EP1749129A1 - Procede de traitement de substrats flexibles - Google Patents

Procede de traitement de substrats flexibles

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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
Authority
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)
English (en)
Other versions
EP1749129B1 (fr
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/fr
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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)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé de traitement de substrats selon lequel (A) au moins un substrat, sélectionné parmi les substrats suivants : (A1) polyacryle, polyester, silicone, polyamide ou (A2) au moins un polymère à base d'un monomère de la formule générale où R1 est sélectionné parmi -Cl, C1-C10-alkyle, -CH=CH2, -C(Cl)=CH2, -C(CH3)=CH2 et -COOC1-C10-alkyle, est en contact avec au moins une formulation aqueuse contenant (B) au moins une cire copolymérique d'éthylène qui contient 60 à 95 % en poids d'éthylène 5 à 40 % en poids d'au moins un acide carboxylique éthyléniquement insaturé et polymérisé et enfin au moins un colorant sélectionné dans (C) au moins un pigment et (D) au moins un colorant.
EP05745338.3A 2004-05-12 2005-05-04 Procede de traitement de substrats flexibles Not-in-force EP1749129B1 (fr)

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DE102004023894A DE102004023894A1 (de) 2004-05-12 2004-05-12 Verfahren zur Behandlung von flexiblen Substraten
PCT/EP2005/004809 WO2005113886A1 (fr) 2004-05-12 2005-05-04 Procede de traitement de substrats flexibles

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DE102004023894A1 (de) 2005-12-08
US20080022466A1 (en) 2008-01-31

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