and then fixed on a fixing cabinet by heating with hot air at 110 ° C. for five minutes
Man erhielt die erfindungsgemäßen Substrate 5.1 und 5.2, auch erfindungsgemäß bedruckte Substrate 5.1 bzw. 5.2 genannt.The substrates 5.1 and 5.2 according to the invention, also called substrates 5.1 and 5.2 printed according to the invention, were obtained.
Zum Vergleich wurde ein Druck mit einer Vergleichsdruckpaste V4.5 durchgeführt, die analog zur erfindungsgemäßen Druckpaste 4.1 hergestellt worden war, jedoch war Ethylencopolymerwachs-Dispersion 2.1 ersetzt durch eine Dispersion (Acrylatbinder- Dispersion) von folgendem Copolymerisat: n-Butylacrylat (66 Gew.-%), Styrol (31 Gew.-%), Acrylsäure (1 Gew.-%),For comparison, printing was carried out with a comparative printing paste V4.5, which had been prepared analogously to printing paste 4.1 according to the invention, but ethylene copolymer wax dispersion 2.1 had been replaced by a dispersion (acrylate binder dispersion) of the following copolymer: n-butyl acrylate (66% by weight) %), Styrene (31% by weight), acrylic acid (1% by weight),
Methylolacrylamid (1 Gew.-%), Acrylamid (1 Gew-.%), quantitativ neutralisiert mit Ammoniak (25 Gew.-%ig in Wasser), mit 2 Gew.-%, bezogen auf Copolymerisat, anMethylolacrylamide (1% by weight), acrylamide (1% by weight), quantitatively neutralized with ammonia (25% by weight in water), with 2% by weight, based on the copolymer
.O. .SO3Na C12H2£" O'.O. .SO 3 Na C 12 H 2 £ "O '
als Emulgator; Feststoffgehalt: 35 Gew.-%. Man erhielt Vergleichssubstrat V5.5.as an emulsifier; Solids content: 35% by weight. Comparative substrate V5.5 was obtained.
Die erfindungsgemäßen Substrate wurden auf Trocken- und Nassreibechtheit nach DIN EN ISO 105-X12 und Waschechtheit nach DIN EN ISO 105-C03 getestet. Best- mögliches Ergebnis: Note 5, schlechtestes mögliches Ergebnis: Note 1.The substrates according to the invention were tested for dry and wet rub fastness according to DIN EN ISO 105-X12 and wash fastness according to DIN EN ISO 105-C03. Best possible result: grade 5, worst possible result: grade 1.
Man erhielt die folgenden erfindungsgemäßen Substrate und Testergebnisse gemäß Tabelle 6. Tabelle 6: Erfindungsgemäß bedruckte Substrate und TestergebnisseThe following substrates and test results according to the invention were obtained in accordance with Table 6. Table 6: Substrates and test results printed according to the invention
6. Herstellung von erfindungsgemäßen Färbeflotten und Pigmentfärbung 6.1. Herstellung von erfindungsgemäßen Färbeflotten 6. Production of dyeing liquors and pigment dyeing according to the invention 6.1. Production of dyeing liquors according to the invention
Allgemeine Rezeptur:General recipe:
In einem Rührgefäß vermischte man durch Zusammenrühren:In a mixing vessel, the following was mixed by stirring:
Vollentsalztes Wasser 774 Pigmentpräparation aus Beispiel 3.1 20 g/l (berechnet auf Pigmentpräparation)Demineralized water 774 pigment preparation from Example 3.1 20 g / l (calculated on pigment preparation)
Wässrige Dispersion 2.1 bzw. 2.2 180 g/l (berechnet auf Feststoffgehalt) EO8PO7EO8 20 g/l als Antimigrationsmittel n-C12H25O(C2H4O)7H 4 g/l als Antibelagmittel HO-(CH2)3-Si[OSi(CH3)3]2 20 g/l als EntschäumerAqueous dispersion 2.1 or 2.2 180 g / l (calculated on solids content) EO 8 PO 7 EO 8 20 g / l as anti-migration agent nC 12 H 25 O (C 2 H 4 O) 7 H 4 g / l as anti-coating agent HO- ( CH 2 ) 3 -Si [OSi (CH 3 ) 3 ] 2 20 g / l as defoamer
und füllte mit vollentsalztem Wasser auf einen Liter auf. Wenn man wässrige Dispersion 2.1 einsetzt, so erhält man die erfindungsgemäße Färbeflotte F6.1; wenn man wässrige Dispersion 2.2 einsetzt, so erhält man die erfindungsgemäße Färbeflotte F6.2.and made up to one liter with deionized water. If aqueous dispersion 2.1 is used, the dye liquor F6.1 according to the invention is obtained; if aqueous dispersion 2.2 is used, the dye liquor F6.2 according to the invention is obtained.
Antimigrationsmittel: Bei dem in der allgemeinen Rezeptur eingesetzten Antimigrationsmittel EO8PO7EO8 steht stets EO für Ethylenoxid und PO für Propylenoxid. Es hat die folgenden Eigenschaften: einen Trübungspunkt in Wasser von 40°C, eine mittleren molaren Masse Mw von 1100 g/ml, Erstarrungspunkt < 5CC, Viskosität bei 25°C: 175 mPa-s.Anti-migration agent: With the anti-migration agent EO 8 PO 7 EO 8 used in the general recipe, EO always stands for ethylene oxide and PO for propylene oxide. It has the following properties: a cloud point in water of 40 ° C, a medium one molar mass M w of 1100 g / ml, solidification point <5 C C, viscosity at 25 ° C: 175 mPa-s.
6.2. Färben von Substraten mit erfindungsgemäßen Färbeflotten6.2. Dyeing substrates with dyeing liquors according to the invention
Mit einem Foulard (Hersteller Fa. Mathis, Typ Nr. HVF12085) wurde ein textiles Substrat (Polypropylen-Gewebe) mit jeweils einer nach 6.1 hergestellten erfindungsgemäßen Flotte gefärbt. Der Anpressdruck der Walzen betrug 2,6 bar. Es resultierte eine Flottenaufnahme von 55%. Die Auftraggeschwindigkeit betrug 2 m/min. Anschließend wurde das Textil bei 80°C in einem Umluftschrank (Hersteller: Fa. Mathis, Typ Nr. LTF89534) 60 s lang getrocknet (Umluft 50%). Die abschließende Fixierung erfolgte 5 Minuten lang bei 110°C unter Umluft (100%).A textile substrate (polypropylene fabric) was dyed with a pad (manufacturer Mathis, type no. HVF12085), each with a liquor according to the invention produced according to 6.1. The contact pressure of the rollers was 2.6 bar. A fleet uptake of 55% resulted. The application speed was 2 m / min. The textile was then dried at 80 ° C. in a circulating air cabinet (manufacturer: Mathis, type no. LTF89534) for 60 s (circulating air 50%). The final fixation was carried out for 5 minutes at 110 ° C. in circulating air (100%).
Man erhielt die folgenden erfindungsgemäßen Substrate, auch erfindungsgemäß gefärbte Substrate genannt, und Testergebnisse gemäß Tabelle 7.The following substrates according to the invention, also called substrates colored according to the invention, and test results according to Table 7 were obtained.
Das Vergleichssubstrat wurde durch Färben mit einer Vergleichsflotte hergestellt, die der erfindungsgemäßen Färbeflotte F6.1 entsprach mit der Ausnahme, dass statt Dispersion 2.1 eine gleiche Menge Acrylatbinder-Dispersion eingesetzt wurde, die auch zur Herstellung der Vergleichsdruckpaste V4.5 eingesetzt wurde.The comparison substrate was produced by dyeing with a comparison liquor which corresponded to the dye liquor F6.1 according to the invention, with the exception that instead of dispersion 2.1 an equal amount of acrylate binder dispersion was used, which was also used to prepare the comparison printing paste V4.5.
Tabelle 7: Erfindungsgemäß gefärbte Substrate und TestergebnisseTable 7: Substrates colored according to the invention and test results
7. Herstellung von Transferdrucken 7.1 Herstellung von erfindungsgemäßen Transferdruckfarben 7. Production of transfer prints 7.1 Production of transfer printing inks according to the invention
Tabelle 8: Herstellung von erfindungsgemäßen Transferdruckfarben 8.1 bis 8.2Table 8: Production of transfer printing inks 8.1 to 8.2 according to the invention
7.2. Herstellung von Transferdrucken 7.2. Production of transfer prints
Ein mit Silikonwachs beschichtetes Papier wurde mit den erfindungsgemäßen Druckpasten, z.B. 8.1 und 8.2 bedruckt und danach bei 100°C getrocknet. Das bedruckte und getrocknete Papier wird zusammen mit Textil auf einer heißen Presse bei 120 °C eine Minute lang behandelt. Während dieses Prozesses kommt es zum Erweichen/Schmelzen der Druckpaste und Übertragung und Fixierung von Papier auf das zu bedruckende Textil. A paper coated with silicone wax was used with the printing pastes according to the invention, e.g. 8.1 and 8.2 printed and then dried at 100 ° C. The printed and dried paper is treated together with textile on a hot press at 120 ° C for one minute. During this process, the printing paste softens / melts and paper is transferred and fixed onto the textile to be printed.

Claims

Patentansprüche claims
1. Verfahren zur Behandlung von flexiblen Substraten, dadurch gekennzeichnet, dass man1. Process for the treatment of flexible substrates, characterized in that
(A) mindestens ein flexibles Substrat, gewählt aus Substraten aus (A1) Polyacryl, Polyester, Silikon, Polyamid oder (A2) einem oder mehreren Polymeren auf Basis von einem Monomer der allgemeinen Formel I(A) at least one flexible substrate selected from substrates made of (A1) polyacrylic, polyester, silicone, polyamide or (A2) one or more polymers based on a monomer of the general formula I.
R1 in denen R1 gewählt wird aus -Cl, d-C10-AIkyI, -CH=CH2, -C(CI)=CH2, -C(CH3)=CH2 und -COOC C10-Alkyl, mit mindestens einer wässrigen Formulierung kontaktiert, enthaltendR 1 in which R 1 is selected from -Cl, dC 10 -alkyl, -CH = CH 2 , -C (CI) = CH 2 , -C (CH 3 ) = CH 2 and -COOC C 10 -alkyl, with contacted at least one aqueous formulation containing
(B) mindestens ein Ethylencopolymerwachs, welches 60 bis 95 Gew.-% Ethylen und 5 bis 40 Gew.-% mindestens einer ethylenisch ungesättigten Carbonsäure einpolymerisiert enthält, weiterhin mindestens ein Farbmittel, gewählt aus (C) mindestens einem Pigment und (D) mindestens einem Farbstoff.(B) at least one ethylene copolymer wax which contains 60 to 95% by weight of ethylene and 5 to 40% by weight of at least one ethylenically unsaturated carboxylic acid in copolymerized form, furthermore at least one colorant selected from (C) at least one pigment and (D) at least a dye.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei mindestens einer ethylenisch ungesättigten Carbonsäure um eine Carbonsäure der all- gemeinen Formel II2. The method according to claim 1, characterized in that it is at least one ethylenically unsaturated carboxylic acid is a carboxylic acid of the general formula II
handelt, wobei die Reste wie folgt definiert sind: R2 gewählt aus Wasserstoff, unverzweigten oder verzweigten Crdo-Alkyl oder COOH, COOCH3, COOC2H5, R3 gewählt aus Wasserstoff, unverzweigten oder verzweigten Crdo-Alkyl. acts, the radicals are defined as follows: R 2 selected from hydrogen, unbranched or branched Crdo-alkyl or COOH, COOCH 3 , COOC 2 H 5 , R 3 selected from hydrogen, unbranched or branched Crdo-alkyl.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass flexible Substrate gewählt werden aus Folien und textilen Substraten. 3. The method according to claim 1 or 2, characterized in that flexible substrates are selected from foils and textile substrates.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass flexible Substrate aus (A2) Polypropylen gewählt werden.4. The method according to any one of claims 1 to 3, characterized in that flexible substrates are selected from (A2) polypropylene.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass flexible Substrate gewählt werden aus Geweben, Gewirken und Nonwovens.5. The method according to any one of claims 1 to 4, characterized in that flexible substrates are selected from fabrics, knitted fabrics and nonwovens.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass mindestens eine wässrige Formulierung6. The method according to any one of claims 1 to 5, characterized in that at least one aqueous formulation
(A) mindestens einen weiteren Stoff enthält, ausgewählt aus Verdickern, Vernetzern, Belagsverhinderern, Echtheitsverbessern, Weichmachern, Ent- schäumern, Netzmitteln und Egalisiermitteln.(A) contains at least one further substance, selected from thickeners, crosslinking agents, deposit inhibitors, fastness improvers, plasticizers, defoamers, wetting agents and leveling agents.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass man behandeltes flexibles Substrat im Anschluss an das Kontaktieren trocknet.7. The method according to any one of claims 1 to 6, characterized in that treated flexible substrate is dried after contacting.
8. Flexible Substrate, behandelt nach einem Verfahren nach einem der Ansprüche 1 bis 7.8. Flexible substrates treated by a method according to any one of claims 1 to 7.
9. Druckpasten, enthaltend (B) mindestens eine wässrige Formulierung, die mindestens ein Ethylencopolymerwachs enthält, welches 60 bis 95 Gew.-% Ethylen und 5 bis 40 Gew.-% mindestens einer ethylenisch ungesättigten Carbonsäure einpolymerisiert enthält, und (C) mindestens ein Pigment.9. Printing pastes containing (B) at least one aqueous formulation which contains at least one ethylene copolymer wax which contains 60 to 95% by weight of ethylene and 5 to 40% by weight of at least one ethylenically unsaturated carboxylic acid, and (C) at least one Pigment.
10. Färbeflotten, enthaltend10. Dyeing liquors containing
(B) mindestens eine wässrige Formulierung, die mindestens ein Ethylencopo- lymerwachs enthält, welches 60 bis 95 Gew.-% Ethylen und 5 bis 40 Gew.-% mindestens einer ethylenisch ungesättigten Carbonsäure einpolymerisiert enthält, und (C) mindestens ein Pigment oder (D) mindestens einen Farbstoff. Verfahren zur Behandlung von Substraten(B) at least one aqueous formulation which contains at least one ethylene copolymer wax which contains 60 to 95% by weight of ethylene and 5 to 40% by weight of at least one ethylenically unsaturated carboxylic acid in copolymerized form, and (C) at least one pigment or ( D) at least one dye. Process for the treatment of substrates
ZusammenfassungSummary
Verfahren zur Behandlung von Substraten, indem manProcess for the treatment of substrates by
(A) mindestens ein Substrat, gewählt aus Substraten aus(A) at least one substrate selected from substrates
(A1 ) Polyacryl, Polyester, Silikon, Polyamid oder(A1) polyacrylic, polyester, silicone, polyamide or
(A2) einem oder mehreren Polymeren auf Basis von einem Monomer der allgemei- nen Formel I =\ R 11 ' in denen R1 gewählt wird aus -Cl, C C10-Alkyl, -CH=CH2, -C(CI)=CH2, -C(CH3)=CH2 und -COOd-do-Alkyl, mit mindestens einer wässrigen Formulierung kontaktiert, enthaltend(A2) one or more polymers based on a monomer of the general formula I = \ R 1 1 'in which R 1 is selected from -Cl, CC 10 -alkyl, -CH = CH 2 , -C (CI) = CH 2 , -C (CH 3 ) = CH 2 and -COOd-do-alkyl, contacted with at least one aqueous formulation, containing
(B) mindestens ein Ethylencopolymerwachs enthält, welches 60 bis 95 Gew.-% Ethylen und 5 bis 40 Gew.-% mindestens einer ethylenisch ungesättigten Carbonsäure einpolymerisiert enthält,(B) contains at least one ethylene copolymer wax which contains 60 to 95% by weight of ethylene and 5 to 40% by weight of at least one ethylenically unsaturated carboxylic acid in copolymerized form,
weiterhin mindestens ein Farbmittel, gewählt ausfurthermore at least one colorant selected
(C) mindestens einem Pigment und(C) at least one pigment and
(D) mindestens einem Farbstoff. (D) at least one dye.
EP05745338.3A 2004-05-12 2005-05-04 Method for the treatment of flexible substrates Not-in-force EP1749129B1 (en)

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WO2005113886A1 (en) 2005-12-01

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